CN102039167A - Method for preparing adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst - Google Patents
Method for preparing adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing an adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst. The method mainly solves the problems of complex preparation process and high cost because a template agent is used in the conventional ZSM-5/Y zeolite symbiotic molecular sieve preparation process. The problems are well solved by adopting the technical scheme that: based on the weight of the shaped and roasted catalyst, 10 to 80 percent of ZSM-5/Y zeolite symbiotic molecular sieve, 0.1 to 10 percent of alkali substance, 0.5 to 20 percent of aluminum compound and 20 to 80 percent of silicon oxide are mixed, shaped and dried, then the mixture is put into water vapor, and the mixture is crystallized for 10 to 200 hours at the temperature of between 100 and 180 DEG C to form the adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst; and the prepared adhesive-free ZSM-5/Y zeolite symbiotic molecular sieve catalyst can be used in the reaction of preparing propylene by catalytic cracking of naphtha.
Description
Technical field
The present invention relates to the preparation method of a kind of adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst.
Background technology
Molecular sieve has good shape selective catalysis performance and absorption property owing to have evenly regular pore passage structure, bigger specific area and higher thermally-stabilised row, is applied in field of petrochemical industry widely.Because molecular sieve powder self intensity is lower, easily disperse to run off, industrially can't directly be applied in use, therefore in use needing to add the binding agent moulding gains in strength, in the catalyst after the moulding, because binding agent parcel molecular sieve, caused the effective rate of utilization of molecular sieve to descend, the duct of the molecular sieve of part is blocked, causes the specific area of catalyst lower, and activity is also lower, again because binding agent is no regular pore passage structure, reaction raw materials and product are in catalyst diffusion difficulty, and carbon deposit has certain influence to life of catalyst easily.Binding agent in the catalyst is converted into the active principle molecular sieve then can overcomes above problem, improve activity of such catalysts and diffusion.
The binder free catalyst is exactly the active principle that the binding agent that is added in the molecular sieve catalyst forming process is changed into molecular sieve, makes not contain the binding agent composition in the whole catalyst, keeps the good intensity of catalyst simultaneously.Be converted into the molecular sieve composition fully owing to binding agent in the binder free catalyst, so just improved the content of molecular sieve in the per volume of catalyst, make activity of such catalysts higher, treating capacity is bigger, simultaneously owing to no longer include binding agent in the catalyst, solved binding agent parcel molecular sieve and reduced the effective rate of utilization of molecular sieve and the problem that binding agent stops up molecular sieve pore passage, the effective rate of utilization of molecular sieve and carbon accumulation resisting ability are improved greatly.General Adhesive-free Molecular Sieve catalyst refers in the catalyst weight of binder content smaller or equal to 5%.
General coexisting molecular sieve is to prepare by the synthetic method of hydro-thermal, is Powdered, and no intensity easily runs off, and can not directly use, and need add binding agent when industry or laboratory applications and carry out extrusion or spray shaping.In the general molecular sieve catalyst forming process, the weight that add binding agent is no less than 40% of total catalyst weight, though the moulding rear catalyst has had intensity, the effective rate of utilization of catalyst reduces, active and diffusion variation.
In the document, the general title of two kinds of molecular sieves of using of the literary style of coexisting molecular sieve is write together at present, and the centre adds one "/" expression, for example, and the coexisting molecular sieve that ZSM-5 and Y zeolite are formed, writing " ZSM-5/Y zeolite coexisting molecular sieve ".
At present the binder free catalyst of report has the adhesiveless ZSM-5 molecular sieve, is to make by gas phase conversion at the presoma that preformed catalyst adds ZSM-5.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent ZSM-5 prepare zeolite method is a primary raw material by adopting with diatomite or white carbon, add the crystal seed directed agents, and with Ludox or sodium metasilicate as the binding agent moulding, handle the technical scheme that is converted into integrated small-grain ZSM-5 with organic amine mutually with the water vapour gas-solid then, mainly solve the weakness that the zeolite powder exists difficult recovery, easy inactivation and gathering in actual applications, and the adding binding agent can cause that effective surface area reduces the problem that influences with diffusion-restricted in the forming process.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.By adopting content is the mixture that the former powder of 5～50 weight % binding agent silica and ZSM type molecule forms, in the aqueous solution that contains halogenation organic amine and alkyl diamine or steam, be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add binding agent in the molecular sieve catalyst forming process and can cause that effective surface area reduces the problem with the diffusion-restricted influence.
Composite molecular screen, coexisting molecular sieve or the mixed crystal molecular sieve of existing report all needs synthetic back of molecular sieve or adding crystal seed directed agents hydro-thermal synthetic, and building-up process is very complicated comparatively.The synthetic ZSM-5/ beta zeolite coexisting molecular sieve of report all is to be prepared from by the synthetic method of hydro-thermal at present.Add crystal seed or template agent in the building-up process, the complicated and pollution again of preparation method.
Directly the method for preparing adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst can be optimized preparation process, avoids the preparation process complicated problems, has tangible economic worth and social value.
Summary of the invention
Technical problem to be solved by this invention is to use template agent, preparation process complexity, cost problem of higher in the process of existing preparation adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst.A kind of new method for preparing adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst is provided.This method has does not use the template agent in the preparation process, preparation process is simple, and cost is lower, advantages such as environmental protection, and the catalyst of preparation has active higher, and the while mechanical strength is advantage of higher also.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of a kind of adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting, after the compound of the ZSM-5/Y zeolite coexisting molecular sieve 10～80%, 0.1～10% alkaline matter, 0.5～20% aluminium and 10～80% the silica mixed-forming drying, obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) mixture I is placed put into water vapour, carry out obtaining adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst precursor after crystallization handles 10～200 hours at 100～180 ℃;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, as the SiO of the ZSM-5/Y zeolite coexisting molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 10～60; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of periodic table of elements IA or IIA element; The compound of aluminium is at least a in the hydroxide of the hydrous oxide of oxide, aluminium of aluminium salt, aluminium or aluminium.
In the technique scheme, IA element preferred version is selected from least a in sodium or the potassium, and IIA element preferred version is selected from least a in magnesium or the calcium; The salt of weak acid preferred version is selected from least a in carbonate, oxalates or the citrate; In the catalyst weight behind the shaping and roasting, the consumption preferable range of organic amine is 10～100%; The compound amount preferable range of aluminium is 2～15%; The consumption preferable range of molecular sieve is 15～70%; The consumption preferable range of alkaline matter is 0.5～5%; The consumption preferable range of silica is 15～70%; The crystallization temperature preferable range is 110～170 ℃; The crystallization time preferable range is 20～100 hours.SiO in the prepared ZSM-5/Y zeolite coexisting molecular sieve
2/ Al
2O
3Preferable range is 10～100; The weight ratio preferable range of ZSM-5 and Y zeolite is 0.1～100: 1 in the ZSM-5/Y zeolite coexisting molecular sieve catalyst, the binder content preferable range is 0～5%, more preferably scope is 0.1～2%, and the preformed catalyst intensity preferable range that makes is 60～180 newton.
It is strip solid cylindrical, that diameter is 0.5～2mm that shape after the catalyst precarsor mixture I extrusion is generally tangent plane, is broken into every grain length degree after the drying and is 5 millimeters short cylindrical shape catalyst bar, is convenient to change brilliant and handles and examination.Catalyst mechanical strength among the present invention is calculated by this shape measure.Catalyst precarsor mixture I also can make cellular as required, clover shape, hollow tubular or shape such as spherical, and its strength criterion is meter in addition.
In the characterization method of binder free catalyst, test the contained thing phase and the content of each thing phase, use the pattern of the molecular sieve of brilliant situation of scanning electron microscopic observation binding agent commentaries on classics and generation with XRD.Change brilliant back binder content determine by the XRD thing mutually quantitatively and in the stereoscan photograph content of binding agent determine.The catalyst silica alumina ratio is determined with chemico-analytic method.The strength test method of catalyst is the crushing strength of the catalyst after test roasting on the pressure testing machine, every of the catalyst of surveying is of a size of 1.5 millimeters of diameters, 5 millimeters of length, be disposed across on the testing machine, suffered maximum pressure when measuring catalyst breakage is got its mean value after testing 10 catalyst crushing strengths.
The present invention is by adding ZSM-5/Y zeolite coexisting molecular sieve crystal seed in preformed catalyst, control is suitable for the alkaline environment and the material proportion of ZSM-5 and Y zeolite growth simultaneously, make binding agent under the inducing of crystal seed, can change into ZSM-5/Y zeolite coexisting molecular sieve active ingredient, obtain binder free type ZSM-5/Y zeolite coexisting molecular sieve catalyst, the content of binding agent can reach below 0.5% in the binder free type ZSM-5/Y zeolite coexisting molecular sieve catalyst that makes, even do not contain binding agent, all ZSM-5/Y zeolite coexisting molecular sieve in the catalyst, improve the content of coexisting molecular sieve in the per volume of catalyst like this, improved activity of such catalysts.Since change the binder free coexisting molecular sieve thing that obtains behind the crystalline substance mutually between staggered growth, in conjunction with tightr, so the intensity of catalyst is also higher, can reach 180 newton/more than.The catalyst that makes can be used in the reaction of naphtha catalytic pyrolysis preparing propylene, and the diene weight yield of ethylene, propylene can reach more than 53%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
Fig. 2 is the ESEM picture of the adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst of embodiment 1 preparation.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Get SiO
2/ Al
2O
3Mol ratio is 20 ZSM-5/Y zeolite coexisting molecular sieve 60 grams, the adding weight percentage is 40% Ludox 40 grams and aluminum sulfate 16 grams, after the mixing and stirring, 10 milliliters of sodium carbonate liquors that add 0.5 mol again, mixing and stirring, agent bar moulding then, preformed catalyst was 80 ℃ of oven dry 3 hours, put into the moisture and hexamethylene diamine mass ratio of inner bag bottom then and be 1: 1 200 milliliters of mixed solution 40 grams autoclave, catalyst does not contact with liquid water, put into baking oven after the autoclave sealing, 165 ℃ of crystallization were taken out after 60 hours, washed then 2 times, put into 120 ℃ of oven dry of baking oven 3 hours, putting into the 400 ℃ of roastings 2 hours that heat up of Muffle furnace internal program, 550 ℃ of roastings 3 hours make adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst, wherein the weight percentage of ZSM-5 molecular sieve is 43.5%, the Y zeolite content is 56.0%, and the XRD figure of the catalyst that makes is composed as shown in Figure 1, and it is shown as the thing phase of ZSM-5/Y zeolite.The ESEM picture of the catalyst that makes as shown in Figure 2, it is shown as the mixture of ball-type ZSM-5 crystal grain and Y zeolite grain, the binder content of unformed state is 0.5%.
[embodiment 2～6]
According to the method for embodiment 1, get SiO respectively
2/ Al
2O
3Mol ratio be 10,20,30,40 and 60 ZSM-5/Y zeolite coexisting molecular sieve as crystal seed, other condition is constant, it is as shown in table 1 that raw material is formed proportioning, the adhesiveless ZSM-5 that makes/Y zeolite coexisting molecular sieve catalyst is as shown in table 2.
[embodiment 7～13]
Method according to embodiment 1, other condition is constant, in forming process, add soluble starch, sesbania powder or methylcellulose, it is as shown in table 1 that raw material is formed proportioning, mixing and stirring, extruded moulding is made adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst by the method for embodiment 1 again, and the result is as shown in table 2.
[embodiment 14]
Method according to embodiment 1 makes the binder free catalyst, it with concentration 5% ammonium nitrate solution, it in the solid-to-liquid ratio of catalyst and ammonium nitrate solution 1: 10 ratio, 90 ℃ of exchanges three times, 550 ℃ of roastings made the adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst of Hydrogen after 3 hours then.The component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index sees Table 3), the examination activity of such catalysts is that 12 millimeters fixed bed reactors normal pressure is checked and rated down with diameter, range of reaction temperature is 650 ℃, reaction pressure is 0.02MPa, mass space velocity is 1 hour
-1, water/feedstock oil mass ratio is 1: 1, and after reaction half an hour, product distributes and to see Table 4, and feed stock conversion is 96%, and the ethene mass yield is 27.0%, and the propylene mass yield is 26.0%, and diene quality total recovery is 53.0%
Table 2
[embodiment 15]
Get the binder free type ZSM-5/Y zeolite that obtains among the embodiment 1, method by embodiment 14 is made hydrogen type catalyst, get 100 grams, with concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.5 mol flooded modification 4 hours at 95 ℃, then sample is taken out 120 ℃ of oven dry 3 hours,, obtain the binder free type ZSM-5/Y zeolite coexisting molecular sieve catalyst of phosphorus modification again 650 ℃ of roastings 3 hours, method according to embodiment 14 is checked and rated, and the results are shown in Table 5.
Table 3 light oil raw material index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.2 |
| Cycloalkane % (weight %) | 28.4 |
| Alkene % (weight %) | 0.2 |
| Aromatic hydrocarbons % (weight %) | 6.2 |
[embodiment 16]
Get binder free type ZSM-5/Y zeolite coexisting molecular sieve catalyst 100 grams of the phosphorus modification that obtains among the embodiment 15, with concentration is that 300 milliliters of the ammonium hydrogen phosphates of 0.2 mol flooded modification 4 hours at 95 ℃, then sample is taken out 120 ℃ of oven dry 3 hours, again 650 ℃ of roastings 3 hours, obtain the binder free type ZSM-5/Y zeolite coexisting molecular sieve catalyst of lanthanum and phosphorus modification, method according to embodiment 14 is checked and rated, and the results are shown in Table 5.
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/Y zeolite mixed crystal molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, then mixed crystal molecular sieve direct tablet compressing, break into pieces, sieve, 20～40 purpose catalyst granules that do not contained binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/Y zeolite mixed crystal molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, and then according to the method extruded moulding of embodiment 1, obtain containing the ZSM-5/Y zeolite mixed crystal molecular sieve catalyst of binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 ZSM-5 molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, then ZSM-5 molecular sieve direct tablet compressing, break into pieces, sieve, 20～40 purpose catalyst granules that do not contained binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 10 Y zeolite, make Hydrogen Y zeolite by the method for embodiment 14, then β zeolite direct tablet compressing, break into pieces, sieve, 20～40 purpose catalyst granules that do not contained binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 5]
The silica alumina ratio that Shanghai petrochemical industry research institute produces is 40 ZSM-5 molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, method by embodiment 14 is made hydrogen type molecular sieve, and then according to the method extruded moulding of embodiment 1, obtain containing the ZSM-5 molecular sieve catalyst of binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 6]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 10 Y zeolite, method by embodiment 14 is made hydrogen type molecular sieve, make Hydrogen Y zeolite by the method for embodiment 14 then, and then according to the method extruded moulding of embodiment 1, obtain containing the beta zeolite coexisting molecular sieve catalyst of binding agent, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
[comparative example 7]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 ZSM-5, silica alumina ratio is 10 Y zeolite, be mixed into mechanical impurity at 1: 1 according to weight ratio, method by embodiment 14 is made hydrogen type molecular sieve, and then, obtain containing the ZSM-5 of binding agent and the catalyst of Y zeolite mechanical impurity according to the method extruded moulding of embodiment 1, put into fixed bed reactors, press the method examination of embodiment 14, the results are shown in Table 5.
Table 4
| Product distributes | Product weight yield (%) |
| Methane | 4.5 |
| Ethane | 6.5 |
| Ethene | 28.0 |
| Propane | 6.1 |
| Propylene | 27.5 |
| Butane | 8.2 |
| Butylene | 7.4 |
| Carbon five above cuts | 8.3 |
| Other | 3.5 |
Table 5
Claims (7)
1. the preparation method of adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting, after the compound of the ZSM-5/Y zeolite coexisting molecular sieve 10～80%, 0.1～10% alkaline matter, 0.5～20% aluminium and 10～80% the silica mixed-forming drying, obtain preformed catalyst precursor mixture I, wherein among the mixture I compound weight content of aluminium less than the weight content of silica;
B) mixture I is placed put into water vapour, carry out obtaining adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst precursor after crystallization handles 10～200 hours at 100～180 ℃;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst through super-dry;
Wherein, in the catalyst weight behind the shaping and roasting, template agent is 5～300%, as the SiO of the ZSM-5/Y zeolite coexisting molecular sieve of crystal seed
2/ Al
2O
3Mol ratio is 10～60; Alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of period of element Table I A or II A element; The compound of aluminium is at least a in the hydroxide of the hydrous oxide of oxide, aluminium of aluminium salt, aluminium or aluminium.
2. the preparation method of adhesiveless ZSM-5 according to claim 1/Y zeolite coexisting molecular sieve catalyst is characterized in that the IA element is selected from least a in sodium or the potassium, and the IIA element is selected from least a in magnesium or the calcium; Salt of weak acid is selected from least a in carbonate, oxalates or the citrate.
3. the preparation method of adhesiveless ZSM-5 according to claim 1/Y zeolite coexisting molecular sieve catalyst, in the catalyst weight behind the shaping and roasting, the consumption of molecular sieve is 20～70%; The consumption of alkaline matter is 0.5～5%; The compound amount of aluminium is 2～15%; The consumption of silica is 15～70%; Template agent is 10～100%.
4. the preparation method of adhesiveless ZSM-5 according to claim 1/Y zeolite coexisting molecular sieve catalyst is characterized in that crystallization temperature is 110～170 ℃, and crystallization time is 20～100 hours.
5. the preparation method of adhesiveless ZSM-5 according to claim 1/Y zeolite coexisting molecular sieve catalyst, it is characterized in that in the catalyst weight behind the shaping and roasting, also contain 0.1～2% the expanding agent at least a in sesbania powder, methylcellulose or the soluble starch that is selected among the preformed catalyst precursor mixture I.
6. the preparation method of adhesiveless ZSM-5 according to claim 1/Y zeolite coexisting molecular sieve catalyst is characterized in that the adhesiveless ZSM-5/Y zeolite coexisting molecular sieve catalyst that makes contains SiO
2/ Al
2O
3Mol ratio is 10～100 ZSM-5/Y zeolite; Weight of binder content 0～5%; The weight ratio of ZSM-5 and Y zeolite is 0.15～100: 1 in the ZSM-5/Y zeolite coexisting molecular sieve, the mechanical strength of preformed catalyst be 60～180 newton/.
7. the preparation method of adhesiveless ZSM-5 according to claim 6-Y zeolite coexisting molecular sieve catalyst, it is characterized in that in the catalyst weight behind the shaping and roasting weight of binder content is 0.1～2% in the adhesiveless ZSM-5 that makes/Y zeolite coexisting molecular sieve catalyst.
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| CN104096590A (en) * | 2013-04-10 | 2014-10-15 | 上海碧科清洁能源技术有限公司 | Hybrid molecular sieve catalyst and its preparation method and application |
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| CN1276873C (en) * | 2004-01-19 | 2006-09-27 | 中国石油化工股份有限公司 | Processfor preparing mordenite and beta zeolite mixed crystal material |
| CN100384735C (en) * | 2005-08-15 | 2008-04-30 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 zeolite in small crystal grain without bonding agent |
| CN100567152C (en) * | 2007-04-04 | 2009-12-09 | 中国石油化工股份有限公司 | Magadiite/ZSM-5 coexisting material and synthetic method thereof |
| CN101514013B (en) * | 2008-02-20 | 2011-05-18 | 中国石油化工股份有限公司 | ZSM-5/Magadiite/mordenite coexisting material and method for synthesizing same |
| CN101514012B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | ZSM-5/Magadiite/beta zeolite coexisting material and method for synthesizing same |
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| CN104096590A (en) * | 2013-04-10 | 2014-10-15 | 上海碧科清洁能源技术有限公司 | Hybrid molecular sieve catalyst and its preparation method and application |
| WO2014166372A1 (en) * | 2013-04-10 | 2014-10-16 | 上海碧科清洁能源技术有限公司 | Mixed molecular sieve catalyst and preparation method and use thereof |
| CN104096590B (en) * | 2013-04-10 | 2016-09-14 | 上海碧科清洁能源技术有限公司 | Mixed molecular sieve catalyst and its preparation method and application |
| US9908111B2 (en) | 2013-04-10 | 2018-03-06 | Shanghai Bi Ke Clean Energy Technology Co., Ltd. | Mixed molecular sieve catalyst and preparation method and use thereof |
| CN112657546A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Xylene olefin reduction catalyst and preparation method and application thereof |
| CN112657546B (en) * | 2019-10-16 | 2023-09-29 | 中国石油化工股份有限公司 | Xylene olefin reduction catalyst and preparation method and application thereof |
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