CN1565726A - Method for preparing palladium/carbon catalyzer by hydrogenising and refining crude terephthalic acid - Google Patents
Method for preparing palladium/carbon catalyzer by hydrogenising and refining crude terephthalic acid Download PDFInfo
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- CN1565726A CN1565726A CN 03129189 CN03129189A CN1565726A CN 1565726 A CN1565726 A CN 1565726A CN 03129189 CN03129189 CN 03129189 CN 03129189 A CN03129189 A CN 03129189A CN 1565726 A CN1565726 A CN 1565726A
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Abstract
A method for preparing Pd/C catalyst for selective hydrogenation is provided. The content of Pd in catalyst is 0.2 to 5% by weight. The preparing process includes the following steps: active carbon carrier is washed by 0.1 to 5N concentration of acid washing liquid selected from hydrochloric acid, nitric acid or phosphoric acid; active carbon carrier is washed to neutrality by water and dried; the active carbon carrier is soaked in nitrite ion containing solution for 2 to 24 hours and dried; the Pd compound is sprayed on the active carbon carrier to form catalyst precursor, after aging and reduction process, the catalyst product is obtained. Metal Pd in catalyst has higher dispersion degree and the content of crystallite is very high.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the supported palladium/carbon catalyst of selective hydrogenation, 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 crude terephthalic acid process for refining, carboxyl benzaldehyde impurity such as (being called for short 4-CBA) is carried out by changing other compound behind the hydrogenation in the crude terephthalic acid, just available crystalline method separate purifies.Because palladium/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 catalyzer really.Because hydrogenation reaction is to carry out on the surface of metal Pd, generally speaking, for the identical catalyzer of metal Pd charge capacity, the dispersity of its metal Pd is higher, crystallite (grain-size is less than the 25 nanometers) content that is the metal Pd of load in the catalyzer is higher, activity of such catalysts is better, and work-ing life is also longer.
If directly will contain Pd compound (as chlorine palladium acid sodium or Palladous chloride) loads on the gac, 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, unbound electrons, very easily make the Pd ion be reduced into the non-valent metal Pd, the dispersity of metal Pd is very low in the catalyzer that makes like this.Experience is in the past told us, and before the reduction operation, the Pd ion that will contain in the steeping fluid of Pd compound is transformed into the effect that insoluble compound can be obtained.As at room temperature the water-soluble cpds hydrolysis of Pd being generated insoluble Pd (OH)
2Or PdOH
2O, back loading and then with reductive agents such as aldehyde, sodium formiate, glucose, formic acid or hydrogen reduction, can prevent migration and the grain growth of Pd on gac, as U.S. Pat 3,138,560 are introduced.But this steeping fluid 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 steeping fluid 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
The invention provides a kind of preparation method who is used for the hydrorefined palladium/carbon catalyst of crude terephthalic acid, its technical problem to be solved is that metal Pd has higher dispersity in the catalyzer that obtains, content of crystallite is higher, and preparation process requires simply, and the raw material of employing is easy to environmental protection treatment.
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 hydrorefined palladium/carbon catalyst of crude terephthalic acid; catalyzer 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 catalyzer, the preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle solution is 0.1～5N, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) carrier active carbon is washed with water to neutral after drying;
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 gac saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the drying support gac is removed moisture;
5) with the solution impregnation that contains the Pd compound or spray carrier active carbon and make and contain that Pd is compound loaded to obtain catalyst precursor in gac, catalyst precursor reduces processing with reductive agent after aging, makes Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
Nitrite ion described in the above-mentioned steps 3 can be preferably Sodium Nitrite from an alkali metal salt of nitrous acid usually.The described Pd of the containing compound of step 5 is generally any in the title complex of the subsalt of the halogenide of taking from Pd, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium or palladium ammonia, is preferably the subsalt of acid of chlorine palladium or the acid of chlorine palladium.The described reductive agent of step 5 is generally takes from any in formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose or the hydrogen, is preferably sodium formiate or hydrazine hydrate.
In aforesaid method, step 1,2,4,5 and existing general palladium/carbon catalyst preparation method basic identical, and known by those skilled in the art, described below only is that the present invention recommends.
Select suitable gac 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 wash 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, concentration is generally 0.01～20wt%, 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 precursor was worn out 1～24 hour in air.
Catalyst precursor after aging is handled with the reductive agent reduction, reductive agent preferable formic acid sodium, 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 reductive agent depends on the dosage of active constituent Pd, is generally normal 1～10 times of reduction reaction, 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 palladium metal.
Compared with prior art, the invention has the advantages that metal Pd has higher dispersity in the catalyzer that makes, content of crystallite is higher, shows active high, long service life on use properties, and the step that increases in the preparation process is very simple, and the raw material of employing is easy to environmental protection treatment.
Below will the invention will be further described by specific embodiment, in an embodiment:
The measuring method of dispersity:
With pack into the sample hose of chemisorption instrument of catalyzer, use nitrogen purging, 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.
Method of calculation:
V inhales: the hydrogen adsorption amount; M (Pd): the measuring method of the nucleidic mass content of crystallite of palladium:
The palladium metal particle diameter records by X-fluorescence spectrophotometer and x-ray diffractometer (XRD).
The activity rating of catalyst condition:
Catalyst consumption: 2.0g
Thick p-Xylol amount: 30.0g
4-CBA amount: 1.0g
Reaction pressure: 70 kilograms
Hydrogen partial pressure: 5.0 kilograms
Reaction times: 1.0 hours
Temperature of reaction: 270 ℃
Embodiment
[embodiment 1]
With 100 grams, 4～8 orders, specific surface 800～1200m
2The cocoanut active charcoal of/g washs with the nitric acid of 0.4N, and wash temperature is 80 ℃, washes with water then to neutrality, and drying is 2～8 hours under 120 ℃.With Sodium Nitrite and water preparation NO
2 -Concentration is the infiltrate of 0.01N, incipient impregnation gac 2～24 hours, and 80～120 ℃ times dry 2～8 hours are standby.
Preparation conversion palladium content is 40 milliliters of the chlorine palladium acid solutions of 0.5wt% then, about 1.0 milliliters of the tartrate that adds 2wt% therein, with alkali pH value is adjusted between 4～6 again, make it form the palladium glue, after stablizing 10～200 minutes, the palladium glue is sprayed on the above-mentioned treated gac obtains catalyst precursor.Catalyst precursor after the aging night sodium formiate 20 grams and pure water 200 grams with 5wt% be mixed with reduced liquid, catalyst precursor is immersed in the reduced liquid 2～4 hours, then with the extremely neutral catalyst prod that gets of pure water washing.
[embodiment 2]
With Sodium Nitrite and water preparation NO
2 -Concentration is the infiltrate of 0.05N, incipient impregnation gac 2～24 hours, and all the other are with embodiment 1.
[embodiment 3]
With Sodium Nitrite and water preparation NO
2 -Concentration is the infiltrate of 0.2N, incipient impregnation gac 2～24 hours, and all the other are with embodiment 1.
[embodiment 4]
With Sodium Nitrite and water preparation NO
2 -Concentration is the infiltrate of 0.5N, incipient impregnation gac 2～24 hours, and all the other are with embodiment 1.
[comparative example]
With 100 grams, 4～8 orders, specific surface 800～1200m
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.
Preparation conversion palladium content is 40 milliliters of the chlorine palladium acid solutions of 0.5wt% then, about 1.0 milliliters of the tartrate that adds 2wt% therein, with alkali pH value is adjusted between 4～6 again, make it form the palladium glue, after stablizing 10～200 minutes, the palladium glue is sprayed on the above-mentioned treated gac obtains catalyst precursor.Catalyst precursor after the aging night sodium formiate 20 grams and pure water 200 grams with 5wt% be mixed with reduced liquid, catalyst precursor is immersed in the reduced liquid 2～4 hours, then with the extremely neutral catalyst prod that gets of pure water washing.
Measure the dispersity and the content of crystallite of the palladium metal of the live catalyst product load that the various embodiments described above and comparative example obtain, and catalyzer is carried out activity rating.The aging rear catalyst that catalyzer is obtained after 100 hours in 300 ℃ of roastings in nitrogen atmosphere is then measured the dispersity and the content of crystallite of the palladium metal of catalyst cupport once more, and catalyzer is carried out activity rating.The results are shown in Table 1.
Table 1.
| Pd content (wt%) | Dispersity (%) | Content of crystallite (%) | Transformation efficiency (%) | ||||
| Before aging | After aging | Before aging | After aging | Before aging | After aging | ||
| Embodiment 1 | ????0.5 | ??23 | ????20 | ??82 | ??79 | ????99.9 | ????99.7 |
| Embodiment 2 | ????0.5 | ??26 | ????23 | ??84 | ??80 | ????99.9 | ????99.8 |
| Embodiment 3 | ????0.5 | ??28 | ????25 | ??86 | ??83 | ????99.9 | ????99.8 |
| Embodiment 4 | ????0.5 | ??28 | ????25 | ??86 | ??83 | ????99.9 | ????99.8 |
| Comparative example | ????0.5 | ??14 | ????8.1 | ??70 | ??60 | ????99.8 | ????96.5 |
Claims (7)
1, a kind of preparation method who is used for the hydrorefined palladium/carbon catalyst of crude terephthalic acid; catalyzer 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 catalyzer, the preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle solution is 0.1～5N, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) carrier active carbon is washed with water to neutral after drying;
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 gac saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the drying support gac is removed moisture;
5) with the solution impregnation that contains the Pd compound or spray carrier active carbon and make and contain that Pd is compound loaded to obtain catalyst precursor in gac, catalyst precursor reduces processing with reductive agent after aging, makes 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 an alkali metal salt of the nitrite ion described in the step 3 from nitrous acid.
3, the preparation method of palladium/carbon catalyst according to claim 2, an alkali metal salt that it is characterized in that described nitrous acid is a Sodium Nitrite.
4, the preparation method of palladium/carbon catalyst according to claim 1 is characterized in that the described Pd of the containing compound of step 5 is any in the title complex of the subsalt of the halogenide of taking from Pd, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium or palladium ammonia.
5, the preparation method of palladium/carbon catalyst according to claim 4 is characterized in that the described Pd of the containing compound of step 5 is the subsalt of acid of chlorine palladium or the acid of chlorine palladium.
6, the preparation method of palladium/carbon catalyst according to claim 1 is characterized in that the described reductive agent of step 5 is to take from any in formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose or the hydrogen.
7, the preparation method of palladium/carbon catalyst according to claim 6 is characterized in that described reductive agent is a sodium formiate.
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| CNB031291899A CN1329118C (en) | 2003-06-12 | 2003-06-12 | Method for preparing palladium/carbon catalyzer by hydrogenising and refining crude terephthalic acid |
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| CNB031291899A CN1329118C (en) | 2003-06-12 | 2003-06-12 | Method for preparing palladium/carbon catalyzer by hydrogenising and refining crude terephthalic acid |
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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 |
| CN103894188A (en) * | 2014-03-14 | 2014-07-02 | 南京中赢纳米新材料有限公司 | Preparation method for palladium/resin carbon catalyst and application of palladium/resin carbon catalyst |
| CN109046337A (en) * | 2018-08-01 | 2018-12-21 | 西安凯立新材料股份有限公司 | A kind of preparation method of Imipenem palladium carbon catalyst |
| CN110551278A (en) * | 2019-08-26 | 2019-12-10 | 浙江绿科安化学有限公司 | Supported catalyst and preparation method and application thereof |
| CN112316968A (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 |
| CN115228467A (en) * | 2021-04-25 | 2022-10-25 | 中国石油化工股份有限公司 | Catalyst for hydrofining crude terephthalic acid and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5127437B2 (en) * | 1973-04-06 | 1976-08-12 | ||
| US4256609A (en) * | 1978-01-20 | 1981-03-17 | Gallaher Limited | Catalysts |
| 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 |
| US4791226A (en) * | 1983-06-23 | 1988-12-13 | Amoco Corporation | Catalyst and process for purification of crude terephthalic acid |
| DE4308101C1 (en) * | 1993-03-15 | 1994-07-28 | Degussa | Process for the production of platinum group metal-containing hydrogenation catalysts on activated carbon |
-
2003
- 2003-06-12 CN CNB031291899A patent/CN1329118C/en not_active Expired - Lifetime
Cited By (10)
| 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 |
| CN103894188A (en) * | 2014-03-14 | 2014-07-02 | 南京中赢纳米新材料有限公司 | Preparation method for palladium/resin carbon catalyst and application of palladium/resin carbon catalyst |
| CN103894188B (en) * | 2014-03-14 | 2016-08-24 | 南京中赢纳米新材料有限公司 | A kind of preparation method and applications of palladium-resin C catalyst |
| CN109046337A (en) * | 2018-08-01 | 2018-12-21 | 西安凯立新材料股份有限公司 | A kind of preparation method of Imipenem palladium carbon catalyst |
| CN109046337B (en) * | 2018-08-01 | 2021-08-17 | 西安凯立新材料股份有限公司 | Preparation method of palladium-carbon catalyst for imipenem |
| CN110551278A (en) * | 2019-08-26 | 2019-12-10 | 浙江绿科安化学有限公司 | Supported catalyst and preparation method and application thereof |
| CN112316968A (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 |
| CN112316968B (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 |
| CN115228467A (en) * | 2021-04-25 | 2022-10-25 | 中国石油化工股份有限公司 | Catalyst for hydrofining crude terephthalic acid and preparation method thereof |
| CN115228467B (en) * | 2021-04-25 | 2024-01-30 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst and preparation method thereof |
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