CN104549452B - Toluene and methanol alkylation catalyst and preparation method and application thereof - Google Patents
Toluene and methanol alkylation catalyst and preparation method and application thereof Download PDFInfo
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a toluene and methanol alkylation catalyst and a preparation method and application thereof. A catalyst carrier contains a hydrogen-type ZSM-48 molecular sieve and a modified element which comprises one or several of lanthanum, magnesium, phosphorus and silicon, the content (in percentage by weight ) of the hydrogen-type ZSM-48 molecular sieve in the carrier is 10wt%-90wt%, and preferably 20wt%-80wt%; the modified element contains one or several of lanthanum, magnesium, phosphorus and silicon and is calculated according to oxides, and the modified element accounts for 0.05%-60% of the weight of the carrier, and preferably 0.5%-40%. The catalyst is used for an alkylation reaction of toluene and methanol, and has the characteristics that the conversion rate of the toluene is high, the selectivity of paraxylene is high, and the like.
Description
Technical field
The present invention relates to a kind of toluene and methanol alkylation catalyst and its preparation method and application.
Background technology
Xylol (px) is one of main basic organic of petrochemical industry, in chemical fibre, synthetic resin, pesticide, doctor
Numerous chemical production field such as medicine, plastics has extensive purposes.In recent years, swift and violent with p-phthalic acid (pta) production capacity
Increase, China presents the xylol situation that supply falls short of demand, price remains high.
Mainly from petroleum reforming product, the c9 aromatic hydrocarbons of drippolene coking benzene-type and toluene disproportionation are anti-in the source of xylol
The mixed xylenes that should obtain, through prepared, the Shao Liangcong of absorption or Crystallization Separation and o-, m- xylene isomerization process
The transalkylation of trimethylbenzene and obtain.Because petroleum resources are limited, and as reformer feed Petroleum in oil average proportions
Less than 1/5, therefore, new raw material sources are sought significant.In recent years, exploitation methanol and alkylation of toluene synthesize two
The process route of toluene, causes the great interest of Chinese scholars.If enabling to be directly synthesized xylol, decreasing and separating
The operation of extractive distillation, and do not need to carry out adsorbing separation to unreacted xylol, reduce production cost, there is stream
Journey is short, the low feature of energy consumption, has very big economic worth.
In the research work in past, the zeolite molecular sieve synthesizing xylol for alkylation of toluene methanol mainly has
Zsm-5, x zeolite, y zeolite, modenite, sapo-5 and sapo-11 etc., but most study, catalytic performance are preferably also
It is zsm-5 zeolite.Zsm-5 zeolite is a kind of mesopore high-silica zeolite, and it has unique three-dimensional channel structure and acid strength is divided
Cloth, most apertures, in 0.55nm, have the characteristic of high silica alumina ratio and oleophilic drainage, a hydrothermally stable simultaneously having had
Property and the high feature of catalysis activity.Therefore, people by zsm-5 molecular sieve be used for toluene react with methanol alkylation carried out a large amount of
Research.Cn1915512a, cn85102699a, cn85102764a, cn1915514a, cn1830927a etc. have reported will
Zsm-5 molecular sieve is used for alkylation of toluene methanol and reacts.Existing methanol and the activity and selectivity of alkylation of toluene catalyst
Also need to improve further.
Cn101722035a reports the catalyst that a kind of core-shell structure compound molecular sieve is main composition, wherein hud typed
The nuclear phase of molecular sieve is selected from zsm-5, zsm-11, zsm-35, zsm-48, β, modenite, mcm-22 or phosphate aluminium molecular sieve, shell
Molecular sieve is continuously fine and close zsm-5 crystal grain.Due to top layer high silica alumina ratio, (silicon oxide is rubbed the catalyst of its preparation with aluminium oxide
You ratio) zsm-5 molecular sieve presence, improve the selectivity of xylol, but be also due to top layer high silica alumina ratio zsm-5
The presence of molecular sieve, the acidity sacrificing surface result in the reduction of xylene conversion rate.
Nineteen eighty-three, patent us4397827 reported first has synthesized zsm-48 molecular sieve.Zsm-48 molecular sieve is a kind of tool
There is the molecular sieve of ten annulus pore passage structures, aperture is 0.53nm × 0.56nm.The zsm-48 molecular sieve of pure silicon is in synthesis gas alkene
In the reaction of hydrocarbon, there is good selectivity of light olefin, and the zsm-48 molecular sieve of low silica-alumina ratio is due to having good catalysis
Performance, has obtained the extensive concern of people.Patent us7482300 b2 and us7625478 b2 describes compared with low silica-alumina ratio
(the zsm-48 molecular sieve of minimum 60) is used in the course of reaction of hydroisomerizing dewaxing, shows good catalytic performance,
Under conditions of conversion ratio reaches 90%, isomerized products yield improves about 4.0%.
Content of the invention
For the deficiencies in the prior art, the present invention provides a kind of toluene and methanol alkylation catalyst and preparation method thereof,
This catalyst is reacted with methanol alkylation for toluene, has the features such as toluene conversion is high, Selectivity for paraxylene is high.
Toluene of the present invention and methanol alkylation catalyst, contain Hydrogen zsm-48 molecular sieve in carrier, modifying element is lanthanum,
One or more of magnesium, phosphorus or silicon；With weight, in carrier Hydrogen zsm-48 molecular sieve content be 10wt% ~
90wt%, preferably 20wt% ~ 80wt%；In terms of oxide, modifying element is the 0.05% ~ 60% of vehicle weight to modifying element, preferably
0.5%~40%.
In catalyst of the present invention, the described silicon oxide of Hydrogen zsm-48 molecular sieve is 25 ~ 50 with the mol ratio of aluminium oxide.
In catalyst of the present invention, in described carrier, contain inorganic refractory oxide, inorganic refractory oxide is permissible simultaneously
Selected from one or more of aluminium oxide, titanium oxide, silicon oxide and clay, preferably aluminium oxide and/or silicon oxide, more preferably
Aluminium oxide.Inorganic refractory oxide is the 10% ~ 90% of vehicle weight, preferably 20% ~ 80%.The precursor of inorganic refractory oxide can
Selected from boehmite, boehmite, diaspore, gibbsite with visit one or more of aluminum stone, preferably to intend
Boehmite.
Toluene of the present invention and the preparation method of methanol alkylation catalyst, including following two modes:
(1) make catalyst carrier by after Hydrogen zsm-48 molecular sieve and inorganic refractory oxide kneading and compacting, then adopt
With the loaded modified elemental constituent of infusion process, drying, roasting obtain toluene and methanol alkylation catalyst；
(2) by after Hydrogen zsm-48 molecular sieve, inorganic refractory oxide and modifying element compound kneading and compacting, warp is dry
Dry, roasting obtains toluene and methanol alkylation catalyst.
Wherein, drying condition is as follows: baking temperature is 15 ~ 300 DEG C, preferably 100 ~ 150 DEG C, and drying time is little for 1 ~ 48
When.Roasting condition is as follows: sintering temperature is 400 ~ 800 DEG C, preferably 500 ~ 700 DEG C, and roasting time is 0.5 ~ 24 hour, preferably
For 2 ~ 8 hours.
In catalyst preparation process of the present invention, can be as needed using suitable binding agent, binding agent can be existing
Conventional binding agent, for example little porous aluminum oxide etc. in technology.During kneading and compacting, can add commonly used in the prior art
Peptization acid and extrusion aid, peptization acid such as nitric acid, hydrochloric acid, acetic acid and citric acid etc., extrusion aid is the material being conducive to extruded moulding,
As graphite, starch, cellulose and sesbania powder etc..
In catalyst of the present invention, Hydrogen zsm-48 molecular sieve is the zsm-48 molecular sieve of synthesis through ammonium ion exchange-roasting
Method obtain, process is as follows: impregnates zsm-48 molecular sieve 2 ~ 6 times at 30 ~ 90 DEG C using ammonium nitrate solution, 400 ~ 600
DEG C roasting 1 ~ 6 hour.
The zsm-48 molecular sieve of present invention synthesis has the property that silicon oxide is 25 ~ 50 with the mol ratio of aluminium oxide.Than
Surface is 250 ~ 400m2/ g, pore volume is 0.25 ~ 0.35cm3/ g, average pore size is 3 ~ 5nm.
The preparation method of the zsm-48 molecular sieve of present invention synthesis, comprises the steps:
(1) crystal seed zsm-48, template, silicon source, silicon source, sodium hydroxide and water mix homogeneously are prepared reactant mixture；
(2) by the reactant mixture of step (1) at 150 ~ 170 DEG C, hydrothermal crystallizing 4 ~ 8 days, crystallization product is through filtering, washing
Wash, be dried and the prepared zsm-48 molecular sieve of roasting.
In the inventive method, the reactant mixture of step (1) has following composition, mol ratio in terms of oxide: r/sio2=
0.05~0.2；sio2/al2o3=30~50；na2o/sio2=0.06~0.1；h2o/sio2=15~23； s/sio2=0.05 ~ 0.5(matter
Amount ratio)；Wherein sio2Do not include the sio in crystal seed zsm-482, s is crystal seed zsm-48 molecular sieve, and r is 12- crown ether -4.
In the inventive method, the temperature preparing reactant mixture between 20 ~ 90 DEG C, between preferably 50 ~ 80 DEG C.
In the inventive method, crystal seed zsm-48 molecular sieve is the sodium form molecular sieve of roasting or the sodium form molecular sieve of non-roasting,
The mol ratio of silicon oxide and aluminium oxide is between 30 ~ 150.
In the inventive method, template is 12- crown ether -4.
In the inventive method, silicon source is White Carbon black, and silicon source is sodium aluminate.
In the inventive method, silicon source will add after silicon source is completely dissolved.
Catalyst of the present invention is used for methanol and alkylation of toluene produces the course of reaction of xylol, and reaction condition is generally
Methanol is 1:1 ~ 1:10 with the mol ratio of toluene, and reaction pressure is 0.1 ~ 5.0mpa, and reaction temperature is 350 ~ 500 DEG C, hydrogen oil
(hydrogen with toluene and methanol standard state under) volume ratio is 300:1 ~ 3000:1, the cumulative volume air speed of toluene and methanol is 0.5 ~
6 h-1.
Zsm-48 molecular sieve provided by the present invention is a kind of molecular sieve with ten annulus two-dimensional channel structures, and aperture is
0.53nm × 0.56nm, has extraordinary shape selectivity.The zsm-48 molecular sieve silica alumina ratio of technology preparation at present is higher (minimum
Also only have 60), lead to acid amount low, show the low phenomenon of catalysis activity during the course of the reaction, directly affecting its industry should
With.Using the zsm-48 molecular sieve between 25 ~ 50 for the silica alumina ratio of the inventive method preparation, improve sour density and the acid of molecular sieve
Amount, is that the carrying out of course of reaction provides more active center.By the introducing of metal, the Acidity to catalyst, especially
That the acidic site of molecular sieve surface is adjusted, the generation of suppression side reaction it is ensured that dominant response occurs all in duct, by
In the particularity of pore passage structure, suppress the generation of by-product, substantially increase the selectivity of purpose product.This catalyst is used for first
In benzyl alcohol alkylation process, with respect to existing molecular sieve catalyst, toluene conversion and Selectivity for paraxylene are all
It is greatly improved.
Brief description
Fig. 1 is X-ray diffraction (xrd) spectrogram of the zsm-48 molecular sieve of the embodiment of the present invention 1 preparation.
Specific embodiment
Further illustrate technology contents and the effect of the present invention with reference to embodiment.
Catalyst of the present invention is evaluated using 10ml fixed-bed micro-reactor, with toluene and methanol as raw material, toluene
It is 2:1 with methanol molar ratio, loaded catalyst is 5g (40 ~ 60 mesh), before charging, catalyst is carried out activating two hours, activation
Condition is: 440 DEG C of temperature, pressure 0.2mpa.Product carries out quantitative analyses on gas chromatograph.Evaluating catalyst technique
Condition is: pressure 0.2mpa, 440 DEG C of temperature, and hydrogen to oil volume ratio is under 900:1(standard conditions), the cumulative volume of toluene and methanol
Air speed is 2.0h-1.
Toluene conversion (%)=(aromatic hydrocarbons total mole number in the molal quantity/product of toluene in 1- product) × 100%.
Dimethylbenzene total mole number × 100% in xylol molal quantity/product in Selectivity for paraxylene (%)=product.
Embodiment 1
(1) sodium hydroxide and sodium aluminate (al are weighed2o3, 43wt%；na2O, 38wt%) it is dissolved in deionized water, then in water
Bath temperature adds template r(12- crown ether -4, content under the conditions of being 60 DEG C while stirring > 97%), after stirring 0.5 hour, add
White carbon, stirring added crystal seed s after 1 hour, moved on in airtight stainless steel cauldron after continuing stirring 2 hours.
(2) crystallization 6 days at 160 DEG C, the crystallization product obtaining is analyzed as zsm-48 molecular sieve through xrd, and concrete raw material is joined
It is shown in Table 1 than with product characteristicses.
Embodiment 2
(1) with embodiment 1 step (1).
(2) crystallization 8 days at 158 DEG C, the crystallization product obtaining is analyzed as zsm-48 molecular sieve through xrd, and concrete raw material is joined
It is shown in Table 1 than with product characteristicses.
Embodiment 3
(1) with embodiment 1 step (1), bath temperature is 80 DEG C.
(2) crystallization 5 days at 160 DEG C, the crystallization product obtaining is analyzed as zsm-48 molecular sieve through xrd, and concrete raw material is joined
It is shown in Table 1 than with product characteristicses.
Embodiment 4
(1) process of zsm-48 molecular sieve
The zsm-48 molecular sieve 400g that Example 1 is obtained, the ammonium nitrate solution being 50% with 800g mass concentration is at 80 DEG C
Exchange 3 times, 2 hours every time.110 DEG C of dryings 6 hours, 550 DEG C of roastings 4 hours, prepared Hydrogen zsm-48 molecular sieve.
(2) preparation of catalyst
Take step (1) be obtained Hydrogen zsm-48 molecular sieve 80g, sb powder 28g, sesbania powder 2.50g, mix homogeneously, then
Add 60g deionized water, 2.50ml concentrated nitric acid (66.5w%) and 2.50ml citric acid, abundant kneading, is allowed on chaser
The cylindrical bars of diameter 1.5mm for paste plastic, are extruded on banded extruder, 110 DEG C of dryings 8 hours, then in air atmosphere
550 DEG C of roastings obtain catalyst carrier z1 in 4 hours；Take appropriate carrier z1, form loaded modified elements La and magnesium by table 1.First
Impregnated using lanthanum nitrate hexahydrate, then in 110 DEG C of dryings 6 hours, 540 DEG C of roastings 4 hours.Soaked with magnesium acetate solution again
Stain, then in 110 DEG C of dryings 6 hours, 540 DEG C of roastings obtain catalyst c1 in 4 hours.Catalyst composition and evaluation result are shown in Table 2.
Embodiment 5
Appropriate carrier z1 in Example 4, is impregnated using lanthanum nitrate hexahydrate, then in 110 DEG C of dryings 6 hours,
540 DEG C of roastings obtain catalyst c2 in 4 hours.Catalyst composition and evaluation result are shown in Table 2.
Embodiment 6
Appropriate carrier z1 in Example 4, is impregnated using magnesium acetate solution, then in 110 DEG C of dryings 6 hours, 540 DEG C
Roasting obtains catalyst c3 in 4 hours.Catalyst composition and evaluation result are shown in Table 2.
Embodiment 7
Appropriate carrier z1 in Example 4, is impregnated using lanthanum nitrate hexahydrate, then in 110 DEG C of dryings 6 hours,
540 DEG C of roastings 4 hours.Impregnated with magnesium acetate solution again, then in 110 DEG C of dryings 6 hours, 540 DEG C of roastings 4 hours, then use phosphorus
Acid dihydride ammonium salt solution dipping obtains catalyst c4.Catalyst composition and evaluation result are shown in Table 2.
Embodiment 8
Appropriate carrier z1 in Example 4, using the cyclohexane solution dipping of tetraethyl orthosilicate, then dry at 110 DEG C
Dry 6 hours, 540 DEG C of roastings obtained catalyst c5 in 4 hours.Catalyst composition and evaluation result are shown in Table 2.
Comparative example 1
With silica/alumina molar ratio be 25 zsm-5 molecular sieve as catalysis material, first according to the method for embodiment 4
It is exchanged for Hydrogen.Take hzsm-5 molecular sieve 80g, sb powder 28g, sesbania powder 2.50g, mix homogeneously, be subsequently adding 60g go from
Son, 2.50ml concentrated nitric acid (66.5w%) and 2.50ml citric acid, on chaser, abundant kneading, makes paste plastic,
The cylindrical bars of diameter 1.5mm are extruded on banded extruder, 110 DEG C of dryings 8 hours, then 550 DEG C of roastings 4 hours in air atmosphere
Obtain catalyst carrier z2；Take appropriate carrier z2, impregnated using lanthanum nitrate hexahydrate, then in 110 DEG C of dryings 6 hours, 540
DEG C roasting 4 hours.Impregnated with magnesium acetate solution again, then in 110 DEG C of dryings 6 hours, 540 DEG C of roastings obtain catalyst in 4 hours
bc1.Catalyst composition and evaluation result are shown in Table 2.
Comparative example 2
Take the appropriate carrier z2 in comparative example 1, impregnated using lanthanum nitrate hexahydrate, then in 110 DEG C of dryings 6 hours,
540 DEG C of roastings obtain catalyst bc2 in 4 hours.Catalyst composition and evaluation result are shown in Table 2.
Comparative example 3
With commercially available silica/alumina molar ratio be 120 zsm-48 molecular sieve as catalysis material, first according to embodiment
4 method is exchanged for Hydrogen zsm-48 molecular sieve.Take Hydrogen zsm-48 molecular sieve 80g, sb powder 28g, sesbania powder 2.50g,
Mix homogeneously, is subsequently adding 60g deionization, 2.50ml concentrated nitric acid (66.5w%) and 2.50ml citric acid, on chaser fully
Kneading, makes paste plastic, extrudes the cylindrical bars of diameter 1.5mm, 110 DEG C of dryings 8 hours, Ran Hou on banded extruder
In air atmosphere, 550 DEG C of roastings obtain catalyst carrier z3 in 4 hours；Take appropriate carrier z3, with magnesium acetate solution dipping, Ran Hou
110 DEG C of dryings 6 hours, 540 DEG C of roastings obtain catalyst bc3 in 4 hours.Catalyst composition and evaluation result are shown in Table 2.
Table 1 zsm-48 Zeolite synthesis proportioning raw materials and product property.
Table 2 catalyst composition and evaluation result.
As can be seen from the table, in the case of composition identical, catalyst of the present invention has higher activity (performance
For toluene conversion) and higher purpose product selectivity (showing as the selectivity of xylol).
Claims (14)
1. a kind of toluene and methanol alkylation catalyst it is characterised in that: carrier is Hydrogen zsm-48 molecular sieve and inorganic refractory
Oxide, modifying element is one or more of lanthanum, magnesium, phosphorus or silicon；In terms of oxide, modifying element is carrier to modifying element
The 0.05% ~ 60% of weight；The wherein said silicon oxide of Hydrogen zsm-48 molecular sieve is 25 ~ 50 with the mol ratio of aluminium oxide；Institute
State inorganic refractory oxide and be selected from one or more of aluminium oxide, titanium oxide, silicon oxide, inorganic refractory oxide is carrier weight
The 10% ~ 90% of amount.
2. the preparation method of the catalyst described in a kind of claim 1, including one of following two modes: (1) is by Hydrogen zsm-
Make catalyst carrier after 48 molecular sieves and inorganic refractory oxide kneading and compacting, then adopt infusion process loaded modified element group
Point, drying, roasting obtain toluene and methanol alkylation catalyst；(2) by Hydrogen zsm-48 molecular sieve, inorganic refractory oxide
After modifying element compound kneading and compacting, drying, roasting obtain toluene and methanol alkylation catalyst.
3. method according to claim 2 it is characterised in that: drying condition is as follows: baking temperature be 15 ~ 300 DEG C, be dried
Time is 1 ~ 48 hour.
4. method according to claim 2 it is characterised in that: roasting condition is as follows: sintering temperature be 400 ~ 800 DEG C, roasting
The burning time is 0.5 ~ 24 hour.
5. catalyst according to claim 1 it is characterised in that: Hydrogen zsm-48 molecular sieve be synthesis zsm-48 molecule
The method through ammonium ion exchange-roasting for the sieve obtains, and process is as follows: impregnates zsm-48 at 30 ~ 90 DEG C using ammonium nitrate solution and divides
Son sieve 2 ~ 6 times, in 400 ~ 600 DEG C of roastings 1 ~ 6 hour.
6. catalyst according to claim 5 it is characterised in that: the zsm-48 molecular sieve of synthesis has the property that oxygen
SiClx is 25 ~ 50 with the mol ratio of aluminium oxide；Specific surface is 250 ~ 400m2/ g, pore volume is 0.25 ~ 0.35cm3/ g, average hole
Footpath is 3 ~ 5nm.
7. the catalyst according to claim 5 or 6 it is characterised in that: the preparation method of the zsm-48 molecular sieve of synthesis, bag
Include following steps: (1) will be anti-for the preparation of crystal seed zsm-48 molecular sieve, template, silicon source, silicon source, sodium hydroxide and water mix homogeneously
Answer mixture；(2) by the reactant mixture of step (1) at 150 ~ 170 DEG C, hydrothermal crystallizing 4 ~ 8 days, crystallization product is through filtering, washing
Wash, be dried and the prepared zsm-48 molecular sieve of roasting.
8. catalyst according to claim 7 it is characterised in that: template be 12- crown ether -4.
9. catalyst according to claim 7 it is characterised in that: silicon source be White Carbon black, silicon source be sodium aluminate.
10. catalyst according to claim 7 it is characterised in that: the reactant mixture of step (1) has following composition,
Mol ratio in terms of oxide: r/sio2=0.05~0.2；sio2/al2o3=30~50；na2o/ sio2=0.06~0.1；h2o/ sio2=
15~23；S and sio2Mass ratio be 0.05 ~ 0.5；Wherein sio2Do not include the sio in crystal seed zsm-48 molecular sieve2, s is crystal seed
Zsm-48 molecular sieve, r is 12- crown ether -4.
11. catalyst according to claim 7 it is characterised in that: prepare the temperature of reactant mixture 20 ~ 90 DEG C it
Between.
12. catalyst according to claim 7 it is characterised in that: crystal seed zsm-48 molecular sieve be roasting sodium form molecule
Sieve or the sodium form molecular sieve of non-roasting, the mol ratio of silicon oxide and aluminium oxide is between 30 ~ 150.
13. catalyst according to claim 7 it is characterised in that: silicon source will add after silicon source is completely dissolved.
Catalyst described in a kind of 14. claim 1 is produced in the course of reaction of xylol with alkylation of toluene in methanol
Application, reaction condition is methanol is 1:1 ~ 1:10 with the mol ratio of toluene, and reaction pressure is 0.1 ~ 5.0mpa, and reaction temperature is
350 ~ 500 DEG C, the hydrogen to oil volume ratio under hydrogen and toluene and methanol standard state is 300:1 ~ 3000:1, toluene and methanol total
Volume space velocity is 0.5 ~ 6 h-1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106540735B (en) * | 2015-09-18 | 2019-12-27 | 华东理工大学 | Catalyst for benzene and methanol alkylation reaction |
| CN109593020B (en) * | 2017-09-30 | 2022-04-08 | 中国石油化工股份有限公司 | Alkylation reaction method |
| CN110871105B (en) * | 2018-08-30 | 2023-06-09 | 惠生工程（中国）有限公司 | ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN109847794B (en) * | 2018-12-17 | 2022-02-22 | 兰州理工大学 | Catalyst for preparing toluene from benzene and methanol, and preparation method and application thereof |
| CN109603903B (en) * | 2018-12-17 | 2022-02-22 | 兰州理工大学 | Catalyst for benzene and methanol alkylation reaction and preparation method and application thereof |
| CN110756218A (en) * | 2019-09-12 | 2020-02-07 | 大连龙缘化学有限公司 | Synthetic method and application of catalyst for producing durene |
| CN110605140B (en) * | 2019-09-26 | 2020-09-15 | 北京化工大学 | Nano ZSM-5 catalyst for alkylation of benzene and methanol and preparation method thereof |
| CN110624600B (en) * | 2019-10-12 | 2021-01-12 | 厦门大学 | Catalyst for preparing ethylbenzene and xylene by alkylating toluene and methanol, preparation and application thereof |
| CN114425422B (en) * | 2020-09-23 | 2024-01-30 | 中国石油化工股份有限公司 | Composite molecular sieve catalyst, preparation method and application thereof |
| CN115340105B (en) * | 2021-05-14 | 2024-02-02 | 沈阳师范大学 | Molecular sieve material with silicon-phosphorus skeleton and preparation method thereof |
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| CN1930083A (en) * | 2004-03-05 | 2007-03-14 | 埃克森美孚研究工程公司 | Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding |
| EP1797952A2 (en) * | 2005-12-15 | 2007-06-20 | Total France | Hydrocarbon product obtained by a catalytic cracking method in fluidised bed using a specific catalytic composition. |
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| CN1930083A (en) * | 2004-03-05 | 2007-03-14 | 埃克森美孚研究工程公司 | Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding |
| EP1797952A2 (en) * | 2005-12-15 | 2007-06-20 | Total France | Hydrocarbon product obtained by a catalytic cracking method in fluidised bed using a specific catalytic composition. |
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