CN117509728A - Method for preparing aluminum vanadate by using waste SCR denitration catalyst, aluminum vanadate and application of aluminum vanadate - Google Patents
Method for preparing aluminum vanadate by using waste SCR denitration catalyst, aluminum vanadate and application of aluminum vanadate Download PDFInfo
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- CN117509728A CN117509728A CN202311282807.4A CN202311282807A CN117509728A CN 117509728 A CN117509728 A CN 117509728A CN 202311282807 A CN202311282807 A CN 202311282807A CN 117509728 A CN117509728 A CN 117509728A
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- denitration catalyst
- scr denitration
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002386 leaching Methods 0.000 claims abstract description 185
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 134
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 134
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002253 acid Substances 0.000 claims abstract description 55
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 239000002244 precipitate Substances 0.000 claims abstract description 29
- 239000002893 slag Substances 0.000 claims abstract description 29
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 6
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 28
- 239000000047 product Substances 0.000 abstract description 19
- 238000000926 separation method Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 147
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 34
- 229910052721 tungsten Inorganic materials 0.000 description 30
- 239000010937 tungsten Substances 0.000 description 29
- 238000001556 precipitation Methods 0.000 description 27
- 239000011734 sodium Substances 0.000 description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 229910052979 sodium sulfide Inorganic materials 0.000 description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 16
- 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 description 15
- 239000012535 impurity Substances 0.000 description 15
- 238000011084 recovery Methods 0.000 description 13
- 239000007800 oxidant agent Substances 0.000 description 12
- 238000005265 energy consumption Methods 0.000 description 11
- 230000001105 regulatory effect Effects 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000004809 Teflon Substances 0.000 description 8
- 229920006362 Teflon® Polymers 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- -1 preferably Substances 0.000 description 8
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 230000001502 supplementing effect Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- HIMLGVIQSDVUJQ-UHFFFAOYSA-N aluminum vanadium Chemical compound [Al].[V] HIMLGVIQSDVUJQ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical group [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention discloses a method for preparing aluminum vanadate by using a waste SCR denitration catalyst, which comprises the following steps: (1) Leaching the waste SCR denitration catalyst by using sulfuric acid and ammonium sulfite, and filtering to obtain acid leaching liquid and acid leaching slag; (2) Introducing ozone into the acid leaching solution obtained in the step (1) for oxidation to obtain a precursor suspension; (3) And (3) carrying out hydrothermal reaction on the precursor suspension obtained in the step (2), collecting precipitate, filtering, washing and drying to obtain aluminum vanadate. The invention also provides aluminum vanadate and application thereof. The method for preparing aluminum vanadate by using the waste SCR denitration catalyst comprehensively and efficiently utilizes vanadium elements and aluminum elements in the waste SCR denitration catalyst, directly synthesizes aluminum vanadate products in the solution on the premise of not carrying out element separation, can be used as an adsorbent for adsorbing uranium, comprehensively utilizes the two elements, greatly reduces the generation of waste liquid, and has short process flow.
Description
Technical Field
The invention belongs to the field of cured waste recovery, and particularly relates to a recovery method of a waste SCR denitration catalyst, a recovery product and application thereof.
Background
NO x Is a common atmospheric pollutant and can cause various problems including environmental pollution and human diseases. Selective Catalytic Reduction (SCR) is the current process of NO x The most effective method, however, requires recovery of the catalyst after it has been deactivated and cannot be regenerated. The waste SCR denitration catalyst contains a plurality of valuable metals such as vanadium, tungsten and the like, the yield is huge, and the annual yield of the waste catalyst is expected to be kept to be about 14.33 ten thousand tons after 2025.
At present, the main recovery methods of the waste SCR denitration catalyst are divided into two main types, namely a wet method and a fire method, wherein the wet method recovery mainly comprises a reduction acid leaching method and a pressurized alkaline leaching method, and the fire method recovery mainly adopts Na 2 CO 3 Roasting and composite roasting. Due to V in acidic solution 4+ Is greater than V 5+ Therefore, the leaching rate of vanadium element is generally improved by adopting a reduction acid leaching method in the wet process flow. The vanadium leaching solution obtained by the existing wet process flow contains aluminum vanadium, and most of the prior art is to remove aluminum element as impurities and then to recycle the vanadium efficiently, so that the process is complex and the aluminum element is not reasonably utilized.
The aluminum vanadate is an adsorbent for adsorbing uranium, and the direct preparation of the aluminum vanadate by utilizing the vanadium leaching solution has great significance. And the vanadium leaching solution obtained in the prior art is V 4+ In the form, in order to ensure the formation of aluminium vanadate, it is necessary to oxidize it to V 5+ The metavanadate form is generated. The oxidant commonly used at present mainly comprises liquid oxidants such as hydrogen peroxide, perchloric acid and the like. For example, patent application publication No. CN104195342A discloses a method for recovering vanadium pentoxide in waste SCR denitration catalyst, firstly reducing pentavalent vanadium in the catalyst into more soluble tetravalent vanadium in an acidic solution by using a reducing agent, and then oxidizing the tetravalent vanadium into pentavalent vanadium by using perchloric acid as an oxidizing agent. The patent application with publication number CN104384167A discloses a comprehensive recovery method of waste titanium-based vanadium SCR catalystThe method adopts hydrogen peroxide as an oxidant to oxidize low-valence vanadium liquid and then separates vanadium and aluminum by an extraction method. The liquid oxidants such as hydrogen peroxide adopted in the prior art are better oxidants for low-valence vanadium oxidation, but the addition of hydrogen peroxide can cause the concentration of the solution to be greatly diluted, and the subsequent recovery is not facilitated especially under the condition that the concentration of vanadium element in the leaching solution is not high.
Therefore, the method for efficiently and comprehensively recovering aluminum vanadium in the vanadium leaching solution and preparing aluminum vanadate has wide market application prospect.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides a method for preparing aluminum vanadate by utilizing a waste SCR denitration catalyst, which can realize the simultaneous and efficient recovery of aluminum and vanadium, aluminum vanadate and application thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) Leaching the waste SCR denitration catalyst by using sulfuric acid and ammonium sulfite, and filtering to obtain acid leaching liquid and acid leaching slag;
(2) Introducing ozone into the acid leaching solution obtained in the step (1) for oxidation to obtain a precursor suspension (yellow);
(3) And (3) placing the precursor suspension obtained in the step (2) into a Teflon reaction kettle for hydrothermal reaction, collecting precipitate (green), filtering, washing (washing with deionized water and ethanol), and drying to obtain aluminum vanadate.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, ammonium hydroxide is added to the acid leaching solution to adjust the pH value of the solution to 2.8-3.2 before the acid leaching solution is oxidized by introducing ozone. The invention can effectively reduce the rapid generation of ammonium vanadate precipitate in the process of firstly oxidizing and then regulating the pH value (if ozone is introduced for oxidation, the pH value of the pentavalent vanadium precipitate is 1.3-6.94, and ammonium vanadate precipitate can be generated in the process of subsequently regulating the pH value to reduce the purity of aluminum vanadate product), and the pH value is firstly regulated, and then the oxidation has a certain speed by the control of the subsequent oxidation processThe rate, the just-generated pentavalent vanadium is not easy to generate ammonium vanadate precipitate through stirring and the action of the surfactant, the amount of ammonium vanadate precipitate can be reduced, and the purity of the final product aluminum vanadate is improved. Moreover, the research shows that the quality of the aluminum vanadate prepared at the pH value of 2.8-3.2 is better than that of other aluminum vanadate prepared at lower pH values, and if the pH value is too high, tetravalent vanadium generates VO (OH) 2 Precipitation affects the purity of the aluminum vanadate product.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, acid liquor is supplemented into the acid leaching solution obtained in the step (1), then the waste SCR denitration catalyst and ammonium sulfite are added into the acid leaching solution for cyclic leaching, the high-concentration low-valence vanadium solution is obtained by cyclic leaching for multiple times, and the high-concentration low-valence vanadium solution is used for replacing the acid leaching solution to carry out the step (2). Aiming at the problem that the subsequent precipitation step is affected by low vanadium element content in leaching liquid of the existing waste SCR denitration catalyst treatment process, the invention adopts a circulating leaching mode to enrich vanadium element, thereby avoiding the problems that the vanadium concentration in the solution is too low to precipitate and a large amount of wastewater is generated. Specifically, in order to increase the content of vanadium in the acid leaching solution, a proper amount of concentrated sulfuric acid is supplemented into the acid leaching solution, and then the waste SCR denitration catalyst powder and ammonium sulfite which are equal to those in the step (1) are added into the acid leaching solution for repeated cycle leaching, such as cycle leaching for 5 times, so that vanadium is enriched, and high-concentration low-valence vanadium solution is obtained after filtration.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, the concentration of sulfuric acid is 1.5-2mol/L, and the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:6-8mL, wherein the mass ratio of the waste SCR denitration catalyst to the ammonium sulfite is 1: (0.01-0.02). The concentration of the sulfuric acid is too high or the dosage is too high, the leaching rate of the vanadium is not greatly improved, meanwhile, the acidity of the solution is increased, more reagent is required to be consumed for the subsequent adjustment of the pH value of the solution, and the leaching rate of the vanadium is reduced due to incomplete leaching of the vanadium when the concentration of the sulfuric acid is too low or the dosage is too small. The addition amount of ammonium sulfite is too large, the reagent is wasted on the basis that the pentavalent vanadium is completely reduced to tetravalent, the addition amount is too small, and the pentavalent vanadium is incompletely reduced.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, when the waste SCR denitration catalyst is leached by sulfuric acid and ammonium sulfite, the waste SCR denitration catalyst is subjected to water bath reaction for 1.5-2 hours at 80-90 ℃. The leaching temperature is too high, the energy consumption is high, the leaching rate is not greatly improved, the temperature is too low, the mass transfer speed is low, the leaching speed is reduced, the reaction time is long, and the energy consumption is wasted. The leaching time is too long, the leaching rate is not greatly improved, the energy consumption is wasted, the time is too short, the leaching reaction is not completely carried out, and the leaching rate is not high.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, ozone is introduced to perform oxidation, the ozone gas flow is controlled to be 10-20mL/min, and the oxidation time is controlled to be 20-30min when ozone is introduced to perform oxidation. The ozone flow rate is too high, the gas-solid reaction contact surface is limited, part of ozone escapes, and the oxidation speed is not greatly increased. Too small flow rate, too slow oxidation speed, longer oxidation time and increased reaction energy consumption. The ozone oxidation time is too long, the oxidation reaction is finished, the reaction energy consumption is increased, the reaction time is too short, the oxidation of tetravalent vanadium is incomplete, the waste of vanadium is caused, and the purity of the generated aluminum vanadate is not high.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, polyvinylpyrrolidone (PVP) is added to the acid leaching solution according to the liquid-solid ratio of 1 mL:20-40 mg while ozone is introduced for oxidation, and the mixture is stirred vigorously. The pentavalent vanadium ions generated by ozone oxidation are easy to precipitate under the pH value environment to generate ammonium vanadate precipitate, so that the purity of the product is influenced.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, the hydrothermal reaction is kept at 160-180 ℃ for 6-8 hours. The hydrothermal reaction temperature is too high or too low, the heat preservation time is too long or too short, and the quality of the synthesized aluminum vanadate product is reduced.
In the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, preferably, the drying is carried out under vacuum, and the temperature is kept at 80-90 ℃ for 10-12 hours.
The acid leaching slag obtained by the method for preparing aluminum vanadate by using the waste SCR denitration catalyst can also be treated and recycled with tungsten by adopting the following process to obtain ammonium paratungstate, and the method specifically comprises the following steps of:
(1) Leaching acid leaching residues by using a mixed solution of sodium sulfide and sodium hydroxide, and carrying out solid-liquid separation to obtain WO 4 2- /WO x S 4-x 2- Solution and titanium-rich slag;
(2) To WO obtained in step (1) 4 2- /WO x S 4-x 2- Adding mixed solution of sulfide and alkali into the solution, adding acid leaching residue into the solution for cyclic leaching, and circularly leaching for multiple times (such as 5 times) to obtain high-concentration WO 4 2- /WO x S 4-x 2- A solution;
(3) To the high concentration WO obtained in step (2) 4 2- /WO x S 4-x 2- Ozone is introduced into the solution for oxidation treatment, thus obtaining WO 4 2- A solution;
(4) For the WO obtained in step (3) 4 2- Carrying out silicon precipitation treatment on the solution, and adding an excessive calcium source to carry out precipitation treatment to obtain calcium tungstate solid;
(5) Adding concentrated ammonia water into the calcium tungstate solid obtained in the step (4) for reaction, filtering to obtain ammonium tungstate solution, evaporating and concentrating, and cooling and crystallizing to obtain ammonium paratungstate. In order to improve the purity of the ammonium paratungstate product, impurities in the ammonium paratungstate product are removed, and the ammonium paratungstate product can be continuously and circularly improved by carrying out recrystallization treatment in the step (5) for a plurality of times.
In the treatment process of the acid leaching slag, the mixed solution of sodium sulfide and sodium hydroxide is obtained by adding sodium hydroxide into the sodium sulfide solution, wherein the concentration of the sodium sulfide solution is 1.5-2mol/L, and the volume ratio of the mass of the acid leaching slag to the sodium sulfide solution is 1g:6-7mL, wherein the mass ratio of the acid leaching slag to the sodium hydroxide is (2-3): 1. the concentration of sodium sulfide and the proportion of alkali are too large, so that the leaching rate of tungsten is not improved greatly, but the leaching rate of impurities is improved, and the leaching rate of tungsten is reduced when the concentration of sodium sulfide and the proportion of alkali are too low. The research of the invention shows that the leaching rate of tungsten and impurities can be balanced by controlling the concentration of sodium sulfate and the proportion of sodium sulfate to alkali.
In the treatment process of the acid leaching slag, when the acid leaching slag is leached by utilizing the mixed solution of sodium sulfide and sodium hydroxide, the water bath temperature is controlled to be 80-90 ℃ and the leaching time is controlled to be 2.5-3h. The leaching temperature is too low, the molecular thermal motion is slowed down, the mass transfer speed is slowed down, the reaction rate is slowed down, the reaction time is prolonged, the reaction energy consumption is increased, the reaction temperature is too high, the reaction energy consumption is increased, and the leaching rate of tungsten is improved without obvious change; the leaching process needs a certain reaction time, the time is too short, the leaching rate is in a rapid growth stage, the leaching is incomplete, the time is too long, the leaching rate cannot be greatly increased, and the energy consumption is increased.
In the acid leaching residue treatment process, when ozone is introduced for oxidation treatment, the flow rate of ozone gas is 10-20mL/min, and the ozone introduction time is 20-30min. The flow rate of the ozone is too low, the supply speed of the oxidant is too slow, the reaction speed is reduced, the concentration of the ozone is too high, the gas-solid reaction contact area is limited, the oxidation reaction speed is not obviously improved, and part of ozone is wasted; the ozone is introduced for too short, the reaction is incomplete, the thiotungstate is not completely oxidized into tungstate, the non-oxidized thiotungstate is precipitated along with the silicon, the ozone is introduced for too long, the thiotungstate is completely oxidized, and the redundant ozone is wasted.
In the treatment process of the acid leaching slag, hydrochloric acid is adopted to adjust the pH value of the solution to 8-9 during the silicon precipitation treatment, and the solution is subjected to water bath reaction for 1.5-2 hours at 80-90 ℃ to carry out the silicon precipitation. The pH of the precipitated silicon is too low or too high, and the silicon cannot be precipitated in the form of silicic acid; the silicon precipitation temperature is too low, the precipitation reaction speed is reduced, the reaction time is increased, the temperature is too high, the reaction energy consumption is increased, and the precipitation rate is not greatly increased. The silicon precipitation time is too short, the silicon in the leaching solution is not completely precipitated, the purity of the subsequent ammonium paratungstate product is affected, the time is too long, the silicon precipitation rate is not greatly increased, and the reaction energy consumption is increased.
In the acid leaching slag treatment process, when excessive calcium source is added for precipitation treatment, excessive calcium chloride is added into the silicon precipitation solution at 80-90 ℃ and reacted for 3-4 hours.
In the acid leaching slag treatment process, concentrated ammonia water is added and then reacts for 1.5-2 hours at the temperature of 80-90 ℃, the mass fraction of the concentrated ammonia water is 25-30%, and the volume ratio of the mass of the calcium tungstate solid to the concentrated ammonia water is 1g:1.3-1.5mL; the evaporation concentration is carried out at 80-90 ℃, and the ammonium paratungstate is obtained after cooling crystallization for 1-2d at room temperature. The reaction rate is not obviously increased when the reaction temperature is too high, the reaction energy consumption is increased, the reaction rate is too slow when the temperature is too low, and the reaction time is increased. Too much concentrated ammonia water is added, the reaction rate is not obviously improved, too little concentrated ammonia water is added, the reaction speed is reduced, the reaction time is prolonged, the reaction is incomplete, the incomplete dissolution of calcium tungstate can be caused, and the loss of tungsten is caused.
In the acid leaching slag treatment process, in order to improve WO 4 2- /WO x S 4-x 2- The content of tungsten element in the solution is Na 2 WO 4 /Na 2 WO x S 4-x Adding a certain amount of sodium sulfide solution and sodium hydroxide solid into the solution, adding acid leaching slag powder into the solution for cyclic leaching to enrich tungsten, and filtering to obtain high-concentration Na 2 WO 4 /Na 2 WO x S 4-x A solution. According to the recycling method of tungsten element in acid leaching slag, the concentration of tungsten element in leaching liquid is improved by adopting a circulating leaching mode, and the method aims at solving the problem that the subsequent precipitation step is affected due to the fact that the content of tungsten element in leaching liquid is low in the existing waste SCR denitration catalyst treatment process.
In the treatment process of the acid leaching slag, sodium sulfide and sodium hydroxide are adopted to leach the acid leaching slag, and sodium thiotungstate is obtained and is a series of substances including sodium monothiotungstate, sodium dithiotungstate, sodium trithiotungstate, tungsten sulfide and sodium tungstate, so that the leaching rate of tungsten is obviously higher than that of sodium tungstate only generated during leaching by sodium hydroxide, and the leaching rate is higher. In addition, sodium sulfide has weak alkalinity and poor binding capacity with silicon as a leaching agent, and compared with the traditional leaching agent such as sodium hydroxide, the leaching rate of impurities is lower (leaching is carried out by adopting the traditional leaching agent such as sodium hydroxide and the like)And the leaching rate of impurity silicon can reach 34.2%, and the leaching rate of tungsten is relatively low. Under the same conditions, sodium sulfide and sodium hydroxide are adopted as leaching agents, the leaching rate of silicon is 16.2%, and the leaching rate of tungsten is improved by about 20%. Considering leachate WO 4 2- /WO x S 4-x 2- The solution contains partial thiotungstate radical which is unfavorable for the subsequent tungsten extraction step, and the invention further adopts ozone as an oxidant to convert the ozone into sodium tungstate, thereby being favorable for the subsequent tungsten precipitation recovery.
In the treatment process of the acid leaching slag, aiming at the acid leaching slag, the tungsten element is efficiently recovered by adopting the all-wet treatment process, and because tungsten has both the sulfur affinity and the oxygen affinity, the invention adopts sodium sulfide coupled with sodium hydroxide as a leaching agent, and adopts sodium sulfide as the leaching agent, not only can the alkali consumption of alkaline leaching be reduced, but also the acid leaching slag has higher leaching efficiency, and the high-efficiency utilization of the tungsten element of the acid leaching slag is realized. Compared with the traditional method adopting sodium hydroxide leaching, which has the defects of high alkali consumption, high impurity leaching rate and the like, the method provided by the invention has the advantages of higher leaching rate, lower alkali consumption, lower impurity leaching rate and realization of efficient leaching of acid leaching residues.
In the acid leaching slag treatment process, the concentration of the solution is ensured by ozone oxidation. The presence of the thiotungstate radical in the solution is unfavorable for the subsequent tungsten extraction step, so that the thiotungstate radical is converted into the tungstate radical by utilizing ozone, the tungsten element concentration is not reduced, the thiotungstate radical is converted into the tungstate radical, the subsequent precipitation recovery is facilitated, and the concentration of the solution is reduced or new impurities are introduced by using hydrogen peroxide or potassium chlorate oxidant. Meanwhile, on the premise of adopting sodium sulfide as a leaching agent, as the combination energy between tungsten and sulfur is larger, the invention adopts ozone oxidation to convert the tungsten into sodium tungstate, and then carries out subsequent impurity removal process, thereby being beneficial to improving the recovery rate of tungsten.
As a general technical conception, the invention also provides the aluminum vanadate prepared by the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, wherein the aluminum vanadate has a sea urchin-shaped microstructure.
As a general technical concept, the invention also provides application of the aluminum vanadate as uranium adsorbent.
Aiming at the waste SCR denitration catalyst, the invention adopts the full wet treatment process to simultaneously recycle aluminum and vanadium. According to exploratory researches and repeated experiments, ammonium sulfite is used as a reducing agent, tetravalent vanadium is reduced and leached by sulfuric acid, high-efficiency leaching of vanadium element is achieved, the concentration of vanadium ions in a solution is improved in a circulating leaching mode, the pH value of the solution is regulated to be 2.8-3.2 by ammonium hydroxide, ozone is used as an oxidizing agent, oxidation of low-valence vanadium is achieved under the condition that the concentration of vanadium ions in the solution is not reduced, and the aluminum vanadate product is prepared by comprehensively utilizing pentavalent metavanadate and aluminum ions through hydrothermal reaction under the action of a surfactant PVP, so that multi-component comprehensive utilization of a waste SCR denitration catalyst is achieved.
Compared with the prior art, the invention has the advantages that:
1. according to the method for preparing aluminum vanadate by using the waste SCR denitration catalyst, ammonium sulfite is used as a reducing agent, and the tetravalent vanadium is leached by sulfuric acid reduction, so that the vanadium element is leached efficiently, other impurity ions are not introduced, and ammonium ions are easy to remove.
2. The method for preparing aluminum vanadate by using the waste SCR denitration catalyst utilizes ozone to replace liquid oxidants such as hydrogen peroxide and the like, and ozone oxidation avoids the reduction of solution concentration. Aiming at the preparation of aluminum vanadate, low-valence vanadium needs to be oxidized into pentavalent metavanadate ions, and then the aluminum vanadate is prepared through hydrothermal reaction. Compared with the existing oxidation mode using hydrogen peroxide, the use of ozone as an oxidant avoids the dilution of vanadium in the oxidation process, does not introduce new impurities, and realizes the efficient precipitation reaction of vanadium and aluminum.
3. The method for preparing aluminum vanadate by using the waste SCR denitration catalyst comprehensively and efficiently utilizes vanadium elements and aluminum elements in the waste SCR denitration catalyst, directly synthesizes aluminum vanadate products in a solution on the premise of not carrying out element separation, can be used as an adsorbent for adsorbing uranium, and compared with the traditional method for preparing ammonium vanadate by extracting vanadium and removing aluminum as impurities, the method for preparing aluminum vanadate by using the waste SCR denitration catalyst comprehensively utilizes the two elements, greatly reduces the generation of waste liquid and has short process flow.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method of the present invention for preparing aluminum vanadate utilizing a spent SCR denitration catalyst.
Fig. 2 is a process flow diagram of a method for preparing aluminum vanadate and ammonium paratungstate using a spent SCR denitration catalyst in example 3.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The main composition of the waste SCR denitration catalyst to be treated in the following examples and comparative examples is V:0.63%, al:9.65%, ti:17.3%, W:1.55%, mg:4.31%, fe:0.26%, si:28.15%.
Example 1:
as shown in fig. 1, a method for preparing aluminum vanadate using a waste SCR denitration catalyst includes the steps of:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:8mL of sulfuric acid solution with the concentration of 1.5mol/L is added, the mixture is placed in a water bath kettle with the temperature of 90 ℃ after being evenly mixed, and 0.05g (NH) 4 ) 2 SO 3 After 2h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid (leaching slag is washed by water, washing liquid returns to the low-concentration low-valence vanadium liquid) and acid leaching slag, and under the reaction condition, the leaching rate of vanadium is 89.58 percent, and the concentration of vanadium in the solution is 538mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration low-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 84.5%, and the concentration of vanadium element in the solution is increased to 2301mg/L.
(4) Adding NH into the high-concentration low-valence vanadium solution 4 And after the pH value of the solution is regulated to 3 by OH, taking 100mL of high-concentration low-valence vanadium leaching solution, introducing ozone with the flow rate of 10mL/min into the leaching solution to oxidize vanadium element, simultaneously taking 3g of PVP as a surfactant, adding the PVP into the leaching solution, and carrying out vigorous stirring (the stirring speed is 1000 rpm) to react for 30min to obtain yellow precursor suspension.
(5) Placing the yellow precursor suspension into a Teflon reaction kettle for hydrothermal reaction, preserving heat for 6 hours at 160 ℃, filtering to obtain green precipitate, washing the precipitate with deionized water and ethanol until the precipitation rate of vanadium reaches 95%, and placing the precipitate into a vacuum drying oven for preserving heat for 12 hours at 80 ℃ to obtain the final product aluminum vanadate HAVO, wherein the purity of the prepared aluminum vanadate product reaches 98%.
The sea urchin-shaped microstructure with small holes distributed in the aluminum vanadate product prepared in the embodiment can be used as a uranium adsorbent, and the relatively complete three-dimensional microstructure can provide more space for storing uranium ions and has more adsorption site areas, so that the aluminum vanadate product has more excellent adsorption performance.
Example 2:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:6mL of sulfuric acid solution with the concentration of 2mol/L is added, the mixture is placed in a water bath kettle with the temperature of 90 ℃ after being evenly mixed, and 0.06g (NH) 4 ) 2 SO 3 After 1.5h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid, the leaching rate of vanadium is 90.32% under the reaction condition, and the concentration of vanadium in the solution is 546mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration high-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 85.6%, and the concentration of vanadium element in the solution is increased to 2339mg/L.
(4) Adding NH into the high-concentration low-valence vanadium solution 4 And after the pH value of the solution is regulated to 2.8 by OH, taking 100mL of high-concentration low-valence vanadium leaching solution, introducing ozone with the flow rate of 10mL/min into the leaching solution to oxidize vanadium element, simultaneously taking 3g of PVP as a surfactant, adding the PVP into the leaching solution, and carrying out vigorous stirring to react for 30min to obtain yellow precursor suspension.
(5) Placing the yellow precursor suspension into a Teflon reaction kettle for hydrothermal reaction, preserving heat for 6 hours at 160 ℃, filtering to obtain green precipitate, washing the precipitate with deionized water and ethanol until the precipitation rate of vanadium reaches 95%, and placing the precipitate into a vacuum drying oven for preserving heat for 12 hours at 80 ℃ to obtain the final product aluminum vanadate HAVO, wherein the purity of the prepared aluminum vanadate product reaches 98%.
Comparative example 1:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g: adding sulfuric acid solution with concentration of 1mol/L at a ratio of 4mL, mixing, placing into a water bath at 50deg.C, and adding 0.02g (NH 4 ) 2 SO 3 After 1h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid, the leaching rate of vanadium is 41.53 percent under the reaction condition, and the concentration of vanadium in the solution is 204mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration high-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 37.2%, and the concentration of vanadium element in the solution is increased to 996mg/L.
(4) Adding NH into the high-concentration low-valence vanadium solution 4 And after the pH value of the solution is regulated to 3 by OH, taking 100mL of high-concentration low-valence vanadium leaching solution, introducing ozone with the flow rate of 10mL/min into the leaching solution to oxidize vanadium element, simultaneously taking 3g of PVP as a surfactant, adding the PVP into the leaching solution, and carrying out vigorous stirring to react for 30min to obtain yellow precursor suspension.
(5) The yellow precursor suspension is put into a Teflon reaction kettle for hydrothermal reaction, the temperature is kept at 160 ℃ for 6 hours, then green precipitate is obtained by filtering, the precipitation rate of vanadium reaches 95%, and the final product aluminum vanadate HAVO obtained by washing with deionized water and ethanol and then placing into a vacuum drying oven for 12 hours at 80 ℃ is less.
Comparative example 2:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:8mL of sulfuric acid solution with the concentration of 1.5mol/L is added, the mixture is placed in a water bath kettle with the temperature of 90 ℃ after being evenly mixed, and 0.05g of Na is added 2 SO 3 After 2h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid, and the leaching rate of vanadium is 89.58 percent under the reaction condition, wherein the concentration of vanadium in the solution is 538mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration high-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 84.5%, and the concentration of vanadium element in the solution is increased to 2301mg/L.
(4) Adding NH into the high-concentration low-valence vanadium solution 4 And after the pH value of the solution is regulated to 3 by OH, taking 100mL of high-concentration low-valence vanadium leaching solution, introducing ozone with the flow rate of 5mL/min into the leaching solution to oxidize vanadium element, simultaneously taking 3g of PVP as a surfactant, adding the PVP into the leaching solution, and carrying out vigorous stirring to react for 10min to obtain yellow precursor suspension.
(5) The yellow precursor suspension is put into a Teflon reaction kettle for hydrothermal reaction, the temperature is kept at 160 ℃ for 6 hours, then green precipitate is obtained by filtering, the precipitation rate of vanadium is about 64%, and the final product aluminum vanadate HAVO obtained by washing with deionized water and ethanol and then placing into a vacuum drying oven for 12 hours at 80 ℃ is less.
Comparative example 3:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:8mL of sulfuric acid solution with the concentration of 1.5mol/L is added, the mixture is placed in a water bath kettle with the temperature of 90 ℃ after being evenly mixed, and 0.05g (NH) 4 ) 2 SO 3 After 2h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid, and the leaching rate of vanadium is 89.58 percent under the reaction condition, wherein the concentration of vanadium in the solution is 538mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration low-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 84.5%, and the concentration of vanadium element in the solution is increased to 2301mg/L.
(4) Adding NH into the high-concentration low-valence vanadium solution 4 And after the pH value of the solution is regulated to 3 by OH, taking 100mL of high-concentration low-valence vanadium leaching solution, adding excessive hydrogen peroxide into the high-concentration low-valence vanadium leaching solution, simultaneously taking 3g of PVP as a surfactant, adding the high-concentration low-valence vanadium leaching solution into the leaching solution, and carrying out vigorous stirring to react for 30min to obtain yellow precursor suspension.
(5) The yellow precursor suspension is put into a Teflon reaction kettle for hydrothermal reaction, the temperature is kept at 160 ℃ for 6 hours, then green precipitate is obtained by filtering, the precipitation rate of vanadium is about 83%, the precipitate is washed by deionized water and ethanol, and the precipitate is put into a vacuum drying oven for 12 hours at 80 ℃ to obtain the final product aluminum vanadate HAVO with relatively less content.
Comparative example 4:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:8mL of sulfuric acid solution with the concentration of 1.5mol/L is added, the mixture is placed in a water bath kettle with the temperature of 90 ℃ after being evenly mixed, and 0.05g of Na is added 2 SO 3 After 2h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid, and the leaching rate of vanadium is 89.58 percent under the reaction condition, wherein the concentration of vanadium in the solution is 538mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration high-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 84.5%, and the concentration of vanadium element in the solution is increased to 2301mg/L.
(4) Taking 100mL of high-concentration low-valence vanadium liquid to flow intoOxidizing vanadium element with ozone at a speed of 10mL/min, and adding NH 4 And regulating the pH value of the solution to 3 by OH, adding 3g PVP as a surfactant into the leaching solution, and carrying out vigorous stirring to react for 30min to obtain yellow precursor suspension.
(5) Placing the yellow precursor suspension into a Teflon reaction kettle for hydrothermal reaction, preserving heat for 6 hours at 160 ℃, filtering to obtain green precipitate, washing the precipitate with deionized water and ethanol until the precipitation rate of vanadium reaches 94%, and placing the precipitate into a vacuum drying oven for preserving heat for 12 hours at 80 ℃ to obtain the final aluminum vanadate HAVO with low purity of not more than 85%.
Comparative example 5:
a method for preparing aluminum vanadate by using a waste SCR denitration catalyst comprises the following steps:
(1) And (3) drying and crushing the waste SCR denitration catalyst, and screening by using an 80-mesh standard screen to ensure that the granularity is controlled below 178 mu m.
(2) Putting 4g of undersize material into a beaker, wherein the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:8mL of sulfuric acid solution with the concentration of 1.5mol/L is added, the mixture is placed in a water bath kettle with the temperature of 90 ℃ after being evenly mixed, and 0.05g (NH) 4 ) 2 SO 3 After 2h of reaction, solid-liquid separation is carried out to obtain low-concentration low-valence vanadium liquid, and the leaching rate of vanadium is 89.58 percent under the reaction condition, wherein the concentration of vanadium in the solution is 538mg/L.
(3) And (3) supplementing a proper amount of concentrated sulfuric acid into the low-concentration low-valence vanadium solution, adding the waste SCR denitration catalyst and ammonium sulfite which are the same as those in the step (2) into the low-concentration low-valence vanadium solution, leaching under the same condition, and obtaining the high-concentration low-valence vanadium leaching solution after five times of cyclic leaching, wherein the leaching rate of vanadium is reduced to 84.5%, and the concentration of vanadium element in the solution is increased to 2301mg/L.
(4) Adding NH into the high-concentration low-valence vanadium solution 4 And after the pH value of the solution is regulated to 2 by OH, taking 100mL of high-concentration low-valence vanadium leaching solution, introducing ozone with the flow rate of 10mL/min into the leaching solution to oxidize vanadium element, simultaneously taking 3g of PVP as a surfactant, adding the PVP into the leaching solution, and carrying out vigorous stirring to react for 30min to obtain yellow precursor suspension.
(5) Placing the yellow precursor suspension into a Teflon reaction kettle for hydrothermal reaction, preserving heat for 6 hours at 160 ℃, filtering to obtain green precipitate, washing the precipitate with deionized water and ethanol until the precipitation rate of vanadium reaches 95%, and placing the precipitate into a vacuum drying oven for preserving heat for 12 hours at 80 ℃ to obtain the final product aluminum vanadate HAVO-2.
Compared with the sea urchin-shaped microstructure with small holes distributed in the aluminum vanadate prepared in the example 1 under the condition of the pH value of 3, the aluminum vanadate product prepared in the comparative example is in a three-dimensional porous sea urchin-shaped microstructure, and the relatively complete three-dimensional microstructure in the example 1 can provide more space for storing uranium ions and has more adsorption site areas, so that the aluminum vanadate product has more excellent adsorption performance.
Example 3:
as shown in fig. 2, a method for preparing aluminum vanadate and ammonium paratungstate by using a waste SCR denitration catalyst comprises the following steps:
step (1) -step (5) was the same as in example 1:
(6) 4g of acid leaching slag is placed in a beaker, and the quality of the acid leaching slag and Na are adopted 2 The volume ratio of the S solution is 1g:6mL of Na was added at a concentration of 2mol/L 2 S, uniformly mixing the solutions, and placing the solutions into a water bath kettle at 80 ℃ according to the mass ratio of alkali residues of 1:3, adding sodium hydroxide solid in proportion, reacting for 2.5h, then carrying out solid-liquid separation, wherein the leaching rate of W is 85.24%, the concentration of tungsten element in the solution is 701mg/L (washing filter residues, collecting water washing liquid and mixing the water washing liquid with filtrate), and obtaining low concentration Na 2 WO 4 /Na 2 WO x S 4-x The leaching rate of the solution and the titanium-rich slag and impurity silicon is 16.2 percent.
(7) To increase the content of tungsten element in the solution, the low concentration Na is mentioned above 2 WO 4 /Na 2 WO x S 4-x Adding a certain amount of sodium sulfide and sodium hydroxide solid into the solution, adding acid leaching slag powder for leaching, and obtaining high-concentration Na after 5 times of circulating leaching 2 WO 4 /Na 2 WO x S 4-x The concentration of tungsten element in the solution is increased to 3926mg/L.
(8) At high concentration of Na 2 WO 4 /Na 2 WO x S 4-x Ozone gas with the flow rate of 10mL/min is introduced into the solution for 30min for oxidation transformation to obtain high-concentration Na 2 WO 4 A solution.
(9) Adjusting high concentration Na with hydrochloric acid 2 WO 4 The pH value of the solution is 9, and the reaction is carried out for 2 hours at the water bath 80 ℃ to lead the silicon in the solution to generate H 2 SiO 3 The precipitate was removed and the silicon precipitation rate reached 95% under this condition. Adding excessive calcium chloride into the solution for precipitation to convert sodium tungstate in the solution into calcium tungstate solid, reacting for 4 hours at the temperature of 80 ℃ in water bath, and separating solid from liquid to obtain calcium tungstate solid, wherein the precipitation rate of tungsten reaches 98.4%.
(10) Mixing calcium tungstate solid with 25-30% of concentrated ammonia water according to the mass fraction of 1g: the solid-liquid ratio of 1.3mL is reacted for 2 hours at the water bath temperature of 90 ℃ to obtain ammonium tungstate solution, wherein the impurity elements such as Ca, fe and the like react with ammonia water to generate insoluble precipitates such as calcium hydroxide, ferric hydroxide and the like, and the precipitates are removed by filtration.
(11) The ammonium tungstate with high solubility is converted into ammonium paratungstate with low solubility by evaporation concentration and cooling crystallization, and the ammonium paratungstate is crystallized and separated from the solution. Heating the ammonium tungstate solution at 90 ℃, cooling and crystallizing the ammonium tungstate solution at room temperature for 1d, filtering to obtain ammonium paratungstate crystals, and when the evaporation capacity of the solution reaches 90%, the crystallization rate of the ammonium paratungstate exceeds 89%, and the purity of the obtained ammonium paratungstate product exceeds 95%. And repeating the step (5) and the step (6) for a plurality of times, and obtaining the ammonium paratungstate crystal with the purity of more than 99.9%.
Claims (10)
1. The method for preparing aluminum vanadate by using the waste SCR denitration catalyst is characterized by comprising the following steps of:
(1) Leaching the waste SCR denitration catalyst by using sulfuric acid and ammonium sulfite, and filtering to obtain acid leaching liquid and acid leaching slag;
(2) Introducing ozone into the acid leaching solution obtained in the step (1) for oxidation to obtain a precursor suspension;
(3) And (3) carrying out hydrothermal reaction on the precursor suspension obtained in the step (2), collecting precipitate, filtering, washing and drying to obtain aluminum vanadate.
2. The method for preparing aluminum vanadate using a waste SCR denitration catalyst as claimed in claim 1, wherein ammonium hydroxide is added to the acid leaching solution to adjust the pH of the solution to 2.8-3.2 before the acid leaching solution is oxidized by introducing ozone.
3. The method for preparing aluminum vanadate from the waste SCR denitration catalyst according to claim 1, wherein acid liquor is supplemented to the acid leaching solution obtained in the step (1), the waste SCR denitration catalyst and ammonium sulfite are added to the acid leaching solution for cyclic leaching, the cyclic leaching is carried out for a plurality of times to obtain high-concentration low-valence vanadium liquor, and the high-concentration low-valence vanadium liquor is used for replacing the acid leaching solution to carry out the step (2).
4. A method for preparing aluminum vanadate using a waste SCR denitration catalyst as claimed in any one of claims 1 to 3, wherein the concentration of sulfuric acid is 1.5 to 2mol/L, and the volume ratio of the mass of the waste SCR denitration catalyst to sulfuric acid is 1g:6-8mL, wherein the mass ratio of the waste SCR denitration catalyst to the ammonium sulfite is 1: (0.01-0.02).
5. A method for preparing aluminum vanadate using a waste SCR denitration catalyst as claimed in any one of claims 1 to 3, wherein when the waste SCR denitration catalyst is leached using sulfuric acid and ammonium sulfite, the reaction is performed in a water bath at 80 to 90 ℃ for 1.5 to 2 hours.
6. The method for preparing aluminum vanadate using a waste SCR denitration catalyst according to any one of claims 1 to 3, wherein the flow rate of ozone gas is controlled to be 10 to 20mL/min when ozone is introduced for oxidation, and the oxidation time is controlled to be 20 to 30min when ozone is introduced for oxidation.
7. A method for preparing aluminum vanadate using a waste SCR denitration catalyst according to any one of claims 1 to 3, wherein polyvinylpyrrolidone is added to the acid leaching solution at a liquid-solid ratio of 1 ml:20-40 mg while ozone oxidation is introduced, while vigorous stirring is performed.
8. A method for preparing aluminum vanadate using a waste SCR denitration catalyst as claimed in any one of claims 1 to 3, wherein the hydrothermal reaction is kept at 160 to 180 ℃ for 6 to 8 hours.
9. An aluminum vanadate prepared by the method for preparing aluminum vanadate using a waste SCR denitration catalyst as claimed in any one of claims 1 to 8, wherein the aluminum vanadate has a sea urchin-like microstructure.
10. Use of the aluminum vanadate prepared by the method for preparing aluminum vanadate using the waste SCR denitration catalyst of any one of claims 1-8 or the aluminum vanadate of claim 9 as uranium adsorbent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311282807.4A CN117509728A (en) | 2023-09-28 | 2023-09-28 | Method for preparing aluminum vanadate by using waste SCR denitration catalyst, aluminum vanadate and application of aluminum vanadate |
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| CN202311282807.4A CN117509728A (en) | 2023-09-28 | 2023-09-28 | Method for preparing aluminum vanadate by using waste SCR denitration catalyst, aluminum vanadate and application of aluminum vanadate |
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| CN (1) | CN117509728A (en) |
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