CN101177306A - Method for recovering rhodium chloride from waste rhodium catalyst - Google Patents
Method for recovering rhodium chloride from waste rhodium catalyst Download PDFInfo
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- CN101177306A CN101177306A CNA2007101771957A CN200710177195A CN101177306A CN 101177306 A CN101177306 A CN 101177306A CN A2007101771957 A CNA2007101771957 A CN A2007101771957A CN 200710177195 A CN200710177195 A CN 200710177195A CN 101177306 A CN101177306 A CN 101177306A
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- Prior art keywords
- rhodium
- acid
- solution
- catalyst
- chloride
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Links
- 239000010948 rhodium Substances 0.000 title claims abstract description 85
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 239000002699 waste material Substances 0.000 title abstract description 4
- 239000000243 solution Substances 0.000 claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000011575 calcium Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 238000007670 refining Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- IDAKEVGCRYXPBQ-UHFFFAOYSA-N [Rh]=O.Cl Chemical compound [Rh]=O.Cl IDAKEVGCRYXPBQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 abstract description 2
- 235000011167 hydrochloric acid Nutrition 0.000 abstract 2
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- PCBNFFXBNCITIF-UHFFFAOYSA-N oxorhodium;hydrate Chemical compound O.[Rh]=O PCBNFFXBNCITIF-UHFFFAOYSA-N 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- TVBSSDNEJWXWFP-UHFFFAOYSA-N nitric acid perchloric acid Chemical compound O[N+]([O-])=O.OCl(=O)(=O)=O TVBSSDNEJWXWFP-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 phosphine compound Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- BALRIWPTGHDDFF-UHFFFAOYSA-N rhodium Chemical compound [Rh].[Rh] BALRIWPTGHDDFF-UHFFFAOYSA-N 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a recovery method of rhodium chloride from waste rhodium catalyst, which is characterized in that the mixed solution of inorganic acid (two or more mixed by sulfuric acid, nitric acid, perchloric acid and chlorhydric acid) and oxidant is prepared to dissolute the waste catalyst; the dissolute solution is neutralized with alkali to prepare the hydrate rhodium oxide sediment; the hydrochloric acid is dissolved and deposited to obtain the solution of rhodium chloride; the hydrate rhodium chloride with high purity is obtained by removing copper, iron, nickel, calcium and other metal impure ions with ion exchange resin and refining with recrystallization; the rhodium recovery rate reaches more than 97% and the impurity content is less than 0.05%. The invention has the advantages of availabe raw material, economical and environmental protection, convenient operation and high recovery rate.
Description
Technical field the present invention relates to catalyst recovery and precious metal chemical technology field, aim to provide a kind of method that from spent rhodium catalyst, reclaims rhodium chloride, more precisely be that liquid phase method reclaims the method that rhodium obtains high purity chlorination rhodium from the useless using rhodium complex catalysts that carbongl group synthesis reaction produces.
Background of invention oxo process (claiming hydroformylation reaction again) is extremely important reaction in the chemical industry; comprise that catalysis of carbonyl is synthetic, olefin hydroformylation, acetic acid synthesis from methanol carbonylation, the synthetic aceticanhydride of ritalin carbonylation etc., rhodium phosphine complex catalyst is the most frequently used catalyzer of carbongl group synthesis reaction.In the above-mentioned reaction used rhodium phosphine have the reaction conditions gentleness, active high, dissolve in organic solvent, purify easily, advantages such as solid is stable in the air, storage convenient transportation.In the industrial production operation, rhodium phosphine complex catalyst is the inactivation owing to the existence of the various high boiling point by-products produced and impurities in raw materials that produces in the reaction process often.Because difficulty is extracted all in the exploitation of rhodium, catalyst preparation process is complicated and cost an arm and a leg, and along with rhodium in the international market price go up day by day, from waste material, reclaim rhodium and caused the attention of many countries, the rhodium yield also is the important factor that influences its industrial application.The parent of the rhodium catalyst of carbongl group synthesis reaction is a lot, as: RhCl (CO) (PPh
3)
2, [RhCl (CO)
2]
2, RhCl (CO) [P (OR)
3]
2, HRh (CO) (PPh
3)
3, HRh (CO) [P (OPh)
3]
3, Rh (C
5H
7O
2) (CO)
2, Rh (C
5H
7O
2) (CO) (PPh
3), HRh (CO) (dpm)
3Or the like.
The rhodium catalyst of carbongl group synthesis reaction inactivation exists with liquid form usually, contains a large amount of organism, as polycondensate of the high boiling point by-products produced and aldehyde of the triphenylphosphine of part and oxidation products thereof, oxo process etc.Rhodium content usually at hundreds of to several thousand ppm, simultaneously, in use also enrichment metals such as copper, zinc, iron, nickel.
The recovery method of spent rhodium catalyst in the past has extraction process, submerged combustion, adsorption method of separation, ashing combustion method etc.
Wherein, the extraction process that the clear 56-2994 of Japanese Patent introduces adopts elder generation that reaction mixture is dropped into the aqueous solution and carries out oxide treatment and acid treatment, generates the organic two-phase mixture of water-polarity; Dewater then; Again lipophilic phosphine or phosphite are dissolved in non-polar solvent (not dissolving each other with aforementioned organic phase) wiring solution-forming, add organic phase, form two-phase mixture, contain rhodium, lipotropy phosphine in the nonpolar organic phase, contain phosphite degraded product and high boiling point organic compound in the polarity organic phase, at last two-phase is separated.The rhodium complex rate of recovery about 90%.Because the Chemical bond power of Noble Metal Rhodium and organic phosphine compound is stronger, and catalyzer raffinate comparison thickness, so the extraction process rhodium rate of recovery is lower.
The submerged combustion that German Patent 2438847 is introduced, it is indoor that employing is sent into submerged combustion with the spent catalyst raffinate with air, and water absorbs combustion gases, rhodium is stayed in the water with suspended state, obtain rhodium after the filtration, this method is to the equipment requirements height, the rhodium rate of recovery about 94%.
The adsorption method of separation that the clear 49-121793 of Japanese Patent introduces, employing bringing Selection In property sorbent material in spent catalyst adsorbs rhodium phosphine complex catalyst, make solvent with benzene then, thorough high boiling point by-products produced in the eccysis catalyzer is with polar organic solvent stripping rhodium phosphine complex from sorbent material of a small amount of phosphine.The rhodium rate of recovery 91%.It is seriously polluted to adopt this method to reclaim rhodium.
The ashing combustion method that Chinese patent CN01136796.2 introduces, carbonate with basic metal or alkaline-earth metal is additive, under 650 ℃～700 ℃, the spent catalyst raffinate is burned ashing, residual residue again with molten state under alkali-metal bisulphate reactant salt, generate the rhodium salt of solubility, adopt electrolysis tech that rhodium is separated then.This method rhodium powder once through yield is more than 96%, rhodium powder purity 99.95%, and this method is handled rhodium catalyst, and rhodium generates volatile components and causes damage in the podzolic process, and produces large quantity of exhaust gas in the treating processes, and seriously polluted, equipment requirements is also higher simultaneously.
Summary of the invention the present invention is directed to problems of the prior art, provides a kind of liquid phase method to reclaim the method for high purity Trichlororhodium from the oxo process spent rhodium catalyst, have simple to operate, reaction conditions is gentle, characteristics such as economic environmental protection, rate of recovery height.
Be described in detail as follows:
What the inventive method was handled is the rhodium-containing spent catalyst of discharging from the carbongl group synthesis reaction device, its component generally is made up of metal ions such as the superpolymer of rhodium complex, high boiling point by-products produced and aldehyde and copper, iron, nickel, after the spent catalyst raffinate is discharged, usually rhodium, rhodium content about 0.1%～0.3% are reclaimed in storing after concentrating.
The object of the present invention is achieved like this, the distillation of spent rhodium catalyst solution decompression is concentrated, and organic matter carbonizing, the alkali neutralization, acidifying, recrystallization obtains the rhodium chloride crystal.The rhodium rate of recovery can reach 97%, and rhodium content 39%～40% in the rhodium chloride.
Reclaim the rhodium rhodium in the inventive method and be adopted as liquid phase method, it is simple, gentle to reclaim technology, rhodium chloride yield height.
The present invention is a kind of method that reclaims rhodium chloride from spent rhodium catalyst.Be characterised in that:
Adopt mineral acid, comprising two or more the mixture in sulfuric acid, nitric acid, perchloric acid, the hydrochloric acid; Same oxygenant is comprising hydrogen peroxide, sodium perchlorate or its mixing solutions; Spent catalyst is cleared up, clear up the solution that obtains with the alkali neutralization again, prepare the aqua oxidation rhodium, obtain rhodium chloride solution with dissolving with hydrochloric acid aqua oxidation rhodium, remove copper, iron, nickel metallic impurity ion through ion exchange resin, and, obtain high purity hydrous rhodium chloride through recrystallizing and refining, the rhodium rate of recovery is greater than 97%, and rhodium chloride purity is greater than 99.95%.
The mineral acid mixing solutions refers to adopt two or more the mixture in sulfuric acid, nitric acid, perchloric acid, the hydrochloric acid, the mixture of the mixture of preferably sulfuric acid and nitric acid or sulfuric acid and hydrochloric acid; With the solution of hydrogen peroxide or sodium perchlorate preparation, at this moment, the ratio of sulfuric acid, nitric acid mixed solution is 0.5: 1～5: 1, and the ratio of nitric acid and perchloric acid is 10: 1～1: 1, and the ratio of hydrochloric acid and oxygenant is 0.1: 1～20: 1.
The volume ratio of mixed solution and useless rhodium liquid is 1: 1～20: 1, preferred 3: 1～10: 1.
Mixed solution can be the solution of simple acid; The solution of at least a acid with strong oxidizing property also can be the mixture solution of acid and oxygenant.
Neutralization is used with alkali and is comprised the wherein mixture of one or more arbitrary proportions of sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, Sodium Nitrite, ammoniacal liquor.
Ion exchange resin adopts Zeo-karb.
The concrete spent rhodium catalyst treating processes of the present invention is divided following several steps:
(a) spent catalyst removes the polycondensate of high boiling point by-products produced and aldehyde in the raw material at 30 ℃, 100 ℃, 150 ℃, 200 ℃, 230 ℃ through underpressure distillation respectively, and rhodium is concentrated, and concentrates rhodium content 0.24%～1% in the residue of back.
(b) in concentrating the back spent rhodium catalyst, add oxidizing acid, make organic matter carbonizing after, add a kind of strong acid dissolving carbide again.In this process, the oxidized generation carbonic acid gas of organism is removed from system, and rhodium is present in the acid solution with the complex anion form, other metal such as copper, and iron, nickel etc. also exist in solution with ionic species.
(c) with rhodium solution with solid or aqueous solution adjusting PH with base value to 1～6, be preferably 4, thickening filtration is removed most of salt; Transfer mother liquor pH to be worth throw out aqua oxidation rhodium again.
(d) with the dissolving with hydrochloric acid rhodium oxide precipitation of 2N～6N, comprise iron, nickel, calcium, copper etc., obtain rhodium chloride solution.
(e) dilution rhodium chloride solution to rhodium content 200～450ppm, with the speed of 4～6m/h, through ion exchange column, removes hetero-ions such as de-iron, nickel, calcium, copper.
(f) will exchange post chlorization rhodium solution evaporation concentrate the rhodium chloride crystal.
The present invention further specifies its preparation and using method by following embodiment, but does not constitute limiting the scope of the invention.
Embodiment 1
With the spent rhodium catalyst solution 76g (rhodium massfraction 0.18%) that produces in the propylene low pressure oxo process,-0.085～-0.1MP is distilled to 230 ℃ of recovered temperatures, residue 19.6g, add sulfuric acid 150ml, heated solution to 200 ℃ adds concentrated nitric acid and clarifies until solution becomes.Mixing solutions (volume ratio 1: 1) to the reaction that adds hydrochloric acid and hydrogen peroxide in clear liquor again finishes, regulate about 4 desalinations of pH value with 10% aqueous sodium hydroxide solution, regulate pH value 7～8 with sodium hydroxide again, solid-liquid separation gets aqua oxidation rhodium precipitation, to precipitate the dissolving with hydrochloric acid with 2N, thin up is to rhodium-containing 200～450ppm, through ion exchange resin removal of impurities, evaporation, recrystallization, obtain rhodium trichloride hydrate, rhodium yield 97.21%.
The rhodium rate of recovery is calculated in the following ways:
The rhodium rate of recovery=(rhodium chloride quality * rhodium content)/(useless rhodium liquid quality * rhodium concentration) * 100%, rhodium content is analyzed with ICP in the solution.
Embodiment 2 to embodiment 4
Change the alkali precipitation agent, other condition such as embodiment 1 the results are shown in following table.
| Embodiment | Precipitation agent | The rhodium rate of recovery |
| Embodiment 2 | ?NH 3·H 2O | ?97.12％ |
| Embodiment 3 | ?NaHCO 3 | ?96.01％ |
| Embodiment 4 | ?NaNO 2+NH 4Cl | ?97.07％ |
Embodiment 5
With spent rhodium catalyst solution 203g, the method for pressing embodiment 1 concentrates, and gets residue 49.2g, adds sulfuric acid 200ml, is heated to 280 ℃, adds concentrated nitric acid 400ml, vitriol oil 100ml more successively, gets settled solution.Be cooled to normal temperature, add hydrochloric acid 20ml respectively, hydrogen peroxide 20ml, with about 20% aqueous sodium hydroxide solution adjust pH to 4, the recrystallization desalination is used sodium hydroxide adjust pH 6～7 again, and solid-liquid separation gets aqua oxidation rhodium precipitation.All the other are with embodiment 1.Rhodium yield 97.46%.
Embodiment 6
With spent rhodium catalyst solution 21.3g, the method of pressing embodiment 1 concentrates, and gets residue 5.4g, adds nitric acid-perchloric acid nitration mixture (volume ratio 4: 1) 10ml, be heated to the solution clarification, cooling is regulated pH approximately to 4 desalinations with 20% sodium hydroxide solution, uses sodium hydroxide adjust pH to 6～7 again, solid-liquid separation gets aqua oxidation rhodium precipitation.All the other are with embodiment 1.Rhodium yield 96.90%.
Claims (2)
1. method that reclaims rhodium chloride from spent rhodium catalyst is characterized in that:
Adopt mineral acid, comprising two or more the mixture in sulfuric acid, nitric acid, perchloric acid, the hydrochloric acid; Same oxygenant is comprising hydrogen peroxide, sodium perchlorate or its mixing solutions; Spent catalyst is cleared up, clear up the solution that obtains with the alkali neutralization again, prepare the aqua oxidation rhodium, obtain rhodium chloride solution with dissolving with hydrochloric acid aqua oxidation rhodium, remove copper, iron, nickel metallic impurity ion through ion exchange resin, and, obtain high purity hydrous rhodium chloride through recrystallizing and refining, the rhodium rate of recovery is greater than 97%, and rhodium chloride purity is greater than 99.95%;
The volume ratio of mixed solution and useless rhodium liquid is 1: 1～20: 1,
Mixed solution can be the solution of simple acid; Or the solution of at least a acid with strong oxidizing property, also can be the mixture solution of acid and oxygenant;
Neutralization is used with alkali and is comprised the wherein mixture of one or more arbitrary proportions of sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, Sodium Nitrite, ammoniacal liquor;
Ion exchange resin adopts Zeo-karb;
The concrete spent rhodium catalyst treating processes of the present invention is divided following several steps:
(a) spent catalyst removes the polycondensate of high boiling point by-products produced and aldehyde in the raw material at 30 ℃, 100 ℃, 150 ℃, 200 ℃, 230 ℃ through underpressure distillation respectively, and rhodium is concentrated, and concentrates rhodium content 0.24%～1% in the residue of back;
(b) in concentrating the back spent rhodium catalyst, add oxidizing acid, make organic matter carbonizing after, add a kind of strong acid dissolving carbide again; In this process, the oxidized generation carbonic acid gas of organism is removed from system, and rhodium is present in the acid solution with the complex anion form, other metal such as copper, and iron, nickel etc. also exist in solution with ionic species;
(c) with rhodium solution with solid or aqueous solution adjusting PH with base value to 1～6, be preferably 4, thickening filtration is removed most of salt; Transfer mother liquor pH to be worth throw out aqua oxidation rhodium again;
(d) with the dissolving with hydrochloric acid rhodium oxide precipitation of 2N～6N, comprise iron, nickel, calcium, copper etc., obtain rhodium chloride solution;
(e) dilution rhodium chloride solution to rhodium content 200～450ppm, with the speed of 4～6m/h, through ion exchange column, removes hetero-ions such as de-iron, nickel, calcium, copper;
(f) will exchange post chlorization rhodium solution evaporation concentrate the rhodium chloride crystal;
2. it is characterized in that in accordance with the method for claim 1: the mineral acid mixing solutions refers to the mixture of sulfuric acid and nitric acid or the mixture of sulfuric acid and hydrochloric acid; With the solution of hydrogen peroxide or sodium perchlorate preparation, at this moment, the ratio of sulfuric acid, nitric acid mixed solution is 0.5: 1～5: 1, and the ratio of nitric acid and perchloric acid is 10: 1～1: 1, and the ratio of hydrochloric acid and oxygenant is 0.1: 1～20: 1; The volume ratio of mixed solution and useless rhodium liquid 3: 1～10: 1.
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