Method of utilisation of solid mercury-containing wastes and device for its realisation

FIELD: chemistry.

SUBSTANCE: group of inventions relates to utilisation of solid mercury-containing wastes, in particular fluorescent lamps. A method of utilisation of solid mercury-containing wastes includes an oxidation stage with further stand, processing a wastes mixture with a demercurised solution of an alkali metal polysulfide with further stand of the reaction mixture. Wastes are divided into two parts. One part, which contains crushed wastes, is processed with an oxidant, and then with a demercurised iodine-alcohol solution or a sodium sulfide solution. The second part of wastes in the form of aeromixture is passed through a nanoporous carbon sorbent NCMS-J. A device for utilisation of mercury-containing wastes contains a unit of loading and crushing, a purification unit and an aeromixture unit. The purification unit is made in the form of a truncated cone, connected by means of a flange to a cylindrical reservoir with a perforated screw, provided with a valve for the solution discharge, and an upper part of the perforated screw is provided with an unloading flange for discharge into a storage hopper. The aeromixture unit is made in the form of a column type adsorber with the nanoporous carbon sorbent NCMS-J.

EFFECT: ensuring reduction of mercury vapour concentration in air and water extract to TLV level, neutralisation of solid wastes of compact fluorescent lamps to IV class of hazard.

7 cl, 1 dwg, 4 ex

 

The invention relates to the field of environmental protection and can be used for the disposal of mercury-containing solid waste, in particular waste and defective compact fluorescent lamps.

Waste recycling of compact fluorescent lamps (CFLs) represent the broken glass with phosphor obtained in the process of disposal of decommissioning and recycling of mercury-containing lighting equipment and electric lamps, and are a waste of hazard class 1, because they contain mercury adsorbed in the layer of phosphor on the inner surface of the glass bulbs these bulbs. As a consequence, waste and defective fluorescent lamps should be cleaned ways and in special installations, eliminating mercury pollution.

The invention relates to the recycling of compact fluorescent lamps (solid waste) and device for its implementation, which is the installation of recycling of mercury-containing waste (EURO), which provides separation of compact fluorescent lamps on the base, the EPR (electron-starting the regulating device) and the broken glass with phosphor, the disposal of mercury-containing waste glass with phosphor by processing demercurization solution (calcium polysulfide, sodium, does the addition of sodium iodine in a solution of potassium iodide) immobilization of mercury and transfer to insoluble compound is a sulfide or mercury iodide, providing residual contamination by mercury compounds plinths and EPR to values less than the MPC mercury in soil (2.1 mg/kg), purge air from the mercury vapor in the absorber is filled with iodine-containing nanoporous carbon by the NCMS sorbent-J to mercury in ambient air is less than the EQS (0.0003 mg/m3), the maximum content of mercury vapor in the air of working zone is not more than 0.01 mg/m3the disposal of solid waste compact fluorescent lamps up to IV class of danger and safe disposal.

Known methods of disposing of fluorescent lamps. By way of demercurization fluorescent lamps (Patent 2052527; C22 In 43/00; 20.01.1996, S.N. Gamayunov) crushing lamps under a layer of water is carried out with simultaneous separation of base and continuous washing of the phosphor. Glass is separated into fine and coarse fractions with subsequent treatment of the fine fraction nitric acid, and a large fraction of chlorine-containing solution. After neutralization of the solution of nitric acid and chlorine-containing solution to pass through a cation exchange resin. After saturation regenerate the resin with subsequent treatment of the eluate with ammonium sulfide or sodium to drop sulphide of mercury in the sediment.

According to the method of recycling the promotion of products, containing mercury or its vapor, for example fluorescent lamps (Patent 2083709, 10.07.1997. Scientific-production Association "ENECO" Bebulin I.N.; Belyaeva LB; Danilkin VI; Puzanov, NV; Semenov IJ) articles containing mercury, split and processed under a layer of an aqueous solution of calcium polysulfide with a sulfur content of 50-90 g/l at a temperature of 20-45°C, followed by washing waste water solution of calcium polysulfide sulfur content of 20-40 g/l at room temperature and sorting of the waste. The proposed method provides a closed process loop that prevents the threat of harmful emissions into the atmosphere and waste water.

There is a method of processing defective fluorescent lamps, representing mercury-containing phosphor that was mixed with a 10%aqueous solution of calcium polysulfide used as a dedicated, in an amount not less than 400 ml per 1,000 g of dry phosphor (Patent 2280670, Timoshin V.N., Kosorukova IV, Makarchenko, GV).

The disadvantage of these methods is the formation of multiple end products contaminated with mercury and its compounds (glass, metal base, the phosphor). Although treated with a solution of calcium polysulfide mercury-containing lamps leads to the formation of sulphide of mercury, which is removed, but all wastes are washed and nakaplivaetsya volume of mercury-containing solutions, additional clear from mercury. All this leads to additional operations - washing, drying and sorting of waste, which complicates the technology.

The closest technical solution is the way of demercurization of mercury-containing waste, in particular phosphor, granosan, mercury-containing soil, which includes processing waste solution of calcium polysulfide. Before treatment with a solution of calcium polysulfide waste is mixed with an oxidant containing active chlorine, in an amount of 0.15 to 10.0 wt.% from the waste mass. Then enter the water and incubated mixture. The resulting mixture was treated with a solution of calcium polysulfide at a ratio of solution of calcium polysulfide to a mixture of equal 1-4:10 wt.% respectively, followed by keeping the reaction mixture. The technical result of the invention is that there is no need for complex equipment; recycled waste is transferred from class 1 to class 4 hazard, contain inclusions of sulphide of mercury, is not harmful to the environment and safe for disposal (Pat EN 2400545 2010, Levchenko L.M. and others)

From the prior art known methods and devices for the disposal of fluorescent lamps, for example, in (A.S. USSR 1102284. MCL SW 43/00, 1989) provides a description of the ie settings for demercurization containing a hopper, a feed dispenser lamps in the crusher, screw conveyor tube breakage in the fuming furnace, the solid waste receiver, the afterburner gases, the condenser and the filter.

In the patent (RF 2009237, MCL SW 43/00, 1994) describes how to install for demercurization of mercury lamps, which realizes thermal method of demercurization of mercury lamps. The installation is made in the form of a module with carrier spatial frame, which has all the elements of the unit, including the hopper feeder and crusher, means for feeding the battle of the lamps in the oven sublimation, etc.

The disadvantage of these patents are increased energy consumption for demercurization, due to the fact that during the processing of the scrap lamps mixed, repeatedly crushed and sorted, and then subjected to further processing. This reduces the efficiency of utilization.

Known installation of recycling fluorescent lamps (closest prototype) and the manner of utilisation (.RU 2365432, 27.08.2009. Makarchenko, GV, Timoshin VN). Installation of recycling fluorescent lamps includes an exhaust ventilation system connected to the cleaning chamber tube of the battle from the phosphor, equipped with loading the site with the valve shutter and the chopper and discharge Assembly purified components of the lamp of the battle. The cleaning chamber tube of the battle from the phosphor is made is in the form of a double cyclone consisting of coaxial upper and lower cyclones at the top of the cyclone partially located in the bottom of the cyclone and is equipped with loading the site with a tangential inlet for input of mixture fractions tube of the battle. The lower part of the lower cyclone made in digest form purified from the phosphor components of the lamp of the battle, which is a mixture of relatively heavy fractions and provided with a discharge Assembly of these fractions is made in the form of a valve hinged shutter.

The method of disposal of waste fluorescent lamps carried out in the above setup, is that recyclable lamp individually destroy and form of the tube of the battle of the Central vortex flow of the mixture fraction, which transform in the opposite twisted peripheral vortex flow. From the transformation of the Central vortex flow sephirot tube fight as a mixture of relatively heavy fractions, and the phosphor as a relatively light fraction, which is removed for recovery of the phosphor. The relatively heavy fraction in the form of cleared phosphor lamp combat derive from their own weight for further processing. The technical result is an increase separation efficiency of the phosphor of the tube of the battle, the exclusion of chemical demercurization processing, as well as snizeni the energy consumption.

The proposed technology is energy intensive, requires the implementation of a large amount of electricity. In addition, the declared developers demercurization installations, based on the use of these methods, their versatility does not find evidence for recycling of such waste containing mercury, as mercury contamination of soils, require specific conditions and related technologies.

The objective of the invention is to simplify the method of disposal of waste containing mercury and a device for its implementation, providing effective cleaning of mercury-containing waste and achievement of long-term (within the limits of perpetuity) of treatment effect from mercury.

The technical result of the invention is a device and method for effective cleaning (demercurization) waste compact fluorescent lamps (CFLs) and other mercury-containing waste (granosan, soil), the decrease in the concentration of mercury vapor in air and water extract to the level of the MPC, as well as the achievement of long-term (within the limits of perpetuity) of treatment effect from mercury.

To avoid these disadvantages, allows our way of chemical neutralization and installations for the disposal of mercury-containing waste (EURO), which represents a set of independent nodes, is the s for processing of various types of lamps and solid waste.

The technical result according to the method is achieved in that in the method of disposal of mercury wastes, including the stage of oxidation, followed by exposure and then processing the mixture of waste with demercurization solution of polysulfide of an alkali metal at a ratio solution of polysulfide of an alkali metal to a mixture of equal 1-4:10 wt.% respectively, followed by keeping the reaction mixture, the waste is divided into two parts, one of which, containing the crushed waste is treated with an oxidant, and then demercurization iodine-alcohol or sulfur sodium solution, and the second part of the waste mixture is passed through nanoporous carbon the NCMS sorbent-J with iodine content of 5-10%, the oxidizing agent is chosen from the series: bleach, bleach, white with a concentration of 1.5 to 20.0%, and as polysulfide of an alkali metal used solution of calcium polysulfide or sodium polysulfide with a concentration of 5.0-10%, and iodine-alcoholic or sodium sulfide with a concentration of 2.0 to 3.0 and 5.0%, respectively, and the exposure time to the oxidizing agent and the exposure time with demercurization solution is 1 hour, respectively.

The technical result for the device is achieved in that the device for disposal of mercury-containing waste, including the download site and grinding, site cleanup, Uzes the mixture, while the download site and grinding made in the form of beveled cylinder with a removable metal tube and equipped with crushing and separation device, a chute removal of heavy fractions from the process container for heavy fractions, the purification unit is made in the form of a truncated cone connected to the flange with a cylindrical container with a perforated auger equipped with a drain valve of the solution, and the upper part of the perforated auger is equipped with discharge flange to drain into the storage hopper, the middle part of the cone is equipped with a feed pipe solution, level, and the upper part of the cone has a drain on the host mixture, the node mixture is made in the form of adsorber column type and provided with Teflon inserts in the top and bottom of the adsorber, between which is nanoporous carbon the NCMS sorbent-J containing iodine 5-10%, while crushing and separation device is designed as a rotating chain, and in the purification unit can be combined oxidation and neutralization.

Distinctive features of the method are:

the processing of selected oxidants and demercurization solutions of solid waste, some waste in the form of mixture treated with selected carbon sorbent, the process parameters.

The distinguishing characteristics of the device are:

you shall olnine download sites and grinding, cleaning mixture and links between nodes and mesopotami.

The drawing shows a functional diagram of the installation recycling of mercury-containing waste, including compact fluorescent lamps (EURO). The device consists of a loading unit and grinding 1 removable metal pipe 2, the chute removal of heavy fractions 3, the crushing and separation device (not shown); purification unit 4 in the form of a truncated cone connected to the flange with a cylindrical container 5 with a perforated screw 6 is equipped with a drain valve solution 7 at the end of the work, and the upper part of the perforated auger is equipped with discharge flange (8) for removal of broken glass, the middle part of the cone is equipped with a feed pipe solution oxidation (mercury removal) 9; level 10; the upper part of the cone is equipped with a drain 11 to node mixture 12, equipped with PTFE inserts (not shown), the device also contains a host of technological container for heavy fractions (for caps and EPR) 13 and the storage hopper cullet with demercurization solution 14.

Mesopotami:

I - CLL; II - bases and EPR; III - broken glass with mercury-containing phosphor; IV - solution oxidation; neutralization; V - broken glass with phosphor after oxidation and neutralization; VI - mercury-containing process gas; VII - purified from mercury breadboard is th gas.

The method of disposal of solid waste and device for implementing the method are as follows.

Before starting installation, installs nodes and filling their working reagents: node mixture - adsorber 12 is filled nanoporous carbon by the NCMS sorbent, connect it through the outlet 11 to the purification unit 4, fill in the purification unit 4 oxidizer solution with water through tube feeding solution oxidation (mercury removal) 9; number of oxidant and demercurization solution into the purification unit is determined with the aid of uravneniya 10. Tightly install removable metal pipe 2 filing lamps download site and grinding 1 of a certain size. Set the storage hopper cullet 14 filled with demercurization solution under discharge flange (8) perforated auger 6. Set the technology container 13 under the chute removal of heavy fractions 3.

After Assembly of nodes and populate the working reagents in the download site and grinding 1 through removable metal pipe 2 serves pre-sorted compact fluorescent lamps (CFLs). After grinding through the chute removal of heavy fractions (plinths and EPR) 3 remove the heavy fraction into the process container 13. Further, the broken glass with phosphor enters the purification unit 4, where the pre-added to the Yes with the oxidant (depending on the type of recyclable waste). After keeping the mixture of glass and phosphor with this oxidant mixture through a cylindrical container 5 hits perforated auger 6, screw the mixture through the discharge flange 8 flows into the storage hopper cullet 14 filled with demercurization solution, and demercurization solution remaining in the purification unit 4, is drained through the drain valve solution 7, another part of the waste in the form of a mixture through the outlet 11 is sent to the node mixture 12 where contaminated mercury vapor the air is passed through the adsorber column type, filled nanoporous carbon by the NCMS sorbent-J, with the iodine content of 5-10%, is achieved where air purification to the level of the MPC (0.0003 mg/m3). The adsorber may optionally be attached to channel the fan. The installation is placed on a movable metal frame rubber-tired.

In the process of oxidation and neutralization consistently occur following reaction:

1) oxidation of mercuryHg0Hg2+; 2)Hg2++CaSnHgSlinking mercury with its translation in h is soluble compound - mercury sulphide, or by reaction (3)Hg2++J2HgJ2iodide of mercury.

The chemical process of oxidation and neutralization schematically described by the following equation:

Hg0+[Ox]Hg2++CaSnnHgS+Ca2+(4)

Originally, the introduction of an oxidant, for example, a chlorine leads to the formation of ionic forms of mercury, and then the introduction of a solution of calcium polysulfide or sodium, sodium sulphide, spirit-iodine solution leads to the formation of low-solubility compounds sulfide, mercury iodide. The use of oxidizing agents, strong oxidizing properties - bleach (CaOCl), bleach, white with a concentration of 1.5-20% and demercurization solutions - 5-10% of resolved calcium or sodium, 2-3% spirit-iodine solution, 5% sodium sulphide solution, the set value of the concentration of the solutions is optimal is generated and the ratio of the solutions of a given concentration to the mixture of waste and oxidant (1-4:10 wt.%), this range of concentrations and ratios are optimal, allowing you to spend disposal (demercurization process) and get the mercury content in the working area and the water extract after washing the precipitate sulfide or mercury iodide is less than the MAC.

With less than specified, the contents of the ingredients effectiveness of the demercurization process is reduced and there is excessive concentrations of mercury in the aqueous extract after deposition of sulphide of mercury, at a higher - efficiency increases slightly, but significantly increases the cost of the composition and increases the flow of components.

The method allows for the conversion of metallic mercury in an oxidized form of mercury, and then in soluble form sulfide or mercury iodide. Mercury sulphide, formed as a result of demercurization, is a natural form of mercury, mercury is converted to the compound from which it is extracted. Water is injected in the amount of 25-50 wt.% from the mass of waste, after the introduction of water and oxidant mixture was incubated for 1 hour, and after processing the mixture of demercurization solution, the reaction mixture was incubated for 1 hour. Experimental data showed that the exposure time in the oxidation and neutralization - 1 hour is sufficient to complete the reactions.

Stage ut the implementation mixture (formed gaseous products, obtained in the grinding process KKL), there is formed a gas mixture of air with mercury vapor, which passes through the node mixture in the adsorber column type with nanoporous carbon by the NCMS sorbent-J, with the iodine content of 5-10%, which is the purification of air from mercury vapor to the level of the MPC. NUM-J - nanoporous carbon modified with iodine adsorbent-based carbon material formed by applying a graphite-like carbon on a porous matrix of carbon (soot), with turbostratic structure (Gavrilov V.Y., fenelonov V.B. have been, Chuvilin A.L. // HTT - 1990 - No. 2 - s-129), characterized by the fact that it consists of particles of 1-5 mm, with a specific surface area by adsorption of argon 300-600 m2/g, a total pore volume of water is 0.6-1.0 cm3/g, a carbon content of 99.5%, of impurities of Fe, Al, Si, K, CA and 0.5%, has a characteristic pore distribution with a maximum attributable to pores with a size of 4-20 nm. Treatment with iodine carbon material can increase the degree of air cleaning from mercury vapor. The iodine content greater than 10% is inefficient because the degree of purification of the air remains constant and less than the claimed interval iodine 5% leads to the decrease of the degree of air cleaning from mercury vapor.

According to the method for installing EURO is a full transfer of mercury in its insoluble compounds and hazard class of waste Pont is supplied, is the removal of mercury vapor from the process gas, which prevents their release into the atmosphere.

State of the waste after the stage of demercurization can be characterized as follows: demercuration waste contains inclusions of sulfide, mercury iodide, is not harmful to the environment (ecology).

The method of disposal is carried out on the installation of OURO using oxidants and demercurization solutions. The sequence of operations consists of loading and grinding CLL, stage of treatment (oxidation of mercury and mercury removal phosphor in glass CFL), the stage of purification of the mixture (formed gaseous products of mercury vapor).

The first stage is to download and grinding CFLs because CFLs consists of the following components: base, electron trigger distribution device (EPR) and bulb with mercury-containing phosphor.

Thus, a necessary condition for the Department of flasks from the EPR and the socle is a preliminary separation of the lamps according to size, which is performed at the point of acceptance of compact fluorescent lamps. Then in the download site and grinding separating flask with a mercury-containing phosphor from the EPR and plinth with subsequent fragmentation. The products of this process are the monolith base - EPR and Steklov the th with mercury-containing phosphor.

The process proceeds with the shortage of the liquid phase, consumed and exported from food processing sludge, caps, broken glass, and thus is not formed drains.

During the rotation of the perforated auger 6 purification unit 4 the mixture of broken glass, phosphor and mercury sulfide, rising along the screw, through the discharge flange 8 flows into the storage hopper cullet 14 sealed with a lid filled demercurization solution. Perforation of the auger allows you to avoid unnecessary loss solution is dedicated to, and in the storage hopper is additional processing of cullet.

The method can reduce the cost of disposal through the use of simple technology, and the lack of specific reagents; receiving in the separation process of the product (base + EPR), which can later be processed with the release of precious metals, in addition, the method can improve the performance of the disposal of CFLs to 1500 lamps/h, using effective and economically feasible demercurization solutions, the concentration of mercury vapor in the air and the water extract is reduced to the level of the MPC, as well as the achievement of long-term (within the limits of perpetuity) of treatment effect from mercury hazard class of waste is reduced, are removed mercury vapor from the process gas,which prevents their release into the atmosphere.

Testing method of disposal of solid waste containing mercury and the device showed that the analysis of air samples (duration of sampling 15 min), held at the Federal state institution "zlati in the Siberian Federal district" in accordance with M 03-06-2000 "Method of measurement of mass concentration of mercury vapor in the atmospheric air, the air of residential and industrial premises atomic absorption spectrometry with Zeeman correction selective absorption using mercury analyzer RA-915", showed the average Hg concentration of 5 measurements 0,0022 mg/m3(MAC air of the working zone of 0.01 mg/m3).

Analysis determine the concentration of mercury in water extract according to the "Method of measurement of mass concentration of mercury in natural and treated wastewater by the method of flameless atomic absorption spectrometry. The Ministry of environment protection and natural resources of the Russian Federation. Main Department of analytical control and Metrology assurance activities PNDF 14.1:2.20-95, Moscow, 1995 has given the value of mercury concentration 0,000002 mg/l (MPC 0.0005 mg/l).

The tests have shown that using the proposed method of disposal of mercury wastes allows the conversion of metallic mercury in difficultly soluble compound is a sulfide of mercury, while the e is required to separate the sulphide of mercury from waste and benefit: the mercury concentration in the aqueous extract at the level < 0,000002 mg/l, the content of mercury in the air over the samples after demercurization 0,0022 mg/m3the transfer of mercury-containing waste from 1 hazard class 4 hazard class and spend the burial.

The implementation of the method is illustrated by examples.

Example 1

For the process of demercurization of broken glass and mercury-containing phosphor with application installation EURO initially before switching installation, the node mixture - adsorber filled nanoporous carbon by the NCMS sorbent in the amount of 37.5 kg and hooked up the drive node mixture. Filled purification unit 2 35 l of a 1.5% solution CaOCl. Firmly established feed tube lamps in the fixture on the download site (size d=40 mm, l=76 mm). Set the storage hopper under the spout hole purification unit. Filled the storage hopper (capacity 90 l) 20 l demerkurizatsiju solution. Established technological container under the discharge chute of the download site and grinding. Then download and grinding was filing pre-sorted CFLs, for example, Wolta 10SSP20E27, 20W vacuum type, with a capacity of 1500 lamps per hour. Within hours the site to download and grinding filed lamp (weighing 180 kg). In the process of grinding and separation of base and EPR was obtained with 90 kg of broken glass with phosphor content of mercury 13,47 µg/g Further broken glass with phosphor did the site cleanup, where you have previously added to 22.5 l of water. Aging time (oxidation) of 1 hour. Then a mixture of broken glass and phosphor with oxidized mercury moved along the screw, and then it arrived in the bunker, filled with 50 l of 5% solution of calcium polysulfide, where the mixture was stirred at room temperature for 1 hour

Then through a sample of broken glass with phosphor and mercury sulfide 85g missed 100 ml of distilled water and the method AAS determined the concentration of mercury in solution, which was 2 ág/L. Thus, of 99.98% of mercury into insoluble mercury sulfide. The soluble portion of the mercury in the phosphor is 0,0023 µg/g, which is significantly below the contents of the TLV for mercury in soils (to 2.1 µg/g).

In parallel, the second part of the waste in the form of a mixture with a speed of 1 m3per hour was passed through the host mixture, in the form of adsorber column type, filled nanoporous carbon by the NCMS sorbent-J (iodine 5%) for the extraction of mercury vapor from the gas phase. Air analysis for mercury at the outlet of the host mixture, carried out on the device "Julia", showed the average Hg concentration of 5 measurements 0,0022 mg/m3(MAC air of the working zone of 0.01 mg/m3).

Example 2

The process of recycling lamps KKL carried out on the installation of EURO (installation recycling of mercury-containing waste). The preparation of the mouth of ovci for operation was carried out similarly to example 1. In the download site and grinding filed lamps CFLs, with a capacity of 1500 lamps per hour. Lots of broken glass with phosphor per hour was 90 kg, mercury 14,97 µg/, Then broken glass with phosphor was admitted to the purification unit, which previously was added to 40 l of 3% iodine alcohol solution and 22.5 liters of water. Aging time (oxidation) of 1 hour. Then through a sample of broken glass with phosphor and mercury sulfide by weight 100 g miss 100 ml of distilled water and determined the concentration of mercury in solution by the method of the AAS instrument "Julia", which was 0.3 µg/l, which is below the TLV for mercury in solution (0.5 ág/l). Mercury concentration at the outlet of the host mixture, a certain method AAS instrument "Julia", showed that the average content of mercury in the air of less than 0.002 mg/m3that below the maximum permissible concentration in the air of working zone 0.01 mg/m3.

Example 3

The number 1634 pieces KKL with E27 size was applied to the site to download and grinding on the installation of EURO, then the resulting mass of broken glass with phosphor in the amount of 80 kg with a mercury content of 26.3 ág/g were reported in site cleanup, which was added to 12 liters of 20% solution of bleach, 20 l of water and kept the mixture under stirring for 1 hour at room temperature, then the mixture was added to 25 l of 5% sodium sulphide solution and kept for 1 hour. The mixture after oxidation and neutralization postupilav sealed storage hopper for storage and subsequent disposal as waste hazard class 4. Control of mercury in solution was determined by the test 10 g demercuration cullet with phosphor, which was washed with 10 ml of distilled water, and the resulting filtrate was determined by the method of the AAS instrument "Julia" concentration of mercury in solution. Determined the mercury content of 0.4 ág/L. Control of mercury in the air at the exit node of the mixture was determined by the method of the AAS instrument "Julia" and showed the amount of mercury content less than 0.002 mg/m3that below the maximum permissible concentration in the air of working zone 0.01 mg/m3.

Example 4

The number 1634 pieces KKL with E27 size was applied to the site to download and grinding on the installation of EURO, then the resulting mass of broken glass with phosphor in the amount of 80 kg with a mercury content of 26.3 µg/g was then admitted to the purification unit, which was added to 12 liters of 20% solution of bleach and 40 liters of water, and kept the mixture under stirring for 1 hour at room temperature, then the mixture was added to 25 l of 10% solution of calcium polysulfide and kept for 1 hour. The mixture after oxidation and neutralization were received in sealed storage hopper - capacity for storage and subsequent disposal as waste hazard class 4. Control of mercury in solution was determined by the test 10 g demercuration cullet with phosphor, which was washed with 10 ml of distilled water, and the obtained f is ltrate were identified by means of AAS on the device "Julia" concentration of mercury in solution. Determined the mercury content of 0.3 ág/L.

The second part of the waste in the form of a mixture with a speed of 1 m3per hour was passed through the host mixture, in the form of adsorber column type, filled nanoporous carbon by the NCMS sorbent-J (iodine 10%) for the extraction of mercury vapor from the gas phase. The monitoring of mercury levels in the air at the exit node of the mixture was determined by the method of the AAS instrument "Julia" and showed the amount of mercury content less than 0.002 mg/m3that below the maximum permissible concentration in the air of working zone 0.01 mg/m3.

1. The method of disposal of mercury wastes, including the stage of oxidation, followed by exposure and then processing the mixture of waste with demercurization solution of polysulfide of an alkali metal at a ratio solution of polysulfide of an alkali metal to a mixture of equal 1-4:10 wt.%, respectively, followed by keeping the reaction mixture, characterized in that the waste is separated into two parts, one of which, containing the crushed waste is treated with an oxidant, and then demercurization iodine-alcohol or sodium sulphide solution, and the second part of the waste mixture is passed through nanoporous carbon the NCMS sorbent-J with iodine content of 5-10%.

2. The method of disposal of solid waste containing mercury according to claim 1, characterized in that the oxidizing agent is chosen from the poison: bleach, chloramine, white with a concentration of 1.5 to 20.0%.

3. The method of disposal of solid waste containing mercury according to claim 1, characterized in that as polysulfide of an alkali metal used solution of calcium polysulfide or sodium polysulfide with a concentration of 5.0-10%, and iodine-alcohol or sodium sulphide with a concentration of 2.0 to 3.0 and 5.0%, respectively.

4. The method of disposal of solid waste containing mercury according to claim 1, characterized in that the exposure time to the oxidizing agent and the exposure time with demercurization solution is 1 hour, respectively.

5. A device for recycling of mercury-containing wastes containing download site and grinding, site cleanup and site mixture, characterized in that the download site and grinding made in the form of beveled cylinder with a removable metal tube and equipped with crushing and separation device, a chute removal of heavy fractions into the process container for heavy fractions, the purification unit is made in the form of a truncated cone connected to the flange with a cylindrical container with a perforated auger equipped with a drain valve of the solution, and the upper part of the perforated auger is equipped with discharge flange to drain into the storage hopper, and the middle part of the cone is equipped with a feed pipe solution, level and the upper part of the cone has a drain on the host mixture, Uzes the mixture is made in the form of adsorber column type and equipped with Teflon inserts in the top and bottom of the adsorber, between them there is a nanoporous carbon the NCMS sorbent-J containing iodine 5-10%.

6. A device for recycling of mercury-containing waste according to claim 5, characterized in that the crushing and separation device is designed as a rotating chain.

7. A device for recycling of mercury-containing waste according to claim 5, characterized in that the purification unit configured to combine the processes of oxidation and neutralization.



 

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FIELD: chemistry.

SUBSTANCE: method includes combined grinding of wastes with sulphur powder and crushing medium in rotary reactor for binding metal mercury into water-insoluble compound. As crushing medium used is sulphur pyrate with fraction 50-150 mm, which is simultaneously agent, binding mercury in ionised and neutral forms. Before combined grinding mixture of sulphur powder, sulphur pyrate and water is preliminarily homogenised, and reactor is filled with nitrogen, supplied at rate 7.5-8.5 m3/h, in amount which is at least 50 times less than weight of sulphur powder. After that mercury-containing wastes are charged and grinding is carried out to complete binding of metal mercury into water-insoluble compound HgS.

EFFECT: simplification of technology and increase of processing process safety.

2 tbl

FIELD: metallurgy.

SUBSTANCE: oxidised zinc-containing materials with coke dross as a hard carbon reducer are supplied into a rotary tubular furnace and exposed to Waelz process with supply of blow in the form of a steam and air mixture into zone of temperatures 1050-1150°C with content of steam in the mixture 14-25%.

EFFECT: reduced consumption of a reducer and content of zinc and lead in a clinker, eliminates softening of material in a furnace.

2 tbl, 2 ex

FIELD: process engineering.

SUBSTANCE: invention relates to extraction of precious metals. Continuous extraction of precious metal composition from raw stock comprises heating of said stock in plasma kiln to produce slag top layer and fused metal bottom layer. Then, slag layer and fused metal layer are removed. Fused metal removed layer is solidified and fragmented for extraction of precious metals from produced fragments. Note here that said raw stock comprises material containing precious metal and collector metal. The latter is either metal or alloy able to form solid solution, alloy or intermetallide compound with one or several precious metals. Proposed device comprises plasma kiln, teeming table for continuous teeming of fused metal pool to form solidified sheet, fragmentation device and separation unit for extraction of precious metals from sheet fragment alloys.

EFFECT: higher yield.

20 cl, 11 dwg, 2 ex

FIELD: ecology.

SUBSTANCE: method of demercurisation of waste luminescent lamps comprises destruction of lamps and vibratory cleaning of lamp breakage from luminophore. At that the destruction of lamps is carried out to the glass particle size of no more than 8 mm. After the destruction of luminescent lamps the lamps bases are separated from the glass on the vibrating grate and removed to the collector which is sent to demercurisation- annealing electric furnace. The heat treatment of bases is carried out at a temperature up to 100°C and the holding time of at least 30 minutes. Division of luminophore from the glass is carried out by blowing it in the counterflow-moving system "broken glass-air" under the conditions of vibration.

EFFECT: increased efficiency and energy saving of recycling luminescent lamps, cost reduction and simplification of disposal technology.

FIELD: metallurgy.

SUBSTANCE: method of pyrometallurgical extraction of silver from secondary lead-bearing stock comprises stock furnacing in two steps. First, lead-bearing stock is furnaced at 1150-1200°C, the melt being cooled to 400°C at the rate of 1950°C/h to 2050°C/h. Then, the melt is heated from 400°C/h to 500°C/h to 1150-1200°C to remove the yellow lead from silver surface.

EFFECT: higher yield of silver.

1 tbl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to cleaning of silver-bearing materials by hydrometallurgy processes, for example, scrap and wastes of microelectronics. Proposed method comprises dilution of silver-bearing material in nitric acid, addition of sodium nitrate to nitrate solution at mixing, extraction of silver salt precipitate and pits treatment to get metal silver. Note here that after addition of sodium nitrate the reaction mix is held for 1 hour to add sodium carbonate or bicarbonate to pulp pH of 8-10. Free silver salt precipitate as silver carbonate is separated from the solution by filtration. Sodium nitrite and carbonate or bicarbonate is added in the dry form. Note here that sodium nitrite is taken with 25% excess of stoichiometry.

EFFECT: higher purity and yield, simplified process.

2 cl, 2 ex

FIELD: metallurgy.

SUBSTANCE: invention relates to hydrometallurgy of scattered elements, particularly, to extraction of bismuth and germanium from secondary stock sources, in particularly, to extraction of bismuth and germanium from oil-abrasive wastes of bismuth orthogermanium crystals production. Proposed method comprises hydrochloride-acid leaching of bismuth and extraction of bismuth from the solution by electrolysis. Said hydrochloride-acid leaching is performed with addition of surfactants to the solution to produce abrasive-germanium-bearing precipitate. Germanium is extracted from said precipitate by distillation of tetrachloride germanium in vapours of hydrochloric acid. Said surfactant represents the commercial mix of oxyethylated alkyl-phenols of commercial grade "АФ" 9-6 at the concentration of 0.01-0.1 wt %.

EFFECT: simplified low-cost process, higher yield.

2 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: mixture, consisting of sulphur powder, granules of floatation sulphur pyrite of grade KSF-4 in mixture with broken stone with fraction 20-70 mm or brick crumbs, which are simultaneously agent binding mercury in ionised and neutral forms, taken in ratio 1:9 by weight, and water. After that, mixture is homogenised at rotation rate 20 rev/min, argon is supplied at rate 5.5-6.5 m3/h and then mercury-containing wastes are charged in amount which is at least 50 times less than weight of sulphur powder. Grinding of wastes is carried out to complete binding of metal mercury into water-insoluble compound HgS.

EFFECT: simplification of technology, increase of ecological safety of the process.

2 tbl

FIELD: chemistry.

SUBSTANCE: method includes combined grinding of wastes with sulphur powder and crushing medium in rotary reactor for binding metal mercury into water-insoluble compound. As crushing medium used is sulphur pyrate with fraction 50-150 mm, which is simultaneously agent, binding mercury in ionised and neutral forms. Before combined grinding mixture of sulphur powder, sulphur pyrate and water is preliminarily homogenised, and reactor is filled with nitrogen, supplied at rate 7.5-8.5 m3/h, in amount which is at least 50 times less than weight of sulphur powder. After that mercury-containing wastes are charged and grinding is carried out to complete binding of metal mercury into water-insoluble compound HgS.

EFFECT: simplification of technology and increase of processing process safety.

2 tbl

FIELD: ecology.

SUBSTANCE: method of demercurisation of waste luminescent lamps comprises destruction of lamps and vibratory cleaning of lamp breakage from luminophore. At that the destruction of lamps is carried out to the glass particle size of no more than 8 mm. After the destruction of luminescent lamps the lamps bases are separated from the glass on the vibrating grate and removed to the collector which is sent to demercurisation- annealing electric furnace. The heat treatment of bases is carried out at a temperature up to 100°C and the holding time of at least 30 minutes. Division of luminophore from the glass is carried out by blowing it in the counterflow-moving system "broken glass-air" under the conditions of vibration.

EFFECT: increased efficiency and energy saving of recycling luminescent lamps, cost reduction and simplification of disposal technology.

FIELD: mining.

SUBSTANCE: method includes grinding of initial material, cyanide leaching with production of a product solution of gold with mercury admixtures, introduction of a sulfide-containing reagent for mercury deposition, sorption of gold onto activated coal with return of the reuse cyanide solution for leaching, desorption of gold and electrolysis of gold from a strippant. The sulfide-containing reagent is introduced in the form of an aqueous solution of a mixture of sodium sulfide and calcium oxide at their mass ratio of 4.3-4.4 per 900-1100 wt parts of the reuse cyanide solution. After separation of mercury in the form of a sparingly soluble residue, the suspension is separated to produce a clarified solution, from which the gold is adsorbed onto activated coal.

EFFECT: practically complete separation of mercury without negative impact at gold sorption.

4 cl, 1 dwg, 1 ex

FIELD: metallurgy.

SUBSTANCE: setup includes a lamp crushing unit, a container with demercurisation solution, a decontamination unit made in the form of a mixer for waste decontamination, which is fixed on the base with possibility of being rotated by means of an actuator and overturned for unloading of derivative product, a loading device with a movable tray, a derivative product collecting tank made in the form of a container installed on the tray with a chute for drainage of waste solution to the receiving tank and pumping of the solution by means of a pump through a filter with sulfonated carbon backfill of KU-2 type, and a furnace for combustion of backfill with sulfonated carbon and obtaining metallic mercury. The lamp crushing unit is made in the form of a continuous-action setup for obtaining fine powder from broken glass, which contains a receiving bunker, a jaw crusher for primary crushing, a screw conveyor for product supply to an elevator, a planetary mill made so that crushed product can be removed from it with an air flow, pipelines for transportation of crushed product to separator, in which the air flow is swirled with inclined blades with possibility of separation of material as to fineness degree by means of appearing centrifugal force, return of coarse material to the mill and transportation of fine product to the cyclone for collection of considerable part of ready product and its supply through a sluice valve via the pipeline to the receiving capacity.

EFFECT: improving efficiency and energy and resource saving of scrap processing and gas cleaning.

2 dwg

FIELD: metallurgy.

SUBSTANCE: method involves connection of an inner volume of a lamp and a reservoir volume to a demercurisator so that contact of mercury vapours to the demercurisator is provided and the demercurisation process is performed in the lamp volume. The reservoir with the demercurisator is arranged in a lamp base. Demercurisation process is performed in a single tight volume formed with inner volumes of the lamp and the reservoir with the demercurisator through a connection of volumes of the lamp and the reservoir to the demercurisator by destructing a partition wall from low-melting material, which separates them, and by increasing pressure in the reservoir with the demercurisator.

EFFECT: providing possibility of utilisation of the lamp in situ after its failure; increasing safety and simplifying utilisation of lamps.

6 cl, 2 dwg

FIELD: process engineering.

SUBSTANCE: proposed method comprises feeding the tubes into grinder, grinding, separating metallic bases and crushed glass containing phosphor and mercury and mercury stabilisation of sulphide form. Heated calcium polysulphide solution is fed drop-by-drop in grinder along with tube feed therein. Device comprises unit of sulfidising and separation and that for process air cleaning. Said unit of sulfidising and separation comprises shell with cover connected with glass mass collector and having opening connected with intake of bases, acceleration tube arranged inclined to cover, service container with demercurisation solution connected feed tube, grinder and grate arranged there under. Grate center has truncated cone open at both sides with vertex directed upward. Note here that container is furnished with solution heater while process air cleaner is connected to acceleration tube.

EFFECT: simplified and faster process, higher degree of disposal.

6 cl, 2 dwg

FIELD: metallurgy.

SUBSTANCE: proposed composition comprises 3.0-5.0 wt % of dichlorisocyanuric acid soda as halogen-bearing compound, 0.5-1.5 wt % of thiourea as complexing agent and water making the rest.

EFFECT: higher efficiency of removal mercury from soil, reduced aggressiveness of used substances relative to rooms interior, instruments and equipment.

1 tbl

FIELD: chemistry.

SUBSTANCE: method involves breaking down said lamps and devices, grinding, heating, evacuating the scrap lamps in a chamber and subsequent condensation of mercury vapour in cooled traps with successive sealing of all processes, wherein a batch of lamps and devices is broken down right away; grinding is carried out to particle size of not more than 20 mm, destruction and extraction of mercury is carried out at temperature of 150-200°C and a vacuum of up to 10 Pa and holding for 30 minutes; a second step for cleaning the scrap with a washing liquid (1 N sulphuric acid or hydrochloric acid solution) is carried out, followed by separation of sockets and scrap glass. When filling the chamber with scrap lamps with washing liquid, circulation mixing is carried out for at least 5 minutes. After separating from the scrap, the washing liquid is subjected to filtration and thermal decomposition to metallic mercury at temperature higher than 500°C. Separation of cleaned sockets and scrap glass is carried out by sieving through a sieve with different cell size under vibration action.

EFFECT: high efficiency and environmental friendliness of the process, efficiency of extracting mercury while reducing power consumption.

5 cl, 6 ex

FIELD: machine building.

SUBSTANCE: plant includes two units, the first one of which is a lamp sorting unit, and the second one is a unit of multistage exit gas cleaning system. The first unit includes a lamp sorting device consisting of a loading assembly, a pneumatic vibrating separator with a crusher and a cyclone, a crushed lamp glass collecting hopper, a lamp base receiving container and a fluorescent dye container. The second unit is made in the form of multistage exit gas cleaning system consisting of a sleeve filter, adsorbers, a gas blower with a compressor, which creates negative pressure in the plant of 5-8 kPa in the lamp loading zone and up to 19-23 kPa before gas blower. The plant is equipped with a series pulverised-coal and gas emission cleaning system consisting of a cyclone, sleeve filters, a working adsorber operating on activated coal, which allows reducing mercury content in exit gases to the level of less than 0.0001 mg/m3.

EFFECT: improving utilisation efficiency owing to excluding the probability of PC-air emissions to a production room and improving energy resource saving of metal scrap processing and gas cleaning.

2 cl, 2 dwg

FIELD: utilization of mercury-containing devices; processing rejected luminescent lamps and mercury-containing devices and devices whose service life has expired.

SUBSTANCE: plant for utilization of mercury-containing devices includes working bath, unit for breaking and treating the mercury-containing devices with liquid medium which is made in form of container with breaking devices and devices for supply of liquid medium, vibrator, working solution reservoir connected with breaking device by means of drainage pipe line laid in lowest point of working bath; plant is also provided with pipe lines equipped with fittings and pump for transfer of liquids; it is also provided with water reservoir which is connected with breaking device by means of drainage pipe line laid at definite height above bottom of working bath; working bath, water reservoir and working solution reservoir are combined in system which makes it possible to fill working bath in turn with water or with working solution by means of one pump; breaking device is made in form of cross-piece with knives secured on it. Proposed method of utilization of mercury-containing devices includes grinding of such devices under layer of water at continuous washing of luminescent substance, forming the suspension and settling mercury in form of finely-dispersed particles on bath bottom, after which mercury is subjected to neutralization with the aid of said plant. Breaking the mercury-containing devices and washing-off the luminescent substance will be performed by vibration; neutralization is accompanied by forming of insoluble calomel.

EFFECT: possibility of performing chemical demercuration at temperature close to surrounding temperature.

3 cl, 5 dwg

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