CN109174084A - A kind of catalytic hydrogenation catalyst and its preparation and the application in tetrahydro farnesyl acetone selective hydrogenation - Google Patents
A kind of catalytic hydrogenation catalyst and its preparation and the application in tetrahydro farnesyl acetone selective hydrogenation Download PDFInfo
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- CN109174084A CN109174084A CN201810976629.8A CN201810976629A CN109174084A CN 109174084 A CN109174084 A CN 109174084A CN 201810976629 A CN201810976629 A CN 201810976629A CN 109174084 A CN109174084 A CN 109174084A
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- catalyst
- palladium
- catalytic hydrogenation
- active carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 33
- LTUMRKDLVGQMJU-UHFFFAOYSA-N famesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O LTUMRKDLVGQMJU-UHFFFAOYSA-N 0.000 title claims abstract description 32
- LTUMRKDLVGQMJU-IUBLYSDUSA-N farnesyl acetone Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)=O LTUMRKDLVGQMJU-IUBLYSDUSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- WHWDWIHXSPCOKZ-UHFFFAOYSA-N hexahydrofarnesyl acetone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)=O WHWDWIHXSPCOKZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- 239000003610 charcoal Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 239000002250 absorbent Substances 0.000 claims abstract description 3
- 230000002745 absorbent Effects 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 210000002966 serum Anatomy 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 150000002940 palladium Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- 239000002096 quantum dot Substances 0.000 claims 1
- NZJMPGDMLIPDBR-UHFFFAOYSA-M tetramethylazanium;hydroxide;hydrate Chemical compound O.[OH-].C[N+](C)(C)C NZJMPGDMLIPDBR-UHFFFAOYSA-M 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006555 catalytic reaction Methods 0.000 description 4
- -1 ketone compound Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- CDOSHBSSFJOMGT-UHFFFAOYSA-N beta-linalool Natural products CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- IUDWWFNDSJRYRV-UHFFFAOYSA-N 3,7-dimethyloct-1-en-3-ol Chemical compound CC(C)CCCC(C)(O)C=C IUDWWFNDSJRYRV-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalytic hydrogenation catalyst and its preparations and the application in tetrahydro farnesyl acetone selective hydrogenation.The catalyst is formed by being coated with the metal quantum point of the absorbent charcoal carrier and load of modified coating on the carrier；The metal is palladium, and the particle size range of metal quantum point is between 3~6nm；The active carbon is random or molding granular activated carbon, and size is not more than 1cm；The pore structure of the active carbon coated with modified coating based on mesoporous, micropore ratio drop to 10% or less and the modified coating component be titanium dioxide, silica and titanium silicate.The invention discloses the catalytic hydrogenation catalyst tetrahydro farnesyl acetone selective catalytic hydrogenation synthesis hexahydrofarnesyl acetone reaction in application, have the characteristics that without additive, high conversion rate, selectivity is good, hydrogenation reaction rate is fast, stability is good, catalyst life grow with and hydrogen can be recycled.
Description
(1) technical field
The present invention relates to a kind of fixed-bed catalytic hydrogenation catalyst and its preparations and application, and in particular to catalyst is in fixation
Application in bed catalysis tetrahydro farnesyl acetone selective hydrogenation.
(2) technical background
6,10,14- trimethyl -2- pentadecanones (hexahydrofarnesyl acetone, PA) are a kind of weights for being used to prepare vitamin E
Chemical intermediate is wanted, the enhancing with people to health-physical fitness demand, VE demand is significantly increased.Industrial PA mainly leads at present
6,7- dihydro linalool or 1,2- dehydrogenation linalool are crossed to prepare.But it in this existing several PA synthetic route, finally all needs
To pass through the catalytic hydrogenation ability of 6,10,14- trimethyl -13- alkene -2- pentadecanones (tetrahydro farnesyl acetone, FA-4H)
PA is obtained, so the output of tetrahydro farnesyl acetone is caused also to increase year by year.Therefore, one kind is developed for demand of industrial production
The catalytic hydrogenation of green has great importance.
Tetrahydro farnesyl acetone is a kind of beta-unsaturated ketone compound containing C=C key, wherein the activation energy ratio of carbon-carbon double bond
Carbonyl is low, therefore the former is easier that hydrogenation reaction occurs compared with the latter.But when existing simultaneously C=C or C=O in compound,
Hydrogen is added to be different from independent C=C or C=O hydrogenation reaction, so to realize that PA is selectively the generation of 100% (no carbonyl hydrogen)
Still very difficult, the selectivity for controlling reaction is particularly important.
The performance of catalyst metals and the selection of carrier are particularly important for this reaction.The property of metal first
Have a significant impact to this catalytic hydrogenation property, the d track bandwidth of metal selected by catalyst is bigger, with four electronics of C=C key
Repulsive interaction is stronger, and the absorption of C=O key easily occurs and generates unsaturated alcohol.Furthermore tetrahydro farnesyl acetone molecule carbon chain is longer,
Steric hindrance prevents long carbochain from being adsorbed in flat metal surface in parallel, but maintains a certain distance, in addition vinyl
The branch of connection is more than carbonyl institute chord chain, and steric effect is obvious, is unfavorable for the absorption of C=C key and carbonyl is made to be easier to adsorb
Hydrogenation reaction.Metallic particles hour, stereoeffect influence it is unobvious, C=C, C=O key can touch metal surface, at this moment with
C=C key is hydrogenated to lead；When metallic particles is larger, due to the presence of steric hindrance, C=O ratio C=C is easier to touch metal watch
Face is conducive to the absorption of C=O key.
The larger then duct of carrier fractions is accordingly longer, and the PA that generation is reacted on inner hole will take longer time spreading through duct
Catalyst granules out, product are not easy to be desorbed from carrier surface and lead to carbonyl hydrogen.Moreover, the catalyst of small grain size is easier to
It is even to be scattered in reaction solution, it increases reactant and is contacted with the effective of catalyst, to accelerate reaction rate.
Carrier specific surface area is to measure the active important parameter of the catalysts, and the carrier of high-ratio surface is additionally favorable for activity
Component is in its Dispersion on surface.But the activity of catalyst is also influenced by pore size.Carrier aperture is smaller, and small-bore makes greatly
Reactant molecule be difficult to enter in hole, i.e. space steric effect (or the shape-selective and confinement effect in duct) is only capable of in catalyst
Catalysis reaction occurs for surface, and inside does not make full use of i.e. effective active sites to reduce, leads to low activity.
Therefore a kind of fixed-bed catalytic hydrogenation catalyst of invention, using one step of method of light deposition prepares metal
The small and controllable Pd/C catalyst of partial size, preparation method is easy to operate and catalyst easily recycles；The catalyst is applied to fixed bed
Under the conditions of catalytic hydrogenation prepare in the reaction of hexahydrofarnesyl acetone, it is not necessary that auxiliary agent is added, catalytic performance is good, and selectivity is high, urges
The agent service life is long, and the hydrogen being catalyzed in reaction can be recycled.
(3) summary of the invention
The object of the present invention is to provide a kind of catalytic hydrogenation catalysts, are particularly suitable for the selective hydrogenation of tetrahydro farnesyl acetone
Synthesize the reaction of hexahydrofarnesyl acetone.
It is a further object to provide a kind of method for preparing the catalytic hydrogenation catalyst, this method operation letters
It is single, it can be achieved that the generation in situ on carbon ball surface of one step of metal dots with grow up, and the particle size distribution range controllable precise of metal dots.
It is anti-in tetrahydro farnesyl acetone catalytic hydrogenation that it is also another object of the present invention to provide the catalytic hydrogenation catalysts
Application in answering has without additive, high conversion rate, selectivity is good, hydrogenation reaction rate is fast, stability is good, the catalyst longevity
Life it is long with and hydrogen can be recycled the characteristics of.
To achieve the above object, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of catalytic hydrogenation catalyst, by be coated with modified coating absorbent charcoal carrier and
The metal quantum point composition of load on the carrier；The metal is palladium, the particle size range of metal quantum point 3~6nm it
Between；The active carbon is random or molding granular activated carbon, and size is not more than 1cm；The described modified coating that is coated with
The pore structure of active carbon based on mesoporous, micropore ratio drop to 10% or less and the modified coating component be dioxy
Change titanium, silica and titanium silicate；In the catalyst, the mass fraction of metal quantum point is 1~2%, modified coating composition
The gross mass of substance is no more than the 15% of quality of activated carbon, and wherein titanium silicate is of low quality in the 1.5% of quality of activated carbon, two
The mass ratio of silica and titanium dioxide is not less than 20.
Further, in the catalyst, the mass fraction of metal quantum point is 1.5~2%.
Further, the gross mass of the modified coating component is the 1~15% of quality of activated carbon.
Further, titanium silicate is of low quality in the 0.5% of quality of activated carbon.
Further, the mass ratio of silica and titanium dioxide is between 30~50.
On the other hand, the present invention provides a kind of preparation methods of catalytic hydrogenation catalyst, comprising:
1) active carbon, methyl orthosilicate and butyl titanate are placed in distilling apparatus, add tetramethyl-ammonium hydroxide
The alcohol that hydrolysis generates is distilled out at 90~100 DEG C, then gained active carbon particle is placed in closed container by object aqueous solution
Heat 5 in 150~200 DEG C~for 24 hours, then it is cooled to room temperature, takes out active carbon to get the active carbon of modified coating is coated with；Institute
The ratio between gross mass of quality of activated carbon and methyl orthosilicate and butyl titanate is stated as 20:0.2~3.0, methyl orthosilicate and titanium
The mass ratio of sour four butyl esters is 20~30:1, and the quality of the tetramethyl-ammonium hydroxide is no more than methyl orthosilicate and metatitanic acid four
The 10% of butyl ester gross mass；
2) mixed serum is made with deionized water, methanol in the active carbon coated with modified coating for obtaining step 1), stirs
10min~20min is mixed, palladium salt aqueous solution is added in the mixed serum of preparation, mixed serum is placed under ultraviolet lamp in function
Illumination is carried out under 350~400nm of rate 250w~300w and wavelength and stirs 10~25min, then takes out mixed serum, it is dry through washing
It is dry to obtain catalytic hydrogenation catalyst.
In step 1) of the present invention, the quality of the tetramethyl-ammonium hydroxide is preferably methyl orthosilicate and butyl titanate
The 1~10% of gross mass.The mass concentration of the tetramethyl-ammonium hydroxide aqueous solution is preferably 15~25%.
Step 2) of the present invention is by the condition of control ultraviolet lighting to control metal spot size.Wherein, it is coated with modified apply
The active carbon of layer and the mass ratio that feeds intake of deionized water are 1g:10~25ml, preferably 1g:15ml；Methanol and deionized water
Volume ratio is 1:2~8, preferably 1:5.The palladium salt can be following one or more combination: palladium nitrate, chlorine palladium acid, second
Diamines palladium chloride, tetrachloro-palladium acid ammonium, chlorine palladium acid sodium, four ammino palladium of nitric acid, two bicarbonate palladium of tetramino.The palladium salt aqueous solution
Middle palladium mass concentration is preferably 0.001~0.05g/mL, the feed ratio of the active carbon coated with modified coating and palladium salt aqueous solution
Preferably 1g:4~20ml.The drying condition is preferred are as follows: washing sample is 12~48 hours dry at 40~80 DEG C.
The third aspect, the choosing of the tetrahydro farnesyl acetone shown in Formulas I that the present invention provides the catalytic hydrogenation catalysts
Selecting property catalytic hydrogenation synthesizes the application in the reaction of hexahydrofarnesyl acetone shown in Formula II；
The application method of the catalyst are as follows:
Catalytic hydrogenation catalyst is encased in tubular reactor, catalyst size is less than the 1/ of tubular reactor internal diameter
10；With the air in nitrogen displacement reaction tube, then with hydrogen displacement nitrogen, make 0.5~1.5MPa of Hydrogen Vapor Pressure in reaction tube,
Temperature is 25~150 DEG C；Tetrahydro farnesyl acetone shown in Formulas I is dissolved in alcoholic solvent (preferably methanol or ethyl alcohol) and is obtained instead
Liquid is answered, the mixing tube before reaction tube is pumped by pressure liquid pump carries out gas-liquid mixed with hydrogen, then enters together and be packed into catalysis
In the reaction tube of agent, open light source irradiation starts to react, illumination wavelength 280~350nm of range of light source, power be 200~
250W, radiation intensity are 3660~3980 μ W/cm2, pass through gas-liquid separation device after reaction, unreacted hydrogen circulation makes
With liquid product separation post-processing obtains hexahydrofarnesyl acetone shown in Formula II；
Further, in the application, tetrahydro farnesyl acetone and alcoholic solvent ratio shown in the Formulas I are not higher than 7g/
10ml, the volume ratio of reaction solution and hydrogen (under standard state) is not higher than 2:1 when gas-liquid mixed, and liquid air speed is 20~
100min-1。
Further, the method for the hydrogenation liquid separation post-processing are as follows: hydrogenation liquid is after rectification under vacuum up to product.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1) carrier of the active carbon as catalyst provides biggish specific surface area, while metal salt solution and active carbon
It is dispersed in metal preferably on carrier under the irradiation of ultraviolet light, it is not easy to reunite, improve metal utilization；Activated carbon surface applies
A small amount of silica+titanium silicate+the coating of titanium dioxide covered, may modify the characteristic electron of metal dots, can also improve adsorption activity
The characteristic electron of the carrier at center, and the presence of modified coating makes aperture be in mesopore range, effectively prevents space bit
Inhibition effect, and then enable catalyst surface and inside while catalysis reaction occurs, improve activity.
2) present invention prepares the Pd/C catalyst of metal size tunable, preparation method operation using one step of method of light deposition
It is easy；
3) present invention is using metal Pd as active component, and the d track bandwidth of Pd is smaller, the row with four electronics of C=C key
Reprimand effect is weak, is conducive to the addition of carbon-carbon double bond, the stereoeffect influence of small particle Pd is unobvious, and C=C, C=O key can be put down
Row touches metal surface, and the bond energy of carbon-carbon double bond lower than carbonyl bond energy therefore is hydrogenated to lead with C=C key, and then improves tetrahydro
The reaction selectivity of farnesyl acetone selective catalytic hydrogenation synthesis hexahydrofarnesyl acetone.Catalyst of the present invention is especially suitable
The reaction of hexahydrofarnesyl acetone is prepared for catalytic hydrogenation under the conditions of fixed bed.
(4) Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of embodiment one, and black particle is palladium metal point in figure.
(5) specific embodiment
Below by specific embodiment, technical scheme is described further, but protection scope of the present invention is not
It is limited to this:
Embodiment 1
It weighs 1.5g water solubility methyl orthosilicate and 0.05g tetrabutyl titanate is added in distilling flask, add after being sufficiently stirred
Enter 20g active carbon, the tetramethyl-ammonium hydroxide aqueous solution (hydroxide containing tetramethyl-ammonium that mass concentration is 20% is then added dropwise
0.075g), distillation is carried out at 95 DEG C and isolates hydrolysate, then by solid matter in flask in 180 DEG C of heating 12h.
Take active carbon made from the above method (being detected mesopore proportion 70%, micropore ratio 30%, size is not more than 1cm)
Mixed serum is made in 1g and 15ml deionized water and 3ml methanol, stirs 15min, and taking the palladium concentration of 10mL is 0.002g/mL chlorine
Palladium acid solution instills in mixed liquor, puts and carries out illumination stirring 20min at power 275w and 386nm in the UV lamp, then takes
After being washed to neutrality, it is 24 hours dry at 60 DEG C to be put into baking oven for mixed serum out.Through detecting SiO2Content 7.5%, TiO2Content
0.15%, silicic acid Ti content 0.1%, mesopore proportion 97.5%, micropore ratio 2.5%, content of metal 2%, metal partial size 4~
5nm。
Embodiment two to embodiment ten third is that according to one preparation process of embodiment prepare catalyst, design parameter such as table 1
It is shown.
Comparative example 1
Weigh untreated active carbon (through detect mesopore proportion 70%, micropore ratio 30%, size be not more than 1cm) 1g and
Mixed serum is made in 15ml deionized water and 3ml methanol, stirs 15min, and taking the palladium concentration of 10mL is 0.002g/mL chlorine palladium acid
Solution instills in mixed liquor, puts and carries out illumination stirring 20min at power 275w and 386nm in the UV lamp, then takes out mixed
Slurries are closed, after being washed to neutrality, it is 24 hours dry at 60 DEG C to be put into baking oven.Through detect mesopore proportion 70%, micropore ratio 30%,
Content of metal 2%, 4~5nm of metal partial size.
Comparative example 2
It weighs 1.5g water solubility methyl orthosilicate and 0.05g tetrabutyl titanate is added in distilling flask, add after being sufficiently stirred
Enter 20g active carbon, dipping took out solid matter in flask after 3 hours, 180 DEG C of heating 12h.Through detecting SiO2Content 0.5%,
TiO2Content 0.01%, silicic acid Ti content 0.0%, mesopore proportion 70.5%, micropore ratio 29.5%.
Take active carbon made from the above method (being detected mesopore proportion 70%, micropore ratio 30%, size is not more than 1cm)
Mixed serum is made in 1g and 15ml deionized water and 3ml methanol, stirs 15min, and taking the palladium concentration of 10mL is 0.002g/mL chlorine
Palladium acid solution instills in mixed liquor, puts and carries out illumination stirring 20min at power 275w and 386nm in the UV lamp, then takes
After being washed to neutrality, it is 24 hours dry at 60 DEG C to be put into baking oven for mixed serum out.Content of metal 2%, metal partial size 4~
5nm。
Comparative example 3
It weighs 1.5g water solubility methyl orthosilicate and 0.05g tetrabutyl titanate is added in distilling flask, quality is then added dropwise
The tetramethyl-ammonium hydroxide aqueous solution (the hydroxide 0.075g containing tetramethyl-ammonium) that concentration is 20%, is distilled at 95 DEG C
Hydrolysate is isolated, then by solid matter in flask in 180 DEG C of heating 12h.
Silica made from the above method and titanium dioxide solids 1g and 15ml deionized water and 3ml methanol is taken to be made
Mixed serum stirs 15min, and taking the palladium concentration of 10mL is that 0.002g/mL chlorine palladium acid solution instills in mixed liquor, is placed on ultraviolet lamp
Under at power 275w and 386nm carry out illumination stir 20min, then take out mixed serum, after being washed to neutrality, be put into baking oven
It is 24 hours dry at 60 DEG C.Content of metal 2%, 4~5nm of metal partial size.
Embodiment 14
1 catalyst of embodiment is encased in the tubular reactor that internal diameter is 20cm, with nitrogen displaced air, then uses hydrogen
Replace nitrogen.It is 1:1, tetrahydro farnesyl acetone and methanol according to tetrahydro farnesyl acetone and methanol total volume and hydrogen volume ratio
Ratio be 2g:5ml, tetrahydro farnesyl acetone is dissolved in methanol solvate, the mixing before reaction tube is pumped by pressure liquid pump
Pipe carries out gas-liquid mixed with hydrogen, then enters together and be fitted into the tubular reactor of catalyst, sets Hydrogen Vapor Pressure 1MPa,
Temperature 50 C, liquid air speed are 50min-1, illumination apparatus is opened, setting illumination power is 325nm, power 225W, and radiation is strong
Degree is 3820 μ W/cm2, starting to react, one way passes through gas-liquid separation device after reaction, and unreacted hydrogen is recycled,
Liquid product separation post-processing obtains product hexahydrofarnesyl acetone.Analyze result are as follows: reaction conversion ratio 100%, selectivity
98.99%.
Embodiment 15~27
Embodiment 15~27 is to evaluate operating procedure according to the fixed-bed catalytic of embodiment 14, chooses 1~13 He of embodiment
Fixed-bed catalytic hydrogenation catalyst prepared by comparative example 1~2 carries out catalyst reaction, and design parameter is as shown in table 2.
Comparative example 4~15
Comparative example 4~15 is under the reaction condition that reaction condition respectively refers to embodiment 14~25, using non-illuminated conditions
The application of the tetrahydro farnesyl acetone catalytic hydrogenation reaction of lower progress is as a result, as shown in table 3 below.
Embodiment 28
Embodiment 28 is that catalyst prepared by Example 1 carries out successive reaction under the evaluation condition of embodiment 14, is examined
The service life of catalyst is examined, as shown in table 4 below.
Conversion per pass and selectivity under 3 comparative example of table, four to 15 non-illuminated conditions
| Embodiment | Conversion ratio % | Selective % |
| Comparative example 4 | 96.7 | 92.29 |
| Comparative example 5 | 97.4 | 92.36 |
| Comparative example 6 | 96.6 | 89.98 |
| Comparative example 7 | 97.2 | 92.25 |
| Comparative example 8 | 96.4 | 89.34 |
| Comparative example 9 | 95.1 | 91.58 |
| Comparative example 10 | 96.2 | 91.85 |
| Comparative example 11 | 97.2 | 92.47 |
| Comparative example 12 | 96.8 | 91.15 |
| Comparative example 13 | 96.5 | 92.47 |
| Comparative example 14 | 97.4 | 93.13 |
| Comparative example 15 | 96.4 | 90.97 |
Conversion ratio and selectivity under 4 embodiment of table, 28 catalyst successive reaction
| Time/h | Conversion ratio/% | Selectivity/% |
| 10 | 100 | 99.37 |
| 50 | 100 | 99.36 |
| 100 | 100 | 99.48 |
| 120 | 100 | 99.55 |
| 150 | 100 | 99.39 |
| 180 | 100 | 99.58 |
| 200 | 100 | 98.88 |
| 220 | 100 | 99.77 |
| 240 | 100 | 99.65 |
| 280 | 100 | 99.57 |
| 300 | 100 | 99.33 |
| 350 | 100 | 98.99 |
Claims (10)
1. a kind of catalytic hydrogenation catalyst, by being coated with the metal of the absorbent charcoal carrier and load of modified coating on the carrier
Quantum dot composition；The metal is palladium, and the particle size range of metal quantum point is between 3~6nm；The active carbon be it is random or
Molding granular activated carbon, size are not more than 1cm；The pore structure of the active carbon coated with modified coating is with mesoporous
It is main, micropore ratio drop to 10% or less and the component of the modified coating be titanium dioxide, silica and titanium silicate；
In the catalyst, the mass fraction of metal quantum point is 1~2%, and the gross mass of modified coating component is no more than activity
The 15% of charcoal quality, wherein titanium silicate of low quality in the 1.5% of quality of activated carbon, the quality of silica and titanium dioxide
Than being not less than 20.
2. catalytic hydrogenation catalyst as described in claim 1, it is characterised in that: in the catalyst, the matter of metal quantum point
Measuring score is 1.5~2%.
3. catalytic hydrogenation catalyst as claimed in claim 1 or 2, it is characterised in that: the modified coating component it is total
Quality is the 1~15% of quality of activated carbon, and titanium silicate is of low quality in the 0.5% of quality of activated carbon, silica and titanium dioxide
The mass ratio of titanium is between 30~50.
4. a kind of preparation method of catalytic hydrogenation catalyst as described in claim 1, comprising:
1) active carbon, methyl orthosilicate and butyl titanate are placed in distilling apparatus, add tetramethyl-ammonium hydroxide water
Solution, at 90~100 DEG C by hydrolysis generate alcohol distill out, then by gained active carbon particle be placed in closed container in
150~200 DEG C of heating 5~for 24 hours, then be cooled to room temperature, active carbon is taken out to get the active carbon of modified coating is coated with；It is described
The ratio between gross mass of quality of activated carbon and methyl orthosilicate and butyl titanate is 20:0.2~3.0, methyl orthosilicate and metatitanic acid
The mass ratio of four butyl esters is 20~30:1, and the quality of the tetramethyl-ammonium hydroxide is no more than four fourth of methyl orthosilicate and metatitanic acid
The 10% of ester gross mass；
2) mixed serum is made with deionized water, methanol in the active carbon coated with modified coating for obtaining step 1), stirs
Palladium salt aqueous solution is added in the mixed serum of preparation by 10min~20min, and mixed serum is placed under ultraviolet lamp in power
Illumination is carried out under 350~400nm of 250w~300w and wavelength and stirs 10~25min, mixed serum is then taken out, through washing and drying
Obtain catalytic hydrogenation catalyst.
5. preparation method as claimed in claim 4, it is characterised in that: in step 1), the matter of the tetramethyl-ammonium hydroxide
Amount is the 1~10% of methyl orthosilicate and butyl titanate gross mass, and the quality of the tetramethyl-ammonium hydroxide aqueous solution is dense
Degree is 15~25%.
6. preparation method as claimed in claim 4, it is characterised in that: in step 2), active carbon coated with modified coating with
The mass ratio that feeds intake of deionized water is 1g:10~25ml, preferably 1g:15ml；The volume ratio of methanol and deionized water be 1:2~
8, preferably 1:5.
7. preparation method as claimed in claim 4, it is characterised in that: in step 2), the palladium salt is following a kind of or more
The combination of kind: palladium nitrate, chlorine palladium acid, ethylenediamine palladium chloride, tetrachloro-palladium acid ammonium, chlorine palladium acid sodium, four ammino palladium of nitric acid, tetramino two
Bicarbonate palladium；Palladium mass concentration is 0.001~0.05g/mL, the active carbon coated with modified coating in the palladium salt aqueous solution
Feed ratio with palladium salt aqueous solution is 1g:4~20ml.
8. preparation method as claimed in claim 4, it is characterised in that: in step 2), the drying condition are as follows: sample will be washed
It is 12~48 hours dry at 40~80 DEG C.
9. catalytic hydrogenation catalyst as described in claim 1 tetrahydro farnesyl acetone selective catalytic hydrogenation shown in Formulas I
Synthesize the application in the reaction of hexahydrofarnesyl acetone shown in Formula II；
The application method of the catalyst are as follows:
Catalytic hydrogenation catalyst is encased in tubular reactor, catalyst size is less than the 1/10 of tubular reactor internal diameter；With
Air in nitrogen displacement reaction tube, then with hydrogen displacement nitrogen, make 0.5~1.5MPa of Hydrogen Vapor Pressure, temperature in reaction tube
It is 25~150 DEG C；Tetrahydro farnesyl acetone shown in Formulas I is dissolved in alcoholic solvent and obtains reaction solution, is pumped by pressure liquid pump
Mixing tube before entering reaction tube carries out gas-liquid mixed with hydrogen, then enters together and be fitted into the reaction tube of catalyst, opens light
Source irradiation starts to react, illumination wavelength 280~350nm of range of light source, power be 200~250W, radiation intensity be 3660~
3980μW/cm2, pass through gas-liquid separation device after reaction, unreacted hydrogen is recycled, liquid product separation post-processing
Obtain hexahydrofarnesyl acetone shown in Formula II；
10. application as claimed in claim 9, it is characterised in that: in the application, tetrahydro farnesyl- third shown in the Formulas I
Ketone and alcoholic solvent ratio are not higher than 7g/10ml, and the volume ratio of reaction solution and the hydrogen under standard state is not high when gas-liquid mixed
In 2:1, liquid air speed is 20~100min-1。
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| CN115400750B (en) * | 2022-09-29 | 2024-06-07 | 西安凯立新材料股份有限公司 | Catalyst for preparing saturated ketone by hydrogenating multi-double bond unsaturated ketone, and preparation method and application thereof |
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