CN101767004B - Preparation method of crude terephthalic acid hydrogenation catalyst - Google Patents
Preparation method of crude terephthalic acid hydrogenation catalyst Download PDFInfo
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- CN101767004B CN101767004B CN2009100568146A CN200910056814A CN101767004B CN 101767004 B CN101767004 B CN 101767004B CN 2009100568146 A CN2009100568146 A CN 2009100568146A CN 200910056814 A CN200910056814 A CN 200910056814A CN 101767004 B CN101767004 B CN 101767004B
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- palladium
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- crude terephthalic
- terephthalic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a preparation method of a crude terephthalic acid hydrogenation catalyst, mainly solving the problems that metal Pd in the catalyst has poor dispersion and low crystallite content in the prior art. Through the technical scheme comprising the following steps of: pre-impregnating an active carbon carrier with organic acid and organic acidic salt, filtering and drying the active carbon carrier, loading an active component of the metal Pd, finally adding a reducing agent for reducing and washing to obtain a finished catalyst, the invention better solves the problems and can be applied to the industrial production of hydrorefining crude terephthalic acid.
Description
Technical field
The present invention relates to a kind of crude terephthalic acid hydrogenization catalyst preparation method, particularly about a kind of preparation method who is used for the refining support type Pd/carbon catalyst of crude terephthalic acid.
Background technology
The support type Pd/carbon catalyst is applicable to the refining of crude terephthalic acid, in the crude terephthalic acid carboxyl benzaldehyde impurity such as (being called for short 4-CBA) is carried out adopting the method for crystallization to separate purification subsequently after hydrogenation changes other compound into.Because Pd/carbon catalyst adopts single active constituent, so dispersion and the distribution situation of Metal Palladium on carrier is very big to the influence of catalyst performance.
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 reactive metal of granule interior because steric influence, and not reaching the bigger reactant molecule component of diameter can not play a role.At this moment, the high catalytic activity that shows of the reactive metal of outer surface.From the consideration that makes full use of noble metal, Pd/carbon catalyst is made eggshell type usually, promptly lets the basic load of active constituent palladium in the surface of carrier.The surface area that palladium contacts with reactant is big more, and activity is also good more.The catalyst that the eggshell type active constituent distributes has higher hydrogenation catalyst ability than the catalyst of distribution wider range.U.S. Pat 4476242 proposes to adopt the palladium salt solution impregnation absorbent charcoal carrier that is dissolved in organic solvent, and the active constituent palladium is all concentrated on the top layer of thickness less than 70～80 μ m.Because the noble metal sum that supports on the carrier is less, therefore, the distribution of palladium has influenced the serviceability and the stability of catalyst largely.
Summary of the invention
Technical problem to be solved by this invention is to have metal Pd decentralization difference and the low problem of content of crystallite in the catalyst in the technology in the past, and a kind of new crude terephthalic acid hydrogenization catalyst preparation method is provided.The Pd/carbon catalyst that makes with this method has the Pd good dispersion degree, and content of crystallite is high, active high advantage.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of crude terephthalic acid hydrogenization catalyst preparation method; With organic acid or acylate pre-preg absorbent charcoal carrier, filter and dry back loading active constituent Metal Palladium, add reducing agent at last it is reduced; Wash finished catalyst, wherein used organic acid or acylate are that carbon number is at least a in 1～6 the low carbon organic acid or the acylate aqueous solution.
In the technique scheme, organic acid that the pre-preg absorbent charcoal carrier is used or acylate preferred version are selected from formic acid, acetate or tartaric acid and corresponding sylvite and sodium salt, and more preferably scheme is selected from tartaric acid and corresponding sylvite.Organic acid or acylate solution concentration preferable range are 0.01～2 mol, and more preferably scope is 0.1～0.5 mol; The dipping temperature preferable range is 0～50 ℃, and more preferably scope is 20～30 ℃; The dip time preferable range is 5～120 minutes, and more preferably scope is 20～60 minutes; The bake out temperature preferable range is 100～200 ℃, and more preferably scope is 120～150 ℃.Palladium precursor preferred version is selected from least a in palladium bichloride, palladium oxide, acid chloride, palladium nitrate, the acid of chlorine palladium and basic salt thereof or the palladium amine complex, and more preferably scheme is selected from the acid of chlorine palladium.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.
Can select particle or pressed active carbon for use among the present invention, preferred particulates or moulding coconut husk charcoal, specific surface is 600～1800m
2/ g, preferred 800～1500m
2/ g; Pore volume is 0.30～0.85ml/g, preferred 0.40～0.60ml/g; Wherein the grain graininess more than 90% is 4～8 orders.
The essential condition that hydrogenation catalyst performance is good is that active component will have high decentralization and good dispersity at catalyst surface, i.e. the distribution of palladium is wanted evenly.Generally speaking, for the identical palladium catalyst of load capacity, the decentralization of palladium is high more, and content of crystallite is high more, and activity of such catalysts is high more, and stability is good more.
Import different oxygen-containing functional groups, the different in kind of activated carbon surface at activated carbon surface.Select the oxygen-containing functional group that suits according to the needs of reaction, thereby can reach the hydrophilic purpose of control activated carbon surface Acidity of Aikalinity and active carbon.The organo-functional group on palladium carbon catalyst carrier active carbon surface makes the active carbon possess hydrophilic property, and decentralization increases with the increase of the amount of surface functional group.The number that increases surface oxygen functional group can increase metal precursor or metallic particles and carrier interactions, thereby has improved the dispersive property of noble metal.For activated carbon supported noble metal catalyst, improving its decentralization is to improve noble metal utilization rate, the main path that reduces cost.
With respect to prior art, improvements of the present invention are to adopt organic acid or acylate pre-preg absorbent charcoal carrier, import the oxygen-containing functional group of suitable type and right quantity at carrier surface, and the dispersive property of active constituent Metal Palladium is improved.The decentralization that the invention has the advantages that the catalyst surface palladium that makes is up to 30%, and the content of crystallite of palladium is up to 98%, and average grain diameter is merely 2.8nm.Catalyst of the present invention is used for the hydrofining reaction of crude terephthalic acid, and catalyst activity can reach 99.6%, has obtained better technical effect.
To every kind of catalyst, in autoclave, carry out intermittent reaction, the initial activity of testing said catalyst is the 4-CBA conversion ratio that is reached, test condition is following: catalyst amount is 2.0 grams; The crude terephthalic acid amount is 30.0 grams; The 4-CBA amount is 1.0 grams; Reaction pressure is 8.0MPa (gauge pressure); With reaction temperature be 280 ℃.
Sample analysis adopts high pressure liquid chromatographic analysis.
The decentralization of palladium carries on the chemisorbed appearance and adopts H
2-O
2Titration method records.
Palladium content of crystallite and grain size are measured through x-ray diffractometer (XRD), at first record the Metal Palladium particle diameter, then through the computes content of crystallite:
The percentage by weight of Pd is recorded by plasma atomic emission spectrometer (ICP-AES) analysis in the catalyst.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
Take by weighing 50 grams, 4～8 orders, laminar cocoanut active charcoal, specific surface is 1078 meters squared per gram, and pore volume is 0.47 a milliliter/gram.After removing the dust and surface porosity part of carbon surface absorption, be the tartaric acid solution pre-preg active carbon 15 minutes at room temperature of 0.1 moles per gram, filter then with concentration, and 120 ℃ dry 2 hours down.Take by weighing 1.25 grams and contain the chlorine palladium acid solution of palladium 20%, to wherein adding an amount of surfactant and sodium carbonate, the pH value of regulator solution is 5.5 again, and the amount that adds deionized water to solution then just submergence absorbent charcoal carrier is advisable.With the catalyst activity component solution impregnating carrier, wear out and reduce with sodium formate solution after 24 hours, obtain catalyst prod with pure water washing to neutral also drying then.The initial activity of catalyst is checked and rated in autoclave, and the result sees table 2.
[embodiment 2～9]
Each step and operating condition according to embodiment 1 prepare catalyst, just change pre-preg solution kind, solution concentration, dipping temperature, dip time, baking temperature, specifically see table 1, and the physical index and the evaluation result of the catalyst of preparation are seen table 2 respectively.
[comparative example 1]
Catalyst preparation process is with embodiment 1, and just wherein absorbent charcoal carrier does not carry out the pre-preg processing, and its physical index and evaluation result are seen table 2.
Table 1
| Pre-preg solution kind | The solution concentration mol | Dipping temperature ℃ | Dip time minute | Baking temperature ℃ | |
| Embodiment 1 | Tartaric acid | 0.1 | 25 | 15 | 120 |
| Embodiment 2 | Potassium tartrate | 0.3 | 20 | 30 | 150 |
| Embodiment 3 | Acetate | 0.02 | 30 | 100 | 180 |
| Embodiment 4 | Sodium acetate | 0.9 | 45 | 60 | 170 |
| Embodiment 5 | Tartaric acid | 0.3 | 25 | 30 | 130 |
| Embodiment 6 | Tartaric acid | 1.5 | 40 | 90 | 120 |
| Embodiment 7 | Potassium tartrate | 0.01 | 50 | 60 | 150 |
| Embodiment 8 | Sodium acetate | 1.8 | 25 | 90 | 120 |
| Embodiment 9 | Formic acid | 0.6 | 10 | 40 | 140 |
Table 2
| Decentralization % | Content of crystallite % | Average crystal grain size nm | 4-CBA conversion ratio % | |
| Embodiment 1 | 27 | 93 | 3.1 | 98.7 |
| Embodiment 2 | 29 | 96 | 2.7 | 99.5 |
| Embodiment 3 | 28 | 95 | 2.8 | 99.3 |
| Embodiment 4 | 28 | 94 | 3.0 | 98.7 |
| Embodiment 5 | 30 | 97 | 2.6 | 99.6 |
| Embodiment 6 | 26 | 94 | 2.8 | 98.5 |
| Embodiment 7 | 27 | 91 | 3.2 | 98.5 |
| Embodiment 8 | 26 | 90 | 3.3 | 98.1 |
| Embodiment 9 | 25 | 89 | 3.5 | 96.9 |
| Comparative example 1 | 20 | 86 | 4.2 | 98.2 |
Claims (5)
1. crude terephthalic acid hydrogenization catalyst preparation method; With organic acid or acylate pre-preg absorbent charcoal carrier, filter and oven dry back loading active constituent Metal Palladium, add reducing agent at last it is reduced; Wash finished catalyst; Wherein used organic acid or acylate are selected from tartaric acid and corresponding sylvite and sodium salt, and described organic acid or acylate solution concentration are 0.1～0.5 mol, and dipping temperature is 20～30 ℃; Dip time is 20～60 minutes, and bake out temperature is 120～150 ℃.
2. crude terephthalic acid hydrogenization catalyst preparation method according to claim 1 is characterized in that said palladium precursor is selected from least a in palladium bichloride, palladium oxide, acid chloride, palladium nitrate, the acid of chlorine palladium and basic salt thereof or the palladium amine complex.
3. crude terephthalic acid hydrogenization catalyst preparation method according to claim 2 is characterized in that it is that the chlorine palladium is sour that said palladium precursor is selected from.
4. crude terephthalic acid hydrogenization catalyst preparation method according to claim 1 is characterized in that said reducing agent is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen.
5. crude terephthalic acid hydrogenization catalyst preparation method according to claim 4 is characterized in that said reducing agent is selected from sodium formate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103028398B (en) * | 2011-09-29 | 2015-04-08 | 中国石油化工股份有限公司 | Method for preparing palladium carbon catalyst for hydrogenation and refining of crude terephthalic acid |
| CN103041818B (en) * | 2011-10-17 | 2016-01-20 | 中国石油化工股份有限公司 | The preparation method of catalytic wet oxidation catalyst and method for processing organic wastewater |
| CN102626619B (en) * | 2012-03-24 | 2014-05-28 | 中国石油化工股份有限公司 | Preparation method of palladium carbon catalyst |
| CN104549264B (en) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | For catalyst that thick 2,6-naphthalenedicarboxylic acid hydrogenation purifies and preparation method thereof |
| CN104549240B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
| CN106423150B (en) * | 2015-08-12 | 2020-09-04 | 中国石油化工股份有限公司 | Catalyst for hydrogenation and purification of crude terephthalic acid |
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457922A (en) * | 2002-05-16 | 2003-11-26 | 中国石化上海石油化工股份有限公司 | Hydrogenating catalyst for refining terephthalic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457922A (en) * | 2002-05-16 | 2003-11-26 | 中国石化上海石油化工股份有限公司 | Hydrogenating catalyst for refining terephthalic acid |
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