CN103566975B - A kind of N-alkene isomerization catalyst and preparation method thereof - Google Patents
A kind of N-alkene isomerization catalyst and preparation method thereof Download PDFInfo
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Abstract
A kind of N-alkene isomerization catalyst, comprise carrier and modified compound, described modified compound is polyalcohol, and the mass ratio of described modified compound and carrier is 0.01 ~ 0.4:1, and described carrier comprises molecular sieve and binding agent.This catalyst uses modified compound to carry out modification to catalytic active component, can significantly improve the isomerisation selectivity of catalyst.
Description
Technical field
The present invention is a kind of olefin isomerization catalyst and preparation method thereof, specifically, is a kind of normal olefin skeleton isomerization Catalysts and its preparation method.
Background technology
Along with the increasingly stringent of environmental requirement, clean gasoline demand constantly increases.By the C of positive structure
4~ C
6the isobutene that alkene is obtained by skeletal isomerization, methylpentene and neohexene, through etherificate, can prepare high-knock rating gasoline additive, to improve gasoline quality.
USP5,382,743 disclose a kind of ZSM-35 molecular sieve that uses aligns the method that amylene carries out skeletal isomerization under the condition of facing hydrogen, finds that reaction is conducive to improving the reactivity of catalyst under hydro condition, reduce deactivation rate, the extending catalyst life-span.
USP5,817, the 907 a kind of methods disclosing straight-chain olefin skeleton isomerization, in used catalyst at least containing a kind of through pretreated molecular sieve, molecular screening is at least one in SAPO-11, the SAPO-31 of 0.4nm ~ 0.8nm, Theta-1, EU-1, OMEGA, modenite, Nu-10, Nu-86, Nu-87, ferrierite ZSM-35, ZSM-12 and ZSM-23 from aperture.Pretreated method is with containing C by described molecular sieve
4~ C
20hydrocarbon molecule contact in the presence of an inert gas, preferred hydrocarbon is C
4~ C
12monoolefine, polyene or alkane etc., more preferably C
4~ C
12alkane.Pretreated air speed is 0.1h
-1~ 45h
-1, temperature 300 DEG C ~ 550 DEG C, pressure 0.1MPa ~ 1.0MPa, 0.5 ~ 48 hour processing time.Pretreatment makes coke deposit in described molecular sieve pore passage, and the pore volume of molecular sieve significantly reduces, thus improves the selective of isomeric olefine, and has good stability.But, adopt hydro carbons to be the step that raw material carries out the process of High Temperature Pre carbon deposit add an inert atmosphere before olefin isomerization reaction under, cause reaction process complicated.
Summary of the invention
The object of this invention is to provide a kind of N-alkene isomerization catalyst and preparation method, this catalyst uses modified compound to carry out modification to catalytic active component, can significantly improve the isomerisation selectivity of catalyst.
N-alkene isomerization catalyst provided by the invention, comprises carrier and modified compound, and described modified compound is polyalcohol, and the mass ratio of described modified compound and carrier is 0.01 ~ 0.4:1, and described carrier comprises molecular sieve and binding agent.
The present invention uses polyalcohol to carry out modification to normal olefin skeleton isomerization catalytic active component, method for preparing catalyst is simple, without the need to increasing the handling process that pair adds, be easy to control, gained catalyst is used for normal olefin skeleton isomerization reaction, isomerisation selectivity significantly improves, and isomerization product yield increases.
Detailed description of the invention
The present invention is using the modified compound of polyalcohol as isomerization activity component-molecular sieve, and with its aqueous impregnation molecular sieve, after drying, polyalcohol is deposited on molecular sieve surface, can effectively improve its physico-chemical property, makes its isomerization performance improve.The present invention adopts simple in-situ treatment method Kaolinite Preparation of Catalyst, processing ease, and modified compound content is in the catalyst easy to control.
The present invention uses polyalcohol to carry out modification to the carrier comprising isomerization catalytic activity component, the preferred C of described polyalcohol for modified compound
2~ C
7polyalcohol.Described C
2~ C
7the preferred ethylene glycol of polyalcohol, propane diols, butanediol, pentanediol, hexylene glycol, glycerine, trimethylolethane, pentaerythrite, one or more in xylitol and sorbierite.
Carrier described in catalyst of the present invention comprises molecular sieve and binding agent.The preferred mesoporous molecular sieve of described molecular sieve.Can be Si-Al molecular sieve, as one or more in ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Theta-1, NU-10, TNU-1, TNU-9, TNU-10, NU-87, MCM-22 zeolite; Also can be non-Si-Al molecular sieve, be selected from phosphate aluminium molecular sieve, as APO-11, HTS, as TS-1, SAPO, as one or more in SAPO-11 molecular sieve.One in preferred ZSM-35, ZSM-22 and SAPO-11 or any two kinds.
Described binding agent is selected from one or more in aluminium oxide, silica, titanium oxide, magnesia, alumina-silica magnesium, silica-alumina, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia clay, preferential oxidation aluminium.
Carrier of the present invention comprises the molecular sieve of 50 ~ 99 quality % and the binding agent of 1 ~ 50 quality %, preferably includes the molecular sieve of 60 ~ 95 quality % and the binding agent of 5 ~ 40 quality %.Modified compound in catalyst of the present invention and the mass ratio of carrier are preferably 0.01 ~ 0.3:1.
Be suitable for catalyst of the present invention and carry out the preferred C of isomerized alkene
4~ C
6normal olefine.
The preparation method of catalyst provided by the invention, comprises molecular sieve and binding agent mixed-forming, and dry, roasting obtains carrier, then uses the aqueous impregnation of modified compound, after dipping solid in 30 ~ 200 DEG C, dry under 0.01 ~ 0.1MPa condition.
One in described molecular sieve preferred ZSM-35, ZSM-22 and SAPO-11 or any two kinds, binding agent preferential oxidation aluminium.
The method of molecular sieve and binding agent mixed-forming is extrusion, drips ball, spin or pressed disc method, preferred extruded moulding by the inventive method.Extruded moulding method is: mixed with binding agent or its precursor by molecular sieve, adds appropriate extrusion aid and/or peptizing agent kneading, then extruded moulding.The preferred sesbania powder of described extrusion aid, peptizing agent preferred inorganic acid, example hydrochloric acid or nitric acid.After wet bar pelletizing, drying, roasting obtain carrier.The temperature of described roasting preferably 400 ~ 650 DEG C, roasting time preferably 1 ~ 10 hour.
In the inventive method, also first molecular sieve modified compound can be carried out pretreatment, and then with binding agent mixed-forming, drying, roasting obtain carrier, and then by the aqueous impregnation of carrier modified compound, after dipping, solid is in 30 ~ 200 DEG C, dry obtained catalyst under 0.01 ~ 0.1MPa condition, and the modified compound in catalyst does not comprise pretreatment modified compound used.
The preprocess method of above-mentioned molecular sieve is: with the aqueous impregnation molecular sieve of modified compound, then will flood solid drying afterwards, then with binding agent mixed-forming, drying, roasting obtain carrier.
During preparation catalyst of the present invention, also by the aqueous impregnation two of carrier modified compound that obtain after roasting to repeatedly, after flooding, all can need drying at every turn.The modified compound that each dipping uses may be the same or different.
Above-mentioned dipping is the solution impregnating carrier with modified compound, and can be saturated dipping, unsaturated dipping or supersaturation dipping, preferred saturated dipping, also claim incipient wetness method dipping, namely maceration extract volume equals the amount of liquid of carrier adsorption; Dip time preferably 0.1 ~ 24 hour, more preferably 0.5 ~ 8 hour.
During preparation maceration extract, the concentration of the modified compound aqueous solution is 0.01 ~ 5.0 mol/L, preferably 0.01 ~ 3.0 mol/L.After dipping, dry desolvation.Control drying condition not decompose with non-volatile to make modified compound.Suitable baking temperature is 40 ~ 150 DEG C, preferably 60 ~ 120 DEG C, and drying time is 1 ~ 24 hour, is preferably 2 ~ 8 hours, and drying pressure is 0.01 ~ 0.1MPa.
Catalyst provided by the invention, is applicable to the skeletal isomerization of normal olefine, is particularly suitable for C
4~ C
6the skeletal isomerization of normal olefine, to prepare isomeric olefine.
Use catalyst of the present invention to carry out normal olefine isomerization reaction to carry out in presence of hydrogen.Reaction temperature is 200 ~ 550 DEG C, preferably 250 ~ 350 DEG C, and pressure is 0.05 ~ 1MPa, preferably 0.1 ~ 0.5MPa, and feed volume air speed is 0.5 ~ 6.0 hour
-1, be preferably 1 ~ 4 hour
-1, hydrogen/hydrocarbon volume ratio is 100 ~ 5000, preferably 200 ~ 2000.
Further illustrate the present invention below by example, but the present invention is not limited to this.
In example, prepare catalyst of the present invention and in carrier, introduce modified compound all adopt saturated infusion process, i.e. incipient wetness method infusion process.In example, molecular sieve used builds the production of long catalyst plant by Hunan, and boehmite is provided by German Condea company, and its butt alumina content is 74 quality %.
Example 1
Get 10788 grams of silica/alumina molar ratio be 25 HZSM-35 molecular sieve mix with 1637.8 grams of boehmites, add nitric acid and 10770 grams of water that 65.5 grams of concentration are 65 quality %, the trilobal bar that diameter is 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S
1, wherein HZSM-35 molecular sieve content is 90 quality %, alumina content is 10 quality %.
Get 2000 grams of carrier S
1, with the aqueous solution 1939 milliliters containing 147.6 grams of (1.603mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
1, its weight is 2146.8 grams, and catalyst C is described
1in containing 146.8 grams of glycerine, contained alcohol and carrier S
1mass ratio be 0.073.
Example 2
Get 2000 grams of carrier S
1, with the aqueous solution 1939 milliliters containing 245.7 grams of (2.668mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
2, its weight is 2245.1 grams, and catalyst C is described
2in containing 245.1 grams of glycerine, contained alcohol and carrier S
1mass ratio be 0.122.
Example 3
Get 2000 grams of carrier S
1, with the aqueous solution 1939 milliliters containing 361.7 grams of (3.928mol) glycerine in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
3, its weight is 2361.2 grams, and catalyst C is described
3in containing 361.2 grams of glycerine, contained alcohol and carrier S
1mass ratio be 0.18.
Example 4
Get 2000 grams of carrier S
1, with the aqueous solution 1939 milliliters containing 68.5 grams of (0.580mol) hexylene glycols in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.01MPa condition dry 3 hours; Again with the aqueous solution 1933 milliliters containing 89.2 grams of (0.969mol) glycerine in 25 DEG C of dippings 2 hours, then in 100 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
4, its weight is 2156.9 grams, and catalyst C is described
4in containing 156.9 grams of glycerine and hexylene glycol, contained alcohol and carrier S
1mass ratio be 0.078.
Example 5
Get 2000 grams of carrier S
1, with the aqueous solution 1939 milliliters containing 53.3 grams of (0.293mol) sorbierites in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.01MPa condition dry 2 hours; And then with the aqueous solution 1928 milliliters containing 260.2 grams of (2.887mol) butanediols in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.02MPa condition dry 4 hours, obtain catalyst C
5, its weight is 2312.8 grams, and catalyst C is described
5in containing 312.8 grams of glycerine and butanediol, contained alcohol and carrier S
1mass ratio be 0.156.
Example 6
By 9600 grams of silica and alumina molar ratio be 25 HZSM-35 molecular sieve mix with 3243.2 grams of boehmites, add nitric acid and 9587 grams of water that 129.7 grams of concentration are 65 quality %, the trilobal bar that diameter is 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S
2, wherein HZSM-35 molecular sieve content is 80 quality %, alumina content is 20 quality %.
Get 2000 grams of carrier S
2, with the aqueous solution 1880 milliliters containing 286.1 grams of (4.609mol) ethylene glycol in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.01MPa condition dry 2 hours; And then with the aqueous solution 1601 milliliters containing 78.2 grams of (0.751mol) pentanediols in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.01MPa condition dry 4 hours, obtain catalyst C
6, its weight is 2363.6 grams, and catalyst C is described
6in containing 363.6 grams of pentanediols and ethylene glycol, contained alcohol and carrier S
2mass ratio be 0.182.
Example 7
By 7764 grams of silica and alumina molar ratio be 25 HZSM-35 molecular sieve mix with 5724.3 grams of boehmites, add nitric acid and 7756 grams of water that 229 grams of concentration are 65 quality %, the trilobal bar that diameter is 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 600 DEG C roastings 4 hours, obtain carrier S
3, wherein HZSM-35 molecular sieve content is 65 quality %, alumina content is 35 quality %.
Get 2000 grams of carrier S
3, with the aqueous solution 1788 milliliters containing 438.9 grams of (4.766mol) glycerine in 25 DEG C of dippings 2 hours, then in 90 DEG C, under 0.01MPa condition dry 3 hours, obtain catalyst C
7, its weight is 2438.2 grams, and catalyst C is described
7in containing 438.2 grams of glycerine, contained alcohol and carrier S
3mass ratio be 0.219.
Example 8
Get the HZSM-35 molecular sieve that 10164 grams of silica and alumina molar ratio are 25, flood 0.5 hour in 25 DEG C with the aqueous solution 10670 milliliters containing 428.6 grams of (4.654mol) glycerine, again in 120 DEG C, under 0.01MPa condition dry 4 hours, obtain pretreated molecular sieve.
Above-mentioned pretreated molecular sieve is mixed with 2481.1 grams of boehmites, add nitric acid and 10152 grams of water that 99.2 grams of concentration are 65 quality %, be extruded into double screw banded extruder the trilobal bar that diameter is 1.1 millimeters, pelletizing, 180 DEG C of dryings, 24 hours, 420 DEG C roastings 4 hours, obtain carrier S
4, wherein molecular sieve content is 85 quality %, alumina content is 15 quality %.
Get 2000 grams of carrier S
4, with the aqueous solution 1908 milliliters containing 113.1 grams of (0.957mol) hexylene glycols in 25 DEG C of dippings 2 hours, then in 92 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
8, its weight is 2112.5 grams, and catalyst C is described
8in containing 112.5 grams hexylene glycol, contained alcohol and carrier S
4mass ratio be 0.056.
Example 9
10566 grams of SAPO-11 molecular sieves are mixed with 1937.8 grams of boehmites, adds nitric acid and 11570 grams of water that 77.5 grams of concentration are 65 quality %, be extruded into double screw banded extruder the trilobal bar that diameter is 1.1 millimeters, pelletizing, 120 DEG C of dryings 4 hours, 550 DEG C of roastings 2 hours, obtain carrier S
5, wherein molecular sieve content is 88 quality %, alumina content is 12 quality %.
Get 2000 grams of carrier S
5, with the aqueous solution 1937 milliliters containing 33.9 grams of (0.368mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
9, its weight is 2033.3 grams, and catalyst C is described
9in containing 33.3 grams of glycerine, contained alcohol and carrier S
5mass ratio be 0.017.
Example 10
10452 grams of HZSM-22 molecular sieves are mixed with 2091.9 grams of boehmites, add nitric acid and 11536 grams of water that 83.7 grams of concentration are 65 quality %, be extruded into the trilobal bar of diameter 1.1 millimeters with double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S
6, wherein molecular sieve content is 87 quality %, alumina content is 13 quality %.
Get 2000 grams of carrier S
6, with the aqueous solution 1935 milliliters containing 90.6 grams of (0.984mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
10, its weight is 2090 grams, and catalyst C is described
10in containing 90 grams of glycerine, contained alcohol and carrier S
6mass ratio be 0.045.
Example 11
6998.0 grams, HZSM-35 molecular sieve, 3790.0 grams, SAPO-11 molecular sieve are mixed with 1637.8 grams of boehmites, add nitric acid and 10770 grams of water that 65.5 grams of concentration are 65 quality %, the trilobal bar of diameter 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S
7, wherein molecular sieve content is 90 quality %, alumina content is 10 quality %.
Get 2000 grams of carrier S
7, with the aqueous solution 1950 milliliters containing 230.6 grams of (2.504mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
11, its weight is 2230.1 grams, and catalyst C is described
11in containing 230.1 grams of glycerine, contained alcohol and carrier S
7mass ratio be 0.115.
Example 12
7998.0 grams, HZSM-35 molecular sieve, 2790.0 grams, HZSM-22 molecular sieve are mixed with 1637.8 grams of boehmites, add nitric acid and 10770 grams of water that 65.5 grams of concentration are 65 quality %, the trilobal bar of diameter 1.1 millimeters is extruded into double screw banded extruder, pelletizing, 120 DEG C of dryings, 4 hours, 550 DEG C roastings 2 hours, obtain carrier S
8, wherein molecular sieve content is 90 quality %, alumina content is 10 quality %.
Get 2000 grams of carrier S
8, with the aqueous solution 1953 milliliters containing 280.4 grams of (3.045mol) glycerine in 25 DEG C of dippings 0.5 hour, then in 90 DEG C, under 0.01MPa condition dry 2 hours, obtain catalyst C
12, its weight is 2279.9 grams, and catalyst C is described
12in containing 279.9 grams of glycerine, contained alcohol and carrier S
8mass ratio be 0.14.
Example 13 ~ 29
Following instance evaluates the isomerization reaction performance of catalyst of the present invention.
With 1-amylene for reaction raw materials, with the carrier of non-modified compound treatment for comparative catalyst, small fixed hydrogenation reaction device evaluates catalyst of the present invention and comparative catalyst respectively.
Concrete operation method is: by the flat-temperature zone of Catalyst packing in reactor, introduces hydrogen and reaction pressure is adjusted to 0.3MPa.Temperature of reactor is risen to 300 DEG C, after stablizing 2 hours, inject 1-amylene in reactor, controlling reaction temperature is 300 DEG C, feed volume air speed 1.7h
-1, reaction pressure is 0.3MPa, hydrogen/hydrocarbon volume ratio is 600, reacts after 12 hours and samples, and adopt gas-chromatography sampling on-line analysis, reaction result is in table 1.
Table 1
From table 1 data, the catalyst that the present invention obtains after alcoholic compound process, than the comparative catalyst of non-modified process, iso-amylene yield and iso-amylene is selective is all significantly improved.
Claims (13)
1. a N-alkene isomerization catalyst, comprises carrier and modified compound, and described modified compound is polyalcohol, and the mass ratio of described modified compound and carrier is 0.01 ~ 0.4:1, and described carrier comprises molecular sieve and binding agent, and described polyalcohol is C
2~ C
7polyalcohol.
2., according to catalyst according to claim 1, it is characterized in that the mass ratio of described modified compound and carrier is 0.01 ~ 0.3:1.
3., according to catalyst according to claim 1, it is characterized in that described C
2~ C
7polyalcohol be selected from ethylene glycol, propane diols, butanediol, pentanediol, hexylene glycol, glycerine, trimethylolethane, pentaerythrite, xylitol and sorbierite one or more.
4., according to catalyst according to claim 1, it is characterized in that described carrier comprises the molecular sieve of 50 ~ 99 quality % and the binding agent of 1 ~ 50 quality %.
5., according to the catalyst described in claim 1 or 4, it is characterized in that described molecular sieve is mesoporous molecular sieve, described binding agent is aluminium oxide.
6., according to catalyst according to claim 5, it is characterized in that described mesoporous molecular sieve is one in ZSM-35, ZSM-22 and SAPO-11 or any two kinds.
7., according to catalyst according to claim 1, it is characterized in that described alkene is C
4~ C
6normal olefine.
8. a preparation method for catalyst described in claim 1, comprises molecular sieve and binding agent mixed-forming, and dry, roasting obtains carrier, then uses the aqueous impregnation of modified compound, after dipping solid in 30 ~ 200 DEG C, dry under 0.01 ~ 0.1MPa condition.
9. in accordance with the method for claim 8, it is characterized in that described molecular sieve is one in ZSM-35, ZSM-22 and SAPO-11 or any two kinds, binding agent is aluminium oxide.
10. in accordance with the method for claim 8, it is characterized in that first molecular sieve modified compound being carried out pretreatment, preprocess method is the aqueous impregnation with modified compound, solid drying after then flooding, again with binding agent mixed-forming, dry, roasting obtains carrier.
11. in accordance with the method for claim 8, and it is characterized in that the aqueous impregnation two of carrier modified compound that obtains after roasting, to repeatedly, all needs drying after each dipping.
12. in accordance with the method for claim 8, it is characterized in that the concentration of the modified compound aqueous solution is 0.01 ~ 3.0 mol/L.
13. in accordance with the method for claim 11, it is characterized in that the modified compound that each dipping uses is identical or different.
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| CN106334570B (en) * | 2015-07-09 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
| CN106311298B (en) * | 2015-07-09 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
| CN112337454B (en) * | 2019-08-09 | 2023-07-25 | 中国石油天然气股份有限公司 | Olefin skeleton isomerisation oxide catalyst and preparation method thereof |
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|---|---|---|---|---|
| US4508836A (en) * | 1982-07-27 | 1985-04-02 | Mobil Oil Corporation | Catalytic conversion process for aromatic feedstocks with hydrogen regeneration of coke-selectivated zeolite catalyst |
| US5382743A (en) * | 1993-04-26 | 1995-01-17 | Mobil Oil Corporation | Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen |
| US5817907A (en) * | 1995-05-04 | 1998-10-06 | Institut Francais Du Petrole | Process for skeletal isomerization of linear olefins using a pretreated molecular sieve, and a catalyst containing a pretreated sieve |
| CN101318141A (en) * | 2008-07-16 | 2008-12-10 | 江苏技术师范学院 | Hydroisomerization catalyst, preparation and application thereof |
| CN102451747A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | C8 alkylaromatic side chain isomerization catalyst and preparation method thereof |
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2012
- 2012-08-03 CN CN201210275195.1A patent/CN103566975B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508836A (en) * | 1982-07-27 | 1985-04-02 | Mobil Oil Corporation | Catalytic conversion process for aromatic feedstocks with hydrogen regeneration of coke-selectivated zeolite catalyst |
| US5382743A (en) * | 1993-04-26 | 1995-01-17 | Mobil Oil Corporation | Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen |
| US5817907A (en) * | 1995-05-04 | 1998-10-06 | Institut Francais Du Petrole | Process for skeletal isomerization of linear olefins using a pretreated molecular sieve, and a catalyst containing a pretreated sieve |
| CN101318141A (en) * | 2008-07-16 | 2008-12-10 | 江苏技术师范学院 | Hydroisomerization catalyst, preparation and application thereof |
| CN102451747A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | C8 alkylaromatic side chain isomerization catalyst and preparation method thereof |
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