CN110195162B - Method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue - Google Patents
Method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue Download PDFInfo
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- CN110195162B CN110195162B CN201910603764.2A CN201910603764A CN110195162B CN 110195162 B CN110195162 B CN 110195162B CN 201910603764 A CN201910603764 A CN 201910603764A CN 110195162 B CN110195162 B CN 110195162B
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- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B30/02—Obtaining antimony
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
A method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue comprises the following steps: adding water, glycerol and caustic soda to the crushed and ground arsenic-soda residue or sending slurry obtained by grinding the arsenic-soda residue, the water, the glycerol and the caustic soda together into a leaching tank, controlling the pH value, leaching and extracting, and performing solid-liquid separation to obtain silicon-aluminum mineral residue and an alkali-glycerol aqueous solution; sequentially carrying out dearsenification, deleading, antimonic removal and purification precipitation treatment on the obtained alkali-glycerol aqueous solution to obtain arsenate crystals, lead slag, antimony oxide, phytate precipitates and glycerol soda aqueous solution; performing nanofiltration or reverse osmosis membrane chromatography on the obtained glycerol soda water solution to obtain nanofiltration concentrated solution and dialysate glycerol water solution; returning the obtained glycerol aqueous solution of the dialysate to leach arsenic alkali residue; spray drying the nanofiltration concentrated solution to prepare sodium carbonate or adding lime to causticize to prepare caustic soda; the obtained antimony oxide is used for returning antimony to be refined or processing antimony or refining antimony oxide and antimonate. The antimony, arsenic and alkali in the arsenic-alkali residue can be synchronously leached and separated, and the solvent can be recycled.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of environment-friendly waste resources, in particular to a resource utilization method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue.
Background
The arsenic alkali slag is a smelting waste slag which is generated in the antimony refining arsenic removal process of antimony pyrometallurgy and mainly contains sodium arsenate, sodium antimonate and sodium carbonate and contains a certain amount of aluminosilicate minerals, lead, bismuth and other compounds, and because the sodium arsenate and sodium arsenite are extremely toxic and easily soluble in water, the arsenic alkali slag is very easy to cause environmental pollution events, so that solid dangerous waste which is difficult to properly treat all the time is always generated, and 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: oxidizing the arsenic-alkali residue with hot water to dissolve the crushed or wet-milled arsenic-alkali residue, separating 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 6-water magnesium ammonium arsenate 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 an arsenic alkali slag reduction smelting treatment method, in which arsenic alkali slag and a carbonaceous reducing agent are mixed and then subjected to reduction smelting to obtain arsenic steam, crude antimony and reducing slag, and the arsenic steam is condensed to obtain a metal arsenic product; the main component of the reducing slag is Na2CO3, which can be directly used as a dearsenization agent to return to the antimony refining dearsenization process, and can also be used for obtaining Na2CO3 crystals through the water leaching-concentration-crystallization process.
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 is difficult, and the problems of environmental protection, economy and the like are prominent. The current domestic wet process is focused on hot water leaching or oxidation water leaching, and no report is found on the research or practice of separating arsenic alkali residue by glycerol aqueous solution leaching.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue, wherein the method can realize synchronous leaching and separation of antimony, arsenic and alkali in the arsenic-alkali residue, and a solvent can be recycled.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue comprises the following steps: adding water, glycerol and caustic soda to the crushed and ground arsenic-soda residue or sending slurry obtained by grinding the arsenic-soda residue, the water, the glycerol and the caustic soda together into a leaching tank, controlling the pH value, leaching and extracting, and performing solid-liquid separation to obtain silicon-aluminum mineral residue and an alkali-glycerol aqueous solution; the alkali-glycerol aqueous solution is a mixed solution containing a glycerol complex, caustic soda, arsenate and soda ash, and the obtained alkali-glycerol aqueous solution is sequentially subjected to dearsenization, deleading, antimony removal, purification and precipitation of divalent ions and heavy metal ions to obtain arsenate crystals, lead slag, antimony oxide, phytate precipitate and glycerol soda ash aqueous solution; carrying out nanofiltration and/or reverse osmosis membrane separation on the obtained glycerin soda water solution to obtain a concentrated solution and a dialysate glycerin water solution; returning the obtained glycerol aqueous solution of the dialysate to leach arsenic alkali residue; spray drying the obtained concentrated solution to obtain soda ash, or adding calcined magnesite or lime to causticize to obtain caustic soda; the obtained antimony oxide is used for returning antimony to be refined or processing antimony or refining antimony oxide and antimonate products.
Further, the mass ratio of the arsenic alkali residue to the water to the glycerol to the caustic soda is 1: 1-8: 0.5-5: 0.3-3.
Further, the control pH = 14. Caustic soda is consumed during leaching reaction, and when the residual quantity of the caustic soda is insufficient and the pH value is lower than 14, 10-30% of the caustic soda is supplemented in time to maintain the leaching capacity of antimony compounds and the stability of the glycerin antimony complex.
Further, the leaching extraction is carried out for 0.5 to 8 hours at the temperature of between 60 and 150 ℃ with stirring; the leaching extraction adopts single-stage leaching or multi-stage leaching or countercurrent leaching in a leaching tank. Fully extracting antimony, arsenic and soda ash in the arsenic-soda residue, or saturating antimony complex, arsenate and soda ash in the alkaline glycerol aqueous solution at the set leaching temperature.
Further, the screening mesh number of the crushed and ground arsenic-alkali residue is 160-800 meshes (preferably 200-400 meshes).
Further, the particle size of the slurry is <100 μm.
Further, the dearsenization is to cool, crystallize and separate the alkali glycerol aqueous solution to obtain arsenate crystals and the dearsenized alkali glycerol aqueous solution; the de-arsenic alkali-glycerol aqueous solution is a mixed solution of antimony-lead-bismuth-glycerol complex, caustic soda and soda ash.
Further, the deleading step comprises the steps of dropwise adding a sodium sulfide solution into the de-arsenized alkali glycerol aqueous solution to react to generate lead sulfide and bismuth sulfide precipitates, and separating the sulfide precipitates to obtain lead slag mainly containing a lead compound and the de-leaded alkali glycerol aqueous solution; the deleading alkali-glycerol aqueous solution is a mixed solution containing a glycerol-antimony complex, caustic soda and soda ash.
Further, the purification precipitation of the divalent ions and the heavy metal ions is carried out by dripping phytic acid into the glycerol aqueous solution after antimony removal at the temperature of 10-90 ℃, reacting all the divalent ions and the heavy metal ions in the precipitation solution, and separating to obtain phytate precipitate and glycerol soda water solution.
Further, the antimony removal is that carbon dioxide is introduced into an alkaline glycerol aqueous solution with lead removed at the temperature of 5-95 ℃, caustic soda is neutralized, the reaction is carried out until the pH value is reduced to 11.5-11.7, a glycerol antimony complex generated by the reaction is resolved and precipitated to obtain antimony oxide powder, and the antimony oxide and the antimony removed glycerol aqueous solution are separated;
further, the antimony removal is to add hydrochloric acid into the deleaded alkaline glycerol aqueous solution to neutralize the alkaline glycerol aqueous solution until the pH value is 6-7.8, and separate the alkaline glycerol aqueous solution to obtain an antimony oxide and a deintonised glycerol aqueous solution.
Furthermore, the glycerol can be partially or completely replaced by mannitol or xylitol; the caustic soda can be replaced by potassium hydroxide.
Further, the obtained silicon-aluminum mineral slag is detected as follows: mainly is an aluminosilicate mineral, the content of antimony is less than 1.0%, the content of arsenic is less than 0.1%, the content of lead is less than 1.0%, the content of soda is less than 2.0%, and the content of arsenic in a TCLP experiment detection solution is less than 5mg/L, is common solid waste and can be used as a raw material for building material production.
Further, the product arsenate, lead bismuth sulfide, antimony oxide, soda ash or salt separated after the alkaline glycerol aqueous solution leaching arsenic alkaline residue is synchronously leached can be directly sold, or used as a raw material for preparing antimony products, arsenic products, refined alkali or salt, and antimony oxide and soda ash or caustic soda can also be used.
The invention has the beneficial effects that:
(1) antimony (containing lead and bismuth) oxide and sodium antimonite can be dissolved in a glycerol aqueous solution of excessive caustic soda to form a glycerol complex, sodium arsenate, sodium arsenite, calcined soda and sodium bicarbonate can be directly dissolved in the glycerol aqueous solution under certain conditions, the caustic soda glycerol aqueous solution is used for directly leaching arsenic-alkali residue, antimony, lead, bismuth, arsenic and calcined soda in the arsenic-alkali residue are leached and separated, and antimony (containing lead and bismuth), arsenic and calcined soda in the alkaline residue can be completely separated in a multi-stage leaching mode;
(2) the method comprises the steps of preferentially separating arsenate arsenite crystals in a cooling crystallization arsenic removal mode by utilizing the fact that the solubility of arsenate in a caustic soda glycerin aqueous solution is increased along with the increase of temperature and is sensitive to the change of the solubility along with the temperature;
(3) the lead and bismuth glycerin complex in the aqueous solution of caustic soda glycerin can react with divalent sulfur ions (such as H)2S、Na2S) decomplexation under the interference to convert into insoluble lead sulfide and bismuth sulfide precipitates, and adding Na for the characteristic that antimony sulfide compounds are not generated under the action of strong alkali2S precipitation is carried out to separate accompanying lead and bismuth;
(4) by utilizing the fact that the complex structure of glycerin antimony complex is disintegrated under the condition of losing strong alkaline support of caustic soda, antimony ions are precipitated in the form of antimony oxide powder and CO2Conversion of NaOH in the neutralized solution to Na2CO3And controlling the pH value of the solution to be 11.5-11.7 to prevent the occurrence of alkali (NaHCO) precipitation3) The purity of the antimony oxide is influenced, the purification difficulty is increased, and the antimony is separated;
(5) the method utilizes the characteristic that phytic acid extracted from natural plants can quickly complex and precipitate all divalent metal ions and heavy metal ions, and removes all the divalent metal ions and heavy metal ions remaining in the glycerin soda water solution after leaching and separating lead, arsenic and antimony. And the glycerol aqueous solution and the concentrated sodium carbonate solution are obtained by nanofiltration and/or reverse osmosis membrane separation. Returning the glycerin water solution to the leaching arsenic alkali residue, and concentrating the pure alkali liquor (without arsenic, antimony and lead) to be used for refining the pure alkali product, or adding calcined magnesia or lime for causticization to produce caustic soda;
(6) the process is simple, the investment is less, the separation effect is good, the treatment capacity is large, and the dust-free operation and the secondary pollution can be easily realized;
(7) provides a brand new technical idea for the effective separation treatment of arsenic-alkali residue, and also provides raw materials which are convenient to utilize for the production of soda ash, caustic soda, arsenic products, antimony products and the like.
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
Arsenic alkaline residue of a certain antimony smelting plant is selected, and 9.73 percent of As, 26.18 percent of Sb, 5.79 percent of Pb and 22.76 percent of Na are detected; commercial industrial glycerin (content 98.5%), caustic soda (content 96% of caustic soda flakes NaOH), hydrochloric acid (content 35%), phytic acid (content 95%), liquefied carbon dioxide are used as raw materials, and tap water is used as water.
The embodiment comprises the following steps: grinding until the powder is 200 meshes, and feeding arsenic alkali residue powder with 3 percent of residue into a leaching tank, wherein the arsenic alkali residue powder comprises the following components in percentage by mass: water: glycerol: adding water, glycerol and caustic soda according to the proportion of caustic soda =1:3:2:0.73, controlling the pH value to be stable at 14, stirring and leaching at the normal pressure and the temperature of 85 ℃ for 3h, and separating to obtain silicon-aluminum mineral slag and an alkali-glycerol aqueous solution (a mixed solution containing a glycerol complex, caustic soda, arsenate and soda); cooling the alkali glycerol aqueous solution to 0 ℃ for crystallization, and separating to obtain arsenate crystals and an arsenic-removed alkali glycerol aqueous solution (a mixed solution of antimony-lead-bismuth glycerol complex, caustic soda and soda); then, dropwise adding a sodium sulfide solution into the dearsenized alkali glycerol aqueous solution at normal temperature to react to generate lead sulfide and bismuth sulfide precipitates, and separating to obtain lead slag and the deleadined alkali glycerol aqueous solution (a mixed solution containing a glycerin antimony complex, caustic soda and soda ash); introducing carbon dioxide gas into the deleading alkali glycerol aqueous solution at 30 ℃, neutralizing caustic soda, reacting until the pH value is reduced to 11.5-11.7, decomposing and precipitating an antimony complex, and separating to obtain an antimony compound and a delentiated glycerol aqueous solution; dropping proper amount of phytic acid into the water solution of the glycerol with antimony removed at 30 ℃, reacting all divalent ions and heavy metal ions in the precipitation solution, separating to obtain phytate precipitate, and performing microfiltration filtration to obtain the water solution of the glycerol and the soda; treating the glycerol soda water solution at 35 deg.C with nanofiltration membrane device, and performing membrane separation to obtain nanofiltration concentrate and dialysate glycerol water solution; returning the dialysate glycerin water solution to leach arsenic alkali residue; spray drying the nanofiltration concentrated solution to prepare a soda powder product.
And (3) detection: synchronously leaching the separated silicon-aluminum mineral slag: mainly comprising an aluminosilicate mineral, wherein the content of antimony is 0.89%, the content of arsenic is 0.08%, the content of lead is 0.23%, the content of soda ash is 0.87%, and the content of arsenic in a TCLP experiment detection solution is 0.37mg/L, and the aluminum silicate mineral is common solid waste.
The arsenic content in the antimony compound is 0.16 percent, and the sodium carbonate content is 1.14 percent; the content of antimony in the lead slag is 0.47%, the content of arsenic is 0.29%, and the content of sodium carbonate is 1.89%; the content of antimony in arsenate is 0.21%, and the content of sodium carbonate is 1.89%; the content of antimony in the soda ash is 0.0009 percent, and the content of arsenic in the soda ash is 0.0002 percent. The recovery rate of antimony is 98.79%, the recovery rate of lead is 98.63%, the recovery rate of arsenic is 99.55% and the recovery rate of soda is 96.87%. The result shows that the effect of leaching and separating antimony, lead, arsenic and alkali by using the alkali-glycerol aqueous solution is good, and harmful impurities in the separated and recovered antimony compound, arsenate, soda ash and lead slag are convenient to remove.
Example 2
Arsenic alkaline residue of a certain antimony smelting plant is selected, and detected by the arsenic alkaline residue, 11.26 percent of As, 24.35 percent of Sb, 2.77 percent of Pb and 24.12 percent of Na; commercial industrial glycerin (content 98.5%), caustic soda (content 96% of caustic soda flakes NaOH), hydrochloric acid (content 35%), phytic acid (content 95%), liquefied carbon dioxide are used as raw materials, and tap water is used as water.
The embodiment comprises the following steps: setting the leaching mass ratio of the arsenic alkali residue as arsenic alkali residue: water: glycerol: caustic soda =1: 3.5: 2.5: 0.95, grinding arsenic caustic sludge, water and glycerol together into slurry with the particle size of less than 74 μm according to the mass ratio of 1:2:1, feeding the slurry into a leaching tank, supplementing the water, the glycerol and the caustic soda, controlling the pH value to be stable at 14, stirring and leaching at the normal pressure and the temperature of 95 ℃ for 1.5h, and separating to obtain silicon-aluminum mineral slag and an alkali-glycerol aqueous solution; cooling the alkali glycerol aqueous solution to 8 ℃ for crystallization, and separating to obtain arsenate crystals and an arsenic-removed alkali glycerol aqueous solution; dropwise adding a sodium sulfide solution into the dearsenized alkali glycerol aqueous solution at normal temperature, carrying out analytical reaction on a lead bismuth complex to generate lead sulfide and bismuth sulfide precipitates, and separating to obtain lead slag and the dearsenized alkali glycerol aqueous solution; introducing carbon dioxide gas into the deleading alkali glycerol aqueous solution at 60 ℃, neutralizing caustic soda, reacting until the pH value is reduced to 11.5-11.7, resolving and precipitating a glycerol antimony complex, and separating to obtain an antimony compound and a delentized glycerol aqueous solution; dropping proper amount of phytic acid into the water solution of the glycerol with antimony removed at 40 ℃, reacting all divalent ions and heavy metal ions in the precipitation solution, separating to obtain phytate precipitate, and performing microfiltration filtration to obtain the water solution of the glycerol and the soda; separating glycerol soda water solution at 37 deg.C with reverse osmosis membrane device to obtain concentrated solution and dialysate glycerol water solution. Returning the dialysate glycerin water solution to leach arsenic alkali residue; the concentrated solution is made into caustic soda by adding lime according to a mature causticization process, and is used for synchronous leaching and separation of arsenic-alkali residue.
And (3) detection: synchronously leaching the separated silicon-aluminum mineral slag: mainly comprising an aluminosilicate mineral, wherein the content of antimony is 0.68%, the content of arsenic is 0.07%, the content of lead is 0.21%, the content of soda is 0.59%, and the content of arsenic in a TCLP experiment detection solution is 0.38mg/L, and the aluminum is common solid waste.
The arsenic content in the antimony compound is 0.19 percent, and the sodium carbonate content is 0.97 percent; the content of antimony in the lead slag is 0.61 percent, the content of arsenic is 0.27 percent, and the content of sodium carbonate is 1.73 percent; the content of antimony in arsenate is 0.29%, and the content of sodium carbonate is 2.11%; the content of antimony and arsenic in the caustic soda is 0.0008 and 0.0002 respectively. The recovery rate of antimony is 98.93%, the recovery rate of lead is 98.97%, the recovery rate of arsenic is 99.36% and the recovery rate of alkali is 98.61%. The result shows that the effect of leaching and separating antimony, lead, arsenic and alkali by using the alkali-glycerol aqueous solution is good, and harmful impurities in the separated and recovered antimony compound, arsenate, soda ash and lead slag are convenient to remove.
Example 3
Selecting arsenic alkaline residue from a certain antimony smelting plant, detecting 17.84% of As, 14.87% of Sb, 3.42% of Pb and 26.70% of Na; commercial industrial glycerin (content 98.5%), caustic soda (content 96% of caustic soda flakes NaOH), hydrochloric acid (content 35%), phytic acid (content 95%), liquefied carbon dioxide are used as raw materials, and tap water is used as water.
The embodiment comprises the following steps: setting the leaching mass ratio of the arsenic alkali residue as arsenic alkali residue: water: glycerol: caustic soda =1: 4: 2.5: 1.3, grinding arsenic caustic sludge, water and glycerol into slurry with the particle size of less than 74 μm according to the mass ratio of 1:2:1, feeding the slurry into a leaching tank, supplementing the water, the glycerol and the caustic soda, controlling the pH value to be stable at 14, stirring and leaching at the normal pressure and the temperature of 90 ℃ for 1.2h, and separating to obtain silicon-aluminum mineral slag and an alkali-glycerol aqueous solution; cooling the alkali glycerol aqueous solution to-2 ℃ for crystallization, and separating to obtain arsenate crystals and an arsenic-removed alkali glycerol aqueous solution; dropwise adding a sodium sulfide solution into the dearsenized alkali glycerol aqueous solution at normal temperature to react to generate lead sulfide and bismuth sulfide precipitates, and separating to obtain lead slag and the dearsenized alkali glycerol aqueous solution; introducing carbon dioxide gas into the deleading alkali glycerol aqueous solution at the temperature of 80 ℃, neutralizing caustic soda, reacting until the pH value is reduced to 11.5-11.7, decomposing and precipitating an antimony complex, and separating to obtain an antimony compound and a delentiated glycerol aqueous solution; dripping a small amount of phytic acid into the de-antimonized glycerin aqueous solution, reacting all divalent ions and heavy metal ions in the precipitation solution, separating to obtain phytate precipitate, and performing microfiltration filtration to obtain glycerin soda aqueous solution; separating the glycerol soda water solution at 38 deg.C with nanofiltration membrane device to obtain nanofiltration concentrated solution and dialysate glycerol water solution. Returning the dialysate glycerin water solution to leach arsenic alkali residue; spray drying the nanofiltration concentrated solution to prepare a soda powder product.
And (3) detection: synchronously leaching the separated silicon-aluminum mineral slag: mainly comprising an aluminosilicate mineral, wherein the content of antimony is 0.36%, the content of arsenic is 0.02%, the content of lead is 0.23%, the content of soda is 0.39%, and the content of arsenic in a TCLP experiment detection solution is 0.17mg/L, and the aluminum silicate mineral is common solid waste.
The arsenic content in the antimony compound is 0.09 percent, and the sodium carbonate content is 0.87 percent; the content of antimony in the lead slag is 0.69%, the content of arsenic is 0.24%, and the content of sodium carbonate is 1.47%; the content of antimony in arsenate is 0.18 percent, and the content of sodium carbonate is 0.89 percent; the content of antimony in the soda ash is 0.0008 percent, and the content of arsenic in the soda ash is 0.0001 percent. The recovery rate of antimony is 99.21%, the recovery rate of lead is 98.43%, the recovery rate of arsenic is 99.51%, and the recovery rate of soda is 93.87%. The result shows that the effect of separating antimony, lead, arsenic and alkali by leaching with the alkali glycerol aqueous solution is good.
Example 4
Selecting arsenic alkaline residue of a certain antimony smelting plant, and detecting 8.76% of As, 21.35% of Sb, 5.32% of Pb and 24.74% of Na; commercial industrial glycerin (content 98.5%), caustic soda (content 96% of caustic soda flakes NaOH), hydrochloric acid (content 35%), phytic acid (content 95%), liquefied carbon dioxide are used as raw materials, and tap water is used as water.
The embodiment comprises the following steps: crushing and grinding the arsenic-alkali residue until the residue is 12 percent of that of a 350-mesh sieve, equivalently feeding the arsenic-alkali residue powder into three leaching tanks, and setting the leaching mass ratio of the arsenic-alkali residue powder: water: glycerol: caustic soda =1:5:3:1.5, adopting three-stage leaching at the normal pressure and 87 ℃, stirring and leaching for 0.7h at the first stage, performing suction filtration and separation, transferring the alkaline glycerin aqueous solution into a second stage leaching tank, stirring and leaching for 0.7h, performing suction filtration and separation, transferring the alkaline glycerin aqueous solution into a third stage leaching tank, stirring and leaching for 0.7h, performing suction filtration and separation, and performing microfiltration filtration to obtain a saturated alkaline glycerin aqueous solution; after the solution is extracted and filtered out from the first-stage leaching tank, newly adding the same amount of new alkali glycerol aqueous solution for leaching for 0.7h, transferring the leaching solution into a second-stage leaching tank, transferring the leaching solution into a third-stage leaching tank after leaching for 0.7h, fully leaching arsenic alkali residue with an alkali glycerol aqueous solution, and separating to obtain silicon-aluminum mineral residue and a saturated alkali glycerol aqueous solution; cooling saturated alkali glycerol aqueous solution to 0 ℃ for crystallization, and separating to obtain arsenate crystals and dearsenified alkali glycerol aqueous solution; dropwise adding a sodium sulfide solution into the dearsenized alkali glycerol aqueous solution at normal temperature to react to generate lead sulfide and bismuth sulfide precipitates, and separating to obtain lead slag and the dearsenized alkali glycerol aqueous solution; adding hydrochloric acid into the deleaded alkaline glycerol aqueous solution at 30 ℃ to neutralize until the pH value is 6.5, resolving the glycerol antimony complex into antimony oxide powder precipitate, and separating to obtain the antimony oxide and the deintonated glycerol aqueous solution. Then, a small amount of phytic acid is dripped into the glycerol aqueous solution for reaction, all divalent ions and heavy metal ions in the solution are precipitated, and the solution is subjected to microfiltration, filtration and separation to obtain phytate precipitate and the glycerol aqueous solution; separating the glycerol salt water solution with nanofiltration membrane at 37 deg.C to obtain nanofiltration concentrate and dialysate glycerol water solution; returning the glycerin water solution of the dialyzate to soak and dissolve the arsenic-alkali residue, and spray-drying the nanofiltration concentrate to prepare a sodium chloride powder finished product.
And (3) detection: synchronously leaching the separated silicon-aluminum mineral slag: mainly comprising an aluminosilicate mineral, wherein the content of antimony is 0.24%, the content of arsenic is 0.01%, the content of lead is 0.19%, the content of soda is 0.13%, and the content of arsenic in a TCLP experiment detection solution is 0.04mg/L, and the aluminum is common solid waste.
The arsenic content in antimony oxidized grain is 0.01%, and the sodium carbonate content is 0.84%; the content of antimony in the lead slag is 0.49%, the content of arsenic is 0.17%, and the content of sodium carbonate is 1.32%; the content of antimony in arsenate is 0.14%, and the content of sodium carbonate is 1.07%; the sodium chloride contains 0.0005% of antimony and 0.0001% of arsenic. The recovery rate of antimony is 99.6%, the recovery rate of lead is 98.79%, the recovery rate of arsenic is 99.71%, and the recovery rate of soda is 0% (all soda is converted into sodium chloride). The result shows that the effect of separating antimony, lead, arsenic and alkali by leaching with the alkali glycerol aqueous solution is good.
Example 5
Arsenic alkaline residue of a certain antimony smelting plant is selected, and 11.32% of As, 19.72% of Sb, 2.57% of Pb and 26.83% of Na are detected; commercial industrial glycerin (content 98.5%), caustic soda (content 96% of caustic soda flakes NaOH), hydrochloric acid (content 35%), phytic acid (content 95%), liquefied carbon dioxide are used as raw materials, and tap water is used as water.
The embodiment comprises the following steps: setting the leaching mass ratio in the first-stage leaching tank as arsenic-alkali residue: water: glycerol: caustic soda =1:3:2: 1, and three-stage leaching is adopted at the normal pressure and the temperature of 87 ℃. Firstly, grinding arsenic caustic sludge, water and glycerol together into slurry with the particle size of less than 80 mu m according to the mass ratio of 1:2:0.5, equivalently feeding the arsenic caustic sludge slurry into three leaching tanks, supplementing the water, the glycerol and the caustic soda in a first-stage leaching tank, controlling the pH value to be stable at 14, stirring and leaching for 1.2h in the first-stage leaching tank, performing suction filtration and separation, transferring an alkali glycerol aqueous solution into a second-stage leaching tank, stirring and leaching for 1.2h, performing suction filtration and separation, transferring an alkali glycerol aqueous solution into a third-stage leaching tank, stirring and leaching for 1.2h, performing suction filtration and separation, and performing microfiltration filtration to obtain a saturated alkali glycerol aqueous solution; after the solution is pumped and filtered out from the first stage leaching tank, newly adding the same amount of new alkali glycerol aqueous solution for leaching for 1.2h, transferring the leaching solution into a second stage leaching tank, transferring the leaching solution into a third stage leaching tank after 1.2h of leaching, fully leaching arsenic alkali residue with alkali glycerol aqueous solution, and separating to obtain silicon-aluminum mineral residue and saturated alkali glycerol aqueous solution; cooling saturated alkali glycerol aqueous solution to 0 ℃ for crystallization, and separating to obtain arsenate crystals and dearsenified alkali glycerol aqueous solution; dropwise adding a sodium sulfide solution into the dearsenized alkali glycerol aqueous solution at normal temperature to react to generate lead sulfide and bismuth sulfide precipitates, and separating to obtain lead slag and the dearsenized alkali glycerol aqueous solution; introducing carbon dioxide gas into the deleaded alkali glycerol aqueous solution at 35 ℃, neutralizing caustic soda, reacting until the pH value is reduced to 11.5-11.7, decomposing and precipitating an antimony complex, and separating to obtain an antimony oxide and a deintonated glycerol aqueous solution; dropping proper amount of phytic acid into the antimonous glycerol aqueous solution at 35 ℃, reacting all divalent ions and heavy metal ions in the precipitation solution, separating to obtain phytate precipitate, and performing microfiltration filtration to obtain glycerol soda aqueous solution; separating the glycerol soda water solution at 35 deg.C by nanofiltration membrane device to obtain nanofiltration concentrated solution and dialysate glycerol water solution. Returning the dialysate glycerin water solution to leach arsenic alkali residue; spray drying the nanofiltration concentrated solution to prepare a soda powder product.
And (3) detection: synchronously leaching the separated silicon-aluminum mineral slag: mainly comprising alumino-silicate mineral, 0.072 percent of antimony, 0.008 percent of arsenic, 0.194 percent of lead and 0.874 percent of soda ash, wherein the TCLP experiment detects that the arsenic content in the solution is 0.05mg/L, and the solution is common solid waste.
The arsenic content in the antimony compound is 0.11 percent, and the sodium carbonate content is 1.03 percent; the content of antimony in the lead slag is 0.37 percent, the content of arsenic is 0.17 percent, and the content of sodium carbonate is 1.49 percent; the content of antimony in arsenate is 0.26 percent, and the content of sodium carbonate is 1.81 percent; the content of antimony in the soda ash is 0.0009 percent, and the content of arsenic in the soda ash is 0.0001 percent. The recovery rate of antimony is 99.4%, the recovery rate of lead is 98.63%, the recovery rate of arsenic is 99.7% and the recovery rate of soda is 96.87%. The result shows that the effect of separating antimony, lead, arsenic and alkali by leaching with the alkali glycerol aqueous solution is good.
Claims (9)
1. A method for synchronously leaching and separating antimony, arsenic and alkali in arsenic-alkali residue is characterized by comprising the following steps: adding water, glycerol and caustic soda to the crushed and ground arsenic-soda residue or sending slurry obtained by grinding the arsenic-soda residue, the water, the glycerol and the caustic soda together into a leaching tank, controlling the pH value, leaching and extracting, and performing solid-liquid separation to obtain silicon-aluminum mineral residue and an alkali-glycerol aqueous solution; the alkali-glycerol aqueous solution is a mixed solution containing a glycerol complex, caustic soda, arsenate and soda ash, and the obtained alkali-glycerol aqueous solution is sequentially subjected to dearsenization, deleading, antimony removal, purification and precipitation of divalent ions and heavy metal ions to obtain arsenate crystals, lead slag, antimony oxide, phytate precipitate and purified glycerol soda ash aqueous solution; sending the obtained glycerin soda water solution to nanofiltration membrane chromatography or reverse osmosis membrane chromatography to obtain concentrated solution and dialysate glycerin water solution; returning the obtained glycerol aqueous solution of the dialysate to leach arsenic alkali residue; spray drying the obtained concentrated solution to obtain soda ash, or adding calcined magnesite or lime to causticize to obtain caustic soda; the obtained antimony oxide is used for returning antimony to be refined or processing antimony or refining antimony oxide and antimonate products; and (3) the precipitation of the divalent ions and the heavy metal ions is carried out at the temperature of 10-50 ℃, phytic acid is dripped into the glycerol aqueous solution subjected to antimony removal, all the divalent ions and the heavy metal ions in the precipitation solution are reacted, and separation is carried out to obtain phytate precipitate and glycerol soda aqueous solution.
2. The method for synchronously leaching and separating antimony, arsenic and alkali from arsenic alkali residue as claimed in claim 1, wherein the mass ratio of the arsenic alkali residue, water, glycerol and caustic soda is 1: 1-8: 0.5-5: 0.3-3.
3. The method for synchronously leaching and separating antimony, arsenic and alkali in the arsenic alkali residue as claimed in claim 1 or 2, wherein the pH is controlled to be = 14.
4. The method for synchronously leaching and separating antimony, arsenic and alkali in the arsenic alkali residue as claimed in claim 1 or 2, wherein the leaching extraction is carried out at 60-150 ℃ for 0.5-8 h by stirring; the leaching extraction adopts single-stage leaching or multi-stage leaching or countercurrent leaching in a leaching tank.
5. The method for synchronously leaching and separating antimony, arsenic and alkali in the arsenic-alkali residue as claimed in claim 1 or 2, wherein the arsenic removal is to cool and crystallize the alkali-glycerin aqueous solution, and separate to obtain arsenate crystals and an arsenic-removed alkali-glycerin aqueous solution; the de-arsenic alkali-glycerol aqueous solution is a mixed solution of antimony-lead-bismuth-glycerol complex, caustic soda and soda ash.
6. The method for synchronously leaching and separating antimony, arsenic and alkali in the arsenic alkali residue as claimed in claim 1 or 2, wherein the deleading comprises the steps of dropwise adding a sodium sulfide solution into an arsenic-removed alkali glycerol aqueous solution to react to generate lead sulfide and bismuth sulfide precipitates, and separating the sulfide precipitates to obtain lead residue mainly containing lead compounds and a deleaded alkali glycerol aqueous solution; the deleading alkali-glycerol aqueous solution is a mixed solution containing a glycerol-antimony complex, caustic soda and soda ash.
7. The method for synchronously leaching and separating antimony, arsenic and alkali from the arsenic alkali residue as claimed in claim 1 or 2, wherein the antimony removal is carried out by introducing carbon dioxide into an alkaline glycerol aqueous solution with lead removed at 5-95 ℃, neutralizing caustic soda, reacting until the pH value is reduced to 11.5-11.7, resolving and precipitating antimony oxide powder from a glycerol antimony complex generated by the reaction, and separating to obtain an antimony oxide and antimony removed glycerol aqueous solution.
8. The method for synchronously leaching and separating antimony, arsenic and alkali in the arsenic alkali residue as claimed in claim 1 or 2, wherein the antimony removal is to add hydrochloric acid into a lead-removed alkali glycerol aqueous solution to neutralize the solution until the pH value is 6-7.8, and separate the solution to obtain antimony oxide and a antimony-removed glycerol aqueous solution.
9. The method for synchronously leaching and separating antimony, arsenic and alkali in the arsenic alkali residue as claimed in claim 1 or 2, wherein the glycerol is partially or completely replaced by mannitol or xylitol; the caustic soda is replaced by potassium hydroxide.
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