CN110451563A - The minimizing technology of sulfate radical and bisulfate ion when preparing sodium molybdate from molybdenum-contained waste catalyst - Google Patents
The minimizing technology of sulfate radical and bisulfate ion when preparing sodium molybdate from molybdenum-contained waste catalyst Download PDFInfo
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- CN110451563A CN110451563A CN201910865560.6A CN201910865560A CN110451563A CN 110451563 A CN110451563 A CN 110451563A CN 201910865560 A CN201910865560 A CN 201910865560A CN 110451563 A CN110451563 A CN 110451563A
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- molybdenum
- sulfate radical
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- waste catalyst
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- -1 bisulfate ion Chemical class 0.000 title claims abstract description 37
- 239000011684 sodium molybdate Substances 0.000 title claims abstract description 36
- 235000015393 sodium molybdate Nutrition 0.000 title claims abstract description 36
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 238000005516 engineering process Methods 0.000 title claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 114
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 67
- 239000011733 molybdenum Substances 0.000 claims abstract description 67
- 239000012074 organic phase Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 239000012071 phase Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 239000006210 lotion Substances 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000013517 stratification Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 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 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 238000010828 elution Methods 0.000 abstract description 4
- UIHQWOOHHYVOGH-UHFFFAOYSA-I sodium molybdenum(4+) pentahydroxide Chemical compound [OH-].[Na+].[Mo+4].[OH-].[OH-].[OH-].[OH-] UIHQWOOHHYVOGH-UHFFFAOYSA-I 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000016768 molybdenum Nutrition 0.000 description 56
- 239000002253 acid Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 6
- 239000000284 extract Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000005837 radical ions Chemical class 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The minimizing technology of sulfate radical and bisulfate ion when preparing sodium molybdate from molybdenum-contained waste catalyst the present invention relates to a kind of tertiary amine extraction includes the following steps: to extract molybdenum-sodium hydroxide solution back extraction-condensing crystallizing sodium molybdate product under mildly acidic conditions to molybdenum-contained waste catalyst use plus alkali oxidizing roasting-water logging filtering-chemical precipitation method dephosphorization-tertiary amine and kerosin.Sulfate radical can be down to 1.96g/L, eluting rate 81.88% by load organic phases 10.82g/L before eluting by eluting load molybdenum organic phase with diluted sodium hydroxide solution by the present invention.Sig water elution through the invention is stripped to obtain Mo/SO in high concentration sodium molybdate solution with lye after carrying molybdenum organic phase4 2‑Greater than 100, SO4 2‑Content is less than 2g/L, and condensing crystallizing obtains SO in sodium molybdate product4 2‑Not higher than 0.05%, reach industrial primes requirement.
Description
Technical field
Sulfate radical and bisulfate ion when preparing sodium molybdate from molybdenum-contained waste catalyst the present invention relates to a kind of tertiary amine extraction
Minimizing technology.
Background technique
From molybdenum-contained waste catalyst molybdenum extract molybdenum prepare sodium molybdate method have 1. using concentrating and precipitating molybdic acid-sodium hydroxide it is molten
Solution-condensing crystallizing, since molybdenum concentration is low, energy consumption is high, metal yield is low；2. solvent extraction, acid using tertiary amine kerosin
Extraction molybdenum-sodium hydroxide is stripped-precipitates molybdic acid-sodium hydroxide dissolution-condensing crystallizing and obtains sodium molybdate；There are technique streams for the method
The disadvantages of journey is long, reagent consumption is high, technique waste water is more；3. ion-exchange adsorbs molybdenum using weak-base anion-exchange resin
Sodium molybdate, the method and solvent extraction are obtained with sodium hydroxide desorption molybdenum-precipitating molybdic acid-sodium hydroxide dissolution-condensing crystallizing afterwards
Have the shortcomings that same.Molybdenum exists generally in the form of polymeric form in weak acid system, such as two molybdenum acid ion (Mo2O7 2-), three molybdic acids
Radical ion (Mo3O10 2-), four molybdenum acid ion (Mo4O13 2-), seven molybdenum acid ion (Mo7O24 6-) and eight molybdenum acid ions
(Mo8O26 4-) etc., tertiary amine is a kind of organic weak base, it needs to be converted into sulfuric acid (hydrogen) salt form with sulfuric acid solution before extracting molybdenum,
Reaction equation is as follows: R3N+H2SO4=[R3NH]+HSO4 -Or 2R3N+H2SO4=[R3NH]2SO4, extractant extracts more molybdenums after transition
Following reaction occurs when acid ion, by taking four molybdenum acid ions as an example:
2[R3NH]HSO4+Mo4O13 2-=[R3NH]2Mo4O13+2HSO4 -
Or [R3NH]2SO4+Mo4O13 2-=[R3NH]2Mo4O13+SO4 2-
Find out from reaction equation, sulfuric acid (hydrogen) radical ion carries out in extractant after polymerization molybdate anion and transition when extraction
Exchange, saturated capacity is not achieved in displacement volume when due to extraction, that is to say, that cannot be complete by sulfuric acid in extractant (hydrogen) radical ion
Portion's displacement, therefore load and still contain a certain amount of sulfuric acid (hydrogen) radical ion, 10% (V/V) trioctylamine kerosin in molybdenum organic phase
It is formed after extraction molybdenum are as follows: Mo 18g/L~22g/L, SO4 2-10g/L~12g/L is stripped together in sodium hydroxide back extraction
It takes off, seriously affects sodium molybdate quality.
Summary of the invention
Sulphur when preparing sodium molybdate from molybdenum-contained waste catalyst an object of the present invention is to provide a kind of tertiary amine extraction
The minimizing technology of acid group and bisulfate ion.
Sulfate radical and bisulfate ion when a kind of tertiary amine extraction of the invention prepares sodium molybdate from molybdenum-contained waste catalyst
Minimizing technology includes the following steps: S101: by molybdenum-contained waste catalyst with sodium carbonate according to mass ratio 20:(4~5) mix after plus
Heat is to 750 DEG C~800 DEG C and keeps the temperature 2h~3h, obtains clinker；S102: by the clinker and water according to weight ratio 1:(2~2.5)
It is heated to 30 DEG C~40 DEG C and leaching 1h~2h after mixing, then leaches ore pulp, refilters and collect filtrate, wash simultaneously
Then the washing lotion for washing filter residue and the filtrate are merged, obtain the first mixed liquor by filter residue；S103: measurement first mixing
Then first mixed liquor is heated to 90 DEG C~95 DEG C and adjusts pH value to be 9.0~9.5 by the mass content of phosphorus in liquid, then
Epsom salt is added under conditions of keeping first pH of mixed more than or equal to 9.0, and stirs 2h~3h and then takes
The mass concentration of sample measurement Molybdenum in Solution and phosphorus；S104: the mass ratio for adjusting Molybdenum in Solution and phosphorus is greater than or equal to 1500, then
Solution is filtered to and collected filtrate, then washs filter residue with the alkalescent water that pH value is 9.0~9.5 and collects washing lotion, then by institute
It states filtrate to merge with the washing lotion, obtains the second mixed liquor；S105: being 3.0 with the pH value that sulfuric acid adjusts second mixed liquor
~3.5, the mass concentration of molybdenum is then measured, extractant is added and is extracted and stirred, be then allowed to stand layering, it is negative to obtain upper layer
Carry the organic phase of molybdenum and the water phase of lower layer；S106: the organic phase of the load molybdenum on upper layer is pressed with the first sodium hydroxide solution
It is 1:(0.8~1.2 according to weight ratio) it is mixed and stirred for, it is then allowed to stand the water for being layered and collecting upper organic phase and lower layer respectively
Phase, then the content of molybdenum and sulfate radical in water phase is measured, then calculate the content of molybdenum and sulfate radical in organic phase；S107: by institute
The processed organic phase of step S106 and the second sodium hydroxide solution are stated according to weight ratio (4~6): 1 be mixed and stirred for after stand
Then layering collects upper organic phase and measures the concentration of molybdenum and sulfate radical therein；S108: the step S107 is obtained
Organic phase is 1:(8~12 according to volume ratio with third sodium hydroxide solution) it is mixed and stirred for rear stratification, under then collecting
Layer water phase, then be successively evaporated, condensing crystallizing, filtering, drying, obtain sodium molybdate.
Sulfate radical and bisulfate ion when a kind of tertiary amine extraction of the invention prepares sodium molybdate from molybdenum-contained waste catalyst
Minimizing technology can be by sulfate radical by eluting preceding load organic phases by eluting load molybdenum organic phase with diluted sodium hydroxide solution
10.82g/L is down to 1.96g/L, eluting rate 81.88%.Sodium hydroxide actual amount under optimum washing engaging condition through the invention
It is 0.836 times of theoretical amount, washing lotion endpoint pH is 3.0~4.0, guarantees to reach 80% in sulfate radical eluting rate, molybdenum elution
Rate ensure that less than 5% and wash the uniform performance of rear organic phase (Second Organic Phase do not occur), make to be stripped extract operation smoothly into
Row.Sig water elution through the invention is stripped to obtain Mo/ in high concentration sodium molybdate solution with lye after carrying molybdenum organic phase
SO4 2-Greater than 100, SO4 2-Content is less than 2g/L, and condensing crystallizing obtains SO in sodium molybdate product4 2-Not higher than 0.05%, reach work
The requirement of industry primes.
In addition, sulfate radical and sulphur when above-mentioned a kind of tertiary amine extraction of the invention prepares sodium molybdate from molybdenum-contained waste catalyst
The minimizing technology of sour hydrogen radical, can also have the following additional technical features:
Further, in the step S108, further include among the concentration crystallization step and the filtration step
Following steps: the mixed liquor after the condensing crystallizing is cooled to 28 DEG C~32 DEG C.
Further, in the step S105, mixing time is 10min~15min；In the step S106, stir
Mixing the time is 25min~35min；In the step S107, mixing time is 8min~12min；In the step S108, stirring
Time is 20min~30min.
Further, in the step S103, the mass ratio of the epsom salt and phosphorus is (80~100): 1.
Further, in the step S105, the preparation method of the extractant includes the following steps: trioctylphosphine uncle
Amine, isooctanol and sulfonated kerosene are 1:1:(7~9 according to volume ratio) mixing, then according to mixture and sulfuric acid solution according to weight
Amount than (1.8~2.2): 1 be mixed and stirred for 0.5h~1h after stand split-phase, then collect upper organic phase, obtain extractant；Its
In, the mass concentration of the sulfuric acid solution is 145g/L~155g/L.
Further, in the step S105, the solid-liquid ratio of molybdenum and extractant is 18g/L~22g/L.
Further, the ratio between amount of substance of first sodium hydroxide solution is 1mol/L；Second sodium hydroxide
The ratio between amount of substance of solution is 0.85mol/L~0.95mol/L；The ratio between the amount of substance of the third sodium hydroxide solution is
4.5mol/L~5.5mol/L.
Further, in the step S108, when carrying out concentration operation, solution is concentrated into specific gravity and is greater than or equal to
1.4。
Further, in the step S108, the temperature of drying is 75 DEG C~85 DEG C, and the time of drying is 3h~5h.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Specific embodiment
The embodiment of the present invention is described below in detail, the embodiment is exemplary, it is intended to it is used to explain the present invention, and
It is not considered as limiting the invention.
Embodiment 1
Embodiment 1 proposes sulfate radical and hydrogen sulfate when a kind of tertiary amine extraction prepares sodium molybdate from molybdenum-contained waste catalyst
The minimizing technology of root, includes the following steps:
(1) it is heated to 800 DEG C after mixing molybdenum-contained waste catalyst according to mass ratio 20:4 with sodium carbonate and keeps the temperature 2h, obtains
Clinker.
(2) it is heated to 30 DEG C and leaching 2h after mixing the clinker according to weight ratio 1:2.5 with water, then leaches
Ore pulp refilters and collects filtrate, while washing filter residue, and the washing lotion and the filtrate that then will wash filter residue merge, and obtains the
One mixed liquor.
(3) mass content for measuring phosphorus in first mixed liquor, is then heated to 90 DEG C simultaneously for first mixed liquor
Adjusting pH value is 9.5, then epsom salt is added under conditions of keeping first pH of mixed more than or equal to 9.0, and
Stir the mass concentration of 2h and then sampling and measuring Molybdenum in Solution and phosphorus.
(4) mass ratio for adjusting Molybdenum in Solution and phosphorus is greater than or equal to 1500, then solution is filtered to and collected filtrate, then
Filter residue is washed with the alkalescent water that pH value is 9.5 and collects washing lotion, and the filtrate is merged with the washing lotion then, obtains second
Mixed liquor.
(5) it is 3.0 with the pH value that sulfuric acid adjusts second mixed liquor, then measures the mass concentration of molybdenum, add extraction
It takes agent to be extracted and stirs 15min, be then allowed to stand layering, obtain the organic phase of upper layer load molybdenum and the water phase of lower layer.Molybdenum with
The solid-liquid ratio of extractant is 18g/L.The preparation method of the extractant include the following steps: by trioctylphosphine tertiary amine, isooctanol and
Sulfonated kerosene is 1:1:9 mixing according to volume ratio, then mixes and stirs according to weight ratio 1.8:1 with sulfuric acid solution according to mixture
Split-phase is stood after mixing 1h, upper organic phase is then collected, obtains extractant；Wherein, the mass concentration of the sulfuric acid solution is
145g/L。
It (6) is that 1:1.2 is mixed according to weight ratio with the first sodium hydroxide solution by the organic phase of the load molybdenum on upper layer
And 25min is stirred, it is then allowed to stand the water phase for being layered and collecting upper organic phase and lower layer respectively, then measure molybdenum and sulfuric acid in water phase
Then the content of root calculates the content of molybdenum and sulfate radical in organic phase.The amount of the substance of first sodium hydroxide solution it
Than for 1mol/L.
(7) step (6) processed organic phase is mixed and is stirred according to weight ratio 6:1 with the second sodium hydroxide solution
Stratification after 8min is mixed, then collect upper organic phase and measures the concentration of molybdenum and sulfate radical therein.Second hydrogen-oxygen
Changing the ratio between amount of substance of sodium solution is 0.95mol/L.
(8) organic phase that the step (7) obtains is mixed and is stirred for 1:8 according to volume ratio with third sodium hydroxide solution
Mix stratification after 30min, then collect lower layer's water phase, then be successively evaporated, condensing crystallizing to specific gravity is greater than or equal to
1.4,28 DEG C are cooled to, filters, dry 3h at a temperature of 85 DEG C, obtains sodium molybdate.The substance of the third sodium hydroxide solution
The ratio between amount be 5.5mol/L.
Embodiment 2
Embodiment 2 proposes sulfate radical and hydrogen sulfate when a kind of tertiary amine extraction prepares sodium molybdate from molybdenum-contained waste catalyst
The minimizing technology of root, includes the following steps:
(1) it is heated to 750 DEG C after mixing molybdenum-contained waste catalyst according to mass ratio 4:1 with sodium carbonate and keeps the temperature 3h, obtains
Clinker.
(2) it is heated to 40 DEG C and leaching 1h after mixing the clinker according to weight ratio 1:2 with water, then leaches mine
Slurry, refilters and collects filtrate, while washing filter residue, then merges the washing lotion for washing filter residue and the filtrate, obtains first
Mixed liquor.
(3) mass content for measuring phosphorus in first mixed liquor, is then heated to 95 DEG C simultaneously for first mixed liquor
Adjusting pH value is 9.0, then epsom salt is added under conditions of keeping first pH of mixed more than or equal to 9.0, and
Stir the mass concentration of 3h and then sampling and measuring Molybdenum in Solution and phosphorus.
(4) mass ratio for adjusting Molybdenum in Solution and phosphorus is greater than or equal to 1500, then solution is filtered to and collected filtrate, then
Filter residue is washed with the alkalescent water that pH value is 9.0 and collects washing lotion, and the filtrate is merged with the washing lotion then, obtains second
Mixed liquor.
(5) it is 3.5 with the pH value that sulfuric acid adjusts second mixed liquor, then measures the mass concentration of molybdenum, add extraction
It takes agent to be extracted and stirs 10min, be then allowed to stand layering, obtain the organic phase of upper layer load molybdenum and the water phase of lower layer.Molybdenum with
The solid-liquid ratio of extractant is 22g/L.The preparation method of the extractant include the following steps: by trioctylphosphine tertiary amine, isooctanol and
Sulfonated kerosene is 1:1:7 mixing according to volume ratio, then mixes and stirs according to weight ratio 2.2:1 with sulfuric acid solution according to mixture
Split-phase is stood after mixing 0.5h, upper organic phase is then collected, obtains extractant；Wherein, the mass concentration of the sulfuric acid solution is
155g/L。
It (6) is that 1:0.8 is mixed according to weight ratio with the first sodium hydroxide solution by the organic phase of the load molybdenum on upper layer
And 35min is stirred, it is then allowed to stand the water phase for being layered and collecting upper organic phase and lower layer respectively, then measure molybdenum and sulfuric acid in water phase
Then the content of root calculates the content of molybdenum and sulfate radical in organic phase.The amount of the substance of first sodium hydroxide solution it
Than for 1mol/L.
(7) step (6) processed organic phase is mixed and is stirred according to weight ratio 4:1 with the second sodium hydroxide solution
Stratification after 12min is mixed, then collect upper organic phase and measures the concentration of molybdenum and sulfate radical therein.Second hydrogen-oxygen
Changing the ratio between amount of substance of sodium solution is 0.85mol/L.
(8) organic phase that the step (7) obtains is mixed simultaneously according to volume ratio for 1:12 with third sodium hydroxide solution
Stir 20min after stratification, then collect lower layer's water phase, then be successively evaporated, condensing crystallizing to specific gravity is greater than or equal to
1.4,32 DEG C are cooled to, filters, dry 5h at a temperature of 75 DEG C, obtains sodium molybdate.The substance of the third sodium hydroxide solution
The ratio between amount be 4.5mol/L.
Embodiment 3
Embodiment 3 proposes sulfate radical and hydrogen sulfate when a kind of tertiary amine extraction prepares sodium molybdate from molybdenum-contained waste catalyst
The minimizing technology of root, includes the following steps:
(1) it is heated to 780 DEG C after mixing molybdenum-contained waste catalyst according to mass ratio 5:1 with sodium carbonate and keeps the temperature 2.5h, obtains
To clinker.
(2) it is heated to 35 DEG C and leaching 1.5h after mixing the clinker according to weight ratio 1:2.2 with water, then soaks
Ore pulp out refilters and collects filtrate, while washing filter residue, then merges the washing lotion for washing filter residue and the filtrate, obtains
First mixed liquor.
(3) mass content for measuring phosphorus in first mixed liquor, is then heated to 93 DEG C simultaneously for first mixed liquor
Adjusting pH value is 9.3, then epsom salt is added under conditions of keeping first pH of mixed more than or equal to 9.0, and
Stir the mass concentration of 2h~3h and then sampling and measuring Molybdenum in Solution and phosphorus.
(4) mass ratio for adjusting Molybdenum in Solution and phosphorus is greater than or equal to 1500, then solution is filtered to and collected filtrate, then
Filter residue is washed with the alkalescent water that pH value is 9.3 and collects washing lotion, and the filtrate is merged with the washing lotion then, obtains second
Mixed liquor.
(5) it is 3.3 with the pH value that sulfuric acid adjusts second mixed liquor, then measures the mass concentration of molybdenum, add extraction
It takes agent to be extracted and stirs 12min, be then allowed to stand layering, obtain the organic phase of upper layer load molybdenum and the water phase of lower layer.Molybdenum with
The solid-liquid ratio of extractant is 20g/L.The preparation method of the extractant include the following steps: by trioctylphosphine tertiary amine, isooctanol and
Sulfonated kerosene is 1:1:8 mixing according to volume ratio, is then mixed and stirred for according to mixture and sulfuric acid solution according to weight ratio 2:1
Split-phase is stood after 0.8h, then collects upper organic phase, obtains extractant；Wherein, the mass concentration of the sulfuric acid solution is
150g/L。
It (6) is that 1:1 is mixed simultaneously according to weight ratio with the first sodium hydroxide solution by the organic phase of the load molybdenum on upper layer
30min is stirred, is then allowed to stand the water phase for being layered and collecting upper organic phase and lower layer respectively, then measure molybdenum and sulfate radical in water phase
Content, then calculate the content of molybdenum and sulfate radical in organic phase.The ratio between the amount of substance of first sodium hydroxide solution
For 1mol/L.
(7) step (6) processed organic phase is mixed and is stirred according to weight ratio 5:1 with the second sodium hydroxide solution
Stratification after 10min is mixed, then collect upper organic phase and measures the concentration of molybdenum and sulfate radical therein.Second hydrogen-oxygen
Changing the ratio between amount of substance of sodium solution is 0.9mol/L.
(8) organic phase that the step (7) obtains is mixed simultaneously according to volume ratio for 1:10 with third sodium hydroxide solution
Stir 25min after stratification, then collect lower layer's water phase, then be successively evaporated, condensing crystallizing to specific gravity is greater than or equal to
1.4,30 DEG C are cooled to, filters, dry 4h at a temperature of 80 DEG C, obtains sodium molybdate.The substance of the third sodium hydroxide solution
The ratio between amount be 5mol/L.
To sum up, sulfate radical and hydrogen sulfate when a kind of tertiary amine extraction of the invention prepares sodium molybdate from molybdenum-contained waste catalyst
The minimizing technology of root can be organic by load before eluting by sulfate radical by eluting load molybdenum organic phase with diluted sodium hydroxide solution
Phase 10.82g/L is down to 1.96g/L, eluting rate 81.88%.Sodium hydroxide is practical under optimum washing engaging condition through the invention uses
Amount is 0.836 times of theoretical amount, and washing lotion endpoint pH is 3.0~4.0, guarantees to reach 80% in sulfate radical eluting rate, molybdenum is washed
The rate of taking off while ensure that less than 5% and wash the uniform performance of rear organic phase (Second Organic Phase do not occur), make to be stripped extract operation smoothly into
Row.Sig water elution through the invention is stripped to obtain Mo/ in high concentration sodium molybdate solution with lye after carrying molybdenum organic phase
SO4 2-Greater than 100, SO4 2-Content is less than 2g/L, and condensing crystallizing obtains SO in sodium molybdate product4 2-Not higher than 0.05%, reach work
The requirement of industry primes.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
- The minimizing technology of sulfate radical and bisulfate ion when 1. a kind of tertiary amine extraction prepares sodium molybdate from molybdenum-contained waste catalyst, It is characterized in that, includes the following steps:S101: by molybdenum-contained waste catalyst with sodium carbonate according to mass ratio 20:(4~5) mix after be heated to 750 DEG C~800 DEG C simultaneously 2h~3h is kept the temperature, clinker is obtained；S102: by the clinker with water according to weight ratio 1:(2~2.5) mix after be heated to 30 DEG C~40 DEG C and leaching 1h ~2h, then leaches ore pulp, refilters and collect filtrate, while washing filter residue, then will wash the washing lotion and the filter of filter residue Liquid merges, and obtains the first mixed liquor；S103: then first mixed liquor is heated to 90 DEG C~95 by the mass content of phosphorus in measurement first mixed liquor DEG C and to adjust pH value be 9.0~9.5, then keeping first pH of mixed that seven water are added under conditions of being greater than or equal to 9.0 Magnesium sulfate, and stir the mass concentration of 2h~3h and then sampling and measuring Molybdenum in Solution and phosphorus；S104: the mass ratio for adjusting Molybdenum in Solution and phosphorus is greater than or equal to 1500, then solution is filtered to and collected filtrate, then use The alkalescent water that pH value is 9.0~9.5 washs filter residue and collects washing lotion, then merges the filtrate with the washing lotion, obtains Second mixed liquor；S105: it is 3.0~3.5 with the pH value that sulfuric acid adjusts second mixed liquor, then measures the mass concentration of molybdenum, add Extractant is extracted and is stirred, and layering is then allowed to stand, and obtains the organic phase of upper layer load molybdenum and the water phase of lower layer；S106: according to weight ratio being 1:(0.8~1.2 by the organic phase of the load molybdenum on upper layer and the first sodium hydroxide solution) It is mixed and stirred for, is then allowed to stand the water phase for being layered and collecting upper organic phase and lower layer respectively, then measure molybdenum and sulfuric acid in water phase Then the content of root calculates the content of molybdenum and sulfate radical in organic phase；S107: by the processed organic phase of step S106 with the second sodium hydroxide solution according to weight ratio (4~6): 1 mixes And stratification after stirring, it then collects upper organic phase and measures the concentration of molybdenum and sulfate radical therein；S108: the organic phase and third sodium hydroxide solution that the step S107 is obtained are 1:(8~12 according to volume ratio) it is mixed Merge stratification after stirring, then collects lower layer's water phase, then be successively evaporated, condensing crystallizing, filtering, drying, obtain molybdenum Sour sodium.
- Sulfate radical and hydrogen sulfate when 2. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S108, among the concentration crystallization step and the filtration step Further include following steps: the mixed liquor after the condensing crystallizing is cooled to 28 DEG C~32 DEG C.
- Sulfate radical and hydrogen sulfate when 3. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S105, mixing time is 10min~15min；In the step In S106, mixing time is 25min~35min；In the step S107, mixing time is 8min~12min；The step In S108, mixing time is 20min~30min.
- Sulfate radical and hydrogen sulfate when 4. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S103, the mass ratio of the epsom salt and phosphorus be (80~ 100):1。
- Sulfate radical and hydrogen sulfate when 5. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S105, the preparation method of the extractant include the following steps: by Trioctylphosphine tertiary amine, isooctanol and sulfonated kerosene are 1:1:(7~9 according to volume ratio) mixing, it is then molten with sulfuric acid according to mixture Liquid is according to weight ratio (1.8~2.2): 1 is mixed and stirred for standing split-phase after 0.5h~1h, then collects upper organic phase, obtains Extractant；Wherein, the mass concentration of the sulfuric acid solution is 145g/L~155g/L.
- Sulfate radical and hydrogen sulfate when 6. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S105, the solid-liquid ratio of molybdenum and extractant is 18g/L~22g/L.
- Sulfate radical and hydrogen sulfate when 7. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that the ratio between amount of substance of first sodium hydroxide solution is 1mol/L；Second hydrogen The ratio between amount of substance of sodium hydroxide solution is 0.85mol/L~0.95mol/L；The amount of the substance of the third sodium hydroxide solution The ratio between be 4.5mol/L~5.5mol/L.
- Sulfate radical and hydrogen sulfate when 8. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S108, when carrying out concentration operation, solution is concentrated into than great In or equal to 1.4.
- Sulfate radical and hydrogen sulfate when 9. tertiary amine extraction according to claim 1 prepares sodium molybdate from molybdenum-contained waste catalyst The minimizing technology of root, which is characterized in that in the step S108, the temperature of drying is 75 DEG C~85 DEG C, and the time of drying is 3h~5h.
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