CN110512095A - A method of arsenic is extracted and stablized from tungsten metallurgy phosphorus and arsenic slag - Google Patents

A method of arsenic is extracted and stablized from tungsten metallurgy phosphorus and arsenic slag Download PDF

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CN110512095A
CN110512095A CN201910775292.9A CN201910775292A CN110512095A CN 110512095 A CN110512095 A CN 110512095A CN 201910775292 A CN201910775292 A CN 201910775292A CN 110512095 A CN110512095 A CN 110512095A
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arsenic
slag
phosphorus
tungsten
metallurgy
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CN110512095B (en
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黄少波
李立
余侃萍
张永伟
史明
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Changsha Research Institute of Mining and Metallurgy Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/11Removing sulfur, phosphorus or arsenic other than by roasting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00Obtaining antimony, arsenic or bismuth
    • C22B30/04Obtaining arsenic
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • C22B7/008Wet processes by an alkaline or ammoniacal leaching
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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Abstract

The method that the invention discloses a kind of to extract from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, comprising the following steps: (1) by tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction, obtain phosphorus and arsenic slag calcium compound mixing slag;(2) the resulting phosphorus and arsenic slag calcium compound mixing slag of step (1) is placed in progress Selectively leaching arsenic in alkaline aqueous solution, is then separated by solid-liquid separation and obtains dearsenification slag and arsenic leachate;(3) lime is added into the resulting arsenic leachate of step (2) and molysite precipitates arsenic, be then separated by solid-liquid separation and obtain the stable slag of arsenic and dearsenification water.The stability that arsenic obtained by this method stablizes slag is good, simple process, at low cost, is able to achieve the Selective Separation of arsenic, content of the arsenic in solid slag is greatly reduced, reduce dangerous solid waste total amount, reduce dangerous fixed-end forces cost and potential environmental hazard.

Description

A method of arsenic is extracted and stablized from tungsten metallurgy phosphorus and arsenic slag
Technical field
The present invention relates to dangerous fixed-end forces and Extraction metallurgy technical field, in particular to one kind from tungsten metallurgy phosphorus The method that arsenic is extracted and stablized in arsenic slag.
Background technique
China is tungsten resource big country, and annual tungsten ore yield and tungsten metallurgic product yield occupy first place in the world, in recent years I State's tungsten metallurgic product yield substantially remains in 100,000 tons or so.With depleted, the low-grade difficulty of high-grade tungsten mineral resource Smelting tungsten mineral and secondary tungsten resource (hard alloy scraps, dead catalyst) are largely used by tungsten metallurgical industry, these tungsten resources it is miscellaneous Matter content is higher, and the impurity based on harmful element P, As, which causes to smelt in separation process, produces a large amount of phosphorus and arsenic slag.Currently, Nearly 1,000,000 tons of Tungsten smelting slag of China's stockpiling.
In general, every production 1 ton of ammonium paratungstate (APT), the about phosphorus and arsenic slag of output 150kg or so.New tungsten some in recent years Mine clean manufacturing extract technology steps into practice, although these technique waste water yield are small, impurity leaching rate is high, after The phosphorus and arsenic slag yield that continuous purification process generates is more and more.The form that is primarily present of As is Mg in phosphorus and arsenic slag3(AsO4)2、Ca3 (AsO4)2Deng being included in national dangerous waste register, improper conduct oneself well is set, and there are great environmental pollution damages, but is also had simultaneously Biggish synthetical recovery value.The WO of typical phosphorus arsenic separation slag3Content is containing for≤3%, As in 18-50% or so, the content of P Therefore amount≤1% needs to take into account recycling under the premise of carrying out innoxious safe handling for this kind of solid waste of phosphorus and arsenic slag and returns It receives, is only the effective measures for meeting current green, environmental protection, sustainable development theory.
Currently, the treatment process of Tungsten smelting phosphorus and arsenic slag has " roasting-alkaline-heating method ", " sour molten-extraction ", " Ore Leaching-hydrogen-oxygen The change iron method of purification ", " the alkali leaching-magnesium salts method of purification ", " alkali leaching-lime purification method ", " being incorporated white tungsten alkali lixiviation process " etc..These Common problem existing for technique are as follows: 1) be to be primarily directed toward to extract valuable metal tungsten, arsenic does not obtain stable curing;2) technique is multiple Miscellaneous, consumption of raw materials is big.Therefore, for the processing of Tungsten smelting phosphorus and arsenic slag, recycling and the stablizing for As that take into account W resource are innoxious, It needs to develop and adapts to As processing disposing technique steady in a long-term.
Summary of the invention
The method that the main purpose of the present invention is to provide a kind of to extract from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, to solve Existing tungsten metallurgy phosphorus and arsenic slag processing method arsenic stability is poor, complex process, problem at high cost.This method is able to achieve the choosing of arsenic The separation of selecting property, is greatly reduced content of the arsenic in solid slag, reduces dangerous solid waste total amount, reduce dangerous fixed-end forces cost and Potential environmental hazard.
To achieve the goals above, the method that the present invention provides a kind of extracted from tungsten metallurgy phosphorus and arsenic slag and stablized arsenic, The following steps are included:
(1) by tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction, phosphorus and arsenic slag calcium compound mixing slag is obtained;
(2) the resulting phosphorus and arsenic slag calcium compound mixing slag of step (1) is placed in alkaline aqueous solution and carries out Selectively leaching Then arsenic is separated by solid-liquid separation and obtains dearsenification slag and arsenic leachate;
(3) lime is added into the resulting arsenic leachate of step (2) and molysite precipitates arsenic, be then separated by solid-liquid separation Stablize slag and dearsenification water to arsenic.
For the present invention first by tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction, tungsten metallurgy phosphorus and arsenic slag is mainly MgWO4、Mg3 (AsO4)2And Mg3(PO4)2;Due to MgWO4Solubility product be Ksp=10-3.1, CaWO4Solubility product be Ksp=10-10, tungsten metallurgy MgWO in phosphorus and arsenic slag4The CaWO of more indissoluble can be generated by mixing calcium compound reaction4;Due to Mg3(PO4)2Solubility product be Ksp=10-24, Ca3(PO4)2Solubility product be Ksp=10-29, Mg in tungsten metallurgy phosphorus and arsenic slag3(PO4)2Also it can pass through calcium mixture Compound reaction generates the Ca of more indissoluble3(PO4)2;And Mg3(AsO4)2And Ca3(AsO4)2Solubility product be Ksp=10-19, molten Degree product quite, does not mutually convert;It is the CaWO of slightly solubility by W, P preferential conversion in tungsten metallurgy phosphorus and arsenic slag4And Ca3(PO4)2, Retain more readily soluble Mg3(AsO4)2;Then mixing slag is subjected to Selectively leaching to arsenic in alkaline aqueous solution, then divided to solid-liquid Arsenic is precipitated from lime and molysite are added in rear resulting arsenic leachate, using molysite and lime by solubilised state in solution Arsenic is converted into the mineral such as stable calcium arsenate, ferric arsenate, and the adsorptivity of the ferric hydroxide colloid substance formed using molysite will Arsenic is fixed in slag, and the arsenic that ambient stable is obtained after separation of solid and liquid stablizes slag;To realize As and W, P in tungsten metallurgy phosphorus and arsenic slag Separation and arsenic stable curing.
By means of the present invention, it can reduce by 50% or more high arsenic slag (As content > 0.05%) total amount, and then save 1/ 2 or more dangerous fixed-end forces cost, the content for separating As in W, P mixing slag of As are reduced to < 0.05%, significantly reduce The latency environment of high arsenic slag endangers.
Further, in step (1), tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction are specifically referred to: by tungsten metallurgy Phosphorus and arsenic slag and calcium compound carry out wet ball grinding.The ingredient in tungsten metallurgy phosphorus and arsenic slag can be made to fill with calcium compound by wet ball grinding Divide haptoreaction.
Further, calcium compound is one in calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium oxide and calcium hydroxide Kind is a variety of.Further preferably, calcium chloride or calcium nitrate.
Further, the additive amount of calcium compound be by tungsten metallurgy phosphorus and arsenic slag tungsten and phosphorus be converted into artificial schellite and phosphoric acid 1.0-3.0 times of calcium theory demands calcium compound amount.Further preferably, 1.2-1.6 times.If the additive amount mistake of calcium compound Greatly, then arsenic can also be converted into calcium arsenate etc., and causing subsequent low alkalinity to decompose arsenic cannot achieve, and influence subsequent selective and decompose arsenic; It is artificial schellite mineral that tungsten can not be converted well if crossing less, and tungsten and arsenic enter solution together in subsequent decomposition, and decomposition does not have Selectivity.
Further, in step (2), alkaline aqueous solution is sodium hydrate aqueous solution, potassium hydroxide aqueous solution or hydroxide Lithium aqueous solution.Preferably sodium hydrate aqueous solution.
Further, in step (2), the pH value of alkaline aqueous solution is 8-11.Further preferably 9-10.5.The dipped journey of alkali In, the pH of alkaline aqueous solution cannot it is excessively high can not be too low, tungsten mineral can dissolve if too high or too low.The present invention is by alkali Dipped journey neutral and alkali aqueous solution pH value control within the above range, inhibit the dissolution of tungsten mineral well, improve tungsten and The separating effect of arsenic.
Further, in step (2), the temperature of Selectively leaching arsenic is 0-200 DEG C.Further preferably 20-160 DEG C. During alkaline leaching, it may cause tungsten mineral if temperature is excessively high and dissolve on a small quantity, valuable metal is caused to lose, if temperature mistake The reaction power rate of low then Selectively leaching arsenic is too low.
Further, in step (3), molysite is ferric sulfate, iron chloride, ferric nitrate, ferrous sulfate, frerrous chloride and nitric acid One of ferrous iron is a variety of, further preferably ferrous sulfate or frerrous chloride;When in molysite include ferrous sulfate, protochloride When iron or ferrous nitrate, oxidant is added into arsenic leachate or blasts air, oxygen carries out oxidation processes.
Further, in step (3), the additional amount of molysite is Fe:As molar ratio (1.0-5.0) in arsenic leachate: 1, into One step is preferably 1.5-3.0;The additional amount of lime is Ca:As molar ratio (1.0-8.0) in arsenic leachate: 1, further preferably 2.0-5.0。
Further, tungsten metallurgy phosphorus and arsenic slag specifically refers to: tungsten hydrometallurgy acid extract and weakbase ion exchange production In technique, using precipitation slag caused by magnesium salts deposition removal phosphorus, arsenic before transition purifies;In tungsten metallurgy phosphorus and arsenic slag, phosphorus, arsenic and Tungsten mainly exists in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively.
Compared with prior art, the beneficial effects of the present invention are:
First by tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction, W, P in tungsten metallurgy phosphorus and arsenic slag are preferentially turned by the present invention Turn to the CaWO of slightly solubility4And Ca3(PO4)2, retain more readily soluble Mg3(AsO4)2;Then by mixing slag in alkaline aqueous solution Selectively leaching is carried out to arsenic, then addition lime and molysite precipitate arsenic into arsenic leachate, and ring is obtained after separation of solid and liquid The stable arsenic in border stablizes slag;To realize As and the separation of W, P and the stable curing of arsenic in tungsten metallurgy phosphorus and arsenic slag.Pass through this The method of invention can reduce by 50% or more high arsenic slag (As content > 0.05%) total amount, and then the danger of 1/2 or more saving is solid Useless processing cost, the content for separating As in W, P mixing slag of As are reduced to < 0.05%, significantly reduce the potential of high arsenic slag Environmental hazard.
Detailed description of the invention
Fig. 1 is the process flow chart for the method that the present invention extracted from tungsten metallurgy phosphorus and arsenic slag and stablized arsenic.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment, But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of method that arsenic is extracted and stablized in the slave tungsten metallurgy phosphorus and arsenic slag of the embodiment of the present invention.Handled by the present embodiment Tungsten metallurgy phosphorus and arsenic slag are as follows: P, As in acid extract strip liquor (ammonium tungstate solution) in certain tungsten hydrometallurgy ammonium paratungstate production technique Content is higher, takes the impurity such as the removing of magnesium chloride sedimentation method P, As, and then the phosphorus arsenic purification slag generated.The tungsten metallurgy phosphorus and arsenic slag In, phosphorus, arsenic and tungsten mainly exist in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, main chemical compositions WO3 12.50%, P 0.92%, As 0.89%, Mg 16.02%, Fe 0.91%, Ca 1.50%, H2(the quality percentage of O 46% Than), the environmental hazard of the phosphorus and arsenic slag is larger, and the leaching rate of tap water at normal temperature As, W is up to 50% or more.
The process flow chart of this method as shown in Figure 1, specifically includes the following steps:
First by phosphorus and arsenic slag 5000g and 560g CaCl2Ball mill is added and carries out the mixing of room temperature wet ball grinding, incorporation time For 3h;
Then gained mixture slag is put into 50L NaOH aqueous solution and carries out selective alkaline leaching reaction, led in reaction The additional amount for crossing NaOH adjusts endpoint pH within the scope of 10-10.5, is stirred to react 2h at 80 DEG C;After being separated by solid-liquid separation and washing Arsenic leachate 55L and dearsenification slag, leaching rate >=96% of arsenic, leaching rate≤5% of tungsten;
FeSO is added into the arsenic leachate4·7H2O 190g is simultaneously passed through air stirring reaction 2h;Add into arsenic leachate Enter quick lime CaO 100g, reacts 1h;Be separated by solid-liquid separation dearsenification solution 50L and arsenic stablize slag 1496g.
Dearsenification slag to above-mentioned resulting low arsenic and the arsenic through lime, the high arsenic of molysite deposition are stablized slag and are dried respectively Dehydration, then respectively carry out toxicity leach analysis, the results show that in dearsenification slag the content of As be reduced to 0.05% hereinafter, The toxicity leaching concentration of As is below the limit value of 5mg/L in two kinds of slags.
Embodiment 2:
A kind of method that arsenic is extracted and stablized in the slave tungsten metallurgy phosphorus and arsenic slag of the embodiment of the present invention.Handled by the present embodiment Tungsten metallurgy phosphorus and arsenic slag are as follows: the phosphorus arsenic magnesium salts purification slag generated in certain Tungsten smelting enterprise hydrometallurgy ammonium paratungstate production technique, it should In tungsten metallurgy phosphorus and arsenic slag, phosphorus, arsenic and tungsten mainly exist in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, primary chemical Ingredient is WO31.50%, P1.03%, As 0.45%, Mg 13.01%, Fe 0.89%, Ca 1.46%, H2O 43%.It should The environmental hazard of phosphorus and arsenic slag is larger, and the leaching rate of tap water at normal temperature As, W is up to 60% or more, it is necessary to carry out at stable curing Reason.
The process flow chart of this method as shown in Figure 1, specifically includes the following steps:
First by phosphorus and arsenic slag 5000g and 100g CaCl2Carry out ball mill room temperature wet-mixing, incorporation time 2.5h;
Then the mixture slag is put into 60L NaOH aqueous solution, terminal pH is adjusted by the additional amount of NaOH in reaction Value is stirred to react 1h at 95 DEG C within the scope of 10-10.5;As leachate 62L is obtained after being separated by solid-liquid separation and washing;
FeSO is added into the leachate4·7H2O 140g is simultaneously passed through air stirring reaction 2h;Life is added into leachate Lime CaO 100g reacts 1h;Be separated by solid-liquid separation de- As solution 50L and arsenic slag 1530g, leaching rate >=93% of arsenic, tungsten Leaching rate≤7%.
To the above-mentioned resulting low arsenic slag for being stripped of As and processing is dried and dehydrated in the high arsenic slag through lime molysite deposition It carries out toxicity and leaches analysis, wherein the leaching concentration of As is in the limit value of 5mg/L hereinafter, the content of As is reduced in low arsenic slag 0.05% or less.
Comparative example 1:
Tungsten metallurgy phosphorus and arsenic slag handled by this comparative example are as follows: and the identical tungsten metallurgy phosphorus and arsenic slag of embodiment 1.The tungsten smelting In golden phosphorus and arsenic slag, phosphorus, arsenic and tungsten mainly exist in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, main chemical compositions For WO312.50%, P 0.92%, As 0.89%, Mg 16.02%, Fe 0.91%, Ca 1.50%, H246% (quality of O Percentage), the environmental hazard of the phosphorus and arsenic slag is larger, and the leaching rate of tap water at normal temperature As, W is up to 50% or more.
This method is implemented according to the following steps:
First by phosphorus and arsenic slag 5000g and 120g CaCl2Ball mill is added and carries out the mixing of room temperature wet ball grinding, incorporation time For 3h;
Then gained mixture slag is put into 50L NaOH aqueous solution and carries out selective alkaline leaching reaction, led in reaction The additional amount for crossing NaOH adjusts endpoint pH within the scope of 10-10.5, is stirred to react 2h at 80 DEG C;After being separated by solid-liquid separation and washing Arsenic leachate 55L and dearsenification slag.The leaching rate about 57% the result shows that arsenic, the leaching rate of tungsten about 32% are analyzed, low alkalinity leaches Process choosing is not strong, and relatively large leaching occurs simultaneously for tungsten and arsenic.
Comparative example 2:
Tungsten metallurgy phosphorus and arsenic slag handled by this comparative example are as follows: and the identical tungsten metallurgy phosphorus and arsenic slag of embodiment 1.The tungsten smelting In golden phosphorus and arsenic slag, phosphorus, arsenic and tungsten mainly exist in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, main chemical compositions For WO312.50%, P 0.92%, As 0.89%, Mg 16.02%, Fe 0.91%, Ca 1.50%, H246% (quality of O Percentage), the environmental hazard of the phosphorus and arsenic slag is larger, and the leaching rate of tap water at normal temperature As, W is up to 50% or more.
This method is implemented according to the following steps:
First by phosphorus and arsenic slag 5000g and 890g CaCl2Ball mill is added and carries out the mixing of room temperature wet ball grinding, incorporation time For 3h;
Then gained mixture slag is put into 50L NaOH aqueous solution and carries out selective alkaline leaching reaction, led in reaction The additional amount for crossing NaOH adjusts endpoint pH within the scope of 10-10.5, is stirred to react 2h at 80 DEG C;After being separated by solid-liquid separation and washing Arsenic leachate 55L and dearsenification slag.The leaching rate about 16% the result shows that arsenic is analyzed, leaching rate < 2% of tungsten, low alkalinity leached Journey selectivity is not strong, and there is no selective decomposition for arsenic.
Comparative example 3:
Tungsten metallurgy phosphorus and arsenic slag handled by this comparative example are as follows: and the identical tungsten metallurgy phosphorus and arsenic slag of embodiment 1.The tungsten smelting In golden phosphorus and arsenic slag, phosphorus, arsenic and tungsten mainly exist in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, main chemical compositions For WO312.50%, P 0.92%, As 0.89%, Mg 16.02%, Fe 0.91%, Ca 1.50%, H246% (quality of O Percentage), the environmental hazard of the phosphorus and arsenic slag is larger, and the leaching rate of tap water at normal temperature As, W is up to 50% or more.
This method is implemented according to the following steps:
First by phosphorus and arsenic slag 5000g and 500g CaCl2Ball mill is added and carries out the mixing of room temperature wet ball grinding, incorporation time For 3h;
Then gained mixture slag is put into 50L NaOH aqueous solution and carries out selective alkaline leaching reaction, led in reaction It is to be stirred to react 2h at 11.5 or so, 80 DEG C that the additional amount for crossing NaOH, which adjusts endpoint pH,;Arsenic leaching is obtained after being separated by solid-liquid separation and washing Liquid 55L and dearsenification slag out.Analyze the leaching rate about 5% the result shows that arsenic, leaching rate < 3% of tungsten, it is difficult to which effective selectivity is decomposed Arsenic.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of method extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which comprises the following steps:
(1) by tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction, phosphorus and arsenic slag calcium compound mixing slag is obtained;
(2) the resulting phosphorus and arsenic slag calcium compound mixing slag of step (1) is placed in progress Selectively leaching arsenic in alkaline aqueous solution, so It is separated by solid-liquid separation afterwards and obtains dearsenification slag and arsenic leachate;
(3) lime is added into the resulting arsenic leachate of step (2) and molysite precipitates arsenic, be then separated by solid-liquid separation and obtain arsenic Stablize slag and dearsenification water.
2. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the step Suddenly in (1), tungsten metallurgy phosphorus and arsenic slag and calcium compound hybrid reaction are specifically referred to: tungsten metallurgy phosphorus and arsenic slag and calcium compound are carried out Wet ball grinding.
3. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the calcium Compound is one of calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium oxide and calcium hydroxide or a variety of.
4. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the calcium The additive amount of compound be by tungsten metallurgy phosphorus and arsenic slag tungsten and phosphorus be converted into artificial schellite and calcium phosphate theory demands calcium compound 1.0-3.0 times of amount.
5. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the step Suddenly in (2), alkaline aqueous solution is sodium hydrate aqueous solution, potassium hydroxide aqueous solution or lithium hydroxide aqueous solution.
6. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the step Suddenly in (2), the pH value of alkaline aqueous solution is 8-11.
7. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the step Suddenly in (2), the temperature of Selectively leaching arsenic is 0-200 DEG C.
8. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the step Suddenly in (3), molysite is one of ferric sulfate, iron chloride, ferric nitrate, ferrous sulfate, frerrous chloride and ferrous nitrate or a variety of; When in molysite including ferrous sulfate, frerrous chloride or ferrous nitrate, oxidant is added into arsenic leachate or blasts air, oxygen Gas carries out oxidation processes.
9. the method according to claim 1 extracted from tungsten metallurgy phosphorus and arsenic slag and stablize arsenic, which is characterized in that the step Suddenly in (3), the additional amount of molysite is Fe:As molar ratio (1.0-5.0) in arsenic leachate: 1, the additional amount of lime in arsenic leachate For Ca:As molar ratio (1.0-8.0): 1.
10. the method for extracting and stablizing arsenic in slave tungsten metallurgy phosphorus and arsenic slag described in any one of -9 according to claim 1, special Sign is that the tungsten metallurgy phosphorus and arsenic slag specifically refers to: in tungsten hydrometallurgy acid extract and weakbase ion exchange production technology, Using precipitation slag caused by magnesium salts deposition removal phosphorus, arsenic before transition purifies;In the tungsten metallurgy phosphorus and arsenic slag, phosphorus, arsenic and tungsten Mainly exist in the form of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057881A (en) * 2019-12-31 2020-04-24 荆门德威格林美钨资源循环利用有限公司 Method for recovering tungsten from purification slag
CN111286619A (en) * 2020-02-03 2020-06-16 袁桐 Recycling device of tungsten smelting waste residues
CN115925080A (en) * 2022-11-23 2023-04-07 江西理工大学 Treatment method of tungsten smelting wastewater
CN117772763A (en) * 2024-02-27 2024-03-29 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) Method for separating and recovering arsenic, phosphorus and aluminum from vanadium-phosphorus-containing arsenic slag

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199708A (en) * 2011-05-18 2011-09-28 南昌航空大学 Method for treating arsenic-alkali residue generated in antimony smelting
CN102634672A (en) * 2012-04-17 2012-08-15 金川集团有限公司 Method for treating arsenic-containing waste copper slag
CN104451198A (en) * 2013-09-16 2015-03-25 中国科学院过程工程研究所 Method enhancing oxidization leaching with arsenic in arsenic-cobalt-nickel containing slag
CN106011475A (en) * 2016-06-17 2016-10-12 同济大学 Method for innocent treatment of low-concentration arsenic-containing waste residue and recovery of arsenic
CN106180138A (en) * 2016-07-15 2016-12-07 深圳市危险废物处理站有限公司 A kind of processing method of arsenic-containing waste
CN108642278A (en) * 2018-04-13 2018-10-12 中南大学 A kind of method that mixture of sulfuric phosphoric acid pressurization decomposes wolframite or Scheelite-Wolframite Mixed Mine to extract tungsten
CN110079664A (en) * 2019-04-19 2019-08-02 崇义章源钨业股份有限公司 The method of Tungsten smelting waste residue arsenic removal

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199708A (en) * 2011-05-18 2011-09-28 南昌航空大学 Method for treating arsenic-alkali residue generated in antimony smelting
CN102634672A (en) * 2012-04-17 2012-08-15 金川集团有限公司 Method for treating arsenic-containing waste copper slag
CN104451198A (en) * 2013-09-16 2015-03-25 中国科学院过程工程研究所 Method enhancing oxidization leaching with arsenic in arsenic-cobalt-nickel containing slag
CN106011475A (en) * 2016-06-17 2016-10-12 同济大学 Method for innocent treatment of low-concentration arsenic-containing waste residue and recovery of arsenic
CN106180138A (en) * 2016-07-15 2016-12-07 深圳市危险废物处理站有限公司 A kind of processing method of arsenic-containing waste
CN108642278A (en) * 2018-04-13 2018-10-12 中南大学 A kind of method that mixture of sulfuric phosphoric acid pressurization decomposes wolframite or Scheelite-Wolframite Mixed Mine to extract tungsten
CN110079664A (en) * 2019-04-19 2019-08-02 崇义章源钨业股份有限公司 The method of Tungsten smelting waste residue arsenic removal

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
喻庆华: "钨冶炼过程中含砷废水的处理", 《矿冶工程》 *
梅东海: "各类钨渣综合利用工艺评价", 《有色金属》 *
王蓉颜: "磷砷渣返回压煮处理的工艺研究", 《硬质合金》 *
雷春吟: "磷砷渣提钨和无害化处理工艺的研究", 《全国稀有金属学术交流会论文集》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057881A (en) * 2019-12-31 2020-04-24 荆门德威格林美钨资源循环利用有限公司 Method for recovering tungsten from purification slag
CN111286619A (en) * 2020-02-03 2020-06-16 袁桐 Recycling device of tungsten smelting waste residues
CN115925080A (en) * 2022-11-23 2023-04-07 江西理工大学 Treatment method of tungsten smelting wastewater
CN117772763A (en) * 2024-02-27 2024-03-29 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) Method for separating and recovering arsenic, phosphorus and aluminum from vanadium-phosphorus-containing arsenic slag
CN117772763B (en) * 2024-02-27 2024-05-17 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) Method for separating and recovering arsenic, phosphorus and aluminum from vanadium-phosphorus-containing arsenic slag

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