CN100402144C - Method for preparing catalyst for refining of crude terephthalic acid - Google Patents
Method for preparing catalyst for refining of crude terephthalic acid Download PDFInfo
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- CN100402144C CN100402144C CNB2004100252668A CN200410025266A CN100402144C CN 100402144 C CN100402144 C CN 100402144C CN B2004100252668 A CNB2004100252668 A CN B2004100252668A CN 200410025266 A CN200410025266 A CN 200410025266A CN 100402144 C CN100402144 C CN 100402144C
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- active carbon
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- catalyst
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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 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000007670 refining Methods 0.000 title claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 211
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000008139 complexing agent Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 halogen ions Chemical class 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 10
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 32
- 239000000460 chlorine Substances 0.000 claims description 32
- 229910052801 chlorine Inorganic materials 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 11
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000004280 Sodium formate Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 5
- 235000019254 sodium formate Nutrition 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 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 claims description 3
- 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 3
- 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 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 3
- 150000008045 alkali metal halides Chemical class 0.000 claims description 3
- 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 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000021110 pickles Nutrition 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 2
- ORIHZIZPTZTNCU-VMPITWQZSA-N 2-[(E)-hydroxyiminomethyl]phenol Chemical compound O\N=C\C1=CC=CC=C1O ORIHZIZPTZTNCU-VMPITWQZSA-N 0.000 abstract 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 abstract 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 abstract 1
- 229960003540 oxyquinoline Drugs 0.000 abstract 1
- 229960004025 sodium salicylate Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 1
- 101100232929 Caenorhabditis elegans pat-4 gene Proteins 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003574 free electron Chemical group 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing a catalyst for refining crude terephthalic acid. The catalyst uses particles or shaped active carbon as a carrier. The content of metal Pd as a load active component is from 0.2 to 4 wt%. The method of the present invention comprises the following steps in sequence that carrier active carbon is washed by acid and is washed by water to be neutral; the carrier active carbon is immersed by water solution containing halogen ions; the carrier active carbon is dried, and the moisture of the carrier active carbon is removed; a water solubility compound containing Pd, a complexing agent and water are prepared into Pd solution to immerse or spray the carrier active carbon. Measured by the content of palladium, the content of the compound containing palladium in the palladium solution accounts for 15 to 20 wt%, and the molar ratio of the complexing agent to the Pd is (0.01 to 1) to 1. The complexing agent is selected from one of 8-hydroxyquinoline, 2, 3, 4-trihydroxy-4-sulfoacid azobenzene, orthophenanthroline, ortho-aminophenol, sodium salicylate or salicylaldehyde oxime. After the complexing agent is reduced by a reducing agent, a catalyst product is obtained.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the supported palladium/carbon catalyst of hydrogenation reaction, particularly be used for making with extra care the preparation method of the supported palladium/carbon catalyst of crude terephthalic acid by selective hydrogenation.
Background technology
Supported palladium/carbon catalyst is mainly used in the selective hydrogenation of unsaturated compounds, be particularly useful for the refining of crude terephthalic acid, in the crude terephthalic acid impurity such as carboxyl benzaldehyde (be called for short 4-CBA) are changed into other compound after by hydrogenation, separate purification with regard to the method for available crystallization subsequently.Because palladium/carbon catalyst usually adopts single active constituent, in the prior art its improvement research is concentrated on always the structure and the distribution situation of metal Pd on carrier of carrier, and this can produce very big influence to the performance of catalyst really.
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 active component of granule interior not play a role, for the consideration that makes full use of noble metal, usually palladium/carbon catalyst is made eggshell type, promptly allows the basic load of active constituent noble metal in the surface of carrier.
Because hydrogenation reaction is to carry out on the surface of metal Pd, therefore usually for the identical catalyst of metal Pd load capacity, the decentralization of its metal Pd is higher, or the content of crystallite of the metal Pd of load is higher in the catalyst, activity of such catalysts is just higher, and service life is also longer.
If directly will contain Pd compound (as chlorine palladium acid sodium or palladium bichloride) loads on the active carbon, activated carbon surface can the very thin glossiness metal Pd layer of very fast appearance, this mainly is because activated carbon surface contains just like reduction groups such as aldehyde radical, free electrons, very easily make the Pd ion be reduced into the metal Pd of zeroth order, thereby the decentralization of metal Pd is very low in the catalyst that causes making.According to experience in the past, the Pd ion that will contain before the operation in the maceration extract of Pd compound in reduction is transformed into the effect that insoluble compound can be obtained, as at room temperature the water soluble compound hydrolysis of Pd being changed into insoluble Pd (OH)
2Or PdOH
2Load on again behind the O on the active carbon,, can prevent migration and the grain growth of Pd so subsequently with the reduction of reducing agents such as formaldehyde, sodium formate, glucose, formic acid or hydrogen.As U.S. Pat 3,138,560 are introduced, and it adds hydrogen peroxide in maceration extract makes the water soluble compound hydrolysis of Pd generate insoluble compound.But because hydrogen peroxide itself also has oxidisability, it can be with the activated carbon surface radical oxidation, thereby will change the Surface Physical Chemistry character of carrier, promptly change the surface group structure of carrier, this has stronger uncertain negative effect, can damage other performance of catalyst, as carrying palladium intensity, catalyst life, selectivity etc.U.S. Pat 4; 476; the maceration extract that contains the Pd compound is prepared in 242 propositions with organic solvents such as methyl alcohol or pyridines; it is said that this is also very effective to the migration and the grain growth that prevent Pd; but production process use methyl alcohol or pyridine are this in human body harmful's organic compound, all are disadvantageous from ring environment protection or labour protection.In addition, there is patent report chlorine palladium acid solution to be transformed into the palladium glue by adjusting pH value, allegedly can prevent that also the reduction group of activated carbon surface directly is reduced into the Pd ion metal Pd of zeroth order, but glue stability is bad, be difficult to even distribution on carrier active carbon, this can influence the dispersiveness of Pd equally.
Summary of the invention
The invention provides a kind of Preparation of catalysts method that is used for refining crude terephthalic acid, its technical problem to be solved is to make that metal Pd has higher decentralization and content of crystallite in the catalyst that makes, and can overcome existing with the existing defective of class methods simultaneously again.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of Preparation of catalysts method that is used for refining crude terephthalic acid, catalyst is a carrier with particle or pressed active carbon, supported active component metal Pd.The content of metal Pd is 0.2～4wt% in the catalyst, and this preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle is 0.1～5mol/L, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) carrier active carbon is washed with water to neutrality;
3) carrier active carbon is with the solution immersion of halogen-containing ion, and the halogen ion concentration of infiltrate is 0.01～0.5mol/L, and the infiltrate consumption is 0.1～3.0 times of active carbon saturated extent of adsorption, and infiltrating time is 2～24 hours;
4) the dry support active carbon is removed moisture;
5) be mixed with Pd solution with the water-soluble Pd of containing compound and a kind of complexing agent and water, with Pd solution impregnation or sprinkling carrier active carbon, make and contain that Pd is compound loaded to obtain catalyst precarsor in active carbon, the content that contains the Pd compound in the Pd solution is counted 0.21wt%, 0.51wt% or 3.7wt% with Pd, the mol ratio of complexing agent and Pd is (0.01～1): 1, complexing agent is taken from oxine, 2,3, any in 4-trihydroxy-4-sulfonic acid azobenzene, Phen, o-aminophenol, septichen sodium or the salicylaldhyde oxime;
6) catalyst precarsor reduces processing with reducing agent after aging, makes divalence Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
Halide ion described in the above-mentioned steps 3 is preferably Br
-1Or I
-1Described halide ion is preferably from alkali-metal halide, and wherein the halide with potassium is the best.
Above-mentioned steps 5 described complexing agents are preferably oxine, 2,3,4-trihydroxy-4-sulfonic acid azobenzene or Phen; And the mol ratio of complexing agent and Pd is preferably (0.05～0.6): 1; The described Pd of containing compound can be taken from any in the complex of the basic salt of halide, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium of Pd or palladium ammonia usually, is the best with acid of chlorine palladium or palladium wherein.
Above-mentioned steps 6 described reducing agents can be taken from any in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen usually, wherein are best with the sodium formate.
In the present invention, remove and to have added complexing agent when having increased carrier active carbon with the preparation of this step of solution immersion of halogen-containing ion and Pd solution, other parts are then basic identical with existing general palladium/carbon catalyst preparation method, and these preparation process are that those skilled in the art are known, can be usually:
Select suitable active carbon for use, remove the dust and surface porosity part of carbon surface absorption after, in the washing still, carry out pickling, spend deionised water after the pickling to neutral.
Carrier active carbon is with the solution immersion of halogen-containing ion, and drying is removed moisture then.
Get and contain the Pd compound and required complexing agent water is mixed with Pd solution, adopt methods such as dipping or sprinkling to make then and contain the compound loaded catalyst precarsor that on carrier, makes of Pd, then with catalyst precarsor in air aging 1～24 hour.
Catalyst precarsor after aging is handled with the reducing agent reduction, and reduction temperature is 0～200 ℃, and the best is 50～120 ℃.The consumption of reducing agent depends on the dosage of active constituent Pd, is generally 1～10 times of reduction reaction equivalent, is preferably 2～5 times, and the recovery time is 1～10 hour, and the best is 1～4 hour.
With respect to prior art, improvements one of the present invention are to have increased step 3 wherein, and carrier active carbon with the solution immersion of halogen-containing ion, makes halide ion be adsorbed in activated carbon surface after pickling.Because halide ion can be distributed in activated carbon surface very equably, and halide ion and palladium and activated carbon surface all have affinity interaction power preferably, this has just increased the grappling effect of activated carbon surface to palladium, thereby the migratory movement that can reduce palladium is to stop or to delay the grain growth of Metal Palladium.
The 2nd, when the preparation of Pd solution, added complexing agent, complexing agent can produce stronger interaction and generate a kind of complex compound with Pd, so can reduce the redox potential of Pd, when Pd loads on the active carbon, the Pd ion just can not reduced by the activated carbon surface group, thereby the Pd ion can be distributed in activated carbon surface very equably.
Compared with prior art, the invention has the advantages that metal Pd has higher decentralization in the catalyst that makes, content of crystallite is higher, on serviceability, show active high, long service life, and the step that increases in the preparation process is very simple, the raw material that adopts is easy to environmental protection treatment, and the method that adopts can not produce any negative effect to catalyst.
Below will the invention will be further described by specific embodiment, just as described above, method for preparing catalyst provided by the invention mainly comprises six steps, wherein except that step 3 and step 5, other parts and prior art are basic identical, so embodiment will pay attention to giving an example of step 3 and step 5.
In an embodiment:
The measuring method of content of crystallite:
Record the Metal Palladium particle diameter by X-XRF and x-ray diffractometer (XRD), calculate content of crystallite by following formula then:
The activity of such catalysts appreciation condition:
Catalyst consumption: 2.0g
Thick paraxylene amount: 30.0g
4-CBA amount: 1.0g
Reaction pressure: 70 kilograms
Hydrogen partial pressure: 5.0 kilograms
Reaction time: 1.0 hours
Reaction temperature: 270 ℃
The specific embodiment
[embodiment 1]
With 100 grams, 4～8 orders, specific surface 800～1800m
2The cocoanut active charcoal of/g washs with the nitric acid of 0.4mol/L, and wash temperature is 80 ℃, is washed with water to neutrality then.
With KBr and water preparation Br
-Concentration is the infiltrate of 0.01mol/L, incipient impregnation active carbon 2～24 hours, and 80～120 ℃ times dry 2～8 hours are standby.
The chlorine palladium acid solution that contains palladium 15wt% of aequum is got in the preparation of Pd solution, adds deionized water to 40 milliliter, adds the acidic aqueous solution that contains oxine 5wt% of aequum more therein, and adds 60 milliliters of deionized water preparation Pd solution.Behind solution-stabilized 10～200 minutes of the Pd, above-mentioned treated active carbon is obtained catalyst precarsor with the Pd solution impregnation after 3 hours.Aging 24 hours of catalyst precarsor is mixed with reducing solution with hydrazine hydrate 20 grams and pure water 200 grams of 5wt%, and catalyst precarsor is immersed in the reducing solution 2～4 hours, also in addition gets catalyst prod after the drying with the pure water washing to neutral then.
[embodiment 2～8]
Select for use different halide to prepare the infiltrate of halogen-containing ion, all the other are with embodiment 1.It is 1 listed that concrete halide and infiltrate halogen ion concentration see Table.
[embodiment 9～31]
Select for use different to contain the Pd compound and complexing agent is prepared Pd solution, all the other are with embodiment 1.
[embodiment 32～37]
Select for use different to contain the Pd compound and complexing agent is prepared Pd solution, Pd obtains catalyst precarsor with the Pd spray solution after solution-stabilized 10～200 minutes on active carbon, and all the other are with embodiment 1.
[comparative example]
Be washed with water to neutrality after the active carbon pickling, drying, active carbon is directly used the Pd solution impregnation then, and preparation Pd does not add complexing agent during solution, and all the other are with embodiment 1.
It is 2 listed that the concrete mol ratio that contains the content (in Pd) that contains the Pd compound in Pd compound, the Pd solution, concrete complexing agent and complexing agent and Pd that each embodiment and comparative example adopt sees Table, the content of the catalyst metals Pd that makes see Table 3 first be listed as listed.
The catalyst that each embodiment and comparative example make carries out decentralization and content of crystallite is measured, and adopts above-mentioned activity of such catalysts appreciation condition to carry out activity rating, and it the results are shown in Table 3.
Table 1.
| Halide | Halide ion | Halogen ion concentration (mol/L) | |
| Embodiment 1 | Australia's potassium | Br - | 0.01 |
| Embodiment 2 | Australia's potassium | Br - | 0.05 |
| Embodiment 3 | KBr | Br - | 0.20 |
| Embodiment 4 | Australia's potassium | Br - | 0.50 |
| Embodiment 5 | KI | I - | 0.01 |
| Embodiment 6 | KI | I - | 0.05 |
| Embodiment 7 | KI | I - | 0.20 |
| Embodiment 8 | KI | I - | 0.50 |
| Embodiment 9～20 | Australia's potassium | Br - | 0.01 |
| Comparative example | / | / | / |
Table 2.
| The Pd compound | Complexing agent | Pd content (wt%) in the solution | Complexing agent/Pd (mol ratio) | |
| Embodiment 1～8 | The acid of chlorine palladium | Oxine | 0.51 | 0.40 |
| Embodiment 9 | The acid of chlorine palladium | Oxine | 0.51 | 0.05 |
| Embodiment 10 | The acid of chlorine palladium | Oxine | 0.51 | 0.10 |
| Embodiment 11 | Palladium | Oxine | 0.51 | 1.00 |
| Embodiment 12 | The acid of chlorine palladium | 2,3,4-trihydroxy-4-sulfonic acid azobenzene | 0.51 | 0.05 |
| Embodiment 13 | The acid of chlorine palladium | 2,3,4-trihydroxy-4-sulfonic acid azobenzene | 0.51 | 0.10 |
| Embodiment 14 | The acid of chlorine palladium | 2,3,4-trihydroxy-4-sulfonic acid azobenzene | 0.21 | 0.40 |
| Embodiment 15 | Palladium | 2,3,4-trihydroxy-4-sulfonic acid azobenzene | 0.51 | 1.00 |
| Embodiment 16 | The acid of chlorine palladium | Phen | 0.51 | 0.05 |
| Embodiment 17 | The acid of chlorine palladium | Phen | 0.51 | 0.10 |
| Embodiment 18 | The acid of chlorine palladium | Phen | 0.51 | 0.40 |
| Embodiment 19 | Palladium | Phen | 3.7 | 1.00 |
| Embodiment 20 | The acid of chlorine palladium | O-aminophenol | 0.51 | 0.02 |
| Embodiment 21 | The acid of chlorine palladium | O-aminophenol | 0.51 | 0.10 |
| Embodiment 22 | The acid of chlorine palladium | O-aminophenol | 0.51 | 0.40 |
| Embodiment 23 | Palladium | O-aminophenol | 0.51 | 1.00 |
| Embodiment 24 | The acid of chlorine palladium | Septichen sodium | 0.51 | 0.05 |
| Embodiment 25 | The acid of chlorine palladium | Septichen sodium | 0.51 | 0.10 |
| Embodiment 26 | The acid of chlorine palladium | Septichen sodium | 0.51 | 0.40 |
| Embodiment 27 | Palladium | Septichen sodium | 0.51 | 1.00 |
| Embodiment 28 | The acid of chlorine palladium | The salicylaldhyde oxime | 0.51 | 0.05 |
| Embodiment 29 | The acid of chlorine palladium | The salicylaldhyde oxime | 0.51 | 0.10 |
| Embodiment 30 | The acid of chlorine palladium | The salicylaldhyde oxime | 0.51 | 0.40 |
| Embodiment 31 | Palladium | The salicylaldhyde oxime | 0.51 | 1.00 |
| Embodiment 32 | The acid of chlorine palladium | Oxine | 0.51 | 0.50 |
| Embodiment 33 | The acid of chlorine palladium | 2,3,4-trihydroxy-4-sulfonic acid azobenzene | 0.51 | 0.50 |
| Embodiment 34 | The acid of chlorine palladium | Phen | 0.51 | 0.50 |
| Embodiment 35 | Palladium | O-aminophenol | 0.51 | 0.50 |
| Embodiment 36 | The acid of chlorine palladium | Septichen sodium | 0.51 | 0.50 |
| Embodiment 37 | Palladium | The salicylaldhyde oxime | 0.51 | 0.50 |
| Comparative example | The acid of chlorine palladium | 0.51 | / |
Table 3.
| Pd content (wt%) | Decentralization (%) | Content of crystallite (%) | Conversion ratio (%) | |
| Embodiment 1 | 0.5 | 34 | 89 | 100 |
| Embodiment 2 | 0.5 | 33 | 90 | 99.9 |
| Embodiment 3 | 0.5 | 32 | 88 | 99.8 |
| Embodiment 4 | 0.5 | 32 | 90 | 99.9 |
| Embodiment 5 | 0.5 | 36 | 91 | 100 |
| Embodiment 6 | 0.5 | 35 | 89 | 100 |
| Embodiment 7 | 0.5 | 36 | 93 | 99.9 |
| Embodiment 8 | 0.5 | 34 | 89 | 100 |
| Embodiment 9 | 0.5 | 16 | 78 | 99.6 |
| Embodiment 10 | 0.5 | 18 | 82 | 99.7 |
| Embodiment 11 | 0.5 | 28 | 86 | 99.8 |
| Embodiment 12 | 0.5 | 17 | 80 | 99.6 |
| Embodiment 13 | 0.5 | 22 | 83 | 99.6 |
| Embodiment 14 | 0.2 | 35 | 95 | 98.3 |
| Embodiment 15 | 0.5 | 29 | 86 | 99.8 |
| Embodiment 16 | 0.5 | 14 | 75 | 99.5 |
| Embodiment 17 | 0.5 | 20 | 85 | 99.7 |
| Embodiment 18 | 0.5 | 23 | 81 | 99.8 |
| Embodiment 19 | 3.6 | 30 | 88 | 100 |
| Embodiment 20 | 0.5 | 15 | 79 | 99.3 |
| Embodiment 21 | 0.5 | 23 | 84 | 99.6 |
| Embodiment 22 | 0.5 | 26 | 88 | 99.7 |
| Embodiment 23 | 0.5 | 32 | 90 | 99.8 |
| Embodiment 24 | 0.5 | 13 | 70 | 99.1 |
| Embodiment 25 | 0.5 | 15 | 73 | 99.2 |
| Embodiment 26 | 0.5 | 18 | 80 | 99.3 |
| Embodiment 27 | 0.5 | 28 | 88 | 99.9 |
| Embodiment 28 | 0.5 | 10 | 69 | 89.3 |
| Embodiment 29 | 0.5 | 12 | 72 | 90.4 |
| Embodiment 30 | 0.5 | 16 | 80 | 99.5 |
| Embodiment 31 | 0.5 | 26 | 87 | 99.8 |
| Embodiment 32 | 0.5 | 35 | 91 | 99.9 |
| Embodiment 33 | 0.5 | 39 | 97 | 100 |
| Embodiment 34 | 0.5 | 38 | 94 | 100 |
| Embodiment 35 | 0.5 | 29 | 89 | 99.9 |
| Embodiment 36 | 0.5 | 30 | 91 | 99.9 |
| Embodiment 37 | 0.5 | 31 | 92 | 99.9 |
| Comparative example | 0.5 | 3 | 50 | 65.6 |
Claims (9)
1. Preparation of catalysts method that is used for refining crude terephthalic acid, catalyst is a carrier with particle or pressed active carbon, supported active component metal Pd, the content of metal Pd is 0.2～4wt% in the catalyst, this preparation method may further comprise the steps successively:
1) carrier active carbon carries out pickling, and the acid concentration of pickle is 0.1～5mol/L, and a kind of in hydrochloric acid, nitric acid or the phosphoric acid taken from acid;
2) carrier active carbon is washed with water to neutrality;
3) carrier active carbon is with halogen-containing ion Br
-1Or I
-1Solution immersion, the halogen ion concentration of infiltrate is 0.01～0.5mol/L, the infiltrate consumption is 0.1～3.0 times of active carbon saturated extent of adsorption, infiltrating time is 2～24 hours;
4) the dry support active carbon is removed moisture;
5) be mixed with Pd solution with the water-soluble Pd of containing compound and a kind of complexing agent and water, with Pd solution impregnation or sprinkling carrier active carbon, make and contain that Pd is compound loaded to obtain catalyst precarsor in active carbon, the content that contains the Pd compound in the Pd solution is counted 0.21wt%, 0.51wt% or 3.7wt% with Pd, the mol ratio of complexing agent and Pd is 0.01～1: 1, complexing agent is taken from oxine, 2,3, any in 4-trihydroxy-4-sulfonic acid azobenzene, Phen, o-aminophenol, septichen sodium or the salicylaldhyde oxime;
6) catalyst precarsor reduces processing with reducing agent after aging, makes divalence Pd in the Pd compound be reduced to metal Pd and promptly gets catalyst prod.
2. Preparation of catalysts method according to claim 1 is characterized in that the halide ion described in the step 3 is from alkali-metal halide.
3. Preparation of catalysts method according to claim 2 is characterized in that described alkali-metal halide is the halide of potassium.
4. Preparation of catalysts method according to claim 1 is characterized in that the described complexing agent of step 5 is an oxine, 2,3,4-trihydroxy-4-sulfonic acid azobenzene or Phen.
5. according to claim 1 or 4 described Preparation of catalysts methods, the mol ratio that it is characterized in that described complexing agent of step 5 and Pd is 0.05～0.6: 1.
6. Preparation of catalysts method according to claim 1 is characterized in that the described Pd of the containing compound of step 5 takes from any in the complex of the basic salt of the halide of Pd, acetate, nitrate, the acid of chlorine palladium, the acid of chlorine palladium or palladium ammonia.
7. Preparation of catalysts method according to claim 6 is characterized in that the described Pd of containing compound is acid of chlorine palladium or palladium.
8. Preparation of catalysts method according to claim 1 is characterized in that the described reducing agent of step 6 takes from any in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or the hydrogen.
9. Preparation of catalysts method according to claim 8 is characterized in that described reducing agent is a sodium formate.
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| CN104549240B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | Hydrofining crude terephthalic acid catalyst and preparation method thereof |
| CN113600181B (en) * | 2021-06-30 | 2023-08-04 | 中海油天津化工研究设计院有限公司 | Preparation method of nano palladium supported catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394299A (en) * | 1981-10-29 | 1983-07-19 | Standard Oil Company (Indiana) | Palladium-rhodium catalyst for purification of crude terephthalic acid |
| US4791226A (en) * | 1983-06-23 | 1988-12-13 | Amoco Corporation | Catalyst and process for purification of crude terephthalic acid |
| CN1104949C (en) * | 1997-05-19 | 2003-04-09 | 舒德化学公司 | Hydrogenation catalysts |
| CN1457922A (en) * | 2002-05-16 | 2003-11-26 | 中国石化上海石油化工股份有限公司 | Hydrogenating catalyst for refining terephthalic acid |
-
2004
- 2004-06-18 CN CNB2004100252668A patent/CN100402144C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394299A (en) * | 1981-10-29 | 1983-07-19 | Standard Oil Company (Indiana) | Palladium-rhodium catalyst for purification of crude terephthalic acid |
| US4791226A (en) * | 1983-06-23 | 1988-12-13 | Amoco Corporation | Catalyst and process for purification of crude terephthalic acid |
| CN1104949C (en) * | 1997-05-19 | 2003-04-09 | 舒德化学公司 | Hydrogenation catalysts |
| CN1457922A (en) * | 2002-05-16 | 2003-11-26 | 中国石化上海石油化工股份有限公司 | Hydrogenating catalyst for refining terephthalic acid |
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