Wastewater treatment method

 

(57) Abstract:

The method is designed to reduce organic chemicals in wastewater. Waste water is fed in at least one reactor is cleaned at a temperature of more than 15oC chlorine and/or chloridebased substance, and the supply of chlorine are more than 1 g of chlorine per 1 g of COD with the chlorine content of the chlorinated and/or chlorides substance, at a molar ratio of OH-to more than 1.5 Cl and pH 6 for more than 0.4 hours Then the waste water is cleaned in a subsequent cycle and/or display, and/or discharge from the reactor. This invention allows to reduce costs. 24 C.p. f-crystals. table 4.

The invention relates to a method of reducing the content of organic chemicals in waste water by chemical oxidation, mainly in the presence of chlorine, and in this case by additional thermoselect processing (cleaning) water.

You already know how to expose the oxidative thermochemical treatment of waste water with undesirable dissolved or dispersed organic matter, and organic substances are oxidized, they become carbon dioxide and water. Such JV is isoamsa burning in the liquid phase. In order to achieve a satisfactory decomposition of organic compounds and sufficient reaction rate of exchange, requires a high concentration of oxygen, high temperature and pressure.

This treatment method because of its high power consumption requires very impressive hardware costs. Used temperature and pressure can, however, be lowered by applying a catalyst of heavy metals, however, this will lead to a subsequent load of waste water catalytically active substances, that in this situation makes it necessary for another cleaning cycle.

Load of wastewater by organic substances characterized by a number of physico-chemical parameters. This includes "chemical oxygen demand" as the value of its consumption by chemical wet oxidation of dissolved or dispersed organic compounds under specific conditions. Using this option can thus calculate the percentage of the chemically oxidizable substances in waste water.

From Japanese patent application N 49/021951 (abstract in the publication "chemical Abstracts CA 81(10) 54117 g) know how to use ultraviolet rays and activated chlorine or GSA purification activated carbon. Application of UV-rays for wastewater treatment is associated, however, with the hardware and costs.

From the application of N DE-OC 3620980 known method of reducing the content of harmful substances depending on the values of COD and AOG in waste water in bleaching operations in the production of pulp. "Og" is another total value for the characteristics of the organic load in the wastewater. She refers to "adsorption of organic halogen compounds" - "Oh" and is defined as part of the share (X=Cl, Br, I), and total adsorbed amount is calculated as X=Cl.

The method according to the application DE-OC 3620980 is carried out mainly in three phases, with the first stage strongly acidic solution is brought to a precipitation of chlorine compounds and thereby lead to a decrease in COD and AOG calcium ions.

The second stage is further reduced AOG by thermal alkaline hydrolysis, which leads to the partial dechlorination neozhidannyh adsorbed organic chlorine compounds.

Harmful substances still contained after the technological cycle in waste water, COD and producing AG, at the third stage is subjected to decomposition by microbes.

The objective of the invention to create a method by which small technical and financial means to decompose the organic compounds produced, in particular, in the processes of large-scale industrial production or in the process of synthesis and often causing significant load of COD in waste water and in the case of halogenated organic compounds - load Aug.

Therefore, the method must allow successful treatment of waste water, which as organic substances may contain not halogenated, and in this case, and halogenated organic compounds, so this opens up the possibility along with a predominant decrease of chemical oxygen demand - COD - to reduce the content AOG in waste water to be treated.

Regardless of your respective content of COD, and in this case AOG, it is necessary, in particular, to be able to initially handle waste water and purification method should lead to a clear, effective reduction of the COD value, and in this case Aug.

To solve this task according to the invention in the method of reducing the content of organic substances in waste water from chemical potrebnosti and clean at temperatures exceeding 15oC chlorine-containing and/or chloridebased substance, and the supply of chlorine are more than 1 g per 1 g of COD with the chlorine content of the chlorinated and/or chloridebased substance, at a molar ratio of OH-to Cl more than 1.5 and the pH value of waste water 6 within more than 0.4 h, and organic compounds at least partially oxidized, and then the waste water is cleaned in a subsequent cycle and/or display, and/or discharge from the reactor.

Through this method economically and technologically simple way reduced the COD of waste water by more than 90%. If the waste water contain additional organic matter, producing AOG, the content AG waste water will also be reduced by applying the method according to the invention. Found that by this method can be effectively reduced the COD content, and in this case AOG, since waste water is present halogenoalkanes connection, and into the sewer and, in particular, in the waste water of industrial production.

By means of the method according to the invention can be processed, in particular, and such waste water, which has already been subjected to pre-cleaning the practical processes. Processed according to the invention mainly wastewater, have preliminary purification by termolonkho, adsorption and/or microbiological process (method). Waste water, however, can be pre-purified by precipitation.

The introduction of chlorine (in the form of chlorinated and/or chloridebased chemicals) according to the invented method in an alkaline aqueous solution, for example in an installation for the production of allylchloride /epichlorhydrine/ glycerol causes imbalance of chlorine with the formation of chlorite and hypochlorite according to the equation.

Cl2+ OH---> Cl-+ HOCl (equation 1)

The oxidative effect of hypochlorite is used to oxidize the content of organic matter (in the case of the above-mentioned waste liquor from installation to allylchloride/epichlorhydrine/ glycerol is mainly glycerol glyceric acid, lactic acid, glycidol) alkaline-active waste water with the formation of CO2and water.

The resulting CO2and possible gaseous intermediate products of oxidation can be prevented by technology without the use of pressure.

In accordance with the invention, the mouth of the certain parameters with strictly defined limit values. Depending on the organic load of the substances contained in the wastewater, producing COD, need accurate dosing of chlorine to ensure the lowest possible concentration of hypochlorite and chlorate in effluent water (the latter with excess chlorine content). For the same reason, is established or maintained a certain proportion of chlorine and alkalinity. Particularly preferred is a molar ratio OH-/Cl in the range of 1.6 to 2.5, mostly 2 to 2.2, and the hydroxide ion can be either free, hydrated, i.e., in unbound form or chemically bound in the waste water. In the latter case must be permanent dissolution of trapped ions hydroxide in accordance with the observed proportion of chlorine and alkalinity. As compounds that produce or forming hydroxide ions in waste water may contain predominantly solid, dissolved and/or suspended alkaline and/or alkaline earth hydroxide and/or oxide.

Is used, in particular, an aqueous solution or suspension containing calcium hydroxide, mainly the milk of lime. The above alkali-active substances are used enhan is mperature.

It was found further that the necessary control of pH for ongoing according to the invention by oxidation of organic compounds by chlorine. Supply of chlorine in alkaline aqueous solution leads to a lowering of the pH factor, and its reduction depends on the deposited amount of chlorine. At lower ratios of pH, in particular in the strongly acidic range is undesirable increase AOG water. In accordance with the invention found that the above disadvantages can be avoided if the pH of the wastewater is retained within the 6. In particular, favorable was to maintain or regulate pH in the range of 10 at the time of making chlorine in waste water. Then at the end of the observed reaction time in the waste water pH is set within 9.

Further according to the invention it is established that increase the rate of oxidation is achieved with increasing temperature, which leads to the reduction of the cycle time, respectively, of the reaction, after making chlorine. Suitable, in particular, is that the waste water is cleaned at a temperature of 40 - 100oC, predominantly 80 - 95oC with chlorine-containing chemical and/or chlorophyllum substance.

The supply of chlorine is mainly amicucci. The reaction, however, can occur when excessive pressure, and found a significant beneficial reduction of adsorbed organic halogen compounds (AOG).

If method according to the invention is implemented without pressure, the educated meanwhile, CO2you can simply withdraw from the treatment reactor. The same applies to gaseous intermediate products of oxidative cleaning content of organic substances in waste water. When version with application of pressure for purification of waste water from installations for the production of allylchloride (epichlorhydrin) glycerol found that gaseous intermediate products of oxidative decomposition of organic substances in waste water formed during the chlorine treatment, are retained in the reactor and the oxidation proceeds with hypochlorite before the formation of CO2subject according to the invention the reaction time.

According to the invention, it is preferable that the supply of chlorine lead in number of 2 to 8 g per 1 g of COD mainly 4 - 6 g Cl/1 g COD. The chlorine content of the chlorinated and/or chlorides matter.

In order to avoid the formation of undesirable by-products when oxidized is sayasane and accurately a certain amount of activated chlorine in waste water. This can be done by adding an effective free chlorine in the form of elementary dissolved chlorine, Podgornoe acid and/or hypochlorite.

But the oxidant can also be used as "associated effective chlorine in the form of oxidative existing chlorosilane compounds or other chlorophyllose substances, such as bleach, can be used containing chloride water, from which chlorine is released by electrochemical method. As the chlorine-containing chemicals in the method according to the invention is used mainly chlorine-containing gas, in particular chlorine gas.

In order to improve the kinetic conditions of the chlorination of waste water and to avoid formation of significant local variations in the concentration of chlorine and related strong sinks pH, flow of chlorine should be possible in small portions, but as chlorinated use of liquefied chlorine gas, preferably chlorine gas mixed with an inert gas such as nitrogen.

The chlorine-containing feed gas is profitable to produce with the use of excessive pressure in the range of 0.1 to 5 bar, mostly 0.2 to 3 bar.

oC, predominantly 80 - 135oC for 0.5 - 8 hours, mostly 3 - 5 hours So once again able to increase the effect of the collapse of COD and, in particular Aug.

By regulation or compliance with certain ratios of the pressure in the reactor was again found to improve standards of decay. During the cleaning in the reactor establish or maintain a pressure in the range from 1 to 11 bar, mainly 1,1 - 4 bars. Cleaning under the excessive pressure has proven particularly successful. If maintained, for example, a pH in the range of 10 temperature of about 130oC and a pressure of about 2.5 bar during the reaction within 60 - 90 minutes, we can forecast the collapse of the COD more than 92%, and the reduction AOG more than 80%.

The method according to the invention can be carried out continuously or intermittently. As treatment tanks or reactors can be applied to the reaction column or tubular reactors. Additive chlorine-containing and/or chlorophyllose substances to water can be produced, for example, the tube current, and the length of the pipe and/or the value of water in a clearing device. To implement the method can be used in series or parallel connected reactors. Next reactor or multiple reactors can be built installation for mixing the water to be purified.

To avoid blockage (clogging) treatment plant settling solids, which in this case are in waste water or are formed during oxidative purification, it may be advantageous to at least partially release the water from suspended solids, mainly by chemical reaction and/or mechanical separation processes such as filtration and/or sedimentation.

In order to further decrease the content of COD, and in this case AOG, waste water can then be performed subsequent purification of water, treated with an oxidizing or thermoslim way. Best when this proved according to the invention a combination of oxidation, termolonkho method, followed by ozone treatment. The high oxidizing power of ozone for wastewater treatment is used long ago to oxidation to decompose the contained organic matter, and it is necessary to observe the reaction time and ozone concentration.

Ozonation of wastewater is carried out, in particular, at room temperature, and in this case should be followed by the cooling water heated by the previous cleaning. However, ozone purification may also be performed at elevated temperatures. Ozonation with appropriate equipment can be done already used in cleaning the reactor. However, the purified water is supplied mainly in another reactor and/or of a special device for ozone treatment. Used conventional, commercially available device, containing at least one ozone generator, one of the treatment reactor made of inert material together with sterowania CO2derived from the treatment reactor in this case with use of special devices. Ozone cleaning can be performed in one or two stages. To enhance the power of collapse during ozonation can be used ultraviolet irradiation. The use of ozone in combination with oxidative and thermoselect method according to the invention leads to a further advantageous reduction of the components forming COD and AOG in the purified water.

Instead of the ozone further purification water purification lead by oxidation and/or adsorption treatment, and it is carried out mainly with the use of hydrogen peroxide and/or activated carbon. Along with cleaning activated carbon are its regeneration mainly by heat treatment using an aqueous solution of alkali.

Further, the method according to the invention can be combined with pre-treatment of water to remove, for example, other harmful organic substances or already at the stage of pre-treatment to produce the collapse of the COD, Aug, CURRENT and/or BSB (for the last two terms decrypt text no - approx. translator) so that you can make subsequent cleaning Appl the cleanup occurs mainly through thermoselect, adsorption and/or microbiological processing. Termology cleaning is carried out when establishing certain specific pH, temperature, pressure and residence time. As the adsorption method is proposed, for example, treatment with activated carbon. Preliminary microbiological cleaning can be performed with the use of anaerobic or aerobic bacteria.

Wastewater treatment method according to the invention can be used for decay components, producing COD (and in the presence and AOG) in any water. Special technical area where this is found, the method can be used preferably is a wastewater treatment after production of gelegenheden, polyol and/or vinyl chloride. According to the method according to the invention particularly preferably purify waste water in the production of glycerol and/or polyglycerol, chlorhydrin, mainly for the synthesis of epichlorohydrin and epichlorohydrin is maintained by exchange reactions in solution containing dichloropropanol at least one alkaline compound, mainly water suspension containing calcium hydroxide, with an excess of calcium hydroxide per applicable dig the production of gelegenheden, polyol and/or vinyl chloride, i.e., for water purification, which are formed by mixing the above in the manufacture of gelegenheden, polyol and/or vinyl chloride.

Next, it is established that the components that form during COD how, in particular, saturated and/or unsaturated aliphatic and/or alicyclic hydrocarbons, ethers, alcohols and preferably polyols, ketones, aldehydes and/or carboxylic acids, very well collapse due to the method of the invention. The same applies to the components, optionally forming values AOG as, in particular, saturated and/or unsaturated aliphatic and/or alicyclic chloride hydrocarbons, ethers, alcohols, ketones, aldehydes, giarini and/or carboxylic acid chloride.

Further, the method according to the invention is used primarily for wastewater treatment, which are formed with the use and/or during transfer reactions gelegenheden, in the production of epoxy resins from gelegenheden and/or polyala. The following examples should clarify the method of the invention without limiting it.

Example 1. 1000 ml of Waste water from installations for the production of allylchloride (epichlorhydrin) giant pH drops in to 6.8. With the completion of the supply of chlorine solution is stirred for further 90 min at 95oC and then dropping out of the reactor.

Identified the following outcome parameters for incoming (raw) and discharged (treated) waste water (PL. 1).

Example 2. 1000 ml of Waste water from installations for the production of allylchloride (epichlorhydrin) glycerin mixed with 100 ml of waste water containing vinyl chloride, and served in a reaction chamber. The solution is heated to 85oC and within 20 minutes give 7 g of chlorine. At this pH falls to 6.3 and 6.4. With the completion of the supply of chlorine solution is stirred for further 90 min and discharged from the reactor.

Identified the following outcome parameters for incoming (raw) and discharged (treated) waste water (PL. 2).

Example 3. As in the example of execution 2 make a mixture of 1000 ml of waste water from installations for the production of allylchloride/epichlorhydrine/glycerin and 100 ml of waste water containing vinyl chloride and fed into the reactor. In this mixture at 95oC for 25 min serves 4.6 g of chlorine, the pH falls to 10.3. The mixture is then transferred to an autoclave and stirred for 1 h at 130oC with a pressure of 2.6 bar. Then the effluent from the reactor discharge.

The definition).

Example 4. 1000 ml of Waste water from installations for the production of allylchloride/epichlorhydrine/glycerol served in a reaction chamber and for 37 min at a temperature of 97oC in water is injected to 5.1 g of chlorine. After the filing of the chlorine solution was transferred to an autoclave and incubated for 1 h at a temperature of 130oC. Then the waste water is discharged.

Identified the following outcome parameters for incoming (raw) and discharged (treated) waste water (PL. 4).

1. The method of reducing the content of organic chemicals in wastewater with chemical oxygen demand (COD) by chemical oxidation in the presence of chlorine, characterized in that the waste water is fed in at least one reactor is cleaned at a temperature of more than 15oC chlorine and/or chloridebased substance, and the supply of chlorine are more than 1 g of chlorine per 1 g of COD with the chlorine content of the chlorinated and/or chlorides substance with a molar ratio of OH-to Cl more than 1.5 and the pH value of waste water 6 within more than 0.4 h, and organic compounds at least partially oxidized, and then the waste water is cleaned in a subsequent cycle, and/or display, and/or dropping out of reactin substance at a temperature of 40 100oC, mostly in the 80 - 95oC.

3. The method according to PP.1 and 2, characterized in that the supply of chlorine lead in number of 2 to 8 g per 1 g of COD mainly 4 - 6 g Cl 1 g COD with the chlorine content of the chlorinated and/or chlorides matter.

4. The method according to PP.1 and 3, characterized in that the supply of chlorine is carried out at normal pressure in the reactor.

5. The method according to PP.1 and 3, characterized in that the supply of chlorine is carried out at a gauge pressure in the reactor.

6. The method according to p. 1, characterized in that establish or maintain the molar ratio of CH-/Cl in the range of 1.6 to 2.5, mainly 2 - 2,2.

7. The method according to p. 1, characterized in that as the chlorine-containing substance used chlorine gas, mainly chlorine.

8. The method according to p. 7, characterized in that the supply of chlorine gas is produced with the use of excess pressure of about 0.1 - 5 bar, mostly 0.2 to 3 bar.

9. The method according to p. 1, characterized in that during the cleaning and/or after wastewater treatment chlorine and/or chloridebased substance pH wastewater, measured at room temperature, install or maintain within 10 - 14, preimuschestvenno 3 - 5 o'clock

10. The method according to p. 9, characterized in that during the cleaning in the reactor establish or maintain a pressure in the range from 1 to 11 bar, mainly 1,1 - 4 bars.

11. The method according to PP.1 and 9, characterized in that establish or maintain the alkalinity and/or pH by adding alkali-active substances, predominantly solid, dissolved and/or suspended alkaline and/or alkaline-earth hydroxide and/or oxide.

12. The method according to p. 11, wherein establishing or maintaining alkalinity and/or pH are by the addition of an aqueous solution or suspension containing calcium hydroxide, mainly lime milk.

13. The method according to p. 1, characterized in that the waste water before, during and/or after cleaning osvobojdayut from suspended solids at least partially, mainly by chemical reaction and/or mechanical separation.

14. The method according to p. 1, wherein the effluent is subjected to further purification using ozonoterapia gas, and purified waste water establish or maintain a pH in the range of 10 measured at room temperature, mainly pH 1 the manual on p. 14, characterized in that the effluent for further processing using ozonoterapia gas serves at least one subsequent reactor and/or the cleaning device of ozone.

16. The method according to p. 1, characterized in that the further treatment of waste water are by oxidation and/or adsorption processing.

17. The method according to p. 16, wherein the further treatment of waste water is produced using hydrogen peroxide and/or activated charcoal.

18. The method according to PP.16 and 17, characterized in that after the purification activated carbon are its regeneration, mainly by heat treatment using an aqueous solution of alkali.

19. The method according to p. 1, wherein the treatment with chlorine is subjected to pre-purified water, and pre-cleaning lead by thermoselect, adsorption and/or microbiological processing.

20. The method according to PP. 1 to 19, characterized in that the purification is subjected to waste water production gelegenheden, polyol and/or vinyl chloride.

21. The method according to p. 20, characterized in that the purification of waste water is subjected to the production of glycerol and/or polyglycerol.

22. but in the process of synthesis of epichlorohydrin, the epichlorohydrin save by exchange reaction solution containing dichloropropanol, at least one alkaline compound, mainly water containing calcium hydroxide, the slurry with an excess of calcium hydroxide per used dichloropropanol.

23. The method according to PP.1 to 19, characterized in that the purification is subjected to waste water containing saturated and/or unsaturated aliphatic and/or alicyclic hydrocarbons, ethers, alcohols and preferably polyols, ketones, aldehydes and/or carboxylic acids.

24. The method according to p. 24, characterized in that the purification is subjected to waste water containing optionally saturated and/or unsaturated aliphatic and/or alicyclic chloride hydrocarbons, ethers, alcohols, ketones, aldehydes, giarini and/or carboxylic acid chloride.

25. The method according to PP.1 to 19, characterized in that the purification is subjected to waste water generated during use and/or transfer reactions gelegenheden and/or polyala.

 

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FIELD: devices for purification of household and industrial sewage.

SUBSTANCE: the invention is dealt with devices for purification of household and industrial sewage and intended for electrical and cavitational treatment of sewage containing a large quantity of organic compounds. The device for purification of sewage consists of a body made out of a dielectric material partitioned by diaphragms for two electrode chambers and one working chamber, that contains a filtering material. The electrode chambers have cavitational field sources installed and the working chamber is supplied with a the bubbler installed in it. The technical result consists in an increase of recuperation of the filtering material at the expense of application of a cavitational field to it, decrease of the microbiological semination, and an increase of cavitational effect on particles.

EFFECT: the invention ensures an increase of the filtering material recuperation, decreased microbiological semination and increased the cavitational effect on particles.

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