GB2187758A - Catalyst for cyclization of pentadiene-1,3 into cyclopentene and cyclopentane - Google Patents
Catalyst for cyclization of pentadiene-1,3 into cyclopentene and cyclopentane Download PDFInfo
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- GB2187758A GB2187758A GB08605807A GB8605807A GB2187758A GB 2187758 A GB2187758 A GB 2187758A GB 08605807 A GB08605807 A GB 08605807A GB 8605807 A GB8605807 A GB 8605807A GB 2187758 A GB2187758 A GB 2187758A
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- mass
- membrane
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- zinc
- gallium
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 121
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 78
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 55
- 239000011701 zinc Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 46
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 37
- 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 23
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 18
- 239000010948 rhodium Substances 0.000 claims abstract description 18
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims 1
- 239000011888 foil Substances 0.000 description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- -1 iodine, hydrogen Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J23/48—Silver or gold
-
- 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 cyclization of pentadiene-1,3 into cyclopentene and cyclopentane comprises a membrane made from an alloy of 84.58-94.95 by mass of palladium, 4.975-14.99% by mass of ruthenium or rhodium and 0.05-0.5% by mass of zinc or gallium and consisting of a non-porous layer and a porous layer positioned on one or both sides of the non-porous layer. The catalyst may be prepared by a process comprising application, on one or both sides of a membrane made from an alloy consisting of 85-95% by mass of palladium and 5-15% by mass of ruthenium or rhodium, of zinc or gallium at a thickness ratio of the layer of zinc or gallium to the membrane of 1:4-20 respectively; keeping the membrane with zinc applied there onto at a temperature of 230-250% and with gallium-at a temperature of 30-120 DEG C to ensure diffusion of zinc or gallium into the membrane; chemical recovery of zinc or gallium from the membrane, the recovery of zinc or gallium being conducted to a content thereof in the catalyst of 0.05 to 0.5% by mass.
Description
SPECIFICATION
Catalyst for cyclization of pentadiene-1,3
into cyclopentene and cyclopentane, pro
cess for making same and method for com
bined preparation of cyclopentene and cyclopentane using this catalyst
The present invention relates to catalysts for
cyclization of hydrocarbons, their preparation and use and, more particularly, to a catalyst for cyclization of pentadiene-1,3 into cyclopentene and cyclopentane, to a process for mak
ing it and to a method for a combined prepa
ration of cyclopentene and cyclopentane using this catalyst. The resulting mixture of cyclopentene with cyclopentane can be useful in the production of rubber with a low glasstransition temperature.
Known in the art is a membrane catalyst from alloys of palladium and ruthenium or rhodium for processes occurring with splitting-off andior addition of hydrogen, e.g. for dehyaro- cyclization of paraffin hydrocarbons with a number of carbon atoms of from 6 to 20.
The catalyst comprises a foil or a thin-wall tube and is manufactured by rolling methods (cf. US Patent No. 3,562,346 Cl. 260-673.5).
However, this catalyst cannot be used for carrying out the process of cyclization of pen tadiene-1,3.
In general, metallic catalysts for carrying-out the process of cyclization of pentadiene-1,3 are unknown in the art.
Known in the art is a method for a combined preparation of cyclopentene and cyclopentadiene by way of cyclization of pentadiene-1,3 using mercaptans, carbon disulphide, ammonium sulphide, hydrogen bromide, iodine, hydrogen sulphide-i.e. compounds initiating the processes proceeding according to a radical-type mechanism. The cyclization process is conducted at a temperature of 575-750"C at a contact time of from 0.01 to 60 seconds (cf. US Patent No. 3,631,209 Cl.
260-666).
This process is carried out at elevated temperatures which causes high losses of the desired products due to side processes and resinification. Furthermore; the use of high temperatures in the process results in the formation of a catalysate having a complex composition incorporating cyclopentadiene and cyclopentene. Cyclopentene employed for the production of a rubber with a low glass-transition temperature should not contain contaminating cyclopentadiene. Purification of cyclopentene from cyclopentadiene results in high losses of cyclopentene. Furthermore, the presence in cyclopentene of impurities of sulphur-containing substances employed during cyclization as initiators of this process results in poisoning of the polymerization catalysts in the manufacture of a cyclopentene-based rubber.
It is an object of the present invention to
provide a catalyst for cyclization of pentadi
ene-1,3 into cyclopentene and cyclopentane
and to provide- a method for a combined pre
paration of cyciopentene and cyclopentane us
ing this catalyst which would make it possible
to carry out the process of cyclization of pen
tadiene-1,3 at lower temperature and to ob
tain the desired products in the form of a
mixture necessitating no purification prior to
the processing thereof into rubber.
This object is accomplished by a catalyst for cyclization of pentadiene-1,3 into cyclopentene and cyclopentane which comprises a
membrane made from an alloy of
84.75-94.9% by mass of palladium,
5-14.75% by mass of ruthenium or rhodium
and 0.05-0.5% by mass of zinc or gallium
and consisting of a non-porous layer and a
porous layer disposed on one or both sides of this non-porous layer, the thickness ratio of
the porous layer to the non-porous layer being
equal to 1:5-25 respectively.
The membrane catalyst according to the
present invention makes it possible to carry out the process of cyclization of pentadiene 1,3 into cyclopentene and cyclopentane while
eliminating a simultaneous formation of cyclo
pentadiene.
The present invention also resides in a process for making the above-mentioned catalyst which comprises applying, onto the surface of a membrane made from an alloy consisting of
85-95% by mass of palladium and 5-15% by
mass of ruthenium of rhodium on one or both sides thereof, zinc or gallium at the thickness ratio of the layer of zinc or gallium to the membrane being equal to 1:4-20 respectively, keeping the membrane with zinc applied thereonto at a temperature of 230-250"C, with gallium-at a temperature or 30-120"C to ensure diffusion of zinc or gallium into the membrane, recovering zinc from the membrane with a 10-20% hydrochloric acid, gallium with a 10-20% aqueous solution of an alkali; the recovery of zinc or gallium being carried out till their content in the catalyst of 0.05-0.5% by mass.
The process according to the present invention makes it possible to obtain a membrane catalyst with a porous layer having a greater catalytically active surface area but without through pores, whereby the catalyst productivity is increased. The presence of zinc or gallium in the catalyst composition ensures a high selectivity of the catalyst in respect of the reaction of cyclization of pentadiene-1,3.
The object of the present invention is also accomplished by a method of a combined preparation of cyclopentene and cyclopentane, wherein cyclization of pentadiene-1,3 is effected on the catalyst according to the present invention at a temperature of 300 to 450"C in a current of argon or of a mixture of argon with hydrogen, or in a current of hydro gen; in doing so, pentadiene-1,3 is passed over one surface of the membrane, while the stream of argon, or the mixture of argon with hydrogen, or.hydrogen--over another surface of the membrane and in the case where the membrane consists of a non-porous layer and a porous layer disposed on one side thereof, pentadiene-1,3 is passed over the membrane surface on the porous layer side, whereas the stream of argon or the mixture of argon with hydrogen or hydrogen is passed over the membrane surface-on the non-porous layer side.
The method according to the present invention, wherein use is made of the catalyst according to the present invention, makes it possible to carry out the process of-cycliza- tion of pentadiene-1,3 within the range of lower temperatures, whereby the formation of coke and losses of pentadiene-1 ,3 due--to the side processes are reduced by 2-3 timers. At the temperature of 300 C-only 1 % by mass of by-products is formed. The mixture of cyclopentene and cyclopentane produced -by the method according- to the present invention requires no- purification prior to the processing thereof into a rubber with a low glass-transition temperature. Furthermore, in the case of using hydrogen or a mixture thereof with argon it is possible by varying partial pressure of hydrogen, to change proportions of the desired products in the resulting mixture.
As it has been already mentioned hereinabove, the catalyst according to the present invention comprises a membrane made from an alloy of 84.75-94.9% by mass of palladium 5-14.75% by mass of ruthenium or rhodium and 0.05-0.5% by mass of zinc or gallium. It is inadvisable to use a membrane catalyst from an alloy with a content of palladium lesser than 84.75% by mass, since hydrogen permeability through such an alloy is very low.
At a content of palladium of more than 94.9% by mass in the alloy the membrane catalyst becomes instable in the atmosphere of hydrogen and gets readily broken. An increased content of zinc or gallium above 0.5% by mass is undesirable due to a lowered activity of the catalyst and a sharp drop of the rate of diffusion of hydrogen through the membrane.
A reduced amount of zinc or gallium below 0.05% by mass brings about a changed selectivity of the catalyst's effect-it loses its cyclization properties in respect of pentadiene1,3.
A thickness ratio of the porous layer to the non-porouslayer above 1:5 results in a reduced-mechanical strength of the membrane catalyst. A lowered thickness ratio of these layers below 1:25 is undesirable, since in-this case the catalyst activity during operation is rapidly decreased.
In the manufacture of the catalyst the thickness ratio of the layer of zinc or gallium to the membrane equal to 1:4-20 respectively is defined by the necessity of ensuring a thickness ratio of the porous and non-porous layers in the final catalyst within the range of
1:5-25 respectively.
It is inadvisable to maintain the membrane with zinc applied thereonto at a temperature below 230"C, since at lower temperatures diffusion of zinc into the membranes very small which does not make it possible to produce a membrane catalyst with a- required zinc content. It is neither expedient to elevate the resi dence temperature above 250"C, since at higher temperatures a more profound diffusion of zinc takes place and -at a subsequent treatment with hydrochloric acid it becomes impossible to remove zinc to its content in the final catalyst not exceeding 0 5% by mass. It should be noted that a greater content- of zinc provides a detrimental effect on properties of the catalyst as it has been already mentioned hereinbefore.
The -tempernture of residence of the membrane with gallium applied thereonto is limited by the range of from 30 to 120"C for the same reasons as in the case of the membrane coated with zinc.
To ensure a partial recovery of zinc diffused into the membrane, the latter is treated with a
10-20% hydrochloric acid. At a concentration of hydrochloric acid below 10% it dissolves zinc but insufficiently, whereas at a concentration above 20% a full recovery of zinc ispos- sible which. is undesirable due to the loss of catalytical properties by the catalyst in respect of pentadiene-1,3.
For the same reasons the lower (10%) and the- upper (20%) limits of the concentration of -the aqueous alkali solution in the case of a partial recovery of diffused gallium from the membrane.
It is inexpedient to carry out the process of cyclization of pentadiene-1,3 into cyclopentene and cyclopentane at a temperature below 300"C due- to a reduced yield of the desired products. At -elevation of the process temperature above 450 C resinification occurs and a great quantity of by-products is formed which results in loss of the starting material and a rapid poisoning of the catalyst.
In- the case of-performing cyclization of pentadiene-1,3 in a current of argon the process proceeds with a predominant formation of cyclopentene. When cyclization of pentadiene
1,3 is carried out in a current of hydrogen or of its mixture with argon, it is possible to obtain the desired products with a predominant yield of cyclopentene or cyclopentane through variatiori of the partial pressure of hy hydrogen.
The membrane catalyst according to the present invention is prepared in the following manner. First of all, onto a clean surface of a membrane shaped, for example as a foil or a tube made from an alloy consisting of 85-95% by mass of palladium and 5-15% by mass of ruthenium or rhodium, a thin layer of zinc or gallium is applied on one or both sides; the thickness ratio of the zinc layer to the membrane is 1:4-20 respectively. Zinc is electrochemically deposited onto the membrane; it is preferable that gallium be applied onto the membrane by the method of dipping or casting. The membrane with zinc or gallium applied thereonto is maintained at a predetermined temperature (230-2500C for zinc and 30-120"C--for gallium). This ensures diffusion of zinc or gallium into the membrane.
Then the membrane is placed into a solvent.
To ensure a partial removal of the diffused zinc from the membrane, a 10-20% hydrochloric acid is used; to partly remove the diffused gallium from the membrane, a 10-20% aqueous solution of an alkali (sodium hydroxide or potassium hydroxide) is used.
After drying a catalyst is obtained which comprises a membrane made from an alloy of 84.75-94.9% by mass of palladium, 5-14.75% by mass of ruthenium or rhodium and 0.05-0.5% by mass of zinc or gallium and consisting of a non-porous layer and a porous layer positioned on one or both sides of this non-porous layer, the thickness ratio of the porous layer to the non-porous one being equal to 1:5-25 respectively.
To carry out the process of a combined preparation of cyclopentene and cyclopentane the resulting membrane catalyst is placed into a reactor in such a manner that it partitions the inside cavity of the reactor into two chambers. Then the temperature in the reactor is elevated to 300-450"C, whereafter into one chamber argon, or a mixture of argon with hydrogen, or hydrogen is admitted, while into the other chamber-vapours of pentadiene1,3, individually or in a mixture with a vehiclegas such as argon.
Pentadiene-1,3 should be passed only over a porous surface of the membrane catalyst in order to ensure a maximum degree of conversion. Therefore, in the case where the membrane catalyst consists of a non-porous layer and a porous layer positioned on one side thereof, pentadiene-1,3 is passed into one chamber on the side of the porous layer of the catalyst, while the stream of argon or a mixture of argon with hydrogen, or hydrogen-into the other chamber on the side of the non-porous layer of the catalyst.
The process of cyclization of pentadiene-1,3 under the above-described conditions results in a catalysate containing cyclopentene and cyclopentane.
The catalysate composition- is determined chromatographically. The thickness of the nonporous and porous layers of the catalyst is determined by means of an electron microscope and the catalyst composition-using a spectrometer.
For a better understanding of the present invention, some specific examples illustrating its particular embodiments are given hereinbelow.
Example 1
A 100 ,um foil made from an alloy consisting of 85% by mass of palladium and 15% by mass of rhodium is degreased and placed into an electrolyte comprising a solution of 130 g of zinc sulphate in 11 of water. Then zinc is deposited on the foil surface on both sides thereof at the temperature of 20"C, current density of 3.5 A/dm2 and pH of the electrolyte of 1.5 using a zinc anode. The foil with zinc layers applied- thereon to the thickness of 4 jim each is heated to the temperature of 230"C and maintained at this temperature for
1 hour, whereafter it is cooled and placed into a 10% hydrochloric acid. The treatment of the foil with hydrochloric acid is carried out till the evolution of hydrogen bubbles stops.A membrane catalyst is thus obtained in the form of a foil made from an alloy, according to the spctral analysis data, of 84.75% by mass of palladium, 14.75% by mass of rhodium and 0.5% by mass of zinc and consisting of a non-porous layer of 94 jim thickness and superficial porous layers positioned on both sides of the non-porous layer and having thickness of 3 jim each.
To carry out the process of cyclization of pentadiene-1,3 into cyclopentene and cyclopentane, the membrane catalyst produced as described hereinabove is placed into a reactor; the latter is divided by this membrane catalyst into two chambers. The temperature in the reactor is elevated to 450"C and at this temperature a mixture of vapours of pentadiene 1 ,3 with argon is fed into one of the reactor chambers at the rate of 10 ml/min under the pressure of pentadiene-1,3 vapours of 5 mm
Hg. A current of hydrogen is passed through the other chamber of the reactor at the rate of 20 ml/min under atmospheric pressure.
A catalysate is thus obtained consisting of
13.4% by mass of cyclopentene, 2.6% by mass of cyclopentane, 8. 1 % by mass of pentane, 0.4% by mass of methane, 29.1% by mass of ethane, 0.1% by mass of propane, 4.6% by mass of propene, 0.2% by mass of butene, 1.6% by mass of pentene-1, 39.0% by mass of pentene-2, 0.9% by mass of pen tadiene-1,3.
Example 2
Onto a 100 Am foil made from an alloy consisting of 95% by mass of palladium and 5% by mass of rhodium a zinc layer of 5 jim thickness is applied on one side. The foil with the zinc layer applied thereonto is heated to the temperature of 240"C and kept at this temperature for 2 hours, whereafter it is cooled and placed into a 15% hydrochloric acid. The foil treatment with hydrochloric acid is conducted till hydrogen bubbles stop to evolve.A membrane catalyst is thus obtained shaped as a foil made, according to thespec- tral analysis data, from an alloy of 94.9% by mass of palladium, 5.0% by mass of rhodium and 0.1% by mass of zinc and consisting of a non-porous layer of 95 jim thickness and a porous layer of 3.8 jim thickness.
To carry out the process of cyclization of pentadiene-1 ,3 into cyclopentene and cyclopentane, the thus-produced membrane catalyst is palced into a reactor is divided by this membrane catalyst into two chambers. The temperature in the reactor is raised to 350"C and at this temperature a mixture of vapours of pentadiene-1 ,3 with argon is fed into one of the reactor chambers on the side of the porous layer of the membrane catalyst at the rate of 10 ml/min under the pressure of pentadiene-1,3 vapours of 5 mm Hg. Through the other chamber, on the side of the non-porous layer of the membrane catalyst, a current of hydrogen is passed at the rate of 10 ml/min under atmospheric pressure.
As a result, a catalysate is obtained having the following composition: 11.3% by mass of cyclopentene, 4.2% by mass of cyclopentane, 9.7% by mass of pentane, 1.7% by mass of pentene-1, 28.2% by mass of pentene-2, 0. 1% by mass of methane, 11.1% by mass of ethane, 0.1% by mass of propane, 0.5% by mass of propene, 0.1% by mass of butene and 33.0% by mass of pentadiene-1,3.
Example 3
Onto both sides of a 100 tm foil made from an alloy consisting of 90.2% by mass of palladium and 9.8% by mass of ruthenium layers of gallium of lOjim thickness each are applied by dipping. The foil with the layers of gallium deposited thereon is kept at the temperature of 30"C for 24 hours, whereafter it is treated with a 20% aqueous solution of sodium hydroxide. A membrane catalyst is thus produced shaped as a foil made, according to the spectral analysis data, from an-alloy of 90.15% by mass of palladium, 9.8% by mass of ruthenium and 0.05% by mass of gallium and consisting of a non-porous layer of 90 jim thickness and superficial porous layers positioned on both sides of this non-porous layer and having thickness of 9 jim each.
The process of cyclization of pentadiene-1,3 into cyclopentene and cyclopentane is carried out in a reactor at the temperature of 300"C using the membrane catalyst produced as described hereinabove and dividing the reactor into two chambers Into one of the chambers vapours of pentadiene-1,3 are fed at the rate of 20 ml/min under the pressure of 400 mm
Hg. Through the other chamber a mixture of argon with hydrogen (volume ratio of 4:1) is passed at the rate of 60 ml/min.
A catalysate is thus obtained consisting of 24.2% by mass of cyclopentene, 5.5% by mass of cyclopentane, 0.1% by mass of methane, 2.6% by mass of ethene, 30.0% by mass of pentane, 0.3% by mass of pentene1, 27.7% by mass of pentene-2, 9.6% by mass of pentadiene-1,3.
Example 4
Onto a 100 jim foil made from an alloy consisting of 85% by mass of palladium and 15% by mass of rhodium layers of gallium are applied on both sides to the thickness of 12.5 jim each. The foil with the layers of gallium deposited thereonto is kept for 4 hours at the temperature of 50"C and then treated with a 10% aqueous solution of potassium hydroxide.
A foil-shaped membrane catalyst is thus obtained consisting, according to the spectralanalysis data, of an alloy of 85.05% by mass of palladium, 14.75% by mass of rhodium and 0.2% by mass of gallium and composed of a non-porous layer of 96 jim thickness and superficial porous layers positioned on both sides of this non-porous layer and having thickness of 8 Am each.
The process of cyclization of pentadiene-1 ,3 into cyclopentene and cyclopentane is conducted in a reactor. at the temperature of 370"C using the membrane catalyst produced as described herein before and dividing the reactor into two chambers. Into one of the chambers vapours- of pentadiene-1,3 are fed at the rate of 30ml/min under the, pressure of the vapours of 400 mm Hg. Through the other chamber a mixture of argon with hydrogen (volume ratio of 1:1) is passed at the rate of 30 ml/min.
A catalysate is obtained consisting of:
19.3% by mass of cyclopentene, 5.4% by mass of cyclopentane, 0.1% by mass of methane, 10.1% by mass of ethene, 0.1% by mass of propane, 1.5% by mass of propene, 0.2% by mass of butene, 4.0% by mass of pentene-1, 17.0% by mass of pentene-2, 42.3% by mass of pentadiene-1,3.
Example 5
Onto the external surface of a tube having the outside diameter of 1 mm, wall thickness of 120 jim, made from an alloy consisting of 94.2% by mass of palladium and 5.8% by mass of ruthenium a zinc layer of 11 jim thickness. is applied. The tube with the zinc layer deposited thereonto is maintained at the temperature of 250"C for 2 hours, whereafter it is cooled and kept in a 20% hydrochloric acid till hydrogen bubbles stop to evolve. A membrane catalyst shaped as a tube is thus obtained; according to the data of spectral analysis the tube wall is made from an alloy of 94.0% by mass. of palladium, 5.7% by mass of ruthenium and 0.3% by mass of zinc; it consists of an inner non-porous layer of
110 jim thickness and an external porous
layer of 8 jim thickness.
The process of cyclization of pentadiene-1,3
into cyclopentene and cyclopentane is conducted in a reactor at the temperature of 300"C using the tube-shaped membrane catalyst produced as described hereinabove and dividing the reactor into two chambers.
Through one chamber formed by the tube cavity a current of argon is passed at the rate of 15 ml/min, while into another chamber formed by the inner wall of the reactor and the external wall of the tube vapours of pentaidiene-1,3 are passed at the rate of 15 ml/min under the pressure of the vapours equal to 400 mm Hg.
A catalysate is thus obtained which consists of 22.2% by mass of cyclopentene, 10.4% by mass of cyclopentane, 5.5% by mass of pentane, 19.1% by mass of pentene-1, 40.2% by mass of pentene-2, 2.6% by mass of pentadi ene-1,3.
Example 6.
On both sides of a 100 jim foil made from an alloy consisting of 90% by mass of palladium and 10% by mass of rhodium layers of gallium of 6 jim thickness each are applied by dipping. The gallium-coated foil is kept at the temperature of 120"C for 24 hours, whereafter it is treated with a 15% aqueous solution of sodium hydroxide. A foil-shaped membrane catalyst is thus obtained which, according to the spectral analysis data, is made from an alloy of 89.9% by mass of palladium, 10% by mass of rhodium and 0.1% by mass of gallium and consists of a non-porous layer of 94 jim thickness and superficial porous layers positioned on both sides of the non-porous layer and having thickness of 5 jim each.
The process of cyclization of pentadiene-1,3 into cyclopentene and cyclopentane is conducted in a reactor at the temperature of 320"C using the thus-produced membrane catalyst dividing the reactor into two chambers. Vapours of pentadiene-1,3 are supplied into one of the reactor chambers under their pressure of 550 mm Hg at the rate of 25 ml/min. Through the other chamber a mixture of argon with hydrogen (volume ratio of 1:0.5) is passed at the rate of 50 ml/min under the pressure of 0.2 MPa.
A catalysate is thus produced which consists of 12.2% by mass of cyclopentene, 22.3% by mass of cyclopentane, 8% by mass of pentane, 11.3% by mass of pentene-1, 37.2% by mass of pentene-2 and 9.0% by mass of pentadiene-1,3.
As it is seen from the above-given
Examples, the catalyst according to the present invention is an active catalyst for cyclization of pentadiene-1,3 into a mixture of cyclopentene and cyclopentane employed as a starting feedstock in the manufacture of a rubber with a low glass-transition temperature.
The process for making a catalyst for cyclization of pentadiene-1,3 according to the present invention makes it possible to produce a membrane catalyst selectively permeable for hydrogen without through pores which provides the possibility of preparing, using this catalyst, cyclopentene and cyclopentane with a high selectivity. Furthermore, the process according to the present invention enables the production of a membrane catalyst with a porous layer having structure common with the non-porous layer of the catalyst, thus ensuring a high mechanical strength of the porous layer and its resistance in the atmosphere of hydrogen and hydrocarbons in carrying out the process of cyclization, as well as resistance in its regeneration with air.
The method for a combined preparation of cyclopentene and cyclopentane is effected, owing to the use of the above-mentioned catalyst, within the range of relatively low temperatures (300-450"C), thus ensuring a considerable reduction of losses of pentadiene-1,3 and eliminating the formation of harmful deposits on the catalyst. The process also permits to carry out cyclization without the formation of cyclopentadiene which, in turn, enables elimination of the operation of a preliminary purification of the mixture of the desired products from this contaminant prior to the processing of this mixture into a rubber.
Claims (10)
1. A catalyst for cyclization of pentadiene1,3 into cyclopentene and cyclopentane which comprises a membrane made from an alloy of 84.58-94.95 by mass of palladium, 4.975-14.99% by mass of ruthenium or rhodium and 0.05-0.5% by mass of zinc or gallium and consisting of a non-porous layer and a porous layer positioned on one or both sides of the non-porous layer.
2. A catalyst according to claim 1 wherein the thickness ratio of the porous layer to the non-porous layer is 1:5-25 respectively.
3. A catalyst for cyclization of pentadiene1,3 into cyclopentene and cyclopentane according to claim 1, substantially as described in the specification and examples 1 to 6 hereinbefore.
4. A process for making a catalyst according to claim 1, comprising application, on one or both sides of a membrane made from an alloy consisting of 85-95% by mass of palladium and 5-15% by mass of ruthenium or rhodium, of zinc or gallium at a thickness ratio of the layer of zinc or gallium to the membrane of 1:4-20 respectively, keeping the membrane with zinc applied thereonto at a temperature of 230-250"C and with gallium applied thereonto at a temperature of 30-120"C to ensure diffusion of zinc or gallium into the membrane, chemical recovery of zinc or gallium from the membrane, the recovery of zinc or gallium being conducted to a content thereof in the catalyst of 0.05 to 0.5% by mass.
5. A process according to claim 4 wherein zinc is recovered from the membrane by treatment with 10-20% hydrochloric acid.
6. A process according to claim 4 wherein gallium is recovered from the membrane by treatment with a 10-20% aqueous solution of an alkali.
7. A process for making a catalyst for cyclization of pentadiene-1,3 into cyclopentene and cyclopentane according to claim 4, substantially as described in the specification and examples 1 to 6 hereinbefore.
8. A method for a combined preparation of cyclopentene and cyclopentane comprising cyclization of pentadiene-1,3 on a catalyst according to claim 1 at a temperature within the range of from 300 to 450"C in a current of argon, or of a mixture of argon and hydrogen or in a current of hydrogen; pentadiene-1,3 individually or a mixture with a vehicle-gas such as argon is passed over one surface of the membrane while the current of argon or of a mixture of argon and hydrogen or hydrogen -over the other surface of the membrane so that where the membrane consists of a nonporous layer and a porous layer disposed on one side thereof, pentadiene-1,3 is passed over the membrane on the side of the porous layer and the current of argon or of a mixture or argon and hydrogen or hydrogen - over the membrane surface on the side of the nonporous layer.
9. A method for a combined preparation of cyclopentene and cyclopentane according to the foregoing claim 8, substantially as described in the specification and examples 1 to 6 hereinbefore.
10. Cyclopentene and cyclopentane when-.
ever prepared by the method according to-the foregoing claims 8 or 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8602942A FR2595093B1 (en) | 1986-03-03 | 1986-03-03 | CATALYST FOR CYCLISATION OF PENTADIENE-1,3 TO CYCLOPENTENE AND CYCLOPENTANE, METHOD FOR THE PREPARATION THEREOF, AND METHOD FOR THE SIMULTANEOUS PREPARATION OF CYCLOPENTENE AND CYCLOPENTANE WITH IMPLEMENTATION OF THE CATALYST |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8605807D0 GB8605807D0 (en) | 1986-04-16 |
| GB2187758A true GB2187758A (en) | 1987-09-16 |
| GB2187758B GB2187758B (en) | 1990-06-20 |
Family
ID=9332694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8605807A Expired - Lifetime GB2187758B (en) | 1986-03-03 | 1986-03-10 | Catalyst for cyclization of pentadiene-1,3 into cyclopentene and cyclopentane, process for making same and method for using it |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS62204847A (en) |
| DE (1) | DE3609262A1 (en) |
| FR (1) | FR2595093B1 (en) |
| GB (1) | GB2187758B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8071503B2 (en) | 2006-07-27 | 2011-12-06 | Johnson Matthey Public Limited Company | Catalyst |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210059A (en) * | 1991-10-10 | 1993-05-11 | Exxon Research & Engineering Company | Multilayered catalyst for controlled transport of reactant |
| US5578652A (en) * | 1995-02-17 | 1996-11-26 | Exxon Chemical Patents, Inc. | Method of producing rigid foams and products produced therefrom |
| US6306919B1 (en) | 1995-07-03 | 2001-10-23 | Exxonmobil Chemical Patents, Inc. | Thermosetting plastic foam |
| US5866626A (en) * | 1995-07-03 | 1999-02-02 | Exxon Chemical Patents Inc. | Method of producing rigid foams and products produced therefrom |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US31104A (en) * | 1861-01-15 | Weight and hitch-strap foe fastening houses | ||
| NL158472B (en) * | 1974-07-01 | 1978-11-15 | Inst Neftechimicheskogo Sintez | PROCEDURE FOR HYDROGENING CYCLOALKADIENES WITH HYDROGEN TO CYCLOALCAMONONES IN THE PRESENCE OF PALADIUM CATALYSTS, PROCEDURE FOR PREPARING A SUITABLE CATALYST AND THE KATALYZOR SO OBTAINED. |
-
1986
- 1986-02-28 JP JP61045145A patent/JPS62204847A/en active Pending
- 1986-03-03 FR FR8602942A patent/FR2595093B1/en not_active Expired
- 1986-03-10 GB GB8605807A patent/GB2187758B/en not_active Expired - Lifetime
- 1986-03-19 DE DE19863609262 patent/DE3609262A1/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8071503B2 (en) | 2006-07-27 | 2011-12-06 | Johnson Matthey Public Limited Company | Catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8605807D0 (en) | 1986-04-16 |
| FR2595093A1 (en) | 1987-09-04 |
| GB2187758B (en) | 1990-06-20 |
| DE3609262A1 (en) | 1987-09-24 |
| FR2595093B1 (en) | 1988-06-24 |
| JPS62204847A (en) | 1987-09-09 |
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| PCNP | Patent ceased through non-payment of renewal fee |