Method for immobilization and storage of condensed hazardous substances

FIELD: processing of condensed hazardous substances and industrial wastes and safe storage of powdered, granulated or liquid hazardous and toxic substances which are chemical wastes, including pesticides, toxic chemicals, defoliants, dangerous compounds of heavy metals, war toxins etc, which are unfit for further utilization.

SUBSTANCE: method involves treating condensed hazardous substances with protective binding material, followed by hardening and forming; preliminarily preparing liquid solution of protective binding material in the form of aluminosilicate solution of nepheline in 10-20%-solution of sulfuric or hydrochloric acid with acid norm of 1.0-1.15 and pH within the range of 2.8-3.8; processing condensed hazardous substances in dispersed state by mixing with aluminosilicate solution; pouring resulted mixture into reservoir for further hardening and forming by gelling said mixture in the form of mineral-matrix system; adjusting time of gelling said mixture of liquid solution of binding material with hazardous substances in dispersed state by adding alkaline into said aluminosilicate solution or mixture.

EFFECT: increased efficiency in immobilization and safe storage during period of time ranging between several months and dozens of years of gel-like mineral-matrix system of comparatively wide class of hazardous, toxic or other hazardous substances in powdered, granulated or liquid state.

2 cl, 8 ex

 

The invention relates to the processing of condensed harmful substances and industrial waste, and in particular to methods of immobilization and safe storage of unusable powdered, granular or liquid hazardous and toxic substances, wastes of chemical products, including pesticides, insecticides, defoliants, dangerous heavy metals, chemical warfare agents and other

Conventional storage of hazardous, toxic or other harmful substances in the condensed state are placing them in a sealed single-layer or multilayer containers of durable construction materials such as metal, glass, etc. in some cases, additional capacity is filled with liquid or gaseous protective environment, for example an inert gas or kerosene, which prevents direct contact of these hazardous or harmful substances from the external environment (see safety and industrial sanitation in the chemical industry - a Collection of ordinances, rules, regulations and instructions, M., Chemistry, 1965).

The disadvantage of such a method of storage of hazardous, toxic or hazardous substances is a principal possibility of accidental spillages or destruction of the protective capacity that may occur, for example, the R, during transportation, during natural disasters, etc.

Additional to the specified storage of hazardous or harmful substances is the way their long-term storage inside sealed containers in a thick layer of protective grease, which in this case is more viscous protective environment. This method of storage is used, in particular, warehousing of alkali metals (see Rules of design and safe operation of facilities operating with alkaline metals. M, STIC, 1968, p.41).

A known method of storage provides a higher degree of safety when storing or transporting solid contaminants, however, it is not possible to neutralize or store hazardous or harmful substances, for example, in a liquid state (pesticides, defoliants, butanol and others)

There is also known a method of equatoriana liquid, plastic and solid industrial wastes on the so-called integration-matrix technology, based on the processes of mineral formation using as reagents cement, lime, silica, clays or clay soils (see knatko VM and other "IMM - technology against waste (Artificial reproduction of natural processes of mineral formation is a promising direction for the disposal and recycling of p is myshlennyh waste) // Energy: Economics, technology, ecology. No. 12, 2001, p.29).

The disadvantages of this method include the complexity of technology and the relatively narrow class of harmful substances, for which you can use this method for their effective protection and neutralization during storage. In particular, it cannot be used when kapsulirovanie a large class of poisonous liquid and solid substances, such as butanol, strychnine, liquid pesticides and other

The closest technical solution to the invention is a method of immobilization and storage of condensed harmful substances by processing their protective bonding material, followed by curing and molding in the form of the matrix system (see RF patent №2208255, IPC 7 09 In 3/00, BIPM No. 19, 2003 - prototype).

The known method provides immobilization, storage and disposal of solid waste contaminated with radioactive materials by two-step processing of aerosol preparations containing a binder of epoxy resin and hardeners, followed by curing and prasowaniem waste in the binder material in the solid matrix of the system in the form of briquettes.

The disadvantage of this method are the relatively narrow specificity, and the area of use for the immobilization and disposal of predominantly solid waste contaminated with radioactive m is materials, as well as the complexity of technology and the high cost of the reagents.

Solved by the present invention is to develop an efficient method for the immobilization and safe storage for several months to tens of years or more in the form of a gel-like mineral matrix of the system is relatively broad class of dangerous, toxic and other harmful substances in solid powdered, granular or liquid state.

The solution of the stated problem is achieved in that in the method of immobilization and storage of condensed harmful substances by processing their protective bonding material, followed by curing and molding, according to the invention pre-prepared liquid solution of a protective binder material in the form of aluminosilicate solution of nepheline in 10-20% solution of sulfuric or hydrochloric acid at the rate of acid 1.0 to 1.15 and a pH in the range of 2.8 to 3.8, then condensed harmful substances in dispergirovannom condition is treated by mixing aluminosilicate solution, the mixture is poured into a container for subsequent curing and molding by gelatinization of the mixture in the form of the mineral matrix of the system.

In addition, the gelling time of a mixture of liquid solution of a binding material with harmful substances in dispergirovannom able to monoregionality the addition of alkali in the above aluminosilicate solution or mixture.

This embodiment of the method of storing the condensed harmful substances provides effective immobilization of hazardous substances, protection from the external environment and temporary neutralization by their encapsulation in a protective matrix system in the form of a mineral gel. The method can be used to secure short-term or long-term storage of a relatively broad class of toxic industrial waste, hazardous and other harmful substances in solid powdered, granular or liquid state.

Upon the dissolution of nepheline in the additional solution of sulfuric or hydrochloric acid with a concentration of less than 10% and the rate of acid more than 1,15, ceteris paribus, the gelatinization aluminosilicate solution is very slow and the resulting gel does not possess sufficient stability and mechanical strength.

When exceeding the specified parameters, respectively, the acid concentration of more than 20% and norms acid is less than 1.0, the gelatinization of the solution comes too quickly, which does not allow to obtain a homogeneous mixture solution with hazardous substances.

It has been experimentally determined that the pH of the obtained aluminosilicate solution should be in the range of 2.8 to 3.1, which is optimal for the organization of the technological process, when mixed with condensers nimi harmful substances in dispergirovannom condition, response capacity and spontaneous gelatinization of the mixture in the form of the mineral matrix of the system, representing a stable gel.

When added to the aluminosilicate solution (or mixture) of alkali to a pH of 3.5 to 3.8 speed gelatinization of the solution is greatly increased and is 1-60 minutes instead of several hours. If the pH is less than 3.5 slightly alters the rate of gelatinization aluminosilicate solution or mixture, and at a pH of more than 3.8 specified gelatinization process does not occur or substantially weakened.

To determine the efficiency of immobilization of various harmful industrial substances were carried out experimental work on their treatment by mixing with the prepared liquid aluminosilicate solution, which coats the solid particles of powdery or granular substances, and when interacting with a liquid substance forms with them the emulsion. In the harmful substances is relatively evenly distributed throughout the aluminosilicate solution, rolling over time in the elastic gel forming mineral-matrix system.

Thus, particles of harmful substances like capsulised in the structure of elastic aluminosilicate gel and could not interact with each other, so the risk pron is knowiny in the environment is minimal. At the same time within the mineral matrix of harmful substances protected from penetration to them in the external environment. The transition aluminosilicate solution in elastic gel depends on its composition and can be adjusted in the range from 1 to 50 hours, which represents great opportunities for developing the necessary technologies neutralization of specific harmful substances.

Aluminosilicate solution in the General case contains in its composition (g/cm3): 42-55 SiO2, 33-40 Al2About3, 15-18 Na2O 6-8 K2O, 95-105 SO4the rest of H2On (pH Zola aluminosilicate solution of 2,8-3,1; density 1,155-of 1.65 g/cm3). Aluminosilicate solution for some time has the properties of a true solution with low viscosity, so it is easily mixed with powdered and liquid substances. After a specified period of time, under specified conditions the mixture begins spontaneously relativelayouts, loses its fluidity and becomes elastic gel.

Getting aluminosilicate solution lead by dissolving the mineral nepheline, for example, in 12-15% sulfuric acid at the rate of acid 1,01-1,10, pH in the range of 2.8-3.1 and with continuous stirring of the solution.

When implementing the proposed method can be various combinations of the properties of aluminosilicate solution and harmful substances.

In the learn the application of this method for the storage of toxic substances, entering into a chemical reaction with the components of the solution, the formation of new compounds, which in some cases may be less toxic than the original substance.

So, for example, present in the composition of the solution SO4when interacting with toxic barium chloride reacts with the formation of barite (BaSO4), which is not a toxic substance. Salts of copper included in the inorganic pesticides (sulfates, carbonates and other salts), in collaboration with SiO2collapse with the formation of silicate of copper. At specific values of pH of the medium is also the reaction of interaction hazardous to health salts of Nickel, lead, zinc aluminosilicate solution with the formation of less harmful silicates of these metals.

A similar interaction aluminosilicate solution with fluoride or crematorium sodium produces significantly less hazardous substance cryolite (Na3AlF6).

Toxic powdered waste is mixed with alumosilicate solution with respect to the waste solution in the range of 0.1 to 1.0 to ensure that the mixture is not lost fluidity and it can be poured into an appropriate container (tank, canister, plastic bag, etc.), where the pulp is spontaneously gelatinized and turns into a gel. With less regard restorepalette inefficient and if greater than 1.0, a thick pulp with difficulty stems from the reactor blending.

Toxic liquid waste, which is able to dissolve in aluminosilicate solution must be mixed with it in respect of 0.1-0.3, because the amount of liquid phase increases, and the content of the aluminosilicate component is reduced accordingly. Gelling time increases (compared to a slurry obtained by mixing the solid waste with the Sol) to several tens of hours.

Toxic liquid waste, not dissolving in aluminosilicate solution and forming two immiscible liquid phases, mix well with a ratio of 0.1 to 0.3, but with the formation of the emulsion. To the resulting emulsion in the process of filling in the appropriate capacity can, if necessary, add alkaline solution in the form 10-15% NaOH solution to establish a pH of medium pH in the range of 3.5 to 3.8. The specified range of pH is determined by the fact that under this condition the rate of gelatinization and the strength of the resulting gel is optimal. At pH greater 3,8 decreases the ability of aluminosilicate solution to gelatinization, i.e. the resulting gel is not sufficiently durable and flexible. Gelling time of the emulsion in the alkalinization, as a rule, is 1-60 minutes

The following are specific examples Alamos ligotage solution for immobilization and storage of a range of toxic substances. In all the examples used aluminosilicate solution containing (g/cm3): 42,82 SiO2; 32,86 AlO3; 15,69 Na2O; 6,61 To2About; 106,6 SO4; the rest is water; pH = 2,87; the density of the solution 1,161 g/cm3.

Example 1. 0.5 kg grey poisonous powder white arsenic As2O3(strychnine) are mixed in a mechanical mixer with 0.5 liters of aluminosilicate solution in an equal weight ratio for 50 min until a homogeneous slurry at pH 2,89, after which the slurry is poured into a plastic bottle and can stand up to its gelatinization. The formation of the gel, in which the structure of enclosure (powder strychnine, was 20 hours, the resulting gel is elastic and is strong enough. Immobilized so strychnine can be transported and save a long time in a relatively safe condition.

Example 2. 0.4 kg toxic drug, "Protaras" for spraying insects (suspension containing 9,85% As2O3; 0,5% free Cao; about 1% moisture and filler - phosphorite flour) mixed with 2 l of aluminosilicate solution (mass ratio of 0.2) in mechanical stirrer for 45 min, after which the slurry with a pH of 3.1 poured into a plastic bottle and can stand up to gelatinization. During the formation of a strong elastic gel was 20 hours. Immobilized so about the time a poisonous drug can also be transported and stored in a relatively safe condition for a long time (several years).

Example 3. 0,5 white powder sodium fluoride (used for impregnation of wood, poisonous) is stirred with 1 l of aluminosilicate solution in mechanical stirrer (the mass ratio of 0.5), after which the pulp at pH 2,87, pour into a plastic bottle and can stand up to gelatinization. During the formation of elastic gel was 24 hours. When alkalization slurry of the same composition with 10% NaOH solution to pH 3.65 time gelatinization was 1-5 minutes Immobilized so toxic, the preparation can also be transported long time to keep a relatively safe condition.

Example 4. 100 g of the powder toxic crystalline barium chloride (herbicide) is stirred with 1 l of aluminosilicate solution in mechanical stirrer (the mass ratio of 0.1) for 40 minutes In the mixing process has been fine selection of barium sulfate, which is evenly distributed throughout the volume of aluminosilicate solution. The resulting slurry is poured into a plastic bottle with a simultaneous supply of 15% NaOH to bring the pH to values of 3.80. The gelatinization of the slurry into a solid gel occurred within 12-15 minutes Immobilized toxic drug can be transported long time to keep a relatively safe condition.

Example 5. The same substances (see example 4) at a ratio of 500 chloride barium 1 l aluminosilicate solution (mass ratio of 0.5) is stirred by mechanical stirrer for 60 minutes In the mixing process has been fine selection of barium sulfate, which is evenly distributed throughout the volume of the pulp. The resulting slurry is poured into a plastic glass and can withstand up to gelatinization. During the formation of elastic, strong enough gel was 45 hours. The efficiency of immobilization of the drug corresponds to the previous example.

Example 6. 1 kg of crystalline powder of barium chloride (a pesticide) is stirred with 1 l of aluminosilicate solution in mechanical stirrer for 60 min (mass ratio 1:1). In the mixing process has been fine selection of barium sulfate, which is evenly distributed throughout the volume of the pulp. The resulting slurry is poured into a plastic bottle with a simultaneous supply of the slurry of 10% NaOH solution to bring the pH to 3,72. The gelatinization of the slurry over 30 minutes with the formation of the gel. Conditions of immobilization and storage are the same as in examples 4 and 5.

Example 7. 1 l suspension poisonous Bordeaux liquid, which is the pesticide (contains 0,45-0,5 kg CuSO4and 0.3-0.35 kg of hydrated lime)was mixed with 1 l of aluminosilicate solution (mass ratio 1:1) in mechanical stirrer for 40 minutes the resulting slurry at pH of 3.1, pour into a plastic bottle and can stand up to gelatinization. The time of year is quite strong elastic gel was 20 hours. The degree of immobilization and the ability to store high.

Similar results were obtained by mixing aluminosilicate solution with other fungicides: drug AB (powder mixture of Cu(Oh)2, CuSO4, CuCO3), Burgundy liquid (suspension 3 C satellite(OH)2·2CuCO3), copper sulphate.

Example 8. 1 l of butanol (harmful intermediate petrochemical plants) with an expired shelf life mixed with 5 l of aluminosilicate solution in mechanical stirrer (the mass ratio of 0.2) for 50 min and poured into a plastic bottle with a simultaneous supply of emulsion 12% NaOH solution. The gelatinization of the emulsion was over in about 15-20 min education sufficiently strong elastic gel. The degree of immobilization and the ability to store encapsulated butanol is also high.

Currently, many industrial facilities have gathered a large amount of harmful substances in the natural state are powders, granules or liquids. At the same time, the conditions of their storage does not always satisfy the requirements of environmental safety.

When the violation of storage conditions, for example during transportation or when disposed of, they can crack, leak, dust and poison the soil, water and air, thus providing a greater danger for the servicing personnel nearby residents and the environment. Accidental destruction capacity elastic gel, and with it, and harmful substances are not themselves derive from the tank, do not evaporate and practically does not dissolve with water for a considerable time. Zakopalova in this way in the aluminosilicate gel solid or liquid toxic materials can be destroyed by one of the known methods or buried for the entire period of stability of the gel.

Immobilized in the mineral-matrix system elastic gel toxic, toxic or harmful substances, then placed in a sealed tank of a material of conventional type (metal, plastic, glass, foil, rubber), fully protected from penetration into the external environment. The gel thus does not age, does not lose elasticity and can be stored for 20-30 years. Immobilized harmful substances can be safely moved, stacked, stored and transported over long distances without danger to the operating personnel and the environment.

1. The method of immobilization and storage of condensed harmful substances by processing their protective bonding material, followed by curing and molding, wherein the pre-prepared liquid solution of a protective binder material in the form of alomisyl the rolling solution of nepheline in 10-20%solution of sulfuric or hydrochloric acid at the rate of acid 1.0 to 1.15 and a pH in the range of 2.8 to 3.8, then condensed harmful substances in dispergirovannom condition is treated by mixing aluminosilicate solution, the mixture is poured into a container for subsequent curing and molding by gelatinization of the mixture in the form of the mineral matrix of the system.

2. The method according to claim 1, characterized in that the gelling time of a mixture of liquid solution of a binding material with harmful substances in dispergirovannom able to regulate the addition of alkali in the above aluminosilicate solution or mixture.



 

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