CN106964395A - A kind of molecular sieve catalysts of MCM 22 for being used to be alkylated and preparation method thereof - Google Patents
A kind of molecular sieve catalysts of MCM 22 for being used to be alkylated and preparation method thereof Download PDFInfo
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- CN106964395A CN106964395A CN201710230893.2A CN201710230893A CN106964395A CN 106964395 A CN106964395 A CN 106964395A CN 201710230893 A CN201710230893 A CN 201710230893A CN 106964395 A CN106964395 A CN 106964395A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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Abstract
The present invention provides a kind of molecular sieve catalysts of MCM 22 for being used to be alkylated and preparation method thereof, the catalyst is made up of the molecular sieves of phosphorous MCM 22 of the process alkali process as reactive component with the binding agent for improving mechanical strength, and the butt mass percent of molecular sieve and binding agent is 65~85%：35~15%；Alkali process is carried out to the phosphorous molecular screen primary powders of MCM 22 using NaOH solution, by washing, desciccate and binding agent after alkali process according to mass percent 65~85%：35~15% (butts) are mixed, and are added a little sesbania powder and are well mixed, kneading, extruded moulding are carried out to it with appropriate dilute nitric acid solution, then through drying, roasting, ion exchange process, Na is made2O mass contents are less than 0.05% finished catalyst；Catalyst of the present invention be used for benzene and ethene liquid-phase alkylation it is active it is high, the characteristics of stability is good there is provided method for preparing catalyst it is simple and easy to apply, be easy to large-scale production, with application value.
Description
Technical field
The invention belongs to heterogeneous catalysis field, and in particular to it is a kind of be used for be alkylated MCM-22 molecular sieve catalysts and its
Preparation method.
Background technology
Ethylbenzene is a kind of important Organic Chemicals, is served many purposes, main to be used to produce styrene, made
Styrene be mainly used to prepare polystyrene, ABS dimers, butadiene-styrene rubber, polystyrene rubber and unsaturated-resin etc..Base
In the premium properties of molecular sieve, current molecular sieve has replaced traditional AlCl3, the master of ethylbenzene is produced as vapor phase method and liquid phase method
Fluid catalyst system.Liquid phase method, which is alkylated ethylbenzene processed, has the characteristics of reaction temperature is relatively low, accessory substance is less, especially dimethylbenzene
Impurity content (<100ppm) well below vapor phase method.The molecule of commercial Application is able in liquid phase method alkylation ethylbenzene processed at present
Sieve includes Y, Beta and MCM-22 molecular sieve, and wherein MCM-22 molecular sieves have the characteristics of benzene alkene is than low and high ethylbenzene selectivity,
But its reactivity is not as good as Beta molecular sieves.
In molecular screen material, especially usually contain non-crystallized amorphous article in the molecular sieve of plant layout metaplasia production
Plant or the incomplete low-crystallinity molecular sieve of crystallization, these materials can be dissolved and removed by appropriate alkali process, certain
Play a part of in degree purifying molecule sieve, such as document (1.M.Ogura, S.Shinomiya, J.Tateno, Y.Nara,
M.Nomura,E.Kikuchi,M.Matsukata,ApplCatal A:Gen,2001,219:33-43.) report for ZSM-
5 molecular sieves carry out alkali process and generate similar effect.But because desiliconization effect alkali process will also tend to the skeleton knot to molecular sieve
Structure and acidity cause certain destruction, have document (2.A.N.C.van laak, L.Zhang, A.N.Parvulescu,
P.C.A.Bruijnincx,B.M.Weckhuysen,K.P.de Jong,P.E.de Jongh.Catalysis Today,
2011,168:When 48-56.) reporting ZSM-5, ZSM-12 and Beta molecular sieve that alkali process contains template, in molecular sieve
Template can play certain protective effect to skeleton, while can introducing mesoporous in molecular sieve, to the skeleton of molecular sieve
It is little with acidity influence.
P Modification with the acidity of modulation molecular sieve, can improve the hydrothermal stability of molecular sieve, and then improve urging for molecular sieve
Change performance.The P Modification of molecular sieve is general by carrying out post processing realization to molecular sieve, wherein, it is in the majority with infusion process.There is document
(3.Guoliang Zhao,Jiawei Teng,ZaikuXie,WenqingJin,Weimin Yang,QinglingChen,Yi
Tang, Journal of Catalysis, 2007,29-37.) report, the phosphorous modified ZSM-5 prepared by maceration extract of phosphoric acid divides
Son sieve, has outstanding reaction stability in butene cracking reaction.Also there are document (4. Tian Ling, Li Jianwei, Li Yingxia, Chen Biao
China, is catalyzed journal, 2008,29：889-894) research uses infusion process, and P Modification is prepared by maceration extract of ammonium dibasic phosphate solution
MCM-22 molecular sieves, illustrate that appropriate phosphorus content is conducive to raising MCM-22 molecular sieves to be combined to for benzene and 1- laurylene alkyl
The selectivity and stability of detergent alkylate.Although however, the after-treatment modification method using infusion process as representative is fairly simple easily
OK, but process step is adds additional, and the phosphorus loss of modified molecular sieve can not be ignored.Directly synthesized using phosphorous system
Phosphorus containing molecular sieve can then save follow-up P Modification step, and one-step method obtains phosphorus containing molecular sieve.
In addition, with the progress of modern characterization technique, although the research to heterogeneous catalysis is increasingly deep, but relevant molecular sieve
The research of catalyst still belongs to experimental very strong ambit, and various conclusions need to be based on experimental data, if by " thus and
That " and " drawing inferences about other cases from one instance " make inferences, it is likely that try to go south by driving the chariot north.
The content of the invention
The present invention, which is directed to, is used to be alkylated particularly benzene and the MCM-22 molecular sieve catalysts of ethylene liquid phase alkylation process
Activity the problem of need further improve, the protective effect and P Modification of comprehensive alkali process, template to molecular sieve structure
The many factors such as the influence to molecular sieve catalytic property, by substantial amounts of research work, developing a kind of is used for what is be alkylated
MCM-22 molecular sieve catalysts and preparation method thereof.
A kind of MCM-22 molecular sieve catalysts for being used to be alkylated of the present invention, the catalyst is by being used as reactive component
The MCM-22 molecular sieves of process alkali process constituted with the binding agent for improving mechanical strength, the butt of molecular sieve and binding agent
Mass percent is 65~85%：15~35%.
The MCM-22 molecular sieves are obtained in phosphorous system by one-step synthesis method；The binding agent be aluminum oxide and
At least one of clay.
A kind of preparation method for the MCM-22 molecular sieve catalysts for being used to be alkylated, comprises the following steps：
(1) solid-to-liquid ratio 1 is pressed to the former powder of phosphorous MCM-22 molecular sieves using 0.1~0.6mol/L NaOH solution：8~
12g/ml carries out alkali process, and alkali process solid product is washed to washing lotion in neutrality, is dried, obtains solid powder A；
(2) it is 65~85% according to mass percent by solid powder A and binding agent：35~15% (butts) are mixed, then
The sesbania powder that addition accounts for butt gross mass 2~4% is well mixed, and is 1~1.3 with butt total mass ratio：1 dilute nitric acid solution
Kneading, extruded moulding are carried out to it, then 4~8h is calcined in 90~110 DEG C of dry 6~15h, at 530~550 DEG C, obtain sodium
Type article shaped B；
(3) ion exchange, deionized water washing, 100 are carried out to sodium form article shaped B using hydrochloric acid solution or ammonium nitrate solution
~120 DEG C of dry 4-6h, 500~520 DEG C of 3~5h of roasting, obtain Na2O mass contents are less than 0.05% finished catalyst.
Its alkali purification temp in the step (1) is 60~90 DEG C, and the alkali process time is 60~150min.
The mass concentration of dilute nitric acid solution is 8~15wt.% in the step (2).
The molar concentration of hydrochloric acid solution is 0.1~0.3mol/L in the step (3), and the molar concentration of ammonium nitrate solution is
0.5~0.7mol/L.
The catalyst is used for the liquid-phase alkylation of benzene and ethene.
The main body of catalyst is synthesized by the phosphorous system of appropriate alkali process in above-mentioned technical proposal of the present invention
MCM-22 molecular sieves, alkali process is carried out for the molecular screen primary powder containing template, can keep the same of MCM-22 molecular sieve structures
When, non-crystallized unformed species that may be present or the incomplete low-crystallinity molecular sieve of crystallization are removed, and phosphorous system is closed
Into MCM-22 molecular sieves there are phosphorus modified molecular sieves, therefore catalyst of the present invention is in the liquid phase of benzene and ethene
There is the reactivity significantly improved in alkylation process, the deficiencies in the prior art can be overcome, with notable application value, and
And method for preparing catalyst is simple and easy to apply, it is easy to large-scale production.
Embodiment
Below by embodiment, the present invention will be further described, but the invention is not limited in listed embodiment.
Comparative example
Take the MCM-22 molecular screen primary powders and 52.9g aluminum oxide of the not phosphorous system synthesis of 100g, the butt quality hundred of the two
Divide than being 70%:30%, after sesbania powder (the accounting for butt gross mass 3%) mixing for adding 3.6g, adding 130g mass concentrations is
12wt.% dilute nitric acid solution (being 1.1/1 with butt total mass ratio) carries out kneading, extruded moulding, then in 100 DEG C of dryings
12h, 540 DEG C of roasting 6h, obtain sodium form article shaped；It is 0.7mol/L ammonium nitrate solution to sodium form article shaped to use molar concentration
Ion exchange (continuous at 80 DEG C to exchange 3 times, each 1.5h, solid-to-liquid ratio 1/5 (g/ml)) is carried out, deionized water is washed, and 120 DEG C are done
Dry 4h, 500 DEG C of roasting 4h, obtains being substantially free of Na2O (mass contents<0.001%) finished catalyst Cat-0.
Embodiment 1
The MCM-22 molecular screen primary powders of the phosphorous system synthesis of 150g are taken, alkali is carried out to it using 0.4mol/L NaOH solution
Handle (solid-to-liquid ratio 1/10 (g/ml)), its alkali purification temp is 75 DEG C, and the alkali process time is 120min, and alkali process solid product is washed
Wash to washing lotion in neutrality, in 110 DEG C of dry 24h, obtain solid powder A1；Take 100g solid powder A1 and 53.5g aluminum oxide, two
The butt mass percent of person is 70%:30%, add after 3.6g sesbania powders (accounting for butt gross mass 3%) mixing, add
The dilute nitric acid solution (being 1.1/1 with butt total mass ratio) that 133g mass concentrations are 12wt.% carries out kneading, extruded moulding, so
Afterwards in 100 DEG C of dry 12h, 540 DEG C of roasting 6h, sodium form article shaped B1 is obtained；Molar concentration is used for 0.7mol/L ammonium nitrate
Solution carries out ion exchange (continuous at 80 DEG C to exchange 3 times, each 1.5h, solid-to-liquid ratio 1/5 (g/ml)) to sodium form article shaped B1, goes
Ion water washing, 120 DEG C of dry 4h, 500 DEG C of roasting 4h, obtains being substantially free of Na2O (mass contents<0.001%) finished product is urged
Agent Cat-1.
Embodiment 2
The MCM-22 molecular screen primary powders of the phosphorous system synthesis of 150g are taken, alkali is carried out to it using 0.6mol/L NaOH solution
Handle (solid-to-liquid ratio 1/8 (g/ml)), its alkali purification temp is 60 DEG C, and the alkali process time is 100min, and alkali process solid product is washed
Wash to washing lotion in neutrality, in 110 DEG C of dry 24h, obtain solid powder A2；Take 100g solid powder A2 and 64.7g aluminum oxide, two
The butt mass percent of person is 65%:35%, add after 2.5g sesbania powders (accounting for butt gross mass 2%) mixing, add
The dilute nitric acid solution (being 1/1 with butt total mass ratio) that 126g mass concentrations are 8wt.% carries out kneading, extruded moulding, Ran Hou
90 DEG C of dry 15h, 530 DEG C of roasting 8h, obtain sodium form article shaped B2；It is 0.1mol/L hydrochloric acid solution to sodium to use molar concentration
Type article shaped B2 carries out ion exchange (continuous at 80 DEG C to exchange 3 times, each 1.5h, solid-to-liquid ratio 1/5 (g/ml)), deionization washing
Wash, 100 DEG C of dry 6h, 520 DEG C of roasting 3h obtain being substantially free of Na2O (mass contents<0.001%) finished catalyst Cat-
2。
Embodiment 3
The MCM-22 molecular screen primary powders of the phosphorous system synthesis of 150g are taken, alkali is carried out to it using 0.1mol/L NaOH solution
Handle (solid-to-liquid ratio 1/12 (g/ml)), its alkali purification temp is 90 DEG C, and the alkali process time is 150min, and alkali process solid product is washed
Wash to washing lotion in neutrality, in 110 DEG C of dry 24h, obtain solid powder A3；Take 100g solid powder A3 and 41.2g aluminum oxide, two
The butt mass percent of person is 75%:25%, add after 3.8g sesbania powders (accounting for butt gross mass 3%) mixing, add
The dilute nitric acid solution (being 1.1/1 with butt total mass ratio) that 123g mass concentrations are 10wt.% carries out kneading, extruded moulding, so
Afterwards in 110 DEG C of dry 8h, 540 DEG C of roasting 5h, sodium form article shaped B3 is obtained；Molar concentration is used for 0.2mol/L hydrochloric acid solution
Ion exchange (continuous at 80 DEG C to exchange 2 times, each 1.5h, solid-to-liquid ratio 1/5 (g/ml)), deionization are carried out to sodium form article shaped B3
Water washing, 110 DEG C of dry 5h, 510 DEG C of roasting 4h, obtains being substantially free of Na2O (mass contents<0.001%) finished catalyst
Cat-3。
Embodiment 4
The MCM-22 molecular screen primary powders of the phosphorous system synthesis of 150g are taken, alkali is carried out to it using 0.6mol/L NaOH solution
Handle (solid-to-liquid ratio 1/8 (g/ml)), its alkali purification temp is 90 DEG C, and the alkali process time is 60min, and alkali process solid product is washed
To washing lotion in neutrality, in 110 DEG C of dry 24h, solid powder A4 is obtained；100g solid powder A4 and 22.9g clays are taken, the two
Butt mass percent is 85%:15%, add after 3.9g sesbania powders (accounting for butt gross mass 4%) mixing, add 127g matter
Measure the dilute nitric acid solution (being 1.3/1 with butt total mass ratio) that concentration is 15wt.% and carry out kneading, extruded moulding, then 105
DEG C dry 10h, 550 DEG C roasting 4h, obtain sodium form article shaped B4；It is 0.3mol/L hydrochloric acid solution to sodium form to use molar concentration
Article shaped B4 carries out ion exchange (continuous at 80 DEG C to exchange 2 times, each 1.5h, solid-to-liquid ratio 1/5 (g/ml)), deionization washing
Wash, 110 DEG C of dry 5h, 500 DEG C of roasting 4h obtain Na2O mass contents are 0.02% finished catalyst Cat-4.
Embodiment 5
The MCM-22 molecular screen primary powders of the phosphorous system synthesis of 150g are taken, alkali is carried out to it using 0.5mol/L NaOH solution
Handle (solid-to-liquid ratio 1/9 (g/ml)), its alkali purification temp is 80 DEG C, and the alkali process time is 120min, and alkali process solid product is washed
Wash to washing lotion in neutrality, in 110 DEG C of dry 24h, obtain solid powder A5；Take 100g solid powder A5 and 30.9g aluminum oxide, two
The butt mass percent of person is 80%:20%, add after 2.7g sesbania powders (accounting for butt gross mass 2.5%) mixing, add
The dilute nitric acid solution (being 1.2/1 with butt total mass ratio) that 126g mass concentrations are 10wt.% carries out kneading, extruded moulding, so
Afterwards in 110 DEG C of dry 7h, 540 DEG C of roasting 5h, sodium form article shaped B5 is obtained；Use molar concentration molten for 0.5mol/L ammonium nitrate
Liquid carries out ion exchange (continuous at 80 DEG C to exchange 3 times, each 1.5h, solid-to-liquid ratio 1/5 (g/ml)) to sodium form article shaped B5, go from
Sub- water washing, 100 DEG C of dry 6h, 520 DEG C of roasting 3h, obtains being substantially free of Na2O (mass contents<0.001%) finished product catalysis
Agent Cat-5.
The alkylated reaction evaluation of comparative example and the gained catalyst of embodiment 1~5
The reactivity worth evaluation of catalyst is carried out on conventional fixed-bed reactor, catalyst amount 5g.Nitrogen atmosphere
Lower catalyst pre-processes 1h at 450 DEG C, is then cooled to reaction temperature；Material bottom in and top out, it is fast to reaction system with plunger pump
Speed injection benzene, question response device reaches the pressure needed for reaction full of benzene (using reaction unit outlet outflow benzene as basis for estimation)
Benzene flow is adjusted to setting value afterwards, ethene (controlling aequum with mass flowmenter) is subsequently passed and is alkylated reaction.On
2wt.% methane is added in the ethylene raw stated as internal standard, gas phase and liquid phase component are all using Agilent
Technologies 7890B gas chromatographs are analyzed, using fid detector, PONA chromatographic columns.In order to relatively more of the invention
The difference of the catalyst and comparative example catalyst, using very harsh reaction condition (high ethene air speed and low benzene ethylene point
Son ratio), respectively by comparative example and embodiment 1~5 gained catalyst Cat-0, Cat-1, Cat-2, Cat-3, Cat-4 and Cat-5
For the liquid-phase alkylation process of benzene and ethene, it is listed in table 1 in reaction time 4h and 52h conversion of ethylene.From shown in table 1
As a result visible, catalyst of the embodiment of the present invention Cat-1, Cat-2, Cat-3, Cat-4 and Cat-5 reactivity and stability are equal
Higher than comparative example catalyst Cat-0, illustrate that catalyst of the present invention effectively increases the alkyl of MCM-22 molecular sieve catalysts
Change activity and stability, there is notable superiority than prior art.
The reactivity of benzene and ethylene liquid phase alkylation in the different catalysts of table 1
Reaction condition is：Pressure P=3.0MPa, T=200 DEG C of temperature, benzene ethylene (mol ratio)=2, weight ethylene air speed
WHSV=6h-1。
Claims (7)
1. a kind of MCM-22 molecular sieve catalysts for being used to be alkylated, it is characterised in that：The catalyst is by being used as reactivity group
Point the MCM-22 molecular sieves of process alkali process constituted with the binding agent for improving mechanical strength, molecular sieve and binding agent it is dry
Base mass percent is 65~85%：35~15%.
2. according to a kind of MCM-22 molecular sieve catalysts for being used to be alkylated described in claim 1, it is characterised in that：It is described
MCM-22 molecular sieves are obtained in phosphorous system by one-step synthesis method；The binding agent be in aluminum oxide and clay at least
It is a kind of.
3. according to a kind of preparation method of MCM-22 molecular sieve catalysts for being used to be alkylated described in claim 1, its is specific
Step is as follows：
(1) solid-to-liquid ratio 1 is pressed to the former powder of phosphorous MCM-22 molecular sieves using 0.1~0.6mol/L NaOH solution：8~10g/ml
Alkali process is carried out, alkali process solid product is washed to washing lotion in neutrality, is dried, obtains solid powder A；
(2) it is 65~85% according to butt mass percent by solid powder A and binding agent：35~15% mixing, add and account for
The sesbania powder of butt gross mass 2~4% is well mixed, and is 1~1.3 with butt total mass ratio：1 dilute nitric acid solution enters to it
Row kneading, extruded moulding, are then calcined 4~8h in 90~110 DEG C of dry 6~15h, at 530~550 DEG C, obtain sodium form shaping
Thing B；
(3) ion exchange is carried out to sodium form article shaped B using hydrochloric acid solution or ammonium nitrate solution, deionized water is washed, 100~
120 DEG C of dry 4-6h, 500~520 DEG C of 3~5h of roasting, obtain Na2O mass contents are less than 0.05% finished catalyst.
4. according to a kind of preparation method of MCM-22 molecular sieve catalysts for being used to be alkylated described in claim 3, its feature
It is：Its alkali purification temp in the step (1) is 60~90 DEG C, and the alkali process time is 60~150min.
5. according to a kind of preparation method of MCM-22 molecular sieve catalysts for being used to be alkylated described in claim 3, its feature
It is：The mass concentration of dilute nitric acid solution is 8~15% in the step (2).
6. according to a kind of preparation method of MCM-22 molecular sieve catalysts for being used to be alkylated described in claim 3, its feature
It is：The molar concentration of hydrochloric acid solution is 0.1~0.3mol/L in the step (3), and the molar concentration of ammonium nitrate solution is 0.5
~0.7mol/L.
7. according to a kind of MCM-22 molecular sieve catalysts for being used to be alkylated described in claim 1, it is characterised in that：The catalysis
Agent is used for the liquid-phase alkylation of benzene and ethene.
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Cited By (3)
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| CN114054070A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Solid acid catalyst, preparation method thereof and alkylation reaction method |
| CN114054071A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Catalyst, method for preparing the same and method for increasing the cycle life of a catalyst in alkylation reactions |
| CN114054069A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Alkylation catalyst, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114054070A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Solid acid catalyst, preparation method thereof and alkylation reaction method |
| CN114054071A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Catalyst, method for preparing the same and method for increasing the cycle life of a catalyst in alkylation reactions |
| CN114054069A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Alkylation catalyst, preparation method and application thereof |
| CN114054070B (en) * | 2020-07-31 | 2024-02-09 | 中国石油化工股份有限公司 | Solid acid catalyst, preparation method thereof and alkylation reaction method |
| CN114054069B (en) * | 2020-07-31 | 2024-02-09 | 中国石油化工股份有限公司 | Alkylation catalyst, preparation method and application thereof |
| CN114054071B (en) * | 2020-07-31 | 2024-02-20 | 中国石油化工股份有限公司 | Catalyst, method for preparing the same and method for improving catalyst cycle life in alkylation reaction |
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