CN106732559B - 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
- Publication number
- CN106732559B CN106732559B CN201611214948.2A CN201611214948A CN106732559B CN 106732559 B CN106732559 B CN 106732559B CN 201611214948 A CN201611214948 A CN 201611214948A CN 106732559 B CN106732559 B CN 106732559B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- palladium
- cherry stone
- carbon
- koh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 241000167854 Bourreria succulenta Species 0.000 title claims abstract description 41
- 235000019693 cherries Nutrition 0.000 title claims abstract description 41
- 239000004575 stone Substances 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 15
- 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 4
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 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
- 238000010792 warming Methods 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- 230000009467 reduction Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000203 mixture 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
- 238000003756 stirring Methods 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
- 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
- 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
- 238000002386 leaching Methods 0.000 claims 1
- 238000005554 pickling Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 48
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229910021385 hard carbon Inorganic materials 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 7
- 241000737241 Cocos Species 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 239000000463 material 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
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 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
- 230000003213 activating effect Effects 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
- 238000001802 infusion Methods 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
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 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
- 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, 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 used as presoma using cherry stone, by high temperature cabonization, then pass through activation of potassium hydroxide and nitrogen atom doping in situ is carried out in activation process, so as to the porous cherry stone hard carbon material for obtaining Large ratio surface, surface nitrogen atom is modified, energy more preferable dispersed catalyst during as carrier, show more excellent catalytic performance, there is more excellent mechanical strength simultaneously, the problems such as being crushed 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 being used to produce fiber, resin, film, is to produce in the world
The high polymer material that amount is maximum, demand speedup is most fast.Industrial p-phthalic acid (PTA) is the important forerunner for producing PET
Body, PTA more than 42,000,000 tons (R.Pellegrini, etc.Journal of Catalysis 280 of annual production
(2011)150-160).Terephthalic acid (TPA) is that Co (OAc) is used in acetic acid by terephthaldehyde's alkane2And Mn (OAc)2As urging
(F.Menegazzo, etc.Catalysis Communications 8 (2007) 876-879) is made in agent oxidation.But the party
Formic acid benzaldehyde (4-CBA), these impurity are reduced containing about 3000ppm in crude terephthalic acid made from 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
Crude terephthalic acid is removed so as to obtain p-phthalic acid (PTA).Industrial generally use graininess cocos active carbon
The Pd of load passes through H as catalyst2, 4-CBA is reduced to p-methylbenzoic acid (PT), and then walk by Crystallization Separation etc.
Suddenly obtained PTA products.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 of one side Pd catalyst and stability have much room for improvement, the machinery of another aspect carrier
Intensity is poor, easily crushes, and 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 Pd catalytic activity and stability how is preferably improved, and use has more high mechanical properties
Carrier be research key.Wang etc. uses C3N4/ AC has found C as carrier loaded Pd catalyst3N4Surface energy is good
Scattered 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 is as carrier, (Applied
Catalysis A:General 498 (2015) 222-229) find that the regular pore structure of this macropore is advantageous to mass transfer, so as to
Show higher activity.S.Tourani etc. promotes the diffusion of reaction molecular using the unique mesopore tubular structure of CNT,
Its catalyst loaded shows the performance more more excellent than Pd/AC (Journal of Industrial and
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 are got 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 pass through 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 uses for existing p -carboxybenzaldehyde refining reaction, easily reunite after reaction and lose
Living, activity carbon carrier bad mechanical strength is easily broken, and causes catalyst inactivation, the problem of contamination of products, utilizes high mechanical properties
Cherry stone carbon as carrier, and in-situ activation is carried out to carbon-coating and nitrogen-atoms surface is modified and then preferably scattered Pd catalysis
Agent, the activated carbon loaded Pd catalyst of obtained cherry stone are expected to substitute the Pd/C catalyst used at this stage in the industry.
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, 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
It is molded 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 made
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 made
Cherry Stone)；Or activated under nitrogenous precursor atmosphere using KOH and nitrogen-atoms is introduced into carbon skeleton, activation is made
And cherry stone carbon material N-Ac-CS (the Nitrogen doped and Activated Cherry that surface nitrogen atom Erbium-doped is miscellaneous
Stone)；
C) supported palladium, Pd/CS, Pd/Ac-CS and Pd/N-Ac-CS catalyst is made；
D) reduce, Pd/CS, Pd/Ac-CS or Pd/N-Ac-CS catalyst of reduction is made.
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.
KOH is mixed after cherry stone roasting in the step b), is warming up to 600-1200 DEG C under an inert atmosphere, heating speed
Rate is 3-10 DEG C/min, and room temperature is down to after reacting 0.1-10h, removes K remaining in sample by acid solution；Or in cherry stone
KOH is mixed after roasting, 600-1200 DEG C of progress situ Nitrogen Doping is warming up under the atmosphere of nitrogenous precursor, after cooling, through acid
Wash away and remove K.
Wherein, KOH and CS mass ratio is 1:5~20:1.
KOH hybrid modes are divided into two kinds, and the first is the cherry stone carbon material mechanical mixture by KOH and roasting,；Second
To be loaded to KOH solution in CS by infusion process, drying obtains KOH and CS mixture.
In the step b) acid solution be nitric acid, hydrochloric acid, sulfuric acid, it is more than one or two kinds of in hydrofluoric acid, nitrogenous forerunner
Body is ammonia, acetonitrile, more than one or both of hydrazine, and nitrogenous precursor flow is 5~200mL/min, preferably 20~
80mL/min。
The step a) and b) in inert atmosphere be nitrogen, argon gas, more than one or both of helium, inert atmosphere stream
Measure 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 stir it is dry, then in 60~100 DEG C dry 12~24 hours.
Preferably, in palladium chloride solution, palladium nitrate solution, palladium solution or palladium acetylacetonate solution palladium mass concentration
For 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 is using cherry stone as presoma, by high temperature cabonization, then by activation of potassium hydroxide and is activating
Nitrogen atom doping in situ is carried out in journey, so as to the porous cherry stone hard carbon material for obtaining Large ratio surface, surface nitrogen atom is modified, is made
For carrier when can more preferable dispersed catalyst, show more excellent catalytic performance, while have more excellent machinery strong
Degree, the problems such as being crushed in carbon carrier course of reaction can be slowed down, 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
Fig. 1 cherry stone carbon CS transmission electron microscope photo；
The N of obtained cherry stone carbon under Fig. 2 different conditions2Isothermal adsorption desorption curve；
Fig. 3 .N-Ac-CS XPS spectrum figure；
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.
Embodiment
The present invention is further elaborated below by embodiment.
【Embodiment 1】The preparation of cherry stone carbon carrier
(a) first, 2g cherry stones are put into tube furnace, are warming up to 800 DEG C being passed through Ar gas atmosphere programs, heating rate
For 5 DEG C/min, Ar flow velocitys are 50mL/min, are incubated 3h, then cool under Ar.Obtained material designation is CS.
As shown in Fig. 1 electromicroscopic photographs, CS is that sheet coke build-up forms.Shown in Fig. 2, CS specific surface areas reach 399m2/ g, pore volume
For 0.29cm3/g。
(b) using KOH activation CS materials, Ac-CS samples are prepared：By CS incipient impregnation KOH solutions, KOH and CS mass
Than for 2:1, after the drying of 80 DEG C of vacuum drying oven, under Ar atmosphere, temperature programming is to 800 DEG C, and heating rate is 5 DEG C/min, Ar flow velocitys
For 50mL/min, 3h is incubated, is then cooled under Ar.Obtained material designation is Ac-CS.Shown in Fig. 2, Ac-CS ratio surface
Product can reach 1040m2/ g, pore volume 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 are 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 N-Ac-CS ratio
Surface area is 1155m2/ g, pore volume 0.58cm3/g.The N dopings as shown in Fig. 3 XPS data are 8.2%.It is from fig. 4, it can be seen that relative
Wider in the spectral peak for the carbon that 2 θ are 23 positions in CS, Ac-CS and N-Ac-CS, this explanation Ac-Cs and N-Ac-CS sample has more
Small crystal grain and more defective bits.
【Embodiment 2】The preparation of cherry stone carbon Pt-supported catalyst
Will【Embodiment 1】0.577g PdCl are instilled dropwise under being stirred in 0.5g carriers (20-40 mesh)2The aqueous solution (Pd matter
Measuring percentage composition is：0.457%), stir to doing, overnight, 300 DEG C of hydrogen (50ml/min) reduce 3 hours, obtain for 80 DEG C of drying
0.5% Pd/CS and Pd/AC-CS, Pd/N-AC-CS sample.To Pd/Ref-carbon (cocos active carbon) catalysis contrasted
Agent, chlorine palladium acid is used 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, Hydrogen Vapor Pressure 0.4MPa of temperature, often
A sample was taken every ten minutes, using the content of the 4-CBA in efficient liquid phase chromatographic analysis course of reaction, utilizes reaction equation ln (C0/
Ci)=kt (C0For the concentration of CBA before reaction, CiFor CBA instant concentration, 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 of catalyst and CBA hydrogenation reactions.200 DEG C, Hydrogen Vapor Pressure 0.40MPa of temperature, ageing time
25 hours.Reactivity measure after aging is 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. a kind of preparation method of the palladium catalyst of cherry stone carbon load, the cherry stone carbon of the catalyst is shaped granule shape,
The weight content of palladium in the catalyst is 0.05~2%, it is characterised in that is comprised the following steps：
A) cherry stone presoma is calcined in an inert atmosphere, the cherry stone carbon material CS of roasting is made；
B) activated under an inert atmosphere using KOH, the cherry stone carbon material Ac-CS of activation is made；Or using KOH before nitrogenous
Drive and activated under body atmosphere, activation and the miscellaneous cherry stone carbon material N-Ac-CS of surface nitrogen atom Erbium-doped is made；
C) supported palladium, Pd/Ac-CS and Pd/N-Ac-CS catalyst is made；
D) reduce, Pd/Ac-CS the or Pd/N-Ac-CS catalyst of reduction is made.
2. the preparation method of catalyst according to claim 1, 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 reacting 0.1-10h.
3. the preparation method of catalyst according to claim 1, it is characterised in that in the step b) after cherry stone roasting
KOH is mixed, is warming up to 600-1200 DEG C under an inert atmosphere, heating rate is 3-10 DEG C/min, and room is down to after reacting 0.1-10h
Temperature, K remaining in sample is removed by acid solution；Or KOH is mixed after cherry stone roasting, under the atmosphere of nitrogenous precursor
600-1200 DEG C of progress situ Nitrogen Doping is warming up to, after cooling, K is removed through pickling；KOH and CS mass ratio is 1:5~20:1,
KOH hybrid modes are divided into two kinds, and the first is the cherry stone carbon material mechanical mixture by KOH and roasting；Second is to pass through leaching
Stain method loads to KOH solution in CS, and drying obtains KOH and CS mixture.
4. the preparation method of catalyst according to claim 3, it is characterised in that acid solution is nitric acid, salt in the step b)
It is more than one or two kinds of in acid, sulfuric acid, hydrofluoric acid, nitrogenous precursor be one or both of ammonia, acetonitrile, hydrazine with
On, nitrogenous precursor flow is 5~200mL/min；The step a) and b) in inert atmosphere be nitrogen, argon gas, in helium
One or more, 10~200mL/min of inert atmosphere flow.
5. the preparation method of catalyst according to claim 1, it is characterised in that according to load needed for palladium in the step c)
Amount, adding palladium chloride solution, palladium nitrate solution, palladium solution or palladium acetylacetonate solution, the mass concentration of wherein palladium is
0.1%-1%, 20~25 DEG C stir it is dry, then in 60~100 DEG C dry 12~24 hours.
6. the preparation method of catalyst according to claim 1, it is characterised in that in the step d) using hydrogen reducing or
Other reducing agent liquid-phase reductions, hydrogen reducing are carried out 2~4 hours at 100~300 DEG C, the ml/min of hydrogen flowing quantity 25~50
Clock, other reducing agents are sodium borohydride or hydrazine hydrate.
7. the palladium that cherry stone carbon prepared by a kind of preparation method according to catalyst described in claim 1-6 any one loads is urged
Agent, it is characterised in that：
A) cherry stone carbon is shaped granule shape；
B) weight content of palladium in the catalyst is 0.05~2%.
8. catalyst according to claim 7, it is characterised in that：The cherry stone carbon carrier is particle diameter 5-80 mesh, averagely
Aperture 1-100 nanometers, specific surface area 30-3000m2/ g shaping porous carbon, it is former doped with N atoms, N in the porous carbon structure
The doping of son is the 1~15% of porous carbon quality.
A kind of 9. application of catalyst as described in claim 7 or 8 in terephthalic acid (TPA) hydrofining reaction.
10. one kind catalyst as described in claim 7 or 8 reacts hydrogenation of chloronitrobenzene, crotonaldehyde hydrogenation and Chinese cassia tree in liquid-phase hydrogenatin
Application in aldehyde hydrogenation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611214948.2A CN106732559B (en) | 2016-12-26 | 2016-12-26 | A kind of palladium catalyst of cherry stone carbon load and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611214948.2A CN106732559B (en) | 2016-12-26 | 2016-12-26 | A kind of palladium catalyst of cherry stone carbon load and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106732559A CN106732559A (en) | 2017-05-31 |
| CN106732559B true CN106732559B (en) | 2017-12-22 |
Family
ID=58920636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611214948.2A Active CN106732559B (en) | 2016-12-26 | 2016-12-26 | A kind of palladium catalyst of cherry stone carbon load and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732559B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092296A (en) * | 2018-08-17 | 2018-12-28 | 中国科学院长春应用化学研究所 | A kind of carbon load palladium oxide nanocluster catalyst and the preparation method and application thereof |
| CN109289886B (en) * | 2018-08-31 | 2019-09-24 | 浙江新和成股份有限公司 | PdIn alloy catalyst and preparation method thereof, application |
| US10737250B2 (en) | 2018-08-31 | 2020-08-11 | Zhejiang Nhu Company Ltd. | PdIn alloy catalyst, method for manufacturing PdIn alloy catalyst and application thereof |
| CN109999811A (en) * | 2019-05-07 | 2019-07-12 | 鲁东大学 | It a kind of preparation of biomass iron carbon composite and degrades bisphenol-A for catalytic activation sodium peroxydisulfate |
| CN112237946B (en) * | 2019-07-17 | 2023-05-02 | 中国石油化工股份有限公司 | Terephthalic acid hydrofining reaction and catalyst thereof |
| CN112237937B (en) * | 2019-07-18 | 2023-08-29 | 中国石油化工股份有限公司 | Nitrogen-doped zirconia carrier, and preparation method and application thereof |
| CN111068667A (en) * | 2019-12-03 | 2020-04-28 | 昆明理工大学 | Preparation method and application of miscanthus sinensis mesoporous activated carbon-based palladium nanoparticle catalyst |
| CN114160126B (en) * | 2021-12-20 | 2023-03-17 | 四川大学 | Palladium-carbon catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
| CN103846100A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Pd/C-SiC catalyst for p-phthalic acid hydrorefining, preparation method and application thereof |
-
2016
- 2016-12-26 CN CN201611214948.2A patent/CN106732559B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103846100A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Pd/C-SiC catalyst for p-phthalic acid hydrorefining, preparation method and application thereof |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
Non-Patent Citations (1)
| Title |
|---|
| 以林果废物为原料制活性炭;无;《资源开发与市场》;19961231;第12卷(第1期);第37页最后1-2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106732559A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732559B (en) | A kind of palladium catalyst of cherry stone carbon load and preparation method and application | |
| CN103316694A (en) | Preparation method of composite material of Zn0.8Cd0.2S and graphene | |
| CN108452799B (en) | Preparation method of supported silver catalyst and application of supported silver catalyst in preparation of benzaldehyde by catalyzing anaerobic dehydrogenation of benzyl alcohol | |
| CN111450843B (en) | High-efficiency Ru/Co limited-area ammonia synthesis catalyst and preparation method and application thereof | |
| CN104353481A (en) | Nitrogen-doped mesoporous carbon catalyst for wastewater degradation as well as preparation method and application thereof | |
| Xie et al. | Carbon supported copper catalyst prepared in situ by one-pot pyrolysis of Bougainvillea glabra: An efficient and stable catalyst for selective oxidation of cyclohexane | |
| CN106984324B (en) | The preparation method of visible-light response type cagelike structure vanadic acid copper hydrate photochemical catalyst | |
| CN103846100A (en) | Pd/C-SiC catalyst for p-phthalic acid hydrorefining, preparation method and application thereof | |
| CN104941642A (en) | Preparation method for nanogold particle loading CeO2-TiO2 composite catalyst | |
| WO2024078051A1 (en) | Biomass skeleton carbon-metal composite micro-nano structure catalytic material, and preparation method and use | |
| CN105618095A (en) | Porous nano-SiC loaded platinum catalyst as well as preparation and application thereof in selective hydrogenation reaction of Alpha-Beta-unsaturated aldehyde | |
| CN103028398A (en) | Method for preparing palladium carbon catalyst for hydrogenation and refining of crude terephthalic acid | |
| CN106391000B (en) | CO dehydrogenation purification reaction Pd (111)/γ-Al2O3Catalyst and preparation method thereof | |
| CN109395719A (en) | A method of in multi-wall carbon nano-tube pipe surface controllable load noble metal nanometer material | |
| CN108479781A (en) | Graphitic carbon wraps up nanometer cobalt mesoporous composite material, preparation method and application | |
| CN105195147A (en) | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst | |
| CN110433858B (en) | Ag/PANI/graphene composite photocatalyst, and preparation method and application thereof | |
| WO2024011905A1 (en) | Metal-supported spinel nickel manganite nanosphere aerogel, preparation method therefor and use thereof | |
| Di et al. | Heteroatom doping effect of Pt/rGO catalysts for formaldehyde abatement at ambient temperature | |
| CN114308061B (en) | NiAu bimetallic alloy nano-catalyst and synthesis and application thereof | |
| CN115283007A (en) | Preparation of platinum metal nanocluster HA molecular sieve and application of platinum metal nanocluster HA molecular sieve in synthesis of 1,2,3, 4-tetrahydroquinoline | |
| CN103223339A (en) | Method for preparing supported Pd-based catalysts | |
| CN113617357A (en) | Preparation method and application of nickel oxide catalyst for removing VOCs (volatile organic compounds) by coupling low-temperature plasma | |
| CN108855209B (en) | Copper-zinc alloy supported hierarchical porous titanium silicalite molecular sieve catalytic material and preparation method thereof | |
| CN107970919A (en) | Modified carbon nano tube material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |