CN101428226A - Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid - Google Patents
Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid Download PDFInfo
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- CN101428226A CN101428226A CNA2007100478757A CN200710047875A CN101428226A CN 101428226 A CN101428226 A CN 101428226A CN A2007100478757 A CNA2007100478757 A CN A2007100478757A CN 200710047875 A CN200710047875 A CN 200710047875A CN 101428226 A CN101428226 A CN 101428226A
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- terephthalic acid
- selective hydrogenation
- hydrogenation catalyst
- cba
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Abstract
The invention relates to a selective hydrogenation catalyst used for purification of terephthalic acid, mainly solves the problems of p-toluic acid (P-TA) generation due to hydrogenation of pcarboxybenzaldehyde (4-CBA), large hydrogen consumption and high operating cost in the prior art, also solves the problem that the prior catalyst is poisoned because the active component Pd is bounded to sulphur via strong bonding and the state and the property of Pd are changed when the activated carbon is adopted as catalyst carrier, and also solves the problem that the quality of the product doped with activated carbon microparticles is poor. The selective hydrogenation catalyst adopts titanium dioxide as a carrier and loads one or more metals selected from Ru, Ni, Zn and Cu. With the technical scheme, the selective hydrogenation catalyst overcomes the problems in the prior art and is applied to the industrial production of hydrofining of terephthalic acid.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst that is used for purification of terephthalic acid.Particularly will generate the hydroxymethyl-benzoic acid catalyst of (being called for short 4-HMBA) carboxyl benzaldehyde (4-CBA) selective hydrogenation about a kind of subtractive process that is used for terephthalic acid (TPA).
Background technology
The support type Pd/carbon catalyst is applicable to the refining of crude terephthalic acid, and impurity such as the 4-CBA in the crude terephthalic acid carry out adopting the method for crystallization to separate purification subsequently after hydrogenation changes other compound into.In industrial production, the 4-CBA hydrogenation in the crude terephthalic acid generates P-TA, and contains the 4-HMBA of minute quantity.
4-HMBA is used for synthetic corresponding homopolymers, poly-para Toluic Acid's salt or corresponding ester as a kind of important monomer, and poly-methyl is to hydroxymethyl-benzoic acid ester (mep-HMB).Because 4-HMBA more is soluble in than PT acid and is easy in the aqueous solvent separate with PTA, each carbonyl hydrogen becomes the pure reactive hydrogen that only needs to consume 1 molecule, and hydrogenolysis becomes hydrocarbon, and then consumption doubles.If select to be hydrogenated to 4-HMBA so can realize 4-CBA, to help improving quality, reduction lock out operation expense and the energy resource consumption of product, existing hydrofining technology is greatly simplified, reduced cost of investment and running cost, improve the PTA competitiveness of product in market.
About the report of 4-HMBA seldom, among the patent US 4892972 of Amoco company application, mentioned the 4-CBA hydrogenation and can generate 4-HMBA, but, do not generated the 4-HMBA reaction at the 4-CBA hydrogenation specially and study report just as the hydrorefined attached reaction of a kind of 4-CBA.On Pd/C and Rh/C catalyst, at 277 ℃, 0.34Mpa, in reactor, the amount of 4-HMBA increases earlier with the prolongation in reaction time, and reduce the back.React 4h at the end, the 4-HMBA amount was more than 0.5%Rh/C when 0.5%Pd/C made catalyst, but all was lower than the amount of PT acid in the whole process.In the patent US 5387726 of Degussa company application, selective hydrogenation compares detailed research to 4-CBA.The 4-CBA aqueous solution with 1% is reactant, with Pd/TiO
2(pure anatase) is catalyst, and at 150 ℃, 1Mpa, 4-CBA conversion ratio are 89%, and the selectivity of 4-HMBA is higher than 95%.But when reaction temperature rises to 250 ℃ by 150 ℃, then generate the ring hydrogenation products 4-methyl cyclohexane acid more than 70%.In the patent CN94100192.X of Degussa company application, under the hydrorefined industrial condition of terephthalic acid (TPA), adopt Pd/TiO
2Catalyst reacted 4 hours, and the 4-CBA conversion ratio is greater than 90%, and the selectivity of 4-HMBA reaches 48.3%.In the patent US 6706658 of Englehard company application, the charcoal of extruding with different pore-size distributions is made carrier, the Pd/C catalyst that load P d makes carries out purification of terephthalic acid, the ratio of HMBA/PT acid is up to 3.25 in the product, the catalyst stability height, deactivation rate is low, but does not have the relevant report of catalyst activity.
Summary of the invention
Technical problem to be solved by this invention is that the P-TA that generates of the 4-CBA hydrogenation that exists in the prior art is water-soluble less, hydrogen-consuming volume is big, the separating energy consumption height, palladium is easily by sulfur poisoning and permanent deactivation in the palladium carbon catalyst, the micro activated carbon particle of sneaking in the product has reduced the problem of product quality, and a kind of new selective hydrocatalyst that is used for purification of terephthalic acid is provided.This catalyst is used for the hydrofining reaction of crude terephthalic acid, have under the reaction condition of HTHP, in highly acid reaction medium, under the prerequisite that guarantees the higher hydrogenation activity of catalyst, improve the selectivity that the 4-CBA reduction generates 4-HMBA, and this catalyst has anti-sulfur poisonous performance preferably, and the characteristics of reaction back p-phthalic acid's product quality raising.
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 selective hydrocatalyst that is used for purification of terephthalic acid comprises following component by weight percentage:
A) 0.05～5% palladium or its oxide;
B) 0.1～10% be selected from least a metal or its oxide in ruthenium, nickel, zinc or the copper;
C) the carrier titanium dioxide of surplus.
In the technique scheme, the consumption preferable range of palladium or its oxide is 0.4～1.5% by weight percentage, and more preferably scope is 0.5～1.0%; Being selected from least a metal in ruthenium, nickel, zinc or the copper or the preferable range of its oxide is 0.2～8%, and more preferably scope is 0.3～6%.
The raw material that active constituent of the present invention is suitable for is as follows:
Palladium: with its chloride, oxide, acetate, nitrate, the acid of chlorine palladium and basic salt thereof, palladium amine complex;
Ruthenium: with its chloride, oxide;
Nickel, zinc, copper: with its oxide, chloride, acetate, nitrate or other soluble-salt.
Preparation of catalysts method of the present invention is as follows:
1. select the TiO of pure anatase crystal for use
2Powder is made binding agent with the methylcellulose of percentage by weight 0.5～3%, makes the plasticizer extruded moulding with the lactic acid of percentage by weight 0.5～3%.120 ℃ of dryings, 500～1200 ℃ of roastings 2～6 hours are made 1～5 millimeter of diameter phi, 3～10 millimeters cylindric carriers of length.
2. active constituent aqueous solution adding surfactant and sodium carbonate are mixed with catalyst activity component solution, adopt methods such as dipping or sprinkling to make active constituent be carried on the TiO 2 carrying surface then, preferred infusion process.0～50 ℃ of dipping temperature is generally room temperature.
3. catalyst in air aging 1～4 hour then adopts reducing agent to reduce processing.Reducing agent can adopt formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose and hydrogen, preferred hydrogen.200～500 ℃ of reduction temperatures, preferred 350～450 ℃.0.5～10 hour recovery time, preferred 1～4 hour.
Than conventional absorbent charcoal carrier much higher crushing strength is arranged because titanium dioxide is made carrier, eliminated the possibility of sneaking into micro activated carbon particle when active carbon is made carrier in the product; Adopt titanium dioxide to improve the anti-sulfur poisonous performance of catalyst as catalyst carrier.Among the present invention owing to be carrier with titanium dioxide, supported palladium and be selected from least a active constituent in ruthenium, nickel, zinc or the copper, make catalyst under the harsh reaction condition of refining crude terephthalic acid, remove impurity 4-CBA high conversion, and its highly selective is converted into 4-HMBA, both satisfied the refining requirement of crude terephthalic acid, to help improving quality, reduction operating cost and the energy resource consumption of product again, existing hydrofining technology is greatly simplified, reduced cost of investment and running cost.Catalyst of the present invention is used for the hydrofining reaction of crude terephthalic acid, at 280 ℃, under the reaction condition of 7.5MPa, the 4-CBA conversion ratio is 93.3%, the selectivity of 4-HMBA is 57.5%, and the yield of 4-HMBA can reach 53.6%, has obtained better technical effect.
Activity of such catalysts appreciation condition in autoclave:
Catalyst amount: 2.0 grams
Crude terephthalic acid amount: 30.0 grams
4-CBA amount: 1.0 grams
Reaction pressure: 7.5Mpa
Reaction temperature: 280 ℃
Sample analysis adopts high pressure liquid chromatographic analysis.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Take by weighing the TiO of the pure anatase crystal of 1000 grams
2Powder is made binding agent with 10 gram methylcellulose, makes plasticizer with 15 gram lactic acid, adds 360 gram water extruded mouldings, 120 ℃ of dryings 5 hours, 550 ℃ of roastings 4 hours, makes the cylindric carrier of 3 millimeters * 5 millimeters of φ again.Take by weighing 50 gram carriers.Take by weighing 1.25 and restrain the chlorine palladium acid solution that contains palladium 20%, again to wherein adding 4.05 gram NiCl
26H
2O adds an amount of surfactant and sodium carbonate again, add at last amount that deionized water is diluted to solution just the submergence titania support be advisable.With the catalyst activity component solution impregnating carrier, wear out and use hydrogen reducing after 24 hours, obtain catalyst prod with pure water washing to neutral and drying then.
[embodiment 2]
Catalyst preparation process and examination condition are with embodiment 1, and wherein the palladium that adds in the active constituent is the chlorine palladium acid solution that 1.5 grams contain palladium 20%, and nickel is 2.12 gram Ni (CH
3COO)
24H
2O.
[embodiment 3]
Catalyst preparation process and examination condition are with embodiment 1, and wherein the palladium that adds in the active constituent is the chlorine palladium acid solution that 2.25 grams contain palladium 20%, and the nickel of adding is 1.12 gram Ni (NO
3)
26H
2O.
[embodiment 4]
Catalyst preparation process and examination condition wherein add 3.78 gram Cu (NO with embodiment 1 in the active constituent
3)
23H
2O.
[embodiment 5]
Catalyst preparation process and examination condition be with embodiment 1, and wherein the palladium that adds in the active constituent is the chlorine palladium acid solution that 1.75 grams contain palladium 20%, adds 1.20 gram ruthenium contents greater than 37.3% RuCl
3NH
2O.
[embodiment 6]
Catalyst preparation process and examination condition wherein add 3.43 gram Zn (NO with embodiment 1 in the active constituent
3)
26H
2O.
[comparative example 1]
Catalyst preparation process and examination condition are with embodiment 1, and wherein carrier adopts active carbon, and active constituent does not add nickel.
[comparative example 2]
Catalyst preparation process and examination condition are with comparative example 1, and wherein active constituent does not add nickel.
Concrete active constituent, active constituent parent, active constituent content that each embodiment and comparative example adopt see Table 1, and what the catalyst that makes adopted that above-mentioned activity rating condition carries out activity rating the results are shown in Table 2.
Table 1
| Activity of such catalysts component, parent and percentage by weight | |
| Embodiment 1 | PdCl 2(0.5％)-NiCl 2(2％)/TiO 2 |
| Embodiment 2 | PdCl 2(0.6％)-Ni(CH 3COO) 2(1％)/TiO 2 |
| Embodiment 3 | PdCl 2(0.9％)-Ni(NO 3) 2(0.5％)/TiO 2 |
| Embodiment 4 | PdCl 2(0.5％)-Cu(NO 3) 2(2％)/TiO 2 |
| Embodiment 5 | PdCl 2(0.7％)-RuCl 3(0.9％)/TiO 2 |
| Embodiment 6 | PdCl 2(0.5％)-Zn(NO 3) 2(1.5％)/TiO 2 |
| Comparative example 1 | PdCl 2(0.5％)/C |
| Comparative example 2 | PdCl 2(0.5％)/TiO 2 |
Table 2
| The 4-CBA conversion ratio, % | The HMBA selectivity, % | The HMBA yield, % | |
| Embodiment 1 | 89.5 | 58.3 | 52.2 |
| Embodiment 2 | 90.6 | 57.9 | 52.5 |
| Embodiment 3 | 93.3 | 57.5 | 53.6 |
| Embodiment 4 | 88.4 | 50.3 | 44.5 |
| Embodiment 5 | 91.9 | 51.5 | 47.3 |
| Embodiment 6 | 88.5 | 48.8 | 43.2 |
| Comparative example 1 | 99.9 | 0.1 | 9.99 |
| Comparative example 2 | 84.6 | 45.5 | 38.5 |
The sulfur poisoning experiment is to inject 10 μ l H in autoclave
2S (saturated aqueous solution), the conversion ratio of detection reaction 4-CBA after 1 hour.Investigate the Pd/TiO of comparative example 2
2The Pd/C catalyst anti-sulfur poisonous performance of catalyst and comparative example 1, its experiment the results are shown in Table 3.Pd/TiO
2The conversion ratio of 4-CBA descends 1.2% when making catalyst, and the conversion ratio of Pd/C catalyst descends 5.3%.This shows with active carbon compares TiO as carrier
2Improved the anti-sulfur poisonous performance of active constituent palladium as carrier.
Table 3
| The 4-CBA conversion ratio, % | The HMBA selectivity, % | The HMBA yield, % | |
| Comparative example 1 | 94.6 | 0.1 | 9.46 |
| Comparative example 2 | 83.4 | 45.6 | 38.0 |
Claims (5)
1, a kind of selective hydrocatalyst that is used for purification of terephthalic acid comprises following component by weight percentage:
A) 0.05～5% palladium or its oxide;
B) 0.1～10% be selected from least a metal or its oxide in ruthenium, nickel, zinc or the copper;
C) the carrier titanium dioxide of surplus.
According to the described selective hydrocatalyst that is used for purification of terephthalic acid of claim 1, it is characterized in that by weight percentage that 2, the consumption of palladium or its oxide is 0.4～1.5%.
According to the described selective hydrocatalyst that is used for purification of terephthalic acid of claim 1, it is characterized in that by weight percentage that 3, the consumption that is selected from least a metal in ruthenium, nickel, zinc or the copper or its oxide is 0.2～8%.
According to the described selective hydrocatalyst that is used for purification of terephthalic acid of claim 2, it is characterized in that by weight percentage that 4, the consumption of palladium or its oxide is 0.5～1.0%.
According to the described selective hydrocatalyst that is used for purification of terephthalic acid of claim 3, it is characterized in that by weight percentage that 5, the consumption that is selected from least a metal in ruthenium, nickel, zinc or the copper or its oxide is 0.3～6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100478757A CN101428226A (en) | 2007-11-07 | 2007-11-07 | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100478757A CN101428226A (en) | 2007-11-07 | 2007-11-07 | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011041151A2 (en) | 2009-09-30 | 2011-04-07 | Bp Corporation North America Inc. | Catalyst, use thereof and process for hydrogenating aryl aldehydes |
| CN102219671A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for selective hydrogenation of aromatic aldehydes for refining terephthalic acid |
| CN102658166A (en) * | 2012-05-07 | 2012-09-12 | 浙江台州清泉医药化工有限公司 | Preparation method and application of ruthenium catalyst for synthesizing 1,4-cyclohexanedicarboxylic acid |
| CN105268434A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| 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
- 2007-11-07 CN CNA2007100478757A patent/CN101428226A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011041151A2 (en) | 2009-09-30 | 2011-04-07 | Bp Corporation North America Inc. | Catalyst, use thereof and process for hydrogenating aryl aldehydes |
| CN102219671A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for selective hydrogenation of aromatic aldehydes for refining terephthalic acid |
| CN102219671B (en) * | 2010-04-15 | 2014-04-23 | 中国石油化工股份有限公司 | Method for selective hydrogenation of aromatic aldehydes for refining terephthalic acid |
| CN102658166A (en) * | 2012-05-07 | 2012-09-12 | 浙江台州清泉医药化工有限公司 | Preparation method and application of ruthenium catalyst for synthesizing 1,4-cyclohexanedicarboxylic acid |
| CN105268434A (en) * | 2014-07-24 | 2016-01-27 | 中国石油化工股份有限公司 | Crude terephthalic acid hydrofining catalyst |
| CN105268434B (en) * | 2014-07-24 | 2018-07-13 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst |
| 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 |
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Application publication date: 20090513 |