CN103041844A - Isomerization catalyst containing modified mordenite and application thereof - Google Patents
Isomerization catalyst containing modified mordenite and application thereof Download PDFInfo
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Abstract
The invention discloses an isomerization catalyst containing modified mordenite and an application thereof. The catalyst is prepared from the following components in percentage by weight: 0.01-5% of noble metal element in the group VIII, 10-80% of phosphorus-modified mordenite, 0.1-10% of additives and the balance of binder containing 0.5-5.0% of halogen, wherein the weight of phosphorus in the modified mordenite accounts for 0.1-10%. The catalyst is used for the isomerization of C4-C12 alkane, has the characteristics of high catalytic activity and high isoolefine selectivity and can be used for producing the high-octane gasoline blending component.
Description
Technical field
The present invention relates to a kind of catalyst for isomerizing light hydrocarbon and application thereof, in particular, the present invention relates to a kind of isomerization catalyst and the application of this catalyst in C4～C12 alkane isomerization reaction that contains modified mordenite.
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 of auxiliary agent and its preparation method and application.This catalyst is used for the isomerization process of low-carbon alkanes, has the selective high of catalytic activity and isomeric olefine, can effectively improve the octane number that improves them.
The present invention contains the modified mordenite isomerization catalyst, by weight percentage, this catalyst has following composition: the binding agent of VIII family precious metal element 0.01% ~ 5%, phosphorus modified mordenite 10% ~ 80%, auxiliary agent 0.1% ~ 10%, surplus halogen-containing 0.5% ~ 5.0%, wherein the weight content of P elements in the phosphorus modified mordenite is 0.1% ~ 10.0%.
In the catalyst of the present invention, phosphorus-containing compound loads on becomes the phosphorus modified mordenite on the modenite, and halogen mixes as binding agent with inorganic refractory oxide, and VIII family precious metal element and auxiliary agent adopt the infusion process load.
In the catalyst of the present invention, the SiO of phosphorus modified mordenite
2/ Al
2O
3Mol ratio is 5 ~ 70, is preferably 10～60, and by weight percentage, the content of phosphorus modified mordenite is preferably 20% ~ 70% in the catalyst; Described phosphorus modified mordenite is the h-type zeolite that contains P elements.Directly synthetic zeolite generally contains the cation of alkali metal or alkaline-earth metal, can obtain h-type zeolite by the method for roasting after the ammonium ion exchange of routine, then the load P elements obtains the phosphorus modified mordenite, also can be through conventional modification, such as hydrothermal treatment consists, acid treatment etc.The weight content of P elements in the phosphorus modified mordenite is preferably 0.5%～5.0%.In the mixture of the described binding agent that contains halogen, the weight content of halogen (in butt) is preferably 1.0% ~ 3.0%; Described halogen is one or more in fluorine, chlorine and the bromine, is preferably chlorine.In the catalyst of the present invention, VIII family precious metal element is preferably platinum and/or palladium, most preferably is platinum, and the content in catalyst is preferably 0.1% ~ 3.0% in metal.Described auxiliary agent rhenium and/or tin, the 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 the 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 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 isomerization reaction temperature is controlled to be 200 ~ 350 ℃, is preferably 230 ~ 300 ℃; Pressure is 1.0 ~ 3.0MPa, is 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 the modenite of P elements modification and the binding agent that contains halogen.Owing to select P elements that molecular sieve is carried out modification, acid position effect by phosphorus and molecular sieve, the acid strength of molecular sieve is reduced, so that the lytic activity of catalyst is down to is minimum, 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 heterogeneous activity of catalyst; Owing to contain aluminium oxide or silica in the binding agent, the binding agent through halogen modified can produce a large amount of L acid sites, and L acid position is affected by Electronic Performance, can improve the isomerization reaction performance of catalyst.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) preparation of phosphorus modified mordenite: in the aqueous solution dipping h-mordenite with phosphorus-containing compound, then pass through conventional drying and roasting, get the phosphorus modified mordenite;
(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 modified mordenite 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 the step (1), described phosphorus-containing compound is selected from phosphoric acid, hydrophosphate or dihydric phosphate, such as ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) etc.Gu the liquid of control phosphorus-containing compound solution during dipping/than being 1 ~ 10(unit: mL solution/g solid), 10 ~ 90 ℃ of dipping temperatures, dip time 1 ~ 24 hour.
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 the used compound of halogen-containing solution and be and be selected from hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and the hydrofluoric acid one or more, 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 hydrochloric acid, ammonium chloride, ammonium fluoride, ammonium bromide, hydrobromic acid and the hydrofluoric acid one or more, 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 the 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 in the aluminium stone one or more.
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 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 (3) 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 weight, is preferably 1% ~ 5%.
The mode that step (4) 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), (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 ℃ and keeps 0.5h ~ 10.0h that step (1), step (3) and the described roasting condition of step (4) 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 isomeric 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, hydrogen hydrocarbon 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) (1) disposes the phosphate aqueous solution of 0.5mol/L, then adopts method and the modenite (SiO of incipient impregnation
2/ Al
2O
3Mol ratio is 18), 80 ℃ of dippings are after 2 hours, and through 120 ℃ of oven dry, roasting is 5 hours in 550 ℃ of air, obtains modified mordenite, is designated as S-1, and wherein the weight content of P elements in zeolite is 1.5%.
(2) be that 10%(is in halogen with 200 gram mass concentration) ammonium chloride solution, 450 gram (take aluminium oxide) aluminium hydroxides (SB that German Condean company produces), 1000ml water and 60ml red fuming nitric acid (RFNA) (mass concentration is 66.5%), fully mix.Obtain the halogen weight content and be 3.2% adhesive (in butt).
(3) get binding agent, the 6 gram sesbania powder that 120 modified mordenites that make of gram steps (1), 100 gram (2) 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.
(4) 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 ammonium chloride with ammonium bromide, replaces phosphoric acid with ammonium dihydrogen phosphate aqueous solution, 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
The preparation of catalyst E-3 of the present invention
The preparation process of catalyst E-3 of the present invention is with embodiment 1, and difference is to replace phosphoric acid with ammonium dibasic phosphate aqueous solution, and the catalyst of the present invention of preparing is numbered E-3, and its catalyst composition sees Table 1, and reaction result sees Table 2.
Embodiment 4 ~ 7
The preparation of catalyst E-4 ~ E-7 of the present invention
The preparation process of catalyst E-4 ~ E-7 of the present invention is with embodiment 1, and the amount of the used phosphorus-containing compound of difference, molecular sieve, halogen and rhenium is different, the catalyst E-4 ~ 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 the processing of the phosphorus-containing compound aqueous solution, 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 the processing of the phosphorus-containing compound aqueous solution, does not contain halogen 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 the processing of the phosphorus-containing compound aqueous solution, does not contain halogen in the binding agent.Also do not contain auxiliary agent in the catalyst, be numbered C-3, its physico-chemical property sees Table 1, and reaction result sees Table 2.
The main physico-chemical property (weight percentage) of table 1 catalyst
| Catalyst | Phosphorus element-containing/modified molecular screen, % | Halogen/binding agent, % | Pt,% | Auxiliary agent, % | Pd,% |
| E-1 | 1.5/50.0 | 3.2/ surplus | 0.3 | 0.8⑦ | - |
| E-2 | 1.5/50.0 | 1.8/ surplus | - | 1.2⑦ | 0.4 |
| E-3 | 1.5/50.0 | 1.5/ surplus
 |
0.4 | 1.5⑧ | - |
| E-4 | 5.0/30.0 | 0.8/ surplus | 0.2 | 2.3⑦ | 0.2 |
| E-5 | 4.1/60.0 | 2.2/ surplus | 1.0 | 3.8⑧ | 0.1 |
| E-6 | 2.3/70.0 | 1.1/ surplus | - | 5.0⑦ | 1.5 |
| E-7 | 3.9/80.0 | 4.6/ surplus | 1.3 | 2.7⑧ | -- |
| C-1 | 0/50.0 | 1.5/ surplus | 1.0 | 2.1⑦ | 0.3 |
| 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:Molecular sieve is h-mordenite in the table 1, is aluminium oxide except particularly pointing out binding agent.
Phosphorus element content 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; Binding agent is 30wt% kaolin and surplus aluminium oxide among the E-3,7. refers to the auxiliary agent rhenium, 8. refers to auxiliary agent tin.
Table 2 evaluating catalyst result (percentage by weight)
| Catalyst | Product＜C 5，% | Product 22DMB, % | Product nC 6，% | Conversion ratio, % | Isomerization rate, % | Isomerization is selective, % |
| E-1 | 0.83 | 18.53 | 15.89 | 84.12 | 83.98 | 18.68 |
| E-2 | 0.62 | 18.08 | 17.3 | 82.7 | 82.60 | 18.20 |
| E-3 | 0.87 | 17.58 | 16.19 | 83.82 | 83.68 | 18.73 |
| E-4 | 0.81 | 17.00 | 17.08 | 82.93 | 82.79 | 17.15 |
| E-5 | 0.64 | 18.23 | 16.32 | 83.68 | 83.58 | 18.35 |
| E-6 | 0.84 | 18.63 | 16.51 | 83.49 | 83.35 | 18.79 |
| E-7 | 0.77 | 17.68 | 16.77 | 83.23 | 83.1 | 17.82 |
| 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 |
22DMB is 2,2-methybutane in the table 2; 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 that contains modified mordenite, it is characterized in that catalyst consists of in catalyst weight percentage: the binding agent of VIII family precious metal element 0.01% ~ 5%, phosphorus modified mordenite 10% ~ 80%, auxiliary agent 0.1% ~ 10%, surplus halogen-containing 0.5% ~ 5.0%; Wherein the weight content of P elements in the phosphorus modified mordenite is 0.1% ~ 10.0%.
2. according to catalyst claimed in claim 1, it is characterized in that: phosphorus-containing compound loads on becomes the phosphorus modified mordenite on the modenite, halogen 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 catalyst claimed in claim 1, it is characterized in that: the SiO of phosphorus modified mordenite
2/ Al
2O
3Mol ratio is 5 ~ 70, and in catalyst weight percentage, the content of phosphorus modified mordenite is 20% ~ 70%, and described phosphorus modified mordenite is the h-type zeolite that contains P elements.
4. according to claim 1 or 3 described catalyst, it is characterized in that: the weight content of P elements in the phosphorus modified mordenite is 0.5%～5.0%.
5. according to catalyst claimed in claim 1, it is characterized in that: contain in the mixture of binding agent of halogen, the weight content of halogen counts 1.0% ~ 3.0% with butt.
6. according to claim 1 or 5 described catalyst, it is characterized in that: halogen is one or more in fluorine, chlorine and the bromine.
7. according to catalyst claimed in claim 1, it is characterized in that: VIII family precious metal element is platinum and/or palladium, and the content in catalyst counts 0.1% ~ 3.0% with metal.
8. according to catalyst claimed in claim 1, it is characterized in that: auxiliary agent is rhenium and/or tin.
9. the application of the described 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 isomerization reaction temperature 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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Cited By (1)
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|---|---|---|---|---|
| CN116477638A (en) * | 2023-03-23 | 2023-07-25 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of high-stability mordenite molecular sieve |
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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477638A (en) * | 2023-03-23 | 2023-07-25 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of high-stability mordenite molecular sieve |
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