CN101347729A - Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid - Google Patents
Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid Download PDFInfo
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- CN101347729A CN101347729A CNA2007100439485A CN200710043948A CN101347729A CN 101347729 A CN101347729 A CN 101347729A CN A2007100439485 A CNA2007100439485 A CN A2007100439485A CN 200710043948 A CN200710043948 A CN 200710043948A CN 101347729 A CN101347729 A CN 101347729A
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- acid
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- hydrofinishing
- active carbon
- isophthalic acid
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Abstract
The invention relates to a preparation method of a Pd/C catalyst which is used for hydrogenation refining of crude isophthalic acid, and the preparation method is mainly used for solving the problems of low dispersion of metal Pd and low microcrystal content in the catalyst which is prepared by the prior art. The preparation method firstly carries out the pickling of activated carbon carrier, then uses water or alkali for washing till neutral nature and carries out the drying, water solution containing nitrite ions is further used for infiltration, wherein, the concentration of the nitrite ions is 0.01 to 0.5N, the using amount of infiltration liquid is 0.1 to 3.0 times of the saturated absorption amount of the activated carbon carrier, the infiltration time is 2 to 24 hours; the activated carbon is then used for removing water, Pd compound is impregnated, and a reducing agent is further used for carrying out the reduction to obtain a catalyst product; therefore, the technical proposal can better solve the problems and can be used in the industrial production for hydrogenation refining of the crude isophthalic acid.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid, particularly about being used for making with extra care the preparation method of the support type Pd/carbon catalyst of coarse isophthalic acid by selective hydrogenation.
Background technology
The support type Pd/carbon catalyst is mainly used in the selective hydrogenation of unsaturated compounds.Contain a certain amount of by product impurity in the coarse isophthalic acid that is obtained by the meta-xylene oxidation, the existence of carboxyl benzaldehyde in the middle of it (being called for short 3-CBA) influence the quality and the color and luster of polyester, and is difficult to common crystallization separating method removal.But after the selective hydrogenation by the support type Pd/carbon catalyst changed m-methyl benzoic acid into, just the method for available crystallization was separated and is purified.Because Pd/carbon catalyst usually adopts single active constituent, its improvement research is concentrated on the structure and the distribution situation of metal Pd on carrier of carrier always, and this can produce very big influence to the performance of catalyst really.Because hydrogenation reaction is to carry out on the surface of metal Pd, generally speaking, for the identical catalyst of metal Pd load capacity, the decentralization of its metal Pd is higher, crystallite (crystallite dimension is less than the 2.5 nanometers) content that is the metal Pd of load in the catalyst is higher, activity of such catalysts is better, 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, the decentralization of metal Pd is very low in the catalyst that makes like this.Experience is in the past told us, and before the reduction operation, the Pd ion that will contain in the maceration extract of Pd compound is transformed into the effect that insoluble compound can be obtained.As at room temperature the water soluble compound hydrolysis of Pd being generated insoluble Pd (OH)
2Or PdOH
2O, back loading and then with reducing agents such as aldehyde, sodium formate, glucose, formic acid or hydrogen reduction, can prevent migration and the grain growth of Pd on active carbon, as U.S. Pat 3,138,560 are introduced.But this maceration extract stability that contains the Pd compound is very poor, and this has just improved the requirement of catalyst preparation process relatively.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.
Summary of the invention
Technical problem to be solved by this invention is to exist the decentralization of metal Pd in the catalyst make low in the prior art, and the problem that content of crystallite is low provides a kind of preparation method of the new Pd/carbon catalyst that is used for hydrofinishing of coarse isophthalic acid.The Pd/carbon catalyst for preparing with this method has the decentralization height of metal Pd in the catalyst, and content of crystallite is higher, and preparation process is simple, and the raw material of employing is easy to the advantage of environmental protection treatment.
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 who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid; catalyst is a carrier with particle or pressed active carbon; supported active component metal Pd; the weight content of metal Pd is 0.1～1.0% in the catalyst, may further comprise the steps successively:
1) carrier active carbon carries out pickling earlier, and the acid concentration of pickle is 0.1～5N;
2) carrier active carbon water or neutralizing treatment are dry to neutral back;
3) the carrier active carbon solution immersion that contains nitrite ion, the nitrite ion concentration of infiltrate is 0.01～0.5N, and the infiltrate consumption is 0.1～3.0 times of active carbon saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the dry support active carbon is to remove moisture;
5) with the solution impregnation that contains the Pd compound or spray carrier active carbon and make and contain the compound loaded catalyst precarsor that on active carbon, obtains of Pd, catalyst precarsor reduces processing with reducing agent after aging, makes Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
Above-mentioned steps 3) the nitrite ion preferred version described in is from the alkali metal salt of nitrous acid, and more preferably scheme is a natrium nitrosum.At least a in the complex of basic salt that contains halide that Pd compound preferred version is selected from Pd, acetate, nitrate, the acid of vinegar palladium, the acid of chlorine palladium, the acid of chlorine palladium described in the step 5) or palladium ammonia, more preferably scheme is selected from the basic salt of acid of chlorine palladium or the acid of chlorine palladium.Reducing agent preferred version described in the step 5) 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.Acid in the step 1) is selected from least a in hydrochloric acid, nitric acid or the phosphoric acid.
In said method, step 1), 2), 4), 5) basic identical with existing general Pd/carbon catalyst preparation method, and known by those skilled in the art, described below only is 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.Extremely neutral with deionized water or neutralizing treatment after the pickling, the purpose of pickling is to adjust the structure of activated carbon surface functional group.
Get and contain Pd compound water and be mixed with the dipping glue, weight concentration is generally 0.01～20%, and the pH value of regulating the dipping glue is 4～6.Adopt methods such as dipping or sprinkling that Pd is carried on the carrier then, the method for recommendation is a spraying, and spraying time was at least 5 minutes.Then catalyst precarsor was worn out 1～24 hour in air.
Catalyst precarsor after aging is handled with the reducing agent reduction, and reducing agent is preferably recommended sodium formate, and its toxicity is little, and the three wastes are few, help environmental protection, and cheap.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 been to increase step 3 wherein, and carrier active carbon is after pickling, and the solution immersion with containing nitrite ion makes nitrite ion be adsorbed in activated carbon surface.Because nitrite ion can be distributed in activated carbon surface very equably, and nitrite ion and palladium and activated carbon surface all have affinity interaction power preferably, this has just increased the grappling effect of activated carbon surface to palladium, thereby the migratory movement that can reduce palladium is to stop or to delay the grain growth of Metal Palladium.
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, has obtained better technical effect.
In an embodiment:
The measuring method of decentralization:
With pack into the sample cell of chemisorbed instrument of catalyst, purge with nitrogen, switch hydrogen, temperature programming to 200 ℃ keeps half an hour.After half an hour, air is switched to nitrogen, purge half an hour, advance pure hydrogen with quantity tube at last, note the milliliter number that at every turn advances hydrogen, by calculating the total milliliter of number that hydrogen reduces.
Computational methods:
V inhales: the hydrogen adsorption amount; M (Pd): the atomic weight of palladium
The measuring method of content of crystallite:
The Metal Palladium particle diameter records by X-XRF and x-ray diffractometer (XRD).
The activity of such catalysts appreciation condition:
Catalyst consumption: 2.0 grams
Thick meta-xylene amount: 30.0 grams
3-CBA amount: 1.0 grams
Reaction pressure: 2.8MPa
Hydrogen partial pressure: 0.5MPa
Reaction time: 1.0 hours
Reaction temperature: 220 ℃
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 800～1200 meters of 100 grams, 4～8 orders, specific surfaces
2The cocoanut active charcoal of/gram washs with the nitric acid of 0.1N, and wash temperature is 80 ℃, washes with water then to neutrality, and drying is 2～8 hours under 120 ℃.With natrium nitrosum and water preparation NO
2 -Concentration is the infiltrate of 0.2N, incipient impregnation active carbon 8 hours, and 80～120 ℃ times dry 2～8 hours are standby.
Preparation conversion palladium weight content is 40 milliliters of 0.5% chlorine palladium acid solutions then, with alkali pH value is adjusted between 4～6 again, makes it form the palladium glue, stablize 10～200 minutes after, the palladium glue is sprayed on the above-mentioned treated active carbon obtains catalyst precarsor.Catalyst precarsor after the aging night sodium formate 20 grams and pure water 200 grams with 5 weight % be mixed with reducing solution, catalyst precarsor is immersed in the reducing solution 3 hours, then with the extremely neutral catalyst prod that gets of pure water washing.
[embodiment 2]
Active carbon washs with the nitric acid of 5.0N, and wash temperature is 80 ℃, washes with water then to neutrality, and all the other are with embodiment 1.
[embodiment 3]
The active carbon phosphoric acid washing of 5.0N, wash temperature is 80 ℃, washes with water then to neutrality, all the other are with embodiment 1.
[embodiment 4]
With natrium nitrosum and water preparation NO
2 -Concentration is the infiltrate of 0.05N, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.
[embodiment 5]
With natrium nitrosum and water preparation NO
2 -Concentration is the infiltrate of 0.2N, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.
[embodiment 6]
With natrium nitrosum and water preparation NO
2 -Concentration is the infiltrate of 0.5N, and 0.3 times of infiltrate was to charcoal absorption amount Immesion active carbon 2 hours, and all the other are with embodiment 1.
[embodiment 7]
With natrium nitrosum and water preparation NO
2 -Concentration is the infiltrate of 0.5N, and 3 times of infiltrates were to charcoal absorption amount Immesion active carbon 8 hours, and all the other are with embodiment 1.
[embodiment 8]
With natrium nitrosum and water preparation NO
2 -Concentration is the infiltrate of 0.5N, incipient impregnation active carbon 24 hours, and all the other are with embodiment 1.
[embodiment 9]
The palladium weight content of preparation catalyst is that 0.1% chlorine palladium acid solution is made the palladium glue, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.
[embodiment 10]
The palladium weight content of preparation catalyst is that 0.5% palladium nitrate solution is made the palladium glue, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.
[embodiment 11]
The palladium weight content of preparation catalyst is that 0.5% palladium solution is made the palladium glue, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.
[comparative example]
With 800～1200 meters of 100 grams, 4～8 orders, specific surfaces
2The cocoanut active charcoal of/gram is with the washing of the nitric acid of 0.4N, and wash temperature is 80 ℃, wash with water then to neutrality, in 120 ℃ down dry 2～8 hours standby.
Preparation conversion palladium content is 40 milliliters of the chlorine palladium acid solutions of 0.5 weight % then, with alkali pH value is adjusted between 4～6, makes it form the palladium glue, stablize 10～200 minutes after, the palladium glue is sprayed on the above-mentioned treated active carbon obtains catalyst precarsor.Catalyst precarsor after the aging night sodium formate 20 grams and pure water 200 grams with 5 weight % be mixed with reducing solution, catalyst precarsor is immersed in the reducing solution 2～4 hours, then with the extremely neutral catalyst prod that gets of pure water washing.
Measure the decentralization and the content of crystallite of the Metal Palladium of the fresh catalyst product load that the various embodiments described above and comparative example obtain, and catalyst is carried out activity rating.The aging rear catalyst that catalyst is obtained after 100 hours in 300 ℃ of roastings in nitrogen atmosphere is then measured the decentralization and the content of crystallite of the Metal Palladium of catalyst cupport once more, and catalyst is carried out activity rating.The results are shown in Table 1.
Table 1
Claims (7)
1, a kind of preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid; catalyst is a carrier with particle or pressed active carbon; supported active component metal Pd, the weight content of metal Pd is 0.1～1.0% in the catalyst, may further comprise the steps successively:
1) carrier active carbon carries out pickling earlier, and the acid concentration of pickle is 0.1～5N;
2) carrier active carbon water or neutralizing treatment are dry to neutral back;
3) the carrier active carbon solution immersion that contains nitrite ion, the nitrite ion concentration of infiltrate is 0.01～0.5N, and the infiltrate consumption is 0.1～3.0 times of active carbon saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the dry support active carbon is to remove moisture;
5) with the solution impregnation that contains the Pd compound or spray carrier active carbon and make and contain the compound loaded catalyst precarsor that on active carbon, obtains of Pd, catalyst precarsor reduces processing with reducing agent after aging, makes Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
2, according to the described preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid of claim 1, it is characterized in that the alkali metal salt of the nitrite ion described in the step 3) from nitrous acid.
3, according to the described preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid of claim 2, the alkali metal salt that it is characterized in that described nitrous acid is a natrium nitrosum.
4,, it is characterized in that any in the complex that contains basic salt that the Pd compound is the halide that is selected from Pd, acetate, nitrate, the acid of vinegar palladium, the acid of chlorine palladium, the acid of chlorine palladium or palladium ammonia described in the step 5) according to the described preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid of claim 1; Acid in the step 1) is selected from least a in hydrochloric acid, nitric acid or the phosphoric acid.
5,, it is characterized in that the basic salt that the Pd compound is acid of chlorine palladium or the acid of chlorine palladium that contains described in the step 5) according to the described preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid of claim 4.
6,, it is characterized in that the reducing agent described in the step 5) is to be selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen according to the described preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid of claim 1.
7,, it is characterized in that described reducing agent is sodium formate or hydrazine hydrate according to the described preparation method who is used for the Pd/carbon catalyst of hydrofinishing of coarse isophthalic acid of claim 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100439485A CN101347729A (en) | 2007-07-18 | 2007-07-18 | Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid |
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| CNA2007100439485A CN101347729A (en) | 2007-07-18 | 2007-07-18 | Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100385A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method and application of palladium/bamboo charcoal catalyst |
| CN103121942A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for hydrofining crude terephthalic acid |
| CN104549237A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydrorefining crude terephthalic acid |
| CN110980638A (en) * | 2013-11-06 | 2020-04-10 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Method for storing and releasing hydrogen |
-
2007
- 2007-07-18 CN CNA2007100439485A patent/CN101347729A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100385A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method and application of palladium/bamboo charcoal catalyst |
| CN103121942A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for hydrofining crude terephthalic acid |
| CN103121942B (en) * | 2011-11-18 | 2015-04-08 | 中国石油化工股份有限公司 | Method for hydrofining crude terephthalic acid |
| CN104549237A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydrorefining crude terephthalic acid |
| CN104549237B (en) * | 2013-10-28 | 2017-01-18 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydrorefining crude terephthalic acid |
| CN110980638A (en) * | 2013-11-06 | 2020-04-10 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Method for storing and releasing hydrogen |
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Open date: 20090121 |