CN106732559A - A kind of palladium catalyst of cherry stone carbon load and preparation method and application - Google Patents
A kind of palladium catalyst of cherry stone carbon load and preparation method and application Download PDFInfo
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- CN106732559A CN106732559A CN201611214948.2A CN201611214948A CN106732559A CN 106732559 A CN106732559 A CN 106732559A CN 201611214948 A CN201611214948 A CN 201611214948A CN 106732559 A CN106732559 A CN 106732559A
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- cherry stone
- palladium
- carbon
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 241000167854 Bourreria succulenta Species 0.000 title claims abstract description 38
- 235000019693 cherries Nutrition 0.000 title claims abstract description 38
- 239000004575 stone Substances 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 12
- 238000001994 activation Methods 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 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 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000000320 mechanical mixture Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 241000522254 Cassia Species 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 42
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 8
- 241000737241 Cocos Species 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 240000003211 Corylus maxima Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FVCOWOGORBTUGF-UHFFFAOYSA-N benzaldehyde;formic acid Chemical compound OC=O.O=CC1=CC=CC=C1 FVCOWOGORBTUGF-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal 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
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/40—
-
- B01J35/615—
-
- B01J35/618—
-
- B01J35/633—
-
- B01J35/635—
-
- 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
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
-
- 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- 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
Abstract
The invention belongs to catalyst technical field, and in particular to a kind of palladium catalyst of cherry stone carbon load with high activity and preparation method and application.Cherry stone carbon is shaped granule shape in the catalyst, used as carrier hard frame；Palladium is carried on carbon-coating surface, and its weight content in the catalyst is 0.05~2%.The present invention is using cherry stone as presoma, by high temperature cabonization, then nitrogen atom doping in situ is carried out by activation of potassium hydroxide and in activation process, so as to obtain the porous cherry stone hard carbon material of Large ratio surface, surface nitrogen atom modification, energy more preferable dispersed catalyst during as carrier, show more excellent catalytic performance, there is more excellent mechanical strength simultaneously, the problems such as crushing in carbon carrier course of reaction can be slowed down, catalyst life is improved, there is the potential industrial application value for substituting commercial activated carbons in terephthalic acid (TPA) hydrofining reaction.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of palladium chtalyst of the cherry stone carbon load with high activity
Agent and preparation method and application.
Background technology
Ethylene glycol terephthalate (PET) is a kind of raw material for producing fiber, resin, film, is to produce in the world
The macromolecular material that amount is maximum, demand speedup is most fast.Industrial p-phthalic acid (PTA) is the important forerunner for producing PET
Body, the annual production of PTA more than 42,000,000 ton of (R.Pellegrini, etc.Journal of Catalysis 280
(2011)150-160).Terephthalic acid (TPA) is that Co (OAc) is used in acetic acid by terephthaldehyde's alkane2And Mn (OAc)2As urging
Agent oxidation is obtained (876-879 of F.Menegazzo, etc.Catalysis Communications 8 (2007)).But the party
Containing about 3000ppm to formic acid benzaldehyde (4-CBA), the reduction of these impurity in crude terephthalic acid obtained in method (CTA)
The average molecular mass of rate of polymerization and polyester, and the color of impurity influences whether the quality of final products, so needing
By crude terephthalic acid removal so as to obtain p-phthalic acid (PTA).It is industrial generally to use graininess cocos active carbon
The Pd of load as catalyst, by H2, 4-CBA is reduced to p-methylbenzoic acid (PT), and then walk by Crystallization Separation etc.
Suddenly PTA products are obtained.The Pd/C catalyst that world wide is used for 4-CBA hydrogenation every year is annual more than 1000 tons.Present Pd/C is urged
Agent has problems in that the reactivity and stability of one side Pd catalyst have much room for improvement, the machinery of another aspect carrier
Intensity is poor, easily crushes, so as to cause coming off for catalyst, the inactivation of accelerator activator, while the carrier crushed can influence
To the quality of product.So the catalysis activity and stability of Pd how are preferably improved, and using with more high mechanical properties
Carrier be research key.Wang etc. uses C3N4/ AC has found C as carrier loaded Pd catalyst3N4Surface can be well
Dispersion Pd catalyst improves its stability (Catal.Sci.Technol., 2015,5,3926).Li et al. uses silicon oxide-wrapped
Pd catalyst be used for 4-CBA hydrogenation reactions, outer silica shell can effectively avoid the loss (Catalysis of catalyst
Communications 9(2008)2257-2260).Zhu etc. uses CNF/TiO2/ monolith as carrier, (Applied
Catalysis A:The 222-229 of General 498 (2015)) find that the regular pore structure of this macropore is conducive to mass transfer, so that
Show activity higher.S.Tourani etc. promotes the diffusion of reaction molecular using the unique mesopore tubular structure of CNT,
The catalyst of its load shows performance (the Journal of Industrial and more more excellent than Pd/AC
Engineering Chemistry 28(2015)202-210).At present, combination property and price, 4-CBA hydrogenation is anti-in industry
It is still active carbon material to answer commonly utilized carrier.Biomass waste material orange peel, peach shell, pomelo peel, filbert skin, wood chip,
Olive shell etc. (Chemical Engineering Journal, 283 (2016) 789-805) is prepared as a kind of cheap raw material
The porous carbon materials of high porosity get the attention, and biomass porous carbon is in ultracapacitor, lithium ion battery, catalysis etc.
Field shows excellent performance.And active carbon material is prepared as presoma using cherry stone, and by pore structure and surface
The modulation of property for p -carboxybenzaldehyde hydrofining reaction as carrier loaded Pd catalyst so that have no report.
The content of the invention
The Pd/C catalyst that the present invention is used for existing p -carboxybenzaldehyde refining reaction, easily reunites after reaction and loses
Living, activity carbon carrier bad mechanical strength is easily broken, and causes catalyst to inactivate, the problem of contamination of products, using high mechanical properties
Cherry stone carbon as carrier, and carry out that in-situ activation and nitrogen-atoms surface be modified and then preferably dispersion Pd catalysis to carbon-coating
Agent, the activated carbon loaded Pd catalyst of obtained cherry stone is expected to substitute in the industry the Pd/C catalyst for using at this stage.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of palladium catalyst of cherry stone carbon load, wherein：
A) cherry stone carbon is shaped granule shape, used as carrier hard frame；
B) palladium is carried on carbon-coating surface, and its weight content in the catalyst is 0.05~2%.
The cherry stone carbon carrier is particle diameter 5-80 mesh, average pore size 1-100 nanometers, specific surface area 30-3000m2/ g's
Shaping porous carbon.
Doped with N atoms in the porous carbon structure, the doping of N atoms is the 1~15% of porous carbon quality.
A kind of preparation method of the catalyst, comprises the following steps：
A) cherry stone presoma is calcined in an inert atmosphere, so that by the organic carbon in coconut palm core carbon, roasting is obtained
Cherry stone carbon material CS (Cherry Stone)；
B) activated under an inert atmosphere using KOH, the cherry stone carbon material Ac-CS (Activated of activation are obtained
Cherry Stone)；Or activated under nitrogenous precursor atmosphere using KOH and nitrogen-atoms is introduced into carbon skeleton, activation is obtained
And surface nitrogen atom Erbium-doped miscellaneous cherry stone carbon material N-Ac-CS (Nitrogen doped and Activated Cherry
Stone)；
C) supported palladium, is obtained Pd/CS, Pd/Ac-CS and Pd/N-Ac-CS catalyst；
D) reduce, Pd/CS, Pd/Ac-CS or Pd/N-Ac-CS catalyst of reduction is obtained.
In the step a) sintering temperature be 600-1200 DEG C, heating rate be 3-10 DEG C/min, reaction 0.1-10h after
Inert atmosphere drops to room temperature.
Mix KOH after cherry stone roasting in the step b), 600-1200 DEG C is warmed up under an inert atmosphere, heat up speed
Rate is 3-10 DEG C/min, and room temperature is down to after reaction 0.1-10h, removes the K of remaining in sample by acid solution；Or in cherry stone
Mix KOH after roasting, 600-1200 DEG C is warmed up under the atmosphere of nitrogenous precursor carries out situ Nitrogen Doping, after cooling, through acid
Wash away except K.
Wherein, the mass ratio of KOH and CS is 1:5~20:1.
KOH hybrid modes are divided into two kinds, the first be by KOH with roasting cherry stone carbon material mechanical mixture,；Second
It is that drying obtains the mixture of KOH and CS during KOH solution loaded into CS by infusion process.
Acid solution is more than the one or two kinds of in nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid nitrogenous forerunner in the step b)
Body be ammonia, acetonitrile, hydrazine in one or more, nitrogenous precursor flow be 5~200mL/min, preferably 20~
80mL/min。
The step a) and b) in inert atmosphere be nitrogen, argon gas, helium in one or more, inert atmosphere stream
Amount 10~200mL/min, preferably 20~80mL/min.
According to load capacity needed for palladium in the step c), palladium chloride solution, palladium nitrate solution, palladium solution or second are added
Acyl acetone palladium solution, 20~25 DEG C are stirred dry, are then dried 12~24 hours in 60~100 DEG C.
Preferably, palladium chloride solution, palladium nitrate solution, palladium solution or in palladium acetylacetonate solution palladium mass concentration
It is 0.1%-1%.
Hydrogen reducing or other reducing agent liquid-phase reductions are used in the step d).
Preferably, hydrogen reducing is carried out 2~4 hours at 100~300 DEG C, the ml/min of hydrogen flowing quantity 25~50, its
His reducing agent is sodium borohydride or hydrazine hydrate.
A kind of application of catalyst in terephthalic acid (TPA) hydrofining reaction.
A kind of catalyst adds in liquid-phase hydrogenatin reaction such as hydrogenation of chloronitrobenzene, the crotonaldehyde of other Pd/C catalysts
Application in hydrogen and hydrogenation on cinnamic aldehyde.
The present invention by high temperature cabonization, then by activation of potassium hydroxide and was being activated using cherry stone as presoma
Nitrogen atom doping in situ is carried out in journey, so as to obtain Large ratio surface, the porous cherry stone hard carbon material of surface nitrogen atom modification, is made
The more preferable dispersed catalyst of energy, shows more excellent catalytic performance during for carrier, while having more excellent machinery strong
Degree, can slow down the problems such as crushing in carbon carrier course of reaction, catalyst life be improved, in terephthalic acid (TPA) hydrofining reaction
There is the potential industrial application value for substituting commercial activated carbons.
Brief description of the drawings
The transmission electron microscope photo of Fig. 1 cherry stone carbon CS；
The N of obtained cherry stone carbon under Fig. 2 different conditions2Isothermal adsorption desorption curve；
The XPS spectrum figure of Fig. 3 .N-Ac-CS；
The XRD spectra of cherry stone carbon under the conditions of Fig. 4 different disposals；
The initial hydrogenation activity comparison diagram of Fig. 5 different carriers Pt-supported catalysts；
The aging back end hydrogenation activity comparison diagram of Fig. 6 different carriers Pt-supported catalysts.
Specific embodiment
The present invention is further elaborated below by embodiment.
【Embodiment 1】The preparation of cherry stone carbon carrier
A () first, 2g cherry stones is put into tube furnace, 800 DEG C, heating rate are warming up to Ar gas atmosphere programs are passed through
It is 5 DEG C/min, Ar flow velocitys are 50mL/min, are incubated 3h, are then lowered the temperature under Ar.Obtained material designation is CS.
As shown in Fig. 1 electromicroscopic photographs, CS is formed for sheet coke build-up.Shown in Fig. 2, CS specific surface areas reach 399m2/ g, pore volume
It is 0.29cm3/g。
B () activates CS materials using KOH, prepare Ac-CS samples：By CS incipient impregnation KOH solutions, KOH and CS mass
Than being 2:1, after 80 DEG C of drying of vacuum drying oven, under Ar atmosphere, to 800 DEG C, heating rate is 5 DEG C/min, Ar flow velocitys for temperature programming
It is 50mL/min, is incubated 3h, then lowers the temperature under Ar.Obtained material designation is Ac-CS.Shown in Fig. 2, the specific surface of Ac-CS
Product can reach 1040m2/ g, pore volume is 0.5cm3/g。
(c)NH3Atmosphere carries out the activation of CS samples, carries out situ Nitrogen Doping, prepares the N-Ac-CS samples of N doping：Will
CS incipient impregnation KOH solutions, KOH is 2 with CS mass ratioes:1, after 80 DEG C of drying of vacuum drying oven, NH3Under atmosphere, temperature programming
To 800 DEG C, heating rate is 5 DEG C/min, NH3Flow velocity is 50mL/min, 3h is incubated, then in NH3Lower cooling.Obtained material
It is named as N-Ac-CS, NH3Be passed through N atoms can be mixed in carbon material activation process, as shown in Fig. 2 the ratio of N-Ac-CS
Surface area is 1155m2/ g, pore volume is 0.58cm3/g.The N dopings as shown in Fig. 3 XPS data are 8.2%.From fig. 4, it can be seen that phase
Wider in the spectral peak of the carbon that 2 θ are 23 positions for CS, Ac-CS and N-Ac-CS, this explanation Ac-Cs and N-Ac-CS sample has
Smaller crystal grain and more defective bits.
【Embodiment 2】The preparation of cherry stone carbon Pt-supported catalyst
Will【Embodiment 1】In 0.5g carriers (20-40 mesh) 0.577g PdCl are dropwise instilled under stirring2The aqueous solution (the matter of Pd
Measuring percentage composition is：0.457%), to doing, overnight, 300 DEG C of hydrogen (50ml/min) reduce 3 hours, obtain for 80 DEG C of drying for stirring
0.5% Pd/CS and Pd/AC-CS, Pd/N-AC-CS sample.It is used to Pd/Ref-carbon (cocos active carbon) catalysis for contrasting
Agent, uses the acid of chlorine palladium to be prepared for presoma method as described above.
【Embodiment 3】CBA hydrogenation reactions
The activity rating of terephthalic acid (TPA) hydrofinishing Pd/C-SiC catalyst, is carried out in batch reactor.By 0.200
Gram 4-CBA is added in 70 milliliters of water, is added【Embodiment 2】Catalyst 0.050g.100 DEG C of temperature, Hydrogen Vapor Pressure 0.4MPa, often
A sample was taken every ten minutes, using the content of the 4-CBA in efficient liquid phase chromatographic analysis course of reaction, using reaction equation ln (C0/
Ci)=kt (C0It is the concentration of CBA before reaction, CiBe the instant concentration of CBA, k is kinetic coefficient, and t is the reaction time) in k
Value reflects the catalytic performance of catalyst.As shown in Figure 5, the Pd catalyst activities of Ac-CS and N-Ac-CS loads are apparently higher than coconut palm
The catalyst of core charcoal load, the Pd catalyst activities of wherein N-Ac-CS loads are 2.2 times of coconut palm core carbon Pt-supported catalyst.
【Embodiment 4】The aging and CBA hydrogenation reactions of catalyst.200 DEG C of temperature, Hydrogen Vapor Pressure 0.40MPa, ageing time
25 hours.Reactivity after aging is determined and carried out according to the condition of embodiment 3.As shown in fig. 6, after aging, N-Ac-CS
The catalyst of sample load still shows performance the most excellent, and its k value is 3 times of coconut palm nuclear activity carbon supported catalyst.
Claims (10)
1. the palladium catalyst that a kind of cherry stone carbon is loaded, it is characterised in that：
A) cherry stone carbon is shaped granule shape；
B) palladium weight content in the catalyst is 0.05~2%.
2. catalyst according to claim 1, it is characterised in that：The cherry stone carbon carrier is particle diameter 5-80 mesh, average
Aperture 1-100 nanometers, specific surface area 30-3000m2The shaping porous carbon of/g, it is preferable that doped with N in the porous carbon structure
Atom, the doping of N atoms is the 1~15% of porous carbon quality.
3. a kind of preparation method of catalyst as claimed in claim 1 or 2, it is characterised in that comprise the following steps：
A) cherry stone presoma is calcined in an inert atmosphere, the cherry stone carbon material CS of roasting is obtained；
B) activated under an inert atmosphere using KOH, the cherry stone carbon material Ac-CS of activation is obtained；Or using KOH before nitrogenous
Activation under body atmosphere is driven, activation and surface nitrogen atom Erbium-doped miscellaneous cherry stone carbon material N-Ac-CS is obtained；
C) supported palladium, is obtained Pd/CS, Pd/Ac-CS and Pd/N-Ac-CS catalyst；
D) reduce, Pd/CS, Pd/Ac-CS or Pd/N-Ac-CS catalyst of reduction is obtained.
4. the preparation method of catalyst according to claim 3, it is characterised in that sintering temperature is 600- in the step a)
1200 DEG C, heating rate is 3-10 DEG C/min, and room temperature is down under an inert atmosphere after reaction 0.1-10h.
5. the preparation method of catalyst according to claim 3, it is characterised in that in the step b) after cherry stone roasting
Mixing KOH, is warmed up to 600-1200 DEG C under an inert atmosphere, and heating rate is 3-10 DEG C/min, and room is down to after reaction 0.1-10h
Temperature, removes the K of remaining in sample by acid solution；Or mix KOH after cherry stone roasting, under the atmosphere of nitrogenous precursor
Being warmed up to 600-1200 DEG C carries out situ Nitrogen Doping, after cooling, K is removed through pickling；Preferably, the mass ratio of KOH and CS is 1:5
~20:1, KOH hybrid mode is divided into two kinds, and the first is by KOH and the cherry stone carbon material mechanical mixture being calcined；It is for second
During KOH solution loaded into CS by infusion process, drying obtains the mixture of KOH and CS.
6. the preparation method of catalyst according to claim 5, it is characterised in that acid solution is nitric acid, salt in the step b)
It is more than the one or two kinds of in acid, sulfuric acid, hydrofluoric acid, nitrogenous precursor be ammonia, acetonitrile, hydrazine in one or two with
On, nitrogenous precursor flow is 5~200mL/min；The step a) and b) in inert atmosphere be nitrogen, argon gas, helium in
One or more, 10~200mL/min of inert atmosphere flow.
7. the preparation method of catalyst according to claim 3, it is characterised in that loaded according to needed for palladium in the step c)
Amount, adds palladium chloride solution, palladium nitrate solution, palladium solution or palladium acetylacetonate solution, it is preferable that the quality of wherein palladium is dense
It is 0.1%-1% to spend, and 20~25 DEG C are stirred dry, is then dried 12~24 hours in 60~100 DEG C.
8. the preparation method of catalyst according to claim 3, it is characterised in that in the step d) using hydrogen reducing or
Other reducing agent liquid-phase reductions, it is preferable that hydrogen reducing is carried out 2~4 hours at 100~300 DEG C, the milli of hydrogen flowing quantity 25~50
Liter/min, other reducing agents are sodium borohydride or hydrazine hydrate.
9. application of a kind of catalyst as claimed in claim 1 or 2 in terephthalic acid (TPA) hydrofining reaction.
10. a kind of catalyst as claimed in claim 1 or 2 reacts hydrogenation of chloronitrobenzene, crotonaldehyde hydrogenation and Chinese cassia tree in liquid-phase hydrogenatin
Application in aldehyde hydrogenation.
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