CN103041843A - Isomerization catalyst composition and application thereof - Google Patents
Isomerization catalyst composition and application thereof Download PDFInfo
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Abstract
The invention discloses an isomerization catalyst composition and application thereof. The catalyst comprises the following components in percentage by weight: 0.01-5% of VIII-family noble metal element in the periodic table of elements, 10-80% of rare-earth modified mordenite, 0.1-10% of assistant and the balance of binding agent of which the sulfur content is 0.5-5.0%, wherein the rare-earth modified mordenite accounts for 5-40 wt% of the rare-earth metal oxide. The catalyst is used in the isomerization process of C4-C12 alkanes, has the characteristics of high catalytic activity, high isomeric olefine selectivity and the like, and can be used for producing a blending component for high-octane gasoline.
Description
Technical field
The present invention relates to a kind of isomerization catalyst composition and application thereof, in particular, the present invention relates to carbon monoxide-olefin polymeric and the application thereof of a kind of C4 of being applicable to～C12 alkane isomerization.
Background technology
Under certain conditions, n-alkane is the undesirable components in the oil product, and the isomerization reaction of n-alkane is the important reaction in the 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 the 10 μ g/g, olefin(e) centent is down to below the 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, then 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 refers to mainly that take crystalline silicate as carrier aluminium oxide or other refractory oxide are binding agent, and load VIII family metal mainly is the catalyst of platinum or palladium preparation.The carrier of this class catalyst has acid function, can impel normal alkane isomerization, and used carrier 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 cost.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 suitable pore volume and regular duct.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 VIII family and VI B family 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 the equilibrium concentration of isomerized products is lower under the high temperature, particularly to n-hexane, higher reaction temperature will affect in the 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 the 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 composition and method of making the same and the application of auxiliary agent.This carbon monoxide-olefin polymeric 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 composition of the present invention, in catalyst weight percentage, this 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 the binding agent of sulfur-bearing 0.5% ~ 5.0%, the rare-earth oxide content 5% ~ 40% take rare earth modified modenite weight as benchmark.
In the carbon monoxide-olefin polymeric of the present invention, rare-earth oxide loads on becomes modified mordenite on the modenite, and sulfur-containing compound mixes as binding agent with inorganic refractory oxide, and VIII family precious metal element and auxiliary agent adopt the infusion process load.
Isomerization catalyst composition of the present invention, the SiO of rare earth modified modenite
2/ Al
2O
3Mol ratio is 5 ~ 70, is preferably 10～60, and by weight percentage, the content of rare earth modified modenite is preferably 20% ~ 70% in the catalyst; Described rare-earth oxide is selected from one or more in the oxide in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and the lutetium, and the preferential oxidation lanthanum is or/and cerium oxide; The content of the rare earth oxide in the rare earth modified modenite is preferably 10% ~ 30%, most preferably is 15% ~ 25%.
In the carbon monoxide-olefin polymeric of the present invention, in the mixture of the described binding agent that contains sulphur, as 0.5% ~ 5.0%, be preferably 1.0% ~ 3.0% in the content (take the binding agent butt) of element wt sulphur; Described sulfur-containing compound is sulfuric acid or ammonium sulfate, is preferably sulfuric acid.Inorganic refractory oxide in the binding agent is aluminium oxide and/or kaolin.The binding agent preparation method of sulfur-bearing is: sulfate ion is loaded on aluminium hydroxide and/or the kaolin, through super-dry and roasting, obtain the inorganic refractory oxide of sulphur modification; With the thick material of the abundant epoxy glue melt into of inorganic refractory oxide, peptizing agent and deionized water of sulphur modification, as the binding agent of catalyst.
In the carbon monoxide-olefin polymeric 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.
In the carbon monoxide-olefin polymeric of the present invention, described auxiliary agent is rhenium and/or tin, and the auxiliary agent weight content in the catalyst is preferably 0.5% ~ 5.0% in metal.
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 is best suited for the reaction of C5-C7 alkane isomerization.Using the form of catalyst can be fixed bed, also can be 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 sulphur.Owing to select the smaller rare earth compound of volume, 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 acid position, when providing more active sites for catalyst, avoided the side reactions such as the coking of strong acidic site and carbon distribution, 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 contain the material of a fixed structure of aluminium and/or silicon in the binding agent, binding agent through the over cure modification, can modify its acidity, cover some strong acid centers, a large amount of middle strong acid active sites can be produced again simultaneously, in the isomerization reaction performance that improves catalyst, lytic activity can be reduced.Catalyst of the present invention adds again auxiliary agent rhenium and/or 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 content of metal, reduce the Catalyst Production cost.
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 the modenite, through super-dry and roasting, obtains rare-earth element modified modenite;
(2) sulfate ion is loaded on aluminium hydroxide and/or the kaolin, through super-dry and roasting, obtain the inorganic refractory oxide of sulphur modification;
The thick material of the abundant epoxy glue melt into of inorganic refractory oxide, peptizing agent and deionized water of the sulphur modification that (3) step (2) is prepared is as the binding agent of preparation catalyst of the present invention;
(4) the abundant kneading of binding agent, extrusion aid and water that the modified mordenite that step (1) is made, step (3) make becomes plastic paste, and extruded moulding through super-dry and roasting, obtains catalyst carrier of the present invention;
(5) VIII element and auxiliary agent are loaded on the catalyst carrier that step (4) makes, through super-dry and roasting, obtain catalyst of the present invention.
Step (1) rare earth elements loads on the molecular sieve and can adopt ion-exchange, infusion process or kneading method, when wherein adopting ion-exchange or infusion process, the used compounds containing rare earth of solution that preparation contains rare earth are selected from one or more in oxide, chloride, nitrate, sulfate and the 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 oxide, chloride, nitrate, sulfate and the carbonate one or more, are preferably oxide and/or nitrate, more preferably nitrate.
Step (2) is described to be loaded to sulfate radical on aluminium hydroxide or the kaolin, adopt the method for conventional dipping, namely with the predecessor of inorganic refractory oxide and the aqueous solution dipping of containing sulfate radicals, the concentration of sulfate radical is generally 0.1 ~ 3.0 mol/L, is preferably 0.1 ~ 2 mol/L.Dip time is 5 ~ 24 hours, is preferably 8 ~ 15 hours.
Described modified oxide, peptizing agent and the water with step (2) preparation of step (3) fully mixes, and peptization becomes thick material.Described peptizing agent is inorganic acid or organic acid, is preferably inorganic acid, and more preferably hydrochloric acid and nitric acid most preferably are nitric acid; Wherein the mass concentration of used salpeter solution 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 (4) is the material that is conducive to extruded moulding, can be selected from graphite, starch, cellulose and the sesbania powder one or more, be preferably the sesbania powder, by weight percentage, the amount of its adding is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
The mode that step (5) noble metal and auxiliary agent are added in the catalyst can adopt infusion process or ion-exchange, is preferably infusion process.Can adopt step impregnation, also can adopt simultaneously dipping.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), (2), (4) and (5) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and step (1), step (2), step (4) and the described drying condition of step (5) can be identical, also can be different.The roasting condition of step (1), (2), (4) and (5) is 400 ℃ ~ 800 ℃ and keeps 0.5h ~ 10.0h that step (1), step (2), step (4) and the described roasting condition of step (5) can be identical, also can be different.
Further specify the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited among the 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 n-hexane under 250 ℃, 1.47MPa condition and carries out isomerization reaction, and the reaction feed weight space velocity is 1.0h
-1, the lighter hydrocarbons mol ratio is 2.7, reaction result sees Table 2, the isomerization rate in the table 2 and selectively by the following method calculating (weight content):
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, and making 450 milliliters of lanthana content is the lanthanum nitrate hexahydrates of 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) get 500 gram (in aluminium oxide) aluminium hydroxides (SB that German Condean company produces), add the sulfuric acid of 3000 milliliter of 1 mol/L to it, room temperature dipping 5 hours.Remove supernatant, 110 ℃ of oven dry, 520 ℃ of roastings obtained the aluminium oxide melt resistant compound of sulfur-bearing after 6 hours.
(3) get the modified aluminas that 450 gram steps (2) are made, 1000ml water and 60ml red fuming nitric acid (RFNA) (mass concentration is 66.5%) fully mix.Obtain the sulphur mass content and be 2.2% adhesive.
(4) get binding agent, the 6 gram sesbania powder that 120 modified mordenites that make of gram steps (1), 100 gram (3) steps make and become plastic paste with the abundant kneading of an amount of water, extruded moulding (1.5 millimeters of diameters), lower dry 16 hours through 100 ℃, then 550 ℃ of roastings obtained catalyst carrier of the present invention in 4 hours in air atmosphere, and bearer number is ES-1
(5) restrain ES-1 with containing perrhenic acid and H with 100
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 lanthanum nitrate with cerous nitrate, replaces sulfuric acid with ammonium sulfate, 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 the used lanthanum nitrate of difference, molecular sieve, content 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 used molecular sieve 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 used molecular sieve without containing the rare earth element solution processing, does not contain sulphur yet in the 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 used molecular sieve without containing the rare earth element solution processing, does not contain sulphur in the binding agent.Also do not contain auxiliary agent in the 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 ①/ modified molecular screen ②,% | Sulphur ③/ binding agent ④,% | Pt,% | Auxiliary agent, % | Pd,% |
| E-1 | 20.0/50.0 | 2.2 9./surplus | 0.3 | 0.8⑦ | - |
| E-2 | 20.0 ⑤/50.0 | 1.8 10./surplus | - | 1.2⑦ | 0.4 |
| E-3 | 20.0/50.0 | 1.5 9./surplus ⑥ | 0.4 | 1.5⑧ | - |
| E-4 | 35.0/30.0 | 0.8 9./surplus | 0.2 | 2.3⑦ | 0.2 |
| E-5 | 30.0/60.0 | 2.2 9./surplus | 1.0 | 3.8⑧ | 0.1 |
| E-6 | 15.0/70.0 | 1.1 9./surplus | - | 5.0⑦ | 1.5 |
| E-7 | 12.0/80.0 | 3.6 10./surplus | 1.3 | 2.7⑧ | -- |
| C-1 | 0/50.0 | 1.5 9./surplus | 1.2 | 2.1⑦ | 0.5 |
| C-2 | /30.0 | 0/ surplus | 0.8 | 3.1⑧ | 0.4 |
| C-3 | 0/70.0 | 0/ surplus | 1.5 | - | 1.8 |
Annotate:There is not dated Re in the table 1
2O
3Be lanthana, molecular sieve is h-mordenite, is aluminium oxide without the binding agent that indicates.1. with respect to modified molecular screen; 2. with respect to catalyst; 3. with respect to binding agent; 4. with respect to catalyst; 5. cerium oxide; 6. binding agent is weight 30% kaolin and surplus aluminium oxide, 7. auxiliary agent rhenium, 8. auxiliary agent tin, 9. sulfuric acid, 10. ammonium sulfate.
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 | 0.91 | 18.47 | 15.63 | 84.38 | 84.24 | 18.63 |
| E-2 | 0.80 | 18.24 | 16.33 | 83.67 | 83.55 | 18.39 |
| E-3 | 0.93 | 17.99 | 15.78 | 84.23 | 84.09 | 18.66 |
| E-4 | 0.90 | 17.7 | 16.22 | 83.79 | 83.64 | 17.87 |
| E-5 | 0.81 | 18.32 | 15.84 | 84.16 | 84.04 | 18.47 |
| E-6 | 0.91 | 18.52 | 15.94 | 84.07 | 83.92 | 18.69 |
| E-7 | 0.88 | 18.04 | 16.07 | 83.94 | 83.80 | 18.2 |
| C-1 | 1.09 | 12.36 | 20.18 | 79.82 | 79.60 | 12.50 |
| 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 the table 22,2-DMB is 2,2-methybutane; NC
6Be n-hexane.
As can be seen from Table 2, be that the catalyst of carrier preparation is compared with modenite, 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 composition, 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 the binding agent of sulfur-bearing 0.5% ~ 5.0%, and the rare-earth oxide content take rare earth modified modenite weight as benchmark is as 5% ~ 40%.
2. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: rare-earth oxide loads on becomes modified mordenite on the modenite, sulfur-containing compound mixes as binding agent with inorganic refractory oxide, and VIII family precious metal element and auxiliary agent adopt the infusion process load.
3. according to carbon monoxide-olefin polymeric 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 claim 1 or 3 described carbon monoxide-olefin polymerics, it is characterized in that: rare-earth oxide is selected from one or more in the oxide in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and the lutetium, and the preferential oxidation lanthanum is or/and cerium oxide; The content of the rare earth oxide in the rare earth modified modenite is 10% ~ 30%.
5. according to carbon monoxide-olefin polymeric claimed in claim 2, it is characterized in that: contain in the binding agent of sulphur, take the content of binding agent butt weighing scale element sulphur as 1.0% ~ 3.0%, sulfur-containing compound is sulfuric acid or ammonium sulfate, and the inorganic refractory oxide in the binding agent is aluminium oxide and/or kaolin.
6. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: VIII family noble metal is platinum and/or palladium in the catalyst.
7. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: auxiliary agent is rhenium and/or tin.
8. according to claim 1 or 2 described carbon monoxide-olefin polymerics, it is characterized in that: the binding agent preparation method of sulfur-bearing is: sulfate ion is loaded on aluminium hydroxide and/or the kaolin, through super-dry and roasting, obtain the inorganic refractory oxide of sulphur modification; With the thick material of the abundant epoxy glue melt into of inorganic refractory oxide, peptizing agent and deionized water of sulphur modification, as the binding agent of catalyst.
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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384176A (en) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | Reforming catalyst containing molecular sieve |
| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN101091920A (en) * | 2006-06-21 | 2007-12-26 | 中国石油化工股份有限公司 | Method for preparing composite molecular sieve of ZSM 5/ mordenite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384176A (en) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | Reforming catalyst containing molecular sieve |
| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN101091920A (en) * | 2006-06-21 | 2007-12-26 | 中国石油化工股份有限公司 | Method for preparing composite molecular sieve of ZSM 5/ mordenite |
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