CN106732742A - Application of supported palladium catalyst in selective hydrogenation reaction - Google Patents
Application of supported palladium catalyst in selective hydrogenation reaction Download PDFInfo
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- CN106732742A CN106732742A CN201611204622.1A CN201611204622A CN106732742A CN 106732742 A CN106732742 A CN 106732742A CN 201611204622 A CN201611204622 A CN 201611204622A CN 106732742 A CN106732742 A CN 106732742A
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- selective hydrogenation
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 70
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 aldehyde ketones Chemical class 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 10
- 238000002803 maceration Methods 0.000 claims description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002444 silanisation Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229940095054 ammoniac Drugs 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 150000002790 naphthalenes Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002808 molecular sieve Substances 0.000 abstract description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 3
- 150000005181 nitrobenzenes Chemical class 0.000 abstract 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000006399 behavior Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 4
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 229930016911 cinnamic acid Natural products 0.000 description 4
- 235000013985 cinnamic acid Nutrition 0.000 description 4
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241000522254 Cassia Species 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GEZYJXGVVUMDHH-UHFFFAOYSA-N [Cl].[O-][N+](=O)C1=CC=CC=C1 Chemical compound [Cl].[O-][N+](=O)C1=CC=CC=C1 GEZYJXGVVUMDHH-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 208000013403 hyperactivity Diseases 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
- C07B35/02—Reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an application of a supported palladium catalyst in selective hydrogenation reaction, wherein the supported palladium catalyst takes Pd as an active component, a mesoporous molecular sieve MCM-41 as a carrier, and nanoparticles of the active component Pd are dispersed on the surface and/or orifices of the carrier. The research of the invention finds that: in the supported catalyst taking Pd as an active component and taking a mesoporous molecular sieve MCM-41 as a carrier, when nano particles of the active component Pd are dispersed on the surface and/or orifices of the carrier, the catalyst activity and/or selectivity are obviously superior to those of a Pd/MCM-41 catalyst without the characteristic, and the catalyst is particularly suitable for selective hydrogenation reaction of unsaturated hydrocarbons, alpha, beta-unsaturated aldehyde ketones and halogenated nitrobenzene compounds.
Description
Technical field
The present invention relates to a kind of application of load type palladium catalyst in selective hydrogenation, belong to heterogeneous catalysis technology
Field.
Background technology
Selection hydrogenation is a main kind of important reaction, occupies important in fields such as petrochemical industry, fine chemistry industry and pharmacy
Status.The noble metal catalyst of support type is the important selective hydrogenation catalyst of a class.Such as noble metal catalyst is in phenylacetylene
Selection hydrogenation (J.Mol.Catal.A, 2014,381:61-69), cinnamic acid selection hydrogenation (J.Catal., 2003,214:78-
87) and nitrohalogen compound selection hydrogenation aspect (J.Mol.Catal.A, 2009,308:Application 79-86) has a large amount of reports
Road.But noble metal hydrogenation hyperactivity, it is therefore desirable to use the distribution of control metal component, add auxiliary agent or reacting
" poisonous substance " is introduced in journey and suppresses the method modulation noble metal catalyst selective hydrogenation behaviors such as the activity or extent of reaction of catalyst.
CN102294269A discloses a kind of resistant to sulfur noble metal hydrogenation desulphurization catalyst, and catalyst disclosed in the case is with silicon
Alkanisation modified silica, silica-rich zeolite, MCM-41 or SBA-15 silicon-based mesoporous molecular sieve porous silica-base materials are used as load
Body, supports noble metal active component, and the case shows that the desulphurizing activated and stability of this kind of catalyst is significantly higher than without silanization
Modified catalyst, and cracking activity is significantly reduced, and shows good hydrodesulfurization performance.The case is not directed to this kind of urging
Application of the agent in selective dehydrogenation reaction.
The content of the invention
Present invention research finds to be urged as active component and using mesostructured material as the support type of carrier using Pd
Agent, when the nano particle of active component Pd is scattered in the surface and/or aperture of the carrier, with good catalysis activity
And/or selective hydrogenation activity, it is substantially better than the catalyst without this feature, example in terms of the conversion ratio and/or in terms of selectivity
Nano particle such as active component Pd is scattered in the Pd/MCM-41 catalyst inside mesopore orbit.
In view of studying above, the present invention provides a kind of application of load type palladium catalyst in selective hydrogenation, institute
It is using Pd as active component, using mesostructured material as carrier, and active component Pd to state load type palladium catalyst
Nano particle is scattered in the surface and/or aperture of the carrier.
In some concrete modes of application of the present invention, the selective hydrogenation reaction includes unsaturated hydrocarbon compound
Selective hydrogenation, the selective hydrogenation of alpha, beta-unsaturated aldehyde ketone compounds or halonitro class compound in nitryl group
Selective hydrogenation.
In some concrete modes of application of the present invention, the selective hydrogenation of the unsaturated hydrocarbon compound is：
The compound of class containing alkynyl (such as phenylacetylene) selective hydrogenation generates corresponding alkenyl class compound (styrene)；Or
Naphthalene compounds (such as naphthalene) selective hydrogenation generates corresponding tetralin quasi-compound (naphthane)；
The selective hydrogenation of the alpha, beta-unsaturated aldehyde ketone compounds is：
Alpha, beta-unsaturated aldehyde ketone compounds (such as cinnamic acid) selective hydrogenation generates corresponding alpha, beta unsaturated alcohol class
Compound (cinnamyl alcohol)；
The selective hydrogenation of nitryl group is in the halonitro class compound：
It is (right that halonitro benzene-like compounds (parachloronitrobenzene) selective hydrogenation generates corresponding halogeno-benzene ammoniac compounds
Chloroaniline).
It should be noted that selective hydrogenation of the invention is not restricted to the above-mentioned reaction for referring to, this area skill
Art personnel carry out selective hydrogenation for optional different substrate is actually needed with catalyst of the invention.
In some concrete modes of application of the present invention, the selective hydrogenation enters in fixed bed reactors
OK.In some concrete modes of application of the present invention, the condition of the selective hydrogenation includes：Reaction temperature 50~
700 DEG C, 1~10.0MPa of pressure, hydrogen to oil volume ratio is no more than 10000Nm3/m3, weight (hourly) space velocity (WHSV) 30~300 hours-1。
In some concrete modes of application of the present invention, the nano particle of active component Pd is fully dispersed in the load
The surface and/or aperture of body.
In some concrete modes of application of the present invention, the carrier is the mesopore molecular sieve MCM- of silylating reagent
41, preferably described carrier is the MCM-41 that trim,ethylchlorosilane is modified.It should be noted that being to realize activity using this carrier
The nano particle of component Pd is scattered in one of the surface of the carrier and/or the mode in aperture, and the present invention is not restricted to this, only
The surface and/or aperture for wanting the nano particle that can realize active component Pd to be scattered in MCM-41 carriers can reach effect of the invention
Really.
The present invention is not construed as limiting to the load capacity of active component Pd, and those skilled in the art can need system according to practical application
The different palladium-carbon catalyst of standby Pd mass contents.Mass content of the present invention should be understood to that the quality of specific components accounts for catalysis
The content ratio of agent gross mass, in a specific embodiment of the invention, with the mass fraction of the load type palladium catalyst
Be 100% meter, the mass content of active component Pd for 0.2~10% (such as 0.5%, 1%, 2%, 3%, 4%, 5%, 6%,
7%th, 8%, 9%).Pd active components of the present invention refer in particular to metal Pd, rather than the compound of palladium.
Load type palladium catalyst of the present invention can be prepared by the following method, and methods described comprises the following steps：
(1) mesostructured material of silylating reagent is provided；
(2) mesostructured material using the silylating reagent prepares catalyst precursor as carrier；
(3) load type palladium catalyst is prepared with catalyst precursor obtained in step (2).
In certain specific embodiments of the invention, step (1) is：Siliceous MCM-41 is placed in organic solvent, so
After add silylating reagent, back flow reaction, filtering, washing is drying to obtain the mesostructured material of the silylating reagent.
In certain specific embodiments of the invention, the organic solvent is toluene, and the silylating reagent is trim,ethylchlorosilane,
The Siliceous MCM-41 is 1~5g with the mass volume ratio of toluene:10~200L, the MCM-41 and the trim,ethylchlorosilane
Mass volume ratio be 1~5g：1~20mL.In certain specific embodiments of the invention, the backflow refer to 80~
1~15h is stirred at reflux at 180 DEG C.
The present invention is not particularly limited the preparation method of catalyst precursor, in certain specific embodiments of the invention
In, step (2) is：Maceration extract infusion process is made with the toluene solution of palladium and prepares the catalyst precursor.In the present invention
Some specific embodiments in, the catalyst precursor is prepared using equi-volume impregnating, be 5~25g/L's by concentration
Toluene solution is dropwise dripped on the mesostructured material of the silylating reagent, 15~55 DEG C of aging 3~12h, 50~150
DEG C 2~20h of drying, is then placed in roasting device, and 200~600 DEG C are warming up to the speed of 1~10 DEG C/min, and roasting 2~
10h, obtains the catalyst precursor.
In certain specific embodiments of the invention, step (3) is：Using described in temperature programmed reduction under hydrogen atmosphere
The method of catalyst precursor prepares the load type palladium catalyst.In certain specific embodiments of the invention, reduction temperature
It is 100~400 DEG C to spend, and hydrogen partial pressure is 1~10MPa, and the recovery time is 1~24h.
In summary, the application invention broadly provides a kind of load type palladium catalyst in selective hydrogenation,
Present invention research finds：Using Pd as active component, using mesostructured material as the loaded catalyst of carrier in, when
When the nano particle of active component Pd is scattered in the surface and/or aperture of the carrier, its catalyst activity and/or selectivity are bright
It is aobvious that better than the Pd/MCM-41 catalyst without this feature, (nano particle of such as active component Pd is scattered in inside mesopore orbit
Pd/MCM-41 catalyst), particularly to unsaturated hydro carbons, α, the selection of beta-unsaturated aldehyde ketone and halonitro benzene-like compounds
Hydrogenation reaction.
Brief description of the drawings
Figure 1A is the transmission electron microscope photo of the Pd/S-MCM-41 that the embodiment of the present invention 3 is prepared.
Figure 1B is the transmission electron microscope photo of the Pd/MCM-41 that the embodiment of the present invention 3 is prepared.
Specific embodiment
In order to be more clearly understood to technical characteristic of the invention, purpose and beneficial effect, in conjunction with specific implementation
Example carries out described further below to technical scheme, it should be understood that these examples are merely to illustrate the present invention rather than limit
The scope of the present invention processed.In embodiment, each Starting reagents material is commercially available, and the experimental technique of unreceipted actual conditions is
Conventional method known to art and normal condition, or according to the condition proposed by apparatus manufacturer.
Embodiment 1
The silylating reagent of Siliceous MCM-41
Weigh 3 grams of Siliceous MCM-41s to be placed in 150mL toluene, be subsequently adding trim,ethylchlorosilane (volumn concentration
5%) 3h, suction filtration, are stirred at reflux at 110 DEG C.Filter cake is washed with toluene, is dried 10 hours at room temperature, obtain silanization
MCM-41, is denoted as S-MCM-41.
Comparative example 1
Prepare the Pd catalyst precursors that Siliceous MCM-41 makees carrier
First by 1 gram of PdCl2(HCl concentration is 0.4mol/L) prepares maceration extract in being dissolved in the HCl solution of 38mL.Weigh
0.33 gram of maceration extract, then weighs 1 gram of MCM-41, and above-mentioned maceration extract is dropwise added drop-wise on carrier.8 hours are stood, in 120 DEG C
Dried 12 hours in baking oven, be calcined 3 hours in 400 DEG C in Muffle furnace, obtain oxidation state presoma.The loading of Pd is with gold
Category Pd is calculated as mass fraction 0.5%.
Embodiment 2
Prepare the Pd catalyst precursors that S-MCM-41 makees carrier
The Pd catalyst precursors that S-MCM-41 makees carrier are prepared with equi-volume impregnating：0.022 gram of palladium is dissolved in
In 5mL toluene, then dropwise it is added drop-wise on 2 grams of S-MCM-41, is stirred when being added dropwise, until whole maceration extract completion of dropping.Room
Temperature is aging 10 hours, is then dried 12 hours in 120 DEG C of baking ovens, and 400 are risen to the heating rate of 1 DEG C/min in Muffle furnace
DEG C, it is calcined 5 hours, obtain catalyst precursor.
Embodiment 3
The preparation of Supported Pd-Catalyst
By the catalyst precursor compression molding described in comparative example 1 and embodiment 2 and 20~40 mesh are crushed to, then will
0.05g catalyst precursors are placed in the fixed bed reactors of internal diameter 8mm, and support type is prepared with the method for temperature programmed reduction
Pd catalyst.Actual conditions is as follows：It is raised to from room temperature with the heating rate of 10 DEG C/min in the hydrogen atmosphere of stagnation pressure 1.0MPa
300 DEG C, gas flow is 75NmL/min, and reaction temperature is naturally cooling to after being kept for 1 hour, and Supported Pd-Catalyst is obtained.Point
Be not designated as Pd/S-MCM-41 and Pd/MCM-41, its transmission electron microscope photo respectively as shown in Figure 1A, Figure 1B, by Figure 1A and Figure 1B institutes
Show electromicroscopic photograph as can be seen that distributions of the Pd in MCM-41 is different from the distribution in S-MCM-41.In Pd/MCM-41,
Pd is distributed in inside the mesopore orbit of MCM-41；And in Pd/S-MCM-41, Pd nano-particles are fully distributed in carrier S-MCM-
41 surfaces or aperture.
Embodiment 4
Phenylacetylene selection hydrogenation preparation of styrene
Catalyst is made with the Pd/MCM-41 and Pd/S-MCM-41 described in embodiment 3, with the phenylacetylene of volume fraction 10%/
Ethanol solution makees the selective hydrogenation behavior that raw material evaluates catalyst in fixed bed reactors.Method system as described in embodiment 3
Get catalyst ready and bed temperature is adjusted into reaction temperature (80 DEG C), Hydrogen Vapor Pressure is adjusted to 1.0MPa, then use high pressure
Measuring pump is to conveying simulation oil product in reactor.Other reaction conditions：0.05 gram of loaded catalyst, weight (hourly) space velocity (WHSV) (WHSV) is
288 hours-1, H2/ oil volume ratio is 500Nm3/m3, as a result raw material and the product gas chromatographic analysis of Agilent 6890 arrange
In table 1.As can be seen from Table 1, phenylacetylene conversion and selectivity of styrene are all higher than Pd/MCM-41 on Pd/S-MCM-41.
Embodiment 5
Naphthalene selects Hydrogenation naphthane
Catalyst is made with the Pd/MCM-41 and Pd/S-MCM-41 described in embodiment 3, with the naphthalene/positive heptan of mass fraction 3%
Alkane solution makees the selective hydrogenation behavior that raw material evaluates catalyst in fixed bed reactors.It is prepared by the method as described in embodiment 3
Bed temperature is simultaneously adjusted to reaction temperature (300 DEG C) by good catalyst, and Hydrogen Vapor Pressure is adjusted into 4.0MPa, then uses high-pressure gauge
Amount pump is to conveying simulation oil product in reactor.Other reaction conditions：0.1 gram of loaded catalyst, weight (hourly) space velocity (WHSV) (WHSV) is 82
Hour-1, H2/ oil volume ratio is 500Nm3/m3, as a result raw material and the product gas chromatographic analysis of Agilent 6890 be listed in table
1.As can be seen from Table 1, Pd/S-MCM-41 and Pd/MCM-41 show naphthane selectivity (99%) very high, but Pd/
S-MCM-41 activity is significantly higher than Pd/MCM-41.
Embodiment 6
Parachloronitrobenzene selects Hydrogenation parachloroanilinum
Catalyst is made with the Pd/MCM-41 and Pd/S-MCM-41 described in embodiment 3, with mass fraction 5% to chlorine nitro
Benzene/n-heptane solution makees the selective hydrogenation behavior that raw material evaluates catalyst in fixed bed reactors.Side as described in embodiment 3
Legal system gets catalyst ready and bed temperature is adjusted to reaction temperature into (100 DEG C), and Hydrogen Vapor Pressure is adjusted into 1.0MPa, Ran Houyong
High-pressure metering pump is to conveying simulation oil product in reactor.Other reaction conditions：0.05 gram of loaded catalyst, weight (hourly) space velocity (WHSV)
(WHSV) it is 82 hours-1, H2/ oil volume ratio is 500Nm3/m3, raw material and the product gas chromatographic analysis of Agilent 6890,
Result is listed in table 1.As can be seen from Table 1, compared with Pd/MCM-41, Pd/S-MCM-41 has activity and parachloroanilinum higher
Selectivity.Without generation dechlorination reaction on Pd/S-MCM-41.
Embodiment 7
Cinnamic acid selects Hydrogenation cinnamyl alcohol
Catalyst is made with the Pd/MCM-41 and Pd/S-MCM-41 described in embodiment 3, with the Chinese cassia tree of mass fraction 3.0%
Aldehyde/ethanol makees the selective hydrogenation behavior that raw material evaluates catalyst in fixed bed reactors.It is prepared by the method as described in embodiment 3
Bed temperature is simultaneously adjusted to reaction temperature (80 DEG C) by good catalyst, and Hydrogen Vapor Pressure is adjusted into 2.5MPa, then uses high-pressure gauge
Amount pump is to conveying simulation oil product in reactor.Other reaction conditions：0.1 gram of loaded catalyst, weight (hourly) space velocity (WHSV) (WHSV) is 24
Hour-1, H2/ oil volume ratio is 500Nm3/m3, as a result raw material and the product gas chromatographic analysis of Agilent 6890 be listed in table
1.As can be seen from Table 1, compared with Pd/MCM-41, Pd/S-MCM-41 has the choosing of cinnamic acid conversion ratio and cinnamyl alcohol higher
Selecting property.
Table 1
The present invention has explicitly disclosed catalyst preparation conditions of the present invention and in hydrogenation reaction side by the description above
The application in face.But, those skilled in the art are fully aware of, and some modification and improvement can be carried out to the present invention.So,
If without departing from spirit of the invention, all should be within the scope of the invention to any modification and improvement that the present invention is carried out.
Claims (16)
1. application of a kind of load type palladium catalyst in selective hydrogenation, the load type palladium catalyst be using Pd as
Active component, using mesostructured material as carrier, and the nano particle of active component Pd is scattered in the table of the carrier
Face and/or aperture.
2. application of the load type palladium catalyst according to claim 1 in selective hydrogenation, wherein, the selection
Hydrogenation reaction include the selective hydrogenation of unsaturated hydrocarbon compound, the selective hydrogenation of alpha, beta-unsaturated aldehyde ketone compounds or
The selective hydrogenation of nitryl group in halonitro class compound.
3. application of the load type palladium catalyst according to claim 2 in selective hydrogenation, wherein：
The selective hydrogenation of the unsaturated hydrocarbon compound is：
The compound selective hydrogenation of class containing alkynyl generates corresponding alkenyl class compound；Or
Naphthalene compounds selective hydrogenation generates corresponding tetralin quasi-compound；
The selective hydrogenation of the alpha, beta-unsaturated aldehyde ketone compounds is：
The selective hydrogenation of alpha, beta-unsaturated aldehyde ketone compounds generates corresponding alpha, beta unsaturated alcohol class compound；
The selective hydrogenation of nitryl group is in the halonitro class compound：
Halogenated nitrobenzene class compound selective hydrogenation generates corresponding halogeno-benzene ammoniac compounds.
4. application of the load type palladium catalyst according to claim 1 in selective hydrogenation, wherein, the selection
Property hydrogenation reaction is carried out in fixed bed reactors.
5. application of the load type palladium catalyst according to claim 4 in selective hydrogenation, wherein, the selection
The condition of property hydrogenation reaction includes：50~700 DEG C of reaction temperature, 1~10.0MPa of pressure, hydrogen to oil volume ratio is no more than
10000Nm3/m3, weight (hourly) space velocity (WHSV) 30~300 hours-1。
6. application of the load type palladium catalyst according to claim 1 in selective hydrogenation, wherein, active component
The nano particle of Pd is fully dispersed in the surface and/or aperture of the carrier.
7. application of the load type palladium catalyst according to claim 1 in selective hydrogenation, wherein, the carrier
It is the mesostructured material of silylating reagent, preferably described carrier is the MCM-41 that trim,ethylchlorosilane is modified.
8. application of the load type palladium catalyst according to any one of claim 1~7 in selective hydrogenation, its
In, to be counted with the mass fraction of the load type palladium catalyst as 100%, the mass content of active component Pd is 0.2~10%.
9. application of the load type palladium catalyst according to claim 8 in selective hydrogenation, wherein, described is negative
Load type palladium catalyst is prepared by the following method, and methods described comprises the following steps：
(1) mesostructured material of silylating reagent is provided；
(2) mesostructured material using the silylating reagent prepares catalyst precursor as carrier；
(3) load type palladium catalyst is prepared with catalyst precursor obtained in step (2).
10. application of the load type palladium catalyst according to claim 9 in selective hydrogenation, step (1) is：Will
Siliceous MCM-41 is placed in organic solvent, is subsequently adding silylating reagent, and back flow reaction, filtering, washing is drying to obtain the silicon
The modified mesostructured material of alkanisation.
Application of 11. load type palladium catalysts according to claim 10 in selective hydrogenation, wherein, it is described to have
Machine solvent is toluene, and the silylating reagent is trim,ethylchlorosilane, and the Siliceous MCM-41 is 1 with the mass volume ratio of toluene
~5g:10~200L, the MCM-41 are 1~5g with the mass volume ratio of the trim,ethylchlorosilane：1~20ml.
Application of 12. load type palladium catalysts according to claim 11 in selective hydrogenation, wherein, described time
Stream refers to be stirred at reflux 1~15h at 80~180 DEG C.
Application of 13. load type palladium catalysts according to claim 9 in selective hydrogenation, wherein, step (2)
For：Maceration extract is made with the toluene solution of palladium the catalyst precursor is prepared using infusion process.
Application of 14. load type palladium catalysts according to claim 10 in selective hydrogenation, wherein, using etc.
Volume impregnation method prepares the catalyst precursor, and the toluene solution that concentration is 5~25g/L is dropwise dripped into the silanization changes
On the mesostructured material of property, then 15~55 DEG C of aging 3~12h, 50~150 DEG C of 2~20h of drying are placed on roasting
In burner, 200~600 DEG C are warming up to the speed of 1~10 DEG C/min, are calcined 2~10h, obtain the catalyst precursor.
Application of 15. load type palladium catalysts according to claim 9 in selective hydrogenation, wherein, step (3)
For：The load type palladium catalyst is prepared using the method for catalyst precursor described in temperature programmed reduction under hydrogen atmosphere.
Application of 16. load type palladium catalysts according to claim 15 in selective hydrogenation, wherein, reduction temperature
It is 100~400 DEG C to spend, and hydrogen partial pressure is 1~10MPa, and the recovery time is 1~24h.
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