CN107442110A - Hydrofining crude terephthalic acid catalyst and preparation method thereof - Google Patents
Hydrofining crude terephthalic acid catalyst and preparation method thereof Download PDFInfo
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- CN107442110A CN107442110A CN201610367518.8A CN201610367518A CN107442110A CN 107442110 A CN107442110 A CN 107442110A CN 201610367518 A CN201610367518 A CN 201610367518A CN 107442110 A CN107442110 A CN 107442110A
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- catalyst
- palladium
- activated carbon
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- 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 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000003377 acid catalyst Substances 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 159
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 128
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 59
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003426 co-catalyst Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 61
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- 239000012018 catalyst precursor Substances 0.000 claims description 45
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000003610 charcoal Substances 0.000 claims description 17
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 14
- 244000060011 Cocos nucifera Species 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000005049 silicon tetrachloride Substances 0.000 claims description 11
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- -1 chromium compound nitrate Chemical class 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 52
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000011260 aqueous acid Substances 0.000 description 20
- 239000004280 Sodium formate Substances 0.000 description 14
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 14
- 235000019254 sodium formate Nutrition 0.000 description 14
- 239000013078 crystal Substances 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- QMABNHIHLIULSZ-UHFFFAOYSA-M sodium formate hydrate Chemical compound [OH-].[Na+].OC=O QMABNHIHLIULSZ-UHFFFAOYSA-M 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 description 6
- FEOIEZBSUVRDJZ-UHFFFAOYSA-N chromium;nitric acid Chemical compound [Cr].O[N+]([O-])=O FEOIEZBSUVRDJZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to hydrofining crude terephthalic acid catalyst and preparation method thereof, mainly solves the problems, such as catalyst heat endurance difference present in prior art, the present invention is by using hydrofining crude terephthalic acid catalyst, including carrier, active component and co-catalyst, the active component is palladium, and the co-catalyst is selected from least one of zirconium and chromium；The carrier is activated carbon or mixes the technical scheme of the activated carbon of Si modification, preferably solves the technical problem, in being produced available for hydrofining crude terephthalic acid.
Description
Technical field
The present invention relates to hydrofining crude terephthalic acid catalyst and preparation method thereof.
Background technology
P-phthalic acid, PTA is commonly called as, is the base stock for synthesizing polyethylene terephthalate (PET).It is negative
Load type Pd/carbon catalyst is applied to the refined of crude terephthalic acid, and the p -carboxybenzaldehyde in crude terephthalic acid is (referred to as
4-CBA) etc. impurity is carried out after hydrogenation is changed into other compounds, then using the method crystallized come separating-purifying.By
Single active constituent is used in Pd/carbon catalyst, so distribution situation of the Metal Palladium on carrier, to catalyst performance
Influence it is very big.
Because terephthalic acid (TPA) hydrofining reaction process is a first order reaction, reaction speed is fast, is reacted in course of reaction
The inside that thing is difficult to be penetrated into catalyst granules is reacted, and this allows for active metal inside particle due to steric hindrance shadow
Ring, not reaching the reactant molecule component being relatively large in diameter can not play a role.Now, the active metal performance of outer surface
The high catalytic activity gone out.For the consideration for making full use of noble metal, usual Pd/carbon catalyst makes eggshell type, that is, allows
The basic load of active constituent palladium is in the surface of carrier.The surface area that palladium contacts with reactant is bigger, and activity is also better.Eggshell
The catalyst of type active constituent distribution has higher hydrogenation catalyst ability than the catalyst for being distributed wider range.Terephthaldehyde
The sour usual reaction pressure of hydrofinishing is 6.5~8.5MPa, and reaction temperature is carried out under the conditions of being 250~290 DEG C, the crystal grain of palladium
Grow up inevitable, at normal reaction conditions, the crystal grain of the inactivation mainly palladium of catalyst is grown up, commercial inactivation
Terephthalic acid (TPA) hydrofinishing palladium carbon catalyst, palladium crystal grain can grow up to more than 20nm, and the palladium of fresh catalyst is brilliant
Grain is between 2~5nm；What the crystal grain of palladium was grown up in commercial Application is faster, then the normal service life of catalyst is then shorter.
The shortening of the service life of catalyst not only causes the waste of the palladium carbon catalyst of costliness, and can cause factory because changing
Catalyst heavy economic losses.A.V.Romanenko et al. proposes the method that Ru is added in active component
(Influence of ruthenium addition on sintering of carbon-supported palladium,Applied
Catalysis A:General 227 (2002) 117-123), the results showed that Ru addition improves the anti-caking power of catalyst,
So as to improve the heat endurance of catalyst；But Ru price is also more expensive than Pd, while Ru addition improves terephthaldehyde
The risk that sour phenyl ring is hydrogenated, United States Patent (USP) US6753290 (Catalytic composition, method for
Manufacturing thereof and method for the purification of terephthalic acid) also there is similar report
Road.United States Patent (USP) US4,892,972 (Purification of crude terephthalic acid) is by using Pd/C and Rh/C
Double-layer catalyst, Pd and Rh ratio are 10:1 is used for hydrofining crude terephthalic acid, as a result finds its catalyst longevity
Life is significantly improved, and Rh crystal grain is not easy to grow up；But Rh price is ten times of Pd, therefore is not applied in practice.
The content of the invention
The problem of one of technical problems to be solved by the invention are catalyst heat endurance differences present in prior art, carries
New be used for hydrofining crude terephthalic acid catalyst, hydrofinishing of the catalyst for crude terephthalic acid for a kind of
Reaction, there is the characteristics of heat-resistant stability is high.
The two of the technical problems to be solved by the invention are the preparation sides of the catalyst corresponding with one of above-mentioned technical problem
Method.
The three of the technical problems to be solved by the invention are the catalyst corresponding with one of above-mentioned technical problem slightly to benzene two
Application in formic acid hydrofinishing.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Hydrofining crude terephthalic acid is urged
Agent, including carrier, active component and co-catalyst, the active component are palladium, and the co-catalyst is selected from zirconium and chromium
At least one of；The carrier is activated carbon or the activated carbon for mixing Si modification.
In above-mentioned technical proposal, Palladium Content in Catalyst is preferably 0.3~1.0wt%.
In above-mentioned technical proposal, cocatalyst content is preferably 0.1~0.5wt%.
In above-mentioned technical proposal, activated carbon mixes silicon compared with normal activated carbon, can improve catalyst stability.
In above-mentioned technical proposal, co-catalyst preferably includes zirconium and chromium simultaneously, and both have in terms of catalyst stability is improved
There is facilitation.
In above-mentioned technical proposal, the silicon amount of mixing in carrier is not particularly limited, as mixing silicon amount in non limiting example carrier
For below 0.5wt%, further, such as, but not limited to 0.1~0.5wt%.
In above-mentioned technical proposal, described activated carbon is preferably ature of coal charcoal, carbo lignius or fruit shell carbon.
In above-mentioned technical proposal, described fruit shell carbon is preferably coconut husk charcoal.
In above-mentioned technical proposal, described coconut husk charcoal is preferably 800~1600m than surface2/ g, pore volume is preferably 0.35~
0.80ml/g。
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The technology of one of above-mentioned technical problem
The preparation method of catalyst described in scheme, including step once：
(1) activated carbon is washed, dried；
(2) by the activated carbon after being dried in step (1) and silicon tetrachloride diethyl ether solution, dimethylsilane diethyl ether solution at least
One kind mixing, then in 30~100 0.5~8h of hydro-thermal process, finally wash, drying obtains catalyst carrier；
(3) pH value containing at least one of palladium and zirconium, the chromium compound aqueous solution is adjusted to 1~10 by alkali compounds,
Obtain catalyst precursor；
(4) catalyst carrier of step (2) is mixed with catalyst precursor, obtains catalyst precarsor i；
(5) it is aged, obtains catalyst precarsor ii；
(6) compound state palladium is reduced to simple substance palladium with reducing agent, obtains catalyst precarsor iii；
(7) washing removes the impurity in catalyst precarsor iii, obtains described catalyst.
In above-mentioned technical proposal, the ratio between pure water and activated carbon volume are preferably (2~10) in step (1) washing：1.
In above-mentioned technical proposal, the content of silicon tetrachloride is preferably 5~15wt% in the silicon tetrachloride diethyl ether solution of step (2).
In above-mentioned technical proposal, the content of dimethylsilane is preferably in the dimethylsilane diethyl ether solution of step (2)
5~15wt%.
In above-mentioned technical proposal, step (2) activated carbon and silicon tetrachloride diethyl ether solution, dimethylsilane diethyl ether solution
In the operation of at least one mixing, with volume basis activated carbon:(silicon tetrachloride diethyl ether solution and dimethylsilane ether are molten
Liquid sum) it is preferably (1.5~2.5):1.
In above-mentioned technical proposal, in step (2) during hydro-thermal process, the ratio between water and activated carbon volume are preferably 1：(2~10).
In above-mentioned technical proposal, step (3) described alkali compounds is preferably alkali metal hydroxide, alkali metal carbonic acid
At least one of salt or ammoniacal liquor, most preferably alkali carbonate, sodium carbonate is most common, generally the least expensive, therefore most optimal
Sodium carbonate is selected, the concentration of aqueous sodium carbonate is 5~15wt%, preferably 10wt%.
In above-mentioned technical proposal, described containing palladium compound may be selected from palladium nitrate, palladium, chlorine palladium acid and its salt and dichloro
At least one of four ammino palladiums, preferably chlorine palladium acid.
In above-mentioned technical proposal, described contains zirconium, at least one of nitrate, acetate is may be selected from containing chromium compound, excellent
Select nitrate.
In above-mentioned technical proposal, the pH value described in step (3) is preferably 3~7.
In above-mentioned technical proposal, catalyst carrier described in step (4) and catalyst precursor hybrid mode for dipping or
Spraying, preferably impregnates, and the volume of maceration extract is preferably 0.3~2.0 times of catalyst support volume, and more preferably 0.3~0.8
Times, most preferably 0.52 times.
In above-mentioned technical proposal, the time of step (5) described ageing is preferably 8~48 hours, more preferably 24 hours.
On step (6), the specific reducing condition such as reducing agent and reductant concentration, recovery time is not the technology of the present invention
Key, those skilled in the art will know that how with reducing agent compound state palladium to be reduced into simple substance palladium.Example reducing agent as mentioned
It is optional to be reduced using at least one of hydrogen, formic acid, formaldehyde or formates.Described formates can be ammonium formate, first
The alkali metal salt of acid, and financially sodium formate is the most frequently used in the alkali metal salt of formic acid.When use sodium formate for reduction
During agent, aqueous sodium formate solution mass percent concentration is preferably 5~10%, and reduction temperature is preferably 30~120 DEG C, more excellent
60~100 DEG C are selected, the recovery time is preferably 0.5~8 hour, and the volume of aqueous sodium formate solution is preferably catalyst precarsor ii
2~4 times.
In above-mentioned technical proposal, step (7) is described to be washed to cleaning solution AgNO3Detection is without Cl-Untill.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The technical scheme of one of above-mentioned technical proposal
Any one of be catalyzed the just application in hydrofining crude terephthalic acid.
Palladium, Zr, Cr content are determined using ICP-AES in the catalyst of the embodiment of the present invention and comparative example, and carrier S i contains
Amount uses XPS measuring.
Catalyst thermal stability determination：
By catalyst in N2Under protection, it is calcined 8 hours at 500 DEG C, is subsequently cooled to room temperature.Use x-ray diffractometer
(XRD) the average crystal grain size of palladium in the catalyst after roasting is surveyed, Debye-Scherrer formula can be used to calculate.
Scherrer formula：Dhkl=k λ/β cos θ, wherein, Dhkl is straight along the crystal grain perpendicular to crystal face (hkl) direction
Footpath, k are Scherrer constants (be usually 0.89), λ be incident X-rays wavelength (Cuka wavelength is 0.15406nm,
Cuka1 wavelength is 0.15418nm.), θ is Bragg diffraction angle (°), and β is the peak width at half height (rad) of diffraction maximum.
The heat endurance of catalyst represents that this value is bigger, surely with the crystal grain Magnification of active component in catalyst before and after roasting
Qualitative smaller, vice versa.Crystal grain Magnification is calculated as：
Crystal grain Magnification=[(Pd of Pd average grain diameter-fresh catalyst average grain diameter after roasting)/fresh catalyst
Pd average grain diameter] × 100%.
The key problem in technology of the inventive method is that the carrier of catalyst of the present invention is the activated carbon through mixing Si modification, is added simultaneously
Zr, Cr metal.Using catalyst of the present invention, after 500 DEG C of processing 8 hours, Pd average crystal grain Magnification is below 72%,
Achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Silicon tetrachloride diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.2 gram of anhydrous nitric acid
Zirconium, regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise while stirring with 10wt% aqueous sodium carbonate, then adds pure water
26ml is settled to, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 2】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Silicon tetrachloride diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.2 gram of anhydrous nitric acid
Chromium, regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise while stirring with 10wt% aqueous sodium carbonate, then adds pure water
26ml is settled to, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 3】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Dimethylsilane diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.2 gram of anhydrous nitric acid
Zirconium, regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise while stirring with 10wt% aqueous sodium carbonate, then adds pure water
26ml is settled to, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 4】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Dimethylsilane diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.2 gram of anhydrous nitric acid
Chromium, regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise while stirring with 10wt% aqueous sodium carbonate, then adds pure water
26ml is settled to, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 5】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Silicon tetrachloride diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.1 gram of anhydrous nitric acid
Zirconium, 0.1 gram of anhydrous nitric acid chromium, regulation chlorine palladium aqueous acid pH is added dropwise while stirring with 10wt% aqueous sodium carbonate
To 4.5, then plus pure water is settled to 26ml, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 6】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Dimethylsilane diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.1 gram of anhydrous nitric acid
Zirconium, 0.1 gram of anhydrous nitric acid chromium, regulation chlorine palladium aqueous acid pH is added dropwise while stirring with 10wt% aqueous sodium carbonate
To 4.5, then plus pure water is settled to 26ml, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 7】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the ratio between the activated carbon of drying and volume
For 1:The dimethylsilane ether mixed solution mixing of 1 10wt% silicon tetrachloride ether and 10wt%, activated carbon is with mixing
It is 2 to close the ratio between volume of solution:1, incorporation time 1h；Then the hydro-thermal process 4h at 50 DEG C, activated carbon and water
The ratio between volume is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.1 gram of anhydrous nitric acid
Zirconium, 0.1 gram of anhydrous nitric acid chromium, regulation chlorine palladium aqueous acid pH is added dropwise while stirring with 10wt% aqueous sodium carbonate
To 4.5, then plus pure water is settled to 26ml, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 1】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry, obtain catalyst carrier.
The preparation of catalyst precursor：Weigh 1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid and 0.2 gram of anhydrous nitric acid
Zirconium, regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise while stirring with 10wt% aqueous sodium carbonate, then adds pure water
26ml is settled to, is uniformly mixing to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 2】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry；By the activated carbon of drying and 10wt%
Silicon tetrachloride diethyl ether solution mixes, and the ratio between volume of activated carbon and solution is 2:1, incorporation time 1h；Then at 50 DEG C
The ratio between volume of lower hydro-thermal process 4h, activated carbon and water is 1:5；Finally wash, drying obtains catalyst carrier.
The preparation of catalyst precursor：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, with 10wt% carbonic acid
Regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise in sodium water solution while stirring, and then plus pure water is settled to 26ml, and stirring is equal
It is even to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 3】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal (is 1100m than surface2/ g, pore volume 0.52ml/g) with pure
Water washing, the ratio between pure water and activated carbon volume are 5:1, then drain, dry and obtain catalyst carrier.
The preparation of catalyst precursor：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, with 10wt% carbonic acid
Regulation chlorine palladium aqueous acid pH to 4.5 is added dropwise in sodium water solution while stirring, and then plus pure water is settled to 26ml, and stirring is equal
It is even to obtain catalyst precursor.
Said catalyst carrier is immersed in catalyst precursor, is aged 24 hours, obtains catalyst precarsor ii；
Temperature is at 80 DEG C, with 8% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, sodium formate water
The volume of solution is 3 times of catalyst precarsor ii volumes, and catalyst precarsor iii is obtained after reduction.It is catalyzed with pure water
Agent precursor iii to cleaning solution AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained
500 DEG C of roastings, 8 hours heat endurances for investigating catalyst under nitrogen protection.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
Table 1.
Table 2
Claims (10)
1. hydrofining crude terephthalic acid catalyst, including carrier, active component and co-catalyst, the active component are
Palladium, the co-catalyst are selected from least one of zirconium and chromium；The carrier is activated carbon or the activated carbon for mixing Si modification.
2. catalyst according to claim 1, it is characterised in that described activated carbon is ature of coal charcoal, carbo lignius or shell
Charcoal.
3. catalyst according to claim 2, it is characterised in that described fruit shell carbon is coconut husk charcoal.
4. catalyst according to claim 1, it is characterised in that described coconut husk charcoal is 800~1600m than surface2/ g,
Pore volume is 0.35~0.80ml/g.
5. the preparation method of the catalyst described in claim 1, including step once：
(1) activated carbon is washed, dried；
(2) by the activated carbon after being dried in step (1) and silicon tetrachloride diethyl ether solution, dimethylsilane diethyl ether solution at least
One kind mixing, then in 30~100 DEG C of 0.5~8h of hydro-thermal process, finally wash, drying obtains catalyst carrier；
(3) pH value containing at least one of palladium and zirconium, the chromium compound aqueous solution is adjusted to 1~10 by alkali compounds,
Obtain catalyst precursor；
(4) catalyst carrier of step (2) is mixed with catalyst precursor, obtains catalyst precarsor i；
(5) it is aged, obtains catalyst precarsor ii；
(6) compound state palladium is reduced to simple substance palladium with reducing agent, obtains catalyst precarsor iii；
(7) washing removes the impurity in catalyst precarsor iii, obtains described catalyst.
6. preparation method according to claim 5, it is characterized in that the alkaline solution alkali metal hydroxide, alkali metal
At least one of carbonate aqueous solution or ammoniacal liquor.
7. preparation method according to claim 5, it is characterised in that described containing palladium compound is selected from palladium nitrate, acetic acid
Palladium, chlorine palladium acid and its at least one of salt and the ammino palladium of dichloro four.
8. preparation method according to claim 5, it is characterised in that it is described be selected from containing zirconium, containing chromium compound nitrate,
At least one of acetate.
9. preparation method according to claim 5, it is characterised in that described reducing agent is selected from hydrogen, formic acid, formaldehyde
Or formates.
10. the just application in hydrofining crude terephthalic acid is catalyzed described in Claims 1 to 4.
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