CN101347727A - Process for preparing Pd/carbon catalyst - Google Patents
Process for preparing Pd/carbon catalyst Download PDFInfo
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- CN101347727A CN101347727A CNA2007100439466A CN200710043946A CN101347727A CN 101347727 A CN101347727 A CN 101347727A CN A2007100439466 A CNA2007100439466 A CN A2007100439466A CN 200710043946 A CN200710043946 A CN 200710043946A CN 101347727 A CN101347727 A CN 101347727A
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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 the Pd/C, wherein, two additives of A and B are added in the solution containing Pd, the additive A is selected from compounds with the above formula, R1 or R2 is selected from one of H, CH3, NH2, OH or COOH, n or m is selected from integrals of 0 to 5; the additive B is selected from compounds with the following formula: CH3(CH2)xO(CH2CH2O)yPO(OM)2(CH3(CH2)xO(CH2CH2O)y)2PO(OM), wherein, y is selected from the integrals of 1 to 5; x is selected from the integrals of 7 to 15; M is selected from Na or K; 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 high advantage.
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 may further comprise the steps:
A) at first with active carbon with the inorganic acid pickling of 0.01～5 mol concentration 0.5～8 hour, be washed with water to neutrality then after, under 80～150 ℃ of conditions dry 0.5～10 hour, absorbent charcoal carrier;
B) with solution impregnation that contains Pd compound and additive or sprinkling absorbent charcoal carrier, make and contain the compound loaded catalyst precarsor that on active carbon, obtains of Pd, wherein additive solution contains additive A and additive B, in the solution in additive A and the Pd compound weight ratio of Pd be 0.01～2: 1, the weight ratio of Pd is 0.01～1: 1 in additive B and the Pd compound, and additive A is selected from the compound of following general formula:
N or m all are selected from 0～5 integer in the formula;
R
1Or R
2All be selected from H, CH
3, NH
2, a kind of among OH or the COOH;
Additive B is selected from the compound of following general formula:
CH
3(CH
2)
xO (CH
2CH
2O)
yPO (OM)
2Or [CH
3(CH
2)
xO (CH
2CH
2O)
y]
2PO (OM)
Y is selected from 1～5 integer in the formula; X is selected from 7～15 integer; M is selected from a kind of among Na or the K; P is a phosphorus;
C) catalyst precarsor is reduced processing with reducing agent, the catalyst of containing metal Pd.
The inorganic acid preferred version is selected from least a in hydrochloric acid, nitric acid or the phosphoric acid in the technique scheme; Pickling time preferable range is 0.5～4 hour; The concentration preferable range of inorganic acid is 0.1～3.0 mol; Drying time, preferable range was 0.5～6 hour.Pd compound preferred version is selected from least a in the complex of the basic salt of nitrate, the acid of chlorine palladium, the acid of vinegar palladium, the acid of chlorine palladium of acetate, the Pd of halide, the Pd of Pd or palladium ammonia, and more preferably scheme is selected from acid of chlorine palladium or the acid of vinegar palladium; The pH value preferable range that contains Pd compound and additive solution is 1～9, and more preferably scope is 6～7; The weight percent concentration preferable range of Pd is 0.01～5% in the solution, and more preferably scope is 0.2～3.6%; In the solution in additive A and the Pd compound weight ratio preferable range of Pd be 0.05～1.0: 1, the weight ratio preferable range of Pd is 0.1～1.0: 1 in additive B and the Pd compound.Catalyst precarsor preferred version before reduction is handled is aging 1～50 hour earlier, and more preferably scheme is aging 1～24 hour earlier; The reducing agent preferred version is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen, and more preferably scheme is selected from sodium formate or hydrazine hydrate; The condition preferred version that reduction is handled is as follows: the reduction treatment temperature is 0～200 ℃, and the reduction processing time is 0.5～24 hour, and more preferably scheme is as follows: the reduction treatment temperature is 50～120 ℃, and the reduction processing time is 1～10 hour.The weight content preferable range of metal Pd is 0.05～5% in the catalyst, and more preferably scope is 0.2～3.5%.
The additive A of using in the technique scheme, when:
R
1=R
2=OH is additive A 1 during n=m=1;
R
1=R
2=NH
2, be additive A 2 during n=m=1;
R
1=R
2=CH
3, be additive A 3 during n=m=0;
R
1=R
2=H is additive A 4 during n=m=0;
R
1=R
2=COOH is additive A 5 during n=m=2;
R
1=H, R
2=OH is additive A 6 during n=m=0.
The additive B that uses in the technique scheme, when:
Y=1, x=7 is additive B 1 during M=Na
Y=2, x=9 is additive B 2 during M=Na
Y=3, x=11 is additive B 3 during M=Na
Y=5, x=15 is additive B 4 during M=Na
Y=1, x=7 is additive B 5 during M=K
Y=2, x=9 is additive B 6 during M=K
Y=3, x=11 is additive B 7 during M=K
Y=5, x=15 is additive B 8 during M=K
In said method, add during except that the preparation of Pd solution the additive, 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.
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 additive 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 1～50 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 0.5～24 hour, is preferably 1～10 hour.
Key of the present invention has added additive when being the preparation of Pd solution, additive can produce stronger interaction and generate a kind of complex compound with Pd, additive also can play the effect of stablizing Pd solution pH value when preparation Pd solution simultaneously, 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, and it is the anti-agglutinatting property energy that while Pd crystallite has high heat endurance.Show active high, long service life on serviceability, and do not increase extra operation in the preparation process, the raw material of employing is easy to environmental protection treatment, and the method that adopts can not produce any negative effect to catalyst, has obtained better technical effect.
Because other parts of the present invention and prior art are basic identical, so embodiment will pay attention to the kind of additive 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: 2.0 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 invention will be 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 nitric acid of 0.4 mol washing 0.5 hour, and drying 2～8 hours is standby down in 120 ℃.
The preparation of Pd solution, get chlorine palladium acid solution 3.2 grams that contain palladium 16 weight %, adding 0.25 gram concentration more therein is 10% additive A 1 aqueous solution, adding 5 gram concentration are 10% additive B 1 aqueous solution, add alkali the palladium solution PH is adjusted to 6～7, and add 44 milliliters of deionized water preparation Pd solution.Above-mentioned treated active carbon is obtained catalyst precarsor after with the Pd solution impregnation.Aging 24 hours of catalyst precarsor is mixed with reducing solution with hydrazine hydrate 20 grams and pure water 200 grams of 5 weight %, 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 2～24]
It is 2 listed that active carbon pickling processes condition sees Table, select for use and different contain the Pd compound and additive is prepared Pd solution, all the other are with embodiment 1, and it is 1 listed that the concrete weight 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 sees Table.
[embodiment 25～31]
It is 2 listed that active carbon pickling processes condition sees Table, and selects for use different to contain the Pd compound and additive is prepared Pd solution, and the Pd spray solution is obtained catalyst precarsor on active carbon, and all the other are with embodiment 1.
[comparative example]
Not doping during preparation Pd solution, all the other are with embodiment 1.
It is 1 listed that the concrete weight ratio that contains Pd compound, Pd content, 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 3 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 3.
Table 1
| The Pd compound | Intercalating agent | Pd/ active carbon (weight %) in the catalyst | Additive A/Pd (weight ratio) | Additive B/Pd (weight ratio) | |
| Embodiment 1 | The acid of chlorine palladium | Additive A 1, B1 | 0.51 | 0.05 | 1.0 |
| Embodiment 2 | The acid of chlorine palladium | Additive A 1, B3 | 0.51 | 0.30 | 0.6 |
| Embodiment 3 | The acid of chlorine palladium | Additive A 1, B5 | 0.22 | 0.60 | 0.3 |
| Embodiment 4 | Palladium | Additive A 1, B8 | 0.51 | 1.0 | 0.1 |
| Embodiment 5 | The acid of chlorine palladium | Additive A 2, B2 | 0.51 | 0.05 | 1.0 |
| Embodiment 6 | The acid of chlorine palladium | Additive A 2, B4 | 0.51 | 0.30 | 0.6 |
| Embodiment 7 | The acid of chlorine palladium | Additive A 2, B6 | 0.51 | 0.60 | 0.3 |
| Embodiment 8 | Palladium | Additive A 2, B7 | 3.55 | 1.0 | 0.1 |
| Embodiment 9 | The acid of chlorine palladium | Additive A 3, B2 | 0.51 | 0.05 | 1.0 |
| Embodiment 10 | The acid of chlorine palladium | Additive A 3, B4 | 0.51 | 0.30 | 0.6 |
| Embodiment 11 | The acid of chlorine palladium | Additive A 3, B6 | 0.51 | 0.60 | 0.3 |
| Embodiment 12 | Palladium | Additive A 3, B7 | 0.51 | 1.0 | 0.1 |
| Embodiment 13 | The acid of chlorine palladium | Additive A 4, B2 | 0.51 | 0.05 | 1.0 |
| Embodiment 14 | The acid of chlorine palladium | Additive A 4, B4 | 0.51 | 0.30 | 0.6 |
| Embodiment 15 | The acid of chlorine palladium | Additive A 4, B6 | 0.51 | 0.60 | 0.3 |
| Embodiment 16 | Palladium | Additive A 4, B7 | 0.51 | 1.0 | 0.1 |
| Embodiment 17 | The acid of chlorine palladium | Additive A 5, B2 | 0.51 | 0.05 | 1.0 |
| Embodiment 18 | The acid of chlorine palladium | Additive A 5, B4 | 0.51 | 0.30 | 0.6 |
| Embodiment 19 | The acid of chlorine palladium | Additive A 5, B6 | 0.51 | 0.60 | 0.3 |
| Embodiment 20 | Palladium | Additive A 5, B7 | 0.51 | 1.0 | 0.1 |
| Embodiment 21 | The acid of chlorine palladium | Additive A 6, B2 | 0.51 | 0.05 | 1.0 |
| Embodiment 22 | The acid of chlorine palladium | Additive A 6, B4 | 0.51 | 0.30 | 0.6 |
| Embodiment 23 | The acid of chlorine palladium | Additive A 6, B6 | 0.51 | 0.60 | 0.3 |
| Embodiment 24 | Palladium | Additive A 6, B7 | 0.51 | 1.0 | 0.1 |
| Embodiment 25 | The acid of chlorine palladium | Additive A 1, B7 | 0.51 | 0.50 | 0.3 |
| Embodiment 26 | The acid of chlorine palladium | Additive A 2, B7 | 0.51 | 0.50 | 0.3 |
| Embodiment 27 | The acid of chlorine palladium | Additive A 3, B7 | 0.51 | 0.50 | 0.3 |
| Embodiment 28 | The acid of chlorine palladium | Additive A 4, B7 | 0.51 | 0.50 | 0.3 |
| Embodiment 29 | The acid of chlorine palladium | Additive A 5, B7 | 0.51 | 0.50 | 0.3 |
| Embodiment 30 | The acid of chlorine palladium | Additive A 6, B7 | 0.51 | 0.50 | 0.3 |
| Comparative example | The acid of chlorine palladium | / | 0.51 | / | / |
Table 2
| The acid that the active carbon pickling is used | Acid concentration (mol) | The pickling time (hour) | |
| Embodiment 1 | Nitric acid | 0.4 | 0.5 |
| Embodiment 2 | Nitric acid | 0.1 | 1.0 |
| Embodiment 3 | Nitric acid | 1.0 | 1.5 |
| Embodiment 4 | Nitric acid | 1.5 | 2.0 |
| Embodiment 5 | Nitric acid | 2.0 | 2.5 |
| Embodiment 6 | Nitric acid | 2.5 | 3.0 |
| Embodiment 7 | Nitric acid | 3.0 | 3.5 |
| Embodiment 8 | Nitric acid | 0.4 | 4.0 |
| Embodiment 9 | Nitric acid | 0.4 | 1.0 |
| Embodiment 10 | Nitric acid | 0.4 | 1.0 |
| Embodiment 11 | Hydrochloric acid | 0.4 | 0.5 |
| Embodiment 12 | Hydrochloric acid | 0.1 | 1.0 |
| Embodiment 13 | Hydrochloric acid | 1.0 | 1.5 |
| Embodiment 14 | Hydrochloric acid | 1.5 | 2.0 |
| Embodiment 15 | Hydrochloric acid | 2.0 | 2.5 |
| Embodiment 16 | Hydrochloric acid | 2.5 | 3.0 |
| Embodiment 17 | Hydrochloric acid | 3.0 | 3.5 |
| Embodiment 18 | Hydrochloric acid | 0.4 | 4.0 |
| Embodiment 19 | Hydrochloric acid | 0.4 | 1.0 |
| Embodiment 20 | Hydrochloric acid | 0.4 | 1.0 |
| Embodiment 21 | Phosphoric acid | 0.4 | 0.5 |
| Embodiment 22 | Phosphoric acid | 0.1 | 1.0 |
| Embodiment 23 | Phosphoric acid | 1.0 | 1.5 |
| Embodiment 24 | Phosphoric acid | 1.5 | 2.0 |
| Embodiment 25 | Phosphoric acid | 2.0 | 2.5 |
| Embodiment 26 | Phosphoric acid | 2.5 | 3.0 |
| Embodiment 27 | Phosphoric acid | 3.0 | 3.5 |
| Embodiment 28 | Phosphoric acid | 0.4 | 4.0 |
| Embodiment 29 | Phosphoric acid | 0.4 | 1.0 |
| Embodiment 30 | Phosphoric acid | 0.4 | 1.0 |
| Comparative example | Nitric acid | 0.4 | 0.5 |
Table 3
Claims (8)
1, a kind of preparation method of Pd/carbon catalyst of high activity may further comprise the steps:
A) at first with active carbon with the inorganic acid pickling of 0.01～5 mol concentration 0.5～8 hour, be washed with water to neutrality then after, under 80～150 ℃ of conditions dry 0.5～10 hour, absorbent charcoal carrier;
B) with solution impregnation that contains Pd compound and additive or sprinkling absorbent charcoal carrier, make and contain the compound loaded catalyst precarsor that on active carbon, obtains of Pd, wherein additive solution contains additive A and additive B, in the solution in additive A and the Pd compound weight ratio of Pd be 0.01～2: 1, the weight ratio of Pd is 0.01～1: 1 in additive B and the Pd compound, and additive A is selected from the compound of following general formula:
N or m all are selected from 0～5 integer in the formula;
R
1Or R
2All be selected from H, CH
3, NH
2, a kind of among OH or the COOH;
Additive B is selected from the compound of following general formula:
CH
3(CH
2)
xO (CH
2CH
2O)
yPO (OM)
2Or [CH
3(CH
2)
xO (CH
2CH
2O)
y]
2PO (OM)
Y is selected from 1～5 integer in the formula; X is selected from 7～15 integer; M is selected from a kind of among Na or the K; P is a phosphorus;
C) catalyst precarsor is reduced processing with reducing agent, the catalyst of containing metal Pd.
2,, it is characterized in that inorganic acid is selected from least a in hydrochloric acid, nitric acid or the phosphoric acid according to the preparation method of the described Pd/carbon catalyst of high activity of claim 1; The pickling time is 0.5～4 hour; The concentration of inorganic acid is 0.1～3.0 mol; Be 0.5～6 hour drying time.
3,, it is characterized in that the Pd compound is selected from least a in the complex of the basic salt of the nitrate of the acetate of the halide of Pd, Pd, Pd, the acid of chlorine palladium, the acid of vinegar palladium, the acid of chlorine palladium or palladium ammonia according to the preparation method of the described Pd/carbon catalyst of high activity of claim 1; The pH value that contains Pd compound and additive solution is 1～9, the weight percent concentration of Pd is 0.01～5% in the solution, in the solution in additive A and the Pd compound weight ratio of Pd be 0.05～1.0: 1, the weight ratio of Pd is 0.1～1.0: 1 in additive B and the Pd compound.
4,, it is characterized in that the Pd compound is selected from acid of chlorine palladium or the acid of vinegar palladium according to the preparation method of the described Pd/carbon catalyst of high activity of claim 3; The pH value that contains Pd compound and additive solution is 6～7, and the weight percent concentration of Pd is 0.2～3.6% in the solution.
5,, 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, glucose or the hydrogen; The condition that reduction is handled is as follows: the reduction treatment temperature is 0～200 ℃, and the reduction processing time is 0.5～24 hour.
6,, 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 5; Reducing agent is selected from sodium formate or hydrazine hydrate; The condition that reduction is handled is as follows: the reduction treatment temperature is 50～120 ℃, and the reduction processing time is 1～10 hour.
7, 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 0.05～5%.
8, according to the preparation method of the described Pd/carbon catalyst of high activity of claim 7, the weight content that it is characterized in that metal Pd in the catalyst is 0.2～3.5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769089A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid |
| CN112316932A (en) * | 2020-11-13 | 2021-02-05 | 中国石油大学(北京) | Crude terephthalic acid hydrofining catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476242A (en) * | 1981-10-29 | 1984-10-09 | Standard Oil Company (Indiana) | Process for preparing palladium on carbon catalysts for purification of crude terephthalic acid |
| US4721808A (en) * | 1987-04-21 | 1988-01-26 | Amoco Corporation | Process for purification of crude p-hydroxymethylbenzoic acid |
| JPH0631181A (en) * | 1992-07-06 | 1994-02-08 | Stonehard Assoc Inc | Production of highly diffused finely powdered metal carrying catalyst |
| CN1709569A (en) * | 2004-06-18 | 2005-12-21 | 中国石油化工股份有限公司 | Method for preparing catalyst for refining of crude terephthalic acid |
| CN1709568A (en) * | 2004-06-18 | 2005-12-21 | 中国石油化工股份有限公司 | Method for preparing catalyst for refining of crude terephthalic acid |
| CN1927456A (en) * | 2005-09-07 | 2007-03-14 | 中国石油化工股份有限公司 | Method for preparing high activity palladium/carbon catalyst |
| CN100428989C (en) * | 2006-09-06 | 2008-10-29 | 大连理工大学 | Method for preparing loading type nano Pd/C catalyst from colloidal solution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769089A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid |
| CN103769089B (en) * | 2012-10-25 | 2016-04-13 | 中国石油化工股份有限公司 | The preparation method of catalyzer and the catalyzer obtained thereof and an anti-form-1, the synthetic method of 4-cyclohexane cyclohexanedimethanodibasic |
| CN112316932A (en) * | 2020-11-13 | 2021-02-05 | 中国石油大学(北京) | Crude terephthalic acid hydrofining catalyst and preparation method and application thereof |
| CN112316932B (en) * | 2020-11-13 | 2022-03-01 | 中国石油大学(北京) | Crude terephthalic acid hydrofining catalyst and preparation method and application thereof |
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