CN101347730A - Hydrogenation catalyst for refinement of crude terephthalic acid - Google Patents
Hydrogenation catalyst for refinement of crude terephthalic acid Download PDFInfo
- Publication number
- CN101347730A CN101347730A CNA200710043949XA CN200710043949A CN101347730A CN 101347730 A CN101347730 A CN 101347730A CN A200710043949X A CNA200710043949X A CN A200710043949XA CN 200710043949 A CN200710043949 A CN 200710043949A CN 101347730 A CN101347730 A CN 101347730A
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- Prior art keywords
- catalyst
- palladium
- distributed
- carrier
- terephthalic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007670 refining Methods 0.000 claims abstract description 13
- 230000002860 competitive effect Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 89
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000002156 adsorbate Substances 0.000 claims description 9
- 239000003610 charcoal Substances 0.000 claims description 8
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 239000002344 surface layer Substances 0.000 abstract 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000008595 infiltration Effects 0.000 abstract 1
- 238000001764 infiltration Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000013081 microcrystal Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000000470 constituent Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 102000002322 Egg Proteins Human genes 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 210000003278 egg shell Anatomy 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 oxide Chemical compound 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- AAZAXQRWFXJMCK-UHFFFAOYSA-N C(=O)(O)C1=C(C=O)C=CC=C1.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound C(=O)(O)C1=C(C=O)C=CC=C1.C(C1=CC=C(C(=O)O)C=C1)(=O)O AAZAXQRWFXJMCK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZDPALFHDPFYJDY-UHFFFAOYSA-N [Na].OC=O Chemical compound [Na].OC=O ZDPALFHDPFYJDY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- VNWKTOKETHGBQD-AKLPVKDBSA-N carbane Chemical compound [15CH4] VNWKTOKETHGBQD-AKLPVKDBSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention relates to a hydrogenation catalyst for refining of crude terephthalic acid. The hydrogenation catalyst is mainly used for solving the problems that active component metal Pd microcrystals in the catalyst of the prior art are distributed in micro-holes of activated carbon, the micro-holes are near the surface, the infiltration is shallower, and Pd loss is caused by wear during the using process, thereby reducing the activity of the catalyst and the stability. The hydrogenation catalyst adopts particles which are pre-impregnated by a competitive adsorbent or formed activated carbon as a carrier for loading an active component metal Pd, wherein, at least 45 percent of Pd is distributed on the surface layer of 0.2 to 20mum of the carrier, the Pd of less than 10 percent is distributed between the surface of the carrier to the surface layer of 0.2mum, and the remaining part of Pd is distributed in the inner layer with the depth of 20 to 400mum; therefore, the technical proposal can better solve the problems and can be used in the industrial production for hydrogenation refining of the crude terephthalic acid.
Description
Technical field
The present invention relates to a kind of refining catalyst of crude terephthalic acid that is used for.
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 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.For the consideration that makes full use of noble metal, Pd/carbon catalyst is made eggshell type usually, promptly allows 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.United States Patent (USP) 4476242 proposes the active constituent palladium is all concentrated on the top layer of thickness less than 70～80 μ m.United States Patent (USP) 6066589 proposes and will be positioned at the top layer of carrier surface less than 50 μ m less than 50%Pd, and remaining palladium is positioned at the top layer of 50～400 μ m.But the Pd/C catalyst that the eggshell type active constituent distributes is because surface abrasion causes the loss of palladium to cause catalysqt deactivation easily, so egg-shell catalyst active constituent palladium is distributed in outer surface unfavorable factor is also arranged.Preparing Pd distribution rational catalyst, is the key factor that improves catalytic performance, prolongs catalyst life.
Summary of the invention
Technical problem to be solved by this invention is to overcome active constituent Metal Palladium crystallite in the catalyst that exists in the prior art to be distributed in the micropore of active carbon near the surface, infiltrate more shallow, in use, wearing and tearing run off because of causing palladium, cause catalyst activity reduction and problem that stability reduces, a kind of new refining hydrogenation catalyst of crude terephthalic acid that is used for is provided.This catalyst is used for the hydrofinishing refining reaction of crude terephthalic acid, has minimizing and causes the loss of catalyst surface active component Metal Palladium because of wearing and tearing, catalyst stability height, long characteristics of life-span.
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 refining hydrogenation catalyst of crude terephthalic acid that is used for; particle or pressed active carbon with competitive adsorbate pre-preg are carrier; and supported active component Metal Palladium; the Metal Palladium percentage by weight is 0.1～5% in the catalyst; wherein have at least 45% palladium to be distributed in the top layer of carrier 0.2～20 μ m; the top layer that is distributed in carrier surface to 0.2 μ m less than 10% palladium is arranged, and the palladium of remainder is distributed in the internal layer that the degree of depth is 20～400 μ m.
In the technique scheme, carrier is particle or moulding coconut husk charcoal, and specific surface is 600～1800m
2/ g, pore volume are 0.30～0.85ml/g, and wherein the grain graininess more than 90% is 4～8 orders.Palladium percentage by weight preferable range is 0.2～0.6%; 45～60% Metal Palladium is distributed in the top layer of carrier 0.2～20 μ m; The Metal Palladium preferred version of remainder is to be distributed in the internal layer that the degree of depth is 20～180 μ m.
Preparation of catalysts method of the present invention is as follows:
1. select particle or pressed active carbon for use, 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.
2. after removing the dust and surface porosity part of carbon surface absorption, in the washing still, carry out pickling, the acid of adopting is a kind of in hydrochloric acid, nitric acid or the phosphoric acid, be preferably nitric acid, acid concentration is 0.1～5N, spend deionised water then to neutral, in 100～200 ℃ of oven dry down, 110～150 ℃ of preferred temperature.
3. adopt competitive adsorbate pre-preg absorbent charcoal carrier, filter then, oven dry.Competitive adsorbate is a kind of in citric acid, maleic acid, oxalic acid, the lactic acid, optimization citric acid.The concentration of competitive adsorbate is 0.01～0.5N, preferred 0.05～0.2N.The competitive adsorbate dipping temperature is 0～50 ℃, generally selects room temperature.Dip time is 5～60 minutes, preferred 10～30 minutes.100～200 ℃ of bake out temperatures, preferred 110～150 ℃.
4. the active constituent aqueous solution is added surfactant and sodium carbonate and be mixed with catalyst activity component solution, wherein the parent of palladium is with its chloride, oxide, acetate, nitrate, the acid of chlorine palladium and basic salt thereof, palladium amine complex, preferably chlorine palladium acid.Surfactant can be selected anion surfactant for use, preferred dodecyl polyoxyethylene ether phosphate sylvite.Adopt methods such as dipping or sprinkling to make Pd be carried on the carrier active carbon surface then, preferred infusion process.0～50 ℃ of dipping temperature is generally room temperature.The percentage by weight of palladium is 0.1～5% in the catalyst, preferred 0.2～0.6%.
5. catalyst in air aging 1～24 hour then adopts reducing agent to reduce processing.Reducing agent can adopt formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose and hydrogen, preferable formic acid sodium.0～200 ℃ of reduction temperature, preferred 50～120 ℃.0.5～10 hour recovery time, preferred 1～4 hour.
Catalyst among the present invention is owing to adopt competitive adsorbate pre-preg absorbent charcoal carrier, the top layer that is distributed in carrier surface to 0.2 μ m less than 10% palladium is only arranged, have minimizing and cause the loss of catalyst surface active component Metal Palladium, catalyst stability height, long characteristics of life-span because of wearing and tearing.Catalyst of the present invention is used for the hydrofining reaction of crude terephthalic acid, and at 280 ℃, under the reaction condition of 7.5MPa, the 4-CBA conversion ratio is 99.1%.Catalyst was carried out ultrasonic processing after 30 minutes, only was 0.01% because the Pd that the top layer wearing and tearing cause runs off, and the 4-CBA conversion ratio still is 98.3%, reduces by 0.8% before the only more ultrasonic processing, has obtained better technical effect.
The appreciation condition of catalyst 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 amount of the amount of≤20 μ m Pd and≤180 μ m Pd records by electron probe power spectrum (EPMA); ≤ 0.2 μ m top layer Pd atomicity ratio records by photoelectron spectroscopy (XPS).The percentage by weight of Pd is recorded by plasma atomic emission spectrometer (ICP-AES) analysis in the catalyst.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Take by weighing 50 grams, 4～8 orders, laminar cocoanut active charcoal, specific surface is 1078m
2/ g, pore volume are 0.47ml/g.After removing the dust and surface porosity part of carbon surface absorption, be that the nitric acid of 0.5N carries out pickling with concentration in the washing still, 80 ℃ of wash temperatures, spend deionised water then to neutrality at 1 hour pickling time.And it is following dry 2 hours at 120 ℃.Be the citric acid solution pre-preg active carbon 15 minutes at room temperature of 0.1N with concentration, filter then, and 120 ℃ dry 2 hours down.Take by weighing 1.25 and restrain the chlorine palladium acid solution that contains palladium 20%, again to wherein adding an amount of surfactant dodecyl polyoxyethylene ether phosphate sylvite and sodium carbonate, the pH value of regulator solution is 5.5, add then deionized water to the amount of solution just the submergence absorbent charcoal carrier be 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.
[embodiment 2]
Catalyst preparation process is with embodiment 1, and wherein competitive adsorbate is a lactic acid.
[embodiment 3]
Catalyst preparation process is with embodiment 1, and wherein citric acid solution is 0.15N, and dip time is 20 minutes.
[embodiment 4]
Catalyst preparation process wherein adds the chlorine palladium acid solution that 0.5 gram contains palladium 20% with embodiment 1.
[comparative example 1]
Catalyst preparation process is with embodiment 1, wherein without competitive adsorbate pre-preg absorbent charcoal carrier.
[comparative example 2]
Catalyst preparation process does not wherein add surfactant dodecyl polyoxyethylene ether phosphate sylvite with embodiment 1 in the active constituent solution.
What concrete active constituent parent, active constituent content, the active constituent degree of depth that each embodiment and comparative example adopt and the catalyst that makes adopted that above-mentioned activity rating condition carries out activity rating the results are shown in Table 1.
Table 1
The catalyst of each embodiment and comparative example carried out the content of Pd in the catalyst of ultrasonic processing after 30 minutes and result that activity of such catalysts is estimated as shown in table 2.
Table 2
| Pd percentage by weight % | The loss amount of Pd, % | The 4-CBA conversion ratio, % | Conversion ratio reduction amount, % | |
| [embodiment 1] | 0.48 | 0.03 | 97.9 | 1.3 |
| [embodiment 2] | 0.48 | 0.02 | 98.0 | 1.4 |
| [embodiment 3] | 0.49 | 0.01 | 98.3 | 0.8 |
| [embodiment 4] | 0.19 | 0.02 | 80.5 | 1.0 |
| [comparative example 1] | 0.42 | 0.07 | 95.5 | 4.4 |
| [comparative example 2] | 0.49 | 0.02 | 93.2 | 1.1 |
Claims (5)
1, a kind of refining hydrogenation catalyst of crude terephthalic acid that is used for; particle or pressed active carbon with competitive adsorbate pre-preg are carrier; and supported active component Metal Palladium; the Metal Palladium percentage by weight is 0.1～5% in the catalyst; wherein have at least 45% palladium to be distributed in the top layer of carrier 0.2～20 μ m; the top layer that is distributed in carrier surface to 0.2 μ m less than 10% palladium is arranged, and the palladium of remainder is distributed in the internal layer that the degree of depth is 20～400 μ m.
2, according to the described refining hydrogenation catalyst of crude terephthalic acid that is used for of claim 1, it is characterized in that described carrier is particle or moulding coconut husk charcoal, specific surface is 600～1800m
2/ g, pore volume are 0.30～0.85ml/g, and the grain graininess of wherein wt percentage more than 90% is 4～8 orders.
3, according to the described refining hydrogenation catalyst of crude terephthalic acid that is used for of claim 1, it is characterized in that the palladium percentage by weight is 0.2～0.6%.
4,, it is characterized in that 45～60% Metal Palladium is distributed in the top layer of carrier 0.2～20 μ m according to the described refining hydrogenation catalyst of crude terephthalic acid that is used for of claim 1.
5, according to the described refining hydrogenation catalyst of crude terephthalic acid that is used for of claim 1, it is characterized in that the Metal Palladium of remainder is distributed in the internal layer that the degree of depth is 20～180 μ m.
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| CN200710043949XA CN101347730B (en) | 2007-07-18 | 2007-07-18 | Hydrogenation catalyst for refinement of crude terephthalic acid |
| DE102008033324.7A DE102008033324B4 (en) | 2007-07-18 | 2008-07-16 | Pd/C hydrogenation catalyst, production and use thereof |
| KR1020080069963A KR101462690B1 (en) | 2007-07-18 | 2008-07-18 | Pd/C hydrogenation catalyst, preparation and use thereof |
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| 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 |
| DE4209832A1 (en) | 1992-03-26 | 1993-09-30 | Henkel Kgaa | Shell catalyst, its production process and its use |
| TW377306B (en) | 1996-12-16 | 1999-12-21 | Asahi Chemical Ind | Noble metal support |
| ITMI971161A1 (en) | 1997-05-19 | 1998-11-19 | Montecatini Tecnologie Srl | HYDROGENATION CATALYSTS |
| EP1186583A1 (en) * | 2000-09-07 | 2002-03-13 | Degussa AG | Process for carrying out C-C coupling reactions |
| JP2003144921A (en) * | 2001-11-08 | 2003-05-20 | Daicel Chem Ind Ltd | Dehalogenation catalyst and method for manufacturing high purity monochloroacetic acid |
| CN1213803C (en) * | 2002-05-16 | 2005-08-10 | 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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| DE102008033324B4 (en) | 2022-03-31 |
| KR101462690B1 (en) | 2014-11-17 |
| KR20090009153A (en) | 2009-01-22 |
| CN101347730B (en) | 2011-07-13 |
| DE102008033324A1 (en) | 2009-02-19 |
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