CN101347728A - Process for preparing Pd/carbon catalyst of high activity - Google Patents
Process for preparing Pd/carbon catalyst of high activity Download PDFInfo
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- CN101347728A CN101347728A CNA2007100439470A CN200710043947A CN101347728A CN 101347728 A CN101347728 A CN 101347728A CN A2007100439470 A CNA2007100439470 A CN A2007100439470A CN 200710043947 A CN200710043947 A CN 200710043947A CN 101347728 A CN101347728 A CN 101347728A
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Abstract
The invention relates to a preparation method of a high activity Pd/C catalyst, and the preparation method is mainly used for solving the problems of poor Pd dispersion in the catalyst, low microcrystal content and poor thermal stability of the prior art. The preparation method adopts activated carbon as a carrier and impregnates or sprays solution containing Pd on the activated carbon for preparing a precursor of the Pd/C catalyst, the precursor of the catalyst is carried out the step-by-step reduction treatment by using a reducing agent after the aging treatment, reduction fluid with the high concentration of 3 to 30 percent by weight is firstly used for carrying out the reduction for 0.1 to 24 hours at the normal temperature, then the reduction fluid with the low concentration of 0.1 to 2 percent by weight is then used for carrying out the reduction for 0.5 to 24 hours at 50 to 120 DEG C, and the Pd/C catalyst is obtained by water washing; therefore, the technical proposal can better solve the problems and can be used in the industrial production of para-toluic acid catalyst by using 4-carboxy benzaldehyde.
Description
Technical field
The present invention relates to a kind of preparation method of Pd/carbon catalyst of high activity, particularly be used for the preparation method that selective hydrogenation is made with extra care the support type Pd/carbon catalyst of crude terephthalic acid about a kind of.
Background technology
The support type Pd/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 Pd/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 Pd/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, heat endurance is good more, and 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 behind the O 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 environmental 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 dispersiveness and the heat endurance of Pd equally.
Summary of the invention
Technical problem to be solved by this invention is the problem that has the low and poor heat stability of metal Pd decentralization difference and content of crystallite in the catalyst in the conventional art, and a kind of preparation method of new Pd/carbon catalyst of high activity is provided.The Pd/carbon catalyst that makes with this method has the Pd good dispersion degree, content of crystallite height, Heat stability is good, active advantages of higher.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of Pd/carbon catalyst of high activity, with the active carbon is carrier, to contain the Pd solution impregnation or be sprayed on and make the Pd/carbon catalyst precursor on the active carbon, after burin-in process catalyst precarsor being carried out step-by-step reduction with reducing agent handles, the first step was at first reduced 0.1～24 hour at normal temperatures with the reducing solution of 3～30 weight % concentration, second step reduced 0.5～24 hour down at 50～120 ℃ with the reducing solution of 0.1～2 weight % low concentration more then, obtained highly active Pd/carbon catalyst after washing.
In the technique scheme, catalyst precarsor wore out 1～50 hour earlier before reduction is handled, and preferable range is aging 1～24 hour earlier; Reducing agent is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate or the glucose, and more preferably scheme is selected from sodium formate or hydrazine hydrate; The condition that reduction is handled is as follows: first step reduction treatment temperature is a normal temperature, and reducing solution concentration preferable range is 10～20 weight %, and the recovery time preferable range is 1～10 hour; Second step reduction treatment temperature preferable range is 70～100 ℃, and reducing solution concentration preferable range is 0.2～1 weight %, and reduction processing time preferable range is 0.5～10 hour.The weight content preferable range of metal Pd is 0.1～1% in the catalyst, and more preferably scope is 0.4～0.6%.Reducing solution weight is 4～15 times of catalyst weight, and wherein first step reducing solution weight is 2～5 times of catalyst weight, and the reducing solution weight of second step reduction is 2～10 times of catalyst weight.
Among the present invention, in order to reduce migration and the gathering because of being subjected to thermogenetic palladium compound in reducing solution of Pd/carbon catalyst precursor, reduction divided for two steps carried out; Earlier at normal temperatures the palladium compound major part is reduced into Metal Palladium, under heating state, reduce remaining palladium compound with the low concentration reducing solution then with the high concentration reducing solution, thus Pd decentralization, content of crystallite and the heat endurance of raising Pd/carbon catalyst.
In said method, except that two stage reduction methods, other parts are then basic identical with existing general Pd/carbon catalyst preparation method, and these preparation process are that those skilled in the art are known.
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, and it is the anti-agglutinatting property energy that while Pd crystallite has high heat endurance.On serviceability, show the advantage of active height, long service life, obtained better technical effect.
Because other parts of the present invention and prior art are basic identical, so embodiment will pay attention to giving an example of reducing solution concentration, consumption and recovery time.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: 2.0 grams
Thick paraxylene amount: 30.0 grams
4-CBA amount: 1.0 grams
Reaction pressure: 7.0MPa
Hydrogen partial pressure: 0.5MPa
Reaction time: 1.0 hours
Reaction temperature: 270 ℃
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 800～1800 meters of 100 grams, 4～8 orders, specific surfaces
2The cocoanut active charcoal of/gram washes with water to neutrality then with the washing of the nitric acid of 0.4 mol, and drying 2～8 hours is standby down in 120 ℃.
Above-mentioned treated active carbon is obtained catalyst precarsor (Pd content is 0.51 gram) after with 44 gram Pd solution impregnation.Aging 24 hours of catalyst precarsor, sodium formate 300 gram reducing solutions with 3 weight % reduced 0.5 hour at normal temperatures, again with the sodium formate 500 gram reducing solutions of 0.2 weight % 70～100 ℃ of reduction 1 hour down, then with the pure water washing to neutral and in addition after the drying catalyst prod.
[embodiment 2～12]
Select different reducing solution concentration, consumption and recovery time for use, different Pd content, all the other are with embodiment 1, see Table 1 listed.
[embodiment 13]
Select for use hydrazine hydrate to make reducing agent, all the other are with embodiment 1.
[comparative example]
Without high concentration normal temperature reduction, directly to reduce with second step, all the other are with embodiment 1, see Table 1 listed.
It is listed that the content of the catalyst metals Pd that each embodiment and comparative example make sees Table 2 first row.
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
| Pd content (weight %) in the catalyst | First step reducing solution concentration (weight %) | The first step recovery time (hour) | First step reducing solution weight/catalyst weight | The second step reducing solution concentration (weight %) | Second recovery time in step (hour) | Second step reducing solution weight/catalyst weight | |
| Embodiment 1 | 0.51 | 3 | 24 | 5 | 2 | 1 | 5 |
| Comparative example 1 | 0.51 | / | / | / | 2 | 1 | 5 |
| Embodiment 2 | 0.51 | 10 | 10 | 3 | 1 | 5 | 10 |
| Comparative example 2 | 0.51 | / | / | / | 1 | 5 | 10 |
| Embodiment 3 | 0.51 | 20 | 1 | 3 | 0.5 | 0.5 | 4 |
| Comparative example 3 | 0.51 | / | / | / | 0.5 | 0.5 | 4 |
| Embodiment 4 | 0.51 | 30 | 0.1 | 2 | 0.1 | 10 | 6 |
| Comparative example 4 | 0.51 | / | / | / | 0.1 | 10 | 6 |
| Embodiment 5 | 0.41 | 3 | 24 | 5 | 2 | 1 | 5 |
| Comparative example 5 | 0.41 | / | / | / | 2 | 1 | 5 |
| Embodiment 6 | 0.41 | 10 | 10 | 3 | 1 | 5 | 10 |
| Comparative example 6 | 0.41 | / | / | / | 1 | 5 | 10 |
| Embodiment 7 | 0.41 | 20 | 1 | 3 | 0.5 | 0.5 | 4 |
| Comparative example 7 | 0.41 | / | / | / | 0.5 | 0.5 | 4 |
| Embodiment 8 | 0.41 | 30 | 0.1 | 2 | 0.1 | 10 | 6 |
| Comparative example 8 | 0.41 | / | / | / | 0.1 | 10 | 6 |
| Embodiment 9 | 0.61 | 3 | 24 | 5 | 2 | 1 | 5 |
| Comparative example 9 | 0.61 | / | / | / | 2 | 1 | 5 |
| Embodiment 10 | 0.61 | 10 | 10 | 3 | 1 | 5 | 10 |
| Comparative example 10 | 0.61 | / | / | / | 1 | 5 | 10 |
| Embodiment 11 | 0.61 | 20 | 1 | 3 | 0.5 | 0.5 | 4 |
| Comparative example 11 | 0.61 | / | / | / | 0.5 | 0.5 | 4 |
| Embodiment 12 | 0.61 | 30 | 0.1 | 2 | 0.1 | 10 | 6 |
| Comparative example 12 | 0.61 | / | / | / | 0.1 | 10 | 6 |
| Embodiment 13 | 0.51 | 3 | 24 | 5 | 2 | 1 | 5 |
| Comparative example 13 | 0.51 | / | / | / | 2 | 1 | 5 |
Table 2
Claims (7)
1, a kind of preparation method of Pd/carbon catalyst of high activity, with the active carbon is carrier, to contain the Pd solution impregnation or be sprayed on and make the Pd/carbon catalyst precursor on the active carbon, after burin-in process catalyst precarsor being carried out step-by-step reduction with reducing agent handles, the first step was at first reduced 0.1～24 hour at normal temperatures with the reducing solution of 3～30 weight % concentration, second step reduced 0.5～24 hour down at 50～120 ℃ with the reducing solution of 0.1～2 weight % low concentration more then, obtained highly active Pd/carbon catalyst after washing.
2,, it is characterized in that catalyst precarsor wore out 1～50 hour earlier before reduction is handled according to the preparation method of the described Pd/carbon catalyst of high activity of claim 1; Reducing agent is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate or the glucose; The condition that reduction is handled is as follows: first step reduction is handled, and reducing solution concentration is 10～20 weight %, and the recovery time is 1～10 hour; Second step reduction treatment temperature is 70～100 ℃, and reducing solution concentration is 0.2～1 weight %, and the reduction processing time is 0.5～10 hour.
3,, it is characterized in that catalyst precarsor wore out 1～24 hour earlier before reduction is handled according to the preparation method of the described Pd/carbon catalyst of high activity of claim 2; Reducing agent is selected from sodium formate or hydrazine hydrate.
4, according to the preparation method of the described Pd/carbon catalyst of high activity of claim 1, the weight content that it is characterized in that metal Pd in the catalyst is 0.1～1%.
5, according to the preparation method of the described Pd/carbon catalyst of high activity of claim 4, the weight content that it is characterized in that metal Pd in the catalyst is 0.4～0.6%.
6,, it is characterized in that reducing solution weight is 4～15 times of catalyst weight according to the preparation method of the described Pd/carbon catalyst of high activity of claim 1.
7, according to the preparation method of the described Pd/carbon catalyst of high activity of claim 6, the reducing solution weight that it is characterized in that first step reduction is 2～5 times of catalyst weight, and the reducing solution weight of second step reduction is 2～10 times of catalyst weight.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593474A (en) * | 2012-02-16 | 2012-07-18 | 厦门大学 | Low-platinum fuel cell catalyst and preparation method thereof |
| CN102872800A (en) * | 2011-07-11 | 2013-01-16 | 北京联合大学生物化学工程学院 | Preparation method of heavy metal mercury-enriched material |
| CN103721706A (en) * | 2012-10-15 | 2014-04-16 | 中国石油化工股份有限公司 | Method for reduction washing of palladium carbon catalyst for terephthalic acid refining |
| CN107413332A (en) * | 2017-06-01 | 2017-12-01 | 南通百应能源有限公司 | The preparation method of high activity platinum carbon catalyst |
| CN109865845A (en) * | 2019-03-29 | 2019-06-11 | 无锡英特派金属制品有限公司 | The preparation method of high-density palladium powder |
| CN112237913A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Preparation method of palladium-based supported hydrogenation catalyst and catalyst thereof |
-
2007
- 2007-07-18 CN CN2007100439470A patent/CN101347728B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872800A (en) * | 2011-07-11 | 2013-01-16 | 北京联合大学生物化学工程学院 | Preparation method of heavy metal mercury-enriched material |
| CN102872800B (en) * | 2011-07-11 | 2015-05-20 | 北京联合大学生物化学工程学院 | Preparation method of heavy metal mercury-enriched material |
| CN102593474A (en) * | 2012-02-16 | 2012-07-18 | 厦门大学 | Low-platinum fuel cell catalyst and preparation method thereof |
| CN103721706A (en) * | 2012-10-15 | 2014-04-16 | 中国石油化工股份有限公司 | Method for reduction washing of palladium carbon catalyst for terephthalic acid refining |
| CN103721706B (en) * | 2012-10-15 | 2016-08-03 | 中国石油化工股份有限公司 | Purification of terephthalic acid palladium carbon catalyst reduction washing methods |
| CN107413332A (en) * | 2017-06-01 | 2017-12-01 | 南通百应能源有限公司 | The preparation method of high activity platinum carbon catalyst |
| CN109865845A (en) * | 2019-03-29 | 2019-06-11 | 无锡英特派金属制品有限公司 | The preparation method of high-density palladium powder |
| CN112237913A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Preparation method of palladium-based supported hydrogenation catalyst and catalyst thereof |
| CN112237913B (en) * | 2019-07-18 | 2024-05-03 | 中国石油化工股份有限公司 | Preparation method of palladium supported hydrogenation catalyst and catalyst thereof |
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