CN103100413A - Isomerization catalyst and its application - Google Patents
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- CN103100413A CN103100413A CN2011103132634A CN201110313263A CN103100413A CN 103100413 A CN103100413 A CN 103100413A CN 2011103132634 A CN2011103132634 A CN 2011103132634A CN 201110313263 A CN201110313263 A CN 201110313263A CN 103100413 A CN103100413 A CN 103100413A
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Abstract
The invention discloses an isomerization catalyst and its application. The catalyst comprises the following components by weight: 0.01%-5% of a group VIII noble metal element in the periodic table of elements, 10%-80% of rare earth modified mordenite, 0.1%-10% of an assistant, and the balance a binder with a halogen content of 0.5%-5%, as well as based on the weight of the rare earth modified mordenite, 5%-40% of a rare-earth oxide. The catalyst is used for an isomerization process of C4-C12 alkanes, has the characteristics of high catalytic activity and high iso-olefin selectivity, and can be used as a blending component for producing high octane gasoline.
Description
Technical field
The present invention relates to a kind of catalyst for isomerizing light hydrocarbon and application thereof, specifically, the present invention relates to catalyst and the application thereof of a kind of C4 of being applicable to～C12 normal alkane isomerization.
Background technology
Under certain conditions, n-alkane is the undesirable components in oil product, and the isomerization reaction of n-alkane is the important reaction in petroleum refining process.Especially mix in the catalytic gasoline of refining residual oil, sulphur and olefin(e) centent are all higher.Gasoline is carried out hydrodesulfurization and falls alkene, sulfur content can be down to below 10 μ g/g, olefin(e) centent is down to below 10v%, but has reduced greatly octane number simultaneously.If will not losing or situation decline low-sulfur, the olefin(e) centent of little loss octane number, need to carry out selective hydrogenation cracking or isomerization.The RON of isoparaffin is high more a lot of than the n-alkane of same carbon number.For example, nC
6RON be 24.8, and 2,2-dimethyl C
4Be 91.8; nC
7Be 0, trimethyl C
4Be 112.1, dimethyl C
5Be 81 ~ 93.Obviously hydroisomerizing is more effective to octane value recovering.In China's gasoline more than 80% from the catalytically cracked gasoline component, hydroisomerizing seems particularly important for improving octane number.Therefore with small-molecular weight (C
5/ C
6) n-alkane change into the octane number that isoparaffin improves light oil distillate, thereby the octane number tool that improves gasoline is of great significance.
Catalyst plays the role of a nucleus in n-alkane hydroisomerization technology.One of isomerization method for light hydrocarbon commonly used is to carry out hydroisomerization reaction more than 250 ℃ with the zeolite type bifunctional catalyst.Hydroisomerisation catalysts is bifunctional catalyst, not only has hydrogenation-dehydrogenation activity but also have acid active.The difunctional isomerization catalyst of described zeolite type mainly refers to take crystalline silicate as carrier, and aluminium oxide or other refractory oxide are binding agent, and load VIII family metal is mainly the catalyst of platinum or palladium preparation.The carrier of this class catalyst has acid function, can impel normal alkane isomerization, and carrier used mainly contains X-type zeolite, y-type zeolite and modenite at present.Acid carrier must have the effect of following several respects: the effective surface area that increases catalyst; Suitable pore structure is provided; Acid centre is provided; Improve the mechanical strength of catalyst; Improve the heat endurance of catalyst; Increase the poison resistance of catalyst; Save the consumption of metal component, reduce costs.The solid acid of different molecular sieve and similar molecular sieve, acidic oxide etc. are commonly used to do acidic components, but are carrier mainly with molecular sieve in actual production and research, because it has larger specific area, have simultaneously the duct of suitable pore volume and rule.Common aluminosilicate-type molecular sieve such as Y, β, ZSM-5, ZSM-22, ZSM-11, ZSM-23 etc.; SAPO molecular sieve analog such as SAPO-11, SAPO-31, SAPO-41 etc.Wherein, remove cationic Y zeolite, beta-molecular sieve, modenite etc. and use extensivelyr, this is main because they have the molecular sieve pore passage of stronger acidic character and distinctive geometrical rule.Metal component is the source of hydrogenation-dehydrogenation activity, it can be rapidly with hydrogenation of olefins avoiding coking and acid centre capped, thereby play the effect of protection acid centre, hygrogenating isomerization reaction is carried out smoothly.Metal component generally is selected from family of VIII family and VI B element in the periodic table of elements, can be divided into noble metal and base metal two classes.The former uses mainly with the metal simple-substance form take (Pt), (Pd) etc. as main, and the latter mainly contains molybdenum (Mo), (Ni), (Co), (W) etc., uses mainly with the oxide morphology that mutually combines, and can improve like this active and stable of catalyst.The precious metal catalyst activity is the highest, only needs just can increase substantially on a small quantity the hydroisomerizing activity of bifunctional catalyst.
USP4,232,181, GB1039246, GB1189850, USP4,665,272 patent documentations such as grade are all described the preparation method of such catalyst in detail, but because the application of temperature of zeolite type bifunctional catalyst is higher, and under high temperature, the equilibrium concentration of isomerized products is lower, particularly to n-hexane, higher reaction temperature will affect in isomerized products 2, and the 2-dimethylbutane (2, concentration 2-DMB), and 2,2-DMB has very high octane number, if its concentration reduces, will directly affect the octane number of isomerized products.Therefore further improve the acidity of modenite, the isomery that improves it selectively seems very necessary.
US6198015 proposes a kind of hydroisomerization catalyst, and the carrier that it is characterized by catalyst is comprised of NU-10 molecular sieve and binding agent.US4440871, US5135638 and CN1392099A have proposed a kind of hydroisomerization catalyst, it is characterized in that adopting SAPO-11 molecular sieve and the molecular sieve carried noble metal platinum of nanometer SAPO-11.CN86102384A etc. are for C
4~ C
7The isomerization of straight-chain low-carbon hydrocarbon has proposed a kind of hydroisomerization catalyst, it is characterized in that catalyst carrier is comprised of modified mordenite and binding agent.However, the preparation of more highly active hydroisomerization catalyst also exists the very large space of improving, and especially in the composite synthetic technology that is applicable to catalyst carrier and scheme day by day when maturation, this improvement can be achieved.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of take modified mordenite as carrier and add hydroisomerization catalyst of auxiliary agent and its preparation method and application.This catalyst is used for C4～C7 isomerization of paraffins process, has the selective high of catalytic activity and isomeric olefine, can effectively improve their octane number.
Isomerization catalyst of the present invention, by weight percentage, catalyst has following composition: VIII family precious metal element 0.01% ~ 5%, rare earth modified modenite 10% ~ 80%, auxiliary agent 0.1% ~ 10% in the periodic table of elements, the binding agent of surplus halogen-containing 0.5% ~ 5.0%, the rare-earth oxide content 5% ~ 40% take rare earth modified modenite weight as benchmark.
In catalyst of the present invention, rare-earth oxide loads on becomes modified mordenite on modenite, and halogen mixes as binding agent with inorganic refractory oxide, and VIII family's precious metal element and auxiliary agent adopt the infusion process load.
In isomerization catalyst of the present invention, the SiO of rare earth modified modenite
2/ Al
2O
3Mol ratio is 5 ~ 70, is preferably 10～60, and in catalyst, by weight percentage, the content of rare earth modified modenite is preferably 20% ~ 70%; Described rare-earth oxide is selected from one or more in oxide in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and lutetium, and the preferential oxidation lanthanum is or/and cerium oxide; The content of the rare earth oxide in rare earth modified modenite is preferably 10% ~ 30%, most preferably is 15% ~ 25%; The described binding agent that contains halogen is halogen-containing inorganic refractory oxide, and in binding agent, the weight content of halogen (take butt) is 1.0% ~ 3.0%; Described halogen is one or more in fluorine, chlorine and bromine, is preferably chlorine.In catalyst of the present invention, active component is VIII family noble metal, is preferably platinum and/or palladium, most preferably is platinum.The content of active component in catalyst is preferably 0.1% ~ 3.0% in metal.Described auxiliary agent is rhenium and/or tin, and the auxiliary agent weight content in catalyst is preferably 0.5% ~ 5.0% in metal.Described inorganic refractory oxide is one or more that are selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, is preferably aluminium oxide and/or kaolin, more preferably aluminium oxide.
It is the isomerization reaction that is suitable for the small-molecular weight n-alkane that catalyst of the present invention is applicable to catalytic reaction, and particularly C4～C12 alkane isomerization reaction, be best suited for the reaction of C5-C7 alkane isomerization.Using the form of catalyst can be fixed bed, can be also fluid bed.Catalytic process is: first catalyst is reduced, reasonable reducing condition is: 550 ~ 650 ℃ of temperature, 5 ~ 15 hours recovery times.The reaction temperature of isomerization reaction is 200 ~ 350 ℃, is preferably 230 ~ 300 ℃; Pressure is 1.0 ~ 3.0MPa, preferably 0.5 ~ 2.0 MPa; The feed weight air speed is 0.2 ~ 10.0h
-1, be preferably 0.5 ~ 5.0h
-1Hydrogen hydrocarbon mol ratio (hydrogen and alkane mol ratio) is 0.5 ~ 10.0, is preferably 1.0 ~ 8.0.
The key component of catalyst of the present invention is rare-earth element modified modenite and the binding agent that contains halogen, coordinates simultaneously active metal component and suitable auxiliary agent.Owing to selecting suitable rare earth compound, can enter into the duct of molecular sieve, B acid position effect with molecular sieve, the acid strength of molecular sieve is reduced, and can produce more sour position, when providing more active sites for catalyst, avoided the side reactions such as the coking of strong acidic site and carbon deposit, the activity of catalyst and stability all are significantly improved.With the Acidity of time modulation molecular sieve surfaces externally and internally and the pore passage structure of molecular sieve.Modulation purpose to acidity makes molecular sieve lip-deep acid site intensity and acid strength distribution satisfy alkane isomerization reaction requirement, improves the activity of catalyst; Owing to containing aluminium oxide or silica in binding agent, the binding agent through halogen modified can produce a large amount of L acid sites, and sour of L is affected by Electronic Performance, can improve the isomerization reaction performance of catalyst.Catalyst of the present invention adds again auxiliary agent rhenium and tin, can improve the decentralization of noble metal component by introducing auxiliary agent, and this may be because auxiliary agent can form alloy phase with noble metal, thereby has avoided the gathering of metal.Can not only make catalyst that more active sites is provided, and can reduce the load capacity of active metal component, reduce the production cost of catalyst.
The specific embodiment
The below provides a kind of concrete preparation method of catalyst of the present invention, but is not limited to the method, and concrete steps are:
(1) rare earth element is downloaded on modenite, through super-dry and roasting, obtains rare earth modified modenite;
(2) with the thick material of the abundant epoxy glue melt into of aluminium hydroxide, halogen compounds, peptizing agent and deionized water, as the binding agent of preparation catalyst of the present invention;
(3) the abundant kneading of binding agent, extrusion aid and water that the rare earth modified modenite that step (1) is made, step (2) make becomes plastic paste, and extruded moulding through super-dry and roasting, obtains catalyst carrier of the present invention;
(4) VIII element and auxiliary agent are loaded on the catalyst carrier that step (3) makes, through super-dry and roasting, obtain catalyst of the present invention.
In step (1), rare earth element loads on molecular sieve can adopt ion-exchange, infusion process or kneading method, when wherein adopting ion-exchange or infusion process, preparation compounds containing rare earth solution compounds containing rare earth used are selected from one or more in oxide, chloride, nitrate, sulfate and carbonate, be preferably and be selected from chloride and/or nitrate, more preferably nitrate.When adopting kneading method, be that compounds containing rare earth are fully mixed with molecular sieve, compounds containing rare earth are to be selected from one or more in oxide, chloride, nitrate, sulfate and carbonate, are preferably oxide and/or nitrate, more preferably nitrate.
The preparation method of the described binding agent of step (2) can mix simultaneously, namely the predecessor of inorganic refractory oxide, halogen-containing solution, peptizing agent and water is fully mixed, and peptization becomes thick material.Prepare halogen-containing solution compound used and be and be selected from one or more in hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and hydrofluoric acid, be preferably hydrochloric acid and/or ammonium chloride, more preferably ammonium chloride.Also can adopt substep to mix, namely first halogen contained compound is fully mixed with the precursor of inorganic refractory oxide, and then fully mix with peptizing agent and water, peptization becomes thick material, wherein halogen contained compound is to be selected from one or more in hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and hydrofluoric acid, be preferably hydrochloric acid and/or ammonium chloride, more preferably ammonium chloride.Inorganic refractory oxide is one or more that are selected from aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay, be preferably aluminium oxide and/or kaolin, aluminium oxide more preferably, the precursor of aluminium oxide can be selected from boehmite, boehmite, diaspore, gibbsite and visit one or more in aluminium stone.
The described peptizing agent of step (2) is inorganic acid or organic acid, is preferably inorganic acid, and more preferably hydrochloric acid and nitric acid, most preferably be nitric acid; Wherein the mass concentration of salpeter solution used is 1.0%～30.0%, is preferably 1.0%～5.0%, and consumption is can make the kneading material be as the criterion as plastic block.
The described extrusion aid of step (3) is the material that is conducive to extruded moulding, can be selected from one or more in graphite, starch, cellulose and sesbania powder, be preferably the sesbania powder, by weight percentage, its amount that adds is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
The mode that step (4) noble metal and auxiliary agent are added in catalyst can adopt infusion process or ion-exchange, is preferably infusion process.Can adopt step impregnation, also can adopt dipping simultaneously.Activity component impregnation solution commonly used is the aqueous solution that contains the reactive metal soluble compound, for example platinum acid chloride solution, platinum ammonium complex solution, palladium ammonium complex solution, palladium nitrate solution, palladium chloride solution and organic coordination compound solution thereof, described rhenium-containing auxiliary agent is perrhenic acid, and stanniferous auxiliary agent is butter of tin or stannous chloride solution.
Drying condition described in step (1), (3) and (4) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and step (1), step (3) and the described drying condition of step (4) can be identical, also can be different.The roasting condition of step (1), (3) and (4) is 400 ℃ ~ 800 ℃ maintenance 0.5h ~ 10.0h, and step (1), step (3) and the described roasting condition of step (4) can be identical, also can be different.
Further illustrate the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited in following embodiment.And with the small fixed reaction unit, catalyst provided by the invention and comparative catalyst are carried out the Isomerization of Hexane reaction test.Isomerization catalyst is packed in the small fixed reactor, and charge weight is 10 milliliters, is warming up to 600 ℃, passes into hydrogen reducing 4 hours, then passes into hexane under 250 ℃, 1.47MPa condition and carries out isomerization reaction, and the reaction feed weight space velocity is 1.0h
-1, hydrogen hydrocarbon mol ratio is 2.7, reaction result sees Table 2, the isomerization rate in table 2 and selectively calculating (weight content) by the following method:
Isomerization rate=(isomery C
6Hexane content in content/product) * 100%
Isomerization is selective=(hexane content in 2,2DMB content/product) * 100%.
Embodiment 1 (if following do not have special indicate, degree all is weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1) getting silica alumina ratio is 18 modenite 300 grams, the lanthanum nitrate hexahydrate that to make 450 milliliters of lanthana content be 50 grams.Above-mentioned solution and the modenite that contains lanthanum nitrate fully mixed, after 4 hours, obtain the modenite of lanthanum modification through 110 ℃ of oven dry, 500 ℃ of roastings, it consists of: lanthana/modenite=1/6.
(2) be that 10%(is in halogen with 200 gram mass concentration) ammonium chloride solution, 450 grams (take aluminium oxide) aluminium hydroxide, 1000ml water and 60ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), fully mix.Obtain the halogen mass content and be 3.2% adhesive (in the butt of adhesive).
(3) get the modified mordenite that 120 gram steps (1) make, binding agent, the 6 gram sesbania powder that 100 grams (2) step makes become plastic paste with the abundant kneading of appropriate water, extruded moulding (1.5 millimeters of diameters), through under 100 ℃ dry 16 hours, then 550 ℃ of roastings obtained catalyst carrier of the present invention in 4 hours in air atmosphere, and bearer number is ES-1.
(4) with 100 gram ES-1 with containing perrhenic acid and H
2PtCl
6The saturated dipping of solution, and then 100 ℃ of dryings 8 hours, 500 ℃ of roasting 3h in air atmosphere make the catalyst of the present invention that contains 1.2wt%, 0.6wt%Pt, are numbered E-1, and its catalyst forms and sees Table 1, and reaction result sees Table 2.
Embodiment 2
The preparation of catalyst E-2 of the present invention
The preparation process of catalyst E-2 of the present invention is with embodiment 1, and difference is to replace ammonium chloride with ammonium bromide, replaces lanthanum nitrate with cerous nitrate, and the catalyst of the present invention of preparing is numbered E-2, and its catalyst composition sees Table 1, and reaction result sees Table 2.
Embodiment 3 ~ 7
The preparation of catalyst E-3 ~ E-7 of the present invention
The preparation process of catalyst E-3 ~ E-7 of the present invention is with embodiment 1, and the amount of difference lanthanum nitrate used, molecular sieve, halogen and rhenium is different, the catalyst E-3 ~ E-7 of the present invention for preparing, and its catalyst composition sees Table 1, and reaction result sees Table 2.
Comparative Examples 1
The preparation of comparative catalyst C-1 of the present invention.
The preparation method of catalyst is with embodiment 1, and difference is that molecular sieve used without containing the rare earth element solution processing, is numbered C-1, and the composition of its catalyst sees Table 1, and reaction result sees Table 2.
Comparative Examples 2
Comparative catalyst C-2 preparation of the present invention.
The preparation method of catalyst is with embodiment 2, and difference is that molecular sieve used without containing the rare earth element solution processing, does not contain halogen yet in adhesive.Be numbered C-2, its physico-chemical property sees Table 1, and reaction result sees Table 2.
Comparative Examples 3
Comparative catalyst C-3 preparation of the present invention.
The preparation method of catalyst is with embodiment 6, and difference is that molecular sieve used without containing the rare earth element solution processing, does not contain halogen in binding agent.Also do not contain the auxiliary agent rhenium in catalyst, be numbered C-3, its physico-chemical property sees Table 2, and reaction result sees Table 3.
The main physico-chemical property (weight percentage) of table 1 catalyst
| Catalyst | Re 2O 3/ modified molecular screen, % | Halogen/binding agent, % | Pt,% | Auxiliary agent, % | Pd,% |
| E-1 | 20.0/50.0 | 3.2/ surplus | 0.3 | 0.8⑦ | - |
| E-2 | 20.0/50.0 | 1.8/ surplus | - | 1.2⑦ | 0.4 |
| E-3 | 20.0/50.0 | 1.5/ surplus | 0.4 | 1.5⑧ | - |
| E-4 | 35.0/30.0 | 0.8/ surplus | 0.2 | 2.3⑦ | 0.2 |
| E-5 | 30.0/60.0 | 2.2/ surplus | 1.0 | 3.8⑧ | 0.1 |
| E-6 | 15.0/70.0 | 1.1/ surplus | - | 5.0⑦ | 1.5 |
| E-7 | 12.0/80.0 | 4.6/ surplus | 1.3 | 2.7⑧ | -- |
| C-1 | 0/50.0 | 3.2/ surplus | 1.2 | 2.1⑦ | 0.5 |
| C-2 | 0/30.0 | 0/ surplus | 0.8 | 3.1⑧ | 0.4 |
| C-3 | 0/70.0 | 0/ surplus | 1.5 | - | 1.8 |
Annotate:There is no dated Re in table 1
2O
3Be lanthana, molecular sieve is h-mordenite, and refractory oxide is aluminium oxide.
Re
2O
3Content is take modified molecular screen weight as benchmark; Modified molecular screen content is take catalyst weight as benchmark; Content of halogen is take weight of binder as benchmark; Binder content is take catalyst weight as benchmark; The E-2 middle rare earth is cerium oxide; In E-3, binding agent is weight content 30% kaolin and surplus aluminium oxide, 7. refers to the auxiliary agent rhenium, 8. refers to auxiliary agent tin.
Table 2 evaluating catalyst result (percentage by weight)
| The catalyst numbering | Product＜C 5，% | Product 2,2-DMB, % | Product nC 6，% | Conversion ratio, % | Isomerization rate, % | Isomerization is selective, % |
| E-1 | 0.98 | 18.4 | 15.36 | 84.64 | 84.49 | 18.58 |
| E-2 | 0.68 | 18.65 | 16.41 | 83.59 | 83.48 | 18.78 |
| E-3 | 0.57 | 17.51 | 18.19 | 81.81 | 81.71 | 17.61 |
| E-4 | 1.05 | 16.5 | 15.96 | 84.04 | 83.87 | 16.68 |
| E-5 | 0.59 | 17.8 | 16.23 | 83.77 | 83.67 | 17.91 |
| E-6 | 1.0 | 18.6 | 16.61 | 83.39 | 83.22 | 18.79 |
| E-7 | 0.86 | 16.7 | 17.13 | 82.87 | 82.72 | 16.85 |
| C-1 | 1.18 | 6.7 | 21.27 | 78.73 | 78.48 | 6.78 |
| C-2 | 1.17 | 5.6 | 22.36 | 77.64 | 77.38 | 5.67 |
| C-3 | 1.25 | 4.80 | 42.24 | 57.76 | 57.23 | 4.9 |
In table 22,2-DMB is 2,2-methybutane; nC
6Be n-hexane.
As can be seen from Table 2, compare with the catalyst that modenite is carrier preparation, the catalyst of the present invention's preparation have higher conversion ratio and isomerization selective.And also lower less than the component output of C5, that is to say with catalyst of the present invention and carry out the light hydrocarbon isomerization reaction, can obtain higher liquid yield, can produce more high-knock rating gasoline.
Claims (10)
1. isomerization catalyst, it is characterized in that: by weight percentage, catalyst has following composition: VIII family precious metal element 0.01% ~ 5%, rare earth modified modenite 10% ~ 80%, auxiliary agent 0.1% ~ 10% in the periodic table of elements, surplus is halogen-containing 0.5% ~ 5.0% binding agent, and the rare-earth oxide content take rare earth modified modenite weight as benchmark is as 5% ~ 40%.
2. according to catalyst claimed in claim 1, it is characterized in that: rare-earth oxide loads on becomes modified mordenite on modenite, halogen mixes as binding agent with inorganic refractory oxide, and VIII family's precious metal element and auxiliary agent adopt the infusion process load.
3. according to catalyst claimed in claim 1, it is characterized in that: the SiO of rare earth modified modenite
2/ Al
2O
3Mol ratio is 5 ~ 70, and in catalyst weight percentage, the content of rare earth modified modenite is 20% ~ 70%.
4. according to the described catalyst of claim 1 or 3, it is characterized in that: rare-earth oxide is selected from one or more in oxide in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and lutetium, and the preferential oxidation lanthanum is or/and cerium oxide; The content of the rare earth oxide in rare earth modified modenite is 10% ~ 30%.
5. according to catalyst claimed in claim 1, it is characterized in that: the binding agent that contains halogen is halogen-containing inorganic refractory oxide, and halogen is one or more in fluorine, chlorine and bromine.
6. according to catalyst claimed in claim 1, it is characterized in that: in catalyst, VIII family noble metal is platinum and/or palladium.
7. according to catalyst claimed in claim 1, it is characterized in that: auxiliary agent is rhenium and/or tin.
8. according to catalyst claimed in claim 2, it is characterized in that: inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silica, boron oxide, magnesia, kaolin and clay.
9. the application of the described heterogeneous catalyst of the arbitrary claim of claim 1 to 8 in C4～C12 alkane isomerization reaction.
10. according to application claimed in claim 9, it is characterized in that: the reaction temperature of isomerization reaction is 200 ~ 350 ℃, and pressure is 1.0 ~ 3.0MPa, and the feed weight air speed is 0.2 ~ 10.0h
-1, hydrogen hydrocarbon mol ratio is 0.5 ~ 10.0.
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| CN104117369A (en) * | 2014-06-26 | 2014-10-29 | 江苏扬子催化剂有限公司 | Normal-paraffin isomerization catalyst, preparation method and application thereof |
| CN105833900A (en) * | 2016-04-06 | 2016-08-10 | 山东成泰化工有限公司 | Isomerization catalyst and preparation method thereof |
| CN104549212B (en) * | 2013-10-28 | 2017-03-15 | 中国石油化工股份有限公司 | Double bond isomerizing catalyst |
| CN109482205A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | Catalyst for normal paraffin isomerization and preparation method thereof |
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| CN105833900A (en) * | 2016-04-06 | 2016-08-10 | 山东成泰化工有限公司 | Isomerization catalyst and preparation method thereof |
| CN109482205A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | Catalyst for normal paraffin isomerization and preparation method thereof |
| CN109482205B (en) * | 2017-09-12 | 2021-10-08 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
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