CN1698952A - Method for preparing supported palladium/carbon catalyst - Google Patents
Method for preparing supported palladium/carbon catalyst Download PDFInfo
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- CN1698952A CN1698952A CN 200410018520 CN200410018520A CN1698952A CN 1698952 A CN1698952 A CN 1698952A CN 200410018520 CN200410018520 CN 200410018520 CN 200410018520 A CN200410018520 A CN 200410018520A CN 1698952 A CN1698952 A CN 1698952A
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Abstract
This invention relates to a method for preparing a hydrogenation palladium or carbon catalyst. The catalyst uses the particles or shaping active carbon as the carrier, loading active component metal Pd, wherein the Pd content is 0.2-5wt%. The preparing method comprises the following steps: a) acid cleaning the carrier active carbon; then flushing with water until neutral; drying; b) preparing Pd solution with water-soluble Pd compound and a chelant; using Pd solution to immerse or spray the carrier active carbon, loading the Pd compound on the active carbon and then getting the catalyst prosoma, wherein the Pd compound content is 10-20wt% computed by Pd, the molecular ratio of chelant and Pd is (0.01-1):1, the chelant is any one from complexon, disodium editate, ethylene diamine tetraacetic acid tetrasodium salt, ethyl group ethanediamine triacetate, diethylene triamine pentacetic acid or amic triacetate; c) aging the catalyst prosoma, then deacidizing and getting the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the supported palladium/carbon catalyst of hydrogenation reaction, particularly be used for making with extra care the preparation method of the supported palladium/carbon catalyst of crude terephthalic acid by selective hydrogenation.
Background technology
Supported palladium/carbon catalyst is mainly used in the selective hydrogenation of unsaturated compounds, be particularly useful for the refining of crude terephthalic acid, in the crude terephthalic acid impurity such as carboxyl benzaldehyde (be called for short 4-CBA) are changed into other compound after by hydrogenation, separate purification with regard to the method for available crystallization subsequently.Because palladium/carbon catalyst usually adopts single active constituent, in the prior art its improvement research is concentrated on always the structure and the distribution situation of metal Pd on carrier of carrier, and this can produce very big influence to the performance of catalyst really.
Because terephthalic acid (TPA) hydrofining reaction process is a first order reaction, reaction speed is fast, react the inside that reactant is difficult to be penetrated into catalyst granules in the course of reaction, this just makes the active component of granule interior not play a role, for the consideration that makes full use of noble metal, usually palladium/carbon catalyst is made eggshell type, promptly allows the basic load of active constituent noble metal in the surface of carrier.
Because hydrogenation reaction is to carry out on the surface of metal Pd, therefore usually for the identical catalyst of metal Pd load capacity, the decentralization of its metal Pd is higher, or the content of crystallite of the metal Pd of load is higher in the catalyst, activity of such catalysts is just higher, and service life is also longer.
If directly will contain Pd compound (as chlorine palladium acid sodium or palladium bichloride) loads on the active carbon, activated carbon surface can the very thin glossiness metal Pd layer of very fast appearance, this mainly is because activated carbon surface contains just like reduction groups such as aldehyde radical, free electrons, very easily make the Pd ion be reduced into the metal Pd of zeroth order, thereby the decentralization of metal Pd is very low in the catalyst that causes making.According to experience in the past, the Pd ion that will contain before the operation in the maceration extract of Pd compound in reduction is transformed into the effect that insoluble compound can be obtained, as at room temperature the water soluble compound hydrolysis of Pd being changed into insoluble Pd (OH)
2Or PdOH
2Load on again after 0 on the active carbon,, can prevent migration and the grain growth of Pd so subsequently with the reduction of reducing agents such as formaldehyde, sodium formate, glucose, formic acid or hydrogen.As U.S. Pat 3,138,560 are introduced, and it adds hydrogen peroxide in maceration extract makes the water soluble compound hydrolysis of Pd generate insoluble compound.But because hydrogen peroxide itself also has oxidisability, it can be with the activated carbon surface radical oxidation, thereby will change the Surface Physical Chemistry character of carrier, promptly change the surface group structure of carrier, this has stronger uncertain negative effect, can damage other performance of catalyst, as carrying palladium intensity, catalyst life, selectivity etc.U.S. Pat 4; 476; the maceration extract that contains the Pd compound is prepared in 242 propositions with organic solvents such as methyl alcohol or pyridines; it is said that this is also very effective to the migration and the grain growth that prevent Pd; but production process use methyl alcohol or pyridine are this in human body harmful's organic compound, all are disadvantageous from ring environment protection or labour protection.In addition, there is patent report chlorine palladium acid solution to be transformed into the palladium glue by adjusting pH value, allegedly can prevent that also the reduction group of activated carbon surface directly is reduced into the Pd ion metal Pd of zeroth order, but glue stability is bad, be difficult to even distribution on carrier active carbon, this can influence the dispersiveness of Pd equally.
Summary of the invention
The invention provides a kind of preparation method who is used for the palladium/carbon catalyst of hydrogenation, its technical problem to be solved is to make that metal Pd has higher decentralization and content of crystallite in the catalyst that makes, and can overcome existing with the existing defective of class methods simultaneously again.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of preparation method who is used for the palladium/carbon catalyst of hydrogenation, catalyst is a carrier with particle or pressed active carbon, supported active component metal Pd, the content of metal Pd is 0.2～5wt% in the catalyst, the preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle is 0.1～5N, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) it is dry that carrier active carbon is washed with water to neutral back;
3) be mixed with Pd solution with the water-soluble Pd of containing compound and a kind of intercalating agent and water, with Pd solution impregnation or sprinkling carrier active carbon, make and contain that Pd is compound loaded to obtain catalyst precarsor in active carbon, the content that contains the Pd compound in the Pd solution is counted 10～20wt% with Pd, the mol ratio of intercalating agent and Pd is (0.01～1): 1, and intercalating agent is taken from any in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, ethyl-3-acetic acid ethylenediamine, diethylenetriaminepeacidcetic acidcetic or the amine triacetic acid;
4) catalyst precarsor reduces processing with reducing agent after aging, makes divalence Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
The above-mentioned steps 3 described Pd of containing compounds can be taken from any in the complex of the basic salt of halide, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium of Pd or palladium ammonia, yet are preferably acid of chlorine palladium or palladium.
Above-mentioned steps 4 described reducing agents can be taken from any in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen, yet are preferably sodium formate.
In step 3, the addition of intercalating agent changes to some extent according to the used difference that contains Pd compound and intercalating agent in the Pd solution, but the mol ratio at intercalating agent and Pd is (0.01～1) usually: all be feasible in 1 the scope, yet the mol ratio of intercalating agent and Pd is preferably (0.05～0.6): 1.
In said method, add during except that the preparation of Pd solution the intercalating agent, other parts are then basic identical with existing general palladium/carbon catalyst preparation method, and these preparation process are that those skilled in the art are known.
Below concrete preparation process only be that the present invention recommends.
Select suitable active carbon for use, remove the dust and surface porosity part of carbon surface absorption after, in the washing still, carry out pickling.Spend deionised water after the pickling to neutral.
Get and contain the Pd compound and required intercalating agent water is mixed with Pd solution, adopt methods such as dipping or sprinkling to make then and contain the compound loaded catalyst precarsor that on carrier, makes of Pd, then with catalyst precarsor in air aging 1～24 hour.
Catalyst precarsor after aging is handled with the reducing agent reduction, and reduction temperature is 0～200 ℃, and the best is 50～120 ℃.The consumption of reducing agent depends on the dosage of active constituent Pd, is generally 1～10 times of reduction reaction equivalent, is preferably 2～5 times, and the recovery time is 1～10 hour, and the best is 1～4 hour.
Key of the present invention has added intercalating agent when being the preparation of Pd solution, intercalating agent can produce stronger interaction and generate a kind of huge legendary turtle compound with Pd, so can reduce the redox potential of Pd, when Pd loads on the active carbon, the Pd ion just can not reduced by the activated carbon surface group, thereby the Pd ion can be distributed in activated carbon surface very equably.
Compared with prior art, the invention has the advantages that metal Pd has higher decentralization in the catalyst that makes, content of crystallite is higher, on serviceability, show active high, long service life, and the step that increases in the preparation process is very simple, the raw material that adopts is easy to environmental protection treatment, and the method that adopts can not produce any negative effect to catalyst.
Below will the invention will be further described by specific embodiment, because other parts of the present invention are basic identical with prior art, so embodiment will pay attention to the kind of intercalating agent and giving an example of consumption.In an embodiment:
The measuring method of content of crystallite:
Record the Metal Palladium particle diameter by X-XRF and x-ray diffractometer (XRD), calculate content of crystallite by following formula then:
The activity of such catalysts appreciation condition:
Catalyst consumption: 2.0g
Thick paraxylene amount: 30.0g
4-CBA amount: 1.0g
Reaction pressure: 70 kilograms
Hydrogen partial pressure: 5.0 kilograms
Reaction time: 1.0 hours
Reaction temperature: 270 ℃
The specific embodiment
[embodiment 1]
With 100 grams, 4～8 orders, specific surface 800～1800m
2The nitric acid washing of the cocoanut active charcoal usefulness 0.4N of/g, wash temperature is 80 ℃, washes with water then to neutrality, and is standby in 120 ℃ times dry 2～8 hours.
Chlorine palladium acid solution 3.2 gram that contains palladium 16wt% is got in the preparation of Pd solution, adds deionized water to 40 milliliter, adds the disodium ethylene diamine tetra-acetic acid aqueous solution of 0.79 milliliter of 10wt% more therein, and adds 60 milliliters of deionized water preparation Pd solution.Behind solution-stabilized 10～200 minutes of the Pd, above-mentioned treated active carbon is obtained catalyst precarsor with the Pd solution impregnation after 3 hours.Aging 24 hours of catalyst precarsor is mixed with reducing solution with hydrazine hydrate 20 grams and pure water 200 grams of 5wt%, and catalyst precarsor is immersed in the reducing solution 2～4 hours, also in addition gets catalyst prod after the drying with the pure water washing to neutral then.
[embodiment 2～16]
Select for use different to contain the Pd compound and intercalating agent is prepared Pd solution, all the other are with embodiment 1, and it is 1 listed that the concrete mol ratio that contains the content (in Pd) that contains the Pa compound in Pd compound, the Pd solution, concrete intercalating agent and intercalating agent and Pd sees Table.
[embodiment 16～20]
Select for use different to contain the Pd compound and intercalating agent is prepared Pd solution, Pd obtains catalyst precarsor with the Pd spray solution after solution-stabilized 10～200 minutes on active carbon, and all the other are with embodiment 1.
[comparative example]
Preparation Pd does not add intercalating agent during solution, and all the other are with embodiment 1.
It is 1 listed that the concrete mol ratio that contains the content (in Pd) that contains the Pd compound in Pd compound, the Pd solution, concrete intercalating agent and intercalating agent and Pd that each embodiment and comparative example adopt sees Table, the content of the catalyst metals Pd that makes see Table 2 first be listed as listed.
The catalyst that each embodiment and comparative example make carries out decentralization and content of crystallite is measured, and adopts above-mentioned activity of such catalysts appreciation condition to carry out activity rating, and it the results are shown in Table 2.
Table 1.
| The Pd compound | Intercalating agent | Pd content (wt%) in the solution | Intercalating agent/Pd (mol ratio) | |
| Embodiment 1 | The acid of chlorine palladium | Disodium ethylene diamine tetraacetate | ????0.51 | ????0.05 |
| Embodiment 2 | The acid of chlorine palladium | Disodium ethylene diamine tetraacetate | ????0.51 | ????0.30 |
| Embodiment 3 | The acid of chlorine palladium | Disodium ethylene diamine tetraacetate | ????0.22 | ????0.60 |
| Embodiment 4 | Palladium | Disodium ethylene diamine tetraacetate | ????0.51 | ????0.20 |
| Embodiment 5 | The acid of chlorine palladium | Ethyl-3-acetic acid ethylenediamine | ????0.51 | ????0.05 |
| Embodiment 6 | The acid of chlorine palladium | Ethyl-3-acetic acid ethylenediamine | ????0.51 | ????0.20 |
| Embodiment 7 | The acid of chlorine palladium | Ethyl-3-acetic acid ethylenediamine | ????0.51 | ????0.60 |
| Embodiment 8 | Palladium | Ethyl-3-acetic acid ethylenediamine | ????3.55 | ????0.30 |
| Embodiment 9 | The acid of chlorine palladium | Diethylenetriaminepeacidcetic acidcetic | ????0.51 | ????0.05 |
| Embodiment 10 | The acid of chlorine palladium | Diethylenetriaminepeacidcetic acidcetic | ????0.51 | ????0.20 |
| Embodiment 11 | The acid of chlorine palladium | Diethylenetriaminepeacidcetic acidcetic | ????0.51 | ????0.60 |
| Embodiment 12 | Palladium | Diethylenetriaminepeacidcetic acidcetic | ????0.51 | ????0.30 |
| Embodiment 13 | The acid of chlorine palladium | Amine triacetic acid | ????0.51 | ????0.05 |
| Embodiment 14 | The acid of chlorine palladium | Amine triacetic acid | ????0.51 | ????0.20 |
| Embodiment 15 | The acid of chlorine palladium | Amine triacetic acid | ????0.51 | ????0.60 |
| Embodiment 16 | Palladium | Amine triacetic acid | ????0.51 | ????0.30 |
| Embodiment 17 | The acid of chlorine palladium | Disodium ethylene diamine tetraacetate | ????0.51 | ????0.20 |
| Embodiment 18 | The acid of chlorine palladium | Ethyl-3-acetic acid ethylenediamine | ????0.51 | ????0.20 |
| Embodiment 19 | The acid of chlorine palladium | Diethylenetriaminepeacidcetic acidcetic | ????0.51 | ????0.20 |
| Embodiment 20 | The acid of chlorine palladium | Amine triacetic acid | ????0.51 | ????0.20 |
| Comparative example | The acid of chlorine palladium | / | ????0.51 | ????/ |
Table 2.
| Pd content (wt%) | Decentralization (%) | Content of crystallite (%) | Conversion ratio (%) | |
| Embodiment 1 | ????0.5 | ????16 | ????77 | ????99.8 |
| Embodiment 2 | ????0.5 | ????18 | ????84 | ????99.3 |
| Embodiment 3 | ????0.2 | ????29 | ????90 | ????99.1 |
| Embodiment 4 | ????0.5 | ????26 | ????88 | ????99.9 |
| Embodiment 5 | ????0.5 | ????14 | ????80 | ????99.0 |
| Embodiment 6 | ????0.5 | ????24 | ????88 | ????99.6 |
| Embodiment 7 | ????0.5 | ????26 | ????87 | ????99.1 |
| Embodiment 8 | ????3.5 | ????15 | ????70 | ????99.0 |
| Embodiment 9 | ????0.5 | ????17 | ????81 | ????99.5 |
| Embodiment 10 | ????0.5 | ????26 | ????86 | ????99.7 |
| Embodiment 11 | ????0.5 | ????27 | ????89 | ????99.3 |
| Embodiment 12 | ????0.5 | ????15 | ????82 | ????99.0 |
| Embodiment 13 | ????0.5 | ????27 | ????89 | ????100 |
| Embodiment 14 | ????0.5 | ????29 | ????87 | ????99.8 |
| Embodiment 15 | ????0.5 | ????28 | ????87 | ????99.8 |
| Embodiment 16 | ????0.5 | ????27 | ????88 | ????99.7 |
| Embodiment 17 | ????0.5 | ????32 | ????86 | ????100 |
| Embodiment 18 | ????0.5 | ????29 | ????88 | ????99.8 |
| Embodiment 19 | ????0.5 | ????28 | ????88 | ????99.8 |
| Embodiment 20 | ????0.5 | ????27 | ????89 | ????99.6 |
| Comparative example | ????0.5 | ????3 | ????50 | ????65.6 |
Claims (6)
1, a kind of preparation method of supported palladium/carbon catalyst, catalyst is a carrier with particle or pressed active carbon, supported active component metal Pd, the content of metal Pd is 0.2～5wt% in the catalyst, the preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle is 0.1～5N, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) it is dry that carrier active carbon is washed with water to neutral back;
3) be mixed with Pd solution with the water-soluble Pd of containing compound and a kind of intercalating agent and water, with Pd solution impregnation or sprinkling carrier active carbon, make and contain that Pd is compound loaded to obtain catalyst precarsor in active carbon, the content that contains the Pd compound in the Pd solution is counted 10～20wt% with Pd, the mol ratio of intercalating agent and Pd is (0.01～1): 1, and intercalating agent is taken from any in ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, ethyl-3-acetic acid ethylenediamine, diethylenetriaminepeacidcetic acidcetic or the amine triacetic acid;
4) catalyst precarsor reduces processing with reducing agent after aging, makes divalence Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
2, the preparation method of palladium/carbon catalyst according to claim 1 is characterized in that the described Pd of the containing compound of step 3 takes from any in the complex of the basic salt of the halide of Pd, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium or palladium ammonia.
3, the preparation method of palladium/carbon catalyst according to claim 2 is characterized in that the described Pd of containing compound is acid of chlorine palladium or palladium.
4, the preparation method of palladium/carbon catalyst according to claim 1 is characterized in that the described reducing agent of step 4 takes from any in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen.
5, the preparation method of palladium/carbon catalyst according to claim 4 is characterized in that described reducing agent is a sodium formate.
6,, it is characterized in that the mol ratio of described intercalating agent of step 3 and Pd is (0.05～0.6): 1 according to the preparation method of claim 1,2,3,4 or 5 described palladium/carbon catalysts.
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|---|---|---|---|---|
| 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 |
| WO2008019582A1 (en) * | 2006-08-11 | 2008-02-21 | China Petroleum & Chemical Corporation | Supported pd/c catalyst and the preparation methodthereof |
| CN102344376A (en) * | 2011-08-17 | 2012-02-08 | 中国石油化工股份有限公司 | Method for preparing p-aminodiphenylamine |
| CN103120937A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing Pd/C catalyst for refining terephthalic acid |
| CN104254516A (en) * | 2012-03-07 | 2014-12-31 | 安格斯化学公司 | Process for the preparation of nitroalcohols |
| RU2551673C1 (en) * | 2013-12-27 | 2015-05-27 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук | Palladium-containing hydrogenation catalyst and method for producing it |
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| CN107887617A (en) * | 2016-09-30 | 2018-04-06 | 通用汽车环球科技运作有限责任公司 | In the easily-controllable property of carbon load PGM base catalyst central hole structures |
| CN108236951A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of the palladium on carbon powder as formaldehyde remover |
| CN108380208A (en) * | 2018-01-25 | 2018-08-10 | 西安凯立新材料股份有限公司 | 2,3,6- trichloropyridine catalytic hydrogenation 2,3- dichloropyridines Pd-Mg/C catalyst and preparation method |
| CN109759058A (en) * | 2019-02-27 | 2019-05-17 | 西安凯立新材料股份有限公司 | The preparation method of one-step synthesis method alkyl-cyclohexyl cyclohexanone analog liquid crystal intermediates Pd/C catalyst |
| CN109967070A (en) * | 2019-03-29 | 2019-07-05 | 华南理工大学 | A kind of activated carbon supported palladium catalyst and preparation method thereof for hydrogenation-dechlorination |
| 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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2004
- 2004-05-20 CN CN 200410018520 patent/CN1698952A/en active Pending
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| 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 |
| WO2008019582A1 (en) * | 2006-08-11 | 2008-02-21 | China Petroleum & Chemical Corporation | Supported pd/c catalyst and the preparation methodthereof |
| CN102344376A (en) * | 2011-08-17 | 2012-02-08 | 中国石油化工股份有限公司 | Method for preparing p-aminodiphenylamine |
| CN102344376B (en) * | 2011-08-17 | 2014-04-02 | 中国石油化工股份有限公司 | Method for preparing p-aminodiphenylamine |
| CN103120937A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing Pd/C catalyst for refining terephthalic acid |
| CN104254516A (en) * | 2012-03-07 | 2014-12-31 | 安格斯化学公司 | Process for the preparation of nitroalcohols |
| CN104254516B (en) * | 2012-03-07 | 2016-11-30 | 安格斯化学公司 | The preparation method of nitroalcohol |
| RU2551673C1 (en) * | 2013-12-27 | 2015-05-27 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской академии наук | Palladium-containing hydrogenation catalyst and method for producing it |
| CN107887617A (en) * | 2016-09-30 | 2018-04-06 | 通用汽车环球科技运作有限责任公司 | In the easily-controllable property of carbon load PGM base catalyst central hole structures |
| CN108236951A (en) * | 2016-12-26 | 2018-07-03 | 天津仁智科技发展有限责任公司 | A kind of preparation method of the palladium on carbon powder as formaldehyde remover |
| CN108380208A (en) * | 2018-01-25 | 2018-08-10 | 西安凯立新材料股份有限公司 | 2,3,6- trichloropyridine catalytic hydrogenation 2,3- dichloropyridines Pd-Mg/C catalyst and preparation method |
| CN108380208B (en) * | 2018-01-25 | 2021-05-28 | 西安凯立新材料股份有限公司 | Pd-Mg/C catalyst for preparing 2, 3-dichloropyridine by catalytic hydrogenation of 2,3, 6-trichloropyridine and preparation method thereof |
| CN109759058A (en) * | 2019-02-27 | 2019-05-17 | 西安凯立新材料股份有限公司 | The preparation method of one-step synthesis method alkyl-cyclohexyl cyclohexanone analog liquid crystal intermediates Pd/C catalyst |
| CN109759058B (en) * | 2019-02-27 | 2021-11-23 | 西安凯立新材料股份有限公司 | Preparation method of Pd/C catalyst for one-step synthesis of alkylcyclohexylcyclohexanone liquid crystal intermediates |
| CN109967070A (en) * | 2019-03-29 | 2019-07-05 | 华南理工大学 | A kind of activated carbon supported palladium catalyst and preparation method thereof for hydrogenation-dechlorination |
| 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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