CN116574916A - Method for extracting noble metal from cellulose carrier noble metal catalyst - Google Patents
Method for extracting noble metal from cellulose carrier noble metal catalyst Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000001913 cellulose Substances 0.000 title claims abstract description 36
- 229920002678 cellulose Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001354 calcination Methods 0.000 claims abstract description 34
- 238000002386 leaching Methods 0.000 claims abstract description 25
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 18
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000002244 precipitate Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 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 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000000605 extraction Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100001244 hazardous air pollutant Toxicity 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920000361 Poly(styrene)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- -1 petrochemical Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—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
- C22B7/001—Dry processes
-
- 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
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting noble metal from cellulose carrier noble metal catalyst, which mainly comprises the following steps of firstly hydrolyzing a dead cellulose carrier noble metal catalyst in a reaction kettle, then calcining the hydrolyzed cellulose carrier noble metal catalyst in sections, and then adding sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of a nitrogenous organic reagent, and finally reducing by using a reducing agent to obtain noble metal. The invention uses the method of hydrolysis and calcination, overcomes the problem of incomplete calcination of cellulose, and the cellulose is hydrolyzed into micromolecular compounds, so that the calcination rate is greatly improved, the subsequent leaching can be complete, and the recovery rate of noble metal is high; the method adopts hydrolysis and calcination, so that the influence of the hydrolyzed micromolecular compound on the leaching process is reduced; the method for extracting noble metal from cellulose supported noble metal catalyst has high extraction rate which can reach more than 99.5 percent, and greatly improvesRecovery efficiency.
Description
Technical Field
The invention relates to the technical field of noble metal regeneration, in particular to a method for extracting noble metal from a cellulose carrier noble metal catalyst.
Background
Catalysts play an irreplaceable important role in the development of the chemical industry. However, as the service life of the catalyst increases, the activity of the catalyst is reduced due to the growth of grains of the active component or even sintering caused by overheating, or the activity is partially or completely lost due to the poisoning of certain poisons, and the activity is reduced due to the accumulation of pollutants on the active surface of the catalyst or the blocking of the pore channels of the catalyst, so that the catalyst finally has to be updated. In the preparation process of the catalyst, in order to ensure the activity, selectivity, toxicity resistance, certain strength, service life and other index performances, noble metals are often selected as main components. Although the morphology, structure and quantity of certain components of the catalyst may vary during use, the spent catalyst may still contain significant quantities of non-ferrous or precious metals, sometimes in amounts far greater than the corresponding components of the lean ore. The waste industrial catalyst produced in each year is about 50-70 ten thousand tons worldwide, and the waste industrial catalyst is recycled as secondary resources, so that the noble metal with extremely high grade can be obtained. The noble metal is recovered from the waste industrial catalyst, so that not only can remarkable economic benefit be obtained, but also the utilization rate of resources can be improved, and the environmental problems caused by the catalyst can be reduced.
The noble metals mainly belonging to platinum group in the spent catalyst. Catalysts containing noble metals are widely used for the abatement of pollution by a number of industries including the chemical, petrochemical, plastics, paint, spray and pharmaceutical industries. Many businesses use catalytic reaction technology to avoid the production of Volatile Organic Compounds (VOCs) and Hazardous Air Pollutants (HAPs). The catalysts used in these reactors contain noble metals, including platinum, palladium, rhodium, ruthenium, gold and silver, singly or in combination. Depending on the different equipment and procedures employed, these noble metals are provided with different supports, such as pellets, granules and monolithic structures (substrates). After these catalysts have been spent, the precious metals therein must be recovered. The data show that about 80 ten thousand t waste catalysts are discharged worldwide each year, and the replacement amount of the Chinese petroleum and chemical catalysts exceeds 10 ten thousand t.
Common carriers of the catalyst are inorganic carriers, synthetic organic polymer carriers and natural polymer carriers. Inorganic carriers, such as activated carbon, silica, alumina, have the general advantages of conventional carriers, namely easy separation from the product and recycling for reuse, but the preparation process often requires high temperature calcination. Synthetic organic polymeric carriers are typically synthetic polymers such as crosslinked polystyrene, polystyrene-polyethylene glycol, whose monomers are organic and are non-renewable energy sources. Typical natural polymeric carriers are cellulose and chitosan. In recent years, with increasing importance of resource recycling, natural polymers, particularly cellulose, are receiving great attention from researchers due to their abundant sources, non-toxicity, biodegradability and renewable properties. The large number of hydroxyl groups contained in the cellulose structure allows the cellulose to participate in a number of reactions, with the advantage of being derivable. The cellulose supported metal catalyst is generally realized in two modes, namely, metal or metal ions are directly complexed with hydroxyl groups in a cellulose main chain structure; and secondly, grafting certain organic micromolecular ligands containing lone pair electrons onto cellulose in a chemical bonding mode, namely, functionalizing the cellulose, and then coordinating the functionalized cellulose with metal or metal ions as ligands.
However, the spent catalyst is mostly contaminated with organic materials in the reaction mixture. These organic materials are often toxic, so that the organic materials must first be removed from the support along with the carbon in the recovery of the precious metal component of the spent catalyst. In the conventional recovery process, a spent catalyst is burned to remove organic matters contained therein, and then a sampling test of the residue is performed, and a noble metal oxide having a noble metal content measured therein is chemically treated.
However, less research is conducted on noble metal extraction from cellulose carrier noble metal catalysts, and experiments prove that the traditional calcination method for extracting noble metal has low extraction rate, high cost and long period, so that an extraction process with high extraction rate, low cost and short period needs to be developed.
Disclosure of Invention
Based on the problems, the invention provides a method for extracting noble metal from a cellulose carrier noble metal catalyst, which comprises the steps of decomposing cellulose, calcining and reducing to obtain the noble metal catalyst. The method comprises the following steps:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Hydrolysis
Placing the spent cellulose carrier noble metal catalyst into an acidic FeCl in a reaction kettle 3 Heating to 300-350deg.C in water solution, and naturally cooling to room temperature;
(2) Calcination
Evaporating the hydrolyzed solution in the step (1) to dryness, calcining for 1-4 hours at 450-550 ℃ in a muffle furnace, then increasing the temperature to 700-800 ℃ and calcining for 2-4 hours to obtain noble metal-containing powder;
(3) Leaching
Adding the noble metal-containing powder calcined in the step (2) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of a nitrogen-containing organic reagent;
(4) Reduction of
Adjusting the pH value to be acidic, removing the precipitate, adjusting the pH value to be alkaline, removing the precipitate, and reducing the precipitate by using a reducing agent to obtain the noble metal.
Wherein step (1) is preferably:
acidic FeCl 3 The acid in the aqueous solution is hydrochloric acid or sulfuric acid;
acidic FeCl 3 The pH value of the aqueous solution is 1-4;
the solid-liquid volume ratio is 1g to (1-10) ml;
the heating rate is 5-10 ℃/s;
maintaining at 300-350deg.C for more than 10 min.
Step (2) is preferably:
calcining in a muffle furnace at 450-500 ℃ for 2-3 hours, then raising the temperature to 750-800 ℃ and calcining for 2-3 hours;
step (3) is preferably:
sodium hypochlorite with molar concentration of 0.1-10mol/L, sulfuric acid with molar concentration of 0.1-10mol/L, feCl 3 The molar concentration is 0.5-20mol/L, and the molar concentration of the nitrogen-containing organic reagent is 0.5-20mol/L;
the nitrogen-containing organic reagent is pyridine, piperidine, imidazole or N, N-dimethylformamide;
in the step (4), it is preferable that,
adjusting pH to 4-6 to acidity, removing precipitate, adjusting to 8-10 alkalinity, and removing precipitate;
the reducing agent is hydrazine hydrate, formic acid or formate.
The beneficial effects of the invention are that
(1) The method solves the problem of incomplete cellulose calcination, the cellulose is hydrolyzed into small molecular compounds, the calcination rate is greatly improved, the subsequent leaching can be complete, and the recovery rate of noble metal is high;
(2) After hydrolysis of the cellulose supported noble metal catalyst, if the cellulose supported noble metal catalyst is directly leached, the leaching rate of the noble metal is lower, and a great amount of experiments and research analysis prove that the small molecular compound after hydrolysis of the cellulose and the noble metal have complexation action, so that the noble metal cannot be completely leached out, therefore, the method adopts the steps of hydrolysis and calcination, and reduces the influence of the small molecular compound after hydrolysis on the leaching process;
(3) The invention uses a combined leaching agent which comprises sodium hypochlorite and sulfuric acid for leaching noble metals and a capturing agent FeCl 3 The method also comprises a complexing agent nitrogen-containing organic reagent, so that the extracted noble metal ions can be more stable in the solution, and the recovery rate of noble metal is greatly improved;
(4) The method for extracting the noble metal from the cellulose supported noble metal catalyst has high extraction rate which can reach more than 99.5 percent, short extraction period and complete the whole process within 8 hours, and greatly improves the recovery efficiency.
Detailed Description
The present invention will be described in further detail with reference to examples, which are not intended to limit the scope of the invention.
Example 1:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Hydrolysis
Placing 1Kg of dead cellulose carrier noble metal catalyst into a reaction kettle, wherein FeCl hydrochloride with pH value of 1 3 Rapidly heating to 300 ℃ in 1000ml of aqueous solution, keeping for 20min at a heating rate of 5 ℃/s, and naturally cooling to room temperature;
(2) Calcination
Evaporating the hydrolyzed solution in the step (1) to dryness, calcining for 2 hours at 500 ℃ in a muffle furnace, and then increasing the temperature to 750 ℃ and calcining for 3 hours to obtain noble metal-containing powder;
(3) Leaching
Adding the noble metal-containing powder calcined in the step (2) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of N, N-dimethylformamide; wherein, the molar concentration of sodium hypochlorite is 5mol/L, the molar concentration of sulfuric acid is 1mol/L, feCl 3 The molar concentration is 10mol/L, and the molar concentration of N, N-dimethylformamide is 1mol/L.
(4) Reduction of
Adjusting the pH value to 4, removing the precipitate, adjusting the pH value to 9, removing the precipitate, and reducing by using a reducing agent hydrazine hydrate to obtain the noble metal.
The noble metal recovery rate was 99.7% as detected.
Example 2:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Hydrolysis
Placing 1Kg of dead cellulose carrier noble metal catalyst in a reaction kettle, wherein FeCl hydrochloride with pH value of 2 3 Rapidly heating 2000ml of aqueous solution to 350 ℃, keeping the heating rate at 10 ℃/s for 30min, and naturally cooling to room temperature;
(2) Calcination
Evaporating the hydrolyzed solution in the step (1) to dryness, calcining for 2 hours at 450 ℃ in a muffle furnace, and then increasing the temperature to 800 ℃ and calcining for 3 hours to obtain noble metal-containing powder;
(3) Leaching
Adding the noble metal-containing powder calcined in the step (2) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of N, N-dimethylformamide; wherein, the molar concentration of sodium hypochlorite is 10mol/L, the molar concentration of sulfuric acid is 5mol/L, and FeCl 3 The molar concentration is 10mol/L, and the molar concentration of N, N-dimethylformamide is 2mol/L.
(4) Reduction of
Adjusting the pH value to 5, removing the precipitate, adjusting the pH value to 8, removing the precipitate, and reducing the precipitate by using a reducing agent formic acid to obtain the noble metal.
The noble metal recovery rate is 99.8% through detection.
Example 3:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Hydrolysis
Placing 1Kg of dead cellulose carrier noble metal catalyst in a reaction kettle, wherein FeCl hydrochloride with pH value of 3 3 Rapidly heating to 330 ℃ in 3000ml of aqueous solution, keeping for 20min at a heating rate of 10 ℃/s, and naturally cooling to room temperature;
(2) Calcination
Evaporating the hydrolyzed solution in the step (1) to dryness, calcining for 3 hours at 480 ℃ in a muffle furnace, and then increasing the temperature to 800 ℃ and calcining for 2 hours to obtain powder containing noble metals;
(3) Leaching
Adding the noble metal-containing powder calcined in the step (2) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of N, N-dimethylformamide; wherein, the molar concentration of sodium hypochlorite is 8mol/L, the molar concentration of sulfuric acid is 3mol/L, feCl 3 The molar concentration is 15mol/L, and the molar concentration of N, N-dimethylformamide is 4mol/L.
(4) Reduction of
Adjusting the pH value to 3, removing the precipitate, adjusting the pH value to 9, removing the precipitate, and reducing the precipitate by using a reducing agent sodium formate to obtain the noble metal.
The noble metal recovery rate is 99.5% through detection.
Example 4:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Hydrolysis
Placing 1Kg of dead cellulose carrier noble metal catalyst in a reaction kettle, wherein FeCl hydrochloride with pH value of 2 3 Rapidly heating to 350deg.C in 3000ml of water solution at 10deg.C/s, maintaining for 10min, and naturally cooling to room temperature;
(2) Calcination
Evaporating the hydrolyzed solution in the step (1) to dryness, calcining for 3 hours at 500 ℃ in a muffle furnace, and then increasing the temperature to 800 ℃ and calcining for 3 hours to obtain noble metal-containing powder;
(3) Leaching
Adding the noble metal-containing powder calcined in the step (2) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of N, N-dimethylformamide; wherein, the molar concentration of sodium hypochlorite is 10mol/L, the molar concentration of sulfuric acid is 5mol/L, and FeCl 3 The molar concentration is 10mol/L, and the molar concentration of N, N-dimethylformamide is 2mol/L.
(4) Reduction of
Adjusting the pH value to 4, removing the precipitate, adjusting the pH value to 9, removing the precipitate, and reducing the precipitate by using a reducing agent sodium formate to obtain the noble metal.
The noble metal recovery rate is 99.8% through detection.
Comparative example 1:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Calcination
Calcining 1Kg of dead cellulose carrier noble metal catalyst in a muffle furnace at 500 ℃ for 2 hours, and then increasing the temperature to 750 ℃ and calcining for 3 hours to obtain noble metal-containing powder;
(2) Leaching
Adding the noble metal-containing powder calcined in the step (1) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of N, N-dimethylformamide; wherein, the molar concentration of sodium hypochlorite is 5mol/L, the molar concentration of sulfuric acid is 1mol/L, feCl 3 The molar concentration is 10mol/L, and the molar concentration of N, N-dimethylformamide is 1mol/L.
(3) Reduction of
Adjusting the pH value to 4, removing the precipitate, adjusting the pH value to 9, removing the precipitate, and reducing by using a reducing agent hydrazine hydrate to obtain the noble metal.
The noble metal recovery rate was detected to be 69.2%.
Comparative example 2:
a method for extracting noble metals from cellulose-supported noble metal catalysts, comprising the steps of:
(1) Hydrolysis
Placing 1Kg of dead cellulose carrier noble metal catalyst in a reaction kettle, wherein FeCl hydrochloride with pH value of 2 3 Rapidly heating to 350deg.C in 1000ml of water solution at 10deg.C/s, maintaining for 30min, and naturally cooling to room temperature;
(2) Leaching
Adding the powder obtained in the step (1) into a mixture containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of N, N-dimethylformamide; wherein, the molar concentration of sodium hypochlorite is 10mol/L, the molar concentration of sulfuric acid is 5mol/L, and FeCl 3 The molar concentration is 10mol/L, and the molar concentration of N, N-dimethylformamide is 2mol/L.
(3) Reduction of
Adjusting the pH value to 5, removing the precipitate, adjusting the pH value to 8, removing the precipitate, and reducing the precipitate by using a reducing agent formic acid to obtain the noble metal.
The noble metal recovery rate is 82.6% through detection.
Therefore, the recovery rate of noble metals in the cellulose carrier noble metal catalyst is greatly improved through four steps of hydrolysis, calcination, leaching and reduction.
Claims (9)
1. A method for extracting noble metals from cellulose-supported noble metal catalysts, characterized in that it comprises the steps of:
(1) Hydrolysis
Placing the spent cellulose carrier noble metal catalyst into an acidic FeCl in a reaction kettle 3 Heating to 300-350deg.C in water solution, and naturally cooling to room temperature;
(2) Calcination
Evaporating the hydrolyzed solution in the step (1) to dryness, calcining for 1-4 hours at 450-550 ℃ in a muffle furnace, then increasing the temperature to 700-800 ℃ and calcining for 2-4 hours to obtain noble metal-containing powder;
(3) Leaching
Adding the noble metal-containing powder calcined in the step (2) into a catalyst containing sodium hypochlorite, sulfuric acid and FeCl 3 Leaching in a solution of a nitrogen-containing organic reagent;
(4) Reduction of
Adjusting the pH value to be acidic, removing the precipitate, adjusting the pH value to be alkaline, removing the precipitate, and reducing the precipitate by using a reducing agent to obtain the noble metal.
2. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, characterized in that in step (1), the acid FeCl 3 The acid in the aqueous solution is hydrochloric acid or sulfuric acid.
3. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, characterized in that in step (1), the acid FeCl 3 Aqueous solutionThe pH value is 1-4; the solid-liquid volume ratio is 1g to (1-10) ml.
4. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, characterized in that the heating rate in step (1) is 5 to 10 ℃/s; maintaining at 300-350deg.C for more than 10 min.
5. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, characterized in that in step (2), the noble metal is calcined in a muffle furnace at 450 to 500 ℃ for 2 to 3 hours, and then the temperature is raised to 750 to 800 ℃ and calcined for 2 to 3 hours.
6. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, wherein in the step (3), the molar concentration of sodium hypochlorite is 0.1 to 10mol/L, the molar concentration of sulfuric acid is 0.1 to 10mol/L, and FeCl is 3 The molar concentration is 0.5-20mol/L, and the molar concentration of the nitrogen-containing organic reagent is 0.5-20mol/L.
7. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 6, wherein the nitrogen-containing organic reagent is pyridine, piperidine, imidazole or N, N-dimethylformamide.
8. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, wherein the pH is adjusted to 4-6 to acidity in the step (4), the precipitate is removed, and the pH is adjusted to 8-10 to alkalinity, and the precipitate is removed.
9. The method for extracting noble metal from cellulose-supported noble metal catalyst according to claim 1, wherein the reducing agent in the step (4) is hydrazine hydrate, formic acid or formate.
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