CN1276794C - Reactivation method of loading type palladium catalyst - Google Patents
Reactivation method of loading type palladium catalyst Download PDFInfo
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- CN1276794C CN1276794C CN 03122845 CN03122845A CN1276794C CN 1276794 C CN1276794 C CN 1276794C CN 03122845 CN03122845 CN 03122845 CN 03122845 A CN03122845 A CN 03122845A CN 1276794 C CN1276794 C CN 1276794C
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- palladium catalyst
- carbon dioxide
- catalyst
- benzoic acid
- hydrogenation
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Abstract
The present invention relates to a reactivation method of a loading type palladium catalyst, which comprises the following steps that: a palladium catalyst, the activity of which is reduced in the nonsaturnated organic compound hydrogenation reaction intermittently and continuously contacts carbon dioxide for 2 to 20 hours under the conditions that the temperature is from 30 to 100 DEG C and the pressure is from 5 to 50MPa; after the carbon dioxide contacts the palladium, catalyst is depressurized to be from 1 to 6MPa, and the temperature of the carbon dioxide is increased to be from 30 to 50 DEG C; after organic substances are separated, the organic substances enter a carbon dioxide storage tank and are circularly used. The method provided by the present invention can effectively recover the activity of the palladium catalyst, which is reduced because of the interaction of the organic substances and the loading type palladium catalyst, and especially has obvious recovery effect to a palladium catalyst the activity is reduced by 70% or by more than 70%.
Description
Technical field
The invention relates to a kind of method that makes the load type palladium catalyst reactivation, more specifically, is the process for reactivation 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 process for reactivation 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 carbon dioxide under the overcritical situation, and organic molecule can rapid diffusion in supercritical solvent and can separate and enrichment by decompression or alternating temperature operation at an easy rate.
The process for reactivation of load type palladium catalyst provided by the invention is with the active load type palladium catalyst that has reduced in unsaturation organic compound hydrogenation reaction and carbon dioxide intermittence or contact 2-20 hour continuously under 5-50MPa, 60-100 ℃ condition, be depressurized to 1-6MPa with the carbon dioxide after palladium catalyst contacts, be warming up to 30-50 ℃, after isolating organic matter, enter the carbon dioxide storage tank and recycle.
The carrier of the load type palladium catalyst that the inventive method 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 process for reactivation 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.
Process for reactivation provided by the present invention can intermittently operated, also can continued operation; Can under postcritical condition, 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: temperature 60-100 ℃, pressure 5-50MPa; Preferred temperature 60-80 ℃, pressure 7-30MPa.
Overcritical or the near supercritical pressure size decision of being adopted when the level of activity that the time that the palladium catalyst of inactivation contacts with overcritical or near supercritical carbon dioxide is recovered by catalyst inactivation, catalyst desire, the treating capacity of decaying catalyst and operation, normally 2-20 hour, preferred 4-10 hour.When intermittently operated, the consumption of carbon dioxide should be 1-20 times of palladium catalyst weight, and preferred 2-10 doubly.When continued operation, the flow of supercritical carbon dioxide is 1-30NL/ (hkgCat), preferred 2-20NL/ (hkgCat).
The more detailed mode of operation of the inventive method is described below: will contact in extraction kettle under above-mentioned overcritical or near super critical condition with carbon dioxide by isolated inactivation palladium catalyst from reaction system.Be dissolved with organic 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, minimum to organic matter solubility when separating for guaranteeing fluid, need temperature to be 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.
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 that process for reactivation provided by the invention can implement under different pressures.
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 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 80 ℃ of following continuous extractions 8 hours then with the flow of 8NL/ (hkgCat) under different separately 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.
For the reactivation Evaluation on effect is to illustrate by the benzoic acid hydrogenation effect of estimating the Pd/C catalyst.The hydrogenation effect is with Z
0Value representation, it is that the Pd/C activity of such catalysts characterizes 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/C 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
| Numbering | Super critical condition | Z 0 | ||
| Temperature, ℃ | Pressure, MPa | CO 2，NL/(h· kgCat) | ||
| Before 5 fresh doses of reactivations of embodiment 1 embodiment, 2 embodiment 3 embodiment, 4 embodiment | 80 80 80 80 80 | 7 10 15 20 30 | 8 8 8 8 8 | 0.50 0.60 0.71 0.72 0.74 1.00 0.19 |
Embodiment 6-10
These embodiment have illustrated that process for reactivation provided by the invention can implement under different temperatures.
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 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., then extraction kettle is cooled off with the continuous extraction 8 hours under 15MPa of the flow of 8NL/ (hkgCat) at liquid carbon dioxide under the different separately temperature.The palladium carbon catalyst that takes out in the extraction kettle is carried out activity rating according to the described method of embodiment 1-5, and its evaluation result is listed in table 2.
Table 2
| Numbering | Super critical condition | Z 0 | ||
| Temperature, ℃ | Pressure, MPa | CO 2，NL/(h· kgCat) | ||
| Embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 | 40 50 60 80 100 | 15 15 15 15 15 | 8 8 8 8 8 | 0.40 0.45 0.60 0.71 0.73 |
Embodiment 11-13
These embodiment illustrate that process for reactivation provided by the invention can implement under different carbon dioxide flows.
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 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.Under different separately flow of liquid carbon dioxide amounts,, then extraction kettle is cooled off 15MPa, 80 ℃ of following continuous extractions 8 hours.The palladium carbon catalyst that takes out in the extraction kettle is carried out activity rating, and its evaluation result is listed in table 3.
Table 3
| Numbering | Super critical condition | Z 0 | ||
| Temperature, ℃ | Pressure, MPa | CO 2，NL/(h· kgCat) | ||
| Embodiment 11 embodiment 12 embodiment 13 | 80 80 80 | 15 15 15 | 2 5 8 | 0.50 0.65 0.71 |
Claims (9)
1, a kind of process for reactivation that is used for the load type palladium catalyst of benzoic acid or substituted benzoic acid hydrogenation reaction, comprise will be in benzoic acid or the substituted benzoic acid hydrogenation reaction active palladium catalyst that has reduced and carbon dioxide intermittence or contact 2-20 hour continuously under 60-100 ℃, the condition of 5-50MPa, the carrier of said load type palladium catalyst is an active carbon.
2, according to the process of claim 1 wherein that 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.
3, according to the process of claim 1 wherein that the hydrogenation reaction of said substituted benzoic acid is an isopropyl acid hydrogenation preparing isopropyl cyclohexane formic acid or to the reaction of ethyl benzoate hydrogenation preparing ethyl cyclohexane formic acid.
4, according to the process of claim 1 wherein that said palladium catalyst and carbon dioxide contact 4-10 hour under temperature 60-80 ℃, the condition of pressure 7-30MPa.
5, when the process of claim 1 wherein that said contact is intermittently operated, the consumption of carbon dioxide be palladium catalyst weight 1-20 doubly.
6, according to the method for claim 5, wherein the consumption of said carbon dioxide be palladium catalyst weight 2-10 doubly.
7, when the process of claim 1 wherein that said contact is continued operation, the flow of carbon dioxide is 1-30NL/ (hkgCat).
8, according to the method for claim 7, wherein the flow of said carbon dioxide is 2-20NL/ (hkgCat).
9, according to the process of claim 1 wherein that carbon dioxide said and after palladium catalyst contacts is depressurized to 1-6MPa, is warming up to 30-50 ℃, recycles after isolating organic matter.
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| CN 03122845 CN1276794C (en) | 2003-04-29 | 2003-04-29 | Reactivation method of loading type palladium catalyst |
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| CN 03122845 CN1276794C (en) | 2003-04-29 | 2003-04-29 | Reactivation method of loading type palladium catalyst |
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| CN1276794C true CN1276794C (en) | 2006-09-27 |
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Families Citing this family (4)
| 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 |
| CN100453176C (en) * | 2007-03-16 | 2009-01-21 | 中国石化扬子石油化工有限公司 | Method for reactivating deactivated palladium/carbon catalyst |
| CN100423835C (en) * | 2007-03-16 | 2008-10-08 | 中国石化扬子石油化工有限公司 | Method for reactivating palledium/carbon catalyst |
| CN114377429A (en) * | 2021-12-24 | 2022-04-22 | 陕西聚泰新材料科技有限公司 | Process for removing organic matters and/or elemental sulfur from supported waste catalyst |
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Granted publication date: 20060927 |