CN110512095B - Method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag - Google Patents
Method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag Download PDFInfo
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Abstract
The invention discloses a method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag, which comprises the following steps: (1) mixing tungsten metallurgy phosphorus-arsenic slag and a calcium compound for reaction to obtain phosphorus-arsenic slag-calcium compound mixed slag; (2) placing the mixed slag of the phosphorus-arsenic slag and the calcium compound obtained in the step (1) into an alkaline aqueous solution for selectively leaching arsenic, and then carrying out solid-liquid separation to obtain arsenic-removed slag and an arsenic leaching solution; (3) and (3) adding lime and ferric salt into the arsenic leaching solution obtained in the step (2) to precipitate arsenic, and then carrying out solid-liquid separation to obtain arsenic stable slag and arsenic removal water. The stable arsenic slag obtained by the method has good stability, simple process and low cost, can realize the selective separation of arsenic, greatly reduce the content of arsenic in solid slag, reduce the total amount of dangerous solid waste and reduce the treatment cost of the dangerous solid waste and potential environmental hazard.
Description
Technical Field
The invention relates to the technical field of dangerous solid waste treatment and extraction metallurgy, in particular to a method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag.
Background
China is a big tungsten resource country, the annual tungsten ore yield and tungsten metallurgy product yield are at the top of the world, and in recent years, the tungsten metallurgy product yield in China is basically kept at about 10 ten thousand tons. With the depletion of high-grade tungsten mineral resources, low-grade refractory tungsten minerals and secondary tungsten resources (waste hard alloys and waste catalysts) are largely used by the tungsten metallurgy industry, the impurity content of the tungsten resources is high, and impurities mainly comprising harmful element P, As cause a large amount of phosphorus-arsenic slag in the smelting separation process. At present, the stockpiled tungsten smelting slag in China is nearly 100 ten thousand tons.
Generally, about 150kg of P-As slag is produced per 1 ton of Ammonium Paratungstate (APT). In recent years, new tungsten ore clean production leaching processes are gradually put into practice, and although the wastewater yield is low, the impurity leaching rate is high, and the yield of phosphorus and arsenic slag generated along with the subsequent purification process is increased. The main existing form of As in the phosphorus-arsenic slag is Mg3(AsO4)2、Ca3(AsO4)2And the like are listed in national hazardous waste lists, have great environmental pollution hazards if not properly disposed, but also have great comprehensive recovery value. WO of typical phosphorus arsenic separating slag3The content is about 18-50%, the content of P is less than or equal to 3%, and the content of As is less than or equal to 1%, so that the method takes resource recovery into consideration on the premise of carrying out harmless and safe treatment aiming at the solid wastes such As phosphorus-arsenic slag, and is an effective measure in accordance with the current green, environment-friendly and sustainable development concept.
At present, the treatment processes of phosphorus and arsenic slag in tungsten smelting include a roasting-alkaline cooking method, an acid dissolution-extraction method, an acid leaching-ferric hydroxide purification method, an alkaline leaching-magnesium salt purification method, an alkaline leaching-lime purification method, a scheelite-added alkaline leaching method and the like. The common problems with these processes are: 1) extracting valuable metal tungsten is used as a main guide, and arsenic is not stably solidified; 2) the process is complex and the raw material consumption is large. Therefore, in order to treat the phosphorus-arsenic slag in tungsten smelting, both the recovery of W resources and the stabilization and harmlessness of As need to be achieved, a treatment process suitable for the long-term stabilization of As needs to be developed.
Disclosure of Invention
The invention mainly aims to provide a method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus-arsenic slag, and aims to solve the problems of poor arsenic stability, complex process and high cost of the existing tungsten metallurgy phosphorus-arsenic slag treatment method. The method can realize the selective separation of arsenic, greatly reduce the content of arsenic in solid slag, reduce the total amount of dangerous solid waste and reduce the treatment cost of the dangerous solid waste and potential environmental hazard.
In order to achieve the aim, the invention provides a method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag, which comprises the following steps:
(1) mixing tungsten metallurgy phosphorus-arsenic slag and a calcium compound for reaction to obtain phosphorus-arsenic slag-calcium compound mixed slag;
(2) placing the mixed slag of the phosphorus-arsenic slag and the calcium compound obtained in the step (1) into an alkaline aqueous solution for selectively leaching arsenic, and then carrying out solid-liquid separation to obtain arsenic-removed slag and an arsenic leaching solution;
(3) and (3) adding lime and ferric salt into the arsenic leaching solution obtained in the step (2) to precipitate arsenic, and then carrying out solid-liquid separation to obtain arsenic stable slag and arsenic removal water.
The invention firstly mixes and reacts the tungsten metallurgy phosphorus-arsenic slag and calcium compound, the tungsten metallurgy phosphorus-arsenic slag is mainly MgWO4、Mg3(AsO4)2And Mg3(PO4)2(ii) a Due to MgWO4Has a solubility product of Ksp of 10-3.1，CaWO4Has a solubility product of Ksp of 10-10MgWO in P-As slag of tungsten metallurgy4Can generate more insoluble CaWO by mixing calcium compound4(ii) a Due to Mg3(PO4)2Has a solubility product of Ksp of 10-24，Ca3(PO4)2Has a solubility product of Ksp of 10-29Mg in P-As slag of tungsten metallurgy3(PO4)2Can also react to form more insoluble Ca by mixing with calcium compound3(PO4)2(ii) a And Mg3(AsO4)2And Ca3(AsO4)2All solubility products of (C) are Ksp ═ 10-19The solubility products are equivalent and are not mutually converted; namely W, P in the tungsten metallurgy phosphorus arsenic slag is preferentially converted into CaWO with difficult solubility4And Ca3(PO4)2Retaining the more soluble Mg3(AsO4)2(ii) a Then the mixed slag is selectively leached out of arsenic in alkaline aqueous solution, lime and ferric salt are added into arsenic leaching solution obtained after solid-liquid separation to precipitate arsenic, ferric salt and lime are utilized to convert arsenic in a dissolved state in the solution into stable minerals such as calcium arsenate, ferric arsenate and the like, and ferric hydroxide colloid formed by ferric salt is utilizedThe adsorption of substances fixes arsenic in the slag, and the arsenic stable slag with stable environment is obtained after solid-liquid separation; thereby realizing the separation of As and W, P in the phosphorus arsenic slag in tungsten metallurgy and the stable solidification of arsenic.
By the method, the total amount of the high-arsenic slag (the content of As is more than 0.05%) can be reduced by more than 50%, so that the dangerous solid waste treatment cost of more than 1/2 is saved, the content of As in the W, P mixed slag for separating As is reduced to less than 0.05%, and the potential environmental hazard of the high-arsenic slag is greatly reduced.
Further, in the step (1), the mixing reaction of the tungsten metallurgy phosphorus arsenic slag and the calcium compound specifically means: carrying out wet ball milling on the tungsten metallurgy phosphorus-arsenic slag and the calcium compound. The components in the phosphorus-arsenic slag in tungsten metallurgy can be fully contacted and reacted with the calcium compound through wet ball milling.
Further, the calcium compound is one or more of calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium oxide and calcium hydroxide. More preferably, calcium chloride or calcium nitrate.
Further, the addition amount of the calcium compound is 1.0-3.0 times of the amount of the calcium compound theoretically required for converting tungsten and phosphorus in the tungsten metallurgy phosphorus-arsenic slag into calcium tungstate and calcium phosphate. More preferably, it is 1.2 to 1.6 times. If the addition amount of the calcium compound is too large, arsenic can be converted into calcium arsenate and the like, so that the subsequent low-alkalinity arsenic decomposition cannot be realized, and the subsequent selective arsenic decomposition is influenced; if the content of the tungsten is too small, the tungsten cannot be well converted into calcium tungstate minerals, and the tungsten and arsenic enter the solution together in the subsequent decomposition without selectivity.
Further, in the step (2), the alkaline aqueous solution is an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution or an aqueous lithium hydroxide solution. Preferably an aqueous sodium hydroxide solution.
Further, in the step (2), the pH value of the alkaline aqueous solution is 8-11. Further preferably 9 to 10.5. In the alkaline leaching process, the pH value of the alkaline aqueous solution cannot be too high or too low, and if the pH value is too high or too low, the tungsten mineral is dissolved. The invention controls the pH value of the alkaline aqueous solution in the alkaline leaching process within the range, well inhibits the dissolution of tungsten minerals, and improves the separation effect of tungsten and arsenic.
Further, in the step (2), the temperature for selectively leaching arsenic is 0-200 ℃. Further preferably 20 to 160 ℃. In the alkaline leaching process, if the temperature is too high, a small amount of tungsten mineral can be dissolved, valuable metal loss is caused, and if the temperature is too low, the reaction kinetic rate for selectively leaching arsenic is too low.
Further, in the step (3), the iron salt is one or more of ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate, ferrous chloride and ferrous nitrate, and is further preferably ferrous sulfate or ferrous chloride; when the ferric salt contains ferrous sulfate, ferrous chloride or ferrous nitrate, adding an oxidant or blowing air and oxygen into the arsenic leaching solution for oxidation treatment.
Further, in the step (3), the adding amount of the iron salt in the arsenic leaching solution is the molar ratio of Fe to As (1.0-5.0): 1, more preferably 1.5 to 3.0; the adding amount of lime in the arsenic leaching solution is Ca: as molar ratio (1.0-8.0): 1, and more preferably 2.0 to 5.0.
Further, the tungsten metallurgy phosphorus arsenic slag specifically refers to: in the production process of tungsten hydrometallurgy acid extraction and weak alkaline ion exchange, magnesium salt is adopted to precipitate and remove precipitation slag generated by phosphorus and arsenic before transformation and purification; in the phosphorus-arsenic slag in tungsten metallurgy, phosphorus, arsenic and tungsten mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively.
Compared with the prior art, the invention has the beneficial effects that:
the method comprises the steps of mixing tungsten metallurgy phosphorus-arsenic slag with calcium compound for reaction, and preferentially converting W, P in the tungsten metallurgy phosphorus-arsenic slag into indissolvable CaWO4And Ca3(PO4)2Retaining the more soluble Mg3(AsO4)2(ii) a Then selectively leaching arsenic from the mixed slag in an alkaline aqueous solution, adding lime and ferric salt into the arsenic leaching solution to precipitate arsenic, and performing solid-liquid separation to obtain arsenic stabilizing slag with stable environment; thereby realizing the separation of As and W, P in the phosphorus arsenic slag in tungsten metallurgy and the stable solidification of arsenic. The method of the invention can reduce the high arsenic slag (As content) by more than 50 percent>0.05%) and thus saving the cost of treating dangerous solid wastes above 1/2, W, P for separating AsThe content of As in the mixed slag is reduced to<0.05 percent, and greatly reduces the potential environmental hazard of the high arsenic slag.
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FIG. 1 is a process flow diagram of the method for extracting and stabilizing arsenic from arsenic-phosphorous slag in tungsten metallurgy according to the present invention.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention provides a method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag. The phosphorus and arsenic slag for tungsten metallurgy treated by the embodiment is as follows: in a certain production process for smelting ammonium paratungstate by a tungsten wet method, the content of P, As in an acidic extraction stripping solution (ammonium tungstate solution) is high, impurities such as P, As and the like are removed by a magnesium chloride precipitation method, and then phosphorus and arsenic purification slag is generated. In the phosphorus-arsenic slag for tungsten metallurgy, phosphorus, arsenic and tungsten mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, and the main chemical components of the phosphorus-arsenic slag are WO312.50％、P 0.92％、As 0.89％、Mg 16.02％、Fe 0.91％、Ca 1.50％、H2O46 percent (mass percentage), the phosphorus arsenic slag has larger environmental hazard, and the leaching rates of As and W of tap water at normal temperature are both As high As more than 50 percent.
The process flow diagram of the method is shown in fig. 1, and specifically comprises the following steps:
firstly, 5000g of phosphorus-arsenic slag and 560g of CaCl2Adding the mixture into a ball mill for ball milling and mixing at normal temperature for 3h by a wet method;
then putting the obtained mixture slag into 50L NaOH aqueous solution for selective alkaline leaching reaction, adjusting the pH value of the end point to be within 10-10.5 by the addition amount of NaOH in the reaction, stirring and reacting for 2h at 80 ℃, and carrying out solid-liquid separation and washing to obtain arsenic leaching solution 55L and arsenic-removing slag, wherein the leaching rate of arsenic is more than or equal to 96 percent, and the leaching rate of tungsten is less than or equal to 5 percent;
adding FeSO into the arsenic leaching solution4·7H2Introducing 190g of O, introducing air, stirring and reacting for 2 hours, adding 100g of quicklime CaO into the arsenic leaching solution, reacting for 1 hour, and carrying out solid-liquid separation to obtain 50L dearsenified solution and 1496g of arsenic stabilized slag.
The arsenic-removed slag with low arsenic and the arsenic-stabilized slag with high arsenic precipitated by lime and iron salt are respectively dried and dehydrated, and then toxicity leaching analysis is respectively carried out, and the results show that the content of As in the arsenic-removed slag is reduced to be below 0.05 percent, and the toxicity leaching concentration of As in both the arsenic-removed slag and the arsenic-stabilized slag is below the limit value of 5 mg/L.
Example 2:
the invention provides a method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag. The phosphorus and arsenic slag for tungsten metallurgy treated by the embodiment is as follows: phosphorus-arsenic-magnesium salt purification slag generated in wet-process ammonium paratungstate smelting production process of certain tungsten smelting enterprise, wherein phosphorus, arsenic and tungsten in the tungsten metallurgy phosphorus-arsenic slag mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, and the main chemical components of the phosphorus-arsenic-magnesium salt purification slag are WO31.50％、P1.03％、As 0.45％、Mg 13.01％、Fe 0.89％、Ca 1.46％、H2And (3) O43 percent. The phosphorus arsenic slag has great environmental harm, the leaching rates of As and W in normal-temperature tap water are both As high As more than 60%, and stable solidification treatment is required.
The process flow diagram of the method is shown in fig. 1, and specifically comprises the following steps:
firstly, 5000g and 100g of CaCl are added into the phosphorus-arsenic slag2Carrying out wet mixing at normal temperature for 2.5h by using a ball mill;
then putting the mixture slag into 60L NaOH aqueous solution, adjusting the pH value of the end point to be within 10-10.5 by the addition amount of NaOH in the reaction, stirring and reacting for 1h at 95 ℃, and carrying out solid-liquid separation and washing to obtain As leachate 62L;
adding FeSO into the leaching solution4·7H2Introducing 140g of O and air, stirring and reacting for 2 hours, adding 100g of quicklime CaO into the leachate, reacting for 1 hour, and carrying out solid-liquid separation to obtain 50L of As-removed solution and 1530g of arsenic slag, wherein the leaching rate of arsenic is more than or equal to 93 percent, and the leaching rate of tungsten is less than or equal to 7 percent.
And (3) carrying out drying dehydration treatment on the obtained low-arsenic slag without As and the high-arsenic slag precipitated by the ferric limestone salt to carry out toxicity leaching analysis, wherein the leaching concentration of As is below the limit value of 5 mg/L, and the content of As in the low-arsenic slag is reduced to be below 0.05%.
Comparative example 1:
the phosphorus and arsenic slag for tungsten metallurgy treated by the comparative example is as follows: the same tungsten metallurgy phosphorus arsenic slag as in example 1. In the phosphorus-arsenic slag for tungsten metallurgy, phosphorus, arsenic and tungsten mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, and the main chemical components of the phosphorus-arsenic slag are WO312.50％、P 0.92％、As 0.89％、Mg 16.02％、Fe 0.91％、Ca 1.50％、H2O46 percent (mass percentage), the phosphorus arsenic slag has larger environmental hazard, and the leaching rates of As and W of tap water at normal temperature are both As high As more than 50 percent.
The method is implemented according to the following steps:
firstly, 5000g of phosphorus-arsenic slag and 120g of CaCl2Adding the mixture into a ball mill for ball milling and mixing at normal temperature for 3h by a wet method;
and then putting the obtained mixture slag into a 50L NaOH aqueous solution for selective alkaline leaching reaction, adjusting the pH value of the end point to be within 10-10.5 by the addition amount of NaOH in the reaction, stirring and reacting for 2h at 80 ℃, and performing solid-liquid separation and washing to obtain an arsenic leaching solution 55L and arsenic-removed slag.
Comparative example 2:
the phosphorus and arsenic slag for tungsten metallurgy treated by the comparative example is as follows: the same tungsten metallurgy phosphorus arsenic slag as in example 1. In the phosphorus-arsenic slag for tungsten metallurgy, phosphorus, arsenic and tungsten mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, and the main chemical components of the phosphorus-arsenic slag are WO312.50％、P 0.92％、As 0.89％、Mg 16.02％、Fe 0.91％、Ca 1.50％、H2O46 percent (mass percentage), the phosphorus arsenic slag has larger environmental hazard, and the leaching rates of As and W of tap water at normal temperature are both As high As more than 50 percent.
The method is implemented according to the following steps:
firstly, 5000g of phosphorus-arsenic slag and 890g of CaCl2Adding the mixture into a ball mill for ball milling and mixing at normal temperature for 3h by a wet method;
and then putting the obtained mixture slag into a 50L NaOH aqueous solution for selective alkaline leaching reaction, adjusting the pH value of the end point to be within 10-10.5 by the addition amount of NaOH in the reaction, stirring and reacting for 2h at 80 ℃, and carrying out solid-liquid separation and washing to obtain an arsenic leaching solution 55L and arsenic-removed slag, wherein an analysis result shows that the leaching rate of arsenic is about 16 percent, the leaching rate of tungsten is less than 2 percent, the selectivity in the low-alkalinity leaching process is not strong, and the arsenic is not selectively decomposed.
Comparative example 3:
the phosphorus and arsenic slag for tungsten metallurgy treated by the comparative example is as follows: the same tungsten metallurgy phosphorus arsenic slag as in example 1. In the phosphorus-arsenic slag for tungsten metallurgy, phosphorus, arsenic and tungsten mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively, and the main chemical components of the phosphorus-arsenic slag are WO312.50％、P 0.92％、As 0.89％、Mg 16.02％、Fe 0.91％、Ca 1.50％、H2O46 percent (mass percentage), the phosphorus arsenic slag has larger environmental hazard, and the leaching rates of As and W of tap water at normal temperature are both As high As more than 50 percent.
The method is implemented according to the following steps:
firstly, 5000g of phosphorus-arsenic slag and 500g of CaCl2Adding the mixture into a ball mill for ball milling and mixing at normal temperature for 3h by a wet method;
then the obtained mixture slag is put into 50L NaOH aqueous solution for selective alkaline leaching reaction, the pH value of the end point is adjusted to be about 11.5 by the adding amount of NaOH in the reaction, the mixture slag is stirred and reacted for 2 hours at 80 ℃, solid-liquid separation and washing are carried out, and arsenic leaching liquid 55L and arsenic-removing slag are obtained.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for extracting and stabilizing arsenic from tungsten metallurgy phosphorus arsenic slag is characterized by comprising the following steps:
(1) mixing tungsten metallurgy phosphorus-arsenic slag and a calcium compound for reaction to obtain phosphorus-arsenic slag-calcium compound mixed slag; the addition amount of the calcium compound is 1.0-3.0 times of the amount of the calcium compound theoretically required by converting tungsten and phosphorus in the tungsten metallurgy phosphorus-arsenic slag into calcium tungstate and calcium phosphate;
(2) placing the mixed slag of the phosphorus-arsenic slag and the calcium compound obtained in the step (1) into an alkaline aqueous solution for selectively leaching arsenic, and then carrying out solid-liquid separation to obtain arsenic-removed slag and an arsenic leaching solution; the pH value of the alkaline aqueous solution is 8-11;
(3) and (3) adding lime and ferric salt into the arsenic leaching solution obtained in the step (2) to precipitate arsenic, and then carrying out solid-liquid separation to obtain arsenic stable slag and arsenic removal water.
2. The method for extracting and stabilizing arsenic from the phosphorus-arsenic slag in tungsten metallurgy according to claim 1, wherein in the step (1), the mixing reaction of the phosphorus-arsenic slag in tungsten metallurgy and the calcium compound specifically comprises: carrying out wet ball milling on the tungsten metallurgy phosphorus-arsenic slag and the calcium compound.
3. The method of claim 1, wherein the calcium compound is one or more of calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium oxide and calcium hydroxide.
4. The method for extracting and stabilizing As from P-As slag in W metallurgy according to claim 1, wherein in the step (2), the alkaline aqueous solution is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or lithium hydroxide aqueous solution.
5. The method for extracting and stabilizing arsenic from P-As slag in W metallurgy according to claim 1, wherein the temperature for selectively leaching arsenic in the step (2) is 0-200 ℃.
6. The method for extracting and stabilizing arsenic from P-As slag in tungsten metallurgy according to claim 1, wherein in the step (3), the iron salt is one or more of ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate, ferrous chloride and ferrous nitrate; when the ferric salt contains ferrous sulfate, ferrous chloride or ferrous nitrate, adding an oxidant or blowing air and oxygen into the arsenic leaching solution for oxidation treatment.
7. The method for extracting and stabilizing arsenic from P-As slag in tungsten metallurgy according to claim 1, wherein in the step (3), the addition amount of the iron salt in the arsenic leaching solution is Fe to As molar ratio (1.0-5.0): 1, adding the lime into the arsenic leaching solution in a ratio of Ca: as molar ratio (1.0-8.0): 1.
8. the method for extracting and stabilizing arsenic from the phosphorus-arsenic slag in tungsten metallurgy according to any one of claims 1 to 7, wherein the phosphorus-arsenic slag in tungsten metallurgy specifically refers to: in the production process of tungsten hydrometallurgy acid extraction and weak alkaline ion exchange, magnesium salt is adopted to precipitate and remove precipitation slag generated by phosphorus and arsenic before transformation and purification; in the phosphorus-arsenic slag for tungsten metallurgy, phosphorus, arsenic and tungsten mainly exist in the forms of magnesium phosphate, magnesium arsenate and magnesium tungstate respectively.
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| CN111286619A (en) * | 2020-02-03 | 2020-06-16 | 袁桐 | Recycling device of tungsten smelting waste residues |
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| 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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