CN103041843B - 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 a kind of carbon monoxide-olefin polymeric and the application thereof that are applicable to C4 ~ C12 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.Carry out hydrodesulfurization and Olefin decrease to gasoline, sulfur content can be down to 10 below μ g/g, olefin(e) centent is down to below 10v%, but reduces octane number greatly simultaneously.To 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 higher than the n-alkane of same carbon number a lot.Such as, 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.Obvious hydroisomerizing is more effective to octane value recovering.In China's gasoline, more than 80% from catalytically cracked gasoline component, and hydroisomerizing seems particularly important for raising octane number.Therefore by small-molecular-weight (C
5/ C
6) n-alkane change into isoparaffin to improve the octane number of light oil distillate, thus the octane number tool improving gasoline is of great significance.
Catalyst plays the role of a nucleus in n-alkane hydroisomerization technology.One of conventional isomerization method for light hydrocarbon more than 250 DEG C, carries out hydroisomerization reaction with 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 crystalline silicate to be carrier, and aluminium oxide or other refractory oxide are binding agent, load VIII race metal, mainly the catalyst prepared of platinum or palladium.The carrier of this kind of catalyst has acid function, can impel normal alkane isomerization, and carrier used at present mainly contains X-type zeolite, y-type zeolite and modenite.Acid carrier must have the effect of following several respects: the effective surface area increasing 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.Different molecular sieve and the solid acid, acidic oxide etc. of similar molecular sieve are commonly used to do acidic components, but are carrier mainly with molecular sieve in actual production and in studying, and because it has larger specific area, have the duct of suitable pore volume Sum fanction simultaneously.Common aluminosilicate-type molecular sieve is as Y, β, ZSM-5, ZSM-22, ZSM-11, ZSM-23 etc.; SAPO molecular sieve analog is as SAPO-11, SAPO-31, SAPO-41 etc.Wherein, remove the application such as cationic Y zeolite, beta-molecular sieve, modenite comparatively wide, 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, and hydrogenation of olefins can be capped to avoid coking and acid centre rapidly by it, thus plays the effect of protection acid centre, and hygrogenating isomerization reaction is carried out smoothly.Metal component is generally selected from VIII race and VI B race element in the periodic table of elements, can be divided into noble metal and base metal two class.The former is based on (Pt), (Pd) etc., and use mainly with metal simple-substance form, the latter mainly contains molybdenum (Mo), (Ni), (Co), (W) etc., uses, can improve activity and the stability of catalyst like this mainly with the oxide morphology be combined with each other.Precious metal catalyst activity is the highest, only needs the hydroisomerizing that just can increase substantially bifunctional catalyst on a small quantity active.
USP4,232,181, GB1039246, GB1189850, USP4,665, the preparation method of such catalyst all described in detail by 272 patent documents such as grade, but due to the application of temperature of zeolite type bifunctional catalyst higher, and under high temperature, the equilibrium concentration of isomerized products is lower, particularly to n-hexane, higher reaction temperature will affect the concentration of 2,2-dimethylbutanes (2,2-DMB) in isomerized products, and 2,2-DMB has very high octane number, if its concentration reduces, will directly affect the octane number of isomerized products.Therefore improve the acidity of modenite further, the stereoselectivity improving it seems very necessary.
US6198015 proposes a kind of hydroisomerization catalyst, and the carrier that it is characterized by catalyst is made up of NU-10 molecular sieve and binding agent.US4440871, US5135638 and CN1392099A propose 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 proposes a kind of hydroisomerization catalyst, it is characterized in that catalyst carrier is made up of modified mordenite and binding agent.However, the preparation of more highly active hydroisomerization catalyst, also also exists very large improvement space, and be especially applicable to the composite synthetic technology of 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 and be a kind ofly carrier with modified mordenite 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 catalytic activity and the selective high of isomeric olefine, effectively can improve their octane number.
Isomerization catalyst composition of the present invention, in catalyst weight percent, this catalyst has following composition: the VIIIth race's 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% being benchmark in rare earth modified modenite weight.
In inventive catalyst composition, rare-earth oxide load becomes modified mordenite on modenite, and sulfur-containing compound mixes as binding agent with inorganic refractory oxide, and VIII race's precious metal element and auxiliary agent adopt 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, and be preferably 10 ~ 60, the content of rare earth modified modenite is preferably 20% ~ 70% in catalyst by weight percentage; Described rare-earth oxide be selected from lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and lutetium in oxide one or more, 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%.
In carbon monoxide-olefin polymeric of the present invention, in the mixture of the described binding agent containing sulphur, in the content of element wt sulphur (in binding agent butt) for 0.5% ~ 5.0%, be preferably 1.0% ~ 3.0%; Described sulfur-containing compound is sulfuric acid or ammonium sulfate, is preferably sulfuric acid.Inorganic refractory oxide in binding agent is aluminium oxide and/or kaolin.The binding agent preparation method of sulfur-bearing is: loaded to by sulfate ion on aluminium hydroxide and/or kaolin, through super-dry and roasting, obtains the inorganic refractory oxide of sulphur modification; By material thick for abundant to the inorganic refractory oxide of sulphur modification, peptizing agent and deionized water epoxy glue melt into, as the binding agent of catalyst.
In carbon monoxide-olefin polymeric of the present invention, active component is the VIIIth race's noble metal, is preferably platinum and/or palladium, most preferably is platinum.Active component content is in the catalyst preferably 0.1% ~ 3.0% in metal.
In carbon monoxide-olefin polymeric of the present invention, described auxiliary agent is rhenium and/or tin, and the auxiliary agent weight content in catalyst is preferably 0.5% ~ 5.0% in metal.
It is the isomerization reaction being suitable for small-molecular-weight n-alkane that catalyst of the present invention is applicable to catalytic reaction, particularly C4 ~ C12 alkane isomerization reaction, is best suited for the reaction of C5-C7 alkane isomerization.The form using catalyst can be fixed bed, also can be fluid bed.Catalytic process is: first reduced by catalyst, and reasonable reducing condition is: temperature 550 ~ 650 DEG C, 5 ~ 15 hours recovery times.The reaction temperature of isomerization reaction is 200 ~ 350 DEG C, is preferably 230 ~ 300 DEG C; Pressure is 1.0 ~ 3.0MPa, preferably 0.5 ~ 2.0 MPa; Feed weight air speed is 0.2 ~ 10.0h
-1, be preferably 0.5 ~ 5.0h
-1; Hydrogen 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 containing sulphur.Due to the rare earth compound selecting volume smaller, the duct of molecular sieve can be entered into, act on the B acid position of molecular sieve, the acid strength of molecular sieve can not only be made like this to reduce, and more sour position can be produced, while catalyst provides more active sites, avoid the side reaction such as coking and carbon distribution of strong acidic site, the activity of catalyst and stability are all significantly improved.With the Acidity of time modulation molecular sieve surfaces externally and internally and the pore passage structure of molecular sieve.Make the acid site intensity on molecular sieve surface and acid strength distribution meet alkane isomerization reaction requirement to the modulation object of acidity, improve the activity of catalyst; Owing to containing the material of a fixed structure of aluminium and/or silicon in binding agent, through the binding agent of over cure modification, can modify its acidity, cover some strong acid centers, a large amount of middle strong acidic activity positions can be produced again simultaneously, can lytic activity be reduced while the isomerization reaction performance improving catalyst.Catalyst of the present invention adds again auxiliary agent rhenium and/or tin, and can improve the decentralization of noble metal component by introducing auxiliary agent, this may be because auxiliary agent can form alloy phase with noble metal, thus avoids the gathering of metal.Catalyst can not only be made to provide more active sites, and can content of metal be reduced, reduce Catalyst Production cost.
Detailed description of the invention
There is provided a kind of concrete preparation method of catalyst of the present invention below, but be not limited thereto method, concrete steps are:
(1) rare earth element is downloaded on modenite, through super-dry and roasting, obtains rare-earth element modified modenite;
(2) sulfate ion is loaded on aluminium hydroxide and/or kaolin, through super-dry and roasting, obtain the inorganic refractory oxide of sulphur modification;
(3) material that the inorganic refractory oxide of sulphur modification step (2) prepared, peptizing agent and deionized water abundant epoxy glue melt into are thick, as the binding agent of preparation catalyst of the present invention;
(4) binding agent modified mordenite obtained for step (1), step (3) obtained, extrusion aid become plastic paste, extruded moulding with the abundant kneading of water, through super-dry and roasting, obtain catalyst carrier of the present invention;
(5) VIII element and auxiliary agent are loaded in the obtained catalyst carrier of step (4), through super-dry and roasting, obtain catalyst of the present invention.
Step (1) rare earth elements loads on molecular sieve can adopt ion-exchange, infusion process or kneading method, when wherein adopting ion-exchange or infusion process, preparation is selected from one or more in oxide, chloride, nitrate, sulfate and carbonate containing the compounds containing rare earth that the solution of rare earth is used, preferably be selected from chloride and/or nitrate, be more preferably nitrate.When adopting kneading method, be that compounds containing rare earth are fully mixed with molecular sieve, compounds containing rare earth be selected from oxide, chloride, nitrate, sulfate and carbonate one or more, preferably oxide and/or nitrate, be more preferably nitrate.
Sulfate radical is loaded on aluminium hydroxide or kaolin described in step (2), adopt the method for conventional dipping, namely by the predecessor of inorganic refractory oxide and the aqueous impregnation 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.
Modified oxide, peptizing agent and water prepared by step (2) fully being mixed described in step (3), peptization becomes thick material.Described peptizing agent is inorganic acid or organic acid, is preferably inorganic acid, is more preferably hydrochloric acid and nitric acid, most preferably is nitric acid; Wherein the mass concentration of salpeter solution used is 1.0% ~ 30.0%, and be preferably 1.0% ~ 5.0%, consumption is that plastic block is as the criterion can make kneading material.
Extrusion aid described in step (4) is the material being conducive to extruded moulding, can be selected from graphite, starch, cellulose and sesbania powder one or more, be preferably sesbania powder, by weight percentage, its amount added is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
The mode that step (5) noble metal and auxiliary agent are added in catalyst can adopt infusion process or ion-exchange, is preferably infusion process.Can step impregnation be adopted, also can adopt and flood simultaneously.Conventional activity component impregnation solution is the aqueous solution containing active metal soluble compound, such as 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.
Step (1), (2), (4) and the drying condition described in (5) are that normal temperature ~ 300 DEG C keep 1h ~ 48h, and step (1), step (2), step (4) can be identical with the drying condition described in step (5), also can be different.The roasting condition of step (1), (2), (4) and (5) is 400 DEG C ~ 800 DEG C and keeps 0.5h ~ 10.0h, and step (1), step (2), step (4) can be identical with the roasting condition described in step (5), 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 small fixed reaction unit, Isomerization of Hexane reaction test is carried out to catalyst provided by the invention and comparative catalyst.Loaded by isomerization catalyst in small fixed reactor, charge weight is 10 milliliters, is warming up to 600 DEG C, passes into hydrogen reducing 4 hours, then 250 DEG C, pass into n-hexane under 1.47MPa condition and carry out isomerization reaction, reaction feed weight space velocity is 1.0h
-1, lighter hydrocarbons mol ratio is 2.7, reaction result in table 2, the isomerization rate in table 2 and selective by the following method calculate (weight content):
Isomerization rate=(isomery C
6hexane content in content/product) * 100%
Isomerisation selectivity=(in 2,2DMB content/product hexane content) * 100%.
embodiment 1 (if do not have special indicating below, degree is all weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1) get the modenite 300 grams that silica alumina ratio is 18, make the lanthanum nitrate hexahydrate that 450 milliliters of lanthana content are 50 grams.The above-mentioned solution containing lanthanum nitrate and modenite are fully mixed, through 110 DEG C of oven dry, 500 DEG C of roastings after 4 hours, obtain the modenite of lanthanum modification, it consists of: lanthana/modenite=1/6.
(2) get 500 grams of (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 immersion 5 hours.Removing supernatant, 110 DEG C of oven dry, 520 DEG C of roastings, after 6 hours, obtain the aluminium oxide refractory compounds of sulfur-bearing.
(3) get the modified aluminas that 450 grams of steps (2) are made, 1000ml water and 60ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), fully mix.Obtain the adhesive that sulphur mass content is 2.2%.
(4) get the obtained modified mordenite of 120 grams of steps (1), the binding agent that 100 grams of (3) steps obtain, 6 grams of sesbania powder become plastic paste with the abundant kneading of appropriate water, extruded moulding (diameter 1.5 millimeters), drying 16 hours at 100 DEG C, then in air atmosphere, 550 DEG C of roastings obtain catalyst carrier of the present invention in 4 hours, and bearer number is ES-1
(5) 100 grams of ES-1 are used containing perrhenic acid and H
2ptCl
6the saturated dipping of solution, and then 100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h in air atmosphere, the obtained catalyst of the present invention containing 1.2wt%, 0.6wt%Pt, is numbered E-1, and its catalyst composition is in table 1, and reaction result is in 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 prepared, is numbered E-2, and its catalyst composition is in table 1, and reaction result is in 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 difference lanthanum nitrate used, molecular sieve, content are different with the amount of rhenium, the catalyst E-3 ~ E-7 of the present invention prepared, and its catalyst composition is in table 1, and reaction result is in table 2.
comparative example 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 is without containing rare earth element solution process, and be numbered C-1, the composition of its catalyst is in table 1, and reaction result is in table 2.
comparative example 2
Prepared by comparative catalyst C-2 of the present invention.
The preparation method of catalyst is with embodiment 2, and difference is that molecular sieve used is without containing rare earth element solution process, also not containing sulphur in adhesive.Be numbered C-2, its physico-chemical property is in table 1, and reaction result is in table 2.
comparative example 3
Prepared by comparative catalyst C-3 of the present invention.
The preparation method of catalyst is with embodiment 6, and difference is that molecular sieve used is without containing rare earth element solution process, not containing sulphur in binding agent.Also not containing auxiliary agent in catalyst, be numbered C-3, its physico-chemical property is in table 2, and reaction result is in 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 |
note:the Re indicated is not had in table 1
2o
3for lanthana, molecular sieve is h-mordenite, is aluminium oxide without the binding agent indicated.1. relative to modified molecular screen; 2. relative to catalyst; 3. relative to binding agent; 4. relative to catalyst; 5. cerium oxide; 6. binding agent is weight 30% kaolin and remainder alumina, 7. auxiliary agent rhenium, 8. auxiliary agent tin, 9. sulfuric acid, 10. ammonium sulfate.
Table 2 evaluating catalyst result (percentage by weight)
| Catalyst is numbered | Product < C 5，% | Product 2,2-DMB, % | Product nC 6，% | Conversion ratio, % | Isomerization rate, % | Isomerisation selectivity, % |
| 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 table 2,2,2-DMB is 2,2-methybutane; NC
6for n-hexane.
As can be seen from Table 2, compared with being the catalyst prepared of carrier with modenite, catalyst prepared by the present invention has higher conversion ratio and isomerisation selectivity.And the component output being less than C5 is also lower, that is carries out light hydrocarbon isomerization reaction with catalyst of the present invention, higher liquid yield can be obtained, more high-knock rating gasoline can be produced.
Claims (10)
1. an isomerization catalyst composition, it is characterized in that: by weight percentage, catalyst has following composition: VIII race's precious metal element 0.01% ~ 5%, rare earth modified modenite 10% ~ 80%, auxiliary agent rhenium and/or tin 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 being benchmark in rare earth modified modenite weight is for 5% ~ 40%.
2. according to carbon monoxide-olefin polymeric according to claim 1, it is characterized in that: rare-earth oxide load is boiled at mercerising
Stone becomes modified mordenite, and sulfur-containing compound mixes as binding agent with inorganic refractory oxide, VIII race's precious metal element
Infusion process load is adopted with auxiliary agent.
3. according to carbon monoxide-olefin polymeric according to claim 1, it is characterized in that: the SiO2/Al2O3 of rare earth modified modenite
Mol ratio is 5 ~ 70, and in catalyst weight percent, the content of rare earth modified modenite is 20% ~ 70%.
4. according to the carbon monoxide-olefin polymeric described in claim 1 or 3, it is characterized in that: rare-earth oxide be selected from lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and lutetium in oxide one or more, the content of the rare earth oxide in rare earth modified modenite is 10% ~ 30%.
5. according to the carbon monoxide-olefin polymeric described in claim 1 or 3, it is characterized in that: rare-earth oxide is selected from lanthana or/and cerium oxide.
6. according to carbon monoxide-olefin polymeric according to claim 2, it is characterized in that: containing in the binding agent of sulphur, with the content of binding agent dry basis element sulphur for 1.0% ~ 3.0%, sulfur-containing compound is sulfuric acid or ammonium sulfate, and the inorganic refractory oxide in binding agent is aluminium oxide and/or kaolin.
7. according to carbon monoxide-olefin polymeric according to claim 1, it is characterized in that: in catalyst, the VIIIth race's noble metal is platinum and/or palladium.
8. according to the carbon monoxide-olefin polymeric described in claim 1 or 2, it is characterized in that: the binding agent preparation method of sulfur-bearing is:
Sulfate ion is loaded on aluminium hydroxide and/or kaolin, through super-dry and roasting, obtain the inorganic refractory of sulphur modification
Oxide; By material thick for abundant to the inorganic refractory oxide of sulphur modification, peptizing agent and deionized water epoxy glue melt into, as the binding agent of catalyst.
9. the application of heterogeneous catalyst described in the arbitrary claim of claim 1 to 8 in the reaction of C4 ~ C12 alkane isomerization.
10. according to application according to claim 9, it is characterized in that: the reaction temperature of isomerization reaction is 200 ~ 350 DEG C, and pressure is 1.0 ~ 3.0MPa, and 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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Patent 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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