CN108642300B - Method for recovering palladium from palladium-containing waste catalyst - Google Patents
Method for recovering palladium from palladium-containing waste catalyst Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 254
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- -1 palladium ions Chemical class 0.000 claims abstract description 6
- 229910003445 palladium oxide Inorganic materials 0.000 claims abstract description 6
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- 238000002386 leaching Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 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 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for recovering palladium from a palladium-containing waste catalyst, which comprises the following steps: 1) pretreatment of waste materials: eluting the palladium-containing waste catalyst by using the composite liquid, and filtering to obtain palladium-containing filter residues; 2) reduction of palladium oxide to palladium: reducing palladium oxide in the waste residue into elemental palladium by using a reducing agent to react with the palladium-containing filter residue; 3) dissolving in acid to obtain palladium ions: reacting inorganic acid with the obtained simple substance palladium to obtain an acid solution system existing in a palladium ion state; 4) replacement to obtain palladium: replacing palladium ions in the acid solution system by adopting a metal replacement method to obtain sponge palladium; 5) refining palladium: and further reducing the obtained metal palladium by using hydrogen to obtain the high-purity metal palladium. The method adopts the organic composite liquid to elute the palladium-containing waste catalyst, avoids the problems of high energy consumption and environmental pollution in the prior art, has short process flow, and can effectively solve the problems of high energy consumption, low recovery rate and the like in the current palladium recovery technology.
Description
Technical Field
The invention relates to a method for recovering palladium from a palladium-containing waste catalyst, belongs to the field of precious metal secondary resource recovery and utilization, and particularly relates to a method for recovering metal palladium, which is mild in reaction condition, high in recovery rate and low in cost.
Background
Palladium is used as a rare noble metal and plays a role as a catalyst in industrial production, such as a plastic electroplating production process, and palladium is used as a catalyst in the synthesis of floxadine, toluene diisocyanate, terephthalic acid hydrofining and the like. Because palladium is a noble metal, the resource is rare, and the price is high, the method has very important significance on how to recover the palladium in the deactivated catalyst.
Currently, methods for recovering palladium from palladium-containing waste catalysts mainly include incineration methods and wet adsorption tower recovery methods, and most of the methods have long process, complicated steps, high requirements for recovered containers, low palladium recovery rate and low quality. For example, the recovery methods disclosed in 201710124234.0, 201710124234.0, 201610617022.1, 201710742025.2, 201710944100.3 generally include the following steps: firstly, the palladium-containing waste is roasted at high temperature, impurities (mainly organic matters attached to the surface of a carrier) in the waste are removed, and the palladium is prepared through the steps of reduction, acid leaching, enrichment, refining and the like. The traditional process not only has high energy consumption and complex process flow, but also has low recovery rate, thereby causing serious waste of the scarce resource of palladium, bringing huge loss to the country and having serious environmental pollution. Therefore, improvements to the currently existing processes are particularly desirable.
Disclosure of Invention
The invention aims to provide a method for recovering palladium from a palladium-containing waste catalyst, which can avoid the pollution of an incineration process means to the environment in the prior art, and has the advantages of short process flow, low production cost, simple operation and high palladium recovery rate.
In order to realize the purpose of the invention, the following technical scheme is specifically provided:
a method for recovering palladium from a palladium-containing spent catalyst, the method comprising the steps of:
1) pretreatment of waste materials: eluting the palladium-containing waste catalyst by using the composite liquid, and filtering to obtain palladium-containing filter residues;
2) reduction of palladium oxide to palladium: using a reducing agent to react with the palladium-containing filter residue obtained in the step 1) to reduce palladium oxide in the waste residue into elemental palladium;
3) dissolving in acid to obtain palladium ions: reacting inorganic acid with the elemental palladium obtained in the step 2) to obtain an acid solution system existing in a palladium ion state;
4) replacement to obtain palladium: replacing palladium ions in the acid solution system obtained in the step 3) by adopting a metal replacement method to obtain sponge palladium;
5) refining palladium: further reducing the metal palladium obtained in the step 4) by using hydrogen to obtain high-purity metal palladium.
Preferably, the composite liquid in the step 1) comprises one or more of carbon tetrachloride, ethanol, methanol, petroleum ether, glacial acetic acid, carbon disulfide, chloroform and ether in any combination, the liquid-solid volume mass ratio of the composite liquid to the palladium-containing waste catalyst is 0.3-5: 1, the washing times are 1-5 times, and the time of each time is 5-120 min.
Preferably, the step 1) further comprises grinding the palladium-containing filter residue into powder with the particle size of 20-200 meshes.
Preferably, the reducing agent in the step 2) is one or more of hydrazine hydrate, formic acid, sodium formate, sodium borohydride, potassium borohydride and formaldehyde, the liquid-solid volume ratio of the reducing agent to the palladium-containing waste catalyst is 0.3-5: 1, the reduction time is 10-60 min, and the reduction temperature is 20-100 ℃.
Preferably, the inorganic acid in step 3) is one of or any combination of a mixed solution of hydrochloric acid and hydrogen peroxide, a mixed solution of hydrochloric acid and sodium chlorate, a mixed solution of hydrochloric acid and sodium nitrate, concentrated nitric acid and aqua regia.
Preferably, step 4) further comprises adding quicklime into the acid solution system before adding the metal.
Preferably, the metal in step 4) includes one or more of zinc, aluminum, iron, copper, magnesium and tin.
Preferably, the hydrogen produced in step 4) is used to refine the palladium in step 5).
The invention has the beneficial effects that: the method adopts the organic composite liquid to elute the palladium-containing waste catalyst, thereby avoiding the problems of high energy consumption and environmental pollution in the prior art; the refining part directly adopts a hydrogen reduction mode, because in an acid solution system, the added replacement metal can release part of hydrogen, the palladium is refined by utilizing the characteristic that the palladium can absorb a large amount of hydrogen, and the palladium can be obtained, thereby avoiding the complex processes of aqua regia dissolution, ammonia complexing, acidification palladium precipitation and the like adopted in the traditional method. The method has the advantages of mild reaction conditions, short process flow, simple operation and high palladium recovery rate, and can effectively solve the problems of high energy consumption, low recovery rate and the like in the current palladium recovery technology.
Drawings
FIG. 1 is a schematic diagram of a process for recovering palladium according to the present invention.
Detailed Description
The present invention will be described in more detail with reference to specific embodiments, and the technical solution of the present invention is verified by referring to the flowchart shown in fig. 1.
Example 1
Adding 100g of waste catalyst containing palladium into a 1000mL flask, adding 300mL of composite liquid, wherein the composite liquid comprises carbon tetrachloride, ethanol, methanol, petroleum ether, glacial acetic acid, carbon disulfide, chloroform and diethyl ether, the adding proportion of each component in the composite liquid is the same, and washing for 3 times, each time for 30 minutes; after filtering, grinding and crushing the palladium-containing waste catalyst into powder with the particle size of 20-200 meshes, adding 100mL of hydrazine hydrate, reducing for 30min at the temperature of 80 ℃, filtering, carrying out acid leaching on filter residues for 30min by using 100mL of aqua regia, then sequentially adding 30g of quicklime and 4g of zinc powder, introducing hydrogen for 10min to obtain sponge palladium, finally boiling the sponge palladium, and filtering to obtain refined palladium, wherein the recovery rate of the palladium reaches 99.4%.
Example 2
Adding 100g of waste catalyst containing palladium into a 1000mL flask, adding 300mL of composite liquid for washing for 3 times, wherein each time is 25 minutes, the composite liquid comprises carbon tetrachloride, ethanol, methanol, glacial acetic acid, carbon disulfide, chloroform and ether, and the adding proportion of each component in the composite liquid is the same; after filtering, grinding and crushing the palladium-containing waste catalyst, adding 100mL of sodium borohydride-methanol solution (the mass fraction is 40%) to reduce for 30min at 80 ℃, filtering, carrying out acid leaching on filter residues for 30min by using 100mL of aqua regia, then sequentially adding 30g of quicklime and 5g of tin powder, introducing hydrogen for 10min to obtain sponge palladium, finally boiling the sponge palladium, and filtering to obtain refined palladium, wherein the recovery rate of the palladium reaches 99.2%.
Example 3
Adding 100g of palladium-containing waste catalyst into a 1000mL flask, adding 300mL of composite liquid, wherein the composite liquid comprises carbon tetrachloride, ethanol, methanol, carbon disulfide, chloroform and ether, the adding proportion of each component in the composite liquid is the same, and washing for 3 times, each time for 50 minutes; after filtering, grinding and crushing the palladium-containing waste catalyst, adding 100mL of formic acid, reducing for 30min at 80 ℃, filtering, carrying out acid leaching on filter residues for 30min by using 100mL of aqua regia, then sequentially adding 25g of quicklime and 6g of magnesium powder, introducing hydrogen for 20min to obtain sponge palladium, finally boiling the sponge palladium, and filtering to obtain refined palladium, wherein the recovery rate of the palladium reaches 99.3%.
Example 4
Adding 100g of palladium-containing waste catalyst into a 1000mL flask, adding 400mL of composite liquid, and washing for 2 times, 60 minutes each time; the components of the composite liquid are the same as those used in the embodiment 1, after filtration, the palladium-containing waste catalyst is ground and crushed, 100mL of formalin solution is added to be reduced for 30min at the temperature of 80 ℃, filtration is carried out, acid leaching is carried out on filter residue for 30min by 100mL of aqua regia, then 30g of quicklime and 6g of copper powder are sequentially added, sponge palladium is obtained after hydrogen is introduced for 20min, finally, the sponge palladium is boiled and filtered, and the recovery rate of the palladium reaches 99.6%.
Example 5
Adding 100g of palladium-containing waste catalyst into a 1000mL flask, adding 300mL of composite liquid, and washing for 3 times, wherein each time lasts for 50 minutes; the components of the composite liquid are the same as those used in the embodiment 2, after filtration, the palladium-containing waste catalyst is ground and crushed, 100mL of sodium formate (20%) is added to reduce the catalyst for 30min at the temperature of 80 ℃, the filter residue is filtered, 100mL of aqua regia is used for acid leaching the filter residue for 30min, then 30g of quicklime and 4g of iron powder are sequentially added, hydrogen is introduced for 10min to obtain sponge palladium, and finally the sponge palladium is boiled and filtered to obtain refined palladium, wherein the recovery rate of the palladium reaches 99.1%.
Example 6
Adding 100g of palladium-containing waste catalyst into a 1000mL flask, adding 300mL of composite liquid, and washing for 3 times, each time for 40 minutes; the components of the composite liquid are the same as those used in the embodiment 3, after filtration, the palladium-containing waste catalyst is ground and crushed, 100mL of hydrazine hydrate is added to reduce the catalyst for 30min at the temperature of 80 ℃, the filter residue is filtered, 100mL of aqua regia is used for acid leaching of the filter residue for 30min, then 30g of quicklime and 4g of aluminum powder are sequentially added, hydrogen is introduced for 10min to obtain sponge palladium, and finally the sponge palladium is boiled and filtered to obtain refined palladium, wherein the recovery rate of the palladium reaches 99.4%.
Further purity tests are carried out on the above examples, and the purity of the recovered palladium reaches over 99 percent. In conclusion, the method adopts the organic composite liquid to elute the palladium-containing waste catalyst, avoids the problems of high energy consumption and environmental pollution in the prior art, has short process flow, simple operation and high palladium recovery rate, and can effectively solve the problems of high energy consumption, low recovery rate and the like in the current palladium recovery technology.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (5)
1. A method for recovering palladium from a palladium-containing spent catalyst, characterized in that the method comprises the following steps:
1) pretreatment of waste materials: eluting the palladium-containing waste catalyst by using the composite liquid, and filtering to obtain palladium-containing filter residues;
2) reduction of palladium oxide to palladium: using a reducing agent to react with the palladium-containing filter residue obtained in the step 1) to reduce palladium oxide in the waste residue into elemental palladium;
3) dissolving in acid to obtain palladium ions: reacting inorganic acid with the elemental palladium obtained in the step 2) to obtain an acid solution system existing in a palladium ion state;
4) replacement to obtain palladium: replacing palladium ions in the acid solution system obtained in the step 3) by adopting a metal replacement method to obtain sponge palladium;
5) refining palladium: further reducing the metal palladium obtained in the step 4) by using hydrogen to obtain high-purity metal palladium;
the composite liquid in the step 1) is any combination of carbon tetrachloride, ethanol, methanol, petroleum ether, glacial acetic acid, carbon disulfide, chloroform and diethyl ether, the liquid-solid volume mass ratio of the composite liquid to the palladium-containing waste catalyst is 0.3-5: 1, the washing times are 1-5 times, and the time of each time is 5-120 min;
step 4) adding quicklime into an acid solution system before adding metal;
the hydrogen generated in the step 4) is used for refining the palladium in the step 5).
2. The method for recovering palladium from the palladium-containing dead catalyst according to claim 1, wherein the palladium-containing filter residue obtained in the step 1) is ground into powder with a particle size of 20-200 meshes.
3. The method for recovering palladium from the palladium-containing waste catalyst according to claim 1, wherein the reducing agent in the step 2) is one or more of hydrazine hydrate, formic acid, sodium formate, sodium borohydride, potassium borohydride and formaldehyde, the liquid-solid mass ratio of the reducing agent to the palladium-containing waste catalyst is 0.3-5: 1, the reduction time is 10-60 min, and the reduction temperature is 20-100 ℃.
4. The method for recovering palladium from the palladium-containing waste catalyst according to claim 1, wherein the inorganic acid in step 3) is one of or any combination of a mixed solution of hydrochloric acid and hydrogen peroxide, a mixed solution of hydrochloric acid and sodium chlorate, a mixed solution of hydrochloric acid and sodium nitrate, concentrated nitric acid and aqua regia.
5. The method for recovering palladium from the palladium-containing dead catalyst as claimed in claim 1, wherein the metal in step 4) is one or more of zinc, aluminum, iron, copper, magnesium and tin.
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| CN110394148A (en) * | 2019-07-05 | 2019-11-01 | 重庆科技学院 | It is a kind of with the composite material and preparation method thereof of methyl acrylate modified silica-gel and product and application |
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| CN1024687C (en) * | 1991-06-24 | 1994-05-25 | 中国有色金属工业总公司昆明贵金属研究所 | Gold and palladium recovery from waste catalyst and liquid carrying valve |
| RU2140999C1 (en) * | 1998-07-13 | 1999-11-10 | Годжиев Сергей Ермолаевич | Method of processing of spent catalytic agents containing metals of platinum group |
| CN100567528C (en) * | 2006-11-17 | 2009-12-09 | 南化集团研究院 | A kind of method that from waste palladium carbon catalyst, reclaims precious metal palladium |
| CN100537800C (en) * | 2007-06-22 | 2009-09-09 | 厦门金达威维生素股份有限公司 | From the waste loading palladium hydrogenation catalyst, reclaim the method for palladium metal and Palladous chloride |
| CN104263945A (en) * | 2014-10-08 | 2015-01-07 | 昆明贵金属研究所 | Method for recovering platinum metal from waste catalyst |
| CN106222437B (en) * | 2016-08-29 | 2018-04-10 | 金川集团股份有限公司 | A kind of method that palladium is refined from alkaline strip liquor |
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