CN110282640B - Method for extracting, separating and recycling arsenic alkali residue - Google Patents
Method for extracting, separating and recycling arsenic alkali residue Download PDFInfo
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- CN110282640B CN110282640B CN201910603286.5A CN201910603286A CN110282640B CN 110282640 B CN110282640 B CN 110282640B CN 201910603286 A CN201910603286 A CN 201910603286A CN 110282640 B CN110282640 B CN 110282640B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/24—Crystallisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/02—Arsenates; Arsenites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/02—Antimonates; Antimonites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A method for extracting, separating and recycling arsenic alkali residue comprises the following steps: adding glycerol into the crushed and ground arsenic-alkali residue or carrying out leaching extraction on the slurry obtained by grinding the arsenic-alkali residue and the glycerol together in a leaching tank, and carrying out solid-liquid separation to obtain antimony-rich residue and a glycerol phase solution; the obtained glycerin phase solution is a mixed solution containing arsenate and soda ash, a mixture of arsenate crystals and soda ash crystals is obtained through cooling crystallization or freezing crystallization separation, and the glycerin separated through cooling crystallization or freezing crystallization is recycled for leaching extraction of arsenic-soda residue; the obtained antimony-rich slag is a solid mixture containing antimonate and aluminosilicate minerals and is used for returning antimony for refining or processing antimony or antimony oxide and antimonate. The invention has short flow, less investment, no wastewater pollutant generated in the separation process, and capability of extracting and separating the arsenic-alkali residue by using a safe solvent, and the solvent can be recycled.
Description
Technical Field
The invention relates to a method for recycling arsenic alkali residue, in particular to a method for extracting, separating and recycling arsenic alkali residue.
Background
The arsenic alkali slag is a smelting waste slag mainly containing sodium arsenate, sodium antimonate and sodium carbonate generated in the antimony refining arsenic removal process of antimony pyrometallurgy, and the solid hazardous waste which is difficult to properly treat all the time is extremely toxic and easy to dissolve in water, so that the healthy development of the antimony smelting industry is restricted to a certain extent.
For arsenic alkali slag which is difficult to be properly treated, a great deal of research and practice is continuously carried out by domestic and foreign science and technology workers, and various technical methods for treating the arsenic alkali slag can be roughly summarized into three types of methods, namely solidification landfill, wet treatment and pyrogenic treatment.
The solidification landfill method of the arsenic-alkali slag comprises the steps of cement solidification, lime/calcium salt solidification, iron salt solidification, plastic solidification, asphalt solidification, melting/vitrification solidification and the like, and then landfill is carried out, although the solidification landfill can realize the fixation of arsenic to a certain extent within a certain time, the solidification landfill methods have the problems of large capacity increase ratio before and after solidification, large land landfill is needed in the later period, long-term pollution hidden danger and the like.
The wet treating method of arsenic alkali slag is mainly characterized by that it utilizes the properties of alkali, sodium arsenate and sodium arsenite in the arsenic alkali slag which can be dissolved in water, and sodium antimonite are insoluble or insoluble in water to implement arsenic-antimony separation and make arsenic be dissolved out, then adopts the chemical precipitation method, such as calcium arsenate precipitation, ferric arsenate precipitation and arsenic sulfide precipitation, etc. or adopts the method of directly crystallizing sodium arsenate and soda mixed salt to further treat leachate.
The existing wet processing method can be summarized as follows:
1) water leaching-sodium arsenate mixed salt method: the arsenic caustic sludge material is leached and crushed by hot water and separated into antimony-containing leaching slag and solution, the leaching slag is dried and then sent to a blast furnace for treatment, and the solution is completely evaporated and dried to obtain sodium arsenate mixed salt (containing sodium arsenate, sodium carbonate, sodium sulfate and a small amount of antimony) which is mainly used as a glass clarifying agent.
2) Water leaching-calcium slag method: wet crushing arsenic alkali slag, stirring and leaching with hot water, separating most of sodium arsenate and sodium carbonate in the solution into antimony-containing leached slag and leached liquid, stoving the leached slag, treating in blast furnace, causticizing the leached liquid with slaked lime and separating into calcium slag containing calcium arsenate and caustic soda solution. Although the precipitation rate of arsenic can reach 98%, arsenic in the calcium slag still reaches 13-126 mg/L in an aqueous solution, and the calcium slag has higher solubility in an acid environment and is still toxic and dangerous solid waste which needs to be treated. The caustic soda solution is evaporated and concentrated to prepare liquid caustic soda or flake caustic soda, the arsenic content reaches about 3 percent, the effect of the arsenic removal agent returned to be used for refining crude antimony is not ideal, and the arsenic is circulated in a smelting system.
3) Oxidative water leaching-CO2And (3) arsenic alkali separation method: the crushed or wet-milled arsenic caustic sludge is subjected to oxidation leaching by hot water and separated into a leaching solution (a solution containing sodium carbonate, sodium arsenate, sodium sulfate, sodium thioantimonate and the like) and a leaching residue (a solid containing sodium antimonate, sodium antimonite, metal antimony and other gangue minerals such as silicon dioxide and the like). Then, the sodium carbonate in the leachate is converted into sodium bicarbonate with low solubility by using carbon dioxide, the crystallized sodium bicarbonate (containing arsenic) is separated, and then a dearsenization agent is added into the solution to precipitate sodium arsenate (containing alkali). The sodium bicarbonate is converted into sodium carbonate (containing arsenic) by heat treatment and is reused for antimony refining and arsenic removal.
4) Oxidizing water leaching-neutralization-sulfuration arsenic precipitation method: by oxidation with hot water, crushing or wet-grindingSeparating the arsenic alkali residue into leaching residue (containing antimonate and the like) and leaching liquid, drying the leaching residue and returning the leaching residue to a blast furnace for treatment; then, a large amount of acid (generally sulfuric acid or hydrochloric acid) is added to the leachate (containing sodium arsenate, sodium arsenite, sodium carbonate, sodium sulfate, etc.) to neutralize the alkali therein, the solution is adjusted to be acidic, and sulfides such As H2S, Na2S, etc. are added to convert the arsenic in the solution into arsenic sulfide precipitate (As)2S3). The method not only needs to consume a large amount of acid to neutralize the alkali in the leaching solution, but also the waste water still contains a certain amount of arsenic and a large amount of inorganic salt.
5) Oxidizing water leaching-ammonium arsenate metal salt precipitation method: after crushing or wet grinding arsenic caustic sludge oxidation water leaching, solid-liquid separation is carried out to obtain leaching solution mainly containing sodium carbonate and sodium arsenate and leaching residue mainly containing antimonate; then, adding a metal ammonium complex ion solution and a crystal growth promoter into the leachate to perform reaction, aging, crystallization and precipitation, and then performing solid-liquid separation to obtain an ammonium arsenate metal salt; and heating the solution to remove ammonium, introducing carbon dioxide to react to separate out sodium bicarbonate crystals, and thermally decomposing the separated sodium bicarbonate into sodium carbonate (containing arsenic) for recycling. The wet precipitation dearsenification method using the metal ammonia complex ion solution increases new metal ions, and has certain limitation, even the current best (best in the purification of ammonium molybdate) magnesium ammonium arsenate method, the solubility of the insoluble magnesium ammonium arsenate hexahydrate in water at 20 ℃ is 0.038 g, and the solubility in water at 80 ℃ is 0.024 g. The precipitation effect of zinc ammonia in the prior art is inferior to that of magnesium ammonia.
The existing wet treatment process needs to dissolve arsenic alkali residue in a large amount of water, the precipitation separation method can generate a large-volume arsenic-containing waste liquid, the direct discharge can bring huge pollution to the environment, the advanced treatment is needed to reach the discharge standard, the treatment cost is high, and the energy consumption is high. The method for directly crystallizing the sodium arsenate and the soda ash also needs to evaporate a large-volume arsenic-containing liquid, and the evaporation process is difficult to avoid splashing of arsenic-containing micro-foam, so that the operation environment is severe; in addition, the produced sodium arsenate product has high impurity content, the market demands of common sodium arsenate, arsenic sulfide and other products are limited, the overstock is large, and the operation of the wet process is not satisfactory on the whole.
The basic technology of the pyrometallurgical treatment of arsenic alkali slag is 'arsenic alkali slag blast furnace volatilization smelting + reverberatory furnace reduction smelting' method, namely putting the arsenic alkali slag into an antimony blast furnace for volatilization smelting, simultaneously adding enough flux and coke, oxidizing arsenic and antimony in the arsenic alkali slag together to enter a flue gas cooling device along with high-temperature flue gas in the form of oxides, adding a reducing agent into a reverberatory furnace to reduce the cooled and recovered high-arsenic crude antimony trioxide into crude antimony, and then adding soda ash or flake caustic soda into the reverberatory furnace to blow and refine repeatedly to obtain qualified antimony ingots. The advantages of the pyrometallurgical treatment of arsenic-alkali slag are high treatment capacity and high production efficiency, and the equipment of an antimony smelting system can be utilized. However, since the raw material/returned product contains high arsenic, the operation environment is poor and the personal safety risk is high on the one hand, and the returned product generated by repeatedly refining the high-arsenic crude antimony contains higher arsenic to form a vicious circle of arsenic, and a perfect and closed cooling dust collection system is required on the other hand.
CN102965517A discloses a method for curing arsenic alkali slag glass, which comprises the steps of selectively reducing sodium antimonate into metallic antimony by using a carbon reducing agent in a molten state of the arsenic alkali slag, wherein arsenic exists in the slag in the form of sodium arsenate; then adding a glass melting agent into the arsenic-containing slag to form a low-temperature glass phase, discharging the glass phase, and then quenching the discharged glass phase into a cullet block or directly casting the cullet block into a glass ingot in an ingot casting mold, so that the glass ingot is convenient to stack and return to a pit for burying.
CN104073644B discloses a synchronous reduction smelting method for proportioning antimony pyrorefining lead-removing slag and arsenic caustic sludge, which comprises the following steps: (1) determining the proportion of the deleading slag and the arsenic alkaline slag according to the content of phosphate ions in the deleading slag and the content of sodium ions in the arsenic alkaline slag by weight, wherein the mass ratio of the sodium ions in the arsenic alkaline slag to the phosphate ions in the deleading slag is 60-80: 90-120; (2) and (2) uniformly mixing the lead-removed slag and the arsenic alkaline slag according to the proportion in the step (1), adding anthracite, wherein the added anthracite accounts for 3-15% of the total weight of the lead-removed slag and the arsenic alkaline slag, treating at the constant temperature of 800-1000 ℃ for 30-60 minutes, cooling to room temperature, and separating antimony-arsenic-lead alloy and trisodium phosphate floating slag to obtain the antimony-arsenic-lead alloy.
CN108220626A discloses a reduction smelting treatment method for arsenic alkali slagThe method comprises the steps of mixing arsenic alkali residue with a carbonaceous reducing agent, then carrying out reduction smelting to obtain arsenic steam, crude antimony and reduction residue, and condensing the arsenic steam to obtain a metal arsenic product; the main component of the reducing slag is Na2CO3Can be directly used as a dearsenization agent to return to the antimony refining dearsenization process, and can also obtain Na by water leaching-concentration-crystallization process2CO3And (4) crystals.
CN106636678A discloses a method for preparing arsenic by directly reducing and roasting an arsenic-containing material, which takes arsenate as a raw material, uniformly mixes the arsenate material and a carbonaceous reducing agent, then places the mixture in an inert or reducing atmosphere, carries out reducing roasting under the condition of negative pressure, and collects roasting smoke to obtain an arsenic product.
According to the pyrogenic process treatment method, the conditions of thermal reduction treatment are harsh, a sealed vacuum arc furnace is required, vacuum pumping is adopted, and forced vacuum pumping is carried out for 1-8 hours under the high-temperature condition, so that the control requirement of the interstitial pyrogenic process reduction treatment is strict, the requirements on equipment and operation control are high, the method can only be suitable for a laboratory or few-batch metallurgical treatment, and the adaptability of large-batch industrial production is questioned; the method is not suitable for treating arsenic alkaline residue containing a large amount of antimony, antimony vapor volatilization and arsenic sublimation (arsenic sublimation at 615 ℃) can occur simultaneously under the condition that a vacuum pump is adopted to continuously and strongly vacuumize at the temperature of more than or equal to 800 ℃, and only arsenic-antimony alloy is obtained frequently; and is difficult to process a large amount of arsenate containing antimonate, carbon is used as a reducing agent to smelt arsenic alkaline residue, the whole reducing capability is still very weak when the reducing temperature is lower than 800 ℃, better reducing performance can be achieved only when the reducing temperature is higher than 900 ℃, the potential accident risk is higher aiming at the problems that the higher the dangerous waste treatment temperature is, the energy consumption is high and the equipment requirement is higher, in addition, because a closed reducing furnace is adopted, the crude antimony lead obtained by the closed reducing furnace is still kept stand for carbon powder reduction and vacuum pumping process still contains arsenic, the reducing residue still contains a small amount of arsenic (including soluble arsenate and insoluble arsenate), the aim of partial reduction and separation is still achieved, and the circulation of the arsenic is caused no matter whether the crude antimony is returned for refining or the reducing residue is returned as a dearsenizing agent. Under the condition of strictly controlling reaction conditions, a certain amount of arsenic is still contained in the water leaching slag separated after the reducing slag is subjected to water leaching, and the water leaching slag is still dangerous solid waste to be treated; arsenic vapor or arsenic flue gas or simple substance arsenic in the treatment process is easy to oxidize, particularly in the process of forcibly pumping the arsenic vapor or arsenic flue gas or simple substance arsenic from a high-temperature furnace to cooling by a vacuum pump, even if mixed atmosphere of inert gas and/or nitrogen and hydrogen and/or carbon monoxide and the like is adopted, the arsenic vapor or arsenic flue gas or simple substance arsenic is extremely difficult to recycle, so that poor economy or atmosphere pollution is easily caused, and the vacuum pump for vacuum pumping of the arsenic flue gas is extremely poor in adaptability to metal particles or flue gas dust, so that normal production operation is difficult to guarantee; or the reaction condition of generating trisodium phosphate by strictly controlling the equivalent ratio of sodium to phosphate radical is required to simultaneously reduce antimonate, arsenate and the like in the arsenic alkali slag into simple substance antimony and simple substance arsenic, the production control habit of an actual antimony smelting enterprise is difficult to ensure the simple reaction condition, the treatment energy consumption is high, the potential pollution hidden danger is large, and especially the trisodium phosphate scum containing arsenic easily flows into the agricultural fertilizer market to cause uncontrollable pollution diffusion.
In conclusion, in the existing treatment process of various arsenic alkali residues, the separation of arsenic, antimony and alkali resources is difficult, and particularly, the problems of high arsenic treatment difficulty, environmental protection, economical efficiency and the like are prominent.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a method for extracting, separating and recycling arsenic-alkali residue by using a safe solvent, wherein the method has the advantages of short flow, low investment and no wastewater pollutants generated in the separation process, and the solvent can be recycled.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for extracting, separating and recycling arsenic alkali residue comprises the following steps: adding glycerol into the crushed and ground arsenic-alkali residue or carrying out leaching extraction on the slurry obtained by grinding the arsenic-alkali residue and the glycerol together in a leaching tank, and carrying out solid-liquid separation to obtain antimony-rich residue and a glycerol phase solution; the obtained glycerin phase solution is a mixed solution containing arsenate and soda ash, a mixture of arsenate crystals and soda ash crystals is obtained through cooling crystallization or freezing crystallization separation, and the glycerin separated through cooling crystallization or freezing crystallization is recycled for leaching extraction of arsenic-soda residue; the obtained antimony-rich slag is a solid mixture containing antimonate and aluminosilicate minerals and is used for returning antimony for refining or processing antimony or antimony oxide and antimonate.
Further, the leaching extraction is carried out for 0.5 to 8 hours at the temperature of between 60 and 150 ℃ with stirring.
Further, the particle size of the slurry is <100 μm.
Further, the screening mesh number of the crushed and ground arsenic-alkali residue is 160-800 meshes (preferably 200-400 meshes).
Further, the using amount of the glycerol is 1-15 times (preferably 2-6 times) of the mass of the arsenic alkali residue.
Further, the leaching extraction comprises single-stage leaching extraction, multi-stage leaching extraction or countercurrent leaching extraction in a leaching tank. Fully extracting arsenate and soda ash in the arsenic alkali residue to ensure that the arsenate and the soda ash in the glycerol phase solution reach saturated solubility at a set leaching extraction temperature;
further, when the pH value of the aqueous solution of the arsenic alkali residue is greater than 11.7, adding sodium bicarbonate for mixed grinding or adding sodium bicarbonate during leaching extraction, and adjusting the pH value of the aqueous solution of the arsenic alkali residue or the pH value of the aqueous solution of the glycerin phase solution to be less than 11.7.
Further, the crystallization product separated by cooling crystallization and/or freezing crystallization of the glycerol phase solution can be directly sold, or used as raw materials for preparing arsenic products, refined sodium carbonate or sodium hydroxide, and the sodium carbonate/sodium hydroxide can also be directly reused for refining antimony.
Further, the glycerol may be partially or completely replaced with mannitol or xylitol.
The invention has the beneficial effects that: (1) sodium arsenate, sodium arsenite, soda ash and sodium bicarbonate can be dissolved in glycerol under certain conditions, the solubility of the sodium arsenite and the sodium antimonite is changed along with the temperature rise, the sodium antimonite and the sodium antimonite are very difficult to dissolve in the glycerol when the pH value is less than 11.7, the lower-cost glycerol without physiological toxicity is used as an extraction solvent, arsenate and soda ash in arsenic-soda residue are selectively leached and extracted when the pH value is less than 11.7, and the antimony-enriched residue with arsenic and alkali removed is obtained by heat preservation and separation; (2) the solubility of arsenate in glycerol is sensitive to temperature change, and cooling is carried out to separate arsenate crystals, and freeze crystallization is carried out to separate soda crystals, or one-time freeze crystallization is carried out to separate mixed salt. The glycerin crystal after the freezing crystallization separation is heated by utilizing the heat exchange waste heat and then is recycled; (3) the process flow is simple, the investment is less, the separation effect is good, the treatment capacity is large, the dust-free operation can be easily realized, and no dust, no process waste gas and no process waste water are discharged in the whole process; (4) provides a brand new technical idea for the effective separation treatment of arsenic-alkali residue and provides raw materials convenient for utilization for the production of soda ash, arsenic products and antimony products.
Detailed Description
The present invention will be further described with reference to the following examples.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
Selecting secondary arsenic alkali slag of certain antimony smelting factory in Hunan, and detecting the content of As 9.68%, the content of Sb 5.68% and the content of sodium carbonate 41.53%; commercial industrial glycerin (content 99.5%) is selected as a solvent, and commercial sodium bicarbonate is selected as a pH value regulator.
The embodiment comprises the following steps: crushing and grinding arsenic-alkali residue, sieving with a 200-mesh sieve, feeding the arsenic-alkali residue powder into a leaching tank, adding glycerol with 6 times of the mass of the arsenic-alkali residue powder, stirring and leaching for 4 hours at normal pressure and 100 ℃, and performing heat preservation and separation to obtain antimony-rich residue and a glycerol phase solution. Cooling the glycerin phase solution to separate out arsenate crystal seeds, filtering out arsenate crystals, and then freezing and crystallizing at-20 ℃ to separate out the soda ash. The glycerin separated by freezing crystallization is recycled for leaching extraction of arsenic alkaline residue.
Through detection, the antimony-rich slag obtained in the embodiment mainly comprises antimonate, aluminosilicate and the like, the arsenic content in the antimony-rich slag is 0.74%, the sodium carbonate content is 0.23%, and the TCLP experiment detects that the arsenic content is 0.08 mg/L. The effect of extracting and separating arsenic and alkali by using the glycerol solvent is good. The antimony-rich slag can be returned to an antimony smelting system or used as a raw material for preparing antimony products. Wherein, the content of antimony in arsenate is 0.069%, and the content of sodium carbonate is 1.87%. The content of antimony in the soda ash is 0.034%, and the content of arsenic in the soda ash is 0.98%.
Taking arsenate as a raw material to produce aluminum arsenate: dissolving arsenate in water, adding hydrochloric acid to neutralize a small amount of soda ash contained in arsenate to pH7.5, adding equivalent aluminum chloride solution for reaction and precipitation, filtering, and washing with water to obtain high-quality aluminum arsenate; phytic acid solution is dripped into the filtrate to purify and precipitate trace heavy metal ions in the filtrate.
Taking soda ash as a raw material to refine a soda ash product: dissolving sodium carbonate in water, dropwise adding an aluminum chloride solution to react and precipitate a small amount of arsenate in the solution, filtering and separating out aluminum arsenate solid, dropwise adding a phytic acid solution into the filtrate until trace residual arsenic ions and other metal ions above divalent are completely precipitated, detecting the arsenic content in the solution by a TCLP (thermal crystallization process) experiment to be 0.002mg/L, and concentrating, crystallizing, drying and grinding the solution according to a mature process to obtain a sodium carbonate product.
Example 2
Selecting secondary arsenic alkali slag of certain antimony smelting factory in Hunan, and detecting the content of As (11.31%), the content of Sb (4.37%) and the content of sodium carbonate (27.21%); commercial industrial glycerin (content 99.5%) is selected as a solvent, and commercial sodium bicarbonate is selected as a pH value regulator.
The embodiment comprises the following steps: crushing arsenic alkali residue, adding 2 times of glycerol, grinding into slurry passing through a 74-micron sieve, feeding into a leaching tank, adding glycerol with the amount 4.5 times of the mass of the arsenic alkali residue, adding sodium bicarbonate to control the pH value to be less than 11.7, stirring at normal pressure and 140 ℃ to leach for 2 hours, and performing heat preservation and separation to obtain antimony-rich residue and glycerol phase solution. The glycerin phase solution is cooled and frozen to-5 ℃ for one time to crystallize and separate out arsenate soda ash mixture. The glycerin separated by freezing crystallization is recycled for leaching extraction of arsenic alkaline residue.
Through detection, the antimony-rich slag obtained in the embodiment mainly comprises antimonate, aluminosilicate and the like, the arsenic content in the antimony-rich slag is 0.59%, the sodium carbonate content is 0.52%, and the TCLP experiment detects that the arsenic content is 0.05 mg/L. The effect of extracting and separating arsenic and alkali by using the glycerol solvent is good. The antimony-rich slag can be returned to an antimony smelting system or used as a raw material for preparing antimony products. Wherein, the content of antimony in the arsenate soda ash mixture is 0.057 percent.
Taking an arsenate soda ash mixture as a raw material to prepare copper arsenate and soda ash: dissolving an arsenate soda ash mixture in water, adding a copper chloride solution with the equivalent of 1.03 times of arsenate to fully react, filtering and separating to obtain copper arsenate, dropwise adding a phytic acid solution into a filtrate until residual copper ions and other metal ions above divalent are completely precipitated, detecting the arsenic content in the solution by a TCLP (temperature controlled discharge) experiment to be 0.004mg/L, and crystallizing and separating according to a mature process to obtain sodium chloride and soda ash products.
Example 3
Selecting arsenic alkali slag of certain antimony smelting plant, wherein the detection components of the plant are as follows: as: 17.98%, Sb: 21.87%, Na: 28.13 percent; commercial industrial glycerin (content 99.5%) is selected as a solvent, and commercial sodium bicarbonate is selected as a pH value regulator.
The embodiment comprises the following steps: crushing and grinding arsenic caustic sludge to 250 meshes, equivalently feeding the arsenic caustic sludge powder into three leaching tanks, extracting at normal pressure and 120 ℃ by adopting three-stage leaching, adding glycerol with the mass of 3 times of that of the arsenic caustic sludge powder into the first-stage leaching, stirring and leaching at normal pressure and 120 ℃ for 1h, carrying out suction filtration and separation, transferring a glycerol phase solution into a second-stage leaching tank for leaching for 1h, carrying out suction filtration and separation, transferring the glycerol phase solution into a third-stage leaching tank for leaching for 1h, carrying out suction filtration and separation, and carrying out microfiltration filtration to obtain a saturated glycerol phase solution; and after the glycerol phase solution is leached from the first-stage leaching tank, newly adding the same amount of the glycerol leaching solution for 1 hour, transferring the leaching solution into a second-stage leaching tank, transferring the leaching solution into a third-stage leaching tank after 1 hour of leaching, fully leaching and extracting the arsenic-alkali residue by using a glycerol solvent, and separating to obtain the antimony-rich residue.
Cooling the saturated glycerin phase solution to separate out arsenate crystal seeds, filtering out arsenate crystals, and then freezing and crystallizing at-13 ℃ to separate out soda ash. The glycerin separated by freezing crystallization is recycled for leaching extraction of arsenic alkaline residue.
Through detection, the main components of the antimony-rich slag obtained in the embodiment are antimonate, aluminosilicate and the like, the content of arsenic in the antimony-rich slag is 0.52%, the content of sodium carbonate is 0.16%, and the content of arsenic is 0.05mg/L detected by TCLP experiments. The effect of extracting and separating arsenic and alkali by using the glycerol solvent is good.
The antimony-rich slag can be returned to an antimony smelting system or used as a raw material for preparing antimony products.
The content of antimony in arsenate is 0.079%, and the content of sodium carbonate is 1.97%.
The content of antimony in the soda ash is 0.073%, and the content of arsenic in the soda ash is 1.75%.
Example 4
Selecting arsenic alkali slag of certain antimony smelting plant, wherein the detection components of the plant are as follows: as: 21.42%, Sb: 34.37%, Na: 28.11 percent; commercial industrial glycerin (content 99.5%) is selected as a solvent, and commercial sodium bicarbonate is selected as a pH value regulator.
The embodiment comprises the following steps: adding 7% sodium bicarbonate when crushing and grinding arsenic caustic sludge to prepare arsenic caustic sludge powder passing through 200 meshes, equivalently feeding the arsenic caustic sludge powder into three leaching tanks, performing three-stage leaching extraction at normal pressure and 135 ℃, adding 2.5 times of glycerol by mass of the arsenic caustic sludge powder into the first-stage leaching, stirring and leaching for 0.8h at normal pressure and 135 ℃, performing suction filtration and separation, transferring a glycerol phase solution into a second-stage leaching tank for leaching for 0.8h, performing suction filtration and separation, transferring the glycerol phase solution into a third-stage leaching tank for leaching for 0.8h, performing suction filtration and separation, and performing ultrafiltration to obtain a saturated glycerol phase solution; and after the glycerol phase solution is leached from the first-stage leaching tank, newly adding the same amount of the new glycerol leaching solution for 0.8h, transferring the leaching solution into a second-stage leaching tank, transferring the leaching solution into a third-stage leaching tank after 0.8h of leaching, fully leaching and extracting the arsenic alkali residue by using a glycerol solvent, and separating to obtain the antimony-rich residue.
The glycerin phase solution is cooled and frozen to-15 ℃ for one time to crystallize and separate out arsenate soda ash mixture. The glycerin separated by freezing crystallization is recycled for leaching extraction of arsenic alkaline residue.
Through detection, the main components of the antimony-rich slag obtained in the embodiment are antimonate, aluminosilicate and the like, the content of arsenic in the antimony-rich slag is 0.24%, the content of sodium carbonate is 0.19%, and the content of arsenic is 0.02mg/L detected by TCLP experiments. The effect of extracting and separating arsenic and alkali by using the glycerol solvent is good.
The antimony-rich slag can be returned to an antimony smelting system or used as a raw material for preparing antimony products. Wherein, the content of antimony in the arsenate soda ash mixture is 0.091 percent.
Taking the antimony-rich slag as a raw material to produce antimony oxide powder: stirring the antimony-rich slag, water, glycerol and sodium hydroxide according to the mass ratio of 1: 3: 1.5, reacting and leaching for 4 hours at 90 ℃, and filtering and separating out silicon-aluminum slag; dropwise adding sodium sulfide into the alkaline glycerol aqueous solution to react and precipitate lead and bismuth, and separating lead sulfide and bismuth sulfide precipitates to obtain lead slag; adding hydrochloric acid into the alkali glycerol aqueous solution to neutralize until the pH value is 6.5, and separating to obtain antimony oxide powder; then, dripping phytic acid solution into the glycerol aqueous solution to react until all divalent ions and heavy metal ions in the solution are precipitated, and separating out phytic acid precipitate; microfiltering and filtering to obtain a glycerin salt water solution; separating the glycerol salt water solution at 37 deg.C by nanofiltration membrane chromatography to obtain nanofiltration concentrate and dialysate glycerol water solution. The glycerin water solution returns to dissolve the antimony-rich slag, and the concentrated solution is sprayed and dried to prepare a sodium chloride product.
Purifying the obtained antimony oxide powder according to a conventional process to obtain an antimony oxide powder product.
The silicon-aluminum slag is detected to be aluminosilicate mineral, the content of antimony is 0.87%, the content of arsenic is 0.009%, and the content of arsenic is 0.007mg/L detected by TCLP experiment.
Example 5
Selecting arsenic alkaline residue of a certain antimony smelting plant, and detecting: 14.57 percent of As, 8.94 percent of Sb and 28.76 percent of sodium carbonate; commercial industrial glycerin (content 99.5%) is selected as a solvent, and commercial sodium bicarbonate is selected as a pH value regulator.
The embodiment comprises the following steps: crushing arsenic alkali residues, adding 2 times of glycerol by mass, adding sodium bicarbonate to control the pH value to be 11.5-11.7, grinding the arsenic alkali residues into slurry passing through a 80-micron sieve, sending the slurry into a continuous countercurrent leaching tank, stirring the countercurrent leaching tank by ultrasonic waves, supplementing the total amount of a countercurrent leaching glycerol solvent to 6 times of the total mass of the arsenic alkali residues, stirring and leaching for 2 hours at normal pressure and 145 ℃, and performing heat preservation and separation to obtain antimony-rich residues and a glycerol phase solution. Cooling and freezing the glycerol phase solution to-10 ℃ for one time, crystallizing and separating out an arsenate soda ash mixture; the glycerin separated by freezing crystallization is recycled for leaching extraction of arsenic alkaline residue.
Through detection, the antimony-rich slag obtained in the embodiment mainly comprises antimonate, aluminosilicate and the like, the arsenic content in the antimony-rich slag is 0.03%, the sodium carbonate content is 0.86%, and the TCLP experiment detects that the arsenic content is 0.09 mg/L. The effect of extracting and separating arsenic and alkali by using the glycerol solvent is good.
The antimony-rich slag can be returned to an antimony smelting system or used as a raw material for preparing antimony products.
The antimony content in the arsenate soda ash mixture is 0.087%.
Claims (28)
1. A method for extracting, separating and recycling arsenic alkali residue is characterized in that: the method comprises the following steps: adding glycerol into the crushed and ground arsenic-alkali residue or adding the arsenic-alkali residue and the glycerol into ground slurry, adjusting the pH value to be less than 11.7, carrying out leaching extraction at the temperature of 60-150 ℃, and then carrying out solid-liquid separation to obtain antimony-rich residue and a glycerol phase solution; the obtained glycerin phase solution is a mixed solution containing arsenate and soda ash, a mixture of arsenate crystals and soda ash crystals is obtained through cooling crystallization or freezing crystallization separation, and the glycerin separated through cooling crystallization or freezing crystallization is recycled for leaching extraction of arsenic-soda residue; the obtained antimony-rich slag is a solid mixture containing antimonate and aluminosilicate minerals and is used for returning antimony for refining or processing antimony or antimony oxide and antimonate.
2. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1, wherein the method comprises the following steps: the leaching and extracting mode is stirring leaching for 0.5-8 h.
3. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: the particle size of the slurry is <100 μm.
4. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: the sieving mesh number of the crushed and ground arsenic-alkali residue is 160-800 meshes.
5. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: the using amount of the glycerol is 1.0-15 times of the mass of the arsenic alkali residue.
6. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 3, wherein the method comprises the following steps: the using amount of the glycerol is 1.0-15 times of the mass of the arsenic alkali residue.
7. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 4, wherein the method comprises the following steps: the using amount of the glycerol is 1.0-15 times of the mass of the arsenic alkali residue.
8. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 5, wherein the method comprises the following steps: the using amount of the glycerol is 2-6 times of the mass of the arsenic alkali residue.
9. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: the leaching extraction comprises single-stage leaching extraction, multi-stage leaching extraction or countercurrent leaching extraction in a leaching tank.
10. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 3, wherein the method comprises the following steps: the leaching extraction comprises single-stage leaching extraction, multi-stage leaching extraction or countercurrent leaching extraction in a leaching tank.
11. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 4, wherein the method comprises the following steps: the leaching extraction comprises single-stage leaching extraction, multi-stage leaching extraction or countercurrent leaching extraction in a leaching tank.
12. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 4, wherein the method comprises the following steps: the leaching extraction comprises single-stage leaching extraction, multi-stage leaching extraction or countercurrent leaching extraction in a leaching tank.
13. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: and when the pH value of the aqueous solution of the arsenic alkali residue is greater than 11.7, adding sodium bicarbonate for mixed grinding or adding sodium bicarbonate during leaching extraction, and adjusting the pH value of the aqueous solution of the arsenic alkali residue or the pH value of the aqueous solution of the glycerin phase solution to be less than 11.7.
14. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 3, wherein the method comprises the following steps: and when the pH value of the aqueous solution of the arsenic alkali residue is greater than 11.7, adding sodium bicarbonate for mixed grinding or adding sodium bicarbonate during leaching extraction, and adjusting the pH value of the aqueous solution of the arsenic alkali residue or the pH value of the aqueous solution of the glycerin phase solution to be less than 11.7.
15. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 4, wherein the method comprises the following steps: and when the pH value of the aqueous solution of the arsenic alkali residue is greater than 11.7, adding sodium bicarbonate for mixed grinding or adding sodium bicarbonate during leaching extraction, and adjusting the pH value of the aqueous solution of the arsenic alkali residue or the pH value of the aqueous solution of the glycerin phase solution to be less than 11.7.
16. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 5, wherein the method comprises the following steps: and when the pH value of the aqueous solution of the arsenic alkali residue is greater than 11.7, adding sodium bicarbonate for mixed grinding or adding sodium bicarbonate during leaching extraction, and adjusting the pH value of the aqueous solution of the arsenic alkali residue or the pH value of the aqueous solution of the glycerin phase solution to be less than 11.7.
17. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 9, wherein: and when the pH value of the aqueous solution of the arsenic alkali residue is greater than 11.7, adding sodium bicarbonate for mixed grinding or adding sodium bicarbonate during leaching extraction, and adjusting the pH value of the aqueous solution of the arsenic alkali residue or the pH value of the aqueous solution of the glycerin phase solution to be less than 11.7.
18. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: the arsenate crystal and the soda crystal separated by cooling crystallization and/or freezing crystallization of the glycerol phase solution and the mixture thereof are directly sold or used as raw materials for preparing arsenic products and/or refined alkali; the obtained soda/caustic soda is used for refining antimony.
19. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 3, wherein the method comprises the following steps: the arsenate crystal and the soda crystal separated by cooling crystallization and/or freezing crystallization of the glycerol phase solution and the mixture thereof are directly sold or used as raw materials for preparing arsenic products and/or refined alkali; the obtained soda/caustic soda is used for refining antimony.
20. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 4, wherein the method comprises the following steps: the arsenate crystal and the soda crystal separated by cooling crystallization and/or freezing crystallization of the glycerol phase solution and the mixture thereof are directly sold or used as raw materials for preparing arsenic products and/or refined alkali; the obtained soda/caustic soda is used for refining antimony.
21. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 5, wherein the method comprises the following steps: the arsenate crystal and the soda crystal separated by cooling crystallization and/or freezing crystallization of the glycerol phase solution and the mixture thereof are directly sold or used as raw materials for preparing arsenic products and/or refined alkali; the obtained soda/caustic soda is used for refining antimony.
22. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 9, wherein: the arsenate crystal and the soda crystal separated by cooling crystallization and/or freezing crystallization of the glycerol phase solution and the mixture thereof are directly sold or used as raw materials for preparing arsenic products and/or refined alkali; the obtained soda/caustic soda is used for refining antimony.
23. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 1 or 2, wherein: the glycerol is partially or completely replaced by mannitol or xylitol.
24. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 3, wherein the method comprises the following steps: the glycerol is partially or completely replaced by mannitol or xylitol.
25. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 4, wherein the method comprises the following steps: the glycerol is partially or completely replaced by mannitol or xylitol.
26. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 5, wherein the method comprises the following steps: the glycerol is partially or completely replaced by mannitol or xylitol.
27. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 9, wherein: the glycerol is partially or completely replaced by mannitol or xylitol.
28. The method for extracting, separating and recycling the arsenic alkali residue as claimed in claim 18, wherein the method comprises the following steps: the glycerol is partially or completely replaced by mannitol or xylitol.
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