CN1436595A - Prepn process of Pd/C loaded noble metal catalyst - Google Patents
Prepn process of Pd/C loaded noble metal catalyst Download PDFInfo
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- CN1436595A CN1436595A CN 02148508 CN02148508A CN1436595A CN 1436595 A CN1436595 A CN 1436595A CN 02148508 CN02148508 CN 02148508 CN 02148508 A CN02148508 A CN 02148508A CN 1436595 A CN1436595 A CN 1436595A
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Abstract
The present invention belongs to the field of catalyst technology, and is especially related to the preparation process of Pd/C loaded noble metal catalyst for hydrofining terephthalic acid. By means of adding oxidant into soaking liquid in advance, the preparation process can control the homogeneous distribution of metal Pd on the surface of the carrier and avoid the direct reduction of carrier to the noble metal during adsorption. The catalyst thus prepared has Pd distributed homogeneously on the outer surface of the active carbon carrier, no direct reduction of Pd during adsorption and obviously raised catalyst activity.
Description
Technical field: the invention belongs to catalysis technical field, be specifically related to the preparation method of the c loaded noble metal catalyst of a kind of hydrogenation that is used for all kinds of organic compounds of industries such as petrochemical industry, pharmacy, certain embodiments, be specially adapted to the hydrorefined particle palladium/carbon catalyst of crude terephthalic acid.
Background technology: well-known, adopt appropriate catalyst, by the mode of hydrogenation, can make with extra care crude terephthalic acid, hydrogenation is an approach the easiest that removes from crude terephthalic acid carboxyl benzaldehyde (4-CBA) impurity.The present invention mainly is at improving Preparation of catalysts technology, by adding the mode of oxidant, make the surface of Metal Palladium uniform deposition at the granulated carbon carrier, Zhi Bei catalyst is hydrogenated in the process of p-methylbenzoic acid at 4-CBA like this, has improved activity and selectivity.
Catalyst is by the Metal Palladium of group VIII in the periodic table of elements, be deposited on the absorbent charcoal carrier and make, this catalyst is applied in many hydrogenation reactions, common preparation method be with carrier impregnation in the salting liquid that contains the group VIII metal, reduce it then for the metal phase.Improve catalyst and mainly be to improve activity of such catalysts, rather than the raising of the hydrogenation selectivity of customizations compound.
The same with other loaded catalyst, the activity that loads on the group VIII metallic catalyst on the carrier is relevant with many factors with selectivity, as the consumption of metal, and the type of carrier, preparation method, i.e. the group VIII metal method that on carrier, deposits or disperse.
The preparation method of relevant carbon load group VIII metallic catalyst, more existing abroad reports, mainly contain following some: the mode of (1), direct impregnation absorption.As having introduced a kind of production technology among the US 2857337, palladium salt is handled with water miscible metal hydroxides or subcarbonate, is reduced to Metal Palladium by reducing agent again, and reducing agent has formaldehyde, glucose, hydrazine, glycerine etc.People such as Keith introduce in US 3138560, and tetrachloro-palladium acid sodium or palladium bichloride are added drop-wise on the carbon carrier, and most of palladium is deposited as glossiness Metal Palladium film immediately, and the catalyst activity of this method preparation is lower.Theoretically, this is that palladium salt directly is reduced into the cause of Metal Palladium by existing functional group such as aldehyde radical or free electron on the activated carbon surface, thereby causes metal migration and grain growth, so the catalyst that adopts this mode to prepare, specific activity is relatively poor, and unstable.(2), add the mode of solvent.Ohara mentions a kind of method for preparing platinum catalyst in US 3953369, add high molecular surfactant, prevents that platinum from entering in the carrier hole, so that obtain highly active catalyst.People such as Dale introduce in US 4256609, by adding the preparation method that organic solvent improves catalyst activity.Mentioning palladium salt in US4791226 is dissolved in the organic solvent, as methyl alcohol, acetate, MEK etc., active carbon is flooded in the organic solvent of palladium salt, palladium is adsorbed on the active carbon, and then be deposited on the carbon carrier, but the catalyst for preparing like this is difficult to absorption, and mainly be the even profile catalyst of palladium, be difficult to obtain the eggshell profile catalyst of palladium.
Any one mode above adopting, all inevitably run into a problem, the direct reduction problem of palladium when promptly adsorbing, the functional group of activated carbon surface such as aldehyde radical or free electron etc., the palladium salt that can directly reduce is palladium metal, improved mode prevents the direct reduction of palladium salt by adding oxidant.Mention the improvement preparation method of palladium-carbon catalyst among the US 3138560, by adding the mode of oxidant, as tert-butyl peroxide, persulfate, perchloric acid etc., preferred hydrogen peroxide.Can prevent that palladium from being reduced immediately by the aldehyde radical of activated carbon surface or free electron after adding oxidant like this, and problems such as metal migration and grain growth can not take place, and be easy to form the palladium layer of skim, even absorption at carrier surface.But adopt the catalyst of its preparation, in the hydrofinishing of crude terephthalic acid, catalyst activity is not high.
Summary of the invention: the objective of the invention is to improve the Preparation of catalysts method that contains the group VIII Metal Palladium, in the reduction process of 4-CBA, improve activity of such catalysts and/or selectivity; Another purpose provides a kind of catalyst, its catalytic activity palladium uniform crystal particles is deposited on the surface of absorbent charcoal carrier, Zhi Bei catalyst is in the crude terephthalic acid subtractive process like this, have higher activity and/or selectivity for the reduction of 4-CBA, and expection has longer service life.
The present invention relates to the palladium metal catalyst that is used for the hydrofinishing terephthalic acid (TPA), terephthalic acid (TPA) is applicable to polyester and the copolymer thereof of preparation in the textile fabric, and this polymer and copolymer thereof can be made by condensation terephthalic acid (TPA) and ethylene glycol and other dihydroxylic alcohols.
The invention provides a kind of improvement preparation method of catalyst, by adding oxidants hydrogen peroxide and clorox before palladium salt is by the reduction of activated carbon surface functional group, carry out hydrolysis earlier, can prevent the direct reduction of palladium salt so effectively, and the catalyst for preparing, Metal Palladium becomes uniform eggshell to distribute.Zhi Bei catalyst is in the hydrofinishing of crude terephthalic acid like this, and catalyst activity is fine.
The technology of being mentioned among the present invention, be primarily aimed at the refining terephthalic acid (TPA) that contains 4-CBA, usual way is to add oxidant to come the Immesion active carbon carrier in the palladium salting liquid, as in palladium chloride solution, adding oxidant hydrogen peroxide, clorox etc., Immesion active carbon carrier then, palladium is adsorbed on the active carbon, and then is deposited on the carbon carrier, adds reducing agent such as formaldehyde, hydrazine, glucose at last, glycerine waits and reduces.
By the catalyst of above method preparation, in crude terephthalic acid refining, be proved to be effectively can make the content of 4-CBA drop to low-down level.
The porous activated carbon carrier is that some specific areas are greater than 600m
2The granular activated carbon of/g; the particle charcoal of high-specific surface area generally comes from plant, animal or mineral matter; method of the present invention is applicable to granulated carbon; also can expand to the active carbon of spherical or other special shape; in general; absorbent charcoal carrier is the organism of plant or animal, and the most suitable is cocoanut active charcoal.
The method for preparing catalyst of being mentioned among the present invention, active carbon directly adsorb the palladium salting liquid that adds oxidant such as hydrogen peroxide and clorox, leave standstill then, add precipitating reagent again and add reduction such as reducing agent such as formaldehyde, hydrazine hydrate, glucose after precipitation a period of time.
The oxidant of Shi Yonging is hydrogen peroxide and clorox in the present invention, its concentration is that 0.01%～10% o'clock effect is better, it is more effective than using clorox separately to use hydrogen peroxide separately, but the two is used in combination, better effects if, the proportioning of the two was at 1: 1～30: 1, this mainly is because the oxidation effectiveness of hydrogen peroxide is more weak, but it helps the dispersion of palladium and eggshell to distribute, and the oxidation effectiveness of clorox is stronger, and the two is used like this, and oxidation effectiveness is good, the direct reduction of palladium in the time of can preventing to adsorb effectively, and help the even eggshell of palladium to distribute.
Catalyst activity is estimated: raise 0.5 and press in the reactor, add the 0.5g catalyst, add stainless steel mesh and isolate stirring arm and contact with catalyst, prevent that catalyst from smashing adding 30g crude terephthalic acid, its 4-CBA content 8000ppm, 270ml water, 0.3Mpa H
2, at 280 ℃ of reaction 1h, active conversion ratio with 4-CBA calculates.
The specific embodiment: the present invention is described in detail by following example:
Catalyst A: take by weighing active carbon 5.0g, absorption is 0.5% palladium salting liquid by amount of calculation palladium content, and adsorption time 2min adds the Na of 5ml 5%
2CO
3Solution adds 5ml formaldehyde reduction 4h again, filters washing, vacuum drying.
Catalyst B: take by weighing active carbon 5.0g, absorption is 0.5% palladium salting liquid by amount of calculation palladium content, only adds the hydrogen peroxide of 5ml 30% in the palladium salting liquid in advance, and adsorption time 5min adds the Na of 5ml 5%
2CO
3, add 5ml formaldehyde reduction 4h again, filter washing, vacuum drying.
Catalyst C: take by weighing active carbon 5.0g, absorption is 0.5% palladium salting liquid by amount of calculation palladium content, only adds the liquor natrii hypochloritis of 0.5ml in the palladium salting liquid in advance, and adsorption time 5min adds the Na of 5ml 5%
2CO
3Solution adds 5ml formaldehyde reduction 4h again, filters washing, vacuum drying.
Catalyst D: take by weighing active carbon 5.0g, absorption is 0.5% palladium salting liquid by amount of calculation palladium content, only adds the mixed solution of 1.5ml hydrogen peroxide with the clorox of 0.3ml in the palladium salting liquid in advance, and adsorption time 7min adds the Na of 5ml 5%
2CO
3Solution adds 5ml formaldehyde reduction 4h again, filters washing, vacuum drying.
Catalyst E: take by weighing active carbon 5.0g, absorption is 0.5% palladium salting liquid by amount of calculation palladium content, only adds the mixed solution of 15.0ml hydrogen peroxide with the clorox of 0.1ml in the palladium salting liquid in advance, and adsorption time 7min adds the Na of 5ml 1%
2CO
3Solution adds 5ml formaldehyde reduction 4h again, filters washing, vacuum drying.
Catalyst F: take by weighing active carbon 5.0g, absorption is 0.5% palladium salting liquid by amount of calculation palladium content, only adds the mixed solution of 1.0ml hydrogen peroxide with the clorox of 0.5ml in the palladium salting liquid in advance, and adsorption time 7min adds the Na of 5ml 10%
2CO
3Solution adds 5ml formaldehyde reduction 4h again, filters washing, vacuum drying.
Experimental result is listed in table 1:
Table 1 Different Preparation is to the influence of catalyst performance
| Catalyst | Surface Pd content | Catalyst P d content/% | 4-CBA conversion ratio/% |
| ????A | ?????5.43 | ?????0.32 | ????60 |
| ????B | ?????23.32 | ?????0.40 | ????68 |
| ????C | ?????13.35 | ?????0.37 | ????61 |
| ????D | ?????20.23 | ?????0.45 | ????96 |
| ????E | ?????18.79 | ?????0.43 | ????94 |
| ????F | ?????17.66 | ?????0.43 | ????93 |
From the table as can be known, add hydrogen peroxide or clorox separately, though all help to improve catalyst P d content and surperficial Pd content, but it is little to the activity of such catalysts influence, add hydrogen peroxide and clorox and mix, can not only improve catalyst surface Pd content and catalyst P d content, and can significantly improve activity of such catalysts, obviously the content that reduces.
Claims (7)
1. the preparation method of a Pd/c loaded noble metal catalyst, it is characterized in that coming the direct impregnation absorbent charcoal carrier by in the palladium salting liquid, adding the oxidant maceration extract in advance, after dipping finishes, add precipitating reagent depositing noble metal component, adding reducing agent at last reduces to it, washing, the dry finished catalyst that gets.
2. a described method as claimed in claim 1 is characterized in that oxidant is the mixture of hydrogen peroxide and clorox, and concentration is 0.01%～10%, and the proportioning of hydrogen peroxide and clorox is 1: 1～30: 1.
3. a described method as claimed in claim 1 is characterized in that oxidant is a hydrogen peroxide.
4. a described method as claimed in claim 1 is characterized in that precipitating reagent is subcarbonate or bicarbonate or alkaline earth metal hydroxide.
5. the described method as claim 1 or 4 is characterized in that precipitating reagent is a sodium carbonate, and concentration is 1%～10%.
6. a described method as claimed in claim 1 is characterized in that reducing agent is formaldehyde, hydrazine hydrate, glucose or hydrogen.
7. the described method as claim 1 or 6 is characterized in that reducing agent is a formaldehyde.
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| CN 02148508 CN1212184C (en) | 2002-12-11 | 2002-12-11 | Prepn process of Pd/C loaded noble metal catalyst |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369673C (en) * | 2006-03-21 | 2008-02-20 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
| US7622416B2 (en) | 2004-12-24 | 2009-11-24 | China Petrochemical Corporation | Hydrogenation catalyst, its preparation and use |
| CN101357333B (en) * | 2008-09-20 | 2010-06-16 | 中国日用化学工业研究院 | Pd/C catalyst for preparing alcohol ether carboxylate and production method and use thereof |
| CN101905158A (en) * | 2010-07-21 | 2010-12-08 | 中国日用化学工业研究院 | Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof |
| CN101966455A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN103007922A (en) * | 2011-09-27 | 2013-04-03 | 中国石油天然气集团公司 | Method for preparing loaded hydrofining catalyst |
| CN106179332A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of catalyst preparing 4-ADPA and preparation method |
| CN109046339A (en) * | 2018-09-03 | 2018-12-21 | 重庆理工大学 | The preparation method of Meropenem palladium-carbon catalyst |
| CN111229216A (en) * | 2018-11-29 | 2020-06-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| CN112439413A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of crude terephthalic acid hydrofining catalyst |
| CN115445607A (en) * | 2021-06-09 | 2022-12-09 | 谷育英 | Preparation method of palladium-carbon catalyst for disproportionated rosin |
| CN115555014A (en) * | 2021-07-01 | 2023-01-03 | 谷育英 | High-activity palladium-carbon catalyst and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180035550A (en) * | 2016-09-29 | 2018-04-06 | 희성금속 주식회사 | PREPARATION METOD OF Pd/C CATALYST CAPABLE OF SCALE UP |
-
2002
- 2002-12-11 CN CN 02148508 patent/CN1212184C/en not_active Expired - Lifetime
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7622416B2 (en) | 2004-12-24 | 2009-11-24 | China Petrochemical Corporation | Hydrogenation catalyst, its preparation and use |
| CN100369673C (en) * | 2006-03-21 | 2008-02-20 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
| CN101357333B (en) * | 2008-09-20 | 2010-06-16 | 中国日用化学工业研究院 | Pd/C catalyst for preparing alcohol ether carboxylate and production method and use thereof |
| CN101905158B (en) * | 2010-07-21 | 2013-04-17 | 中国日用化学工业研究院 | Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof |
| CN101905158A (en) * | 2010-07-21 | 2010-12-08 | 中国日用化学工业研究院 | Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof |
| CN101966455A (en) * | 2010-09-25 | 2011-02-09 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN101966455B (en) * | 2010-09-25 | 2012-07-04 | 郴州高鑫铂业有限公司 | Method for preparing high-selectivity palladium-carbon catalyst by attachment and precipitation process |
| CN103007922B (en) * | 2011-09-27 | 2015-01-07 | 中国石油天然气集团公司 | Method for preparing loaded hydrofining catalyst |
| CN103007922A (en) * | 2011-09-27 | 2013-04-03 | 中国石油天然气集团公司 | Method for preparing loaded hydrofining catalyst |
| CN106179332A (en) * | 2015-05-07 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of catalyst preparing 4-ADPA and preparation method |
| CN109046339A (en) * | 2018-09-03 | 2018-12-21 | 重庆理工大学 | The preparation method of Meropenem palladium-carbon catalyst |
| CN109046339B (en) * | 2018-09-03 | 2021-03-23 | 重庆理工大学 | Preparation method of palladium-carbon catalyst for meropenem |
| CN111229216A (en) * | 2018-11-29 | 2020-06-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| CN111229216B (en) * | 2018-11-29 | 2022-08-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| CN112439413A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Preparation method of crude terephthalic acid hydrofining catalyst |
| CN115445607A (en) * | 2021-06-09 | 2022-12-09 | 谷育英 | Preparation method of palladium-carbon catalyst for disproportionated rosin |
| CN115555014A (en) * | 2021-07-01 | 2023-01-03 | 谷育英 | High-activity palladium-carbon catalyst and preparation method and application thereof |
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| CN1212184C (en) | 2005-07-27 |
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