CN114672672A - Method for recovering tungstic acid from tungsten-containing solution - Google Patents
Method for recovering tungstic acid from tungsten-containing solution Download PDFInfo
- Publication number
- CN114672672A CN114672672A CN202210405008.0A CN202210405008A CN114672672A CN 114672672 A CN114672672 A CN 114672672A CN 202210405008 A CN202210405008 A CN 202210405008A CN 114672672 A CN114672672 A CN 114672672A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- solution
- containing solution
- acid
- tungstic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 423
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 423
- 239000010937 tungsten Substances 0.000 title claims abstract description 423
- 238000000034 method Methods 0.000 title claims abstract description 92
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 title claims abstract description 91
- 238000001556 precipitation Methods 0.000 claims abstract description 137
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002253 acid Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 27
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims description 61
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000001704 evaporation Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 230000008020 evaporation Effects 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 238000010025 steaming Methods 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 description 39
- 238000012360 testing method Methods 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000012535 impurity Substances 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000002893 slag Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 150000004965 peroxy acids Chemical class 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of tungsten recovery, and relates to a method for recovering tungstic acid from a tungsten-containing solution. The invention provides a method for recovering tungstic acid from a tungsten-containing solution, which comprises the following steps: adding the tungsten-containing solution into an acid solution for tungsten precipitation reaction, and then carrying out first solid-liquid separation to obtain the tungstic acid. The method for recovering tungstic acid from the tungsten-containing solution breaks through the characteristics of long process, high cost, large pollution and the like of the traditional tungsten-containing solution treatment, has simple process flow, environmental protection and low energy consumption, can realize the recovery and the reutilization of the treated tungsten, can realize the recovery and the reutilization of ammonium bicarbonate and sulfuric acid which are raw and auxiliary materials, has better environmental protection and economic value, is suitable for the tungsten-containing solution generated in various APT (ammonium paratungstate) production processes, and has good application prospect in the tungsten smelting industry.
Description
Technical Field
The invention belongs to the technical field of tungsten recovery, and relates to a method for recovering tungstic acid from a tungsten-containing solution.
Background
Ammonium Paratungstate (APT) is an important intermediate product in a tungsten smelting process, a crystallization process and a slag washing process of the ammonium paratungstate are involved in a production process of the ammonium paratungstate, a large amount of crystallization mother liquor and slag washing solution (tungsten-containing solution) are generated, the crystallization mother liquor and the slag washing solution contain a large amount of tungsten and a large amount of impurity elements such As Sb, P, As and the like, and in addition, the crystallization mother liquor and the slag washing solution in some APT production processes also contain high content of ammonium bicarbonate, so that the ammonium paratungstate cannot be directly returned to the process for use. Therefore, how to efficiently recover the tungstic acid from the tungsten-containing solution and reasonably and effectively utilize the tungsten-containing solution is very important.
At present, tungsten in tungsten-containing solutions such as crystallization mother liquor generated in the production process of ammonium paratungstate is usually recovered by methods such as an artificial scheelite method, an alkali conversion method, hydrochloric acid adjustment method and the like. The main purpose of the artificial white tungsten method is to convert tungsten in the tungsten-containing dilute solution into calcium tungstate (artificial white tungsten) which is very difficult to dissolve, and the main used precipitator is CaCl2. The artificial scheelite method is mainly divided into two process flows: (1) CaCl2Artificial scheelite is precipitated → acid decomposed and partially molybdenum removed → crude tungstic acid → returns to the main process; (2) molybdenum removal → CaCl2Precipitating artificial scheelite → returning to ball milling for alkali decomposition; the method has long process, low tungsten deposition rate, high secondary consumption of raw and auxiliary materials in the main process returning to the front end and large secondary consumptionThis method is not commonly used now for the above reasons, which greatly increases the processing cost. The alkali conversion method mainly utilizes alkali to convert (NH) in a tungsten-containing dilute solution4)2WO4And (NH)4)2MoO4Conversion to Na2WO4And Na2MoO4Then, the molybdenum is removed by vulcanization, and Na is removed after molybdenum removal2WO4The solution is directly mixed into a crude sodium tungstate solution according to a tungsten smelting method for ion exchange or mixed into the sodium tungstate solution for extraction after impurities such As P, As, Si and the like are removed, and then the solution enters a main flow. The method has long process flow and S in the solution2-Leading to the problem of resin poisoning, and reintroducing impurity sodium ions. The hydrochloric acid adjusting method is mainly divided into two process flows: (1) hydrochloric acid adjusting acid-tungstic acid precipitation method; (2) hydrochloric acid adjusting acid-ion exchange method. The method (1) adds hydrochloric acid into a tungsten-containing dilute solution to a certain pH value to obtain a certain tungstic acid solid, but the tungsten deposition rate of the method is reduced, the filtrate still contains a large amount of tungsten and needs further treatment, the consumption of the hydrochloric acid is large, the introduction of chloride ions affects the quality of subsequent products and has high requirements on equipment, and the environment is severe and has high requirements on environmental protection; the method (2) adjusts the tungsten-containing solution to a certain pH value by using hydrochloric acid, then the solution is put into a large-aperture weak-acid resin, then the resin is returned by alkaline desorption, and the solution is mixed with the sodium tungstate solution and enters a main flow path.
Therefore, the existing method for recovering tungstic acid from tungsten-containing solutions such as crystallization mother liquor generated in the ammonium paratungstate process has the defects of introducing impurities outside a system, large environmental pollution, high cost, low tungsten precipitation rate, high impurity content of tungsten precipitation filtrate and the like.
Disclosure of Invention
The invention aims to overcome the defects of impurity introduction outside a system, large environmental pollution, high cost, low tungsten precipitation rate, high impurity content of tungsten precipitation filtrate and the like in the method for recovering tungstic acid from tungsten-containing solutions such as crystallization mother liquor, slag washing liquor and the like generated in an ammonium paratungstate process, and further provides a method for recovering tungstic acid from the tungsten-containing solutions.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for recovering tungstic acid from a tungsten-containing solution comprises the following steps: adding the tungsten-containing solution into an acid solution for tungsten precipitation reaction, and then carrying out first solid-liquid separation to obtain the tungstic acid.
Preferably, the addition rate of the tungsten-containing solution is not more than 30% times of the volume of the acid solution per hour, and preferably, the addition rate of the tungsten-containing solution is 10-30% times of the volume of the acid solution per hour. At 10m3For example, the addition rate of the solution containing tungsten is not more than 3m3H is used as the reference value. The invention discovers that when the adding speed of the tungsten-containing solution is more than 3m through research3At the time of/h, tungstic acid can not be formed due to the high speed and no local peracid environment, and when the adding speed of the tungsten-containing solution is less than 1m3In the hour of per hour, the tungsten deposition effect is good and is less than 1m3H and 1-2m3The tungsten deposition rate/h is not very different, but the operation efficiency is not high, so that it is preferable to use 10m3The adding speed of the tungsten-containing solution is 1-3m based on the acid solution3/h。
Preferably, the concentration of the acid solution is not less than 350g/L, and the tungsten precipitation reaction end point is that the concentration of the acid in the reaction solution is not less than 5 g/L; preferably, the concentration of the acid solution is 350-400g/L, and the end point of the tungsten precipitation reaction is that the concentration of the acid in the reaction solution is 5-10 g/L. Optionally, the tungsten precipitation reaction end point is that the concentration of sulfuric acid or hydrochloric acid in the reaction solution is 5-10 g/L. According to the invention, the research shows that when the concentration of the acid solution is less than 350g/L, the tungsten deposition rate is obviously reduced due to insufficient acid concentration; when the concentration of the acid solution is more than 400g/L, the tungsten deposition effect is good, but the tungsten deposition rate is not much different from 400g/L, therefore, the concentration of the acid solution is preferably 350-400 g/L; when the concentration of the sulfuric acid in the reaction solution is less than 5g/L, the tungsten precipitation rate is reduced, and the too low acid cannot form tungstic acid, and when the concentration of the sulfuric acid in the reaction solution is more than 10g/L, the tungsten precipitation effect is good, but the residual acid is wasted, and the acid consumption is increased, so that the tungsten precipitation reaction end point is the concentration of the acid in the reaction solution, and the concentration of the acid is preferably 5-10 g/L.
Preferably, the tungsten precipitation reaction temperature is 75-90 ℃, and the tungsten precipitation reaction stirring speed is 200-250 r/min.
Preferably, the method further comprises the step of heating and evaporating ammonium from the tungsten-containing solution before adding the tungsten-containing solution into the acid solution.
Preferably, the end point of heating and ammonium evaporation is controlled to be 6.5-7 of the pH value of the tungsten-containing solution. When the end point of heating and ammonium evaporation is controlled to be the pH value of the tungsten-containing solution to be less than 6.5, impurities precipitated in the tungsten-containing solution can be dissolved again, and when the end point of heating and ammonium evaporation is controlled to be the pH value of the tungsten-containing solution to be more than 7, impurities such as antimony and the like in the tungsten-containing solution can not be precipitated.
Preferably, the temperature for heating and evaporating the ammonium is 75-85 ℃.
Preferably, the method further comprises a step of performing a second solid-liquid separation on the tungsten-containing solution obtained after the ammonium is steamed by heating to obtain a purified tungsten-containing solution after the ammonium is steamed by heating.
Preferably, the method comprises the following steps:
1) heating the tungsten-containing solution to evaporate ammonium to obtain an ammonium-evaporated tungsten-containing solution;
2) carrying out solid-liquid separation on the tungsten-containing solution after ammonium evaporation to obtain a purified tungsten-containing solution;
3) adding the purified tungsten-containing solution into a sulfuric acid solution for tungsten precipitation reaction, and then carrying out solid-liquid separation on the reaction solution to obtain tungstic acid solid.
Preferably, in the step 3), the addition rate of the tungsten-containing solution is not more than 30% of the volume of the acid solution per hour, and preferably, the addition rate of the tungsten-containing solution is 10-30% of the volume of the acid solution per hour;
the concentration of the acid solution is not less than 350g/L, and the end point of the tungsten precipitation reaction is that the concentration of the acid in the reaction solution is not less than 5 g/L;
preferably, the concentration of the acid solution is 350-400g/L, and the end point of the tungsten precipitation reaction is that the concentration of the acid in the reaction solution is 5-10 g/L;
the tungsten deposition reaction temperature is 75-90 ℃, and the tungsten deposition reaction stirring speed is 200-.
Preferably, the end point of the heating ammonium evaporation in the step 2) is controlled to be the pH value of the tungsten-containing solution to be 6.5-7, and the temperature of the heating ammonium evaporation is 75-85 ℃.
Preferably, the ammonium bicarbonate gas obtained by heating and evaporating ammonium can be recycled by condensation;
the tungsten precipitation filtrate obtained after the first solid-liquid separation is used for preparing an acid solution or used as an absorbent, for example, residual acid in the tungsten precipitation filtrate is used for inorganization absorption in the whole production to absorb ammonia gas.
Preferably, the acid solution is a hydrochloric acid solution or a sulfuric acid solution, and preferably, the acid solution is a sulfuric acid solution.
Preferably, the tungsten-containing solution is a crystallization mother liquor and/or a slag washing solution generated in the production process of ammonium paratungstate.
Preferably, the tungsten-containing solution comprises the following components: the tungsten-containing solution comprises the following components: WO3The content is 15-55g/L, the content of P element is 0.008-0.025g/L, and the content of As element is 0.001-0.6 g/L.
Preferably, the tungsten-containing solution further comprises Sb with the content of 0.04-1g/L and/or CO3 2-The content is 50-150 g/L.
Optionally, the pH of the tungsten-containing solution is 6-14.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention provides a method for recovering tungstic acid from a tungsten-containing solution, which comprises the following steps: adding the tungsten-containing solution into an acid solution for tungsten precipitation reaction, and then carrying out first solid-liquid separation to obtain the tungstic acid. The method comprises the steps of adding a tungsten-containing solution into an acid solution to carry out tungsten precipitation reaction, enabling the tungsten-containing solution to be partially peracid, and adding WO in the tungsten-containing dilute solution4 2-Direct formation of tungstic acid H2WO4Preventing tungsten from polymerizing into HW6O21 5-、W12O41 10-、HW12O41 9-、H2W12O41 8-、W12O39 6-、HW12O39 5-When the tungsten heteropoly acid radical is in the form, most of the anion impurities such As P, As, Si and the like in the tungstic acid solution and the cations in the solution form precipitates to enter the slag, thereby effectively improving the tungsten precipitation rate, and the tungsten precipitation filtrate has few impurities and can enter the next cycle for preparationThe sulfuric acid is used or returned to the main process for unorganized absorption, and the continuous recycling of waste liquid is realized. In addition, the method has the advantages of high acidity, low consumption of sulfuric acid, environmental friendliness and low cost.
2) In the method for recovering tungstic acid from tungsten-containing solution, the addition rate of the tungsten-containing solution is not more than 30% of the volume/h of the acid solution, preferably 10-30% of the volume/h of the acid solution. According to the invention, the addition speed of the tungsten-containing solution is controlled, so that the tungsten-containing solution can be effectively ensured to form a local peracid environment, the formation of heteropoly tungstic acid is inhibited, tungstic acid is formed by one-step tungsten precipitation, the tungstic acid can be directly recycled, the tungsten precipitation rate is effectively improved, and the tungsten precipitation filtrate impurities are reduced.
3) The method for recovering tungstic acid from the tungsten-containing solution further comprises the steps that the concentration of the acid solution is not less than 350g/L, and the tungsten precipitation reaction end point is that the concentration of acid in the reaction solution is not less than 5 g/L; preferably, the concentration of the acid solution is 350-400g/L, and the end point of the tungsten precipitation reaction is that the concentration of the acid in the reaction solution is 5-10 g/L. According to the invention, the concentration of the acid solution and the tungsten precipitation reaction end point are controlled to further ensure that the tungsten-containing solution forms a local peracid environment, inhibit the formation of heteropoly tungstic acid, precipitate tungsten in one step and form tungstic acid, effectively improve the tungsten precipitation rate and reduce the tungsten precipitation filtrate impurities.
4) The method for recovering tungstic acid from the tungsten-containing solution further comprises the steps of precipitating tungsten at the temperature of 75-90 ℃ and precipitating tungsten at the stirring speed of 200-250 r/min. The invention promotes the growth and formation of tungstic acid particles by controlling the reaction temperature and the stirring speed of tungsten precipitation, and can better realize liquid-solid separation by adopting a common filtering mode. In addition, the tungsten deposition temperature is controlled to be 75-90 ℃, tungstic acid is easy to form and grow at the temperature, and a large amount of heat is released in the tungsten deposition reaction process, so that extra heating is not needed in the tungsten deposition process, and the tungsten deposition energy consumption is low.
5) The invention provides a method for recovering tungstic acid from tungsten-containing solution, when the tungsten-containing solution contains ammonium bicarbonate, the existence of ammonium bicarbonate is not beneficial to the proceeding of tungsten deposition reaction, the ammonium bicarbonate preferentially reacts with acid and dilutes the tungsten-containing concentration of the solution, thereby affecting the tungsten deposition rate, the impurity content of tungsten deposition filtrate and increasing the acid consumption. Further, the end point of heating and ammonium evaporation is controlled to be 6.5-7 of the pH value of the tungsten-containing solution. Under the condition, residual ammonium bicarbonate is almost completely removed, impurity Sb in the dilute solution containing tungsten is precipitated in a solid form, and the purified solution containing tungsten can be obtained through liquid-solid separation. According to the method, the ammonium steaming temperature is controlled, the pH value of the tungsten-containing solution at the ammonium steaming end point is heated, so that the aim of steaming ammonium is fulfilled, and meanwhile, the vulcanized antimony in the tungsten-containing solution can be separated out in a precipitation mode, and the antimony in the tungsten-containing solution can be further removed.
6) The method for recovering tungstic acid from the tungsten-containing solution provided by the invention has the advantages that the acid solution is a sulfuric acid solution, and compared with hydrochloric acid, the method has the advantages of stronger acidity, less acid consumption, higher tungsten precipitation rate, less impurity content of tungsten precipitation filtrate and more environment-friendly property.
7) The method for recovering tungstic acid from the tungsten-containing solution breaks through the characteristics of long process, high cost, large pollution and the like of the traditional tungsten-containing solution treatment, has simple process flow, environmental protection and low energy consumption, can realize the recovery and the reutilization of tungsten after treatment, can realize the recovery and the reutilization of ammonium bicarbonate and sulfuric acid which are raw and auxiliary materials, has better environmental protection and economic value, is suitable for the tungsten-containing solution generated in various APT (alkaline peroxide mechanical polishing) production processes, and has good application prospect in the tungsten smelting industry.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor generated in the production process of ammonium paratungstate, and the tungsten-containing solution comprises the following components: WO337g/L of Sb element, 0.02g/L of P element, 0.06g/L of As element, and CO3 2-The content is 105g/L, the pH value of the tungsten-containing solution is 13, and the method comprises the following steps:
1) heating the tungsten-containing solution to evaporate ammonium so as to expel ammonium carbonate gas from the tungsten-containing solution to obtain an ammonium-evaporated tungsten-containing solution, wherein the temperature of heating and evaporating ammonium is 75 ℃, and the end point of heating and evaporating ammonium is controlled to be the pH value of the tungsten-containing solution to be 7;
2) carrying out solid-liquid separation on the tungsten-containing solution after ammonium evaporation, and collecting a liquid phase to obtain a purified tungsten-containing solution;
3) adding the purified tungsten-containing solution to 10m3The tungsten precipitation reaction is carried out in the sulfuric acid solution, and the adding speed of the tungsten-containing solution is 1m3And h, the concentration of the sulfuric acid solution is 400g/L, the tungsten precipitation reaction temperature is 90 ℃, the tungsten precipitation reaction stirring speed is 200r/min, when the concentration of sulfuric acid in the reaction solution is 10g/L, the tungsten-containing solution is stopped to be added, and the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate and the tungstic acid purity; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution3The content of the element is 52.84g/L, the content of Sb element is 0.007g/L, the content of P element is 0.028g/L, the content of As element is 0.088g/L, CO3 2-The content is 10 g/L; WO in tungsten precipitation filtrate3The content is 0.096g/L, the P content is 0.0025g/L, and the As content is 0.016 g/L; the tungsten deposition rate is 99.6%, the purity of the tungstic acid is 91.6%, and the removal rate of the metal Sb is 99.11%.
Example 2
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor generated in the production process of ammonium paratungstate, and comprises the following components: WO328.5g/L of Sb element, 0.41g/L of P element, 0.019g/L of As element, 0.07g/L of CO3 2-The content is 103g/L, the pH value of the tungsten-containing solution is 13, and the method comprises the following steps:
1) heating the tungsten-containing solution to evaporate ammonium so as to expel ammonium carbonate gas from the tungsten-containing solution to obtain an ammonium-evaporated tungsten-containing solution, wherein the temperature of heating and evaporating ammonium is 80 ℃, and the end point of heating and evaporating ammonium is controlled to be the pH value of the tungsten-containing solution to be 7;
2) carrying out solid-liquid separation on the tungsten-containing solution after ammonium evaporation, and collecting a liquid phase to obtain a purified tungsten-containing solution;
3) adding the purified tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 2m3And h, stopping adding the tungsten-containing solution when the concentration of sulfuric acid in the reaction solution is 5g/L, and performing solid-liquid separation on the reaction solution to obtain tungsten precipitation filtrate and tungstic acid solid, wherein the concentration of the sulfuric acid solution is 350g/L, the tungsten precipitation reaction temperature is 80 ℃, the tungsten precipitation reaction stirring speed is 250 r/min.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution340.72g/L of Sb element, 0.0075g/L of P element, 0.027g/L of As element, 0.098g/L of CO3 2-The content is 13 g/L; precipitating tungsten filtrateWO of Zhong3The content is 0.11g/L, the content of P element is 0.0032g/L, and the content of As element is 0.0025 g/L; the tungsten precipitation rate is 99.67%, the purity of the tungstic acid is 89.43%, and the removal rate of the metal Sb is 98.72%.
Example 3
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor generated in the production process of ammonium paratungstate, and comprises the following components: WO336.7g/L of Sb element, 0.49g/L of P element, 0.0084g/L of As element, 0.03g/L of CO3 2-The content is 96g/L, the pH value of the tungsten-containing solution is 13, and the method comprises the following steps:
1) heating the tungsten-containing solution to evaporate ammonium so as to expel ammonium carbonate gas from the tungsten-containing solution to obtain an ammonium-evaporated tungsten-containing solution, wherein the temperature of heating and evaporating ammonium is 85 ℃, and the end point of heating and evaporating ammonium is controlled to be the pH value of the tungsten-containing solution to be 6.5;
2) carrying out solid-liquid separation on the tungsten-containing solution after ammonium evaporation, and collecting a liquid phase to obtain a purified tungsten-containing solution;
3) adding the purified tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 3m3And h, the concentration of the sulfuric acid solution is 400g/L, the tungsten precipitation reaction temperature is 75 ℃, the tungsten precipitation reaction stirring speed is 250r/min, when the concentration of sulfuric acid in the reaction solution is 10g/L, the tungsten-containing solution is stopped to be added, and the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution352.49g/L, 0.0048g/L of Sb element, 0.012g/L of P element, 0.043g/L of As element, CO3 2-The content is 4 g/L; WO in tungsten precipitation filtrate3The content is 0.19g/L, the content of P element is 0.00022g/L, and the content of As element is 0.0015 g/L; the tungsten deposition rate is 98.26%, the purity of the tungstic acid is 90%, and the removal rate of the metal Sb is 99.32%.
Example 4
This example provides a process for recovering tungstic acid from a tungsten-containing solution, which differs from example 3 in that the purified tungsten-containing solution is added to 10m in step 3)3Carrying out tungsten precipitation reaction in hydrochloric acid solution, wherein the adding speed of the tungsten-containing solution is 3m3And h, stopping adding the tungsten-containing solution when the concentration of the hydrochloric acid in the reaction solution is 7.5g/L, and performing solid-liquid separation on the reaction solution to obtain a tungsten precipitation filtrate and a tungstic acid solid, wherein the concentration of the hydrochloric acid solution is 300g/L, the tungsten precipitation reaction temperature is 75 ℃, and the tungsten precipitation reaction stirring speed is 250 r/min.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution352.49g/L, 0.0048g/L of Sb element, 0.012g/L of P element, 0.043g/L of As element, CO3 2-The content is 4 g/L; WO in tungsten precipitation filtrate3The content is 1.56g/L, the content of P element is 0.0032g/L, and the content of As element is 0.0083 g/L; the tungsten precipitation rate is 96.93%, and the metal Sb removal rate is 99.32%.
Example 5
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor generated in the production process of ammonium paratungstate, and comprises the following components: WO3The method comprises the following steps of preparing a tungsten-containing solution, wherein the content of the tungsten-containing solution is 24.6g/L, the content of Sb is 0.049g/L, the content of P is 0.02g/L, the content of As is 0.043g/L, and the pH value of the tungsten-containing solution is 6:
adding tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 1m3H, concentration of sulfuric acid solutionThe temperature is 400g/L, the tungsten precipitation reaction temperature is 90 ℃, the tungsten precipitation reaction stirring speed is 200r/min, when the concentration of sulfuric acid in the reaction solution is 10g/L, the tungsten-containing solution is stopped to be added, and the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid.
Respectively testing the component contents of the tungsten-containing solution and the tungsten deposition filtrate, and further calculating the tungsten deposition rate and the purity of tungstic acid; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in tungsten precipitation filtrate3The content of 0.59g/L, the P content of 0.0064g/L, the As content of 0.0033g/L, the Sb element content of 0.025g/L, the tungsten deposition rate of 97.44 percent and the purity of the tungstic acid of 89.8 percent.
Example 6
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor generated in the production process of ammonium paratungstate, and comprises the following components: WO3The method comprises the following steps of preparing a tungsten-containing solution, wherein the content of the tungsten-containing solution is 17.88g/L, the content of Sb is 0.091g/L, the content of P is 0.019g/L, the content of As is 0.043g/L, and the pH value of the tungsten-containing solution is 6:
adding tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 2m3And h, the concentration of the sulfuric acid solution is 350g/L, the tungsten precipitation reaction temperature is 85 ℃, the tungsten precipitation reaction stirring speed is 250r/min, the reaction is stopped when the concentration of sulfuric acid in the reaction solution is 5g/L, and the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid.
Respectively testing the component contents in the tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate; the formula of the tungsten precipitation rate is (C1 & V1-C2 & V2)/C1 & V1 & 100%, wherein C1 and V1 are the concentration and the solution volume of tungsten-containing liquid WO3 respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate respectively, and the test results show that: WO in tungsten precipitation filtrate3The content is 0.13g/L, the content of Sb element is 0.045g/L, the content of P is 0.0035g/L, and the content of As is 0.0035 g/L; tungsten deposition rate is 98.71%, tungstic acidThe purity was 88.5%.
Example 7
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a slag washing solution generated in the production process of ammonium paratungstate, and the tungsten-containing solution comprises the following components: WO3The content of P element is 0.057g/L, the content of As element is 0.001g/L, the content of CO is 20g/L3 2-The content is 112g/L, the pH value of the tungsten-containing solution is 13.5, and the method comprises the following steps:
1) heating the tungsten-containing solution to evaporate ammonium so as to remove ammonium carbonate and free ammonia gas from the tungsten-containing solution to obtain an ammonium-evaporated tungsten-containing solution, wherein the temperature of heating and evaporating ammonium is 80 ℃, the end point of heating and evaporating ammonium is controlled to be the pH value of the tungsten-containing solution at 6.5, and the ammonium-evaporated gas obtained after ammonium evaporation is condensed and recycled;
2) carrying out solid-liquid separation on the tungsten-containing solution after ammonium evaporation, and collecting a liquid phase to obtain a purified tungsten-containing solution;
3) adding the purified tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 1m3And h, the concentration of the sulfuric acid solution is 350g/L, the tungsten precipitation reaction temperature is 85 ℃, the tungsten precipitation reaction stirring speed is 200r/min, when the concentration of sulfuric acid in the reaction solution is 10g/L, the tungsten-containing solution is stopped to be added, the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid, and the obtained tungsten precipitation filtrate can be used for preparing the sulfuric acid solution.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution329.41g/L, 0.088g/L of P element, 0.017g/L of As element and CO3 2-The content is 5 g/L; WO in tungsten precipitation filtrate3The content is 0.13g/L, the content of P element is 0.0089g/L, and the content of As element is 0.01 g/L; the tungsten deposition rate is 98.71 percent, and the purity of the tungstic acid is 87.3 percent.
Example 8
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor and a slag washing solution generated in the production process of ammonium paratungstate, and the tungsten-containing solution comprises the following components: WO320g/L of P element, 0.057g/L of As element, 0.001g/L of CO3 2-The content is 112g/L, the pH value of the tungsten-containing solution is 13.5, and the method comprises the following steps:
1) heating the tungsten-containing solution to evaporate ammonium so as to expel ammonium carbonate gas from the tungsten-containing solution to obtain an ammonium-evaporated tungsten-containing solution, wherein the temperature of heating and ammonium evaporation is 80 ℃, the end point of heating and ammonium evaporation is controlled to be 6.5 of the pH value of the tungsten-containing solution, and the ammonium-evaporated gas obtained after ammonium evaporation is condensed and recycled;
2) carrying out solid-liquid separation on the tungsten-containing solution after ammonium evaporation, and collecting a liquid phase to obtain a purified tungsten-containing solution;
3) adding the purified tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 2m3And h, the concentration of the sulfuric acid solution is 350g/L, the tungsten precipitation reaction temperature is 80 ℃, the tungsten precipitation reaction stirring speed is 250r/min, when the concentration of sulfuric acid in the reaction solution is 5g/L, the tungsten-containing solution is stopped to be added, the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid, and the obtained tungsten precipitation filtrate can be used for preparing the sulfuric acid solution.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution329.41g/L, 0.088g/L of P element, 0.017g/L of As element and CO3 2-The content is 5 g/L; WO in tungsten precipitation filtrate3The content is 0.19g/L, the content of P element is 0.0072g/L, and the content of As element is 0.0095 g/L; the tungsten deposition rate is 99.3 percent, and the purity of the tungstic acid is 88 percent.
Example 9
This example provides a process for recovering tungstic acid from a tungsten-containing solution, which differs from example 3 in that the addition rate of the tungsten-containing solution in step 3) is 5m3/h。
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the purity of tungstic acid and the removal rate of metal Sb; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution352.49g/L, 0.0048g/L Sb, 0.012g/L P, 0.043g/L As, CO3 2-The content is 4 g/L; WO in tungsten precipitation filtrate3The content is 0.23g/L, the P content is 0.0041g/L, and the As content is 0.01 g/L; the tungsten deposition rate is 89%, the purity of the tungstic acid is 85.3%, and the removal rate of the metal Sb is 99.32%.
Example 10
This example provides a process for recovering tungstic acid from a tungsten-containing solution, which differs from example 3 in that the reaction is stopped in step 3) when the concentration of sulfuric acid in the reaction solution is 2 g/L.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution352.49g/L, 0.0048g/L Sb, 0.012g/L P, 0.043g/L As, CO3 2-The content is 4 g/L; WO in tungsten precipitation filtrate3The content is 5g/L, the P content is 0.0095g/L, and the As content is 0.033 g/L; the tungsten deposition rate is 84.75%, the purity of the tungstic acid is 75%, and the removal rate of the metal Sb is 99.32%.
Example 11
This example provides a process for recovering tungstic acid from a tungsten containing solution which differs from example 3 in that the endpoint of the heating to distill ammonium in step 1) is controlled to be at a pH of 9 for the tungsten containing solution.
Respectively testing the component contents of the purified tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution338.24g/L, 0.6g/L Sb, 0.01g/L P, 0.039g/L As, CO3 2-The content is 43 g/L; WO in tungsten precipitation filtrate3The content is 13.2g/L, the P content is 0.09g/L, and the As content is 0.035 g/L; the tungsten deposition rate is 44.77%, and the removal rate of metal Sb is 0.
Example 12
The embodiment provides a method for recovering tungstic acid from a tungsten-containing solution, wherein the tungsten-containing solution is a crystallization mother liquor generated in the production process of ammonium paratungstate, and comprises the following components: WO327.27g/L of Sb element, 0.55g/L of P element, 0.012g/L of As element, 0.05g/L of CO3 2-The content is 79g/L, the pH value of the tungsten-containing solution is 13, and the method comprises the following steps:
adding tungsten-containing solution to 10m3Carrying out tungsten precipitation reaction in sulfuric acid solution, wherein the adding speed of the tungsten-containing solution is 3m3And h, the concentration of the sulfuric acid solution is 400g/L, the tungsten precipitation reaction temperature is 75 ℃, the tungsten precipitation reaction stirring speed is 250r/min, the reaction is stopped when the concentration of sulfuric acid in the reaction solution is 10g/L, and the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid.
Respectively testing the component contents of the tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and volume of WO3 in the purified tungsten-containing solution, C2 and V2 are the concentration and volume of WO3 in the tungsten precipitation filtrate,the test result shows that: WO in tungsten precipitation filtrate3The content is 15g/L, the P content is 0.01g/L, the As content is 0.041g/L, the tungsten precipitation rate is 6.49 percent, and the removal rate of the metal Sb is 0.
Comparative example 1
This comparative example provides a process for recovering tungstic acid from a tungsten-containing solution, which differs from example 3 in that the sulfuric acid solution in step 3) was added to 10m3Carrying out tungsten precipitation reaction in the purified tungsten-containing solution, wherein the adding speed of the sulfuric acid solution is 3m3And h, the concentration of the sulfuric acid solution is 400g/L, the tungsten precipitation reaction temperature is 75 ℃, the tungsten precipitation reaction stirring speed is 250r/min, the tungsten precipitation reaction time is kept the same as that in the embodiment 3, and after the reaction is finished, the reaction solution is subjected to solid-liquid separation to obtain tungsten precipitation filtrate and tungstic acid solid.
Respectively testing the component contents of the tungsten-containing solution and the tungsten precipitation filtrate, and further calculating the tungsten precipitation rate, the tungstic acid purity and the metal Sb removal rate; the formula of the tungsten deposition rate is as follows: (C1 XV 1-C2 XV 2)/(C1 XV 1). times.100%, wherein C1 and V1 are the concentration and the solution volume of WO3 in the purified tungsten-containing solution, respectively, and C2 and V2 are the concentration and the solution volume of WO3 in the tungsten precipitation filtrate, respectively, and the test results show that: WO in purified tungsten-containing solution352.49g/L, 0.0048g/L Sb, 0.012g/L P, 0.043g/L As, CO3 2-The content is 4 g/L; WO in tungsten precipitation filtrate3The content of the metal Sb is 34.17g/L, the P content is 0.011g/L, the As content is 0.033g/L, the tungsten deposition rate is 4.98 percent, and the metal Sb removal rate is 99.32 percent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (13)
1. A method for recovering tungstic acid from a tungsten-containing solution is characterized by comprising the following steps: adding the tungsten-containing solution into an acid solution for tungsten precipitation reaction, and then carrying out first solid-liquid separation to obtain the tungstic acid.
2. The method for recovering tungstic acid from a tungsten containing solution according to claim 1 characterised in that the tungsten containing solution is added at a rate of no more than 30% times the volume of the acid solution per hour based on the volume of the acid solution, preferably at a rate of 10-30% times the volume of the acid solution per hour.
3. The method for recovering tungstic acid from a tungsten-containing solution according to claim 1 or 2, characterized in that the concentration of the acid solution is not less than 350g/L and the tungsten precipitation reaction ends at a concentration of the acid in the reaction solution of not less than 5 g/L;
preferably, the concentration of the acid solution is 350-400g/L, and the end point of the tungsten precipitation reaction is that the concentration of the acid in the reaction solution is 5-10 g/L.
4. The method for recovering tungstic acid from a solution containing tungsten as claimed in any one of claims 1 to 3, characterized in that the tungsten precipitation reaction temperature is 75-90 ℃, and the stirring speed of the tungsten precipitation reaction is 200-250 r/min.
5. A process for recovering tungstic acid from a tungsten containing solution according to any one of claims 1 to 4 characterised in that it further comprises the step of heat steaming the tungsten containing solution prior to adding it to the acid solution.
6. The method for recovering tungstic acid from a tungsten containing solution as claimed in claim 5 characterised in that the endpoint of the heating to distill ammonium is controlled at the pH of the tungsten containing solution to 6.5-7.
7. A process for recovering tungstic acid from a solution containing tungsten as claimed in claim 5 or 6 characterised in that the temperature of the heated steamed ammonium is 75-85 ℃.
8. The method for recovering tungstic acid from a solution containing tungsten according to any one of claims 5 to 7, characterised in that after the ammonium evaporation by heating is finished, the method further comprises the step of carrying out a second solid-liquid separation on the solution containing tungsten obtained after the ammonium evaporation by heating to obtain a purified solution containing tungsten.
9. A process for recovering tungstic acid from a solution containing tungsten according to any one of claims 1 to 8 characterised in that the ammonium carbonate gas obtained by heating to distill ammonium can be recovered by condensation;
and (3) the tungsten precipitation filtrate obtained after the first solid-liquid separation is used for preparing an acid solution or is used as an absorbent.
10. A process for recovering tungstic acid from a tungsten containing solution according to any one of claims 1 to 9 characterised in that the acid solution is a hydrochloric acid solution or a sulphuric acid solution, preferably the acid solution is a sulphuric acid solution.
11. A process for recovering tungstic acid from a tungsten containing solution according to any one of claims 1 to 10 characterised in that the tungsten containing solution is a crystallisation mother liquor and/or a sluicing solution produced during the production of ammonium paratungstate.
12. A process for recovering tungstic acid from a tungsten containing solution according to any one of claims 1 to 11 characterised in that the tungsten containing solution comprises the following components: WO3The content is 15-55g/L, the content of P element is 0.008-0.06g/L, and the content of As element is 0.001-0.08 g/L.
13. A process for recovering tungstic acid from a tungsten containing solution according to any one of claims 1 to 12 characterised in that the tungsten containing solution further comprises Sb element in an amount of 0.04 to 1g/L and/or CO3 2-The content is 50-150 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210405008.0A CN114672672B (en) | 2022-04-18 | 2022-04-18 | Method for recovering tungstic acid from tungsten-containing solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210405008.0A CN114672672B (en) | 2022-04-18 | 2022-04-18 | Method for recovering tungstic acid from tungsten-containing solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114672672A true CN114672672A (en) | 2022-06-28 |
| CN114672672B CN114672672B (en) | 2024-04-16 |
Family
ID=82078663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210405008.0A Active CN114672672B (en) | 2022-04-18 | 2022-04-18 | Method for recovering tungstic acid from tungsten-containing solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672672B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838750A (en) * | 2010-05-17 | 2010-09-22 | 赣州华兴钨制品有限公司 | Method for performing direct acid adjusting closed cycle on ammonium paratungstate crystallization mother liquor |
| CN102329962A (en) * | 2011-10-17 | 2012-01-25 | 中南大学 | Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution |
| CN102912129A (en) * | 2012-11-14 | 2013-02-06 | 中湘钨业股份有限公司 | Method for recycling tungsten in liquids after tungsten smelting exchanges |
| CN102963933A (en) * | 2012-12-01 | 2013-03-13 | 中南大学 | Preparation method of ammonium paratungstate |
| 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 |
| CN103103358A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering metal by use of APT (ammonium paratungstate) waste slag |
| CN103395841A (en) * | 2013-08-08 | 2013-11-20 | 北京赛科康仑环保科技有限公司 | Process of resource comprehensive utilization of tungsten crystal-containing mother solution and washing water |
| RU2571244C1 (en) * | 2014-09-02 | 2015-12-20 | Андрей Вилорьевич Доронин | Method for obtaining pure tungstic acid |
| CN105969982A (en) * | 2016-05-20 | 2016-09-28 | 中南大学 | Method for preparing tungstate solution by means of treating wolframine by using sulfuric acid |
| CN108441629A (en) * | 2018-04-20 | 2018-08-24 | 中南大学 | A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder |
| CN110760703A (en) * | 2019-11-20 | 2020-02-07 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for recovering tungsten from waste APT powder |
| CN113802020A (en) * | 2021-10-21 | 2021-12-17 | 江西钨业股份有限公司 | Deep antimony removal method for tungstate solution |
-
2022
- 2022-04-18 CN CN202210405008.0A patent/CN114672672B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838750A (en) * | 2010-05-17 | 2010-09-22 | 赣州华兴钨制品有限公司 | Method for performing direct acid adjusting closed cycle on ammonium paratungstate crystallization mother liquor |
| CN102329962A (en) * | 2011-10-17 | 2012-01-25 | 中南大学 | Method for deeply separating tungsten and molybdenum from high-tungsten and high-molybdenum mixed solution |
| CN102912129A (en) * | 2012-11-14 | 2013-02-06 | 中湘钨业股份有限公司 | Method for recycling tungsten in liquids after tungsten smelting exchanges |
| CN103103358A (en) * | 2012-11-23 | 2013-05-15 | 陈泉兴 | Method for recovering metal by use of APT (ammonium paratungstate) waste slag |
| CN102963933A (en) * | 2012-12-01 | 2013-03-13 | 中南大学 | Preparation method of ammonium paratungstate |
| 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 |
| CN103395841A (en) * | 2013-08-08 | 2013-11-20 | 北京赛科康仑环保科技有限公司 | Process of resource comprehensive utilization of tungsten crystal-containing mother solution and washing water |
| RU2571244C1 (en) * | 2014-09-02 | 2015-12-20 | Андрей Вилорьевич Доронин | Method for obtaining pure tungstic acid |
| CN105969982A (en) * | 2016-05-20 | 2016-09-28 | 中南大学 | Method for preparing tungstate solution by means of treating wolframine by using sulfuric acid |
| CN108441629A (en) * | 2018-04-20 | 2018-08-24 | 中南大学 | A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder |
| CN110760703A (en) * | 2019-11-20 | 2020-02-07 | 中国有色集团（广西）平桂飞碟股份有限公司 | Method for recovering tungsten from waste APT powder |
| CN113802020A (en) * | 2021-10-21 | 2021-12-17 | 江西钨业股份有限公司 | Deep antimony removal method for tungstate solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114672672B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101182037B (en) | Method for reclaiming vanadium oxide from dephosphorization underflow slag | |
| CN110143604B (en) | Method for recovering alkali, selenium and arsenic from antimony smelting arsenic alkali slag | |
| CN108707748B (en) | Method for purifying stone coal pickle liquor and recovering aluminum, potassium and iron | |
| CN110563041A (en) | Method for deeply purifying ammonium tungstate solution | |
| CN108793200B (en) | Method for separating potassium sulfate by using sodium-potassium-sulfur-chlorine quaternary system | |
| CN109336141B (en) | Method for improving recovery rate of lithium in wastewater | |
| US4044106A (en) | Reclamation of phosphate from bright dip drag-out | |
| CA1076364A (en) | Process for concentrating and recovering gallium | |
| CN114672672B (en) | Method for recovering tungstic acid from tungsten-containing solution | |
| CN116102211A (en) | Method for treating synthesis wastewater of battery anode material precursor | |
| CN115385366B (en) | Treatment method of magnesium-containing waste liquid | |
| CN115010149B (en) | Method for recycling sodium sulfate and ammonium sulfate by mixed salt | |
| CN113149048B (en) | Method for treating sodium oxalate solid waste residues in alumina production process | |
| CN110422876B (en) | Method for preparing ammonium fluotitanate from titanium liquid by fluorination | |
| CN108946767B (en) | Method for separating potassium sulfate by using sodium-potassium-sulfur-chlorine quaternary system | |
| CN114107698A (en) | Production method of high-stability high-purity arsenic | |
| US2840455A (en) | Production of lithium carbonate | |
| CN113526557A (en) | Method for preparing ammonium paratungstate by utilizing tungsten smelting crystallization mother liquor and desorption front liquor | |
| CN108751229B (en) | Method for recovering dicyclohexyl disulfide mother liquor | |
| US4599223A (en) | Separation of tungsten from rhenium | |
| CN115818603B (en) | Method for preparing battery grade ferric phosphate from lithium iron phosphate anode powder containing copper, aluminum and graphite through oxidizing and extracting lithium from residue | |
| CN115181854B (en) | Double acid leaching method for fluorine-containing rare earth ore | |
| CN113800566B (en) | Method for preparing ammonium molybdate from crude molybdic acid | |
| CN116573782B (en) | Method for treating desulfurization waste liquid | |
| CN115180661B (en) | Method for recovering nickel-cobalt-copper mixed sulfate from iron-aluminum waste residues |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |