GB2092017A - Membrane catalyst for hydrogenation of organic compounds and method of preparing the same - Google Patents
Membrane catalyst for hydrogenation of organic compounds and method of preparing the same Download PDFInfo
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- GB2092017A GB2092017A GB8102827A GB8102827A GB2092017A GB 2092017 A GB2092017 A GB 2092017A GB 8102827 A GB8102827 A GB 8102827A GB 8102827 A GB8102827 A GB 8102827A GB 2092017 A GB2092017 A GB 2092017A
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- heterogenized
- membrane catalyst
- film
- catalyst
- palladium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000012528 membrane Substances 0.000 title claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 239000011195 cermet Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 230000003993 interaction Effects 0.000 claims abstract description 9
- 238000004073 vulcanization Methods 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- -1 polydimethylsiloxane Polymers 0.000 claims description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 4
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NBBFKOVTVMIXLG-UHFFFAOYSA-N [ethoxy(dimethyl)silyl]methyl-diphenylphosphane Chemical group C=1C=CC=CC=1P(C[Si](C)(C)OCC)C1=CC=CC=C1 NBBFKOVTVMIXLG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZUMFQVCCEQIJHQ-UHFFFAOYSA-N C[Si](N(C(C)C)CC)(OCC)C Chemical compound C[Si](N(C(C)C)CC)(OCC)C ZUMFQVCCEQIJHQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000003961 organosilicon compounds Chemical group 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A membrane catalyst for hydrogenation of organic compounds comprises a cermet substrate having deposited thereon, as a film, a product of interaction of a polyorganosiloxane polymer and a heterogenized palladium complex of the general formula: <IMAGE> wherein R is an alkyl group, an alkoxy group, or chlorine; R' is -C6H4-, or -(CH2)n- where n = 1-10; D is -PR''2, where R'' is an alkyl or phenyl group; or -NR'''2, where R''' is an alkyl group; or -C5H4N; and L is -C1, -Br, or -OCOH3. Such a membrane catalyst is prepared by application onto a cermet substrate of a mixture of a polyorganosiloxane polymer and a heterogenized palladium complex of the above formula, and vulcanization thereof in the presence of a vulcanizing agent at a temperature of from 20 to 150 DEG C until the formation of a film with a thickness of from 0.3 to 1.0mm occurs.
Description
SPECIFICATION
Membrane catalyst for hydrogenation of organic compounds and method of preparing the same
The present invention relates to a membrane catalyst for hydrogentation of organic compounds and to a method of preparing the same.
These catalysts are useful in the chemical and petrochemical industries owing to the possibility, obtained thereby, of carrying out two processes with detachment and addition of hydrogen without intermixing of the reaction products and at higher speed than on conventional catalysts.
There are known polymer-based compositions, employed for improvement of adsorption of hydrocarbons and separation of hydrogen isotopes.
U.S. Patent No. 2 722 504 teaches a composition consisting of a metal oxide (Al2O3, MoO3,
CuO, V205), an oxide or sulphide of a transition metal with an atomic weight of from 22 to 42, and silicone adapted for improvement of selective adsorption of hydrocarbons compared to oxide materials untreated with silicone.
U.S. Patent No. 3 981 976 teaches a composite catalyst for separation of hydrogen isotopes composed of a mixture of oxides of metals such as Awl203, WO3, MgO, and SiO2, or of graphite with oxides of metals pertaining to Group VIII of the periodic system and a polymer possessing hydrophobic properties.
These known compositions, however, cannot serve as membrane catalysts selectively permeable to hydrogen.
At the present time, as hydrogen-permeable membrane catalysts use is made of palladiumbased alloys manufactured as a foil, for example an alloy containing 85% by weight of Pd and 15% by weight of Pt (cf. Japanese Patent No. 11362), or as a tube (U.S. Patent No.
3 201 620). For the manufacture of such membranes a considerable consumprion of palladium per 1 cm2 of the catalyst surface area is required. Thus, for the manufacture of a catalyst as taught in Japanese Patent No. 11362, it is required to use 0.24 g of palladium per 1 cm2 of the catalyst surface; according to U.S. Patent No. 3 201 620, 0.20 g of Pd per 1 cm2 of the catalyst surface area is required.
There is also known a method for producing a hydrogen-permeable membrane catalyst by rolling a foil with a thickness of from 0.05 to 0.1 mm composed of palladium or an alloy thereof (cf. Doklady Akademii Nauk SSSR, 211, No. 3, 624, 1973).
With a view to reducing the use of noble metals, there has been suggested a method for the manufacture of a membrane catalyst by sublimation of an alloy based on palladium onto a polymeric film selectively permeable for hydrogen; this film is applied onto a reinforcing substrate made of a cermet material and does not hinder penetration of the reagents (cf. USSR
Inventor's Certificate No. 593351 of October 21, 1977; U.S. Patent No. 4 1 32 668).
This method makes it possible to produce a membrane catalyst in the form of a three-layered composition consisting of a cermet substrate based, for example, on copper, nickel or stainless steel, a polyorganosiloxane polymer film, and a thin layer of a catalytically active palladiumbased component.
In this catalyst the catalytically active component is used insufficiently due to the non-uniform thickness of the layer of palladium over a large area of the catalyst. Furthermore, the size of this composite catalyst is limited, thus causing limitation of the unit capacity of a catalytic hydrogenation plant. The limited size of this catalyst is due to the small size of the vacuum chambers employed for sublimation of palladium. The composite membrane catalyst contains palladium or an alloy thereof in a low-disperse form, as a result of which the manufacture of a unit area of the catalyst surface involves the consumption of a rather great amount of palladium.
The present invention in one aspect provides a membrane catalyst for hydrogenation of organic compounds, comprising a metal-ceramic substrate having applied thereon, as a film, a product of interaction of a polyorganosiloxane polymer and a heterogenized palladium complex of the formula:
wherein R is an alkyl group, an alkoxy group, or chlorine;
R' is -C6H4-, or -(CH2)n- where n = 1-10;
D is -PR2', where R" is an alkyl or phenyl group;
or -NR2', where R"' is an alkyl group; or -C5H4N; and
L is -Cl-Br, or -OCOCH3.
The membrane catalyst according to the invention has a high productivity per unit weight of palladium owing to the distribution of the active component throughout the volume of the membrane as well as owing to the possibility of ensuring substantially unlimited unit capacity of hydrogenation plants.
Furthermore, the catalyst according to the present invention possesses a combination of properties of both a hydrogenation catalyst and a hydrogen-permeable membrane, and also involves the use of a relatively low consumption of palladium in the manufacture thereof.
For improvement of the catalytic properties and hydrogen permeability, the membrane catalyst according to the present invention preferably comprises the following components taken in the following proportions, in per cent by weight: cermet structure 50 to 89 polyorganosiloxane polymer 10 to 39 heterogenized palladium complex 1 to 4.
The membrane catalyst according to the present invention preferably contains in order to enhance its activity, as a film, product of interaction of a polyorganosiloxane polymer and a heterogenized palladium complex which is a complex compound of palladium attached to silica gel by means of chemically bonded (through a g Si-O-Si-C system of bonds) organosilicon ligands with nitrogen- or phosphorus-containing electron donor groups.
The thickness of the film in the catalyst is preferably from 0.3 to 1 .Omm, in order to improve its hydrogen permeability.
The invention in another aspect provides a method of preparing a membrane catalyst for hydrogenation of organic compounds, comprising applying onto a metal-ceramic substrate a mixture of a polyorganosiloxane polymer and a heterogenized palladium complex of the formula:
wherein R is an alkyl group, an alkoxy group, or chlorine;
R' is -C6H4-, or (CH2)n where n = 1.10;
D is -PR2', where R" is an alkyl or phenyl group;
or -NR'2', where R"' is an alkyl group; or -C5H4N; and
L is -Cl, -Br, or -OCOCH3 and effecting vulcanization thereof in the presence of a vulcanizing agent at a temperature of from 20 to 150"C until the formation of a film with a thickness of from 0.3 to 1.Omm occurs.
The method according to the present invention makes it possible to substantially simplify and shorten the duration of the catalyst manufacture due to the elimination of the stage of deposition, by spraying, of a catalytically active component based on palladium, the latter being introduced into the catalyst in the form of a heterogenized complex. The method according to the invention also permits the production of a catalyst of any size irrespective of the size of a high-vacuum spraying unit.
It is preferable to use, as the polyorganosiloxane polymer, polydimethylsiloxane or polymethylphenylsiloxane, containing 5 to 25 per cent by weight of phenyl groups.
The method according to the invention will now be described in more detail.
A catalytic component is preliminarily prepared, which is a heterogenized palladium complex of the general formula:
wherein R is an alkyl group, an alkoxy group, or chlorine;
R' is -C6H4-, or -(CH2)n- where n = 1-10;
D is -PR2', where R" is an alkyl or phenyl group;
or -NR'2', where R"' is an alkyl group; or -C5H4N; and
L is -Cl, -Br, or -OCOCH3.
For this purpose a modified inorganic oxide carrier, e.g. silica gel, is treated with a solution of a palladium salt, the inorganic carrier being modified with organosilicon compounds containing hydrolyzable groups attached to silicon and hydrocarbon radicals with functional groups capable of co-ordinating with compounds of metals of variable valency of the type: R3 SiR'D, wherein
R3Si contains at least one hydrolyzable group, R' is a hydrocarbon biradical, and D is a nitrogenor phosphorus-containing group.
The resulting catalytically active component in the form of a heterogenized palladium complex is mixed with a polyorganosiloxane-a,-diol containing, as the vulcanizing agent, for example an aminosubstituted silane or alkyltriacetoxysilane and a filler such as zinc oxide, in a ratio of from 1:5 to 1:1 5 by weight. This mixture is applied in a thin layer (with a thickness of from 0. 1 to 1 .Omm) onto the surface of a cermet sheet material based, for example, on nickel, copper or stainless steel and subjected to vulcanization at a temperature from 20 to 150"C. The film formed as a result of the vulcanization of the mixture of an organosilicon polymer and a heterogenized palladium complex possesses characteristics of a hydrogenation catalyst and a hydrogen-permeable membrane.The thickness of the reinforcing substrate, a cermet material, is preferably varied within the range of from 0.1 to 1 .Omm depending on the necessity of adjusting the gas-permeability of the whole composition. A thickness exceeding 1 mm may hinder hermetization of the membrane catalyst in a reactor, since upon increasing the material thickness metal-ceramic sheets become brittle. The use of a metal-ceramic sheet with a thickness of below 0.1 mm may be limited by the high gas-permeability of the material. The hydrogenpermeability of the membrane catalyst is also adjusted by varying the thickness of the polyorganosiloxane film within the range of from 0.3 to 1.0 mm. Optimization of the properties of the polyorganosiloxane film is attained by varying the time, vulcanization temperature, type and quantity of the filler and vulcanizing agent.The catalyst productivity in reactions of hydrogenation of organic compounds can be adjusted by varying the ratio of the polyorganosiloxane polymer and heterogenized palladium complex within the range of from 5:1 to 15:1.
It is desirable to vary the proportions of the ingredients in the process of manufacture of the membrane catalyst in such a manner that the components be contained in the following amounts, in per cent by weight: cermet substrate 50 to 89 polyorganosiloxane polymer 10 to 39 heterogenized palladium complex 1 to 4.
This membrane catalyst has a high catalytic activity and a high productivity per unit weight of palladium.
The resulting membrane catalyst comprises a bi-layered composition consisting of a layer of a porous cermet material employed as a reinforcing substrate and a thin polymeric film which is catalytically active and hydrogen-permeable; it also contains palladium in a highly active state, in contrast to membrane catalysts made of palladium alloys.
Consumption of palladium per 1 cm2 of the surface area of the catalyst according to the present invention is 0.004g, or about 100 times less than in conventional membrane catalysts manufactured from palladium alloys.
The invention will be further described with reference to the following illustrative Examples.
EXAMPLE 1
To 2g of silica gel modified by dimethylethoxy (methyldiethylamino)silane in 60 ml of a benzene ethanol solution (1:1) there was added 0.6g of palladium chloride as a 40% aqueous solution. The reaction mixture was kept at room temperature for 24 hours. Then silica gel was filtered off, washed twice (50 ml each time) with a benzene-ethanol solution and twice (50 ml each time) with pure ethanol; thereafter silica gel was dried under a vacuum of 1.10-4 mm Hg during 6 hours at room temperature. A heterogenized complex with a palladium content of 2.2% by weight was thus obtained.
0.18 g of the resulting catalyst with a particle size of less than 0.1 mm was mixed with 0.9 g of polydimethylsiloxane-a,-diol containing zinc oxide as a filler and methyltriacetoxysilane as a vulcanizing agent (in ratio of 3 parts by weight: 100 parts by weight of the polymer). This mixture was applied onto a sheet of porous copper with dimensions of 119 X > ( 22 X 0.1 mm.
After vulcanization in air at room temperature for two days the sample was placed under a vacuum of 10-3 mm Hg for 6 hours to give a polymeric film having a thickness of 0.3 mm.
The resulting membrane catalyst was mounted and sealed in a flow-type reactor adapted for carrying out hydrogenation reactions. To one side of the membrane catalyst was supplied hydrogen, while to the other side was supplied a mixture of cyclopentadiene vapour with argon at a rate of 10 ml/min. The partial pressure of the cyclopentadiene was 8.5 mm Hg, and that of hydrogen in the hydrogenation zone was 11.4 mm Hg. At a temperature of 161 C the conversion of cyclopentadiene was 89.9%, at the selectivity relative to cyclopentene of 0.95.
EXAMPLE 2
A membrane catalyst was produced by following the procedure as described in the foregoing
Example 1, except that use was made of silica gel modified with dimethylethoxy(diphenylphosphinomethyl)silane. A heterogenized palladium complex with a content of palladium equal to 4.6 per cent by weight was obtained. A mixture of polydimethylsiloxane and heterogenized palladium complex in a ratio of 5:1 was applied as a 0.5 mm thick film onto a sheet of porous nickel of size 11 9 x 22 x I mm. The resulting catalyst had the following composition, in per cent by weight: cermet material - 76 polydimethylsiloxane polymer - 20 palladium complex - 4.
In a flow-type catalytic reactor, hydrogen was fed to one side of the membrane catalyst and a mixture of cyclopentadiene vapour with argon was fed to the other side of the membrane catalyst at a rate of 10 ml/min; the partial pressure of the cyclopentadiene in the reaction zone was 8.5 mm Hg, and that of hydrogen was 11.4 mm Hg at a temperature of 100"C. The achieved cyclopentadiene conversion was 86.6%, at a selectivity of 0.82 relative to cyclopentene.
EXAMPLE 3
On the basis of silica gel modified by triethoxy GB-(2-ethylpyridyl)l silane, by following the procedure described in Example 1, a heterogenized palladium complex was obtained containing 5.5% by weight of palladium.
Further, a membrane catalyst was prepared as described in Example 1, but the mixture of polydimethylsiloxane and palladium complex heterogenized on silica gel was applied as a 1 mm thick film onto a sheet of porous copper of size 119 X 22 X 0.5 mm. The resulting catalyst had the following composition, in per cent by weight: cermet base 57 polydimethylsiloxane 39 heterogenized palladium complex 4.
This catalyst was employed in a reactor at a temperature of 88"C, the supply rate of cyclopentadiene vapour with argon being 10 ml/min, and the partial pressure of cyclopentadiene in the hydrogenation zone being 8.5 mm Hg and that of hydrogen being 11.4 mm Hg; a conversion of cyclopentadiene of 98.9% was attained, at a selectivity of 0.79 relative to cyclopentene.
EXAMPLE 4
A membrane catalyst was produced by following the procedure described in Example 2. A heterogenized palladium complex prepared on the basis of silica gel, modified by dimethylethoxy-(diphenylphosphinomethyl)silane, with a particle size of 0.1 mm, containing 2.8% by weight of palladium, was mixed with a polymethylphenysiloxane polymer (containing 5% of phenyl substituents at the silicon) in a ratio of 1:1 0 and applied onto a sheet of porous copper of size 119 X 22 X 0.5 mm. Vulcanization was conducted at a temperature of 25"C for 3 hours and then at a temperature of 150"C for one hour to obtain a film with a thickness of 0.3 mm.
The resulting catalyst had the following composition, in per cent by weight: cermet substrate 89 polydimethylphenylsiloxane 10 heterogenized palladium complex 1.
There was obtained on this catalyst in a reactor at a temperature of 1 Q0 C, the rate of supply of a mixture of cyclopentadiene vapour and argon being 1Q ml/min, and the partial pressure in the zone of cyclopentadiene (CPD) hydrogenization being 8.5 mm Hg and that of hydrogen being 11.4 mm Hg, a conversion of CPD of 86.6%, at a selectivity of 0.82 relative to cyclopentene.
EXAMPLE 5
A membrane catalyst was produced as described in Example 1, the modification of silica gel being carried out with the use of dimethylethoxy (y-diphenylphosphinopropyl)silane. A heterogenized palladium complex with a particle size of 0.1 mm containing 3.0% by weight of palladium was mixed with polydimethylsiloxane polymer in a ratio of 1:1 5 and applied onto a sheet of porous copper of size 11 9 X 22 X 0.5 mm. Vulcanization was conducted at a temperature of 25"C for 8 hours and then at 70"C for two hours to obtain a film with a thickness of 0.4 mm.
The thus-produced catalyst had the following composition, in per cent by weight: cermet substrate 80 polydimethylsiloxane polymer 1 6 heterogenized palladium complex 4.
There was obtained on this catalyst in a reactor at a temperature of 20"C, the rate of supply of a mixture of cyclopentadiene vapour with argon being 10 ml/min, and the partial pressure of cyclopentadiene in the hydrogenation zone being 8.5 mm Hg and that of hydrogen being 11.4 mm, a conversion of cyclopentadiene of 97.7%, at a selectivity of 0.75 relative to cyclopentene.
Claims (13)
1. A membrane catalyst for hydrogenation of organic compounds, comprising a metalceramic substrate having applied thereon, as a film, a product of interaction of a polyorganosiloxane polymer and a heterogenized palladium complex of the formula:
wherein R is an alkyl group, an alkoxy group, or chlorine;
R' is -C6H4-, or -(CH2)n- where n = 1-10;
D is -PRi", where R" is an alkyl or phenyl group;
or -NR2,,,, where R"' is an alkyl group; or -C5H4N; and
L is -Cl, -Br, or -OCOCH3.
2. A membrane catalyst as claimed in Claim 1, comprising the following components in the following proportions, in per cent by weight: cermet substrate 50 to 89 polyorganosiloxane polymer 10 to 39 heterogenized palladium complex 1 to 4.
3. A membrane catalyst as claimed in Claim 1 or 2, containing, as a film, a product of interaction of a polyorganosiloxane polymer and palladium complex heterogenized through a pyridinium ligand.
4. A membrane catalyst as claimed in Claim 1 or 2, containing, as a film, a product of interaction of a polyorganosiloxane polymer and palladium complex heterogenized through a tertiary amine ligand.
5. A membrane catalyst as claimed in Claim 1 or 2, containing, as a film, a product of interaction of a polyorganosiloxane polymer and a palladium complex heterogenized through a tertiary phosphine ligand.
6. A membrane catalyst as claimed in any of Claims 1 to 5, containing, as a film, a product of interaction of a heterogenized complex of palladium and polydimethylsiloxane.
7. A membrane catalyst as claimed in any of Claims 1 to 5, containing, as a film, a product of interaction of a heterogenized complex of palladium and polymethylphenylsiloxane.
8. A membrane catalyst as claimed in any of Claims 1 to 7, wherein the film thickness is equal to 0.3-1.0mm.
9. A membrane catalyst according to Claim 1, substantially as herein described in any of the foregoing Examples.
1 0. A method of preparing a membrane catalyst for hydrogenation of organic compounds, comprising applying onto a metal-ceramic substrate a mixture of a polyorganosiloxane polymer and a heterogenized palladium complex or the formuala:
wherein R is an alkyl group, an alkoxy group, or chlorine;
R' is -C6H4-, or ~(CH2)n- where n = 1-10;
D is -PR2', where R" is an alkyl or phenyl group;
or -NR, where R"' is an alkyl group;
or -CsH4N; and
L is -Cl, -Br, or -OCOCH3 and effecting vulcanization thereof in the presence of a vulcanizing agent at a temperature of from 20 to 150"C until the formation of a film with a thickness of from 0.3 to 1 .Omm occurs.
11. A method as claimed in Claim 10, wherein the polyorganosiloxane polymer is polydimethylsiloxane.
12. A method as claimed in Claim 10, wherein the polyorganosiloxane polymer is polymethylphenylsiloxane.
13. A method according to Claim 1 of preparing a membrane catalyst, substantially as herein described in any of the foregoing Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8102827A GB2092017B (en) | 1981-01-30 | 1981-01-30 | Membrane catalyst for hydrogenation of organic compounds and method of preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8102827A GB2092017B (en) | 1981-01-30 | 1981-01-30 | Membrane catalyst for hydrogenation of organic compounds and method of preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2092017A true GB2092017A (en) | 1982-08-11 |
| GB2092017B GB2092017B (en) | 1985-05-22 |
Family
ID=10519333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8102827A Expired GB2092017B (en) | 1981-01-30 | 1981-01-30 | Membrane catalyst for hydrogenation of organic compounds and method of preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2092017B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0269080A1 (en) * | 1986-11-28 | 1988-06-01 | E.I. Du Pont De Nemours And Company | Substrates with sterically-protected, stable, covalently-bonded organo-silane films |
| EP0332970A1 (en) * | 1988-03-17 | 1989-09-20 | Hoechst Aktiengesellschaft | Supported catalyst for monocarboxylic acid anhydrides preparation |
| EP0464459A1 (en) * | 1990-06-29 | 1992-01-08 | Bayer Ag | Preparation of a palladium containing catalyst |
| US6184171B1 (en) * | 1998-10-05 | 2001-02-06 | W.R. Grace & Co. -Conn | Supported bidentate and tridentate catalyst compositions and olefin polymerization using same |
| EP1487563A4 (en) * | 2002-03-05 | 2005-07-20 | Eltron Research Inc | HYDROGEN TRANSPORT MEMBRANES |
| US7148173B2 (en) * | 1998-04-27 | 2006-12-12 | Repsol Quimica, S.A. | Catalytic systems for the polymerization and copolymerization of alpha-olefins |
| US7211538B2 (en) | 1996-10-31 | 2007-05-01 | Repsol Quimica S.A. | Catalytic systems for the polimerization and copolimerization of alpha-olefins |
-
1981
- 1981-01-30 GB GB8102827A patent/GB2092017B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0269080A1 (en) * | 1986-11-28 | 1988-06-01 | E.I. Du Pont De Nemours And Company | Substrates with sterically-protected, stable, covalently-bonded organo-silane films |
| US4847159A (en) * | 1986-11-28 | 1989-07-11 | E. I. Du Pont De Nemours And Company | Substrates coated with organo-silanes that are sterically-protected |
| EP0332970A1 (en) * | 1988-03-17 | 1989-09-20 | Hoechst Aktiengesellschaft | Supported catalyst for monocarboxylic acid anhydrides preparation |
| US4965234A (en) * | 1988-03-17 | 1990-10-23 | Hoechst Aktiengesellschaft | Supported catalyst for the preparation of monocarboxylic anhydrides |
| EP0464459A1 (en) * | 1990-06-29 | 1992-01-08 | Bayer Ag | Preparation of a palladium containing catalyst |
| US5185458A (en) * | 1990-06-29 | 1993-02-09 | Bayer Aktiengesellschaft | Palladium-containing catalyst preparation |
| US7211538B2 (en) | 1996-10-31 | 2007-05-01 | Repsol Quimica S.A. | Catalytic systems for the polimerization and copolimerization of alpha-olefins |
| US7148173B2 (en) * | 1998-04-27 | 2006-12-12 | Repsol Quimica, S.A. | Catalytic systems for the polymerization and copolymerization of alpha-olefins |
| US6184171B1 (en) * | 1998-10-05 | 2001-02-06 | W.R. Grace & Co. -Conn | Supported bidentate and tridentate catalyst compositions and olefin polymerization using same |
| EP1487563A4 (en) * | 2002-03-05 | 2005-07-20 | Eltron Research Inc | HYDROGEN TRANSPORT MEMBRANES |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2092017B (en) | 1985-05-22 |
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