Method of purifying raw water, containing substances which are hard to decompose


FIELD: chemistry.

SUBSTANCE: to purify raw water which contains one or more substances which are hard to decompose, where the said substances can be halogenated dibenzodioxines, halogenated dibenzofurans, polychlorinated biphenyls, substances which damage the endocrine system different from dioxins, carcinogenic substances and organic halogenated compounds, which can be directly removed through photodecomposition or chemical decomposition, the substances which are hard to decompose are concentrated and neutralised on the following stages: (B) adsorption purification stage, (C) membrane filtration purification stage and (D) chemical decomposition of substances which are hard to decompose, adsorbed on an adsorbent using peroxide without desorption from the adsorbent. The preferred version of the method also includes the following stages: (A) membrane concentration, (E) chlorine neutralisation, (F) photodecomposition, (G) back washing the filtration membrane, (H) flocculation separation. The device for realising the methods has the corresponding sections for carrying out the water purification stages. The method is used to purify water which contains a reducing agent, which neutralises free chlorine.

EFFECT: efficient and cheap neutralisation of substances which are hard to decompose in purified water.

22 cl, 9 dwg, 13 ex

 

The technical field

The present invention relates to a method of purification of raw water containing recalcitrant substances such as dioxins and other substances that have a destructive effect on the endocrine system.

In 1999, Japan was legally adopted special measures to limit emissions of dioxins, which was established rate of emission of dioxins is not higher than 10 PG TE/l (picograms equivalents toxicity). However, in some cases, runoff from waste incineration plants, industrial discharges some installations, waste water drainage systems, etc. have high concentrations of dioxins, significantly exceeding this norm, so there is a need to develop methods of cleaning to reduce the concentration or removal of dioxins.

In addition to dioxins recalcitrant substances also include substances that Deplete the endocrine system (the so-called environmental disruptors of the endocrine system or chemical disruptors of the endocrine system), such as bisphenol, as well as various organic compounds chlorine type trichloroethane and the like, and their emissions were also adopted special regulations. As in the case of dioxins, there is a great need to develop methods of cleaning, aimed at the reduction or complete removal of such prophetic the TV.

There is a method of separation and removal of recalcitrant substances, such as dioxins, from the vent (exhaust) water containing these recalcitrant substances (contaminated water), in which for the chemical decomposition of dioxins waste water is subjected to chemical decomposition of dioxins ozone, vodorazreshimye or hydrogen peroxide, the decomposition by microorganisms or separation/removal with adsorbent or flocculant. However, these methods of separation and removal of inefficient and require large investments in equipment, because you need to directly handle the liquid containing these recalcitrant substances in very low concentrations. In addition, when the waste water has a high level of pollution, in some cases it is impossible to satisfy the norm of emissions, so it is impossible to consider these methods are appropriate.

The known method of neutralization of recalcitrant organic compounds, for example, for the removal of dioxins, in which dioxins are subjected to chemical decomposition of ozone, vodorazreshimye and hydrogen peroxide, the decomposition by microorganisms or separation/removal with adsorbent or flocculant. Used in this processing, at which dioxin add an oxidizer to their chemical decomposition in order to obiturary the project, since this cleaning operation is simple. In addition, as an oxidant for the chemical decomposition of dioxins, are known, for example, a method using persulfate (for example, JP-A-2003-93999 and JP-A-2003-285043).

On the other hand, there is a method of wastewater treatment in which contaminated water is subjected to settling cleaning, filter it through a mesh with an average pore diameter of 10-100 μm, treated filtrate UV light in the presence of photocatalyst for the implementation of catalytic cracking and purified using ultrafiltration membranes (for example, JP-A-2003-144857).

Also known purification method, in which waste water is cleaned by the method of separation using reverse osmosis membrane (RO membrane), and a concentrated liquid serves on the stage of oxidation for the chemical decomposition of the active oxygen (for example, JP-A-H11-347591 and JP-A-2000-354894).

In addition, known methods such prevent discharge of recalcitrant substances, physical methods, chemical methods and biological methods. Physical methods include adsorption methods, among which the well-known method of adsorption, in which activated carbon is injected into the water (see, for example, "Countermeasure technique against dioxins", edited by Naomichi HIRAYAMA, CMC, pages 197-205 (1998)), and the way in which activated carbon is injected in the exhaust is AZ. However, in this case activated carbon, adsorbirovavshyei recalcitrant substance that keeps it within himself, and therefore the coal in this form cannot be removed to waste.

Activated carbon used for adsorption, the destroy method of combustion, thermal decomposition or disposal. However, with this method there is a risk of release of adsorbate together with the exhaust gas, which causes secondary pollution, or seepage from reclaimed land, causing secondary contamination. There is therefore a need for safe and economical method of cleaning.

Known methods such decomposition of recalcitrant substances in discharged water, soil or sediment containing recalcitrant substance, such as thermal decomposition, chemical decomposition with the use of alkali, a method of using a fluid in the supercritical state, the method using a combination of ozone, peroxide, such as hydrogen peroxide or hydrochloride with UV light. In addition, we study biological methods using fungi white rot or enzymes produced by microorganisms.

Each of these methods has its own distinctive features, some of them are easy to apply, and other difficult to use, depending on the state of the present recalcitrant, washes the VA. For example, the method of thermal decomposition and decomposition using supercritical water require expensive equipment and energy, and there are many cases in which they cannot be used from an economic point of view. Furthermore, the method using a combination of ozone or hydrogen peroxide with UV light cannot be used for suspensions that can't easily skip ultraviolet light, or solids, such as soil or sludge. Therefore, the waste water containing suspended matter or floating matter can be cleared only after the removal of such substances by filtering or settling for his Department. When this recalcitrant substance adsorbed on suspended solids must be cleaned separately.

Known methods of cleaning water discharge, as a means of chemical decomposition using a combination of hydrogen peroxide with iron salt and the method of chemical decomposition using persulfate or permanganate.

For example, in JP-A-2000-189945 described purification method, which can remove a chemical substance that Deplete the endocrine system, using a simple device and within a short period of time, so that its concentration decreases to a low level. In this way a chemical razreshau the e endocrine system, adsorb water on activated carbon or the like, then it is concentrated by Stripping and the resulting concentrated liquid is brought into contact with a peroxide, such as persulfate and the like, to effect the decomposition. A common problem associated with harmful substances that Deplete the endocrine system, is that with the increasing complexity of their processing increases the likelihood of re-contamination of the human body or the environment.

Therefore, if it were possible to decompose recalcitrant substance adsorbed on the solid, without elution, this operation would be very simple and would eliminate the risk of re-contamination of the human body or the environment. In addition, it would provide many advantages, namely: adsorbent, used for separating recalcitrant substances by decomposition, can be used repeatedly; the processed substance can be transported, and this method could be applied to solid contaminants from the soil or sediment; therefore, there is a need to develop appropriate methods.

Next will be described the purification of discharged water containing recalcitrant substance.

A source of formation of discharged water containing recalcitrant substance that can be set is for chlorine bleaching in pulp and paper industry, installation for decomposition disposed of PCBs (polychlorinated biphenyls) or substances formed during the processing of PCBs, the equipment for washing materials contaminated with PCB or formed during processing of PCBs, treating equipment, furnaces, etc. for the production of aluminum or its alloys, equipment, wet scrubbers, sewers discharging waste water, etc.

In addition, the Agency for environmental protection has made changes in the norms for pollutants of the aquatic environment and complement the list of environmentally dangerous substances contained before heavy metals as basic substances, organic compounds such as trichloroethylene, tetrachloroethylene, PCBs, etc.

The known method that provides the maximum possible removal of recalcitrant substances from the treated water that contains this recalcitrant substance, by using the filtering device, method, membrane separation, etc. and decomposition of recalcitrant substances in the treated water (for example, see JP-A-H11-99395).

For cleaning containing recalcitrant substance discharged water is described by way of a filtration treatment, biological treatment, etc. perform as pre-cleaning and cleaning with ozone, ultraviolet irradiation, catalytic cleaning the or purification activated carbon performed as a follow-up cleaning. Therefore, this decomposition and removal requires a large effort and a large number of materials.

In addition, if we take for example the cleaning of ultraviolet radiation, this method can only be used in the reaction system, which is capable of passing ultraviolet light, however, it cannot be used for liquids containing solid matter, and solids. Also recalcitrant substance removed by preliminary treatment, must be separately cleaned, to prevent secondary pollution.

Therefore, there is a great need to develop effective decomposition of such recalcitrant substances in a closed system, eliminating re-contamination of the human body and the environment.

The chemical decomposition of recalcitrant organic compounds by adding persulfate described in the above JP-A-2003-93999 and JP-A-2003-285043, the efficiency of decomposition of recalcitrant organic compounds is low, and therefore very difficult to clean from compounds having a high concentration. On the other hand, there are cases when such organic compound having a high concentration is treated with persulfate to which the added metal salt such as a salt of ruthenium. However, such metal salt is very expensive, and its use uneconomical.

When applying the method described in JP-A-2003-144857 for treatment of discharged water containing a small amount of solids in decayed matter, the layer that would be formed by deposition of solid substances in the form of a decomposed substance, is formed on the metal mesh, and containing dioxin solid, or small particles of decomposed substance, or dissolved dioxin pass through the mesh, making cleanup sometimes inadequate.

When applying the method described in JP-A-H11-347591 and JP-A-2000-354894, if contaminated water is free of chlorine, it is necessary to add an excess amount of reducing agent, such as a bisulfite, or the like, to neutralize free chlorine. This bisulfite or the like prevents chemical degradation, therefore, cannot be considered an effective method for the separation and removal of recalcitrant substances.

The aim of the present invention is to provide a method of purification of water containing recalcitrant substance intended for concentration and disposal of recalcitrant substances, such as dioxins contained in polluted water (purified raw water, such as runoff from waste incineration plants, industrial waste water determined the CSOs equipment, drain some water drainage systems and the like, and this method should be applicable to water containing a reducing agent, such as a bisulfite, which will neutralize free chlorine and should provide efficient and economical disposal of recalcitrant substances, regardless of its properties.

The aim of the present invention is to provide a method for the effective decomposition of recalcitrant substances adsorbed on the solid as it is, without performing procedures desorption, and the way of regeneration of the adsorbent used for the separation of recalcitrant substances by adsorption.

The second objective of the invention is to provide a method of cleaning the drawdown of water in which recalcitrant substance is separated from the discharged water containing harmful recalcitrant substance, by deposition, and in which recalcitrant substance effectively decomposes in the solid state, allowing a closed system.

A third object of the invention is to provide a reliable system for cleaning discharge water, uniting various stages of division and decay, which could reliably meet established emission standards even when changing the concentration of recalcitrant substances in discharged water.

Summary SunOS and inventions

To solve the above problems, the authors have conducted extensive studies and found that it is possible to reduce the concentration of recalcitrant substances, such as dioxins, in discharge of water or waste to a low level, by combining the method of concentration-based membrane separation, chemical decomposition and/or method fotorazlozheniya.

In addition, it was found that when combining purification using reverse osmosis membrane (RO membrane) or nanofiltration membrane (NF membrane), which can be used to concentrate the salt, and purification using ultrafiltration membrane (UF membrane), which skips salt, you can stop the increase in osmotic pressure caused by the concentration during the process of salts contained in the dirty water and the like, and to suppress the reduction of the filter capacity.

It was also found that the use of the adsorbent of titanium dioxide having a high adsorption capacity, can improve the effectiveness of chemical decomposition, and because titanium dioxide acts as a photocatalyst, and therefore is used as a catalyst for fotorazlozheniya, you can also apply vodorazreshimye in combination that will create a more reliable system for purification of water containing trudnorazlichimo the substance. These findings were the basis of the present invention.

Thus, according to the first aspect of the present invention proposed the following methods of water purification, containing recalcitrant substance.

1. The method of purification of water containing recalcitrant substance, including the stage at which

(B) type adsorbent in water containing recalcitrant substance (purify raw water)to cause the adsorption of recalcitrant substances on the adsorbent (adsorption stage purification);

(C) separating the liquid that has passed through the filtration membrane for concentration of adsorbent, adsorbirovavshyei recalcitrant substance (cleaning stage membrane filtration) and

(D) perform chemical decomposition of recalcitrant substances adsorbed on concentrated adsorbent, using peroxide without surgery desorption of adsorbent (stage chemical decomposition).

2. The method of purification of water containing recalcitrant substance according to claim 1, above, in which in stage (D) apply peroxide in the amount of at least 100 times larger than in a molar ratio of the number of recalcitrant substances.

3. The method of purification of water containing recalcitrant substance according to claim 1 or 2, above, which additionally includes a step (A) separation from water containing the Tr is northleave substance, fluid that has passed through the reverse osmosis membrane (RO-membrane) or nanofiltration membrane (NF-membrane), for concentration of recalcitrant substances (phase concentration of cleaning).

4. The method of purification of water containing recalcitrant substance according to claim 1, above, which additionally includes a step (E) neutralizing the chlorine in the water containing recalcitrant substance (stage neutralize the chlorine).

5. The method of purification of water containing recalcitrant substance according to claim 1, above, which additionally includes a step (F) performing irradiation with ultraviolet light to decompose recalcitrant substances (phase fotorazlozheniya).

6. The method of purification of water containing recalcitrant substance according to claim 1, above, which additionally includes a step (G) the implementation of the backwashing of the filtration membrane used in stage (C), removal of the adsorbent, adsorbirovavshyei recalcitrant substance of the filtration membrane (stage backwashing).

7. The method of purification of water containing recalcitrant substance according to claim 1, above, which additionally includes a step (H) adding a flocculant into the water containing the adsorbent, adsorbirovavshyei recalcitrant substance for flocculation and separation of the adsorbent, adsorbirovavshyei recalcitrant substance (stage the flock is anionnogo split).

8. The method of purification of water containing recalcitrant substance according to claim 1, above, in which the adsorbent is added in stage (B)is one of the inorganic adsorbent, or two or more inorganic adsorbents selected from the group consisting of titanium dioxide, zeolite, acid clay, activated clay, diatomaceous earth, metal oxide, metal powder, activated carbon and carbon black.

9. The method of purification of water containing recalcitrant substance of claim 8, above, in which the adsorbent is added to step (B), use titanium dioxide.

10. The method of purification of water containing recalcitrant substance according to claim 1, above, in which the filtration membrane for use in stage (C) are selected from the group consisting of ultrafiltration membrane (UF membrane), nanofiltration membrane (NF membrane), microfiltration membrane (MF membrane) and reverse osmosis membrane (RO membrane).

11. The method of purification of water containing recalcitrant substance according to claim 1, above, in which the peroxide used in stage (D)use persulfate.

12. The method of purification of water containing recalcitrant substance according to claim 1, above, in which at least part of recalcitrant substances, concentrated on the stage (A), and/or adsorbent, adsorbirovavshyei traderslog is my stuff on stage (C), return to the water containing recalcitrant substance (purify raw water), or the stage prior to stage (A) or stage (S).

According to the second aspect of the present invention proposed a device for purification of water containing recalcitrant substance intended to implement the above options according to the first aspect of the invention.

13. Device for purification of water containing recalcitrant substance containing

section adding the adsorbent that is used to add the adsorbent in water containing recalcitrant substance (purify raw water);

the partition membrane filtration, designed to separate the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance, and

section cleaning chemical decomposition that is used for the oxidative decomposition of recalcitrant substances adsorbed on the adsorbent, with the use of peroxide.

14. Device for purification of water containing recalcitrant substance containing

section introducing a reducing agent intended for the introduction of a reductant in water containing recalcitrant substance (purify raw water)to neutralize the chlorine in the water;

section purification membrane concentration, before oznachennoe for the Department of water, containing recalcitrant substance, liquid, passed through the reverse osmosis membrane (RO-membrane) or nanofiltration membrane (NF-membrane)in order to concentrate recalcitrant substance;

section adding the adsorbent that is used to add the adsorbent in concentrated recalcitrant substance to cause the adsorption of recalcitrant substances by adsorbent;

section cleaning membrane filtration, designed to separate the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance;

the section adding a flocculant, designed to add a flocculant in water containing adsorbent, adsorbirovavshyei recalcitrant substance in order to carry out the flocculation of the adsorbent, adsorbirovavshyei recalcitrant substance;

partition separating solids and liquids, designed to separate the adsorbent, adsorbirovavshyei recalcitrant substance and flocculated flocculant, and

section cleaning chemical decomposition that is used for the oxidative decomposition of recalcitrant substances adsorbed on the separated adsorbent, with the use of peroxide.

According to a third aspect of the present invention proposed the following methods is koncentrirovannaya water, containing recalcitrant substance.

15. A method for concentrating recalcitrant substances in water containing recalcitrant substance, including the stage at which:

(B) type adsorbent in water containing recalcitrant substance (purify raw water), to perform the adsorption of recalcitrant substances on the adsorbent (adsorption stage purification) and

(C) separating the liquid that has passed through the filtration membrane for concentration of adsorbent, adsorbirovavshyei recalcitrant substance (cleaning stage membrane filtration).

16. A method for concentrating recalcitrant substances in water containing recalcitrant substance indicated in paragraph 15 above, which additionally includes the stage

(A) separation from water containing recalcitrant substance, liquid, passed through the reverse osmosis membrane (RO-membrane) or nanofiltration membrane (NF-membrane), for concentration of recalcitrant substances (processing stage membrane concentration).

17. A method for concentrating recalcitrant substances in water containing recalcitrant substance according to item 16 above, in which at least part of recalcitrant substances, concentrated on the stage (A), return to the water containing recalcitrant substance (purify raw water)

According to a fourth aspect of the present invention, a method of water purification, the concentrated according to a third aspect of the invention.

18. The method of purification of water containing recalcitrant substance, including the irradiation of light recalcitrant substances, concentrated way the concentration of recalcitrant substances in water containing recalcitrant substance according to any one of PP-17, for the decomposition of recalcitrant substances.

According to the first and second aspects of the present invention recalcitrant substances, such as dioxins, etc. that are contained in the water, can effectively decompose and remove regardless of their concentration.

According to the first and second aspects of the present invention the chemical decomposition-based oxidizer and vodorazreshimye on the basis of irradiation with ultraviolet light are combined to effectively reduce the content of recalcitrant substances in the water to a low level and to create a very reliable purification system.

According to the first and second aspects of the present invention described above, the cleaning chemical decomposition is performed in a state in which recalcitrant substance adsorbed on the solid, without performing desorption, which allows you to regenerate the adsorbent and use it on the view.

According to a third aspect of the present invention recalcitrant substance in water containing recalcitrant substance can be efficiently concentrated.

According to the first, second, and fourth aspects of the present invention water containing recalcitrant substance that can effectively and safely be cleaned in a closed system, and all the cleaning can be carried out at the place of origin of this water, containing recalcitrant substance that eliminates the need for transportation of recalcitrant substances, which could lead to environmental pollution, and there is no impact on the environment.

Brief description of drawings

Figure 1 schematically depicts the main stages of the implementation of the method of purification of water containing recalcitrant substance, according to the present invention;

figure 2 depicts the sequence of operations one variant of the method of purification of water containing recalcitrant substance, according to the present invention;

figure 3 depicts schematically water purification device for implementing one variant of the method of purification of water containing recalcitrant substance, according to the present invention;

figure 4 depicts one variation of the device to which the stages of the multiple filter according to astasia invention;

figure 5 depicts another variant of the device to which the stages of the multiple filter according to the present invention;

6 schematically depicts the device used in example 1;

7 schematically depicts the device used in example 2;

Fig schematically depicts the device used in example 3;

Fig.9 depicts schematically a device used in example 4;

figure 10 schematically depicts the device used in example 5;

11 schematically depicts the device used in example 6;

Fig schematically depicts the device used in example 7;

Fig schematically depicts the device used in examples 8 and 9;

Fig schematically depicts the device used in example 10;

Fig schematically depicts the device used in example 11;

Fig schematically depicts the device used in example 12.

The preferred method of carrying out the invention

Next will be explained in more detail the present invention.

The method of purification of water containing recalcitrant substance, according to the first aspect of the invention (hereinafter referred to as the "proposed method") includes a stage on which:

(B) type adsorbent in water containing trudnoca the proposed substance (purify raw water), to cause the adsorption of recalcitrant substances on the adsorbent (adsorption stage purification);

(C) separating the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance (cleaning stage membrane filtration) and

(D) perform chemical decomposition of recalcitrant substances, absorbirowawrzegosa concentrated on the adsorbent, using peroxide without surgery desorption of adsorbent (stage chemical decomposition).

The proposed method is a method in which recalcitrant substance contained in the water are concentrated by filtration through the membrane and are removed from the water, and concentrated recalcitrant substance is neutralized by the method of chemical decomposition and optional method fotorazlozheniya.

In the context of the present invention "concentration" recalcitrant substances or adsorbent, adsorbirovavshyei recalcitrant substance, implies an increased concentration of recalcitrant substances containing water or on the adsorbent, adsorbirovavshyei recalcitrant substance.

The main stages of the proposed method is illustrated in figure 1.

Examples of recalcitrant substances, which can be cleaned using predlozhenogo.potom, include dioxins, which are dangerous pollutants in soil or sediment, as well as other destructive endocrine system substances and carcinogenic substances, etc.

Above dioxins will include, for example, halogenated dibenzodioxins, halogenated dibenzofurans, PCBs (in particular, coplanar PCBs, in which a chlorine atom is substituted in any position other than the ortho position).

Examples of halogenated dibenzodioxins include 2,3,7,8-tetrachlorobenzo-p-dioxin, 1,2,3,7,8-pentachlorodibenzo-p-dioxin, 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin and 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin.

Examples of halogenated dibenzofurans include 2,3,7,8-tetrachlorodibenzofuran, 1,2,3,7,8-pentachlorodibenzofuran, 1,2,3,4,7,8-hexachlorodibenzofuran, 1,2,3,4,6,7,8-heptachlorodibenzofuran and 1,2,3,4,6,7,8,9-octachlorodibenzofuran.

Examples of PCBs (in particular, coplanar PCBs, in which a chlorine atom is substituted in any position other than the ortho-position) include 3,3',4,4',5-tetrachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl and 3,3',4,4',5,5'-hexachlorobiphenyl.

Destroying the endocrine system agents, in addition to dioxins and carcinogenic substances include ALKYLPHENOLS such as tert-butylphenol, Nonylphenol and op, halogenated phenols, such as tetrachlorophenol and pentachlorophenol, bispen the crystals, such as 2,2,-bis(4-hydroxyphenyl)propane (bisphenol a) and 1-bis(4-hydroxyphenyl)cyclohexane, polycyclic aromatic hydrocarbons, such as benzo (a) pyrene, chrysin, benzanthracene, benzofluoranthene and pizen and esters of phthalic acid such as dibutyl phthalate, butylbenzylphthalate and di-2-ethylhexylphthalate.

In addition to the above dioxins and PCBs, method fotorazlozheniya or chemical decomposition according to the proposed method can also remove recalcitrant organic halogenated compounds such as dichloropropane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichlorethylene.

The proposed method includes a stage (C) adsorption purification stage (S) of filtration and stage (D) chemical decomposition, and may also optionally include at least one phase selected from the group consisting of stage (A) purification using membrane concentration, stage (E) neutralizing chlorine, stage (I) pre-filtering stage (F) fotorazlozheniya, stage (G) backwashing and stage (N) flocculation compartment. Each of these stages can be performed once, twice or more. During repeated execution of one or two stages increase the reliability of the proposed method and the possibility of decomposition and removal of recalcitrant substances to more n is skogo level. Each stage will be described in detail below with reference to figure 2

(E) stage neutralize chlorine

This stage consists in the neutralization of residual chlorine in water containing recalcitrant substance. Residual chlorine is preferably removed in advance, as it oxidizes reverse osmosis membrane, and this may degrade its properties. The chlorine concentration is measured by measuring the concentration of chlorine and add the appropriate amount of reducing agent.

The reducing agent includes sodium bisulfite, sodium metabisulfite and sulfur dioxide, and most preferred is sodium bisulfite.

(I) stage pre-filtration

This stage is filtration of water containing recalcitrant substance, for example, through the pre-filter with pores of 10 μm, to prevent clogging of the reverse osmosis membrane by the foreign particles contained in the water.

(A) cleaning stage membrane concentration

This stage is to separate the liquid that has passed through the reverse osmosis membrane (RO-membrane) or nanofiltration membrane (NF-membrane), from water containing recalcitrant substance, for concentration of recalcitrant substances. For example, because dioxin has a molecular weight of 200 or more, it can from the ed through a reverse osmosis membrane or a nanofiltration membrane at the molecular level. Reverse osmosis membrane and a nanofiltration membrane does not pass through not only recalcitrant substance, but also the salt contained in the water. Therefore, at the same time concentrates salts, which increases the osmotic pressure of water containing recalcitrant substance, and reduced filtration efficiency.

The term "salt" in this context includes all types of salts (inorganic salts of alkali metals)contained in the water containing recalcitrant substance, and mainly includes chloride, metabisulfite or sodium bisulfite and sodium bisulfate. The sodium chloride formed during the neutralization of residual chlorine, and a greater amount of sodium chloride contained in the purified water containing recalcitrant substance.

Working pressure when cleaning the membrane concentration using reverse osmosis membrane is not particularly limited. However, with increasing operating pressure usually increases the ratio of removal of recalcitrant substances, such as dioxin, it is preferable to perform this operation at 1 MPa or higher, more preferably at 1.5 MPa or higher, which is higher than usually applied pressure of 0.3 MPa. In addition, to enable operation of the reverse osmosis membrane for a long period of time and predot is atiti reduction in the rate of removal, caused by the concentration of circulating water, it is possible to determine the ratio of the concentrated water to last through the membrane water needs depending on the properties of the discharged water. This ratio typically ranges from 1:99 to 80:20, preferably from 30:70 to 60:40, particularly preferably 50:50.

The material for the performance of reverse osmosis membrane (sometimes hereinafter referred to as "GS-membrane") includes such materials from a number of polymer resins as polyamide material (including cross-linked polyamide and aromatic polyamide materials), the condensation of aliphatic amines, heterocyclic polymers, cellulose acetate, polyethylene material, polyvinyl alcohol and polyester material.

The shape of the membrane is not specifically limited and can be asymmetric or composite.

In addition, the membrane module can be made flat, hollow-fiber, spiral, cylindrical, corrugated, etc. depending on the needs.

The material for the performance of nanofiltration membrane (NF membrane) includes materials from a number of polymer resins, such as polyamide material (including cross-linked polyamide and aromatic polyamide materials), the condensation of aliphatic amines, heterocyclic polymers, cellulose acetate, polyethylene material, polyvinyl JV is RT and polyester material.

Form nanofiltration membrane has no special limitation, and, like reverse osmosis membrane, it can be asymmetric or composite.

In addition, the membrane module can be made flat, hollow-fiber, spiral, cylindrical, corrugated or the like, depending on the needs.

Although the removal of salt through the membrane (the ratio of removal of sodium chloride) has no specific limitation, it is preferable to choose a reverse osmosis membrane with a selectivity of about 95% or more. In addition, when using a nanofiltration membrane, it is preferable to use a membrane having a selectivity of approximately 40% or more based removal of salt.

In addition, when cleaning the membrane concentration using the above-described reverse osmosis membrane or a nanofiltration membrane of the fluid which has not passed through the membrane (concentrated water)can be returned as containing recalcitrant substance water, which had not been cleaned.

(C) stage adsorption purification

This stage consists of adding the adsorbent in water containing recalcitrant substance (purify raw water), or water in which recalcitrant substance was concentrated at the stage of (A)to call the AMB adsorption recalcitrant substances on the adsorbent. When recalcitrant substance or water, concentrated when cleaning the membrane concentration, is subjected to membrane filtration stage (C), recalcitrant substance impossible to concentrate because the membrane filter has a large cut-off molecular weight as compared with the size of recalcitrant substances, such as dioxin. So add the adsorbent to cause the adsorption of small recalcitrant substances in large particles of the adsorbent, and then carry out stage (C) purification of membrane filtration, providing the concentration of recalcitrant substances.

The adsorbent for use in the proposed method includes an inorganic porous material and organic porous material. In particular, the adsorbent comprises an inorganic porous material such as zeolite, diatomaceous earth, acid clay, activated clay and carbon black, metal oxides such as titanium dioxide, inorganic adsorbents, such as metal powder, activated carbon, organic porous materials, such as ion exchange resin. They can be used separately or in combination of at least two materials. The preferred adsorbents are inorganic adsorbents, and of these the most preferred titanium dioxide with high the Oh adsorption capability.

Further, in the description of stages (F-1) and (F-2) fotorazlozheniya the preferred adsorbent is an adsorbent, which can act as a photocatalyst, and an example of such adsorbent is titanium dioxide.

The required number of added adsorbent can be determined by the type of adsorbent, adsorption capacity, type and quantity of treated pollutant, processing time, cost, etc. it Usually takes from 1 to 1000 ppm, preferably 10-100 h/million

When using titanium dioxide as the adsorbent, the amount of adsorbed recalcitrant substances increases with increasing amounts of titanium dioxide, but increases the cost. The amount of added titanium dioxide should be determined depending on needs and cost, etc. and it is usually from 1 to 100,000 ppm, more preferably 10-1000 h/million

In addition, to improve the efficiency of adsorption and decomposition is preferable to use an adsorbent having a large specific surface area. For example, if the adsorbent is titanium dioxide, it is preferable to choose titanium dioxide having a particle diameter determined by x-ray, approximately 7 nm.

In addition, with increasing time of contact of the adsorbent with water containing recalcitrant in the society, increases the efficiency of adsorption. However, the required contact time should be determined based on the size of the treatment tank or the like, and it is preferably from 1 to 2 hours.

(F) stage fotorazlozheniya

This stage consists in the irradiation of water containing recalcitrant substance, or adsorbent, adsorbirovavshyei recalcitrant substance with ultraviolet light to decompose recalcitrant substances. Thus decompose recalcitrant substance that was not adsorbirovannoi on the adsorbent in the water, and part of recalcitrant substances, absorbirowawrzegosa on the adsorbent in the water. If this stage is carried out, the waste water after treatment can be reduced to a lower concentration of recalcitrant substances.

In addition, at this stage, if the adsorbent for use in the present invention is titanium dioxide, recalcitrant substance in water can more effectively be fotorazlozheniya by irradiation with light (preferably 250-380 nm). The longer the period of time fotorazlozheniya, the higher the efficiency of decomposition. For example, adding 20 ppm of titanium dioxide and irradiated with ultraviolet light (254 nm) for 30 minutes, the efficiency of decomposition of dioxins is approximately 60-70%.

(C) cleaning stage of the membranes of the second filtering

This stage consists in the separation of liquids containing salt, but essentially not containing recalcitrant substance which has passed through the filtration membrane is impermeable to the adsorbent, adsorbirovavshyei recalcitrant substance, but permeable to salt, to produce water with high concentration of adsorbent, adsorbirovavshyei recalcitrant substance. Using this stage you can remove the salt.

Membrane for use in the purification of membrane filtration has no special restrictions, if she has mentioned separation ability. From the viewpoint of excellent separation ability and ease of operation, it is preferable to choose a membrane, for example, ultrafiltration membrane (UF membrane), nanofiltration membrane (NF membrane), microfiltration membrane (MF membrane), reverse osmosis membrane (RO membrane) or the like

Of the above membranes ultrafiltration membrane (also referred to as "UV-membrane") is able to completely remove the fine adsorbent, adsorbirovavshyei dioxins and fine particles of water-insoluble dioxin, and she has excellent working and economic characteristics.

The material for the performance of ultrafiltration membrane (UF membrane) includes materials from a number of polymer resins, such as zitat cellulose, polyacrylonitrile, polysulfone and polyethersulfone.

The membrane module can be made flat, hollow-fiber, spiral, cylindrical, corrugated or the like, depending on the needs.

Although the cut-off ultrafiltration membrane molecular weight has no special limitation, you can use ultrafiltration membrane with a cutoff molecular weight from about 3000 to 150000.

The material for the performance of microfiltration membrane (MF membrane) includes materials from a number of polymer resins, such as cellulose ester, polyacrylonitrile, polysulfone and polyethersulfone. You can choose, depending on needs, a flat shape, filter cartridge, disposable cartridge, etc.

Although the size of the openings (pores) in the microfiltration membrane can be determined by the needs depending on the particle diameter of the adsorbent used in an adsorption purification, preferably they can be from 0.01 to 1 μm.

In addition, the reverse osmosis membrane (RO membrane) and nanofiltration membrane (NF membrane) correspond to the membranes described in connection with stage (A) purification of membrane concentration.

(G) stage backwashing

This stage is in the backwash filtration membrane used in stage (C), above, in which osvobojdenie adsorbent, adsorbirovavshyei recalcitrant substance of the filtration membrane. If at the stage (C), above, is used ultrafiltration membrane, adsorbent, adsorbirovavshyei recalcitrant substance (in particular, if the adsorbent used titanium dioxide), scored ultrafiltration membrane. Therefore, in order to prevent the reduction of permeability in the above-described filtration membrane, preferably periodically wash the filter membrane. Although the frequency of backwashing, you can choose depending on the needs, preferably it is performed, for example, every 30-120 minutes for about 1-10 minutes each time. Also when performing backwashing is preferable to use pure water, not containing solid substances. From an economic point of view it is preferable to use as wash water passed through the membrane liquid obtained in stage (A) purification of membrane concentration, or passed through the membrane liquid obtained in stage (C) purification of membrane filtration. Passed through the membrane liquid obtained in stage (A) purification of membrane concentration, is especially preferred.

It is also preferable to add a bactericide, such as sodium hypochlorite or the like, the washing water to erase the implementation, and sodium hypochlorite can be added in an amount such that the residual chlorine concentration after backwashing ranged from 1 to 100 mg/L.

To improve the efficiency of decomposition of recalcitrant substances at the following stages of the water supplied to the step (D) chemical decomposition, which will be described below, preferably consists only of the discharge of flush water from which was washed adsorbent, adsorbirovavshyei recalcitrant substance. Alternatively, in stage (D) chemical decomposition may be supplied, depending on the needs, concentrating recalcitrant substance water obtained in stage (A) purification of membrane concentration.

(H) stage flocculation compartment

This stage consists of adding a flocculant into the water containing the adsorbent, adsorbirovavshyei recalcitrant substance for flocculation and separation of the adsorbent, adsorbirovavshyei recalcitrant substance. More specifically, at this stage add the flocculant into the water containing the adsorbent, adsorbirovavshyei recalcitrant substance is concentrated at the stage (C), above, or wash waste water obtained in stage (G), above, for additional flocculation of the adsorbent, adsorbirovavshyei recalcitrant substance, and receive flocculated substance containing TRU is Norzagaray substance. Flocculated substance is usually a settled matter (sludge), although it may also be flocculated substance (floating matter), which swims and accumulated on the surface of the liquid.

The liquid (usually supernatant)obtained by separation of the flocculated substances containing recalcitrant substance, at this stage you can return at any stage of purification according to the invention. In addition, if the concentration of recalcitrant substances are lower than the fixed rate of release, then it can be removed to waste.

The adsorbent, adsorbirovavshyei recalcitrant substance is small, and the separation of solids and liquids takes a long time. This stage is to reduce the time and increase the efficiency of decomposition at the next stage (N) chemical decomposition.

As the flocculant can be used inorganic or organic flocculant flocculant, separately or together. Examples of inorganic flocculant include aluminum sulfate, iron chloride, iron sulfate, polychloride aluminum and reagent-based zeolite.

Examples of organic flocculant include various anionic polymer flocculants and cationic polymer flocculants, such as sodium polyacrylate, a copolymer of acrylate Natrii acrylamide.

The flocculant has no special limitation, enough so that it does not adversely impact on the stage (D) chemical decomposition. However, it is preferable reagent, consisting mainly of inorganic material, which gives flocculated substance greater bulk density when it is used in a small amount.

Like the adsorbent, the required amount of flocculant can be defined depending on the type of flocculant, adsorption capacity, cost, etc. it Usually is 1-10000 h/million, preferably 10-1000 ppm If the number is finally discharged solids must be reduced to the lowest possible, it is preferable that the amount of flocculant has not led to excess.

(D) phase chemical decomposition

This stage consists of adding peroxide to the adsorbent, adsorbirovavshyei recalcitrant substance at the stage (C), or in flocculated substance (precipitate or suspension)obtained in stage (H), for the oxidative decomposition of recalcitrant substances. When performing the chemical decomposition of peroxide interacts with recalcitrant substance adsorbed on the adsorbent, without surgery desorption recalcitrant substances from the adsorbent, which allows to neutralize recalcitrant substance method the m decomposition, not calling him selection to the outside.

Peroxide for chemical decomposition of recalcitrant substances can interact with recalcitrant substance being in the form of the parent compound. Otherwise, it can interact with recalcitrant substance in the form of compounds formed as a result of changes in water, ion, radical, or the like

Peroxide for use in this stage include various metal salts, such as permanganate, persulfate, sodium peroxide, barium peroxide, peroxide zinc, cadmium peroxide, potassium peroxide, calcium peroxide and chromium peroxide, hydrogen peroxide, ozone, as well as a system using a combination of a metal catalyst and a material supplying hydrogen.

Of these preferred peroxides peroxides used as the oxidant, are the permanganate and persulfate.

The permanganate includes permanganate zinc permanganate cadmium, potassium permanganate permanganate calcium permanganate silver permanganate strontium, cesium permanganate, sodium permanganate, permanganate barium, magnesium permanganate, lithium permanganate permanganate rubidium.

The persulfate includes ammonium persulfate, sodium persulfate, potassium persulfate, hydropersulfides potassium persulfate lead and persulfate rubidium. In ka is este oxidant, in particular, preferred are persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate. They can be used alone or two or more compounds together. Their number is calculated on the molar amount of recalcitrant substances adsorbed on the adsorbent, preferably at least 100 times in moles, more preferably in 104-1012times in moles, even more preferably 107-1010times in moles. When the molar amount of the peroxide is at least 100 times greater than the molar amount of recalcitrant substances, recalcitrant substance adsorbed on the adsorbent, can stably chemically decompose in an amount to provide a set rate of release (3000 PG TE/g) for industrial waste or below, even if the concentration of recalcitrant substances in water containing recalcitrant substance is changed.

In particular, the required amount of peroxide can be defined depending on the type and the concentration of recalcitrant substances in the material containing recalcitrant substance, and the type and concentration together present matter. If material containing recalcitrant substance is in the liquid state, the above quantity is preferably what is 100-100000 ppm, particularly preferably 1000-50000 h/million If the material containing recalcitrant substance is a solid, the amount of peroxide on the basis of material containing recalcitrant substance is preferably 0.01 to 100 wt.%, particularly preferably 0.1 to 20 wt.%.

The amount of added peroxide varies depending on the pH of the treated water, and to stimulate the reaction, you can add peroxide with regard to the oxidative capacity of the persulfate.

To stimulate decomposition of the peroxide, it is preferable to give the peroxide to react with recalcitrant substance in a state where the peroxide is dissolved in the water. In addition, there may also be other oxidants such as hydrogen peroxide and ozone.

For effective management of the above decomposition reaction in this reaction system, you can add the appropriate amount of organic solvent. An organic solvent selected from hydrocarbons having from 2 to 12 carbon atoms, such as n-hexane, toluene, xylene, methylphthalic or similar

The persulfate decomposes when heated with the formation of the bisulfite ion-radical, sulfate ion radical and hydroxyl radical, these radicals decompose recalcitrant substance, such as dioxins. As these free radicals, electrons within a short period of time, it is preferable to cause the adsorbent, adsorbing recalcitrant substance in the suspension and mix it to improve the efficiency of decomposition. The more intense is the mixing, the higher the probability of contact radicals with recalcitrant substance. Therefore, it is preferable to intensive mixing. However, the mixing has its own limit, and it is preferable to perform the mixing intensively to such an extent that it is cost-effective depending on the volume of the tank for decomposition and the viscosity of the suspension.

The reaction temperature chemical decomposition of recalcitrant substances adsorbed on the adsorbent, with the use of peroxide is preferably in the range from room temperature to 100°C, more preferably from 40 to 100°C. In some cases, when the reaction temperature below 40°C, the decomposition may take more time.

The higher temperature chemical decomposition, the higher the rate of decomposition. For decomposition at the temperature of boiling water (above 100°C under high salt concentration or higher is required vessel working under pressure, it is preferable to perform decomposition at atmospheric pressure at the boiling point or below. In addition, when the decomposition is performed at atmospheric pressure at a temperature of the andsinging or higher, the water evaporates and recalcitrant substance such as dioxin or the like, also evaporates with increasing temperature, therefore there is a need for equipment for purification of exhaust gas, to prevent secondary pollution.

When using heating in the present invention to a method of heating does not impose special restrictions, and you can use any of the methods of electric heating, hot water, feed water steam, boiler method, etc. With hot water; be careful that the water content was not excessive. With a too high water content decreases the concentration of persulfate for the reaction. Although the period of time necessary for the chemical decomposition, it is impossible to determine the same, as it depends on the processing temperature and other conditions, it is usually from about 10 minutes to 500 hours.

As for the adsorbent, adsorbing recalcitrant substance was subjected to chemical decomposition, this adsorbent can be removed as normal industrial waste, first making sure that the content of recalcitrant organic compounds in the adsorbent after chemical decomposition corresponds to a set rate of release (3000 PG TE/g) or below.

In addition, adsorbe is t, used once for adsorption of recalcitrant substances, can be used repeatedly without removing it immediately, until such time as will not decrease its effectiveness as adsorbent, and waste water can be cleaned in place in a closed system. Therefore, the proposed method is very reliable and economical. In addition, when the adsorbent used for the adsorption of recalcitrant substances, permanently deleted, it can be thrown away after completely reduced to a residual content of recalcitrant substances, so that the adsorbent is not harmed natural environment.

To further reduce waste decomposed substance can advocate for the separation of solid and liquid after completion of the chemical decomposition stage (D). The supernatant liquid obtained by separating the decomposed substances in solid and liquid can be returned at any stage of purification according to the present invention. In addition, if the concentration of recalcitrant substances corresponds to a set rate of emission or below it, then the supernatant can be removed to waste.

On the other hand, the precipitated substance can be removed as industrial waste, making sure before doing this that the content of recalcitrant substances is 3000 ppm-TE/g or less.

Device is istwo for water purification, containing recalcitrant substance, according to the second aspect of the invention (hereinafter referred to as "the device"), contains

section adding the adsorbent that is used to add the adsorbent in water containing recalcitrant substance (purify raw water);

section cleaning membrane filtration, designed to separate the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance, and

section cleaning chemical decomposition that is used for the oxidative decomposition of recalcitrant substances adsorbed on the adsorbent, with the use of peroxide.

Each of these sections can be provided in one or more instances. Figure 3-5 shows the cases in which there are two or more sections for each of the above sections.

In a particularly preferred variant of the proposed device contains

section introducing a reducing agent intended for the introduction of a reductant in water containing recalcitrant substance (purify raw water)to neutralize the chlorine in the water;

section purification membrane concentration, designed to separate from water containing recalcitrant substance, liquid, passed through obratnomu the mini-membrane (RO-membrane) or nanofiltration membrane (NF-membrane), in order to concentrate recalcitrant substance;

section adding the adsorbent that is used to add the adsorbent in concentrated recalcitrant substance, so that the adsorbent was adsorbing recalcitrant substance;

section processing membrane filtration, designed to separate the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance;

the section adding a flocculant, designed to add a flocculant in water containing adsorbent, adsorbirovavshyei recalcitrant substance in order to carry out the flocculation of the adsorbent, adsorbirovavshyei recalcitrant substance;

partition separating solids and liquids, designed to separate the adsorbent, adsorbirovavshyei recalcitrant substance and flocculated flocculant, and

section cleaning chemical decomposition that is used for the oxidative decomposition of recalcitrant substances adsorbed on the separated adsorbent, with the use of peroxide.

All the technological sequence of purification of waters containing recalcitrant substance will be explained below on the example of the preferred option the proposed device with reference to figure 3.

Figure 3 shows schematically device which has 1 to clear, designed to implement one variant of the method of purification of water containing recalcitrant substance, according to the present invention. The device 1 for cleaning, is shown in figure 3, contains the main elements of section 10 of the introduction of a reductant, section 20 of the clean membrane concentration, section 30 adding adsorbent, section 40 cleaning membrane filtration, section 60 of adding a flocculant, section 70 of separation of solids and liquids and section 80 of cleaning chemical decomposition. Figure 3 also shows a section 50 of ultraviolet irradiation, which can be provided if necessary.

Section 10 of the introduction of reductant

First, the water containing recalcitrant substance, such as dioxins, are placed in the tank 11 for the introduction. Sodium bisulfite is introduced into the tank 11 for insertion through a pump (not shown) of part 12 of the supply of reducing agent to neutralize free chlorine in the raw water. In the tank 11 for introducing raw water and the sodium bisulfite is stirred with a stirring means and measure the concentration of residual chlorine in the raw water with chlorine meter (not shown).

Section 20 of the clean membrane concentration

Water containing recalcitrant substance, neutralized with sodium bisulfite, is passed through pedwar the positive filter 21, with the help of which you can remove suspended solids and other Water that has passed through the pre-filter 21, is directed to the reverse osmosis membrane 22 through the pump, not shown in the drawing, and cleanse with this reverse osmosis membrane 22. Water is separated into the liquid that has passed through the reverse osmosis membrane 22, and the liquid part (concentrate)that has not passed through the membrane.

From these fluids are passed through the reverse osmosis membrane 22, the liquid can be removed outwards, if the content of recalcitrant substances in it is a set rate of ejection (10 PG TE/l) or lower. An alternative that has passed through the membrane, the liquid can be stored in the reservoir 42 for backwashing section 40 cleaning membrane filtration, as will be described below, and used as wash water for backwashing ultrafiltration membrane 41.

In addition, as shown in figure 3, the liquid part (concentrate), which has not passed through the reverse osmosis membrane 22, again purified using reverse osmosis membranes by mixing it with containing recalcitrant substance is water, which has passed through the pre-filter 21.

Thus, the concentrate is re-processed several times. The concentrate, which has not passed through the reverse osmosis membrane 22 in the same procedure, is directed to the treatment tank 31 provided for in section 30 of adding the adsorbent and ultraviolet radiation.

Section 30 adding adsorbent

In section 30 of adding the adsorbent in the liquid portion (concentrate)directed to the treatment tank 31 add adsorbent received from section 32 of the filing of the adsorbent through a feeder (not shown). In a clearing tank 31 of the liquid portion of the concentrate and the adsorbent was stirred mixing means to recalcitrant substance remaining in the liquid portion, effectively adsorbirovannoi added the adsorbent.

In addition, when using as the adsorbent of titanium dioxide recalcitrant substance contained in the liquid part, is adsorbed on the adsorbent and simultaneously recalcitrant substance can be fotorazlozheniya by irradiating UV light of the UV lamp 33. In this case, the titanium dioxide used as the adsorbent, also acts as a photocatalyst and stimulates vodorazreshimye recalcitrant substances.

Section 40 cleaning membrane filtration

The liquid part (concentrate) with added adsorbent is subjected to membrane filtration using an ultrafiltration membrane 41 via a pump (not shown), section 40 of membrane filtration. During cleaning of the membrane is filtered through an ultrafiltration membrane 41 deterioration of the filtering capacity of the ultrafiltration membrane 41 can be prevented by backwashing. On the other hand, the liquid that has passed through the reverse osmosis membrane 22 in section 20 of the clean membrane concentration, can be used for backwashing as wash water, as shown in figure 3.

In wash water from the reservoir 42 to the wash water, you can add the sodium hypochlorite from the part 43 of the filing of the fungicide through the pump (not shown).

When cleaning membrane filtration using an ultrafiltration membrane 41 of the liquid portion of water containing recalcitrant substance, with the added adsorbent is divided into the past through the membrane liquid and concentrate (liquid obtained for the backwash). Thus passed through the membrane, the liquid could be taken out as waste water, if the content of recalcitrant substances equal to or lower than the set emission standards (10 PG TE/l).

Section 50 UV irradiation

In section 50 of ultraviolet irradiation concentrate (liquid obtained for the backwash), did not pass through the ultrafiltration membrane 41 in section 40 of cleaning membrane filtration, can be directed into the tank 51 decomposition and to irradiate UV light ultraviolet lamp 53 without mixing mixing means to decompose recalcitrant substance. In section 50 of UV irradiation for when emulatie fotorazlozheniya UV light can be added aqueous hydrogen peroxide from the part 52 of the filing of the activator through the pump, (not shown).

For the implementation of fotorazlozheniya according to the present invention the adsorbent is added to section 30 of adding the adsorbent must be titanium dioxide, which acts as a photocatalyst. When using titanium dioxide cleaning vodorazreshimye occurs with high degrading ability.

Section 60 of adding a flocculant

In section 60 of adding a flocculant flocculant, which comes from part 62 of the flocculant through a feeder (not shown), is added to the concentrate (the liquid obtained for the backwash)containing recalcitrant substance, which (concentrate) send in the flocculation tank 61, which is concentrated using ultrafiltration membranes and which are optional fotorazlozheniya. In the flocculation tank 61 of the liquid portion of the concentrate (the liquid obtained for the backwash) and flocculant mix mixing tool, resulting adsorbed on the adsorbent recalcitrant substance remaining in the liquid portion, effectively flowlines added flocculant and therefore can easily be deposited.

Section 70 of the separation of solids and liquids

In section 70 of separation of solids and liquids recalcitrant substance flocculated flocculant in section 60, precipitated the settling tank 71, to separate the supernatant and settled the matter (sludge).

Provided not shown in the drawings, a mixing agent, and mixing is performed at a moderate speed settling tank 71 1 rpm to prevent solidification of the deposited substance on the bottom of the settling tank 71.

Clean the supernatant returned to the treatment tank 31 section 30 adding an adsorbent, or it can be removed in waste if the concentration of recalcitrant substances equal to or lower than the set emission standards (10 PG TE/l).

Section 80 chemical decomposition

In section 80 of the chemical decomposition of the peroxide of the part 82 of the supply of oxidant added to the settled matter (sludge), which is sent to the vessel 81 decomposition and which is discharged from the lower outlet of settling tank 71 section 70 separation of solids and liquid, and the mixture is stirred mixing software for chemical decomposition of recalcitrant substances in the settled matter (sludge).

After the chemical decomposition of pure supernatant returned to the treatment tank 31 section 30 adding an adsorbent, or it can be removed in waste if the concentration of recalcitrant substances equal to or lower than the set emission standards (10 PG TE/l).

On the other sides of the, the hard part produced by a solid substance) can be removed as industrial waste, ensuring that it meets the established norm of emission factors for industrial waste, or it can be reused as an adsorbent.

Passed through the membrane of the liquid formed in stage (A) reverse osmosis purification stage and (C) membrane filtration, is used as wash water for backwashing or return to the step (C) adsorption purification, as described above, and, in addition, they can be let out as waste water, if the concentration of recalcitrant substances equal to or lower than the set emission standards (10 PG TE/l). Under the issue out typically involve a discharge into the river, etc.

If the concentration of recalcitrant substances in raw water changes, together with changes the output concentration of the discharged water after treatment, and may release, discharge water containing recalcitrant substance, the concentration of which exceeds the rate of release. However, the measurement of the concentration of recalcitrant substances, such as dioxin and the like, in the drawdown water according to the official method takes about a month, and according to the simplified method is approximately two weeks, and it is almost impossible to store waste water in ECENA such a period of time.

Therefore, according to the present invention, it is preferable to perform several steps (C) purification of membrane filtration for passing through the liquid membrane to maintain a steady concentration of recalcitrant substances in discharged water at a set rate of emission or below, even if the concentration of recalcitrant substances in raw water changes. In addition, after the addition of the adsorbent in the past through the membrane, the liquid is preferably carry out stage (C) purification of membrane filtration.

Experiments conducted by the inventors confirmed that the cleaning membrane filtration two or more times not only maintains the stable concentration of recalcitrant substances at the level of the established emission standards (10 PG TE/l) or below, but even reduces it to environmentally friendly emission standards (1 PG TE/l) or below.

The table shows the change in the concentration of dioxins in passing through the liquid membrane and the ratio of removal of dioxins (%) two-purification membrane filtration.

The first filtration membrane filtrationThe concentration of dioxins
(PG TE/l)
The second cleaning membrane filtrationConcentrate the radio dioxins
(PG TE/l)
Water passed through the reverse osmosis membrane2,13Water passed through the reverse osmosis membrane≤1,0
Water which has passed through the ultrafiltration membrane2,5Water that passes through nanofilter≤1,0
Water which has passed through the ultrafiltration membrane + water passed through the reverse osmosis membrane1,63Water that passes through nanofilter≤1,0
Water which has passed through the ultrafiltration membrane + water passed through the reverse osmosis membrane + adding 20 ppm TiO21,63Water which has passed through the ultrafiltration membrane≤1,0
Water which has passed through the ultrafiltration membrane5,8Water which has passed through the ultrafiltration membrane≤1,0
Water that passes through ultrafiltration the Yu membrane, + adding 20 ppm TiO2and stirring for 1 hour5,8Water which has passed through the ultrafiltration membrane≤1,0

Figs.4 and 5 show variants of the contaminated water treatment system that involves several stages (C) purification of membrane filtration.

For example, in the variant shown in figure 4(a), the adsorbent is added to the water containing recalcitrant substance (raw water) (stage (B-1) adsorption purification), and the mixture is separated into a concentrate and passed through the membrane fluid through the purification membrane filtration (stage (s-1) purification of membrane filtration). The concentrate is cleaned at the above stage (D) chemical decomposition. In the past through the membrane, the liquid addition type adsorbent (stage (b-2) adsorption purification), and the mixture is then again subjected to membrane filtration (stage (2) purification of membrane filtration). The concentrate, which has not passed through the filtration membrane, return to the step (B-1) adsorption purification, and passed through the membrane, the liquid has a concentration of recalcitrant substances corresponding to a set rate of emission or below that allows you to let it out as waste water.

In the variant shown in figure 4(b), provided the us one stage (In) adsorption purification and two-stage (C) purification of membrane filtration, this option represents a more economical system.

As shown in figure 5, the water containing recalcitrant substance, purified (A) membrane concentration before the addition of the adsorbent. As a filtration membrane in this case it is preferable to apply the reverse osmosis membrane or a nanofiltration membrane.

The concentrate described above stage (A) purification of membrane concentration at this initial stage is subjected to cleaning (C) membrane filtration after addition of the adsorbent (C) obtaining passed through the membrane and liquid concentrate. The concentrate is directed to the step (D) chemical decomposition.

Figure 5(C) in the past through the membrane liquid from step (A) purification of membrane concentration at the initial stage additionally add the adsorbent (In-2), and the mixture was subjected to purification by membrane filtration (C-2), and then receive waste water. The concentrate from step (C-2) purification of membrane filtration purified (C) membrane filtration after addition of the adsorbent (In), like the concentrate from step (A) purification of membrane concentration at the initial stage.

In the past through the membrane liquid from step (C-2) purification of membrane filtration additionally add the adsorbent (In-3), and this mixture is subjected to PTS is the site of membrane filtration (C-3) obtaining the drawdown of the water. The concentrate with the cleanup phase (C-3) membrane filtration purified (C) membrane filtration after addition of the adsorbent (In) like the concentrate from step (A) purification of membrane concentration at the initial stage.

In the variant shown in figure 5(d), provided one stage (A) purification of membrane concentration, one stage (In) adsorption purification and three stage (C) purification of membrane filtration, and this option represents a more economical system than option, shown in figure 5(C), which provides three stages of (In) adsorption purification.

In the variant shown in figure 5(e), provided by one stage (A) purification of membrane concentration, one stage (In) adsorption purification and two-stage (C) membrane filtration, and this option is more cost effective than option, shown in figure 5(d), which provides for three stages (C) purification of membrane filtration.

In the proposed method and the device provided by stage (A) purification of membrane concentration and several stages of membrane filtration, as shown in Fig.3-5, which enables stable to reduce the concentration of recalcitrant substances, such as dioxins and the like, to discharge the water to the set emission standards or below.

In addition, in the proposed method and device is ve recalcitrant substances, contained in contaminated water, is removed by a combination of concentration, fotorazlozheniya and chemical decomposition, which allows extremely stable to reduce the concentration of recalcitrant substances.

A method for concentrating recalcitrant substances in water containing recalcitrant substance, according to the third aspect of the present invention (hereinafter also referred to as "the proposed method concentration") includes a stage on which:

(B) type adsorbent in water containing recalcitrant substance (purify raw water)to cause the adsorption of recalcitrant substances on the adsorbent (adsorption stage purification), and

(C) separating the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance (cleaning stage membrane filtration).

The above solution allows you to efficiently and economically concentrated water containing recalcitrant substance, regardless of the properties and method of decomposition of the contained recalcitrant substances.

The proposed method concentration preferably includes a step (A) separation from water containing recalcitrant substance, liquid, passed through the reverse osmosis membrane (RO-membrane) or nanofiltration IU is the bran (NF-membrane), for the concentration of recalcitrant substances (cleaning stage membrane concentration) before stage (B).

This allows you to reduce the amount of discharged water to be treated, at the stage before adding the adsorbent and thereby reduce the amount of added adsorbent and reduce the amount of concentrate (water containing concentrated adsorbent, adsorbirovavshyei recalcitrant substance). In addition, you can reduce the size of the equipment for the implementation of stage (C) the adsorption treatment and the next stage (C) purification of membrane filtration.

In the proposed method concentration preferably, at least part of recalcitrant substances, concentrated on the stage (A), returned in water containing recalcitrant substance (purify raw water).

This allows as much as possible to concentrate recalcitrant substance on the stage (A) purification of membrane concentration.

Details of the stages (A), (b) and (C) the proposed method according to the third aspect of the invention explained in connection with the first aspect of the invention and therefore will not be described again. In addition, any optional stage described in connection with the method according to the first aspect of the invention, it is possible to enter in the method according to the third aspect of the invention.

The way the eyes of the TCI water, containing recalcitrant substance according to a fourth aspect of the invention, includes a step of irradiation with the light of recalcitrant substances, concentrated as described above for the decomposition of recalcitrant substances.

This technical solution allows you to remove recalcitrant substance so that you can get purified water (waste water)in which the concentration of recalcitrant substances reduced to the set emission standards (10 PG TE/l) or below, and concentrate recalcitrant substances subject to fotorazlozheniya so that it can be harmless.

Under fotorazlozheniya in the proposed method according to the fourth aspect, it is preferable to use ultraviolet light, but you can also use such light sources, such as a mercury lamp, low pressure mercury lamp, medium pressure mercury lamp, high pressure, excimer laser, natural light and fluorescent lamp.

When titanium dioxide, having a photocatalytic effect, is used as the adsorbent, which need to be added to stage (C) In the method according to the third aspect of the invention, recalcitrant material in the concentrate can be very effectively subjected to fotorazlozheniya under fotorazlozheniya in the method according to the fourth aspect of this is the future of invention.

Examples

Hereinafter the present invention will be described in more detail by way of examples, without limiting value.

Example 1(see Fig.6)

(C) stage adsorption purification

Raw water (concentration of dioxins 6500 PG TE/l) were placed in the adsorption tank 1 hour and was added to 1000 ppm of diatomaceous earth as an adsorbent. The mixture was stirred to ensure adsorption.

(C) cleaning stage membrane filtration

The water, which was added to the adsorbent was subjected to purification by membrane filtration using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 150,000); part of the liquid which has not passed through the ultrafiltration membrane, was added (returned) in raw water and finished filtering at an operating pressure of 0.3 MPa. In this case passed through the membrane, the liquid had a dioxin concentration of 2.5 PG TE/l, which was below the established emission standards (10 PG TE/l). The ultrafiltration membrane was subjected to the backwash passed through the membrane by the liquid, which amount to 4 times the amount of liquid that has passed through the ultrafiltration membrane for 1 minute, and the liquid obtained during the backwash, was adopted as a concentrate (slurry).

(D) phase chemical decomposition

The concentrate obtained is output at stage (C), added persulfate sodium so that the mixture has a concentration of sodium persulfate 10 wt.%, and gave the mixture to react at 70°C for 7 hours. Solid in the decomposition product after the reaction had a dioxin concentration of 1000 PG TE/g, which was below the established emission standards (3000 PG TE/g).

Example 2(see Fig.7.)

(A) cleaning stage membrane concentration

Raw water (concentration of dioxins 6500 PG TE/l) was filtered using reverse osmosis membrane (spiral type with retention of sodium chloride 95%). Part of the liquid (water concentrate), which has not passed through the reverse osmosis membrane, was added (returned) in the raw water and the mixture was filtered at an operating pressure of 1 MPa or higher. 2/3 cleared number received in the past through the membrane liquid. Thus passed through the membrane, the liquid has a concentration of dioxins 1 PG TE/l to below the emission standards (10 PG TE/l).

(C) stage adsorption purification

Water concentrate in number, amounting to 1/3 of a cleared number obtained in stage (A), above, was placed in an adsorption vessel for 1 hour and added to 2000 ppm of activated clay as adsorbent. The mixture was stirred to ensure adsorption.

(C) cleaning stage membrane filtration

The above-mentioned aqueous conc Strat, to which was added the adsorbent was subjected to purification by membrane filtration using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 10,000). Part of the liquid portion (concentrate), which did not pass through the ultrafiltration membrane, was added (returned) in the aqueous concentrate was added to the adsorbent obtained in stage (C), and the mixture was filtered at an operating pressure of 0.3 MPa. The liquid which has passed through the ultrafiltration membrane, had a dioxin concentration of 1.8 PG TE/l, which was below the established emission standards (10 PG TE/l). In addition, part of the concentrate obtained in stage (C), can be returned to the adsorption tank on stage (In).

Passed through the reverse osmosis membrane liquid obtained in stage (A), and the liquid that has passed through the ultrafiltration membrane at the stage (C), were combined and taken as the drawdown of water (concentration of dioxin 1,3 PG TE/l).

(G) stage backwashing

The hard part (concentrate), adhering to the ultrafiltration membrane at the stage (C), were subjected to the backwash passed through the membrane by the liquid with the stage of purification of membrane concentration in an amount 4 times the amount of liquid that has passed through the ultrafiltration membrane for 1 minute, and the liquid obtained at about the military flushing, took over concentrate.

(D) phase chemical decomposition

To the concentrate obtained in stage (G), was added sodium persulfate so that the mixture has a concentration of sodium persulfate 10 wt.%, and gave the mixture to react at 70°C for 7 hours in the same way as in example 1. Solid in the decomposition product after the reaction had a dioxin concentration of 950 PG TE/g, which was below the established emission standards (3000 PG TE/g).

Example 3(see Fig)

(E) stage neutralize the chlorine and (A) cleaning stage membrane concentration

In raw water (concentration of dioxin 6500 PG TE/l and the concentration of free chlorine of 50 mg/l) was added sodium bisulfite so that its number was 150 mg/l, which exceeded 3 times the amount of free chlorine, and the mixture was stirred. This mixture was filtered using reverse osmosis membrane (spiral type with retention of sodium chloride 95%). Part of the liquid portion (water concentrate), which has not passed through the reverse osmosis membrane, was added (returned) in raw water, to which was added sodium bisulfite and the mixture was filtered at an operating pressure of 1 MPa or higher. 2/3 cleared number received in the past through the membrane liquid. Thus passed through the membrane, the liquid had a dioxin concentration of 1.1 PG TE/l, which was below the set nor the s emission (10 PG TE/l).

(C) stage adsorption purification

Water concentrate in number, amounting to 1/3 of a cleared number obtained in stage (A), was placed in an adsorption vessel for 1 hour as in example 1, was added to 2000 h/million activated clay as adsorbent and the mixture was stirred to ensure adsorption.

(C) cleaning stage membrane filtration

The aqueous concentrate was added to the adsorbent was subjected to ultrafiltration using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 10,000). Part of the liquid portion (concentrate), which did not pass through the ultrafiltration membrane, was added (returned) in the aqueous concentrate was added to the adsorbent, and the mixture was filtered at an operating pressure of 0.1 MPa. The liquid which has passed through the ultrafiltration membrane, had a dioxin concentration of 1.7 PG TE/l, which was below the established emission standards (10 PG TE/l).

Passed through the reverse osmosis membrane liquid obtained in stage (A), and passed through the ultrafiltration membrane liquid obtained in stage (C), were combined and taken as the drawdown of water (concentration of dioxin 1,3 PG TE/l).

(G) stage backwashing

The hard part (concentrate), adhering to the ultrafiltration membrane at the stage (C), were subjected to reverse the St flushing passed through the membrane by the liquid with the stage of purification of membrane concentration in number, greater than 4 times the amount of liquid that has passed through the ultrafiltration membrane for 1 minute, and the liquid obtained during the backwash, took over concentrate.

(D) phase chemical decomposition

To the concentrate obtained in stage (G), was added sodium persulfate, so that the mixture has a concentration of sodium persulfate 10 wt.%, and gave the mixture to react at 70°C for 7 hours in the same way as in example 1. Solid in the decomposition product after the reaction had a dioxin concentration 970 PG TE/g, which was below the established emission standards (3000 PG TE/g).

Thus, it was confirmed that the treatment with sodium bisulfite to neutralize free chlorine, which degrades the properties of the membranes, does not adversely affect the chemical reaction of decomposition.

Example 4(see Fig.9)

(E) stage neutralize the chlorine and (A) cleaning stage membrane concentration

In raw water (concentration of dioxins 6500 PG TE/l and the concentration of free chlorine of 50 mg/l) was added sodium bisulfite so that its number was 150 mg/l, exceeding the amount of free chlorine in 3 times, and the mixture was stirred. This mixture was filtered using reverse osmosis membrane (spiral type with retention of sodium chloride 95%). Part of the liquid portion (water concentrate), which has not passed the via reverse osmosis membrane, added (returned) in raw water, to which was added sodium bisulfite and the mixture was filtered at an operating pressure of 1.5 MPa or higher. 2/3 cleared number received in the past through the membrane liquid. Thus passed through the membrane, the liquid has a concentration of dioxin 1,1 PG TE/l, which was below the established emission standards (10 PG TE/l). Water concentrate, the amount of which was 1/3 of a cleared number, has a concentration of dioxin 20000 PG TE/HP

(C) stage adsorption purification and (F) stage fotorazlozheniya

Water the concentrate obtained in stage (A), was placed in an adsorption vessel for 1 hour, was added 15 ppm titanium dioxide as the adsorbent and the mixture was irradiated with UV light (wavelength 254 nm) under stirring to ensure adsorption. Water concentrate after fotorazlozheniya has a concentration of dioxin 6000 PG TE/HP

(C) cleaning stage membrane filtration

The aqueous concentrate was added to the adsorbent and which was irradiated with ultraviolet light, was subjected to purification by membrane filtration using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 10,000). The liquid part (concentrate), which did not pass through the ultrafiltration membrane, was added (returned) in the aqueous concentrate was added adcor the UNT and was irradiated with ultraviolet light, and the mixture was filtered at an operating pressure of 0.3 MPa. The liquid which has passed through the ultrafiltration membrane has a concentration of dioxin 1,2 PG TE/l, which was below the established emission standards (10 PG TE/l).

(G) stage backwashing

The hard part (concentrate), adhering to the ultrafiltration membrane at the stage (C), were subjected to the backwash passed through the membrane by the liquid with the stage of purification of membrane concentration in an amount 4 times the amount of liquid that has passed through the ultrafiltration membrane for 1 minute, and the liquid obtained during the backwash, took over concentrate (slurry).

(D) phase chemical decomposition

To the concentrate obtained in stage (G), was added sodium persulfate so that the mixture has a concentration of sodium persulfate 10 wt.%, and gave the mixture to react at 70°C for 7 hours in the same way as in example 1. Solid in the decomposition product after the reaction had a dioxin concentration 900 PG TE/g, which was below the established emission standards (3000 PG TE/g).

Thus, it was found that a concentrate that does not pass through the reverse osmosis membrane can be expanded by adding titanium oxide to concentrate and irradiating it with ultraviolet light.

Example 5(see figure 10)

Stage of example 4 to stage (G) vklyuchitel is but performed as well as in example 4, followed by the following steps.

(F-2) the Second stage of fotorazlozheniya

The concentrate (the liquid obtained for the backwash, with the concentration of dioxin 15000 PG TE/l)obtained in stage (G), above, was irradiated with UV light (wavelength 254 nm) for 24 hours. After irradiation with ultraviolet light concentrate has a concentration of dioxin 750 PG TE/HP

(D) phase chemical decomposition

In concentrate (slurry)obtained in stage (G), was added sodium persulfate so that the mixture has a concentration of sodium persulfate 10 wt.%, and gave the mixture to react at 70°C for 7 hours in the same way as in example 1. Solid in the decomposition product after the reaction has a concentration of dioxin 850 PG TE/g, which was below the established emission standards (3000 PG TE/g).

Thus, it was found that a concentrate that does not pass through the reverse osmosis membrane can be decomposed by irradiating it with ultraviolet light.

Example 6(see 11)

(H) stage flocculation separation

In concentrate (slurry)obtained in stage (G) of example 5, was added 100 ppm of polychloride aluminum as the inorganic flocculant and the mixture was stirred. After 12 hours, the precipitated substance was removed in the form of suspended concentrate having a concentration of 10 wt.%.

D) stage chemical p is slorenia

In a suspension concentrate obtained in stage (H), was added sodium persulfate so that the mixture has a concentration of sodium persulfate 20 wt.%, and gave the mixture to react at 90°C for 24 hours. After the reaction, the reaction mixture has a concentration of dioxin 550 PG TE/g, which was below the established emission standards (3000 PG TE/g).

Example 7(an example of a multiple filter) (see Fig)

Stage (V) adsorption purification stage (C) purification of membrane filtration and stage (D) chemical decomposition of example 1 was performed as in example 1 and passed through the membrane liquid obtained in stage (C)was further purified as follows.

(2) the Second cleaning stage membrane filtration

Passed through the membrane liquid obtained in stage (C) membrane filtration of raw water in example 1 (concentration of dioxins 6500 PG TE/l), were placed in the adsorption tank 1 hour, was added 100 ppm of diatomaceous earth as an adsorbent, and the mixture was stirred to ensure adsorption. Passed through the membrane liquid, which was added to the adsorbent was subjected to membrane filtration using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 150,000) (stage (C) purification of membrane filtration). Part of the liquid portion (concentrate), which has not passed through ultrafiltration the membrane, added (returned) in the liquid, which has passed through the ultrafiltration membrane at the stage (C-2), which was added to the adsorbent, and the mixture was filtered at an operating pressure of 0.2 MPa. Received passed through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

The concentrate obtained by ultrafiltration membrane at the stage (C-2), returned to the adsorption tank located in front of stage (C) purification of membrane filtration in example 1, there has been no marked changes in the concentration of dioxins in treated water (discharge water) and the product of chemical decomposition.

Example 8(an example of a multiple filter) (see Fig)

Stage (V) adsorption purification stage (C) purification of membrane filtration and stage (D) chemical decomposition of example 1 was performed as in example 1 and passed through the membrane liquid obtained in stage (C)was further purified as follows.

(2) the Second cleaning stage membrane filtration

Passed through the membrane liquid obtained in stage (C) membrane filtration of raw water in example 1 (concentration of dioxin 6500 PG TE/l)was filtered using an ultrafiltration membrane (hollow fiber type with a cut-off molecular mA is 3000 CE). The liquid part (concentrate), which did not pass through the ultrafiltration membrane, was added (returned) in the past through the membrane liquid obtained in stage (1) purification of membrane filtration, and the mixture was filtered at an operating pressure of 0.2 MPa. Thus obtained passes through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

The concentrate obtained by ultrafiltration membrane at the stage (C-2), returned to the adsorption tank located in front of stage (C) purification of membrane filtration in example 1, there has been no marked changes in the concentration of dioxins in treated water (discharge water) and the product of chemical decomposition.

Example 9(an example of a multiple filter) (see Fig)

Stage (V) adsorption purification stage (C) purification of membrane filtration and stage (D) chemical decomposition of example 1 was performed as in example 1 and passed through the membrane liquid obtained in stage (C)was further purified as follows.

(2) the Second cleaning stage membrane filtration

Passed through the membrane liquid obtained in stage (C) membrane filtration in example 1, was filtered using a nanofiltration membrane (hollow fiber type with zade is the lid of sodium chloride 30%). Part of the liquid portion (concentrate), which has not passed through the nanofiltration membrane, was added (returned) in the past through the membrane liquid obtained in stage (C) purification of membrane filtration, and the mixture was filtered at an operating pressure of 0.5 MPa. Thus obtained passes through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

The concentrate obtained by nanofiltration membranes at the stage (C-2), returned to the adsorption tank located in front of stage (C) purification of membrane filtration in example 1, there has been no marked changes in the concentration of dioxins in treated water (discharge water) and the product of chemical decomposition.

Example 10(an example of a multiple filter) (see Fig)

Stage (A) purification of membrane concentration, stage (C) adsorption purification stage (C) purification of membrane filtration and stage (D) chemical decomposition in example 2 was performed as in example 2, and passed through the membrane liquid obtained in stages (a) and (C)optionally purified as follows.

(1) (b-2) Second stage adsorption treatment and (2) the second cleaning stage membrane filtration to last through the membrane liquid obtained in stage (A)

Ask the Shui through the membrane liquid, obtained in stage (A) purification of membrane concentration according to example 2, were placed in the adsorption tank 1 hour, was added 100 ppm of activated clay as adsorbent and the mixture was stirred to ensure adsorption. Passed through the membrane liquid, which was added to the adsorbent was filtered using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 150,000). Part of the liquid portion (concentrate), which did not pass through the ultrafiltration membrane, was added (returned) in the past through the membrane liquid from step (b-2), which was added to the adsorbent, and the mixture was filtered at an operating pressure of 0.2 MPa. Received passed through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

(2) (3) the Third stage adsorption purification, and (3) the third stage of purification of membrane filtration for passing through the membrane liquid obtained in stage (C)

Passed through the membrane liquid obtained in stage (C) purification of membrane filtration in example 2, were placed in the adsorption tank 1 hour, was added to 1000 ppm of activated clay as adsorbent and the mixture was stirred to ensure adsorption. Passed through the membrane liquid, in which is was added to the adsorbent, was filtered using an ultrafiltration membrane (hollow fiber type with a cutoff molecular weight of 150,000). Part of the liquid portion (concentrate), which did not pass through the ultrafiltration membrane, was added (returned) in the past through the membrane liquid from step (b-3), which was added to the adsorbent, and the mixture was filtered at an operating pressure of 0.3 MPa. Received passed through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

Each of the concentrates were returned to the adsorption tank on stage (In) adsorption purification, there has been no marked changes in the concentrations of dioxin in purified water (discharge water) and the product of chemical decomposition in each case.

Example 11(an example of a multiple filter) (see Fig)

Stage (A) purification of membrane concentration, stage (C) adsorption purification stage (C) purification of membrane filtration and stage (D) chemical decomposition in example 2 was performed as in example 2, and passed through the membrane liquid obtained in stages (a) and (C)optionally purified as follows.

(1) (2) the Second cleaning stage membrane filtration to last through the membrane liquid obtained in stage (A)

Passed through memb the Anu liquid, obtained in stage (A) of example 2 was filtered using reverse osmosis membrane (spiral type with retention of sodium chloride 95%). Part of the liquid portion (concentrate), which has not passed through the reverse osmosis membrane, was added (returned) in the past through the membrane liquid from step (A), after which it was filtered at an operating pressure of 1 MPa or higher. Passed through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

(2) (3) the Third stage of purification of membrane filtration for passing through the membrane liquid obtained in stage (C)

Passed through the membrane liquid obtained in stage (C) of example 2, was filtered using a nanofiltration membrane (hollow fiber type with retention of sodium chloride 30%). Part of the liquid portion (concentrate), which has not passed through the nanofiltration membrane, was added (returned) in the past through the membrane liquid obtained in stage (C), and the mixture was filtered at an operating pressure of 0.6 MPa. Thus passed through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or lower, which is consistent with ecologically safe normal emission (1 PG TE/l) or below.

The concentrate obtained in stage (C-2), and the concentrate obtained in stage (C-3), returns the whether in the adsorption tank on stage (In) adsorption purification, it was not observed any changes in the concentrations of dioxin in purified water (discharge water) and the product of chemical decomposition in any case.

Example 12(an example of a multiple filter) (see Fig)

Stage (A) purification of membrane concentration, stage (C) adsorption purification stage (C) purification of membrane filtration and stage (D) chemical decomposition in example 2 was performed as in example 2, and passed through the membrane liquid obtained in stages (a) and (C)optionally purified as follows.

(2) the Second stage of the treatment and membrane filtration to last through the membrane liquid obtained in stage (a) and passed through the membrane liquid obtained in stage (C)

Waste water (concentration of dioxin 1,2 PG TE/l), obtained by combining passed through the membrane liquid obtained in stage (A) in example 2, and passed through the membrane liquid obtained in stage (C) in example 2 was filtered using a nanofiltration membrane (hollow fiber type with retention of sodium chloride 30%). Part of the liquid portion (concentrate), which has not passed through the nanofiltration membrane, was added (returned) in the waste water obtained by combining passed through the membrane liquid obtained in stage (A), and passed through the membrane liquid, recip is authorized at the stage (C), and the mixture was filtered at an operating pressure of 0.5 MPa. In this case passed through the membrane, the liquid has a concentration of dioxin 1 PG TE/l or less, which is environmentally safe normal emission (1 PG TE/l) or below.

The concentrate obtained in stage (C-2), returned to the adsorption tank on stage (In), and there wasn't observed any changes in the concentrations of dioxin in purified water (discharge water) and the product of chemical decomposition.

Example 13

Contaminated water containing dioxins, was purified in order to neutralization by using the cleaning device shown in figure 3.

(A) Purification of membrane concentration (including the stage (E) neutralizing chlorine) and stage (I) pre-filtering)

In section 10 the introduction of the reductant was added sodium bisulfite in contaminated water containing dioxins (dioxin concentration 6300 PG TE/l, the concentration of free chlorine of 50 mg/l) so that the mixture contained 150 mg/l of sodium bisulfite, which is 3 times higher than the amount of free chlorine, and the mixture was stirred.

In section 20 of the reverse osmosis purification of contaminated water (conductivity of 3000 µs/cm), which was added sodium bisulfite was passed through a pre-filter to remove large fractions of the suspended matter, and then the dirty water was purified using obratnomu the practical membrane with retention of salt at least 95%. When the reverse osmosis purification portion of the liquid portion, which has not passed through the reverse osmosis membrane, combined with contaminated water, which has passed through the pre-filter, and the mixture was again sent to the reverse osmosis membrane. In this operation, the conductivity of the liquid portion brought up to 9000 µs/cm or lower, which is 3 times or less than the conductivity of polluted water. The concentration of dioxins in passing through the liquid membrane was 1.9 PG TE/l, which was below the established emission standards (10 PG TE/l).

(C) stage adsorption purification and (F-1) the first stage of fotorazlozheniya

In section 30 of the addition of the adsorbent, and ultraviolet irradiation was added 10 ppm of titanium dioxide, which can act as a photocatalyst, in the liquid part (the concentration of dioxins 3000 PG TE/l), which did not pass through the reverse osmosis membrane, and stirred, and then was irradiated with ultraviolet light with a wavelength of 254 nm for fotorazlozheniya dioxins. In this case, the concentration of dioxins in the liquid part was 1200 PG TE/l, and it was noted that 60% of them were fotorazlozheniya.

(C) cleaning stage membrane filtration (including the stage (G) backwashing)

In section 40 of cleaning membrane filtration the liquid part obtained after fotorazlozheniya was passed through ultrafiltration membrane with cut-off molecular weight of 150000 for cleaning membrane filtration. When this cleaning membrane filtration ultrafiltration membrane was washed with wash water obtained by adding 3 ppm hypochlorous acid in the past through the membrane liquid obtained clearance (A) using a reverse osmosis membrane in an amount 4 times larger than the amount of fluid that has passed through the ultrafiltration membrane, every 60 minutes. The dioxin concentration in the liquid passing through the ultrafiltration membrane, comprised of 0.65 PG TE/l, which is lower than the set emission standards (10 PG TE/l).

The liquid that has passed through the reverse osmosis membrane, and the liquid that has passed through the ultrafiltration membrane, were combined and the combined liquid was taken for waste water dioxin concentration of 1.5 PG TE/l).

(F-2) the Second stage of fotorazlozheniya

The concentrate (the liquid obtained for the backwash), is obtained by purification of membrane filtration, directed in section 50 of ultraviolet irradiation, was added 100 ppm of hydrogen peroxide as an activator fotorazlozheniya and the mixture was irradiated with ultraviolet light with a wavelength of 254 nm for fotorazlozheniya dioxins. In this case, the concentration of dioxins in the liquid portion was 120 PG TE/l, and it was noted that 90% of them were fotorazlozheniya.

(H) stage flocculation separation

p> In section 60 of adding a flocculant was added 100 ppm of polychloride aluminum in the concentrate after fotorazlozheniya and the mixture was moderately stirred to ensure complete flocculation of the adsorbent, adsorbirovavshyei dioxins. Then, while stirring the mixture with a rotation speed of 1 rpm to prevent solidification of the flocculated matter at the bottom, gave flocculated substance to settle for 18 hours. Clean the supernatant was returned to the section 30 adding adsorbent and ultraviolet radiation.

(D) phase chemical decomposition

In section 80 cleaning chemical decomposition was added 4 g (100 times greater molar amount than the amount of dioxins) powdered sodium persulfate in settled the matter and added water to bring the total volume of the mixture to 40 ml. and Then the mixture was heated at 70°C for 24 hours under stirring to implement the cleanup of chemical decomposition. After completion of the chemical decomposition razorivshegosya substance was allowed to stand for separation of solid and liquid.

The dioxin concentration in the supernatant was 32 PG TE/l Supernatant was neutralized with 20% aqueous sodium hydroxide solution and returned to the section 30 adding adsorbent and ultraviolet radiation.

It was found that the number of di is xinou in concentrate (solid) after chemical decomposition was 270 PG TE/g, that was below the established emission standards (3000 PG TE/g) for industrial waste.

Industrial applicability

The proposed method can be widely used as a cleaning method, allowing to neutralize recalcitrant organic compounds such as dioxins and PCBs contained in industrial waste waters, waste waters, drainage systems, waste waters generated during the leaching of waste incinerators, and their concentrates, and enables stable to reduce the concentration of recalcitrant substances to values below the established norms of release.

1. The method of purification of water containing one or more recalcitrant substances selected from the group comprising halogenated dibenzodioxins, halogenated dibenzofurans, polychlorinated biphenyls - PCBs, destroying the endocrine system agents, other than dioxin, a carcinogenic substances and organic halogenated compounds which can be removed by the method of fotorazlozheniya or chemical decomposition, comprising the following stages:
(B) stage adsorption purification, which is added to the adsorbent in the treated raw water containing recalcitrant substance to cause the adsorption of recalcitrant substances on the adsorbent, where the added adsorbent is one inorganic adsorbent is, or two or more inorganic adsorbents selected or selected from the group consisting of titanium dioxide, zeolite, acid clay, activated clay, diatomaceous earth, metal oxide, metal powder, activated carbon and carbon black,
(C) cleaning stage membrane filtration, which separates the liquid that has passed through the filtration membrane for concentration of adsorbent, adsorbirovavshyei recalcitrant substance, and perform several stages (C) purification of membrane filtration to last through the membrane liquid, and
(D) phase chemical decomposition, which carry chemical decomposition of recalcitrant substances adsorbed concentrated on the adsorbent, with the use of peroxide directly in the form in which it is added, where the peroxide is chosen from the group including persulfates, sodium peroxide, barium peroxide, peroxide zinc, cadmium peroxide, potassium peroxide, calcium peroxide, chromium peroxide, hydrogen peroxide, ozone, as well as a system using a combination of a metal catalyst and a material supplying hydrogen.

2. The method of purification of water containing recalcitrant substance of claim 1, wherein in stage (D) apply peroxide in the amount of at least 100 times larger than the number of recalcitrant substances the STV in moles.

3. The method of purification of water containing recalcitrant substance according to claim 1 or 2, which further includes:
(A) purification stage membrane concentration, which is led by the Department of water containing recalcitrant substance, liquid, passed through the reverse osmosis membrane or a nanofiltration membrane for concentration of recalcitrant substances.

4. The method of purification of water containing recalcitrant substance according to claim 1, which further includes:
(E) the stage of neutralization of chlorine in water containing recalcitrant substance, which is led by adding a reducing agent, where the reducing agent is chosen from the group comprising sodium bisulfite, sodium metabisulfite and sulfur dioxide.

5. The method of purification of water containing recalcitrant substance according to claim 1, which further includes:
(F) stage fotorazlozheniya, which carried out the irradiation with ultraviolet light to decompose recalcitrant substances.

6. The method of purification of water containing recalcitrant substance according to claim 1, which further includes:
(G) stage backwashing, which carry out backwashing of the filtration membrane used in stage (C), removal of the adsorbent, adsorbirovavshyei recalcitrant substance of the filtration membrane.

7. SPO is about water purification, containing recalcitrant substance according to claim 1, which further includes:
(H) stage flocculation separation, which add a flocculant in water containing adsorbent, adsorbirovavshyei recalcitrant substance, to ensure the flocculation and separation of the adsorbent, adsorbirovavshyei recalcitrant substance, where the flocculant selected from the group including aluminum sulfate, iron chloride(III), iron sulfate(II), polychloride aluminum and reagent-based zeolite, sodium polyacrylate and copolymer of sodium acrylate and acrylamide.

8. The method of purification of water containing recalcitrant substance according to claim 1, in which the adsorbent is added to the stage (In), use titanium dioxide.

9. The method of purification of water containing recalcitrant substance according to claim 1, in which the filtration membrane used in stage (C), selected from the group consisting of ultrafiltration membranes, nanofiltration membranes, microfiltration membranes and reverse osmosis membranes.

10. The method of purification of water containing recalcitrant substance according to claim 1, in which the peroxide used in stage (D), apply persulfate.

11. The method of purification of water containing recalcitrant substance according to claim 1, in which at least part of recalcitrant substances, to concentrate the new stage (A), and/or adsorbent, adsorbirovavshyei recalcitrant substance at the stage (C), return in the treated raw water containing recalcitrant substance, or the stage prior to stage (A) or stage (S).

12. The method of purification of water containing recalcitrant substance according to claim 1, where the specified recalcitrant substance is a halogenated dibenzodioxins selected from 2,3,7,8-tetrachlorobenzo-p-dioxin, 1,2,3,7,8-pentachlorodibenzo-p-dioxin 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin and 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin.

13. The method of purification of water containing recalcitrant substance according to claim 1, where the specified recalcitrant substance is a halogenated dibenzofuran selected from 2,3,7,8-tetrachlorodibenzofuran, 1,2,3,7,8-pentachlorodibenzofuran, 1,2,3,4,7,8-hexachlorodibenzofuran, 1,2,3,4,6,7,8-heptachlorodibenzofuran and 1,2,3,4,6,7,8,9-octachlorodibenzofuran.

14. The method of purification of water containing recalcitrant substance according to claim 1, where the specified recalcitrant substance is a polychlorinated biphenyl selected from 3,3',4,4',5-tetrachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl and 3,3',4,4',5,5'-hexachlorobiphenyl.

15. The method of purification of water containing recalcitrant substance according to claim 1, where the specified recalcitrant substance is harmful the endocrine system substance, selected from alkyl phenols, including tert-butylphenol, Nonylphenol and op, halogenated phenols, including tetrachlorophenol and pentachlorophenol, bisphenol, including 2,2,-bis(4-hydroxyphenyl)propane (bisphenol a) and 1-bis(4-hydroxyphenyl)cyclohexane, polycyclic aromatic hydrocarbons, including benzo (a) pyrene, chrysin, benzanthracene, benzofluoranthene, picene and esters of phthalic acid, including dibutyl phthalate, butylbenzylphthalate and di-2-ethylhexylphthalate.

16. The method of purification of water containing recalcitrant substance according to claim 1, where the specified recalcitrant substance is a recalcitrant organic halogenated compound selected from dichloropropane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichlorethylene.

17. The water treatment device containing one or more recalcitrant substances selected from the group comprising halogenated dibenzodioxins, halogenated dibenzofurans, polychlorinated biphenyls, destroying the endocrine system agents, other than dioxins, carcinogenic substances, and organic halogenated compounds which can be removed by the method of fotorazlozheniya or chemical decomposition, containing:
section adding the adsorbent that is used for adding the adsorbent to purify raw water containing hard is oslagaemoe substance, where the added adsorbent is one of the inorganic adsorbent, or two or more inorganic adsorbents selected or selected from the group consisting of titanium dioxide, zeolite, acid clay, activated clay, diatomaceous earth, metal oxide, metal powder, activated carbon and carbon black,
section cleaning membrane filtration, designed to separate the liquid that has passed through the filtration membrane to concentrate the adsorbent, adsorbirovavshyei recalcitrant substance, and
section cleaning chemical decomposition that is used for the oxidative decomposition of recalcitrant substances adsorbed on the adsorbent, with the use of peroxide, where the peroxide is chosen from the group including persulfates, sodium peroxide, barium peroxide, peroxide zinc, cadmium peroxide, potassium peroxide, calcium peroxide, chromium peroxide, hydrogen peroxide, ozone, as well as a system using a combination of a metal catalyst and a material supplying hydrogen.

18. The water treatment device containing one or more recalcitrant substances selected from the group comprising halogenated dibenzodioxins, halogenated dibenzofurans, polychlorinated biphenyls, destroying the endocrine system agents, other than dioxins, kantse ogenyi substances and organic halogenated compounds which can be removed by the method of fotorazlozheniya or chemical decomposition, containing:
section introducing a reducing agent intended for the introduction of the reducing agent in the treated raw water containing recalcitrant substance to neutralize the chlorine in the water, where the reducing agent is chosen from the group comprising sodium bisulfite, sodium metabisulfite and sulfur dioxide,
section purification membrane concentration, designed to separate from water containing recalcitrant substance liquid that has passed through the reverse osmosis membrane or a nanofiltration membrane to concentrate recalcitrant substance
section adding the adsorbent that is used to add the adsorbent in concentrated recalcitrant substance to cause the adsorption of recalcitrant substances by adsorbent, where the added adsorbent is one of the inorganic adsorbent, or two or more inorganic adsorbents selected or selected from the group consisting of titanium dioxide, zeolite, acid clay, activated clay, diatomaceous earth, metal oxide, metal powder, activated carbon and carbon black,
section cleaning membrane filtration, designed to separate the liquid that has passed through the filtration membrane to skoncentrisem the th adsorbent, adsorbirovavshyei recalcitrant substance
the section adding a flocculant, designed to add a flocculant in water containing adsorbent, adsorbirovavshyei recalcitrant substance in order to carry out the flocculation of the adsorbent, adsorbirovavshyei recalcitrant substance, where the flocculant selected from the group including aluminum sulfate, iron chloride (III), iron sulfate (II), polychloride aluminum and reagent-based zeolite, sodium polyacrylate and copolymer of sodium acrylate and acrylamide,
partition separating solids and liquids, designed to separate the adsorbent, adsorbirovavshyei recalcitrant substance and flocculated flocculant, and
section cleaning chemical decomposition that is used for the oxidative decomposition of recalcitrant substances adsorbed on the separated adsorbent, with the use of peroxide, where the peroxide is chosen from the group including persulfates, sodium peroxide, barium peroxide, peroxide zinc, cadmium peroxide, potassium peroxide, calcium peroxide, chromium peroxide, hydrogen peroxide, ozone, as well as a system using a combination of a metal catalyst and a material supplying hydrogen.

19. A method for concentrating recalcitrant(s) substance (s) in water, containing one or more recalcitrant substances the TV, selected from the group comprising halogenated dibenzodioxins, halogenated dibenzofurans, polychlorinated biphenyls, destroying the endocrine system agents, other than dioxins, carcinogenic substances, and organic halogenated compounds which can be removed by the method of fotorazlozheniya or chemical decomposition, including:
(C) stage adsorption purification, which is added to the adsorbent in the treated raw water containing recalcitrant substance, to perform the adsorption of recalcitrant substances on the adsorbent, with the added adsorbent is one of the inorganic adsorbent, or two or more inorganic adsorbents selected or selected from the group consisting of titanium dioxide, zeolite, acid clay, activated clay, diatomaceous earth, metal oxide, metal powder, activated carbon and carbon black,
(C) purification stage membrane filtration, which separates the liquid that has passed through the filtration membrane for concentration of adsorbent, adsorbirovavshyei recalcitrant substance.

20. The way the concentration of recalcitrant(s) substance (s) in water containing recalcitrant(s) substance(s)according to claim 19, which further includes:
(A) purification stage membrane concentration, on to the second separated fluid, passed through the reverse osmosis membrane or a nanofiltration membrane from water containing recalcitrant substance, for concentration of recalcitrant substances.

21. A method for concentrating recalcitrant(s) substance (s) in water containing recalcitrant(s) substance(s)according to claim 20, in which at least part of recalcitrant substances, concentrated on the stage (A), return in the treated raw water containing recalcitrant substance.

22. The method of purification of water containing one or more recalcitrant substances selected from the group comprising halogenated dibenzodioxins, halogenated dibenzofurans, polychlorinated biphenyls - PCBs, destroying the endocrine system agents, other than dioxins, carcinogenic substances, and organic halogenated compounds which can be removed by the method of fotorazlozheniya or chemical decomposition, including irradiation recalcitrant(s) substance (s), concentrated(-s) concentration of recalcitrant(s) substance (s) in water containing recalcitrant(s) substance(s), for any from PP-21, for the decomposition of recalcitrant (s) substance (s).



 

Same patents:

FIELD: chemistry.

SUBSTANCE: device for reagentless water purification - module for intense aeration and degassing contains a reactor-tank 7, two injectors 4, 5, injector section 3, hydrocyclone 2 and fan 6. Reactor-tank 7 is a rectangular container with a bottom, lying at an angle α to its largest vertical wall, and if fitted with level sensors. The air space τ above the water level in the reactor-tank should not be less than 0.2 metres, and faces of mixing chambers of the injectors are at a height h of not less than 0.5 metres above the water level in the reactor-tank 7.

EFFECT: cheap reagentless water purification.

2 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: device for reagentless water purification - module for intense aeration and degassing contains a reactor-tank 7, two injectors 4, 5, injector section 3, hydrocyclone 2 and fan 6. Reactor-tank 7 is a rectangular container with a bottom, lying at an angle α to its largest vertical wall, and if fitted with level sensors. The air space τ above the water level in the reactor-tank should not be less than 0.2 metres, and faces of mixing chambers of the injectors are at a height h of not less than 0.5 metres above the water level in the reactor-tank 7.

EFFECT: cheap reagentless water purification.

2 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a photocatalyst composition based on carbon material with large specific surface area with a deposited photocatalyst based on titanium dioxide or titanium dioxide which is modified with noble metals, mainly used for photocatalytic purification of air and water, contaminated with molecular impurities of organic or inorganic nature. A photocatalyst-adsorbent is described, which is characterised by that, it consists of an inorganic fabric on a woven or non-woven base, soaked with a composition which contains an inorganic binder, adsorbent and photocatalytically active titanium dioxide. Surface area of the adsorbent is at least twice larger than the surface area of the photocatalytically active titanium dioxide. A photocatalyst-adsorbent is also described, which is characterised by that, it consists of an inorganic fabric on a woven or non-woven base, soaked with a composition which contains an inorganic binder and adsorbent, on which photocatalytically active titanium dioxide is deposited. Surface area of the adsorbent is at least twice larger than surface area of photocatalytically active titanium dioxide.

EFFECT: above described catalysts-adsorbents combine sorbent and photocatalyst properties, have low hydrodynamic resistance, sufficient hardness and have value of photocatalytic activity with respect to decomposition of organic and inorganic substances in water and air.

12 cl, 1 tbl, 2 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to water treatment technology and can be used for ozone treatment of drinking water in centralised water supply systems. The device has an ozone gas mixture generator, a reservoir with a water supply system and a system for discharging water to the consumer, in the near-bottom part of which are fitted gas dispersing elements, connected by pipes with the ozone gas mixture generator. The gas dispersing elements are in form of hollow two-layered panels with a uniformly perforated top layer, uniformly fitted on the cross section of the reservoir and forming a bouble bottom and double bottom space - a high pressure zone between the bottom layer of the panels and the bottom of the reservoir. The gas dispersing elements are fitted with centres for swirling the water stream in form of slot-type swirl atomisers, inlet openings of which are linked with the double bottom space, outlet slot nozzles are placed above the perforated surface of gas-permeable elements and are parallel the said surface. The double bottom space is linked with the system for supplying water to the reservoir. One face of the panels is placed on corner hinged bearings, and the ozone gas mixture pipes are the axis of rotation of the corner hinged bearings of the gas dispersing elements.

EFFECT: proposed invention increases mass-transfer surface between water and the ozone gas mixture; also reduces operating costs by cutting time for decontaminating the reservoir.

2 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to methods of removing oxygen dissolved in organic liquids using a solid-phase catalyst and a reducing agent. The method is realised using the following operations: a) a reducing agent in form of hydrogen is added to organic liquid, b) excess undissolved reducing agent is removed if necessary, c) dissolved oxygen is reacted with the reducing agent on a catalyst, d) after virtually complete removal of dissolved oxygen, the organic liquid is brought into contact with sulphur-containing inorganic or organic compounds or mixtures containing said sulphur-containing compounds. Preferred versions of realising the method involve: passing a reducing agent directly through a catalyst or over the catalyst, reacting dissolved oxygen with the reducing agent in a fixed bed of a bulk catalyst, where the catalyst used is a solid substance which contains a noble metal (Pd). Organic solvents, for example methanol, are used as the organic liquid.

EFFECT: method allows for preventing side reactions and creation of dangerous conditions in chemical plants which violate safety rules.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of removing oxygen dissolved in organic liquids using a solid-phase catalyst and a reducing agent. The method is realised using the following operations: a) a reducing agent in form of hydrogen is added to organic liquid, b) excess undissolved reducing agent is removed if necessary, c) dissolved oxygen is reacted with the reducing agent on a catalyst, d) after virtually complete removal of dissolved oxygen, the organic liquid is brought into contact with sulphur-containing inorganic or organic compounds or mixtures containing said sulphur-containing compounds. Preferred versions of realising the method involve: passing a reducing agent directly through a catalyst or over the catalyst, reacting dissolved oxygen with the reducing agent in a fixed bed of a bulk catalyst, where the catalyst used is a solid substance which contains a noble metal (Pd). Organic solvents, for example methanol, are used as the organic liquid.

EFFECT: method allows for preventing side reactions and creation of dangerous conditions in chemical plants which violate safety rules.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to electrochemical water treatment. The device for electrochemical treatment of water and aqueous solutions comprises coaxially arranged positive and negative electrodes, an ion exchange diaphragm, coaxially placed between the electrodes and dividing the interelectrode space into electrode chambers, a polymer thread or polymer tube with variable cross section, placed in the electrode chambers along a helical line around the axis of the electrodes.

EFFECT: device increases efficiency due to uniform treatment of liquid while increasing reliability and longevity of electrodes and preventing formation of gas pockets.

4 dwg

FIELD: technological processes, filters.

SUBSTANCE: invention is related to device for cleaning of storm waters from oil products and suspended matters and may be used for cleaning of rain storm water sewage. Device comprises zone of setting, thin-layer settling tank, filter with floating bed, sorption filter with activated coal. Setting zone is equipped with container for oil product removal, flow distributor. In lower part of semi-submerged plate there is a coalescent filter from corrugated cells made from oleophilic material. Zone of coalescence is separated from thin-layer setting tank by additional inclined semi-submerged plate. In zone of coalescence tray is installed for collection of oil product film, which is removed from tray to zone of setting by means of pump. Downstream thin-layer unit there are double-level cylindrical mechanical filters with large working surface from oleophilic sorption material, (for instance, sipron, megasorb, etc). Drain of cleaned water from sorption filter with activated coal is done from upper part.

EFFECT: improved extent of drain water cleaning from oil products and suspended matters.

3 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method is meant for non-reagent softening natural water and can be used in public facilities in centralised and decentralised water supply systems, and industrial water supply systems. Natural water is softened through effect of magnetic and electric field, where water is successively filtered in ferromagnetic material, magnetised with an external magnetic field, and then filtered in granular material which is in an electric field created by an electrochemical current source. Strength of the external magnetic field ranges from 500 to 1000 A/m. Water is filtered in a granular ferrite with particle size ranging from 5 to 10 mm at a rate of 20 to 40 m/h. The electric field is created through spatial separation of electronegative and electropositive electrodes, between which granular filtering material is placed. Filtering is done in an electric field at a rate of 0.6 to 1.0 m/h.

EFFECT: method allows for softening very hard water through effect of magnetic and electric field and extraction of formed hardness salts by filtering in a granular filter bed.

3 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method is meant for non-reagent softening natural water and can be used in public facilities in centralised and decentralised water supply systems, and industrial water supply systems. Natural water is softened through effect of magnetic and electric field, where water is successively filtered in ferromagnetic material, magnetised with an external magnetic field, and then filtered in granular material which is in an electric field created by an electrochemical current source. Strength of the external magnetic field ranges from 500 to 1000 A/m. Water is filtered in a granular ferrite with particle size ranging from 5 to 10 mm at a rate of 20 to 40 m/h. The electric field is created through spatial separation of electronegative and electropositive electrodes, between which granular filtering material is placed. Filtering is done in an electric field at a rate of 0.6 to 1.0 m/h.

EFFECT: method allows for softening very hard water through effect of magnetic and electric field and extraction of formed hardness salts by filtering in a granular filter bed.

3 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: device for reagentless water purification - module for intense aeration and degassing contains a reactor-tank 7, two injectors 4, 5, injector section 3, hydrocyclone 2 and fan 6. Reactor-tank 7 is a rectangular container with a bottom, lying at an angle α to its largest vertical wall, and if fitted with level sensors. The air space τ above the water level in the reactor-tank should not be less than 0.2 metres, and faces of mixing chambers of the injectors are at a height h of not less than 0.5 metres above the water level in the reactor-tank 7.

EFFECT: cheap reagentless water purification.

2 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: device for reagentless water purification - module for intense aeration and degassing contains a reactor-tank 7, two injectors 4, 5, injector section 3, hydrocyclone 2 and fan 6. Reactor-tank 7 is a rectangular container with a bottom, lying at an angle α to its largest vertical wall, and if fitted with level sensors. The air space τ above the water level in the reactor-tank should not be less than 0.2 metres, and faces of mixing chambers of the injectors are at a height h of not less than 0.5 metres above the water level in the reactor-tank 7.

EFFECT: cheap reagentless water purification.

2 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a photocatalyst composition based on carbon material with large specific surface area with a deposited photocatalyst based on titanium dioxide or titanium dioxide which is modified with noble metals, mainly used for photocatalytic purification of air and water, contaminated with molecular impurities of organic or inorganic nature. A photocatalyst-adsorbent is described, which is characterised by that, it consists of an inorganic fabric on a woven or non-woven base, soaked with a composition which contains an inorganic binder, adsorbent and photocatalytically active titanium dioxide. Surface area of the adsorbent is at least twice larger than the surface area of the photocatalytically active titanium dioxide. A photocatalyst-adsorbent is also described, which is characterised by that, it consists of an inorganic fabric on a woven or non-woven base, soaked with a composition which contains an inorganic binder and adsorbent, on which photocatalytically active titanium dioxide is deposited. Surface area of the adsorbent is at least twice larger than surface area of photocatalytically active titanium dioxide.

EFFECT: above described catalysts-adsorbents combine sorbent and photocatalyst properties, have low hydrodynamic resistance, sufficient hardness and have value of photocatalytic activity with respect to decomposition of organic and inorganic substances in water and air.

12 cl, 1 tbl, 2 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to water treatment technology and can be used for ozone treatment of drinking water in centralised water supply systems. The device has an ozone gas mixture generator, a reservoir with a water supply system and a system for discharging water to the consumer, in the near-bottom part of which are fitted gas dispersing elements, connected by pipes with the ozone gas mixture generator. The gas dispersing elements are in form of hollow two-layered panels with a uniformly perforated top layer, uniformly fitted on the cross section of the reservoir and forming a bouble bottom and double bottom space - a high pressure zone between the bottom layer of the panels and the bottom of the reservoir. The gas dispersing elements are fitted with centres for swirling the water stream in form of slot-type swirl atomisers, inlet openings of which are linked with the double bottom space, outlet slot nozzles are placed above the perforated surface of gas-permeable elements and are parallel the said surface. The double bottom space is linked with the system for supplying water to the reservoir. One face of the panels is placed on corner hinged bearings, and the ozone gas mixture pipes are the axis of rotation of the corner hinged bearings of the gas dispersing elements.

EFFECT: proposed invention increases mass-transfer surface between water and the ozone gas mixture; also reduces operating costs by cutting time for decontaminating the reservoir.

2 cl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to methods of removing oxygen dissolved in organic liquids using a solid-phase catalyst and a reducing agent. The method is realised using the following operations: a) a reducing agent in form of hydrogen is added to organic liquid, b) excess undissolved reducing agent is removed if necessary, c) dissolved oxygen is reacted with the reducing agent on a catalyst, d) after virtually complete removal of dissolved oxygen, the organic liquid is brought into contact with sulphur-containing inorganic or organic compounds or mixtures containing said sulphur-containing compounds. Preferred versions of realising the method involve: passing a reducing agent directly through a catalyst or over the catalyst, reacting dissolved oxygen with the reducing agent in a fixed bed of a bulk catalyst, where the catalyst used is a solid substance which contains a noble metal (Pd). Organic solvents, for example methanol, are used as the organic liquid.

EFFECT: method allows for preventing side reactions and creation of dangerous conditions in chemical plants which violate safety rules.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of removing oxygen dissolved in organic liquids using a solid-phase catalyst and a reducing agent. The method is realised using the following operations: a) a reducing agent in form of hydrogen is added to organic liquid, b) excess undissolved reducing agent is removed if necessary, c) dissolved oxygen is reacted with the reducing agent on a catalyst, d) after virtually complete removal of dissolved oxygen, the organic liquid is brought into contact with sulphur-containing inorganic or organic compounds or mixtures containing said sulphur-containing compounds. Preferred versions of realising the method involve: passing a reducing agent directly through a catalyst or over the catalyst, reacting dissolved oxygen with the reducing agent in a fixed bed of a bulk catalyst, where the catalyst used is a solid substance which contains a noble metal (Pd). Organic solvents, for example methanol, are used as the organic liquid.

EFFECT: method allows for preventing side reactions and creation of dangerous conditions in chemical plants which violate safety rules.

12 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to electrochemical water treatment. The device for electrochemical treatment of water and aqueous solutions comprises coaxially arranged positive and negative electrodes, an ion exchange diaphragm, coaxially placed between the electrodes and dividing the interelectrode space into electrode chambers, a polymer thread or polymer tube with variable cross section, placed in the electrode chambers along a helical line around the axis of the electrodes.

EFFECT: device increases efficiency due to uniform treatment of liquid while increasing reliability and longevity of electrodes and preventing formation of gas pockets.

4 dwg

FIELD: technological processes, filters.

SUBSTANCE: invention is related to device for cleaning of storm waters from oil products and suspended matters and may be used for cleaning of rain storm water sewage. Device comprises zone of setting, thin-layer settling tank, filter with floating bed, sorption filter with activated coal. Setting zone is equipped with container for oil product removal, flow distributor. In lower part of semi-submerged plate there is a coalescent filter from corrugated cells made from oleophilic material. Zone of coalescence is separated from thin-layer setting tank by additional inclined semi-submerged plate. In zone of coalescence tray is installed for collection of oil product film, which is removed from tray to zone of setting by means of pump. Downstream thin-layer unit there are double-level cylindrical mechanical filters with large working surface from oleophilic sorption material, (for instance, sipron, megasorb, etc). Drain of cleaned water from sorption filter with activated coal is done from upper part.

EFFECT: improved extent of drain water cleaning from oil products and suspended matters.

3 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: method is meant for non-reagent softening natural water and can be used in public facilities in centralised and decentralised water supply systems, and industrial water supply systems. Natural water is softened through effect of magnetic and electric field, where water is successively filtered in ferromagnetic material, magnetised with an external magnetic field, and then filtered in granular material which is in an electric field created by an electrochemical current source. Strength of the external magnetic field ranges from 500 to 1000 A/m. Water is filtered in a granular ferrite with particle size ranging from 5 to 10 mm at a rate of 20 to 40 m/h. The electric field is created through spatial separation of electronegative and electropositive electrodes, between which granular filtering material is placed. Filtering is done in an electric field at a rate of 0.6 to 1.0 m/h.

EFFECT: method allows for softening very hard water through effect of magnetic and electric field and extraction of formed hardness salts by filtering in a granular filter bed.

3 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method is meant for non-reagent softening natural water and can be used in public facilities in centralised and decentralised water supply systems, and industrial water supply systems. Natural water is softened through effect of magnetic and electric field, where water is successively filtered in ferromagnetic material, magnetised with an external magnetic field, and then filtered in granular material which is in an electric field created by an electrochemical current source. Strength of the external magnetic field ranges from 500 to 1000 A/m. Water is filtered in a granular ferrite with particle size ranging from 5 to 10 mm at a rate of 20 to 40 m/h. The electric field is created through spatial separation of electronegative and electropositive electrodes, between which granular filtering material is placed. Filtering is done in an electric field at a rate of 0.6 to 1.0 m/h.

EFFECT: method allows for softening very hard water through effect of magnetic and electric field and extraction of formed hardness salts by filtering in a granular filter bed.

3 cl, 1 dwg, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: device for reagentless water purification - module for intense aeration and degassing contains a reactor-tank 7, two injectors 4, 5, injector section 3, hydrocyclone 2 and fan 6. Reactor-tank 7 is a rectangular container with a bottom, lying at an angle α to its largest vertical wall, and if fitted with level sensors. The air space τ above the water level in the reactor-tank should not be less than 0.2 metres, and faces of mixing chambers of the injectors are at a height h of not less than 0.5 metres above the water level in the reactor-tank 7.

EFFECT: cheap reagentless water purification.

2 cl, 2 dwg

Up!