CN115679128B - Method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag - Google Patents
Method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag Download PDFInfo
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 70
- 239000010937 tungsten Substances 0.000 title claims abstract description 70
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002893 slag Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 24
- 238000004090 dissolution Methods 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- 239000006228 supernatant Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000000243 solution Substances 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 2
- 238000005406 washing Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical group [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag, which comprises the following steps: acid dissolution: adding acid liquor and water into the tungsten-containing dephosphorization precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A; sedimentation: settling the material A, and collecting supernatant; adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-exchange liquid; analysis: soaking, washing and resolving the anion resin in the column body after the adsorption is finished, and collecting resolved liquid, namely an ammonium tungstate solution; alkali regulation: adding alkali into the crossed liquid, and uniformly stirring to obtain a material B; and (3) filter pressing: carrying out filter pressing on the material B, removing sediment, and collecting filtrate; ammonia recovery: and (3) introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor. The method can efficiently recycle tungsten and ammonia in the slag, can recycle 100% of tungsten and more than 99% of ammonia, and has good application prospect.
Description
Technical Field
The invention relates to a tungsten recovery technology, in particular to a method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag.
Background
The method for removing phosphorus in the two-stage liquid of tungsten smelting is a salt precipitation method, the product is phosphate precipitation, the phosphorus removal effect is achieved after filtration, but part of tungsten is remained in the precipitation in the process, the tungsten content of the part reaches 1.5-5%, tungsten loss is avoided due to no recovery, the recovery effect is poor by using the traditional alkali cooking, and the auxiliary materials and the energy consumption are high.
The existing method for recovering tungsten from the dephosphorization precipitated slag is mainly an alkaline cooking method, the recovery rate of the method is low, the complete recovery of tungsten in the type of slag cannot be realized, meanwhile, the method needs high-temperature alkaline cooking, the auxiliary material and the energy consumption are high, the alkalinity is difficult to control, the residual alkali is not enough, the tungsten content in the tailings is high, the residual alkali is too high to form hydroxide flocculent sticky slag, and the problems of difficult filtration and difficult washing are solved. The tungsten-containing liquid is boiled to contain carbonate radical, and the precipitation of the artificial white tungsten by using a calcium salt precipitator needs excessive calcium to realize complete tungsten precipitation, and the consumption of auxiliary materials for tungsten precipitation is high.
Therefore, the existing method has low treatment efficiency and insufficient recovery depth for recovering tungsten from the dephosphorization and precipitation slag, and also greatly wastes auxiliary materials and energy consumption in the treatment process and the subsequent tungsten precipitation process.
Patent application CN109881012A discloses a treatment method for recovering tungsten from dephosphorization slag of tungsten metallurgy, which comprises the following steps of mixing water for dephosphorization slag and heating to 40-90 ℃; adding dilute acid to regulate the pH value to 2-4, and stirring and reacting for 0.5-4h; filtering to obtain a decomposition liquid and trace non-decomposition residues, continuously returning the non-decomposition residues to the step of size mixing and heating to continuously decompose, and allowing valuable metal tungsten to enter the decomposition liquid; and adsorbing tungsten by the decomposition solution through a large-aperture anion exchange resin, and desorbing by alkali to obtain a sodium tungstate solution for subsequent flow. The efficiency of tungsten recovery by this method is to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the existing tungsten metallurgy dephosphorization slag for recovering tungsten, and provides a method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitation slag.
The invention preferably adopts waste acid for acid dissolution, and the waste acid can be one of hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid and other strong acids or mixed acid, so that the waste acid generated in industry can be reused, the selection range is wide, and the conversion of changing waste into valuable can be realized.
In order to improve the recovery rate of tungsten, the inventor explores the leaching effect under different conditions, and discovers that when acid liquor is added and then added into tungsten-containing dephosphorization precipitated slag, the pH is measured by stirring, the complete dissolution of the slag can be realized when the pH is less than 2, and if the pH is between 2 and 4, the dissolution rate is slow, and about 2 to 8 percent of the slag is not dissolved, and when the pH is more than 5, the slag is basically insoluble.
Therefore, the use of a pH of less than 2 is advantageous for the tungsten in the slag to go into solution as much as possible. But this also causes new problems. Because the acidity is very low, a large amount of metal ion impurities are dissolved out together, and enter the supernatant liquid during solid-liquid separation in the material A, and are adsorbed on the resin in an adsorption link, so that the column is blocked in the analysis process, the analysis liquid cannot flow out smoothly, and the analysis fails.
For this reason, the inventors have further found that the above failure is caused by the fact that a large amount of white precipitate adheres to the surface of the resin, and further confirmed that the precipitate is formed under alkaline analysis conditions as an impurity metal element, and therefore, the resin is immersed with hydrochloric acid before the analysis to remove the metal ion impurities adsorbed by the resin, thereby ensuring the smooth progress of the analysis.
The specific scheme is as follows:
a method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag comprises the following steps:
(1) Acid dissolution: adding acid liquor and water into the tungsten-containing dephosphorization precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A;
(2) Sedimentation: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-exchange liquid;
(4) Analysis: soaking the anion resin in the column body after adsorption is finished, wherein the soaking solution is hydrochloric acid aqueous solution with the concentration of 40-80g/l, the soaking time is 4-8 hours, then washing the resin with water, finally resolving the resin with sodium hydroxide solution, and collecting resolved solution, namely ammonium tungstate solution;
(5) Alkali regulation: adding alkali into the crossed liquid, and uniformly stirring to obtain a material B;
(6) And (3) filter pressing: carrying out filter pressing on the material B, removing sediment, and collecting filtrate;
(7) Ammonia recovery: and (3) introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor.
Further, the tungsten content in the tungsten-containing dephosphorization precipitation slag is 1.5-10wt%, the ammonia content is 1-10wt%, preferably, the tungsten content is 1.5% -5%, the ammonia content is 6% -6.45%, and the tungsten-containing dephosphorization precipitation slag contains Mg and P impurity elements.
Further, in the step (1), the acid liquid comprises at least one of hydrochloric acid, sulfuric acid, phosphoric acid and carbonic acid; preferably, the slurry is stirred and the pH of the solution 1 is controlled to be less than or equal to 2.
Further, in the step (3), the anionic resin is a weakly basic anionic resin.
Further, in the step (4), the resin is washed with water in an amount of 3 to 5 times the volume of the resin.
Further, in the step (4), the concentration of the sodium hydroxide solution is 80-150g/l, and the adding amount of the sodium hydroxide solution is 1-2 times of the target tungsten adsorption amount according to the amount of sodium hydroxide in the solution.
Further, in the step (5), sodium hydroxide is added in the alkali adding treatment, and the addition amount of the alkali is controlled to control the residual alkali concentration in the solution after the reaction to be 5-10g/l.
Further, in the step (7), the temperature of the steam is 95-99 ℃, and the alkali liquor is added in an amount of ensuring the alkali concentration in the solution to be 5-10g/l.
Further, in the step (4), the analysis liquid is collected, and the recovery rate of tungsten is 99-100%.
Further, in the step (7), the gas is collected, and the recovery rate of ammonia is more than or equal to 99%.
The beneficial effects are that:
The method can realize the high-efficiency recovery of tungsten from the dephosphorization and precipitation slag, simultaneously realize the recovery of ammonia, reduce auxiliary materials and energy consumption, realize 100% of tungsten recovery, realize more than 99% of recovery reflux process of ammonia in the recovery slag by the matched ammonia recovery device, directly generate economic benefit and simultaneously relieve environmental protection pressure; the acid solvent is waste acid from the process, and the waste is changed into valuable.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
FIG. 1 is a schematic illustration of a process flow provided in one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the examples below, "%" refers to weight percent, unless explicitly stated otherwise.
The following main raw materials were used:
The dephosphorization precipitation slag is a magnesium salt precipitation method generated by dephosphorization in tungsten smelting secondary liquid, the product is ammonium magnesium phosphate salt precipitation, and the reaction equation is ：Mg2++NH4 ++PO4 3-+H2O＝MgNH4PO4·6H2O( dephosphorization precipitation slag).
Example 1
The phosphorus removal precipitated slag is taken and treated, as shown in figure 1, and comprises the following steps:
(1) Acid dissolution: adding acid liquor and water into the tungsten-containing dephosphorization precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A;
(2) Sedimentation: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-exchange liquid;
(4) Analysis: soaking the anion resin in the column body after adsorption, wherein the soaking solution is hydrochloric acid aqueous solution with the concentration of 50g/l for 5 hours, then washing the resin with water, finally resolving the resin with sodium hydroxide solution, and collecting resolved solution, namely ammonium tungstate solution;
(5) Alkali regulation: adding alkali into the crossed liquid, and uniformly stirring to obtain a material B;
(6) And (3) filter pressing: carrying out filter pressing on the material B, removing sediment, and collecting filtrate;
(7) Ammonia recovery: and (3) introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor.
Specifically, this example explores the effect of pH on acid dissolution, as follows:
1000kg of dephosphorized and precipitated slag sample (WO 3, content 4.25% and water content 32%) is taken, slurried with 3m 3 water, slowly fed with process waste acid (mixed acid of sulfuric acid, phosphoric acid and hydrochloric acid), 90g/l of acidity, stirring and reacting for 30min when the pH is 5, filtering the slag and measuring the volume of solution and WO 3, wherein the slag is 456.7kg, water is 35%, the volume of solution is 7.2m 3, and the solution WO3:2.1g/l; so the slag dissolution rate is calculated as: 56.34%, the dissolution rate of WO 3 is: 52.32%;
The above procedure was repeated except that the slag dissolution rate was 93.2% when the pH was adjusted to 4, and the WO 3 dissolution rate was: 94.47%.
The above procedure was repeated except that the slag dissolution rate was 97.54% when the pH was adjusted to 3, and the WO 3 dissolution rate was: 98.18%.
The above operations were repeated except that the dissolution rate of the slag was 99.12% when the pH was adjusted to 2, and the dissolution rate of WO 3 was: 99.54%.
The above procedure was repeated except that the slag dissolution rate was 99.98% when the pH was adjusted to 1 (test paper acid limit), and the WO 3 dissolution rate was: 100%, the dissolution is completed instantly, the dissolution speed is high, and the dissolution is thorough.
It can be seen that the dissolution rate of WO 3 is improved after the pH of the acid solution is reduced.
In the present invention, acidity means milligrams of potassium hydroxide (KOH) required for neutralizing 1 g of chemical substance.
Example 2
The embodiment explores the analysis process, and the phosphorus removal precipitated slag is taken for treatment, which comprises the following steps:
(1) 1000kg of dephosphorized and precipitated slag sample (WO 3, content 4.25% and water content 32%) is taken, 3m 3 water is used for size mixing, the process waste acid is slowly fed in, and the pH=1.5 is obtained to obtain a material A.
(2) Sedimentation: settling the material A, and collecting supernatant; the process aims to settle insoluble matters mixed in slag and avoid the insoluble matters entering the exchange column to influence the adsorption flow of the exchange column.
(3) Adsorption: and sending the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-exchange liquid.
The adsorption is carried out by adopting weak alkaline anion resin (large aperture anion resin, AH-80 II), the resin can adsorb WO 3 with equal mass under the acidic condition, and the adsorption flow is controlled in the adsorption flow interval of 5-12m 3/h because the concentration of tungsten dissolved out by acid is not too high, so that the tungsten adsorption rate can be more than 99.9%.
(4) Analysis:
The column which has adsorbed the supernatant and reached saturation is operated according to the steps of back flushing (with water), washing (with water), and feeding of alkali (sodium hydroxide solution). The discovery is as follows: the back flushing and washing flow can reach 7m 3 to 9m 3, which belongs to normal flow, but after alkali is fed, the flow starts to drop from 8m 3 all the time, the column is leaked after the flow drops below 1m 3, the desorption operation can not be carried out any more, the resin is discharged to find all the attached white sediment, and the white sediment is filled between the resins, so that no flow is caused by desorption.
The column was then taken up to saturation and operated in accordance with the steps of back flushing (with water), soaking in acid (with 50g/l hydrochloric acid in water for 5 hours), washing (with water) and feeding with alkali (sodium hydroxide solution). The discovery is as follows: the back flushing and washing flow can reach 7m 3 -9 m 3, after alkali is fed, the flow can be stabilized between 7m 3 -9 m 3, the desorption process is smooth, resin is discharged for checking, and the resin is clean and has no sediment.
In the embodiment, the resin is resolved by sodium hydroxide solution, the alkali concentration (namely, the concentration of sodium hydroxide) is controlled to be 100g/l, the alkali dosage is 1.2 times of the tungsten adsorption amount, and the resolved solution is collected to obtain the ammonium tungstate solution. And (5) alkali adjustment: and adding alkali (sodium hydroxide solution) into the mixed solution, and uniformly stirring to obtain a material B.
The step is to add alkali to the exchanged liquid after the tungsten is adsorbed by the exchange column, reversely regulating and separating out hydroxide precipitate, etc., and the concentration of residual alkali (namely the concentration of sodium hydroxide) after alkali addition is controlled to be about 5-10g/l, so that the step aims to separate out slag in advance, and the problem that the pH change has slag precipitation caused by removing other elements in the subsequent water treatment process is avoided, thereby influencing the effect of removing other elements in the water treatment.
The residual alkali concentration means the alkali concentration remaining after the reaction, that is, the concentration of sodium hydroxide.
(6) And (3) filter pressing: carrying out filter pressing on the material B, removing sediment, avoiding slag from being brought into a stripping device, and collecting filtrate;
(7) Ammonia recovery: adding alkali liquor (sodium hydroxide solution) into the filtrate, introducing steam, collecting gas, and condensing in a condenser to obtain ammonia liquor.
In the invention, the resin is soaked for 4-8 hours by dilute hydrochloric acid with the concentration of 40-80g/l before desorption, and the concentration is mainly selected by comprehensively considering that metal cations (calcium, magnesium and the like) and salts thereof and the like can be dissolved out, and the residual acid is not too high, so that the cost of alkali and water treatment in the next step is facilitated, and the resin is washed by water with the volume of 4-5 times of the resin, so that hydroxide precipitate is prevented from being separated out during alkaline tungsten hydrolysis, and the tungsten dissolving flow and sodium tungstate quality are prevented from being influenced. The method is a key step, if dilute hydrochloric acid is absent for soaking, desorption cannot be performed, and the technical route of adsorption after acid dissolution cannot be performed.
Example 3
A method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag comprises the following steps:
(1) Taking 1000kg of dephosphorization sediment sample (WO 3 content 4.25 percent, water content 32 percent), mixing slurry with 3m 3 water, slowly adding process waste acid, and obtaining a material A by pH=1;
(2) Sedimentation: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-exchange liquid;
(4) Analysis: soaking the anion resin in the column body after the adsorption is finished, wherein the soaking liquid is hydrochloric acid water solution with the concentration of 40g/l for 8 hours, then washing the resin with water, finally analyzing the resin by using sodium hydroxide solution with the concentration of 100g/l, and collecting analysis liquid, namely ammonium tungstate solution, wherein the addition amount of the sodium hydroxide solution is 1.1 times of the target tungsten adsorption amount according to the amount of sodium hydroxide in the solution;
(5) Alkali regulation: adding alkali into the solution after the cross-over, adding sodium hydroxide solution, controlling the concentration of residual alkali in the solution after the reaction to be 6g/l by adding the alkali, and uniformly stirring to obtain a material B;
(6) And (3) filter pressing: carrying out filter pressing on the material B, removing precipitates, and collecting filtrate, wherein the ammonia concentration in the filtrate is 3680ppm, and the pH value is 13;
(7) Ammonia recovery: introducing steam into the filtrate at 95-99 ℃, adding alkali liquor (sodium hydroxide solution) to ensure that the alkali concentration in the solution is 10g/l, carrying out steam stripping deamination by adopting a traditional steam stripping operation method, condensing and recycling ammonia (the ammonia can be recycled by 100% after stripping), wherein the ammonia content in the feed liquid after steam stripping is only 8.8ppm, and the ammonia recycling is over 99%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (3)
1. A method for efficiently recovering tungsten and ammonia from tungsten-containing dephosphorization precipitated slag is characterized in that: the method comprises the following steps:
(1) Acid dissolution: adding acid liquor and water into the tungsten-containing dephosphorization precipitation slag, mixing slurry, and controlling the pH value of the solution 1 to be less than or equal to 2 to obtain a material A; the tungsten content in the tungsten-containing dephosphorization precipitation slag is 1.5-10wt% and the ammonia content is 1-10wt% and contains Mg and P impurity elements;
(2) Sedimentation: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-exchange liquid; the anion resin is weak alkaline anion resin;
(4) Analysis: soaking the anion resin in the column after adsorption is completed for 4-8 hours in a hydrochloric acid aqueous solution with the concentration of 40-80g/l, then flushing the resin with water, and finally resolving the resin by using a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 80-150g/l, the adding amount of the sodium hydroxide solution is 1-2 times of the target tungsten adsorption amount according to the amount of sodium hydroxide in the solution, and collecting resolving liquid, namely ammonium tungstate solution, and the recovery rate of tungsten is 99-100%;
(5) Alkali regulation: adding alkali into the crossed liquid, and uniformly stirring to obtain a material B; the alkali adding treatment is to add sodium hydroxide, and the addition amount of the alkali is controlled to control the concentration of residual alkali in the solution after the reaction to be 5-10g/l;
(6) And (3) filter pressing: carrying out filter pressing on the material B, removing sediment, and collecting filtrate;
(7) Ammonia recovery: introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor; the temperature of the introduced steam is 95-99 ℃, and the amount of the added alkali liquor is 5-10g/l of the alkali concentration in the solution; and collecting the gas, wherein the recovery rate of ammonia is more than or equal to 99 percent.
2. The method for efficiently recovering tungsten and ammonia from tungsten and phosphorous containing precipitation slag according to claim 1, wherein the method comprises the steps of: in the step (1), the acid liquid comprises at least one of hydrochloric acid, sulfuric acid, phosphoric acid and carbonic acid.
3. The method for efficiently recovering tungsten and ammonia from tungsten and phosphorous containing precipitation slag according to claim 1, wherein the method comprises the steps of: in step (4), the resin is washed with water in an amount of 3 to 5 times the volume of the resin.
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Citations (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108735A (en) * | 1976-06-14 | 1978-08-22 | Bethlehem Steel Corporation | Method for improved distillation of ammonia from weak ammonia liquor |
| US4115513A (en) * | 1977-08-16 | 1978-09-19 | Westinghouse Electric Corp. | Processing of ammonium paratungstate from tungsten ores |
| CN1377980A (en) * | 2002-02-06 | 2002-11-06 | 王旭升 | Process for preparing high purity ammonium para-tungstate using hihg-molybdenum tungsten ore |
| WO2008030235A2 (en) * | 2006-09-06 | 2008-03-13 | Fassbender Alexander G | Ammonia recovery process |
| CN101696036A (en) * | 2009-10-24 | 2010-04-21 | 刘向文 | Preparation process of ammonium paratungstate |
| JP2011179038A (en) * | 2010-02-26 | 2011-09-15 | Mitsubishi Materials Corp | Method for collecting tungsten from scrap of hard metal |
| CN102212697A (en) * | 2011-05-18 | 2011-10-12 | 湖南稀土金属材料研究院 | Tungsten slag treatment method |
| CN102296179A (en) * | 2011-08-31 | 2011-12-28 | 鹤山市沃得钨钼实业有限公司 | Method for producing tungsten-molybdenum product by processing tungsten-molybdenum symbiotic mixed ore |
| CN102557139A (en) * | 2011-12-26 | 2012-07-11 | 大余隆鑫泰钨业有限公司 | Method for dephosphorizing low-phosphorus ammonium tungstate solution |
| CN103014343A (en) * | 2013-01-18 | 2013-04-03 | 成都西顿硬质合金有限公司 | Process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor |
| CN103060563A (en) * | 2013-01-18 | 2013-04-24 | 成都西顿硬质合金有限公司 | Technology of deep purification and impurity removal of ammonium tungstate or ammonium molybdate solution |
| CN103290224A (en) * | 2013-05-31 | 2013-09-11 | 刘甲祥 | Recovery process for valuable metals in tungsten residues |
| CN104108883A (en) * | 2014-08-11 | 2014-10-22 | 中国地质大学（北京） | High-strength lithium disilicate glass ceramic and preparation method thereof |
| JP2015045041A (en) * | 2013-08-27 | 2015-03-12 | 京セラ株式会社 | Method for recovering tungsten compound |
| CN104611559A (en) * | 2015-03-02 | 2015-05-13 | 湖南有色金属研究院 | Method for comprehensively recovering rubidium, tungsten and potassium from rubidium-tungsten-containing fluorite middlings |
| CN104817115A (en) * | 2015-04-15 | 2015-08-05 | 赣州海创钨业有限公司 | Method for removing micro-phosphorus in ammonium tungstate solution |
| CN107746966A (en) * | 2017-09-29 | 2018-03-02 | 湖南行者环保科技有限公司 | A kind of method that joint disposal ammonium paratungstate slag charge reclaims micro rare metal |
| CN108046326A (en) * | 2017-12-07 | 2018-05-18 | 崇义章源钨业股份有限公司 | The method for preparing ammonium paratungstate |
| JP2019034273A (en) * | 2017-08-15 | 2019-03-07 | 国立研究開発法人産業技術総合研究所 | Manufacturing method of aqueous solution containing ammonium ion or/and ammonia, manufacturing method of ammonium salt, and manufacturing apparatus therefor |
| CN109881012A (en) * | 2019-03-29 | 2019-06-14 | 厦门钨业股份有限公司 | A kind of processing method of tungsten metallurgy dephosphorized slag recycling tungsten |
| WO2019125293A1 (en) * | 2017-12-19 | 2019-06-27 | Easymining Sweden Ab | Chemical processing of struvite |
| CN110004309A (en) * | 2019-03-04 | 2019-07-12 | 中南大学 | The method of soda acid combined extracting tungsten from tungsten mineral |
| CN110194568A (en) * | 2019-06-21 | 2019-09-03 | 见嘉环境科技（苏州）有限公司 | A kind of processing method of high ammonia-nitrogen wastewater |
| CN110790312A (en) * | 2019-11-13 | 2020-02-14 | 厦门钨业股份有限公司 | Method for preparing ammonium paratungstate by utilizing tungsten-containing waste material |
| CN113666419A (en) * | 2021-08-12 | 2021-11-19 | 崇义章源钨业股份有限公司 | Method for preparing ammonium paratungstate by one-step ammonia solution dephosphorization of tungstic acid |
| CN113943871A (en) * | 2021-10-21 | 2022-01-18 | 崇义章源钨业股份有限公司 | Method for treating magnesium ammonium phosphate slag containing tungsten |
| CN114657368A (en) * | 2022-03-01 | 2022-06-24 | 信丰华锐钨钼新材料有限公司 | High-efficiency treatment method for low-grade mixed tungsten ore containing high flotation agent |
| CN114873645A (en) * | 2022-06-08 | 2022-08-09 | 赣州海盛钨业股份有限公司 | Method for preparing sodium tungstate by recycling tungsten waste |
| CN115069313A (en) * | 2022-06-30 | 2022-09-20 | 金川集团股份有限公司 | Ion exchange column desorption regeneration process |
| CN115072917A (en) * | 2022-04-25 | 2022-09-20 | 信丰华锐钨钼新材料有限公司 | Efficient treatment method for high-concentration ammonia nitrogen wastewater in tungsten smelting |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2868634B1 (en) * | 2013-11-05 | 2021-07-07 | Ivoclar Vivadent AG | Lithium disilicate apatite glass ceramic with transition metal oxide |
-
2022
- 2022-11-08 CN CN202211388265.4A patent/CN115679128B/en active Active
Patent Citations (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4108735A (en) * | 1976-06-14 | 1978-08-22 | Bethlehem Steel Corporation | Method for improved distillation of ammonia from weak ammonia liquor |
| US4115513A (en) * | 1977-08-16 | 1978-09-19 | Westinghouse Electric Corp. | Processing of ammonium paratungstate from tungsten ores |
| CN1377980A (en) * | 2002-02-06 | 2002-11-06 | 王旭升 | Process for preparing high purity ammonium para-tungstate using hihg-molybdenum tungsten ore |
| WO2008030235A2 (en) * | 2006-09-06 | 2008-03-13 | Fassbender Alexander G | Ammonia recovery process |
| CN101696036A (en) * | 2009-10-24 | 2010-04-21 | 刘向文 | Preparation process of ammonium paratungstate |
| JP2011179038A (en) * | 2010-02-26 | 2011-09-15 | Mitsubishi Materials Corp | Method for collecting tungsten from scrap of hard metal |
| CN102212697A (en) * | 2011-05-18 | 2011-10-12 | 湖南稀土金属材料研究院 | Tungsten slag treatment method |
| CN102296179A (en) * | 2011-08-31 | 2011-12-28 | 鹤山市沃得钨钼实业有限公司 | Method for producing tungsten-molybdenum product by processing tungsten-molybdenum symbiotic mixed ore |
| CN102557139A (en) * | 2011-12-26 | 2012-07-11 | 大余隆鑫泰钨业有限公司 | Method for dephosphorizing low-phosphorus ammonium tungstate solution |
| CN103014343A (en) * | 2013-01-18 | 2013-04-03 | 成都西顿硬质合金有限公司 | Process for recycling ammonium tungstate from ammonium paratungstate crystallization mother liquor |
| CN103060563A (en) * | 2013-01-18 | 2013-04-24 | 成都西顿硬质合金有限公司 | Technology of deep purification and impurity removal of ammonium tungstate or ammonium molybdate solution |
| CN103290224A (en) * | 2013-05-31 | 2013-09-11 | 刘甲祥 | Recovery process for valuable metals in tungsten residues |
| JP2015045041A (en) * | 2013-08-27 | 2015-03-12 | 京セラ株式会社 | Method for recovering tungsten compound |
| CN104108883A (en) * | 2014-08-11 | 2014-10-22 | 中国地质大学（北京） | High-strength lithium disilicate glass ceramic and preparation method thereof |
| CN104611559A (en) * | 2015-03-02 | 2015-05-13 | 湖南有色金属研究院 | Method for comprehensively recovering rubidium, tungsten and potassium from rubidium-tungsten-containing fluorite middlings |
| CN104817115A (en) * | 2015-04-15 | 2015-08-05 | 赣州海创钨业有限公司 | Method for removing micro-phosphorus in ammonium tungstate solution |
| JP2019034273A (en) * | 2017-08-15 | 2019-03-07 | 国立研究開発法人産業技術総合研究所 | Manufacturing method of aqueous solution containing ammonium ion or/and ammonia, manufacturing method of ammonium salt, and manufacturing apparatus therefor |
| CN107746966A (en) * | 2017-09-29 | 2018-03-02 | 湖南行者环保科技有限公司 | A kind of method that joint disposal ammonium paratungstate slag charge reclaims micro rare metal |
| CN108046326A (en) * | 2017-12-07 | 2018-05-18 | 崇义章源钨业股份有限公司 | The method for preparing ammonium paratungstate |
| WO2019125293A1 (en) * | 2017-12-19 | 2019-06-27 | Easymining Sweden Ab | Chemical processing of struvite |
| CN110004309A (en) * | 2019-03-04 | 2019-07-12 | 中南大学 | The method of soda acid combined extracting tungsten from tungsten mineral |
| CN109881012A (en) * | 2019-03-29 | 2019-06-14 | 厦门钨业股份有限公司 | A kind of processing method of tungsten metallurgy dephosphorized slag recycling tungsten |
| CN110194568A (en) * | 2019-06-21 | 2019-09-03 | 见嘉环境科技（苏州）有限公司 | A kind of processing method of high ammonia-nitrogen wastewater |
| CN110790312A (en) * | 2019-11-13 | 2020-02-14 | 厦门钨业股份有限公司 | Method for preparing ammonium paratungstate by utilizing tungsten-containing waste material |
| CN113666419A (en) * | 2021-08-12 | 2021-11-19 | 崇义章源钨业股份有限公司 | Method for preparing ammonium paratungstate by one-step ammonia solution dephosphorization of tungstic acid |
| CN113943871A (en) * | 2021-10-21 | 2022-01-18 | 崇义章源钨业股份有限公司 | Method for treating magnesium ammonium phosphate slag containing tungsten |
| CN114657368A (en) * | 2022-03-01 | 2022-06-24 | 信丰华锐钨钼新材料有限公司 | High-efficiency treatment method for low-grade mixed tungsten ore containing high flotation agent |
| CN115072917A (en) * | 2022-04-25 | 2022-09-20 | 信丰华锐钨钼新材料有限公司 | Efficient treatment method for high-concentration ammonia nitrogen wastewater in tungsten smelting |
| CN114873645A (en) * | 2022-06-08 | 2022-08-09 | 赣州海盛钨业股份有限公司 | Method for preparing sodium tungstate by recycling tungsten waste |
| CN115069313A (en) * | 2022-06-30 | 2022-09-20 | 金川集团股份有限公司 | Ion exchange column desorption regeneration process |
Non-Patent Citations (9)
| Title |
|---|
| 724 型阳离子树脂从钨酸铵溶液吸附除镁的动力学;张永会;中国钨业(第05期);第36-40页 * |
| 724型阳离子树脂从钨酸铵溶液吸附除镁的动力学;张永会;杨亮;;中国钨业;20191026(05);全文 * |
| 仲钨酸铵结晶母液深度脱除氨氮的研究;万林生;龚丹丹;付赞辉;李红超;孙丽;;稀有金属与硬质合金(04);全文 * |
| 折流反应器中鸟粪石类共沉淀法对脱氨尿液的处理;郭旭慧;苏冯婷;徐康宁;张驰;李继云;谢淘;汪诚文;;中国给水排水(13);全文 * |
| 现代钨冶炼过程中废水处理现状与发展;史明;唐忠阳;陈星宇;;稀有金属与硬质合金(02);全文 * |
| 用离子交换法从钨溶液中分离钼;袁斌, 邓舜勤;湿法冶金;20030615(02);全文 * |
| 磷酸铵镁法脱除废水中氨氮的技术现状;陈启华;罗冬浦;梁江浩;肖贤明;;工业水处理(06);全文 * |
| 钨绿色冶炼工艺研究方向和技术进展;万林生;邓登飞;赵立夫;李红超;徐国钻;梁勇;;有色金属科学与工程(05);全文 * |
| 钨酸铵溶液中镁离子的深度去除;傅楠;刘旭恒;赵中伟;;稀有金属与硬质合金(04);全文 * |
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