CN112374541A - Method for recycling ammonium paratungstate by using waste SCR catalyst - Google Patents
Method for recycling ammonium paratungstate by using waste SCR catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 24
- 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 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 33
- 229910052721 tungsten Inorganic materials 0.000 claims description 27
- 239000010937 tungsten Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003456 ion exchange resin Substances 0.000 claims description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- -1 tungsten anions Chemical class 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 4
- 230000029219 regulation of pH Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
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- 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
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1254—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using basic solutions or liquors
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- 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
- C22B7/007—Wet processes by acid leaching
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/80—Compositional purity
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Abstract
The embodiment of the invention discloses a method for recovering ammonium paratungstate by using a waste SCR catalyst, which is characterized in that alkali liquor is recovered after the alkali leaching reaction is finished, so that the production cost is further saved, the recovered alkali liquor is used for carrying out water-soluble operation on crystallization to realize extraction of ammonium paratungstate, the pH regulation by a large amount of acid liquor is avoided on the basis of recycling the alkali liquor, and the use of harmful medicaments is effectively reduced on the basis of improving the process.
Description
Technical Field
The embodiment of the invention relates to the field of denitration catalyst recovery, and particularly relates to a method for recovering ammonium paratungstate by using a waste SCR catalyst.
Background
The Selective Catalytic Reduction (SCR) denitration technology is an efficient and stable flue gas denitration technology in the related technologies, wherein an SCR catalyst is a key material for efficiently and cheaply removing nitric oxide in flue gas, and is widely applied to a coal-fired flue gas denitration process of a thermal power plant, and the service life of the catalyst is only about 3-4 years due to the fact that flue gas is scoured and abraded and various impurities are continuously accumulated in the catalyst.
The main component of the SCR catalyst is titanium dioxide (containing TiO approximately)275-85%), tungsten oxide (containing about WO)34-8%) and vanadium pentoxide, and a large amount of retired catalysts belong to hazardous waste (HW50), so that not only can environmental pollution be caused, but also resource waste can be caused.
Therefore, the waste denitration catalyst is used for recovering precious metals, waste materials can be changed into valuable materials, environmental pollution is reduced, recycling and reduction of dangerous waste are effectively realized, and the method has good economic benefit and social benefit. At present, related patents also exist in China for recovering precious metals by using waste denitration catalysts.
Chinese patent CN107419104B discloses a comprehensive recovery method of a waste SCR denitration catalyst: carrying out alkaline leaching reaction on the crushed and ground waste SCR denitration catalyst powder, and filtering to obtain titanium slag and filtrate 1; adjusting the pH value of the filtrate 1 to 9-11 by using acid, adding excessive ammonium chloride for reaction, and filtering to obtain ammonium metavanadate precipitate and a filtrate 2; continuously adjusting the pH value of the filtrate 2 to 5-7 with acid, and performing liquid-liquid extraction with an organic phase containing decyl dihexyl methyl quaternary ammonium carbonate to obtain a loaded organic phase; carrying out multi-stage countercurrent back extraction on the loaded organic phase by using an alkaline aqueous solution to obtain a back extraction solution; and concentrating and crystallizing the strip liquor to obtain ammonium paratungstate. The method has the advantages that the titanium dioxide is efficiently separated, and the purity of the titanium dioxide is improved; the method not only improves the recovery rate of tungsten trioxide and vanadium pentoxide in the waste SCR denitration catalyst, but also improves the purity of the obtained tungsten trioxide and vanadium pentoxide and simultaneously reduces the content of impurities contained in the tungsten trioxide and the vanadium pentoxide. However, the method proposed in chinese patent CN107419104B focuses on recovering tungsten and vanadium, and the alkali solution in the recovery production process is not recycled, but the PH is directly added with acid, which wastes the alkali solution, and needs a large amount of acid to adjust the PH, and a large amount of medicament cost is consumed in the actual production process, and the titanium dioxide filter residue has no further purification process.
It can be seen that, in the related art, the related process for recovering resources from the waste denitration catalyst is not mature, that is, the existing method still has room for improvement in terms of clean energy conservation, recovery and purification.
Disclosure of Invention
The embodiment of the invention provides a method for recovering ammonium paratungstate by using a waste SCR catalyst, which mainly aims to solve the following technical problems in the related art: one of the technical problems is to improve the recovery rate of the titanium dioxide of the waste denitration catalyst; the second technical problem is to realize the recycling of ammonium paratungstate.
The invention discloses a method for recovering ammonium paratungstate by using a waste SCR catalyst, which comprises the following specific steps:
(1) alkaline leaching reaction: carrying out alkaline leaching reaction on the crushed and ground waste SCR denitration catalyst powder, and filtering to obtain titanium slag and filtrate;
(2) extracting tungsten and vanadium: performing tungsten-vanadium extraction on the filtrate treated in the step (1) by using sulfate type quaternary ammonium salt to obtain a tungsten-containing solution and a vanadium-containing organic phase, wherein the ratio of the sulfate type quaternary ammonium salt to the sulfate type quaternary ammonium salt is 1:1, the temperature is 10-30 ℃, the pH of a feed liquid is 9-12, and the single-stage extraction rate is 98%;
(3) primary crystallization: crystallizing tungsten-containing liquid to obtain mother liquor 1 and sodium tungstate crystals, wherein the specific gravity of the crystals and the mother liquor is controlled to be 1.60 mg/L in the primary crystallization process, and the NaOH content of the mother liquor 1 is 600-750 g/L;
(4) alkali liquor recovery: recovering alkali liquor after the tungsten and vanadium extraction in the step (2);
(5) dissolving in water: carrying out water-soluble operation on the sodium tungstate crystal by using the recycled alkali liquor to prepare a crude sodium tungstate solution containing 25-30 g/L tungsten;
(6) ion exchange: carrying out ion exchange on the solution obtained by water dissolving in the step (5), wherein the ion exchange is carried out by ion exchange resin, and in the ion exchange process, tungsten anions and impurities in the crude sodium tungstate solution form anions which exist as monomers;
(7) ammonia precipitation: precipitating tungsten from the ion exchange resin by ammonia through 160g/L of ammonium chloride and 2mol of ammonia water solution to obtain ammonium tungstate solution, wherein the tungsten is adsorbed on the ion exchange resin;
(8) removing molybdenum: adding ammonium sulfide and copper sulfate into the ammonium tungstate solution treated in the step (7), and precipitating molybdenum in the ammonium tungstate solution to obtain molybdenum removing solution;
(9) secondary crystallization: and (4) crystallizing the molybdenum-removed liquid treated in the step (8) to obtain mother liquid 2 and ammonium paratungstate.
Optionally, the method further includes:
(10) acid hydrolysis: and (3) carrying out acidolysis on the titanium slag treated in the step (1) by using dilute sulfuric acid to obtain high-titanium powder.
Optionally, the concentration of the dilute sulfuric acid in the step (10) is 2-8%.
Optionally, the purity of the high titanium powder in the step (10) is more than or equal to 95%.
Optionally, in the step (6), the ion exchange resin is w201 × 7 strong base anion exchange resin.
Optionally, the method further includes:
(11) back extraction: carrying out back extraction on the vanadium-containing organic phase treated in the step (2) by using 0.5mol/L NaOH and 1.5mol/L Na2CO 3;
(12) ammonia precipitation: and (5) carrying out precipitation treatment on the back-extracted material in the step (11) by using ammonia water to obtain ammonium metavanadate.
Optionally, the back extraction rate in the step (12) is more than or equal to 94%.
Compared with the related art, the invention has the following beneficial effects:
compared with the prior art, the method has the advantages that the alkali liquor is recycled after the alkali leaching reaction is finished, the production cost is further saved, the recycled alkali liquor is used for carrying out water-soluble operation on the crystals so as to realize extraction of ammonium paratungstate, the pH regulation through a large amount of acid liquor is avoided on the basis of recycling the alkali liquor, and the use of harmful medicaments is effectively reduced on the basis of improving the process.
Drawings
FIG. 1 is a process flow diagram of the present invention for recovering ammonium paratungstate using a spent SCR catalyst;
FIG. 2 is a flow diagram of a process for recovering titanium powder using a spent SCR catalyst according to the present invention;
FIG. 3 is a flow diagram of a process for recovering ammonium metavanadate from a spent SCR catalyst according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Reference herein to "a plurality" means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The invention is further illustrated in the following examples in connection with fig. 1 to 3.
Example 1
(1) Alkaline leaching reaction: and carrying out alkaline leaching reaction on the crushed and ground waste SCR denitration catalyst powder, and filtering to obtain titanium slag and filtrate.
(2) Extracting tungsten and vanadium: and (2) performing tungsten-vanadium extraction on the filtrate treated in the step (1) by using sulfuric acid type quaternary ammonium salt to obtain a tungsten-containing solution and a vanadium-containing organic phase, wherein the ratio of the sulfuric acid type quaternary ammonium salt to the sulfuric acid type quaternary ammonium salt is 1:1, the temperature is 10-30 ℃, the pH of the feed liquid is 9-12, and the single-stage extraction rate is 98%.
(3) Primary crystallization: and crystallizing the tungsten-containing solution to obtain mother solution 1 and sodium tungstate crystals, wherein the specific gravity of the crystals and the mother solution is controlled to be 1.60 mg/L in the primary crystallization process, and the NaOH content of the mother solution 1 is 600-750 g/L.
(4) Alkali liquor recovery: and (3) recovering the alkali liquor after the tungsten and vanadium extraction in the step (2).
(5) Dissolving in water: and carrying out water-soluble operation on sodium tungstate crystals by using the recovered alkali liquor to prepare a crude sodium tungstate solution containing 25-30 g/L tungsten.
(6) Ion exchange: and (4) carrying out ion exchange on the solution after water dissolution in the step (5), wherein the ion exchange is carried out through ion exchange resin, and in the ion exchange process, tungsten anions in the crude sodium tungstate solution and anions formed by impurities exist as monomers.
(7) Ammonia precipitation: the ammonium tungstate solution was obtained by precipitating tungsten from the ion exchange resin with ammonia by 160g/L of ammonium chloride and 2mol of aqueous ammonia solution, wherein tungsten was adsorbed on the ion exchange resin.
(8) Removing molybdenum: and (4) adding ammonium sulfide and copper sulfate into the ammonium tungstate solution treated in the step (7), and precipitating molybdenum in the ammonium tungstate solution to obtain molybdenum removing solution.
(9) Secondary crystallization: and (4) crystallizing the molybdenum-removed liquid treated in the step (8) to obtain mother liquid 2 and ammonium paratungstate.
In the embodiment of the application, compare with the correlation technique, this application has been retrieved alkali liquor after accomplishing the alkaline leaching reaction, has further practiced thrift manufacturing cost, and the alkali liquor after the recovery is used for carrying out water-soluble operation to the crystallization to the realization is to ammonium paratungstate's extraction, still avoids carrying out PH through a large amount of acidizing fluids and adjusts on the basis to alkali liquor cyclic utilization, has effectively reduced the use to harmful medicament on the basis of improving technology.
Example 2
On the basis of the above embodiments, the steps in the embodiments of the present application are further illustrated, and as shown in fig. 2, in addition to the extraction of ammonium paratungstate, the present application also includes the extraction of titanium powder.
(1) Alkaline leaching reaction: and carrying out alkaline leaching reaction on the crushed and ground waste SCR denitration catalyst powder, and filtering to obtain titanium slag and filtrate.
(10) Acid hydrolysis: and (3) carrying out acidolysis on the titanium slag treated in the step (1) by using dilute sulfuric acid to obtain high-titanium powder. Wherein, the concentration of the dilute sulphuric acid in the step (10) is 2-8%, and the purity of the high titanium powder is more than or equal to 95%.
In the embodiment of the application, on the basis of the above embodiment, not only is the recycling of the alkali liquor realized, but also the recycling of the titanium powder is realized through acidolysis of the titanium slag which is a waste after the alkaline leaching reaction, and the purity of the recycled titanium powder is as high as 95%.
Example 3
On the basis of the above embodiments, the steps in the embodiments of the present application are further illustrated, and as shown in fig. 3, in addition to the extraction of ammonium paratungstate and titanium powder, the contents of extracting ammonium metavanadate are also included.
(1) Alkaline leaching reaction: and carrying out alkaline leaching reaction on the crushed and ground waste SCR denitration catalyst powder, and filtering to obtain titanium slag and filtrate.
(2) Extracting tungsten and vanadium: and (3) carrying out tungsten-vanadium extraction on the filtrate treated in the step (1) by using sulfuric acid type quaternary ammonium salt to obtain a tungsten-containing solution and a vanadium-containing organic phase.
(11) Back extraction: with 0.5mol/L NaOH and 1.5mol/L Na2CO3And (3) carrying out back extraction on the vanadium-containing organic phase treated in the step (2).
(12) Ammonia precipitation: and (5) carrying out precipitation treatment on the back-extracted material in the step (11) by using ammonia water to obtain ammonium metavanadate.
Optionally, the back extraction rate in the step (12) is more than or equal to 94%.
In the embodiment of the application, on the basis of the embodiment, the filtrate obtained after the alkaline leaching reaction is recycled, the filtrate is recycled again after the titanium slag is recycled, and the ammonium metavanadate is obtained through back extraction and ammonia precipitation, so that the production cost is further saved.
In conclusion, the method and the device have the advantages that the alkali liquor is recycled, ammonium paratungstate is recycled through the main process flow, the production of titanium powder and ammonium metavanadate is realized on the basis of recycling the alkali liquor, and compared with the related technology, the method and the device have the advantages that the production cost is further saved, and the environment friendliness is better.
The invention is not to be considered as limited to the particular embodiments shown and described, but is to be understood that various modifications, equivalents, improvements and the like can be made without departing from the spirit and scope of the invention.
Claims (7)
1. A method for recovering ammonium paratungstate by using a waste SCR catalyst is characterized by comprising the following steps:
(1) alkaline leaching reaction: carrying out alkaline leaching reaction on the crushed and ground waste SCR denitration catalyst powder, and filtering to obtain titanium slag and filtrate;
(2) extracting tungsten and vanadium: performing tungsten-vanadium extraction on the filtrate treated in the step (1) by using sulfate type quaternary ammonium salt to obtain a tungsten-containing solution and a vanadium-containing organic phase, wherein the ratio of the sulfate type quaternary ammonium salt to the sulfate type quaternary ammonium salt is 1:1, the temperature is 10-30 ℃, the pH of a feed liquid is 9-12, and the single-stage extraction rate is 98%;
(3) primary crystallization: crystallizing tungsten-containing liquid to obtain mother liquor 1 and sodium tungstate crystals, wherein the specific gravity of the crystals and the mother liquor is controlled to be 1.60 mg/L in the primary crystallization process, and the NaOH content of the mother liquor 1 is 600-750 g/L;
(4) alkali liquor recovery: recovering alkali liquor after the tungsten and vanadium extraction in the step (2);
(5) dissolving in water: carrying out water-soluble operation on the sodium tungstate crystal by using the recycled alkali liquor to prepare a crude sodium tungstate solution containing 25-30 g/L tungsten;
(6) ion exchange: carrying out ion exchange on the solution obtained by water dissolving in the step (5), wherein the ion exchange is carried out by ion exchange resin, and in the ion exchange process, tungsten anions and impurities in the crude sodium tungstate solution form anions which exist as monomers;
(7) ammonia precipitation: precipitating tungsten from the ion exchange resin by ammonia through 160g/L of ammonium chloride and 2mol of ammonia water solution to obtain ammonium tungstate solution, wherein the tungsten is adsorbed on the ion exchange resin;
(8) removing molybdenum: adding ammonium sulfide and copper sulfate into the ammonium tungstate solution treated in the step (7), and precipitating molybdenum in the ammonium tungstate solution to obtain molybdenum removing solution;
(9) secondary crystallization: and (4) crystallizing the molybdenum-removed liquid treated in the step (8) to obtain mother liquid 2 and ammonium paratungstate.
2. The method of claim 1, wherein after step (1), the method further comprises:
(10) acid hydrolysis: and (3) carrying out acidolysis on the titanium slag treated in the step (1) by using dilute sulfuric acid to obtain high-titanium powder.
3. The method according to claim 2, wherein the concentration of the dilute sulfuric acid in the step (10) is 2-8%.
4. The method of claim 2, wherein the purity of the high titanium powder in step (10) is 95% or more.
5. The method according to any one of claims 1 to 4, wherein the ion exchange resin in step (6) is w201 x 7 strongly basic anion exchange resin.
6. The method of claim 1, wherein after step (2), the method further comprises:
(11) back extraction: with 0.5mol/L NaOH and 1.5mol/L Na2CO3Carrying out back extraction on the vanadium-containing organic phase treated in the step (2);
(12) ammonia precipitation: and (5) carrying out precipitation treatment on the back-extracted material in the step (11) by using ammonia water to obtain ammonium metavanadate.
7. The method of claim 2, wherein the stripping rate in step (12) is at least 94%.
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|---|---|---|---|---|
| CN114602504A (en) * | 2022-04-12 | 2022-06-10 | 江苏龙净科杰环保技术有限公司 | Novel automatic batching system |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045958A (en) * | 1989-03-31 | 1990-10-10 | 吉林锗厂 | Ion exchange method prepares pure ammonium paratungstate method |
| JP2010229017A (en) * | 2009-03-02 | 2010-10-14 | Mitsubishi Materials Corp | Method for producing high-purity ammonium paratungstate |
| CN102936039A (en) * | 2012-11-15 | 2013-02-20 | 攀枝花市晟天钛业有限公司 | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium |
| CN105621483A (en) * | 2016-01-21 | 2016-06-01 | 洛阳创举环保科技有限公司 | Process for reclaiming honeycomb SCR waste catalyst |
| CN105714118A (en) * | 2016-03-01 | 2016-06-29 | 成都万里蓝环保科技有限公司 | Technology for extracting and recovering tungsten and vanadium from waste SCR catalyst |
| CN106435197A (en) * | 2016-12-09 | 2017-02-22 | 武汉凯迪电力环保有限公司 | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification |
-
2020
- 2020-11-12 CN CN202011263069.5A patent/CN112374541A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045958A (en) * | 1989-03-31 | 1990-10-10 | 吉林锗厂 | Ion exchange method prepares pure ammonium paratungstate method |
| JP2010229017A (en) * | 2009-03-02 | 2010-10-14 | Mitsubishi Materials Corp | Method for producing high-purity ammonium paratungstate |
| CN102936039A (en) * | 2012-11-15 | 2013-02-20 | 攀枝花市晟天钛业有限公司 | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium |
| CN105621483A (en) * | 2016-01-21 | 2016-06-01 | 洛阳创举环保科技有限公司 | Process for reclaiming honeycomb SCR waste catalyst |
| CN105714118A (en) * | 2016-03-01 | 2016-06-29 | 成都万里蓝环保科技有限公司 | Technology for extracting and recovering tungsten and vanadium from waste SCR catalyst |
| CN106435197A (en) * | 2016-12-09 | 2017-02-22 | 武汉凯迪电力环保有限公司 | Process and device for alkaline extraction and recovery from waste catalysts in SCR (selective catalytic reduction) denitrification |
Non-Patent Citations (3)
| Title |
|---|
| 周连江等: "《无机盐工业手册 下》", 30 June 1996, 化学工业出版社 * |
| 李强等: "季铵盐N263萃取分离钨酸钠中的钒", 《稀有金属与硬质合金》 * |
| 邱定蕃等: "《稀贵金属冶金新进展》", 30 April 2019, 冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602504A (en) * | 2022-04-12 | 2022-06-10 | 江苏龙净科杰环保技术有限公司 | Novel automatic batching system |
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