CN115679128A - Method for efficiently recovering tungsten and ammonia from tungsten-containing phosphorus removal precipitation slag - Google Patents
Method for efficiently recovering tungsten and ammonia from tungsten-containing phosphorus removal precipitation slag Download PDFInfo
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- CN115679128A CN115679128A CN202211388265.4A CN202211388265A CN115679128A CN 115679128 A CN115679128 A CN 115679128A CN 202211388265 A CN202211388265 A CN 202211388265A CN 115679128 A CN115679128 A CN 115679128A
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 84
- 239000010937 tungsten Substances 0.000 title claims abstract description 84
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002893 slag Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000001556 precipitation Methods 0.000 title claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011574 phosphorus Substances 0.000 title claims abstract description 23
- 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 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004090 dissolution Methods 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 150000001450 anions Chemical class 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 239000006228 supernatant Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 238000009396 hybridization Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 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 7
- 238000003795 desorption Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002699 waste material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000002184 metal 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
- 239000010452 phosphate Substances 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
- 230000001502 supplementing effect Effects 0.000 description 2
- 229910017958 MgNH Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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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Abstract
The invention relates to a method for efficiently recovering tungsten and ammonia from tungsten-containing phosphorus removal precipitation slag, which comprises the following steps: acid dissolution: adding acid liquor and water into the tungsten-containing phosphorus removal precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A; and (3) settling: settling the material A, and collecting supernatant; adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting effluent post-hybridization liquid; and (3) analysis: soaking, washing and resolving the anion resin in the column after adsorption is finished, and collecting resolving liquid, namely ammonium tungstate solution; alkali adjustment: adding alkali into the post-crossing liquid, and uniformly stirring to obtain a material B; and (3) filter pressing: carrying out filter pressing on the material B, removing precipitates, and collecting filtrate; ammonia recovery: and introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor. The method can efficiently recover tungsten and ammonia in the slag, the tungsten recovery can be realized by 100 percent, and the ammonia recovery is more than 99 percent, so that the method has better 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 phosphorus removal precipitation slag.
Background
The salt precipitation method is used for removing phosphorus in the tungsten smelting secondary liquid, the product is phosphate precipitation, the phosphorus removal effect is achieved after the phosphate precipitation is filtered, but part of tungsten is left in the precipitation in the process, the content of the part of tungsten reaches 1.5-5%, tungsten loss is caused by non-recovery, the recovery effect is poor by using the traditional soda boiling, and the auxiliary materials and the energy consumption are high.
The method for recovering tungsten from dephosphorization precipitation slag at present is mainly an alkali boiling method, has low recovery rate, can not realize the complete recovery of tungsten in the slag, and simultaneously has the problems of high-temperature alkali boiling, high auxiliary material and energy consumption, difficult control of alkalinity, high tungsten content in tailings due to insufficient alkali, formation of hydroxide flocculent viscous slag due to excessively high alkali and difficult filtration and washing. The boiled tungsten-containing liquid contains carbonate radical, the artificial white tungsten precipitated by calcium salt precipitator needs excessive calcium to realize complete tungsten precipitation, and the consumption of tungsten precipitation auxiliary materials is high.
Therefore, the existing method for recovering tungsten from the dephosphorization precipitation slag not only has low treatment efficiency and insufficient recovery depth, but also brings great waste to 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 tungsten metallurgy dephosphorized slag, which comprises the following steps of, pulping dephosphorized slag with water and heating to 40-90 ℃; adding dilute acid to regulate pH to 2-4, and stirring for reaction for 0.5-4 hr; filtering to obtain a decomposition liquid and trace undecomposed slag, continuously returning the undecomposed slag to the slurry mixing and heating step for continuous decomposition, and allowing valuable metal tungsten to enter the decomposition liquid; and adsorbing tungsten in the decomposition liquid by using large-aperture anion exchange resin, and then desorbing by using alkali to obtain a sodium tungstate solution for subsequent processes. The efficiency of the method for recovering tungsten is to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of tungsten recovery from the existing tungsten metallurgy dephosphorization residues and provide a method for efficiently recovering tungsten and ammonia from the tungsten-containing dephosphorization precipitation residues.
The invention preferably adopts waste acid for acid dissolution, the waste acid can be one or mixed acid of strong acids such as hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid and the like, the discovery has the advantages that the waste acid generated in the industry can be reused, the selection range is wide, and the conversion of changing waste into valuables can be realized.
In order to improve the recovery rate of tungsten, the inventor explores leaching effects under different conditions, and finds that the tungsten-containing dephosphorization precipitation slag is added after acid liquor is added, the slag can be completely dissolved when the pH is measured by stirring, the dissolution speed is slow when the pH is between 2 and 4, about 2 to 8 percent of the slag cannot be dissolved, and the slag is basically not dissolved when the pH is more than 5.
Therefore, the condition that the pH is less than 2 is favorable for tungsten in the slag to enter the solution as much as possible. However, this also causes new troubles. Because the acidity is very low, a large amount of metal ion impurities are dissolved out together, and enter a supernatant liquid along with the material A during solid-liquid separation and are adsorbed on resin in an adsorption link, so that a column body is blocked in the analysis process, analysis liquid cannot flow out smoothly, and analysis fails.
Therefore, the inventors further searched for and found that the reason for the failure is that a large amount of white precipitates are attached to the surface of the resin, and further, it was confirmed that the impurity metal elements are precipitated under the alkaline analysis conditions, and therefore, the resin was immersed with hydrochloric acid before the analysis to remove the metal ion impurities adsorbed on 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 phosphorus removal precipitation slag comprises the following steps:
(1) Acid dissolution: adding acid liquor and water into the tungsten-containing phosphorus removal precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A;
(2) And (3) settling: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting effluent post-crosslinking liquid;
(4) And (3) analysis: soaking the anion resin in the column after adsorption is finished, wherein the soaking solution is hydrochloric acid water 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 the resolving solution, namely ammonium tungstate solution;
(5) Alkali adjustment: adding alkali into the liquid after the crossing, 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;
(7) Ammonia recovery: and introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor.
Further, the content of tungsten in the tungsten-containing dephosphorization precipitation slag is 1.5-10wt%, the content of ammonia is 1-10wt%, preferably, the content of tungsten is 1.5-5%, the content of ammonia is 6-6.45%, and meanwhile, impurity elements of Mg and P are contained.
Further, in the step (1), the acid solution contains at least one of hydrochloric acid, sulfuric acid, phosphoric acid and carbonic acid; preferably, the pH of the solution is adjusted to 1-2.
Further, in the step (3), the anion resin is a weak base anion 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 by washing the resin with water.
Further, in the step (4), the concentration of the sodium hydroxide solution is 80-150g/l, and the addition amount of the sodium hydroxide solution is 1-2 times of the target tungsten adsorption amount according to the amount of the sodium hydroxide in the solution.
Further, in the step (5), the alkali treatment is to add sodium hydroxide, and the adding amount of the alkali is to control the concentration of the residual alkali in the solution after the reaction to be 5-10g/l.
Further, in the step (7), the temperature of the introduced steam is 95-99 ℃, and the amount of the alkali liquor added is 5-10g/l to ensure the alkali concentration in the solution.
Further, in the step (4), the desorption solution 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%.
Has the beneficial effects that:
the method can realize the high-efficiency recovery of tungsten from the dephosphorization precipitation slag, simultaneously realize the recovery of ammonia, reduce the consumption of auxiliary materials and energy consumption, realize 100 percent of tungsten recovery, simultaneously realize more than 99 percent of recovery of ammonia in the slag by matching with an ammonia recovery device, directly generate economic benefits and relieve the environmental protection pressure; the acid solvent adopts process waste acid, and changes waste into valuable.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a schematic process flow diagram provided by one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
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 phosphate magnesium salt precipitation, and the reaction equation is as follows: mg (magnesium) 2+ +NH 4 + +PO 4 3- +H 2 O＝MgNH 4 PO 4 ·6H 2 O (phosphorus removal sludge).
Example 1
Taking the dephosphorization precipitation slag for treatment, as shown in figure 1, comprising the following steps:
(1) Acid dissolution: adding acid liquor and water into the tungsten-containing phosphorus removal precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A;
(2) And (3) settling: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting effluent post-hybridization liquid;
(4) And (3) resolving: soaking the anion resin in the column after adsorption is finished, wherein the soaking solution is hydrochloric acid water solution with the concentration of 50g/l, soaking time is 5 hours, then washing the resin with water, finally, resolving the resin with sodium hydroxide solution, and collecting the resolving solution, namely ammonium tungstate solution;
(5) Alkali adjustment: adding alkali into the liquid after the crossing, 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;
(7) Ammonia recovery: and 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 the acid dissolution effect, as follows:
1000kg of phosphorus-removing sediment sample (WO) 3 Content 4.25%, water content 32%), use 3m 3 Mixing with water, slowly adding waste acid (mixed acid of sulfuric acid, phosphoric acid, and hydrochloric acid) with acidity of 90g/l, stirring to react for 30min when pH is 5, filtering to remove residue, measuring volume of solution and WO 3 456.7kg of slag, 35% of water and 7.2m of solution 3 Solution WO3:2.1g/l; therefore, the slag dissolution rate is calculated as follows: 56.34%, WO 3 The dissolution rate is as follows: 52.32 percent;
the above operations were repeated except that the dissolution rate of the slag was 93.2% when the pH was adjusted to 4, and WO 3 The dissolution rate is as follows: 94.47 percent.
The above operations were repeated except that the slag dissolution rate was 97.54% when the pH was adjusted to 3, WO 3 The dissolution rate is as follows: 98.18 percent.
The above operation was repeated except that the slag dissolution rate was 99.12% when the pH was adjusted to 2, and WO 3 The dissolution rate is as follows: 99.54 percent.
The above operations were repeated except that the dissolution rate of the slag was 99.98% when the pH was adjusted to 1 (the limit was measured by a test paper for acid), and WO 3 The dissolution rate is as follows: 100 percent, the dissolution is completed instantly, the dissolution speed is high, and the dissolution is complete.
It can be seen that after the pH of the acid solution has dropped, WO 3 The dissolution rate is improved.
In the present invention, the acidity is defined as the number of milligrams of potassium hydroxide (KOH) required for neutralizing 1 gram of chemical substance.
Example 2
In this embodiment, the method for exploring the analysis process and taking the phosphorous removal precipitation slag for treatment comprises the following steps:
(1) 1000kg of phosphorus-removing sediment sample (WO) 3 Content 4.25%, water content 32%), use 3m 3 And (3) mixing the slurry with water, slowly supplementing process waste acid, and obtaining a material A with the pH = 1.5.
(2) And (3) settling: settling the material A, and collecting supernatant; the process is to settle insoluble substances contained in the slag and avoid the insoluble substances entering the exchange column to influence the adsorption flow of the exchange column.
(3) Adsorption: and (3) delivering the supernatant into a column filled with anion resin for adsorption, and collecting the effluent post-crosslinking liquid.
Adsorbing with weakly basic anion resin (large pore anion resin, AH-80 II) capable of adsorbing WO with equal mass under acidic condition 3 The concentration of tungsten dissolved out by acid is not too high, and the adsorption flow is controlled to be 5-12m 3 The tungsten adsorption rate can reach more than 99.9% in the adsorption flow interval of/h.
(4) And (3) analysis:
the column, which has absorbed the supernatant and reached saturation, is operated according to the steps of back-flushing (with water), washing (with water), feeding the base (sodium hydroxide solution). The following are found: the back-flushing and washing flow can reach 7m 3 To 9m 3 While the flow rate is normal, but the flow rate starts to be 8m after the alkali is fed 3 Is always lowered to 1m 3 Thereafter, the column was leaked, and the desorption operation was not performed any more, and the resin was released to find that all white precipitates were adhered, and the space between the resins was filled with the white precipitates, so that the desorption was not performed at a flow rate.
The column saturated was further subjected to the steps of back washing (with water), acid soaking (with a 50g/l aqueous hydrochloric acid solution for 5 hours), washing (with water), and feeding an alkali (sodium hydroxide solution). The following are found: the front backflushing and the washing flow can reach 7m 3 To 9m 3 To after the alkali is fed, flowThe amount can also be stabilized at 7m 3 To 9m 3 Meanwhile, the desorption process is smooth, the discharged resin is checked, the resin is clean, and no precipitate exists.
In this example, the resin was resolved with a sodium hydroxide solution, the alkali concentration (i.e., the concentration of sodium hydroxide) was controlled at 100g/l, the amount of alkali was 1.2 times the amount of tungsten adsorbed, and the resolved solution was collected, i.e., an ammonium tungstate solution. (5) alkali adjustment: and adding alkali (sodium hydroxide solution) into the solution after the crossing, and uniformly stirring to obtain a material B.
The method comprises the steps of carrying out alkali treatment on the post-exchange liquid after tungsten is adsorbed by the exchange column, precipitating oxyhydrogen precipitates and the like after reverse adjustment, and controlling the concentration of residual alkali (namely the concentration of sodium hydroxide) after alkali addition to be about 5-10g/l.
The residual alkali concentration refers to 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 precipitates, avoiding slag from being brought into a stripping device, and collecting filtrate;
(7) Ammonia recovery: and 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, before desorption, the resin is soaked for 4-8 hours by using dilute hydrochloric acid with the concentration of 40-80g/l, the concentration selection mainly considers that metal cations (calcium, magnesium and the like) and salts thereof and the like can be solved, meanwhile, the residual acid is not too high, the cost of next alkali regulation and water treatment is facilitated, and the dilute hydrochloric acid is used for washing the resin by using water with the volume of 4-5 times of the resin, so that the condition that the flow of tungsten dissolving and the quality of sodium tungstate are influenced by separating out hydroxide precipitates during alkaline tungsten dissolving is avoided. The step is a key step, if the dilute hydrochloric acid is not soaked, desorption cannot be carried out, and the adsorption technical route after acid dissolution cannot be realized.
Example 3
A method for efficiently recovering tungsten and ammonia from tungsten-containing phosphorus removal precipitation slag comprises the following steps:
(1) 1000kg of phosphorus-removing sediment sample (WO 3 content 4.25%, water content 32%) is taken, and 3m is used 3 Mixing the slurry with water, slowly supplementing process waste acid, and obtaining a material A with the pH = 1;
(2) And (3) settling: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting effluent post-hybridization liquid;
(4) And (3) analysis: soaking the anion resin in the column after adsorption is finished, wherein the soaking solution is hydrochloric acid water solution with the concentration of 40g/l, the soaking time is 8 hours, then washing the resin with water, finally, resolving the resin with sodium hydroxide solution with the concentration of 100g/l, the addition of the sodium hydroxide solution is 1.1 times of the target tungsten adsorption amount according to the amount of the sodium hydroxide in the solution, and collecting the resolving solution, namely ammonium tungstate solution;
(5) Alkali adjustment: adding alkali into the solution after the hybridization, adding a sodium hydroxide solution, wherein the adding amount of the alkali is controlled so as to control the concentration of the residual alkali in the solution after the reaction to be 6g/l, and uniformly stirring to obtain a material B;
(6) And (3) filter pressing: performing pressure filtration 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 deg.C, adding alkali solution (sodium hydroxide solution) to make alkali concentration in the solution be 10g/l, stripping deamination by adopting traditional stripping operation method, and condensing to recover ammonia (the ammonia content can be recovered by 100%), and the ammonia content in the feed liquid is only 8.8ppm after stripping, and the ammonia recovery is up to above 99%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for efficiently recovering tungsten and ammonia from tungsten-containing phosphorus removal precipitation slag is characterized by comprising the following steps: the method comprises the following steps:
(1) Acid dissolution: adding acid liquor and water into the tungsten-containing phosphorus removal precipitation slag, mixing slurry, and controlling the pH value of the solution to be less than 2 to obtain a material A;
(2) And (3) settling: settling the material A, and collecting supernatant;
(3) Adsorption: sending the supernatant into a column filled with anion resin for adsorption, and collecting effluent post-hybridization liquid;
(4) And (3) resolving: soaking the anion resin in the column after adsorption is finished, wherein the soaking solution is hydrochloric acid water 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 the resolving solution, namely ammonium tungstate solution;
(5) Alkali adjustment: adding alkali into the post-crossing liquid, 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;
(7) Ammonia recovery: and introducing steam into the filtrate, adding alkali liquor, collecting gas and condensing to obtain ammonia liquor.
2. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to claim 1, which is characterized by comprising the following steps: the tungsten content in the tungsten-containing dephosphorization precipitation slag is 1.5-10wt%, the ammonia content is 1-10wt%, and meanwhile, the tungsten-containing dephosphorization precipitation slag contains Mg and P impurity elements.
3. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to claim 1, which is characterized in that: in the step (1), the acid solution contains at least one of hydrochloric acid, sulfuric acid, phosphoric acid and carbonic acid; preferably, the pH of the solution is adjusted to 1-2.
4. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to claim 3, characterized in that: in the step (3), the anion resin is weak-base anion resin.
5. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to any one of claims 1 to 4, characterized in that: in the step (4), the resin is washed by water with the volume of 3-5 times of the resin.
6. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to claim 5, characterized in that: in the step (4), the concentration of the sodium hydroxide solution is 80-150g/l, and the addition amount of the sodium hydroxide solution is 1-2 times of the target tungsten adsorption amount according to the amount of the sodium hydroxide in the solution.
7. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to any one of claims 1 to 4, characterized in that: in the step (5), the alkali adding treatment is to add sodium hydroxide, and the adding amount of the alkali is used for controlling the concentration of the residual alkali in the solution after the reaction to be 5-10g/l.
8. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to claim 1, which is characterized in that: in the step (7), the temperature of the introduced steam is 95-99 ℃, and the amount of the alkali liquor added is 5-10g/l to ensure the alkali concentration in the solution.
9. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to any one of claims 1 to 4, characterized in that: in the step (4), the desorption solution is collected, and the recovery rate of tungsten is 99-100%.
10. The method for efficiently recovering tungsten and ammonia from the tungsten-containing phosphorus removal precipitation slag according to any one of claims 1 to 4, characterized in that: in the step (7), the gas is collected, and the recovery rate of ammonia is more than or equal to 99%.
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| CN116924472A (en) * | 2023-09-14 | 2023-10-24 | 崇义章源钨业股份有限公司 | Comprehensive utilization method of tungsten-containing magnesium ammonium phosphate slag |
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