CN1541769A - Method for regenerating a palladium catalyst - Google Patents
Method for regenerating a palladium catalyst Download PDFInfo
- Publication number
- CN1541769A CN1541769A CNA031228445A CN03122844A CN1541769A CN 1541769 A CN1541769 A CN 1541769A CN A031228445 A CNA031228445 A CN A031228445A CN 03122844 A CN03122844 A CN 03122844A CN 1541769 A CN1541769 A CN 1541769A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- catalyst
- solvent
- palladium catalyst
- contact
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The regeneration process of supported Pd catalyst includes intermittent or continuous contact between the Pd catalyst with activity lowered in the hydrogenation reaction of unsaturated organic compound and organic solvent, which is one or several selected from toluene, benzene, n-hexane, methane dichloride, ethane dichloride, ethanol and cyclohexane, and CO2 successively or simultaneously; and processing organic solvent and CO2 after contacted with Pd catalyst through separating for reuse. The said method can restore Pd catalyst with activity lowered in the interaction with organic matter, especially Pd catalyst with activity lowered by 70 % or more, effectively.
Description
Technical field
The invention relates to a kind of method that makes palladium catalyst regeneration, more specifically, is the renovation process that is used for the load type palladium catalyst of unsaturation organic compound hydrogenation about a kind of.
Technical background
Load type palladium catalyst is widely used in the unsaturation organic compound owing to having high activity and selectivity, in the hydrogenation reaction as alkene, unsaturated carboxylic acid etc., especially be applied to aryl carboxylic acid, in the hydrogenation/process for refining as benzoic acid, terephthalic acid (TPA), cumfrey.
Usually, in the unsaturation hydrogenation reaction of organic compounds, the main cause that catalyst activity reduces is that reaction environment changes, as reaction temperature and reaction heat (sintering), and the physical change in the catalyst that causes self activated centre, or the accumulation of poisonous substance on the catalyst.For avoiding the reduction of catalyst activity, the industrial measure of having adopted various control reaction temperatures or having prevented catalyst poisoning.
Though load type palladium catalyst also exists because the situation that the activity that the accumulation of poisonous substance causes on the physical change of catalyst self or the catalyst reduces because of repeatedly and continuous use in unsaturation organic compound hydrogenation reaction, but the reduction of verified its activity of people more has other reason place.
For example, SNIA company discovers, some material in the benzoic acid greatly influences the activity of Pd/carbon catalyst.These materials comprise accessory substance benzaldehyde, phenmethylol, formic acid, phenylacetic acid, biphenyl, benzoic ether, phthalic acid of toluene oxidation etc., and a small amount of existence of these impurity will cause the decline of Pd/carbon catalyst activity.For example, when phenmethylol or benzaldehyde content reach 0.5%, fresh catalyst is lost activity fully.Up to now, though the long-term use of palladium catalyst can cause activity to reduce in the well-known hydrogenation reaction, there be not simple or suitable method regeneration activity reduction by 70% (comparing) or lower catalyst effectively with initial activity.
For stablizing of Pd/carbon catalyst activity in the assurance device, can only adopt the method for adding fresh catalyst continuously to keep activity in the industrial production.For example, in chemical fibre factory, the Shijiazhuang benzoic acid hydrogenation device, Pd/carbon catalyst one-time pad amount is 5.4 tons, per hour need add 6 kilograms of fresh catalysts in the actual production, draws off the catalyst of equivalent simultaneously from reaction unit.The catalyst burning-off carrier active carbon that draws off, the palladium that reclaims is used further to prepare the fresh catalyst of adding usefulness.This process complexity, tediously long not only causes noble metal loss increasing, fresh catalyst to be equipped with amount and increases, and becomes the bottle footpath of production, has a strong impact on the benefit of production.Again for example, in cumfrey and technical process, make the lost of life of palladium catalyst equally owing to the absorption of organic impurities to ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid.The regeneration expensive palladium catalyst has important and practical meanings so take some countermeasures.
Purpose of the present invention is exactly in order to solve the problem in the production reality, a kind of renovation process that is used for the load type palladium catalyst of unsaturation organic compound hydrogenation to be provided.
Summary of the invention
The method of recovery palladium catalyst activity provided by the invention is based on insoluble to the dissolubility of the liquid phase organic molecule of ADSORPTION STATE and to catalyst carrier of some solvent and the carbon dioxide under overcritical situation, and organic molecule can rapid diffusion in solvent and supercritical carbon dioxide and can separate and enrichment by decompression or alternating temperature operation at an easy rate.
The renovation process of load type palladium catalyst provided by the invention has two kinds of modes of operation:
Mode of operation one:
Will be in the unsaturation organic compound hydrogenation reaction active load type palladium catalyst that has reduced be selected from toluene, benzene, n-hexane, carrene, dichloroethanes, one or more organic solvents and carbon dioxide are 1 according to the weight ratio of solvent and carbon dioxide in ethanol and the cyclohexane: 1-1: 100 consumption, at 5-50MPa, under 30-100 ℃ the condition intermittently or contact 2-16 hour continuously, be depressurized to 1-6MPa with organic solvent and carbon dioxide after palladium catalyst contacts, be warming up to 30-50 ℃ and separate, isolated solvent and carbon dioxide recycle respectively.
This mode of operation may be carried out batchwise, and also can carry out continuously; Solvent can be brought into by carbon dioxide, also can inject separately; Can under the super critical condition of carbon dioxide, carry out, also can under nearly postcritical condition, carry out.Because the super critical point of carbon dioxide is: 34 ℃ of temperature, pressure 78kg/m
2, so the operating condition that adopts in this method is: pressure 5-50MPa, temperature 30-100 ℃; Preferred pressure 7-30MPa, temperature 40-80 ℃.The weight ratio of solvent and carbon dioxide is preferably 1: 20-1: 50.
The pressure size decision of being adopted when the level of activity that the time that the palladium catalyst of inactivation contacts with solvent-carbon dioxide is recovered by catalyst inactivation, catalyst desire, the treating capacity of decaying catalyst and operation is generally 2-16 hour, preferred 4-12 hour.When intermittently operated, the consumption of solvent-carbon dioxide should be 1-20 times of palladium catalyst weight, and preferred 2-10 doubly.When continued operation, the flow of solvent-supercritical carbon dioxide is 1-30NL/ (hkgCat), preferred 2-20NL/ (hkgCat).
This mode of operation more detailed description is as follows: will contact in extraction kettle under above-mentioned overcritical or near super critical condition with solvent-carbon dioxide by isolated inactivation palladium catalyst from reaction system.Be dissolved with organic solvent-carbon dioxide such as organic alcohol of making the palladium catalyst inactivation, aldehyde and be depressurized to 1-6MPa, in the gas-liquid separation still, isolate organic matter, and discharge from the separating still bottom by turbine expansion device or pressure-reducing valve.Because the pressure reduction can cause temperature to descend, lower and guarantee that organic matter does not solidify to organic matter solubility when separating for guaranteeing fluid, need temperature is increased to 30-50 ℃ through heat exchanger.Compressed machine of low pressure CO 2 after the separation or CO 2 high pressure pump and through heat exchanger and the cooling after, enter the carbon dioxide storage tank and recycle.Can mend at any time into a certain amount of carbon dioxide according to circumstances in the carbon dioxide storage tank.Solvent is discharged from the separator bottom with the organic matter that extracts, and recycles after separated.
Mode of operation two:
Will be in the unsaturation organic compound hydrogenation reaction active load type palladium catalyst that has reduced be selected from toluene, benzene, n-hexane, carrene, dichloroethanes, ethanol and cyclohexane in one or more organic solvents at normal pressure, room temperature to 100 ℃ following intermittence or contact 2-20 hour continuously, isolated solvent recycles; Isolated catalyst again with carbon dioxide under 5-50MPa, 30-100 ℃ condition intermittently or contact 2-20 hour continuously, be depressurized to 1-6MPa, be warming up to 30-50 ℃ with carbon dioxide after catalyst contact, after separation, carbon dioxide recycles.
Catalyst may be carried out batchwise with contacting of solvent, also can carry out continuously.When intermittently operated, the consumption of solvent should be 0.5-10 times of palladium catalyst weight, and preferred 1-4 doubly.When continued operation, the flow of solvent is 0.1-1.0NL/ (hkgCat), preferred 0.2-0.5NL/ (hkgCat).Preferred temperature during contact is 30-50 ℃.
Catalyst may be carried out batchwise with contacting of carbon dioxide, also can carry out continuously; This contact can be carried out under super critical condition, also can carry out under nearly postcritical condition.Because the super critical point of carbon dioxide is: 34 ℃ of temperature, pressure 78kg/m
2, so catalyst contacts the condition that adopts and is with carbon dioxide: pressure 5-50MPa, temperature 30-100 ℃; Preferred pressure 7-30MPa, temperature 40-80 ℃.
The pressure size decision of being adopted when the level of activity that the time that the palladium catalyst of inactivation contacts with solvent, carbon dioxide is recovered by catalyst inactivation, catalyst desire, the treating capacity of decaying catalyst and operation, usually catalyst contacts 2-20 hour with solvent, preferred 2-10 hour; Catalyst contacts 2-20 hour with carbon dioxide, preferred 4-12 hour; Solvent and carbon dioxide and catalyst were generally 6-16 hour total time of contact.
This mode of operation more detailed description is as follows: will contact with solvent by isolated inactivation palladium catalyst from reaction system, dissolve part and make the compounds such as organic alcohol, aldehyde of palladium catalyst inactivation, adopt means such as centrifugal, filtration to isolate catalyst then, solvent uses through separating to reclaim.The catalyst that contains a small amount of solvent contacts in extraction kettle with carbon dioxide under overcritical or near super critical condition, be dissolved with organic carbon dioxide such as organic alcohol of making the palladium catalyst inactivation, aldehyde and be depressurized to 1-6MPa by turbine expansion device or pressure-reducing valve, isolated organic matter is discharged from the separating still bottom in the gas-liquid separation still.Because the pressure reduction can cause temperature to descend, lower and guarantee that organic matter does not solidify to organic matter solubility when separating for guaranteeing fluid, need temperature is increased to 30-50 ℃ through heat exchanger.The compressed machine of low-pressure fluid after the separation and through heat exchanger and the cooling after, enter the carbon dioxide storage tank and recycle.Can mend at any time into a certain amount of carbon dioxide according to circumstances in the carbon dioxide storage tank.
The carrier of the load type palladium catalyst that renovation process of the present invention is suitable for can be selected from various porous inorganic oxides, as silica, aluminium oxide, titanium oxide, active carbon, zeolite etc.Such load type palladium catalyst is to be used for the unsaturation organic compound, the palladium catalyst that comprises the hydrogenation process of the nuclear of aromatic hydrocarbons in alkene, ketone, aldehydes, especially the aromatic carboxylic acids class for example is used for the catalyst for reaction such as hydrogenation of hydrofinishing, aliphatic unsaturated carboxylic acid or its ester of hydrogenation, the terephthalic acid (TPA) of benzoic acid or substituted benzoic acid.Wherein the hydrogenation reaction of said substituted benzoic acid typically has C
1-C
5The benzoic acid hydrogenation that alkyl replaces prepares C
1-C
5The naphthenic acid that alkyl replaces, isopropyl acid or to the reaction of ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid.
Before adopting renovation process provided by the invention, should at first palladium catalyst be separated from the hydrogenation reaction system, that is: the separation of by-products that produces in catalyst and unreacted unsaturation organic compound raw material, hydrogenation reaction product and the hydrogenation process be opened.
Method provided by the invention can make owing to the interaction between organic matter and load type palladium catalyst has reduced active palladium catalyst to be recovered effectively, especially to those active reduce by 70% or lower palladium catalyst recovery effects more obvious.
The specific embodiment
The following examples will be described further method provided by the invention, but not thereby limiting the invention.
The palladium catalyst of inactivation that is used for following examples is from the inactivation palladium/activated-carbon catalyst in the benzoic acid hydrogenation industrial process.The activity of fresh palladium carbon catalyst is decided to be 1.0, and the relative activity of decaying catalyst is 0.19, and the latter's activity reduces about 80%.
Embodiment 1-5
These embodiment have illustrated the regeneration effect of toluene-carbon dioxide to catalyst.
500g has been reduced active palladium carbon catalyst, and to place volume be the container of 1 liter, adds toluene (Shijiazhuang Oil Refinery product, chemical pure) by 1: 1 weight ratio then, and temperature remains on 40-80 ℃, stirs after 4 hours, leaches toluene.
To place volume with the palladium carbon catalyst after toluene contacts is the airtight extraction kettle of 1 liter, liquid carbon dioxide from the liquid carbon dioxide steel cylinder pressurizes through high-pressure metering pump, order is by high-pressure buffer still, extraction kettle, one-level pressure-reducing valve, second depressurized valve, separating still, after wet flow indicator metering emptying.Liquid carbon dioxide cools off extraction kettle then with the flow continuous extraction of 8NL/ (hkgCat) 8 hours under different separately temperature, pressure.The palladium carbon catalyst that takes out in the extraction kettle is carried out activity rating, and its evaluation result is listed in table 1.
Evaluation for regeneration effect is to illustrate by the benzoic acid hydrogenation effect of estimating Pd/carbon catalyst.The hydrogenation effect is with Z
0Value representation, it is the activity characterization of Pd/carbon catalyst, the hydrogen-absorption speed of representation unit time catalyst.Usually the depletion rate according to beginning hydrogen calculates.
Z
0The assay method of value can be with reference to described in " caprolactam device analysis method compilation " (chemical fibre Co., Ltd in Shijiazhuang writes).Basic step is: get Pd/carbon catalyst 2g and place autoclave, add the 200g benzoic acid again, with high purity nitrogen displacement 3-4 time, begin heating when filling nitrogen to 20 atmospheric pressure, with High Purity Hydrogen displacement 3-4 time, fill hydrogen to 110 atmospheric pressure during to 150 ℃, start stirring and pick up counting simultaneously, when reducing to 90 atmospheric pressure, recording reacting time and reaction temperature.Fill simultaneously hydrogen to 110 atmospheric pressure rapidly, according to identical method, repetitive operation repeatedly, and continuation recording reacting time (reducing to 90 atmospheric pressure) from 110 atmospheric pressure, catalyst sample is finished circular response usually 7 times, utilizes γ=Δ P/ Δ t formula to calculate the wear rate of hydrogen, is abscissa with time, γ is ordinate mapping, is the hydrogen consumption speed γ of beginning with the ordinate intersection point
0, catalyst activity is Z
0=γ
0/ 4.
Table 1
| Embodiment | Toluene contact temperature ℃ | The carbon dioxide contact conditions | ????Z 0 | ||
| Temperature, ℃ | Pressure MPa | ????CO 2Flow NL/ (hkgCat) | |||
| ????1 ????2 ????3 ????4 ????5 | ????40 ????40 ????60 ????60 ????80 | ????60 ????80 ????80 ????100 ????80 | ????15 ????15 ????25 ????25 ????25 | ????8 ????8 ????8 ????8 ????8 | ????0.64 ????0.68 ????0.76 ????0.78 ????0.80 |
Embodiment 6-9
These embodiment have illustrated the regeneration effect of carrene-carbon dioxide to catalyst.
500g has been reduced active palladium carbon catalyst, and to place volume be the container of 1 liter, adds carrene (great crane chemical industry Co., Ltd product, chemical pure) by 1: 1 weight ratio then, and temperature remains on 40-60 ℃, stirs after 4 hours, leaches carrene.
To place volume with the palladium carbon catalyst after carrene contacts is the airtight extraction kettle of 1 liter, liquid carbon dioxide from the liquid carbon dioxide steel cylinder pressurizes through high-pressure metering pump, order is by high-pressure buffer still, extraction kettle, one-level pressure-reducing valve, second depressurized valve, separating still, after wet flow indicator metering emptying.Liquid carbon dioxide cools off extraction kettle then with the flow continuous extraction of 8NL/ (hkgCat) 8 hours under different separately temperature, pressure.The palladium carbon catalyst that takes out in the extraction kettle is carried out activity rating according to the method for embodiment 1-5, and its evaluation result is listed in table 2.
Embodiment 10-15
These embodiment have illustrated the regeneration effect of solvent-carbon dioxide provided by the invention to catalyst.
500g has been reduced active palladium carbon catalyst, and to place volume be the airtight extraction kettle of 1 liter, liquid carbon dioxide from the liquid carbon dioxide steel cylinder, pressurize through high-pressure metering pump, the solvent of carrying secretly from another high-pressure metering pump passes through high-pressure buffer still, extraction kettle, one-level pressure-reducing valve, second depressurized valve, separating still in proper order, after wet flow indicator metering emptying.Solvent-carbon dioxide, cools off extraction kettle 15MPa, 80 ℃ of following continuous extractions 8 hours then with the flow of 8NL/ (hkgCat).The palladium carbon catalyst that takes out in the extraction kettle is carried out activity rating according to the method for embodiment 1-5, and its evaluation result is listed in table 3.
Table 2
| Embodiment | Carrene contact temperature ℃ | The carbon dioxide contact conditions | ????Z 0 | ||
| Temperature, ℃ | Pressure MPa | ???CO 2Flow NL/ (hkgCat) | |||
| ????6 ????7 ????8 ????9 | ????40 ????40 ????60 ????60 | ????60 ????80 ????80 ????80 | ????15 ????15 ????15 ????25 | ????8 ????8 ????8 ????8 | ????0.63 ????0.67 ????0.76 ????0.80 |
Table 3
| Embodiment | Solvent species | Solvent: carbon dioxide (weight ratio) | ????Z 0 |
| ????10 ????11 ????12 ????13 ????14 ????15 | Toluene carrene n-hexane cyclohexane dichloroethanes ethanol | ????1∶20 ????1∶20 ????1∶20 ????1∶20 ????1∶20 ????1∶20 | ????0.90 ????0.86 ????0.62 ????0.65 ????0.76 ????0.67 |
Claims (14)
1, a kind of renovation process of load type palladium catalyst, comprise will be in the unsaturation organic compound hydrogenation reaction active palladium catalyst that has reduced and be selected from toluene, benzene, n-hexane, carrene, dichloroethanes, one or more organic solvents and carbon dioxide are 1 according to the weight ratio of solvent and carbon dioxide in ethanol and the cyclohexane: 1-1: 100 consumption, at 5-50MPa, under 30-100 ℃ the condition intermittently or contact 2-16 hour continuously, be depressurized to 1-6MPa with organic solvent and carbon dioxide after palladium catalyst contacts, be warming up to 30-50 ℃ and separate, isolated solvent and carbon dioxide recycle respectively.
2, according to the process of claim 1 wherein that said palladium catalyst and the solvent-carbon dioxide weight ratio according to solvent and carbon dioxide is 1: 20-1: 50 consumption, contact is 4-12 hour under 7-30MPa, 40-80 ℃ condition.
3, when the process of claim 1 wherein that said contact is intermittently operated, the 1-20 that the consumption of solvent-carbon dioxide should be palladium catalyst weight doubly; During continued operation, the flow of solvent-carbon dioxide is 1-30NL/ (hkgCat).
4, according to the method for claim 3, when wherein said contact was intermittently operated, the consumption of solvent-carbon dioxide should be 2-10 times of palladium catalyst weight; During continued operation, the flow of solvent-carbon dioxide is 2-20NL/ (hkgCat).
5, a kind of renovation process of load type palladium catalyst, one or more organic solvents are at normal pressure, room temperature to 100 ℃ following intermittence or contact 2-20 hour continuously in comprising will be in the unsaturation organic compound hydrogenation reaction active palladium catalyst that has reduced and being selected from toluene, benzene, n-hexane, carrene, dichloroethanes, ethanol and cyclohexane, and isolated solvent recycles; Isolated catalyst again with carbon dioxide under 5-50MPa, 30-100 ℃ condition intermittently or contact 2-20 hour continuously, be depressurized to 1-6MPa, be warming up to 30-50 ℃ with carbon dioxide after catalyst contact, after separation, carbon dioxide recycles.
6, according to the method for claim 5, wherein said catalyst is to contact 2-10 hour under 30-50 ℃ with solvent in temperature.
7, according to the method for claim 5, when wherein said catalyst was intermittently operated with contacting of solvent, the consumption of solvent should be 0.5-10 times of palladium catalyst weight; When continued operation, the flow of solvent is 0.1-1.0NL/ (hkgCat).
8, according to the method for claim 7, when wherein said catalyst was intermittently operated with contacting of solvent, the consumption of solvent should be 1-4 times of palladium catalyst weight; When continued operation, the flow of solvent is 0.2-0.5NL/ (hkgCat).
9, according to the method for claim 5, wherein said catalyst contacts 4-12 hour with carbon dioxide under pressure 7-30MPa, temperature 40-80 ℃.
10, according to the method for claim 5, when wherein said catalyst was intermittently operated with contacting of carbon dioxide, the consumption of carbon dioxide should be 1-15 times of palladium catalyst weight; When continued operation, the flow of carbon dioxide is 1-30NL/ (hkgCat).
11, according to the method for claim 10, when wherein said catalyst was intermittently operated with contacting of carbon dioxide, the consumption of carbon dioxide should be 2-10 times of palladium catalyst weight; When continued operation, the flow of carbon dioxide is 2-15NL/ (hkgCat).
12, according to the method for claim 1 or 5, wherein the carrier of said load type palladium catalyst is the porous inorganic oxide that comprises silica, aluminium oxide, titanium oxide, active carbon, zeolite.
13, according to the method for claim 1 or 5, wherein said unsaturation organic compound hydrogenation reaction is the hydrogenation reaction of benzoic acid or substituted benzoic acid.
14, according to the method for claim 13, wherein the hydrogenation reaction of said substituted benzoic acid is C
1-C
5The benzoic acid hydrogenation that alkyl replaces prepares C
1-C
5The reaction of the naphthenic acid that alkyl replaces, isopropyl acid or to the reaction of ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03122844 CN1261223C (en) | 2003-04-29 | 2003-04-29 | Method for regenerating a palladium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03122844 CN1261223C (en) | 2003-04-29 | 2003-04-29 | Method for regenerating a palladium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1541769A true CN1541769A (en) | 2004-11-03 |
| CN1261223C CN1261223C (en) | 2006-06-28 |
Family
ID=34321124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03122844 Expired - Lifetime CN1261223C (en) | 2003-04-29 | 2003-04-29 | Method for regenerating a palladium catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261223C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355718C (en) * | 2005-09-21 | 2007-12-19 | 扬子石油化工股份有限公司 | Regeneration method of catalyst of hydrofinishing terephthalic acid |
| CN101760627B (en) * | 2008-12-24 | 2012-08-22 | 中国石油化工股份有限公司 | Method for recovering noble metal in waste noble metal catalysts |
| CN103691452A (en) * | 2013-12-23 | 2014-04-02 | 江西汉氏铂业有限公司 | Activating method of inactive platinum/palladium catalyst |
| WO2015138129A1 (en) * | 2014-03-12 | 2015-09-17 | Dow Global Technologies Llc | Process for regenerating catalyst used in hydrogenation of aromatic epoxides |
| CN105032503B (en) * | 2015-05-13 | 2018-01-30 | 辽宁石油化工大学 | A kind of renovation process of noble metal catalyst |
| CN111111790A (en) * | 2019-12-30 | 2020-05-08 | 新乡中新化工有限责任公司 | Activation method of catalyst for preparing oxalate through CO coupling |
-
2003
- 2003-04-29 CN CN 03122844 patent/CN1261223C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355718C (en) * | 2005-09-21 | 2007-12-19 | 扬子石油化工股份有限公司 | Regeneration method of catalyst of hydrofinishing terephthalic acid |
| CN101760627B (en) * | 2008-12-24 | 2012-08-22 | 中国石油化工股份有限公司 | Method for recovering noble metal in waste noble metal catalysts |
| CN103691452A (en) * | 2013-12-23 | 2014-04-02 | 江西汉氏铂业有限公司 | Activating method of inactive platinum/palladium catalyst |
| WO2015138129A1 (en) * | 2014-03-12 | 2015-09-17 | Dow Global Technologies Llc | Process for regenerating catalyst used in hydrogenation of aromatic epoxides |
| CN106102911A (en) * | 2014-03-12 | 2016-11-09 | 陶氏环球技术有限责任公司 | Regeneration is for the method for the catalyst of hydrogenated aromatic epoxides |
| CN106102911B (en) * | 2014-03-12 | 2020-06-09 | 陶氏环球技术有限责任公司 | Process for regenerating a catalyst for the hydrogenation of aromatic epoxides |
| CN105032503B (en) * | 2015-05-13 | 2018-01-30 | 辽宁石油化工大学 | A kind of renovation process of noble metal catalyst |
| CN111111790A (en) * | 2019-12-30 | 2020-05-08 | 新乡中新化工有限责任公司 | Activation method of catalyst for preparing oxalate through CO coupling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1261223C (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Anderson et al. | Heterogeneously catalysed selective hydrogenation reactions in ionic liquids | |
| CN1261223C (en) | Method for regenerating a palladium catalyst | |
| Cimpeanu et al. | Preparation of rhodium nanoparticles in carbon dioxide induced ionic liquids and their application to selective hydrogenation | |
| TWI462874B (en) | Method for manufacturing hyorogen peroxide | |
| Tilloy et al. | Cyclodextrins as inverse phase transfer catalysts for the biphasic catalytic hydrogenation of aldehydes: a green and easy alternative to conventional mass transfer promoters | |
| KR20070075282A (en) | Liquid-phase (amm)oxidation process | |
| CN1276794C (en) | Reactivation method of loading type palladium catalyst | |
| CN103964997A (en) | Treatment method for butylene oxydehydrogenation products | |
| CN1071734C (en) | Method for processing the mixture from cyclohexane oxidation | |
| CN1162390C (en) | Ethylene recovery system | |
| KR100271507B1 (en) | Method for reactivating ruthenium catalyst | |
| EP1268383A1 (en) | Catalytic oxidation of organic substrates by transition metal complexes in organic solvent media expanded by supercritical or subcritical carbon dioxide | |
| CN1762600A (en) | A kind of method of reproducing catalyst by supercritical fluid | |
| Salminen et al. | Alkaline modifiers as performance boosters in citral hydrogenation over supported ionic liquid catalysts (SILCAs) | |
| Bogel-Łukasik et al. | Study on selectivity of β-myrcene hydrogenation in high-pressure carbon dioxide catalysed by noble metal catalysts | |
| JP5016920B2 (en) | Process for producing α, β-unsaturated carboxylic acid | |
| CN100395030C (en) | Process for reproducing catalyst by supercritical fluid | |
| JPH01159059A (en) | Recovering method for activity of catalyst | |
| CN101036887A (en) | Load type nano-au catalyst and the preparing method | |
| CN1253950A (en) | Production method of d, 1-alpha-tocopherol | |
| CN101463102A (en) | Hydrogenation of diene-based polymers | |
| CN106102911B (en) | Process for regenerating a catalyst for the hydrogenation of aromatic epoxides | |
| Jessop | Homogeneous catalysis and catalyst recovery using supercritical carbon dioxide and ionic liquids | |
| US8779210B2 (en) | Process for the treatment of an aqueous mixture comprising a dipolar aprotic compound | |
| CN114479914A (en) | Method for removing oxygen-containing compounds in Fischer-Tropsch synthetic oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060628 |
|
| CX01 | Expiry of patent term |