CN116716483A - Method for efficiently recycling metal palladium in palladium-containing spent catalyst - Google Patents
Method for efficiently recycling metal palladium in palladium-containing spent catalyst Download PDFInfo
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- CN116716483A CN116716483A CN202310568645.4A CN202310568645A CN116716483A CN 116716483 A CN116716483 A CN 116716483A CN 202310568645 A CN202310568645 A CN 202310568645A CN 116716483 A CN116716483 A CN 116716483A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 319
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 153
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004064 recycling Methods 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 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 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 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 2
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 32
- 239000000047 product Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000013043 chemical agent Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for efficiently recycling metal palladium in a palladium-containing spent catalyst, which comprises the following steps: soaking the palladium-containing dead catalyst in a soaking solution, and filtering to obtain a first palladium-containing leaching solution, wherein the soaking solution comprises sulfuric acid and an oxidant; then enriching and filtering the first palladium-containing leaching solution to obtain a second palladium-containing leaching solution; and adding a reducing agent into the second palladium-containing leaching solution for reaction, filtering, washing and drying to obtain a palladium product. The method utilizes chemical agents to leach, enrich and purify valuable palladium metal resources in the palladium-containing spent catalyst, and finally can produce palladium products and aluminum-containing byproducts with market value. The method can not only recycle the palladium-containing waste catalyst to obtain a high-purity palladium product so as to improve the recycling rate of the palladium-containing waste catalyst, but also produce no waste, namely no secondary pollution, and can realize the full recycling of palladium and aluminum, thereby finally achieving the effects of environmental protection, greenness, energy conservation, emission reduction and clean production.
Description
Technical Field
The invention relates to the technical field of recycling of palladium resources in a palladium-containing waste catalyst, and in particular relates to a method for efficiently recycling metal palladium in the palladium-containing waste catalyst.
Background
Platinum group metal Palladium (Pd) exhibits excellent catalytic activity due to its unique physicochemical properties, and is widely used as a catalyst in various fields such as petrochemistry, medicine, and new energy. In recent years, china has been the largest worldwide platinum group metal consuming country. Palladium is still very strongly required as the platinum group metal currently being consumed in the largest amount, especially in chemical catalyst applications. However, domestic palladium metal resources are seriously deficient, and a large amount of palladium metal still needs to be imported.
The deactivation of palladium catalysts is mainly caused by the large change of specific surface area, the coverage of impurities and poisoning caused by the growth of palladium grains. The palladium has good corrosion resistance, high temperature performance and stable electrical characteristics, so that the loss of palladium in the reaction process is not great, and the difference of the palladium content of the waste palladium catalyst compared with that of the fresh catalyst is not great. The metal palladium content (about 1000-9000 g/t) in the waste palladium catalyst is far more than the content (about 2-10 g/t) in palladium ore, and a large amount of waste palladium catalyst is treated in China every year, so that the palladium in the waste palladium catalyst can be completely recovered. In addition, if the waste palladium catalyst is not treated in time, the waste palladium catalyst causes serious pollution to the surrounding environment and threatens the health of people, so that the recovery of the metal palladium from the waste palladium catalyst has important significance and great economic benefit.
At present, the technology for recycling the metal palladium in the waste palladium catalyst comprises a fire method, a wet method, a fire-wet combined technology and the like. The pyrogenic process has large investment, high equipment requirement and long recovery period. The fire-wet combined process flow is complex, and large-scale industrialization is difficult to realize. The wet process has the characteristics of simple technology, less investment and short flow, and gradually becomes the most widely applied method. The traditional wet process mode uses aqua regia (nitric acid + hydrochloric acid) for recovery. However, aqua regia itself has high corrosiveness, chemical waste liquid generated in the recovery process not only can harm the environment, but also the generated waste gas and nitrogen oxides in the waste liquid can increase the treatment cost of environmental protection facilities of enterprises. Therefore, the technology for recovering the metal palladium in the waste catalyst containing palladium with high efficiency is researched, and the technology for recovering the metal palladium has important significance in achieving the environment-friendly and green effects.
Disclosure of Invention
The invention aims to provide a method for efficiently recycling metal palladium in a palladium-containing waste catalyst, which takes a mixture of sulfuric acid and an oxidant as a soaking solution to soak the palladium-containing waste catalyst, and then realizes the efficient recycling of palladium resources in the palladium-containing waste catalyst through enrichment and purification, and simultaneously achieves the aims of environmental protection, green, energy conservation, emission reduction and clean production.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a method for efficiently recycling metal palladium in a palladium-containing waste catalyst, which comprises the following steps:
s1, soaking a palladium-containing dead catalyst in a soaking solution, and filtering to obtain a first palladium-containing leaching solution, wherein the soaking solution comprises sulfuric acid and an oxidant;
s2, enriching and filtering the first palladium-containing leaching solution to obtain a second palladium-containing leaching solution;
s3, adding a reducing agent into the second palladium-containing leaching solution for reaction, filtering, washing and drying to obtain a palladium product.
The method for efficiently recycling the metal palladium in the palladium-containing waste catalyst has the beneficial effects that:
the invention adopts a green (wet) metallurgical method to recycle and treat the dead palladium-containing waste catalyst in the production of chemical plants, and finally can produce palladium products and aluminum-containing byproducts with market value by leaching, enriching and purifying valuable palladium metal resources in the palladium-containing waste catalyst by using chemical agents. The method can not only recycle the palladium-containing waste catalyst to obtain a high-purity palladium product so as to improve the recycling rate of the palladium-containing waste catalyst, but also produce no waste, namely no secondary pollution, and can realize the full recycling of palladium and aluminum, thereby finally achieving the effects of environmental protection, greenness, energy conservation, emission reduction and clean production.
The method of the invention can also avoid harm to human and environment caused by the random discarding of the palladium dead catalyst into solid waste, reduce the total amount of industrial solid waste, and simultaneously achieve the purpose of recycling the palladium dead catalyst, and avoid the bad consequence that valuable palladium metal resources contained in the palladium dead catalyst cannot be continuously recycled, thereby realizing industrial sustainable development.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the invention for efficiently recycling metallic palladium in a palladium-containing spent catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The method for efficiently recycling metallic palladium in the palladium-containing spent catalyst according to the embodiment of the invention is specifically described below.
Referring to fig. 1, the method for efficiently recycling metallic palladium in a palladium-containing spent catalyst provided by the embodiment of the invention comprises the following steps:
s1, soaking the palladium-containing dead catalyst in a soaking solution, and filtering to obtain a first palladium-containing leaching solution and an aluminum-containing byproduct, wherein the soaking solution comprises sulfuric acid and an oxidant. The aluminum-containing byproduct obtained by the invention can be recycled as raw materials of building materials, aluminum production and the like, thereby improving the utilization rate of resources.
Further, in the preferred embodiment of the present invention, the step of immersing the palladium-containing spent catalyst in the immersion liquid comprises the steps of: the palladium-containing spent catalyst is added to the sulfuric acid before the oxidant.
Further, in a preferred embodiment of the present invention, the sulfuric acid has a molar concentration of 0.025 to 9mol/L.
Further, in the preferred embodiment of the present invention, the ratio of the sulfuric acid to the palladium-containing spent catalyst is 0.5 to 200:1 (mL/g).
Further, in a preferred embodiment of the present invention, the oxidizing agent is selected from one of sodium hypochlorite, sodium chlorate, hydrogen peroxide, chlorine gas, ozone, oxygen, peracetic acid, sodium percarbonate. Preferably, the volume ratio of sulfuric acid (or palladium-containing catalyst) to the oxidizing agent is 1 to 50.
Further, in the preferred embodiment of the present invention, the soaking time is 0.1-12 hours, and the soaking temperature is 50-100 ℃.
S2, enriching and filtering the first palladium-containing leaching solution to obtain a second palladium-containing leaching solution.
Further, in a preferred embodiment of the present invention, the enrichment includes a primary enrichment and a secondary enrichment, the primary enrichment is to heat-concentrate the first palladium-containing leaching solution, and the heat-concentrate temperature is 50-105 ℃.
Further, in the preferred embodiment of the present invention, the secondary enrichment adopts an ammonium chloropalladate precipitation method to enrich the palladium-containing leaching solution after the primary enrichment, and the enrichment steps are as follows:
(1) Adding a certain amount of ammonium chloride into the second palladium-containing leaching solution, and then adding a proper amount of oxidant; filtering, washing a filter cake by using saturated ammonium chloride, adding a certain amount of pure water into the filter cake, heating and boiling for 1-10 h, cooling, and repeating the step (1) for at least 3 times to obtain a cooled solution.
(2) Adding ammonia water into the cooled solution until the pH value is 8-12, filtering, adding hydrochloric acid into the filtrate until the pH value is 0.1-4, filtering, washing, adding ammonia water to dissolve filter cakes, adjusting the pH value to 8-12, repeating the step (2) for at least 3 times, adding a reducing agent into the solution, filtering, washing, and drying to obtain the sponge palladium.
Further, in the preferred embodiment of the invention, the secondary enrichment adopts a dichloro-diamino-palladium-method combination method to enrich the palladium-containing leaching solution after the primary enrichment.
S3, adding a reducing agent into the second palladium-containing leaching solution for reaction, filtering, washing and drying to obtain a palladium product. The sponge palladium product obtained by the palladium metal recovery method can be used for secondary manufacturing of palladium catalysts, so that the recovery utilization rate of the metal palladium is improved. In addition, the palladium product can also be used in other fields, such as three-way catalysts for vehicles.
Further, in a preferred embodiment of the present invention, the reducing agent is selected from one of hydrazine hydrate, zinc powder, zinc flake, iron powder, iron flake, aluminum powder, aluminum flake, copper powder, copper flake, formic acid, formaldehyde, titanium trichloride, and hypophosphorous acid.
The invention adopts a green (wet) metallurgical method to recycle and treat the dead palladium-containing waste catalyst in the production of chemical plants, and finally can produce palladium products and aluminum-containing byproducts with market value by leaching, enriching and purifying valuable palladium metal resources in the palladium-containing waste catalyst by using chemical agents. The method can recycle the palladium-containing waste catalyst to obtain a high-purity palladium product, so that the recycling rate of the palladium-containing waste catalyst is improved, no waste is generated during production, namely no secondary pollution is generated, the palladium and the aluminum can be fully recycled, and the effects of environmental protection, greenness, energy conservation, emission reduction and clean production are finally achieved.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The method for efficiently recycling the metal palladium in the palladium-containing waste catalyst provided by the embodiment comprises the following steps:
(1) 35mL of 3mol/L sulfuric acid was added to 5g of a palladium-containing spent catalyst, wherein the liquid-to-solid ratio of sulfuric acid to the palladium-containing spent catalyst was 7:1. Then adding 5mL of sodium hypochlorite solution with mass fraction of 8%, heating in water bath at 90 ℃ for 30min, cooling, and filtering to obtain a first palladium-containing leaching solution and an aluminum-containing byproduct.
(2) And (3) heating and concentrating (primary enrichment) the first palladium-containing leaching solution, and then carrying out secondary enrichment and filtration on the palladium-containing leaching solution after primary enrichment by adopting an ammonium chloropalladate precipitation method to obtain a second palladium-containing leaching solution.
(3) And adding a proper amount of reducing agent formic acid (calculated by adding 3mL of formic acid into 1g of palladium) into the second palladium-containing leaching solution, and continuously stirring at room temperature until no palladium is separated out.
(4) Filtering the reduced leaching solution, washing with pure water, and drying to obtain the target palladium product.
Example 2
The method for efficiently recycling the metal palladium in the palladium-containing waste catalyst provided by the embodiment comprises the following steps:
(1) 40mL of 6mol/L sulfuric acid was added to 5g of the palladium-containing spent catalyst, wherein the liquid-to-solid ratio of sulfuric acid to the palladium-containing spent catalyst was 8:1. Then adding 4mL of sodium hypochlorite solution with mass fraction of 8%, heating in water bath at 90 ℃ for 30min, cooling, and filtering to obtain a first palladium-containing leaching solution and an aluminum-containing byproduct.
(2) And (3) heating and concentrating (primary enrichment) the first palladium-containing leaching solution, and then carrying out secondary enrichment and filtration on the palladium-containing leaching solution after primary enrichment by adopting a dichloro-diammine palladium-subunit method combination method to obtain a second palladium-containing leaching solution.
(3) And adding a proper amount of reducing agent formic acid (calculated by adding 3mL of formic acid into 1g of palladium) into the second palladium-containing leaching solution, and continuously stirring at room temperature until no palladium is separated out.
(4) Filtering the reduced leaching solution, washing with pure water, and drying to obtain the target palladium product.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The method for efficiently recycling the metal palladium in the palladium-containing spent catalyst is characterized by comprising the following steps of:
s1, soaking a palladium-containing dead catalyst in a soaking solution, and filtering to obtain a first palladium-containing leaching solution, wherein the soaking solution comprises sulfuric acid and an oxidant;
s2, enriching and filtering the first palladium-containing leaching solution to obtain a second palladium-containing leaching solution;
s3, adding a reducing agent into the second palladium-containing leaching solution for reaction, filtering, washing and drying to obtain a palladium product.
2. The method for efficiently recycling metallic palladium in a spent palladium-containing catalyst according to claim 1, wherein in the step S1, the step of immersing the spent palladium-containing catalyst in an immersion liquid is: the palladium-containing spent catalyst is added to the sulfuric acid before the oxidant.
3. The method for efficiently recycling metallic palladium in a spent palladium-containing catalyst according to claim 2, wherein in the step S1, the molar concentration of sulfuric acid is 0.025 to 9mol/L.
4. The method for efficiently recycling metallic palladium in a palladium-containing spent catalyst according to claim 3, wherein the ratio of the sulfuric acid to the palladium-containing spent catalyst is 0.5 to 200:1 (mL/g).
5. The method for efficiently recycling metallic palladium in a palladium-containing spent catalyst according to claim 1, wherein the oxidizing agent is one selected from the group consisting of sodium hypochlorite, sodium chlorate, hydrogen peroxide, chlorine, ozone, oxygen, peracetic acid, sodium percarbonate.
6. The method for efficiently recycling metallic palladium in a spent palladium-containing catalyst according to claim 1, wherein in the step S1, the soaking time is 0.1 to 12 hours and the soaking temperature is 50 to 100 ℃.
7. The method for efficiently recycling metallic palladium in a palladium-containing spent catalyst according to claim 1, wherein in the step S2, the enrichment includes a primary enrichment and a secondary enrichment, the primary enrichment is to heat-concentrate the first palladium-containing leaching solution, and the heat-concentrate temperature is 50-105 ℃.
8. The method for efficiently recycling metallic palladium in a spent palladium-containing catalyst according to claim 7, wherein in the step S2, the secondary enrichment is performed on the palladium-containing leaching solution after the primary enrichment by an ammonium chloropalladate precipitation method.
9. The method for efficiently recycling metallic palladium in a palladium-containing spent catalyst according to claim 7, wherein in the step S2, the secondary enrichment is performed on the palladium-containing leachate after the primary enrichment by adopting a dichloro-diamino palladium-sulfite combined method.
10. The method for efficiently recycling metallic palladium in a palladium-containing spent catalyst according to claim 1, wherein in the step S3, the reducing agent is one selected from hydrazine hydrate, zinc powder, zinc flakes, iron powder, iron flakes, aluminum powder, aluminum flakes, copper powder, copper flakes, formic acid, formaldehyde, titanium trichloride, hypophosphorous acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310568645.4A CN116716483A (en) | 2023-05-19 | 2023-05-19 | Method for efficiently recycling metal palladium in palladium-containing spent catalyst |
Applications Claiming Priority (1)
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