CN101760627B - Method for recovering noble metal in waste noble metal catalysts - Google Patents
Method for recovering noble metal in waste noble metal catalysts Download PDFInfo
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- CN101760627B CN101760627B CN2008102408645A CN200810240864A CN101760627B CN 101760627 B CN101760627 B CN 101760627B CN 2008102408645 A CN2008102408645 A CN 2008102408645A CN 200810240864 A CN200810240864 A CN 200810240864A CN 101760627 B CN101760627 B CN 101760627B
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Abstract
The invention provides a method for recovering noble metal in waste noble metal catalysts, which comprises the following steps: making the waste noble metal catalysts be in contact with chelating agents and extracting agents under the condition of supercutical fluid extraction; separating out extraction liquid; and removing the extracting agents in the extraction liquid. The chelating agents are materials which can form chelate compounds with the noble metal in the waste noble metal catalysts, and the extracting agents are solvents which can dissolve the chelate compounds in the supercutical state. Compared with a traditional recovering method, the method for recovering noble metal in waste noble metal catalysts provided by the invention has the advantages of simple process, easy operation, no waste liquid generation and no environment pollution, so the environment protection cost is low.
Description
Technical field
The present invention relates to a kind of method that reclaims the precious metal in the useless noble metal catalyst.
Background technology
In catalysis technical field, precious metal is widely used in the numerous areas of industries such as refining of petroleum, pharmacy, fine chemistry industry as good catalyzer.
Noble metal catalyst is used especially extensive in refining of petroleum and petrochemical complex production; For example; The toluene method of SNIA company prepares the reactions such as benzoic acid hydrogenation, tolylene diisocyanate (TDI) production DNT (DNT) process and terephthalic acid unifining of caprolactam technology route and all adopts palladium-carbon catalyst; And in petroleum reforming technology, mostly use platinum catalyst.In order to guarantee the activity stabilized of in Industrial processes noble metal catalyst, must replenish a certain amount of raw catalyst on time, and regularly discharge the spent catalyst of inactivation.Because palladium, platinum etc. are rare precious metals, resource scarcity costs an arm and a leg; So be necessary very much from the useless noble metal catalyst of industrial application such as palladium, platinum catalyst, to reclaim precious metal; So both can waste reclaimation, make full use of the precious metal resource, can reduce environmental pollution again.
Useless noble metal catalyst descends with respect to the content of live catalyst precious metal to some extent, and useless noble metal catalyst surface coverage has a large amount of organism, contains impurity such as Fe, Ni, Cu simultaneously.At present, the method for recovery precious metal mainly contains three kinds from useless noble metal catalyst.
First kind is if chlorination volatilization, is under 600-750 ℃ high temperature, in dead palladium catalyst, feeds and contains CO and Cl
2Mixed gas, or feed CCl
4, COCl
2Deng organic chloride steam, make palladium generate muriate and volatilize, and water absorbs this volatile matter, the recovery of palladium can reach 90%.But the shortcoming of this method is, no matter is CO and Cl
2Mixed gas, or CCl
4, COCl
2Deng organic chloride all is poisonous, dangerous material, when operation, can damage health of operators, and contaminate environment.
Second kind is wet processing, at first uses CCl
4Palladium in the dead palladium catalyst is leached, remove organism, add NaOH solution and Cl then
2, making the pH value of solution value is about 9.4, adds concentrated hydrochloric acid again and dissolves palladium, obtains palladium metal with the hydrazine solution reduction at last.This method is to comparatively suitable by the recovery of the palladium catalyst of high boiling point tar pollution, and shortcoming is that long flow path, cost are high, palladium recovery rate is very low, only has an appointment 70%, and can produce a large amount of waste liquids in the removal process, and the environmental protection cost is also higher.
The third is a burning method, and this method is comparatively commonly used, and this method becomes CO with carbon burning under 900-1200 ℃ high temperature oxidation condition
2Effusion is removed, and the incendiary residue is dissolved palladium with formic acid reduction back with hydrochloric acid and oxygenant (like chlorine, hydrogen peroxide or nitric acid etc.), and gained solution is re-refined into the palladium metal product, and the recovery of palladium is generally more than 80%.The most long flow path of these methods, cost are high, palladium recovery rate is low and removal process in can produce a large amount of waste liquids, the environmental protection cost is higher.
Summary of the invention
The objective of the invention is to overcome the more and environmental protection defect of high cost of the complex process, the waste liquid that exist in the above-mentioned prior art, the method that a kind of technology is simple, do not have the precious metal in waste liquid produces and the environmental protection cost is the very low useless noble metal catalyst of recovery is provided.
The invention provides a kind of method that reclaims the precious metal in the useless noble metal catalyst; This method comprises that under the condition of supercritical fluid extraction, the noble metal catalyst that will give up contacts with extraction agent with sequestrant; Isolate extraction liquid; And remove the extraction agent in this extraction liquid, said sequestrant be with this useless noble metal catalyst in precious metal form the material of inner complex, said extraction agent be the solvent that under the condition of said supercritical fluid extraction, dissolves said inner complex.
According to the method for the precious metal in the useless noble metal catalyst of recovery provided by the invention, to compare with traditional recovery method, method technology of the present invention is simple, and easy handling does not have waste liquid to produce, and do not have environmental pollution, thereby the environmental protection cost is very low.
Embodiment
" supercritical fluid extraction " as herein described is meant the mass transfer lock out operation that from solid or liquid, extracts soluble constituent with supercutical fluid as extraction agent.Supercutical fluid has density close with liquid and the viscosity close with gas; Have the molecular diffusivity more much bigger again, so have bigger loading capacity (amount of unit volume fluid ability extract solutes) and good flowing property and mass-transfer performance than liquid.The employed extraction agent of supercritical fluid extraction is generally carbonic acid gas, hydro carbons, ammonia and water etc.
The method of the precious metal in the useless noble metal catalyst of recovery provided by the invention comprises; Under the condition of supercritical fluid extraction; The noble metal catalyst that will give up contacts with extraction agent with sequestrant, isolates extraction liquid, and removes the extraction agent in this extraction liquid; Said sequestrant be with this useless noble metal catalyst in precious metal form the material of inner complex, said extraction agent be the solvent that under the condition of said supercritical fluid extraction, dissolves said inner complex.
According to method provided by the invention, in above-mentioned extraction agent, because the reactive behavior of carbonic acid gas is very low and low price, be easy to obtain, so the present invention preferably adopts carbonic acid gas as extraction agent.Said supercritical fluid extraction can carry out under supercritical state, criticality or the nearly criticality of extraction agent.Under preferable case, the condition of said supercritical fluid extraction comprises that pressure is 5-50MPa, is preferably 7-30MPa, and temperature is 30-100 ℃, is preferably 40-80 ℃, is 0.5-20 hour, is preferably 4-12 hour duration of contact.
According to method provided by the invention, under preferable case, the weight ratio of said sequestrant and extraction agent is 1: 1-100, be preferably 1: 10-50.
According to method provided by the invention; Said sequestrant can adopt the various sequestrants that can generate inner complex with precious metal such as palladium, platinum; For example the example of said sequestrant can be methyl ethyl diketone, thenoyl difluoro acetone, tributyl phosphate, MGD and two (2; 4,4-tri-methyl-amyl) one or more in single phosphonothionic acid.Wherein, MGD can be nabam or dithiocarbamic acid potassium.
According to method provided by the invention, under preferable case, the ratio of the gross weight of said sequestrant and extraction agent and the weight of said useless noble metal catalyst is 1-30, be preferably 2-20.
According to method provided by the invention; The said noble metal catalyst that will give up contacts with extraction agent with sequestrant and can be periodical operation; Also can be operate continuously; Can simultaneously the noble metal catalyst that gives up, sequestrant and extraction agent be contacted, also can earlier the noble metal catalyst that gives up contacted with sequestrant and then contact with extraction agent.
When the said noble metal catalyst that will give up contacted to periodical operation with sequestrant with extraction agent, under preferable case, the ratio of the gross weight of said sequestrant and extraction agent and the weight of said useless noble metal catalyst was 1-20, be preferably 2-10.
When the said noble metal catalyst that will give up contacted to operate continuously with sequestrant with extraction agent, under preferable case, total flow of said sequestrant and said extraction agent was the 1-30kg/hkg catalyzer, be preferably the 2-20kg/hkg catalyzer.
According to method provided by the invention; In order to improve the solvability of extraction agent to the inner complex of precious metal; Under preferable case, said useless noble metal catalyst, sequestrant contact in the presence of improving agent with extraction agent and carry out, and said improving agent is sodium hydroxide or nitric acid.The consumption of said improving agent and the weight ratio of sequestrant are 1: 1-10.Sodium hydroxide or concentration that preferred working concentration is 20-40 weight % are the nitric acid of 20-60 weight %.
According to method provided by the invention, under preferable case, said condition of removing the extraction agent in the extraction liquid comprises that pressure is 1-6MPa, and temperature is 30-50 ℃.When separating, thereby because the pressure that needs to reduce extraction liquid discharges extraction agent, the pressure the when pressure when therefore removing extraction agent in the extraction liquid need be than supercritical fluid extraction is low.
When will give up simultaneously noble metal catalyst, sequestrant contact with extraction agent, can sequestrant be brought into through extraction agent, also can add sequestrant separately.Detailed process is following:
The noble metal catalyst that will give up contacts under above-mentioned supercritical extraction condition with extraction agent with sequestrant; Make useless precious metal and sequestrant form inner complex, come this inner complex of dynamic extraction and remaining sequestrant, isolate the extraction liquid that in extraction agent, is dissolved with inner complex and remaining sequestrant with extraction agent; Extraction liquid is separated through reducing the laggard promoting the circulation of qi liquid of pressure; Removing extraction agent, extraction agent is reclaimed and recycles, obtain containing the extract of the inner complex of precious metal simultaneously.Because the pressure reduction can cause temperature to descend, lower to the solubleness of extract when separating for guaranteeing extraction agent, preferably temperature is increased to 30-50 ℃.
When the noble metal catalyst that will give up earlier contacted with sequestrant and then contacts with extraction agent, detailed process was following:
The noble metal catalyst that will give up contacts with sequestrant; Fully stirring fully acts on precious metal and sequestrant and is completed into inner complex; At this moment, the temperature of contact is preferably 30-80 ℃, and useless noble metal catalyst contacts 0.5-20 hour, is preferably 2-4 hour with sequestrant.The consumption of sequestrant be noble metal catalyst weight 0.5-10 doubly, be preferably 1-4 doubly.Then resulting mixture is contacted with extraction agent under the supercritical extraction condition of above-mentioned qualification, be preferably 1-16 hour duration of contact, isolate the extraction liquid of the inner complex that in extraction agent, is dissolved with precious metal.Extraction liquid is reduced the laggard promoting the circulation of qi liquid of pressure separate, extraction agent is reclaimed and recycles, and obtain containing the inner complex of precious metal and the extract of remaining sequestrant.Because the pressure reduction can cause temperature to descend, lower to the solubleness of extract when separating for guaranteeing extraction agent, preferably temperature is increased to 30-50 ℃.
Method of the present invention is except going for Rare Metals in the various useless noble metal catalysts; Also go for the non-noble metal recovery in the useless noble metal catalyst of depleted in the transition metal, the sequestrant that only needs to select to form inner complex with the metal that needs reclaim gets final product.
Above-mentioned noble metal catalyst is preferably and is used for the unsaturation organic cpds and comprises alkene, ketone, aldehydes, the especially palladium catalyst of the hydrogenation process of aromatic carboxylic acid class aromatic hydrocarbons; For example be used for the catalyst for reaction such as hydrogenation of unifining, aliphatics unsaturated carboxylic acid or its ester of hydrogenation, the terephthalic acid of phenylformic acid or substituted benzoic acid, perhaps can be for being applied to the platinum catalyst of catforming process.The carrier of catalyzer can be various carriers well known by persons skilled in the art, for example porous inorganic oxide such as silicon oxide, aluminum oxide and titanium oxide etc., gac, zeolite etc.
Said useless noble metal catalyst can be the noble metal catalyst of various used inactivations, also can be the noble metal catalyst product of various fresh performance inconsistency lattice.
Adopt embodiment that the present invention is explained in further detail below.
Embodiment 1-5
Useless noble metal catalyst adopts the palladium-carbon catalyst from inactivation in the benzoic acid hydrogenation commercial run, and palladium content is about 5 weight % in the fresh palladium-carbon catalyst, and through measuring, palladium content is 4.7 weight % in the waste palladium carbon catalyst after the use.
Palladium Determination on content method does in this waste palladium carbon catalyst, and using earlier weight ratio is that 3: 1 concentration is that HCl and the concentration of 34 weight % is the HNO of 63 weight %
3The mixing acid of forming soaks testing sample and all dissolves until sample; Solution is transferred to quantitatively to be diluted to concentration in the volumetric flask be 100 μ g/g, adopts U.S.'s Thermo Elemental IRIS Intrepid inductively coupled plasma atomic emission (ICP-AES) appearance to carry out the ICP test then.
Sequestrant adopts methyl ethyl diketone (U.S. Acros Organics chemical company, analytical pure).
It is 1 liter container that the above-mentioned waste palladium carbon catalyst of 500g is placed volume, adds the 500g methyl ethyl diketone then, under temperature shown in the table 1, stirs 4 hours.It is in 1 liter the airtight extraction kettle that resulting mixture is moved into volume; And will from the liquid carbon dioxide of liquid carbon dioxide steel cylinder as extraction agent after the high-pressure metering pump pressurization; Add in this extraction kettle with each flow shown in the table 1; In this extraction kettle, under the differing temps shown in the table 1, different pressures, use liquid carbon dioxide continuous extraction 8 hours, obtain containing the extraction liquid of liquid carbon dioxide and precious metal inner complex and residue sequestrant.
Then resulting extraction liquid is sent in the separating still through being decompressed to the different pressures shown in the table 1; And be heated to 30 ℃ and distill; Separate the extraction agent carbonic acid gas that obtains and after the wet flow indicator metering, reclaim and recycle, and obtain containing the inner complex of precious metal and the extract of residue sequestrant.Measure the metallic palladium content in the extract, according to the amount calculating palladium recovery rate of metallic palladium in the amount of the metallic palladium in this extract and the waste palladium carbon catalyst.The result lists in the table 1.
Palladium content in the extract adopts U.S.'s Thermo Elemental IRIS Intrepid inductively coupled plasma atomic emission (ICP-AES) appearance directly to measure.
Table 1
Embodiment 6-9
Adopt the waste palladium carbon catalyst identical with embodiment 1, and sequestrant employing tributyl phosphate (U.S. Acros Organics chemical company, analytical pure).
It is 3 liters container that the above-mentioned waste palladium carbon catalyst of 500g is placed volume, adds the 2000g tributyl phosphate then, under temperature shown in the table 1, stirs 2 hours.It is in 3 liters the airtight extraction kettle that resulting mixture is moved into volume; And will from the liquid carbon dioxide of liquid carbon dioxide steel cylinder after the high-pressure metering pump pressurization as extraction agent; Flow with 20kg/h adds in this extraction kettle; In this extraction kettle, under different temperature, different pressure, use liquid carbon dioxide continuous extraction 4 hours, the extraction liquid that obtains containing liquid carbon dioxide and precious metal inner complex and remain sequestrant.
Then resulting extraction liquid is sent in the separating still through being decompressed to the different pressures shown in the table 2; And be heated to 50 ℃ and distill; Separate the extraction agent carbonic acid gas that obtains and after the wet flow indicator metering, reclaim and recycle, and obtain containing the inner complex of precious metal and the extract of residue sequestrant.Measure the metallic palladium content in the extract, according to the amount calculating palladium recovery rate of metallic palladium in the amount of the metallic palladium in this extract and the waste palladium carbon catalyst.The result lists in the table 2.
Palladium Determination on content in the extract is carried out according to the method for describing among the embodiment 1-5.
Table 2
Embodiment 10-14
Adopt the waste palladium carbon catalyst identical with embodiment 1, and the various sequestrants shown in the sequestrant employing table 3, these sequestrants are U.S. Acros Organics chemical company product, analytical pure.
It is 1 liter airtight extraction kettle that the above-mentioned waste palladium carbon catalyst of 500g is placed volume; Will be after high-pressure metering pump be forced into 15MPa from the liquid carbon dioxide of liquid carbon dioxide steel cylinder; Carry secretly from the sequestrant of another high-pressure metering pump with the flow of 8kg/h and to get in this extraction kettle 15MPa, 80 ℃ of following continuous extractions 12 hours, the extraction liquid that obtains containing liquid carbon dioxide and precious metal inner complex and remain sequestrant with total flow of 1kg/h.Wherein, in embodiment 14, be that the salpeter solution of 50 weight % is entrained in this extraction kettle by carbonic acid gas with sequestrant also with concentration, and the HNO in this salpeter solution
3With the weight ratio of sequestrant be 1: 2.
Resulting then extract gets in the separating still through being decompressed to 3MPa; And be heated to 40 ℃ and distill; Separate the extraction agent carbonic acid gas that obtains and after the wet flow indicator metering, reclaim and recycle, and obtain containing the inner complex of precious metal and the extract of residue sequestrant.Measure the metallic palladium content in the extract, according to the amount calculating palladium recovery rate of metallic palladium in the amount of the metallic palladium in this extract and the waste palladium carbon catalyst.The weight ratio and the calculation result of the kind of sequestrant, sequestrant and carbonic acid gas are listed in the table 3.
Palladium Determination on content in the extract is carried out according to the method for describing among the embodiment 1-5.
Table 3
| Embodiment | The sequestrant kind | Sequestrant: carbonic acid gas (weight ratio) | Palladium recovery rate % |
| 10 | Thenoyl difluoro acetone | 1∶10 | 93.8 |
| 11 | Nabam | 1∶10 | 96.5 |
| 12 | The single phosphonothionic acid in two (2,4, the 4-tri-methyl-amyl) | 1∶10 | 98.3 |
| 13 | The single phosphonothionic acid in two (2,4, the 4-tri-methyl-amyl) | 1∶20 | 99.2 |
| 14 | Tributyl phosphate | 1∶50 | 98.5 |
Can find out that from top embodiment method technology of the present invention is simple, easy handling does not have waste liquid to produce, and do not have environmental pollution, thereby the environmental protection cost is very low, and noble metal recovery is still very high.
Claims (8)
1. method that reclaims the precious metal in the useless noble metal catalyst; This method comprises; Under the condition of supercritical fluid extraction, the noble metal catalyst that will give up contacts with extraction agent with sequestrant, isolates extraction liquid; And remove the extraction agent in this extraction liquid; Said sequestrant be with this useless noble metal catalyst in precious metal form the material of inner complex, said extraction agent be the solvent that under the condition of said supercritical fluid extraction, dissolves said inner complex, said sequestrant is thenoyl difluoro acetone and/or MGD; Said useless noble metal catalyst carries out with contacting in the presence of improving agent of sequestrant and extraction agent, and said improving agent is sodium hydroxide or nitric acid.
2. method according to claim 1, wherein, the weight ratio of said sequestrant and extraction agent is 1: 1-100.
3. method according to claim 2, wherein, the weight ratio of said sequestrant and extraction agent is 1: 10-50.
4. according to any described method among the claim 1-3, wherein, said extraction agent is a carbonic acid gas, and the condition of said supercritical fluid extraction comprises that pressure is 5-50MPa, and temperature is 30-100 ℃, and be 0.5-20 hour duration of contact.
5. method according to claim 4, wherein, the condition of said supercritical fluid extraction comprises that pressure is 7-30MPa, and temperature is 40-80 ℃, and be 4-12 hour duration of contact.
6. method according to claim 1, wherein, the ratio of the gross weight of said sequestrant and extraction agent and the weight of said useless noble metal catalyst is 1-30.
7. method according to claim 6, wherein, the ratio of the gross weight of said sequestrant and extraction agent and the weight of said useless noble metal catalyst is 2-20.
8. method according to claim 1, wherein, it is 1-6MPa that said method of removing the extraction agent in the extraction liquid is included in pressure, temperature is that extraction agent is removed in evaporation under 30-50 ℃ the condition.
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| CN102251098B (en) * | 2011-07-04 | 2013-02-27 | 沈少波 | Method for extracting rare noble metals |
| CN102994759B (en) * | 2012-11-28 | 2015-09-30 | 大连东泰产业废弃物处理有限公司 | The retrieving arrangement of precious metal in a kind of waste catalyst |
| WO2023018527A1 (en) | 2021-08-11 | 2023-02-16 | Exxonmobil Chemical Patents Inc. | Processes for dehydrogenating alkanes and alkyl aromatic hydrocarbons |
| CA3228648A1 (en) | 2021-08-13 | 2023-02-16 | Exxonmobil Chemical Patents Inc. | Processes for dehydrogenating alkanes and alkyl aromatic hydrocarbons |
| CN114681857B (en) * | 2022-04-14 | 2023-02-28 | 呼和浩特市联合鼎盛固体废物处理有限公司 | Comprehensive utilization method of catalyst |
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| CN1207777A (en) * | 1995-11-03 | 1999-02-10 | 爱达荷研究基金公司 | Process for extracting metals directly from metal oxides |
| CN1265160A (en) * | 1996-07-26 | 2000-08-30 | 爱达荷研究基金公司 | Fluid extraction of metals of metalloids |
| CN1541769A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Method for regenerating a palladium catalyst |
| US7309675B1 (en) * | 1999-08-24 | 2007-12-18 | Degussa Ag | Method for regenerating platinum catalysts |
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| CN1207777A (en) * | 1995-11-03 | 1999-02-10 | 爱达荷研究基金公司 | Process for extracting metals directly from metal oxides |
| CN1265160A (en) * | 1996-07-26 | 2000-08-30 | 爱达荷研究基金公司 | Fluid extraction of metals of metalloids |
| US7309675B1 (en) * | 1999-08-24 | 2007-12-18 | Degussa Ag | Method for regenerating platinum catalysts |
| CN1541769A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Method for regenerating a palladium catalyst |
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