GB2187759A - Catalyst for hydrogen hydrogenation of carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds - Google Patents
Catalyst for hydrogen hydrogenation of carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds Download PDFInfo
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- GB2187759A GB2187759A GB08605812A GB8605812A GB2187759A GB 2187759 A GB2187759 A GB 2187759A GB 08605812 A GB08605812 A GB 08605812A GB 8605812 A GB8605812 A GB 8605812A GB 2187759 A GB2187759 A GB 2187759A
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- membrane
- catalyst
- zinc
- carbon
- porous layer
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 16
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 15
- 125000003172 aldehyde group Chemical group 0.000 title claims abstract description 14
- 150000007824 aliphatic compounds Chemical class 0.000 title claims abstract description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 title claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 45
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims 6
- 239000012528 membrane Substances 0.000 claims abstract description 90
- 239000011701 zinc Substances 0.000 claims abstract description 40
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 239000010948 rhodium Substances 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000011084 recovery Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 30
- 239000011888 foil Substances 0.000 description 29
- 230000035699 permeability Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 6
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 6
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- SUGZATOHBPXTDV-UHFFFAOYSA-N 2-nitrobutane Chemical compound CCC(C)[N+]([O-])=O SUGZATOHBPXTDV-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- MOVBPUIMHBKLTA-UHFFFAOYSA-N C=CC=CC.CC=CCC.C=CCCC.CCCCC Chemical compound C=CC=CC.CC=CCC.C=CCCC.CCCCC MOVBPUIMHBKLTA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WPNJAUFVNXKLIM-UHFFFAOYSA-N Moxonidine Chemical compound COC1=NC(C)=NC(Cl)=C1NC1=NCCN1 WPNJAUFVNXKLIM-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- -1 carbbxybenzaldehyde Chemical compound 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- BZEVNDPHINRVAB-UHFFFAOYSA-N ethane ethanol Chemical compound CC.CCO.CCO.CCO BZEVNDPHINRVAB-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- WWQAGDWTJOKFQB-UHFFFAOYSA-N penta-1,2,3-triene Chemical compound CC=C=C=C WWQAGDWTJOKFQB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- B01J35/59—
-
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- 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
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
Abstract
A catalyst for hydrogenation of carbon-carbon double bonds, nitro groups and aldehyde groups in aliphatic and aromatic compounds comprises a membrane made from an alloy consisting of 80 to 95% by mass of palladium and 5 to 20% by mass of ruthenium or rhodium and consists of a non-porous layer and a porous layer positioned on one or both sides of the non-porous layer, having a well developed porous surface without through pores. The catalyst can be prepared by a process comprising application of zinc onto one or both sides of the surface of a membrane made from the above mentioned alloy, the layer-thickness of zinc to the membrane being equal 1:10-100, keeping the membrane with zinc applied there onto at a temperature of 20 to 250%, followed by a chemical recovery of zinc from the membrane.
Description
SPECIFICATION
Process for preparing catalyst for hydrogen hydrogenation of carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds
The present invention relates to the preparation of catalysts and, more particularly, to processes for the preparation of catalysts for hydrogenation of carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds.
In the present-day catalytical chemistry known are processes for the preparation of metallic catalysts with a well-developed surface employed, for example for hydrogenation of carboncarbon double bond, nitro and aldehyde groups in- aliphatic and aromatic compounds. These processes comprise application of a metal in a highly dispersed form onto a carrier. Furthermore, metal catalysts with a well-developed surface (skeleton-type catalysts) are also prepared, for example, by leaching of some alloys of catalytically active metals with aluminium, silicon and the like (cf. G.N. Setterfield, "Heterogeneous Catalysts in Practice", McCraw Hill Inc., New York, 1980).
These processes for the preparation of catalysts do not make it possible to produce membrane catalysts with a well-developed surface which would also possess a selective permeability for hydrogen and a high mechanical strength.
Known in the art is a process for producing a membrane catalyst with a well-developed surface useful in processes of hydrogen hydrogenation of unsaturated hydrocarbons comprising a chemical or electrochemical deposition, onto the surface of a membrane shaped as a foil or a tube from a palladium based alloy, e.g. with silver or nickel, of a layer of palladium black or black of any other catalytically active metal (cf. V.M. Gryaznov, V.S. Smirnov, L.K. Ivanova, A.P.
Mischenko, -Doklady AN SSSR, 1970, vol. 190, p. 144).
This prior art process, however, does not ensure a durable coating of the membrane with palladium or other metal black. Furthermore, the use of another catalytically active metal for coating of a membrane frequently results in a lowered permeability of the membrane catalyst for hydrogen, since a considerable portion of the surface of a membrane from a palladium alloy becomes inaccessible fpr molecules of hydrogen and an organic substance. At a long-time operation in the atmosphere of hydrogen, air and a hydrocarbon, the black layer gets destroyed and stripped-off.
Also known in the art is a process for the preparation of a catalyst for hydrogen hydrogenation of unsaturated hydrocarbons comprising a substrate made from a structural metallic material with a porous layer of a catalytically active metal such as nickel palladium or platinum provided on its surface. The process resides in that à layer of a catalytically active metal is applied onto the substrate surface and then coated with a layer of a catalytically inactive metal such as zint or aluminium, kept at a temperature within the range of from 300 to 1,000 C for an interdiffusion of the catalytically active and catalytically inactive metals, followed by a chemical recovery of zinc or aluminium from the catalytically active metal by bleaching with sodium hydroxide or potassium hydroxide.The layer thickness of the catalytically inactive metal is equal to the layer thickness of the active metal or by 10 times greater (cf. USSR Inventor's Certificate no. 218830,
Int. Cl. B 01 J 25/00, published in Bulletin of Inventions No. 24, 1967).
This prior art process does not make it possible to produce a membrane catalyst, whereupon the hydrogenation processes occur with the use of active (elemental) hydrogen diffusing through the membrane. On a catalyst produced by this process the processes proceed with the use of molecular hydrogen at a competitive adsorption of the reagent and hydrogen, whereby the hydrogenation rate and the process selectivity are lowered. The hydrogenation of nitro compound under atmospheric pressure on such a catalyst does not substantially proceed at all which is due to a strong adsorption of the nitro compound on the catalyst surface which hinders the access of hydrogen to the active centers of the catalyst.
It is an object of the present invention to provide a process for preparing a catalyst with a well-developed porous surface but without through pores which would have an increased selective permeability for hydrogen in processes of hydrogenation of a carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds, as well as a high mechanical strength of the porous layer.
This object is accomplished by a process for preparing a catalyst for hydrogen hydrogenation of a carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds by way of depositing zinc onto a catalytically active metal, keeping these metals at a temperature ensuring their mutual diffusion, follow by a chemical recovery of zinc from the catalytically active metal, wherein according to the present invention on the- catalytically active metal is used in the shape of a membrane from an alloy consisting of 80 to 95 /O by mass of palladium and 5 to 20% by mass of ruthenium or rhodium; zinc is applied onto the membrane surface on one or both sides thereof at the layer thickness ratio of zinc to the membrane equal to 1:10-100; the membrane with the zinc layer applied thereonto is kept at a temperature within the range of from 20 to 250"C and the chemical recovery of zonc from the membrane is effected by treating the membrane with hydrochloric acid.
The- process according to the present invention makes it possible to prepare a catalyst which comprises a membrane made from an alloy consisting of 95 to 80% by mass of palladium and
5 to 20% by mass of ruthenium or rhodium and comprising a nonporous layer and a porous
layer position on one or both sides of this non-porous layer; the porous surface area is equal to
150-1,500 cm2 of pores per cm2 of the membrane surface and the thickness ratio of the porous layer to the non-porous layer is 1 : 5.7-100 respectively. The membrane catalyst according- to the present invention has a well-developed porous surface face without through
pores which enables an enhanced productivity of the catalyst in the process of hydrogenation owing to the use of elemental hydrogen. The selective permeability for hydrogen is considerably
increased.Thus, at room temperature (18-25"C) the hydrogen permeability of a membrane catalyst prepared by the process according to the present invention is by 5-10 times higher than that of a known membrane catalyst which makes it possible to use the membrane catalyst prepared by the process according to the present invention for carrying out the process of
hydrogen hydrogenation of a carbon-carbon double bond, nitro or aldehyde groups in aliphatic and aromatic compounds at low temperatures (within the range of from 20 to 40"C). Furthermore, the catalyst produced by the process according tithe present invention features a high mechanical strength of the porous layer which does not get broken during operation and regeneration of the membrane catalyst.
As it has been already mentioned hereinabove, as the catalytically active metal use is made of an alloy consisting of 80 to 95% by mass of palladium and 5 to 20% by mass of ruthnium or rhodium. It is inadvisable to use an alloy with a smaller (than 80% by mass) content of palladium, since hydrogen permeability through such alloys-is very low, whereas at a content of palladium of more than 95% by mass such alloys become very unstable in the atmosphere of hydrogen and get readily broken.
It is neither advisable to use the layer thicknessiratio .of zinc to the membrane above 1:10, since a greater amount of zinc results in the formation of through pores in the membrane. A thickness ratio of below 1:100 results in an insufficient lossening of the- membrane surface which does not make is possible to obtain a highly active hydrogenation catalyst.
The temperature of residence of the membrane with the zinc layer should not be elevated over 250"C, since at higher temperatures a deep diffusion of zonc into the superficial layer of palladium occurs, thus making it impossible to fully remove zinc in a subsequent-treatment with hydrochloric acid which provides a negative effect on the activity of the membrane catalyst.
Below 20"C the diffusion of zinc into the palladium alloy is very slow and a porous layer is not substantially formed upon dissolution of-zinc with hydrochloric acid.
The process for preparing a membrane catalyst for hydrogenation of a carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds according to the present invention is performed in the following manner.
First of ali, onto a clean surface of a membrane such as a foil or a tube made- from an alloy consisting of 80 to- 95% by mass of palladium and 5 to 20% by mass of ruthenium or rhodium a thin layer of zinc is electrochemically deposited on one or both sides at a thickness ratio of the zinc layer to the membrane of 1:10-100. The membrane with the zinc layer deposited thereonto is kept at a temperature within the range of from 20 to- 250"C, whereafter it is placed into hydrochloric acid with a concentration of 10 to 37%. After drying a membrane catalyst is obtained which is based-on the alloy of the same composition as the starting material and consists of a non-porous layer and a porous one; the porous layer may be positioned either on both sides of the non-porous layer or on one side thereof.In the latter case the hydrogenation process is conducted on the porous layer side.
The membrane catalyst prepared by the process according to the present invention is tested for hydrogen permeability by the direct-flow method using a thermal conductivity sensor-katharometer.
In order to carry-out the process of-hydrogenation of aliphatic and aromatic compounds with a carbon-carbon double bond, nitro and aldehyde groups, e.g. 1 ,3-pentadiene, nitroethane, acetaldehyde, nitrobenzene, carbbxybenzaldehyde, styrene, a membrane catalyst is placed into a reactor in such a manner that it divides the inner space of the- reactor into two compartments. Into one compartment hydrogen is supplied, while into the other 3 a-compound to be hydrogenated.
Hydrogen diffuses through the m-embrane catalyst into the other compartment and interacts, in an active elemental form, with the hydrogenated compound on the porous surface of the membrane catalyst with the formation of the -desired product. The catalyzate composition is determined chromatographically. The thickness of the porous and non-porous layers of thecatalyst iF determined by means of an electron microscope.
For a better understanding of the present invention, some specific examples illustrating its particular embodiments are given hereinbelow.
Example 1
A 100 jim foil made from an alloy consisting of 90.2% by mass of palladium and 9.8% by mass of ruthenium is degreased, rinsed with distilled water and placed into an electrolyte comprising a solution of 130 g of zinc sulphate in 1 I of water. Then zinc is deposited on the surface of the foil on one side thereof at the temperature of 20 C, current density of 3.5A/dm2 and the electrolyte pH of 1.5 for 12 minutes using a zinc anode.
The foil with the zinc layer of 10 jim thickness deposited thereonto is heated to the temperature of 250"C and kept at this temperature for 2 hours. Then the foil is cooled, placed into a boiling 20% hydrochloric acid, kept therein till a complete removal of zinc which is controlled by the stoppage of evolution of hydrogen bubbles and washed with water till the absence of the reaction on chlorine ion. A membrane catalyst is thus obtained in the shape of a foil made from the above specified alloy and consisting of a 90 jim thick non-porous layer and a 9 Am thick porous layer. The porous surface is measured by the BET method (Brunauer S., Emmet P.H.,
Teller E.); the obtained data show that 1,500 cm2 of pores are present in 1 cm2 of the membrane surface.
The hydrogen permeability (J) of the membrane catalyst produced as described hereinabove is shown in Table 1.
Table 1
Temperature, C 25 45 80 100 180
Hydrogen permeability, J . 104, 6.31 7.13 7.76 7.57 6.50 cm.s-1.MPa-0,5
The hydrogen permeability of the starting foil (i.e. of the foil which has not been subjected to the treatment) at the temperature of 25 C is equal to 4.7 X 10 6 cm2.s 1. .MPa 0-5; at 1000C-5.21 X 10 5 cm2.s 1.MPa 05. As it is seen from the above data, the permeability of the membrane catalyst prepared as described hereinabove is increased by 15 times at the temperature of 100 C, while at room temperature it is increased by 130 times.
Exa?nThple 2
A membrane catalyst is prepared as described in the foregoing Example 1 using a foil of an alloy having the same composition. The foil with the zinc layer of 10 jim thickness applied thereonto is kept at the temperature of 20 C for one day. Then zinc is removed by dissolution thereof in a 30% hydrochloric acid to give a membrane catalyst shaped as a foil made from the above-specified alloy and consisting of a non-porous layer of 85 jim thickness and a porous layer of 15 jim thickness. The porous surface area of the membrane catalyst is 1,200 cm2 of pores per cm2 of the membrane surface. The hydrogen permeability of the membrane catalyst is shown in the following Table 2.
Table 2
Temperature, C 54 94 105 144
Hydrogen permeabili
2.95 4.52 4.27 4.08
ty, Jx104, cm.s-1.
.MPa-0.5 From the data of the above in Table 2 it follows, after comparison with the data for permeability of to the starting foil shown in-Example 1, that the hydrogen permeability of the catalyst prepared according to the present invention is considerably higher (by about 8 times at the temperature of 100 C).
Example 3
Onto the outer surface of a tube having the outside diameter of 1 mm, wall thickness of 100 m and made from an alloy consisting of 94% by mass of palladium and 6% by mass of ruthenium a layer of zinc is deposited to the thickness of 1 m as described in Example 1 hereinbefore. Then the tube is heated to the temperature of 230 C, kept at this temperature for 30 minutes and then cooled, whereafter zinc is removed with a 25% hydrochloric acid. A membrane catalyst shaped as a tube is thus obtained; the tube is made from the abovespecified alloy and consists of an inner non-porous layer of 99 m thickness and an external porous layer of 1 m thickness. The porous surface area of the membrane catalyst is 150 cm of pores per cm of the membrane surface.The hydrogen permeability of the membrane catalyst at the temperature of 24 C is equal to 5.02x10-5 cm.s .MPa0.5, i.e. by one order of magnitude higher than the permeability of the initial tube.
Example 4 Onto both sides of a 100 m foil made from an alloy consisting of 80% by mass of palladium and 20% by mass of rhodium layers of zinc of 4 m each are applied. The foil with the zinc layers aplied thereonto is kept at the temperature of 150 C for 4 hours. After cooling of the fo foil, zinc is removed by boiling in a 20% hydrochloric acid. A membrane catalyst is obtained as a foilmade from the above-specified alloy and consisting of a non-porous layer of 98 m thickness of superficial porous layers positioned on both sides of the non-porous layer and having thickness of 3 m each. The porous surface area of the membrane catalyst is 470 cm of pores per cm2 of the membrane surface. The hydrogen permeability of this catalyst at the temperature of 125 C is 2,82x104 cm. .s MPa.0.5.
Example 5 A membrane catalyst is prepared from 50 m foil made of an alloy consisting of 95% by mass of palladium and 5% by mass of rhodium. A zinc layer of 4.7 m thickness is deposited on one side of the foil in a manner similar to the described in Example 1 hereinbefore. The foil with the zinc layer deposited thereonto is heated to the temperature of 250 C and maintained at this temperature for 5 hours. Zinc is removed by threating the membrane with a 37% hydrochloric acid. A membrane catalyst is thus obtained in the shape of a foil made from the abovementioned alloy and consisting of a non-porous layer of 49 m thickness and a 2 m porous layer. The porous surface area of the membrane catalyst is 540 cm of pores per cm of the membrane surface. The hydrogen permeability of the catalyst at 24 C is 7.94x 10 4 cm.s .MPa 0.5, at 120 C-10.2x104 cm.s .MPa-0.5.
Example 6
Onto a 100 m thick foil made from an alloy consisting of 95% by mass of palladium and 5% by mass of rhodium a zinc layer of 6 m thickness is deposited as described in Example 1.
Then the foil is kept at the temperature of 200 C for 3 hours and zinc is removed by boiling in a 10% hydrochloric acid. A membrane catalyst is obtained as a foil made from the above mentioned alloy and consisting of a non-porous layer of 96 m thickness and a porous layer of 4 m thickness. The porous surface area of the membrane catalyst is 810 cm of pores per cm of the membrane surface. The hydrogen permeability of this catalyst at 125 C is 1.0x 10-3 cm2.S-1 .MP-0.5
As it follows from the above-given data, the membrane catalyst produced as described in
Example 1 through 6 hereinbefore exhibits a high hydrogen permeability. It enables a higher productivity of the catalyst in hydrogenation processes.
Given hereinbelow are Examples 7 through 12 illlustrating the process of hydrogenation of 1,3pentadiene, nitrobenzene, para-carboxybenzaldehyde, acetaldehyde, nitroethane, styrene on a membrane catalyst produced according to Examples 1-6.
Example 7
The study of catalytical properties of a membrane catalyst produced as described in Example 1 herein before in the shape of a foil is conducted by hydrogenation of 1,3-pentadiene in a reactor divided into two chambers by the above-mentioned catalyst. into one chamber, on the side of the non-porous layer of the membrane catalyst, hydrogen is admitted at the rate of 30 ml/min, whereas into the other chamber, on the side of the porous layer of the catalyst, a mixture of argon with vapours of 1,3-pentadiene, is supplied at the rate of 10 ml/min under the pressure of 1,3-pentadiene, vapours of 10 mm Hg.
The composition of the catalysate obtained at different temperatures of the hydrogenation process is shown in Table 3 hereinbelow.
Table 3 n Temperature, Catalysate composition, mol. %
C pentane cyclopen- cyclo- 1,3-penta
tane pentene diene 1 24 99.8 - - 0.2 50 100 - - 3 100 94.9 2,2 1.4 1.5 4 120 96.0 2.1 1.3 0.6 5 140 97.0 1.9 0.2 0.9 6 160 97.7 2.0 0.2 0.1 7 180 97.8 1.9 0.3 - 8 190 97.8 1.8 0.4
For the purpose of comparison, in Table 4 the composition of a catalysate obtained upon hydrogenation of 1,3-pentadiene on the initial foil is shown.
Table 4
Temperature, Catalysate composition, mol. %
pentane 1-pentene 2-pentene 1,3-pentadiene C
100 1.0 13.0 36.0 50.0
150 1.9 23.3 4 .7 25.1
As it is seen from the data given in Tables 3 and 4, the depth of hydrogenation attained using the membrane catalyst according to the present invention is considerably higher. Thus, at the temperature of 100"C the yield of pentane is increased from 1 to 95 mol.%. The selectivity of the hydrogenation process is. also changed towards the formation of cyclic hydrocarbons.
Example 8
The study of catalytical properties of a membrane catalysti produced as in Example 2 hereinbefore as a foil is conducted by hydrogenation of styrene in a reactor divided into two chambers by the above mentioned membrane catalyst. Into one chamber, on the side of the non-porous layer of the membrane catalyst, hydrogen is supplied at the rate of 50 ml/min, while into the second chamber, on the side of the porous layer of the catalyst, styrene in a mixture with argon is admitted at the rate of 50 ml/min under the pressure of styrene vapours of 150 mm Hg. The composition of the catalysate obtained at different temperatures of the hydrogenation process is given in Table 5 hereinbelow.
Table 5
Temperature, Catalgsate composition, molt0 OC ethylbenzene ethylcyclohezane styrene
60 25.6 - 74.4
100 45.3 12.1 42.6 180 38.7 33.5 27.8 250 23.4 28.1 48.5
From the data shown in Tables 4 and 5 it is seen that the membrane catalyst prepared according to the present invention is active in hydrogenation of a carbon-carbon double bond in aliphatic and aromatic compounds.
Example 9
The study of catalytical properties of a membrane catalyst produced as in Example 3 hereinbefore as a tube is carried out by hydrogenation of para-carboxybenzaldehyde. The hydrogenation is conducted in a reactor containing a bundle of such tubes. Inside the tubes hydrogen is fed under the pressure of 6 MPa at the rate of 50 ml/min, while into the intertubulare space a 10% aqueous solution of para-carboxybenzaldehyde is supplied. The temperature in the reactor is elevated to 2540C and hydrogenation is conducted for 1 hour under the pressure of 5.4 MPa.
The analysis of the resulting catalyst shows that paracarboxybenzaldehyde is substantially fully converted into para-toluic acid. The amount of the non-converted para-carboxybenzaldehyde is 0.04% of the initial amount thereof.
Example 10
The study of catalytical properties of a membrane catalyst produced as in Example 4 as a foil is carried out by hydrogenation of acetaldehyde in a reactor divided into two chambers by this membrane catalyst. Into one chamber a hydrogen stream is fed at the rate of 60 ml/min, into the other vapours of acetaldehyde in a mixture with argon at the rate of 30 ml/min under the pressure of acetaldehyde vapours of 400 mm Hg.
The composition of the catalysate produced at different temperatures of the hydrogenation process is shown in Table 6.
Table 6 Temperature, C Catalysate composition, mol.%
Ethane Ethanol Acealdehyde- 50 - 5.7 94.3
100 - 15.4 84.6
200 4.3 56.7 39.0
250 13.2 24.2 62.6
Example 11
The study of catalytical properties of a membrane catalyst produced as in Example 5 hereinbefore as a foil is carried out by hydrogenation of nitrobenzene in a reactor partitioned into two chambers by the above-mentioned membrane catalyst. Into one chamber, on the side of the non-porous layer of the membrane catalyst, hydrogen is admitted at the rate of 45 ml/min, while into the other chamber vapours of nitrobenzene in a mixture with argon are supplied on the side of the porous layer of the catalyst at the rate of 30 ml/min under the pressure of nitrobenzene vapours of 100 mm Hg.At the temperatures of 250, 272 and 310 C a full conversion of nitrobenzene into aniline is observed. At the temperature of 170"C 0.5% of the unreacted nitrobenzene is contained in the reaction products.
Example 12
The study of catalystical properties of a membrane catalyst produced as in Example 6 in the shape of a foil is conducted by hydrogenation of nitroethane in a reactor partitioned into two chambers by the above-mentioned membrane catalyst. Into one chamber, on the side of the non-porous layer of the catalyst, hydrogen is supplied at the rate of 50 ml/min and into the other chamber-nitroethane vapours in a mixture with argon at the supply rate of 40 ml/min under the pressure of nitroethane vapours of 400 mm -Hg. The composition of the catalysate obtained at different temperatures of the hydrogenation process is given in Table 7 hereinbelow
(the catalysate composition is shown without account of water).
Table 7
Temperature, Catalysate composition, mol. % Ethyl- Nitroethane Decomposition C
amine products 65 96.4 re 3.6- 120 100.0
210 100.0
300 97.1 1.0 1.9
350 83.6 10.4 6.0
From the above-given Examples 8 through 12 it follows that the membrane catalyst prepared by the process according to the present invention is highly active in processes of hydrogenation of a carbon-carbon double bond in various organic compounds. This enables a broad use of the above-mentioned membrane catalyst in diverse chemical processes.
Claims (9)
1. A catalyst suitable for hydrogen hydrogenation of carbon-carbon double bonds, nitro groups and aldehyde groups in aliphatic and aromatic compounds which comprises a membrane made from an alloy-consisting of -80 to 95% by mass of palladium and 5 to 20% by mass of ruthenium or rhodium and consists of a non-porous layer and a porous layer positioned on one or both sides of-the non-porous layer, having a well developed porous surface without through pores.
2. A catalyst as claimed in claim 1 wherein the area- of the porous surface is equal to 150-1,500 cm2 of pores per cm2 of the membrane surface.
3. A catalyst as claimed in claim 1 and or claim 2 wherein the thickness ratio of the porous layer to the non-porous layer is 1:5.7-100 respectively.
4. A process for preparing a catalyst for hydrogen hydrogenation of carbon-carbon double bonds, nitro/groups and aldehyde groups in aliphatic and aromatic compounds comprising application of zinc onto one or both sides of the surface of a membrane formed from an alloy consisting of 80 to 95% by mass of palladium and 5 to 20% by mass of ruthenium or rhodium, the layer thickness of zinc to the membrane being equal to 1:10-100; keeping the membrane with zinc applied thereonto at a temperature of 20 to 250 C, followed by a chemical recovery of zinc from the membrane.
5. A process according to claim 4 wherein the zinc is recovered from the membrane by treatment with an acid.
6. A process according to claim 5 wherein the acid is hydrochloric acid.
7. A process for preparing a catalyst for hydrogen hydrogenation of carbon-carbon double bonds, nitro/groups and aldehyde groups in aliphatic and aromatic compounds according to claim 4, substantially as described in the specification and examples 1 through 6 hereinbefore.
8. A catalyst for hydrogen hydrogenation of carbon-carbon double bonds, nitro/groups and aldehyde groups in aliphatic and aromatic compounds, whenever prepared by a process according to claim 4.
9. The use of a catalyst as claimed in claim 1 in the hydrogen hydrogenation of an organic compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8602943A FR2595056B1 (en) | 1986-03-03 | 1986-03-03 | PROCESS FOR THE PREPARATION OF A CATALYST FOR HYDROGENATION BY HYDROGEN OF THE C = C DOUBLE BINDING, NITRO- AND ALDEHYDE GROUPS IN ALIPHATIC AND AROMATIC COMPOUNDS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8605812D0 GB8605812D0 (en) | 1986-04-16 |
| GB2187759A true GB2187759A (en) | 1987-09-16 |
| GB2187759B GB2187759B (en) | 1990-04-18 |
Family
ID=9332695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8605812A Expired - Lifetime GB2187759B (en) | 1986-03-03 | 1986-03-10 | Process for preparing catalyst for hydrogen hydrogenation of carbon-carbon double bond, nitro and aldehyde groups in aliphatic and aromatic compounds |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS62204848A (en) |
| DE (1) | DE3609264A1 (en) |
| FR (1) | FR2595056B1 (en) |
| GB (1) | GB2187759B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2850664A1 (en) * | 2003-01-31 | 2004-08-06 | Inst Francais Du Petrole | Selective hydrogenation of polyunsaturated compounds in hydrocarbon charge, e.g. in petrochemistry, involves using catalytic reactor having hydrogen-selective membrane |
| FR2850665A1 (en) * | 2003-01-31 | 2004-08-06 | Inst Francais Du Petrole | Total hydrogenation of polyunsaturated compounds in hydrocarbon charge involves using catalytic reactor having hydrogen-selective membrane with specific reaction conditions |
| US8071503B2 (en) | 2006-07-27 | 2011-12-06 | Johnson Matthey Public Limited Company | Catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2646990B2 (en) * | 1993-12-28 | 1997-08-27 | 日本電気株式会社 | Hydrogen reduction apparatus and method and hydrogen reduction material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE31104E (en) * | 1973-01-31 | 1982-12-14 | Alloy Surfaces Company, Inc. | Catalytic structure |
| BE817113A (en) * | 1974-07-01 | 1975-01-02 | CYCLO-ALKENES PREPARATION PROCESS |
-
1986
- 1986-02-28 JP JP61045146A patent/JPS62204848A/en active Pending
- 1986-03-03 FR FR8602943A patent/FR2595056B1/en not_active Expired
- 1986-03-10 GB GB8605812A patent/GB2187759B/en not_active Expired - Lifetime
- 1986-03-19 DE DE19863609264 patent/DE3609264A1/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| DOKLADY AN 555R VOL. 190, 1970, V. M. GRYAZNOV ET AL. P.144. * |
| USSR INVENTORS CERTIFICATE NO. 218830 (1967) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2850664A1 (en) * | 2003-01-31 | 2004-08-06 | Inst Francais Du Petrole | Selective hydrogenation of polyunsaturated compounds in hydrocarbon charge, e.g. in petrochemistry, involves using catalytic reactor having hydrogen-selective membrane |
| FR2850665A1 (en) * | 2003-01-31 | 2004-08-06 | Inst Francais Du Petrole | Total hydrogenation of polyunsaturated compounds in hydrocarbon charge involves using catalytic reactor having hydrogen-selective membrane with specific reaction conditions |
| US7223894B2 (en) | 2003-01-31 | 2007-05-29 | Institut Francais Du Petrole | Process for total hydrogenation using a catalytic reactor with a hydrogen-selective membrane |
| US7250544B2 (en) | 2003-01-31 | 2007-07-31 | Institut Francais Du Petrole | Process for selective hydrogenation using a catalytic reactor with a hydrogen-selective membrane |
| US8071503B2 (en) | 2006-07-27 | 2011-12-06 | Johnson Matthey Public Limited Company | Catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3609264A1 (en) | 1987-09-24 |
| FR2595056B1 (en) | 1988-06-24 |
| GB8605812D0 (en) | 1986-04-16 |
| GB2187759B (en) | 1990-04-18 |
| FR2595056A1 (en) | 1987-09-04 |
| JPS62204848A (en) | 1987-09-09 |
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| PCNP | Patent ceased through non-payment of renewal fee |