CN107376991A - A kind of generation is to alkylation catalyst of methyl-ethyl benzene and preparation method thereof - Google Patents

A kind of generation is to alkylation catalyst of methyl-ethyl benzene and preparation method thereof Download PDF

Info

Publication number
CN107376991A
CN107376991A CN201710469627.5A CN201710469627A CN107376991A CN 107376991 A CN107376991 A CN 107376991A CN 201710469627 A CN201710469627 A CN 201710469627A CN 107376991 A CN107376991 A CN 107376991A
Authority
CN
China
Prior art keywords
solution
zsm
methyl
races element
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710469627.5A
Other languages
Chinese (zh)
Other versions
CN107376991B (en
Inventor
陈福存
谢素娟
徐龙伢
张爽
李洪星
刘盛林
朱向学
李秀杰
王玉忠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201710469627.5A priority Critical patent/CN107376991B/en
Priority to PCT/CN2017/000584 priority patent/WO2018232546A1/en
Publication of CN107376991A publication Critical patent/CN107376991A/en
Application granted granted Critical
Publication of CN107376991B publication Critical patent/CN107376991B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of generation is to alkylation catalyst of methyl-ethyl benzene and preparation method thereof.The composition of the catalyst by weight percentage is：The cocrystallization molecular sieves 50%~80% of ZSM 5/ZSM 11, binding agent 14%~41%, IV A or V A races element oxide 2%~10%, II A or III A races element oxide 2%~14%.The preparation of catalyst to the cocrystallization molecular sieves of ZSM 5/ZSM 11 by first carrying out acid treatment, again by acid-treated product and binding agent kneading, extruded moulding, processing is then modified to realize using solution, the solution containing II A races or III A group element compounds containing IV A races or V A group element compounds successively.Catalyst of the present invention is used for first benzene alkylation with ethylene and generated to methyl-ethyl benzene, shows the characteristics of activity is high, selectivity is good in conditions of non-hydrogen, has application value.

Description

A kind of generation is to alkylation catalyst of methyl-ethyl benzene and preparation method thereof
Technical field
The invention belongs to heterogeneous catalysis field, and in particular to a kind of alkylation catalyst and its system generated to methyl-ethyl benzene Preparation Method.
Background technology
To methyl-ethyl benzene (PET) it is production p-methylstyrene (PMS) and then produces high-end resin, high-performance rubber, new The critical materials of many high-end specialty chemicals such as plastic and sapecial coating, product is in automobile, the energy, chemical industry and material downstream All conglomeraties such as material have extensive use.The PMS poly- p-methylstyrene of condensate (PPMS) is the external height developed in recent years Performance plastics variety, the polymer has same good molding processibility with polystyrene (PS), in proportion, heat resistance, resistance Combustion property, transparency and shrinkage factor etc. are then better than PS.Meanwhile methyl-ethyl benzene can be copolymerized with other monomers (such as styrene), The heat resistance and anti-flammability of polymer are improved, is largely used to the manufacture of engineering plastics, phthalic resin coating etc., thus is synthesized The importance of methyl-ethyl benzene is increasingly highlighted.
The alkylated reaction of toluene and ethene can be used for preparing to methyl-ethyl benzene, but conventional Friedel-Crafts catalyst Obtained methyl-ethyl benzene be composition for thermodynamical equilibrium three isomers (wherein PET 30% or so, remaining be between methyl second Benzene MET and adjacent methyl-ethyl benzene OET).Therefore, to improve PET selectivity (selectivity of the PET in methyl-ethyl benzene, as follows), Exploitation with shape-selective effect catalyst is most important.USP5698756 is disclosed using silicone polymer to ZSM-5 molecular sieve Multiple siliceous deposits modification is carried out, then is exchanged through alkali metal ion, obtained catalyst under hydro condition there is very high PET to select Selecting property.CN201110217577.4 is disclosed first to be modified with alkaline earth metal compound, copper-containing compound respectively to modenite, IV A group element compounds and binding agent extruded moulding are added, the catalyst obtained by drying, roasting is under hydro condition PET selectivity is up to more than 95%.CN201410424434.4 is disclosed the Hydrogen EU-1 molecular sieves and oxygen of citric acid-modified Change aluminium shaping, the catalyst obtained again through 450~600 DEG C of steam treatments after drying is used for the alkylation of toluene and ethene Journey, although the PET under conditions of non-hydrogen is selectively far above thermodynamical equilibrium, it is less than 95%.
Although selectively producing the research to the alkylation catalyst of methyl-ethyl benzene to have made some progress, still not to the utmost such as people Meaning.In addition, the experimental very strong ambit of research category about molecular sieve catalyst, various conclusions need to be based on experimental data, If made inferences by " from one to the other " and " drawing inferences about other cases from one instance ", it is likely that far from each other.
The content of the invention
The present invention is directed to the deficiencies in the prior art for being used for first benzene alkylation with ethylene high selectivity generation PET catalyst (hydro condition adds process complexities, reduces economy, and the PET of non-hydrogen reaction selectively has much room for improvement), with ZSM- 5/ZSM-11 cocrystallization molecular sieve is main body, comprehensive acid treatment, different element modified to acidic zeolite, the influence etc. of pore structure Many factors, by substantial amounts of research work, a kind of generation is developed to the alkylation catalyst of methyl-ethyl benzene and its preparation side Method, catalyst of the present invention under conditions of non-hydrogen, can high selectivity generation to methyl-ethyl benzene (PET selectivity>95%, without adjacent first Base ethylbenzene).
The present invention relates to a kind of generation to alkylation catalyst of methyl-ethyl benzene and preparation method thereof.
A kind of alkylation catalyst generated to methyl-ethyl benzene, the composition of the catalyst by weight percentage are： ZSM- 5/ZSM-11 cocrystallization molecular sieve 50%~80%, binding agent 14%~41%, IV A or V A races element oxide 2%~ 10%, II A or III A races element oxide 2%~14%.
The ZSM-5/ZSM-11 cocrystallization molecular sieve contains 50%~90wt.% ZSM-5 molecular sieve, and passes through watery hydrochloric acid Or dilute nitric acid solution processing；The binding agent is aluminum oxide or silica；The IV A races element oxide is silica, described V A races element oxide is phosphorous oxide；The II A races element oxide is magnesia or calcium oxide, the III A races element oxide Thing is boron oxide or aluminum oxide.
A kind of preparation method generated to the alkylation catalyst of methyl-ethyl benzene, comprises the following steps：
(1) watery hydrochloric acid or dilute nitric acid solution of the concentration for 0.1~0.3M are used, to ZSM-5/ZSM-11 cocrystallization molecular sieves Carry out acid treatment twice, solid-to-liquid ratio 1：5~10g/ml, condition per treatment are：60~90 DEG C of temperature, 1~3h of time；At acid Reason solid product is washed to washing lotion in neutrality, in 100~120 DEG C of dry 8~20h, obtains solid powder a；
(2) it is 55~85% according to butt quality percentage by solid powder a and binding agent：15~45% mixing, then add The sesbania powder for entering to account for butt gross mass 2~4% is well mixed, and is 0.4~0.8 with butt total mass ratio：1 mass concentration Kneading, extruded moulding are carried out to it for 8~15% dilute nitric acid solutions, then 100~120 DEG C of dry 4~15h, 530~550 DEG C roasting 4~8h, obtain article shaped b；
(3) using the solution containing IV A races element silicon compound or the solution containing V A races element phosphorus compound to article shaped b Impregnated, by 100~120 DEG C of dry 4~10h, 500~530 DEG C of 3~6h of roasting, obtain containing modified silicon oxide or oxidation The article shaped c of phosphorus.
(4) using the solution containing II A races element magnesium or calcium compound or the solution pair containing III A races element boron or aluminium compound Article shaped c is impregnated, and by 100~120 DEG C of dry 4~10h, 500~530 DEG C of 3~6h of roasting, obtains final catalyst.
The solution of IV A races element silicon compound is the cyclohexane solution containing tetraethyl orthosilicate in the step (3), V A races The solution of element phosphorus compound is any one in phosphoric acid,diluted, ammonium hydrogen phosphate solution and ammonium dihydrogen phosphate；The step (4) solution of II A races element magnesium compound is at least one of magnesium nitrate solution, magnesium chloride solution and magnesium acetate solution in, The solution of II A races element calcium compound is calcium acetate solution or calcium chloride solution, and the solution of III A races element boron compound is boric acid Solution, the solution of aluminium compound is aluminum nitrate solution.
A kind of application generated to the alkylation catalyst of methyl-ethyl benzene, the catalyst are used for first benzene alkylation with ethylene High selectivity prepares p-methyl-ethylbenzene process.
The main body of catalyst is that the ZSM-5/ZSM-11 by appropriate acid treatment is total in above-mentioned technical proposal of the present invention Crystalline molecular sieve, acid treatment can be distributed with the acid of modulation molecular sieve, then can profit using ZSM-5/ZSM-11 cocrystallization molecular sieve With the collaboration advantage of ZSM-5 and ZSM-11 molecular sieves, to the acidity of molecular sieve molded thing and knitted in combination with different modifying elements The modification of structure property, can make the catalyst of preparation have during first benzene alkylation with ethylene outstanding reactivity and Very high PET selectivity, can overcome the deficiencies in the prior art, there is significant application value.
Embodiment
Below by embodiment, the present invention will be further described, but the invention is not limited in listed embodiment.
Embodiment 1
ZSM-5/ZSM-11 cocrystallization molecular sieves of the 150g containing 80%ZSM-5 is taken, using 0.3M dilute hydrochloric acid solution to it Acid treatment twice, solid-to-liquid ratio 1/5 (g/ml) are carried out, acid treatment temperature is 75 DEG C, time 2h, acid treatment solid product is washed To washing lotion in neutrality, in 120 DEG C of dry 8h, solid powder a1 is obtained；100g solid powder a1 and 41.4g aluminum oxide is taken, the two Butt quality percentage be 75%:25%, after adding 3.5g sesbania powders (accounting for butt gross mass 3%) mixing, add 70g The dilute nitric acid solution that mass concentration is 10% (is 0.6 with butt total mass ratio:1) kneading, extruded moulding are carried out, then 110 DEG C dry 8h, 540 DEG C roasting 6h, obtain article shaped b1；B1 is impregnated using the cyclohexane solution of tetraethyl orthosilicate, passed through 100 DEG C of dry 10h, 530 DEG C of roasting 3h, obtain the article shaped c1 containing modified silicon oxide；C1 is soaked using magnesium nitrate solution Stain, by 110 DEG C of dry 7h, 500 DEG C of roasting 6h, obtain the finished catalyst Cat-1 containing modified silicon oxide and magnesia, its group Into being shown in Table 1.
Embodiment 2
ZSM-5/ZSM-11 cocrystallization molecular sieves of the 150g containing 50%ZSM-5 is taken, using 0.1M dilute nitric acid solution to it Acid treatment twice, solid-to-liquid ratio 1/10 (g/ml) are carried out, acid treatment temperature is 60 DEG C, time 3h, acid treatment solid product is washed Wash to washing lotion in neutrality, in 100 DEG C of dry 20h, obtain solid powder a2；Take 100g solid powder a2 and 39g Ludox, two The butt quality percentage of person is 85%:15%, after adding 4.2g sesbania powders (accounting for butt gross mass 4%) mixing, add 42g The dilute nitric acid solution that mass concentration is 15% (is 0.4 with butt total mass ratio:1) kneading, extruded moulding are carried out, then 100 DEG C dry 15h, 530 DEG C roasting 8h, obtain article shaped b2；B2 is impregnated using dilute phosphoric acid solution, by 120 DEG C of dryings 4h, 500 DEG C of roasting 6h, obtain the article shaped c2 containing modified oxidized phosphorus；C2 is impregnated using calcium acetate solution, by 100 DEG C dry 10h, 530 DEG C roasting 3h, obtain the finished catalyst Cat-2 containing modified oxidized phosphorus and calcium oxide, its composition is shown in Table 1.
Embodiment 3
ZSM-5/ZSM-11 cocrystallization molecular sieves of the 150g containing 70%ZSM-5 is taken, using 0.2M dilute hydrochloric acid solution to it Acid treatment twice, solid-to-liquid ratio 1/7 (g/ml) are carried out, acid treatment temperature is 80 DEG C, time 2h, acid treatment solid product is washed To washing lotion in neutrality, in 110 DEG C of dry 12h, solid powder a3 is obtained；100g solid powder a3 and 29.4g aluminum oxide is taken, the two Butt quality percentage be 80%:20%, after adding 3.2g sesbania powders (accounting for butt gross mass 3%) mixing, add 85g The dilute nitric acid solution that mass concentration is 8% (is 0.8 with butt total mass ratio:1) kneading, extruded moulding are carried out, then at 110 DEG C 8h, 540 DEG C of roasting 5h are dried, obtain article shaped b3；B3 is impregnated using ammonium hydrogen phosphate solution, by 110 DEG C of dryings 6h, 520 DEG C of roasting 4h, obtain the article shaped c3 containing modified oxidized phosphorus；C3 is impregnated using boric acid solution, by 120 DEG C 4h, 530 DEG C of roasting 3h are dried, obtain the finished catalyst Cat-3 containing modified oxidized phosphorus and boron oxide, its composition is shown in Table 1.
Embodiment 4
ZSM-5/ZSM-11 cocrystallization molecular sieves of the 150g containing 90%ZSM-5 is taken, using 0.1M dilute hydrochloric acid solution to it Acid treatment twice, solid-to-liquid ratio 1/8 (g/ml) are carried out, acid treatment temperature is 90 DEG C, time 1h, acid treatment solid product is washed To washing lotion in neutrality, in 110 DEG C of dry 12h, solid powder a4 is obtained；70g solid powder a4 and 72g aluminum oxide is taken, the two Butt quality percentage is 55%:45%, after adding 2.3g sesbania powders (accounting for butt gross mass 2%) mixing, add 79g matter It (is 0.7 with butt total mass ratio to measure the dilute nitric acid solution that concentration is 12%:1) kneading, extruded moulding are carried out, then at 110 DEG C 8h, 540 DEG C of roasting 5h are dried, obtain article shaped b4；B4 is impregnated using ammonium dihydrogen phosphate, by 110 DEG C of dryings 6h, 520 DEG C of roasting 4h, obtain the article shaped c4 containing modified oxidized phosphorus；C4 is impregnated using aluminum nitrate solution, by 120 DEG C dry 4h, 530 DEG C roasting 3h, obtain the finished catalyst Cat-4 containing modified oxidized phosphorus and aluminum oxide, its composition is shown in Table 1.
Embodiment 5
ZSM-5/ZSM-11 cocrystallization molecular sieves of the 150g containing 70%ZSM-5 is taken, using 0.2M dilute hydrochloric acid solution to it Acid treatment twice, solid-to-liquid ratio 1/8 (g/ml) are carried out, acid treatment temperature is 70 DEG C, time 2.5h, acid treatment solid product is washed Wash to washing lotion in neutrality, in 110 DEG C of dry 15h, obtain solid powder a5；100g solid powder a5 and 39g aluminum oxide is taken, the two Butt quality percentage be 75%:25%, after adding 3.7g sesbania powders (accounting for butt gross mass 3.2%) mixing, add The dilute nitric acid solution that 57.5g mass concentrations are 12% (is 0.5 with butt total mass ratio:1) kneading, extruded moulding are carried out, then In 120 DEG C of dry 4h, 540 DEG C of roasting 6h, article shaped b5 is obtained；B5 is impregnated using dilute phosphoric acid solution, by 120 DEG C 4h, 530 DEG C of roasting 3h are dried, obtain the article shaped c5 containing modified oxidized phosphorus；C5 is carried out using magnesium chloride and magnesium acetate solution Dipping, by 110 DEG C of dry 7h, 530 DEG C of roasting 3h, the finished catalyst Cat-5 containing modified oxidized phosphorus and magnesia is obtained, its Composition is shown in Table 1.
Embodiment 6
ZSM-5/ZSM-11 cocrystallization molecular sieves of the 150g containing 60%ZSM-5 is taken, using 0.2M dilute nitric acid solution to it Acid treatment twice, solid-to-liquid ratio 1/7 (g/ml) are carried out, acid treatment temperature is 80 DEG C, time 1.5h, acid treatment solid product is washed Wash to washing lotion in neutrality, in 110 DEG C of dry 15h, obtain solid powder a6；100g solid powder a6 and 29g aluminum oxide is taken, the two Butt quality percentage be 80%:20%, after adding 3.8g sesbania powders (accounting for butt gross mass 3.5%) mixing, add The dilute nitric acid solution that 75.6g mass concentrations are 12% (is 0.7 with butt total mass ratio:1) kneading, extruded moulding are carried out, then In 110 DEG C of dry 12h, 540 DEG C of roasting 6h, article shaped b6 is obtained；B6 is impregnated using ammonium dihydrogen phosphate, passed through 120 DEG C of dry 4h, 520 DEG C of roasting 4h, obtain the article shaped c6 containing modified oxidized phosphorus；C6 is soaked using calcium chloride solution Stain, by 110 DEG C of dry 7h, 530 DEG C of roasting 3h, obtain the finished catalyst Cat-6 containing modified oxidized phosphorus and calcium oxide, its group Into being shown in Table 1.
Embodiment 7
The gained catalyst of embodiment 1~6 is used for the alkylation process of toluene and ethene.The reactivity worth evaluation of catalyst Carried out on conventional fixed-bed reactor, catalyst amount 5g.Catalyst pre-processes 1h at 450 DEG C under nitrogen atmosphere, then It is cooled to reaction temperature；Material upper entering and lower leaving, toluene, question response device outlet outflow are rapidly injected to reaction system with plunger pump After toluene, it is passed through ethene (controlling aequum with mass flowmenter) and is alkylated reaction.Added in above-mentioned ethylene raw 1.5wt.% methane all uses Agilent Technologies 7890B gas-chromatographies as internal standard, gas phase and liquid phase component Instrument is analyzed, using FID detectors, PONA chromatographic columns.Reaction condition is：Pressure 0.5MPa, 380 DEG C of temperature, toluene/second Alkene (mol ratio) 7, weight ethylene air speed 0.5h-1.Reaction 7h result is listed in table 1.As seen from Table 1, the embodiment of the present invention is catalyzed Agent Cat-1, Cat-2, Cat-3, Cat-4, Cat-5 and Cat-6 have high reaction activity and height to methyl under not hydro condition Ethylbenzene selectivity, there is notable superiority than prior art.
The performance that the present invention prepares catalyst judges as follows：
Conversion of ethylene=100% × (ethene/methane of ethene/methane-discharging of charging)/(ethene/first of charging Alkane)
PET selectivity=100% × (PET growing amounts/methyl-ethyl benzene growing amount)
The gained catalyst of 1 embodiment of table 1~6 forms and toluene and ethylene alkylation result

Claims (8)

  1. A kind of 1. alkylation catalyst generated to methyl-ethyl benzene, it is characterised in that：The catalyst by weight percentage, have with Lower composition：ZSM-5/ZSM-11 cocrystallization molecular sieve 50%~80%, binding agent 14%~41%, IV A or V A races element oxide Thing 2%~10%, II A or III A races element oxide 2%~14%.
  2. 2. according to a kind of alkylation catalyst generated to methyl-ethyl benzene described in claim 1, it is characterised in that：The ZSM-5/ ZSM-5 molecular sieve of the ZSM-11 cocrystallization molecular sieve containing mass percent 50%~90%, and it is molten by watery hydrochloric acid or dust technology Liquid processing.
  3. 3. according to a kind of alkylation catalyst generated to methyl-ethyl benzene described in claim 1, it is characterised in that：The binding agent For aluminum oxide or silica.
  4. 4. according to a kind of alkylation catalyst generated to methyl-ethyl benzene described in claim 1, it is characterised in that：The IV A races Element oxide is silica, and the V A races element oxide is phosphorous oxide；The II A races element oxide be magnesia or Calcium oxide, the III A races element oxide are boron oxide or aluminum oxide.
  5. 5. according to a kind of preparation generated to the alkylation catalyst of methyl-ethyl benzene described in any claim of Claims 1 to 4 Method, it is characterised in that comprise the following steps：
    (1) watery hydrochloric acid or dilute nitric acid solution of the concentration for 0.1~0.3M are used, ZSM-5/ZSM-11 cocrystallization molecular sieve is carried out Acid treatment twice, solid-to-liquid ratio 1：5~10g/ml, condition per treatment are：60~90 DEG C of temperature, 1~3h of time；Acid treatment is consolidated Body product is washed to washing lotion in neutrality, in 100~120 DEG C of dry 8~20h, obtains solid powder a；
    (2) it is 55~85% according to butt quality percentage by solid powder a and binding agent：15~45% mixing, add and account for The sesbania powder of butt gross mass 2~4% is well mixed, and is 0.4~0.8 with butt total mass ratio：1 mass concentration be 8~ 15% dilute nitric acid solution carries out kneading, extruded moulding to it, then in 100~120 DEG C of dry 4~15h, 530~550 DEG C of roastings 4~8h, obtain article shaped b；
    (3) article shaped b is carried out using the solution containing IV A races element silicon compound or the solution containing V A races element phosphorus compound Dipping, 3~6h are calcined by 100~120 DEG C of drys 4~10h, 500~530 DEG C, are obtained containing modified silicon oxide or phosphorous oxide Article shaped c；
    (4) use containing II A races element magnesium or the solution of calcium compound or the solution containing III A races element boron or aluminium compound to shaping Thing c is impregnated, and by 100~120 DEG C of dry 4~10h, 500~530 DEG C of 3~6h of roasting, obtains final catalyst.
  6. 6. according to a kind of preparation method generated to the alkylation catalyst of methyl-ethyl benzene described in claim 5, it is characterised in that： The solution of IV A races element silicon compound is the cyclohexane solution containing tetraethyl orthosilicate in the step (3)；V A races element phosphatization The solution of compound is any one in phosphoric acid,diluted, ammonium hydrogen phosphate solution and ammonium dihydrogen phosphate.
  7. 7. according to a kind of preparation method generated to the alkylation catalyst of methyl-ethyl benzene described in claim 5, it is characterised in that： In the step (4) solution of II A races element magnesium compound be magnesium nitrate solution, magnesium chloride solution and magnesium acetate solution in extremely Few one kind, the solution of II A races element calcium compound is calcium acetate solution or calcium chloride solution；III A races element boron compound it is molten Liquid is boric acid solution, and the solution of aluminium compound is aluminum nitrate solution.
  8. 8. according to a kind of application generated to the alkylation catalyst of methyl-ethyl benzene described in any claim of Claims 1 to 4, It is characterized in that：The catalyst prepares p-methyl-ethylbenzene process for first benzene alkylation with ethylene high selectivity.
CN201710469627.5A 2017-06-20 2017-06-20 A kind of alkylation catalyst and preparation method thereof generated to methyl-ethyl benzene Active CN107376991B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201710469627.5A CN107376991B (en) 2017-06-20 2017-06-20 A kind of alkylation catalyst and preparation method thereof generated to methyl-ethyl benzene
PCT/CN2017/000584 WO2018232546A1 (en) 2017-06-20 2017-09-14 Alkylation catalyst for selectively producing p-methylethylbenzene and preparation method for catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710469627.5A CN107376991B (en) 2017-06-20 2017-06-20 A kind of alkylation catalyst and preparation method thereof generated to methyl-ethyl benzene

Publications (2)

Publication Number Publication Date
CN107376991A true CN107376991A (en) 2017-11-24
CN107376991B CN107376991B (en) 2019-09-17

Family

ID=60332445

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710469627.5A Active CN107376991B (en) 2017-06-20 2017-06-20 A kind of alkylation catalyst and preparation method thereof generated to methyl-ethyl benzene

Country Status (2)

Country Link
CN (1) CN107376991B (en)
WO (1) WO2018232546A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722474A (en) * 2018-05-25 2018-11-02 中国科学院大连化学物理研究所 A kind of form selected methylation catalyst and its preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1169338A (en) * 1996-06-24 1998-01-07 中国石油化工总公司 Alkyl catalyst and application thereof
CN106669818A (en) * 2016-12-27 2017-05-17 西安元创化工科技股份有限公司 Preparation method of catalyst for preparing p-methyl ethylbenzene by alkylation and application of catalyst

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197413A (en) * 1978-12-14 1980-04-08 Mobil Oil Corporation Production of 3-methylphenol
CN101172250B (en) * 2006-10-31 2010-10-20 中国石油化工股份有限公司 Light hydrocarbon aromatization catalyst and its preparing process
CN101455978B (en) * 2008-12-26 2010-12-01 大连理工大学 Shape-selective catalyst preparation method
CN103007982B (en) * 2011-09-22 2015-02-25 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst comprising zeolite molecular sieve, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1169338A (en) * 1996-06-24 1998-01-07 中国石油化工总公司 Alkyl catalyst and application thereof
EP0913196A4 (en) * 1996-06-24 2000-03-22 China Petrochemical Corp An alkylation catalyst and the application thereof
CN106669818A (en) * 2016-12-27 2017-05-17 西安元创化工科技股份有限公司 Preparation method of catalyst for preparing p-methyl ethylbenzene by alkylation and application of catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722474A (en) * 2018-05-25 2018-11-02 中国科学院大连化学物理研究所 A kind of form selected methylation catalyst and its preparation method and application
WO2019222865A1 (en) * 2018-05-25 2019-11-28 中国科学院大连化学物理研究所 Molecular sieve alkylation catalyst having improved para-selectivity, preparation method therefor and application thereof
CN108722474B (en) * 2018-05-25 2022-03-22 中国科学院大连化学物理研究所 Shape-selective alkylation catalyst and preparation method and application thereof

Also Published As

Publication number Publication date
CN107376991B (en) 2019-09-17
WO2018232546A1 (en) 2018-12-27

Similar Documents

Publication Publication Date Title
CN108722474A (en) A kind of form selected methylation catalyst and its preparation method and application
CN103055930B (en) Low carbon alkane dehydrogenation catalyst and preparation method
CN104549479A (en) Catalyst for preparing aromatics by use of methanol and preparation method of catalyst
CN104624224A (en) Zn/ZSM-11 molecular sieve catalyst modification method
CN104117384A (en) Toluene methylation catalyst and method for producing p-xylene in presence of same
CN107376991B (en) A kind of alkylation catalyst and preparation method thereof generated to methyl-ethyl benzene
CN101352690A (en) Preparation method and use of molecular sieve catalyst for producing phenylethane from alkylation of benzene with dilute ethylene
CN106964395A (en) A kind of molecular sieve catalysts of MCM 22 for being used to be alkylated and preparation method thereof
CN103028430B (en) A kind of MWW type molecular sieve carrier catalyst and its preparation method and application
WO2013162626A1 (en) The addition of a base to enhance product yield in alkylation reactions
CN102875315B (en) The method of ethanol and benzene producing ethyl benzene through alkylation in gas phase
CN102247885B (en) Method for preparing AlCl3/zeolite molecular sieve solid acid catalyst
CN105642351A (en) Heteropolyacid ammonium salt catalyst and preparation method thereof
CN101190869B (en) Production increasing method for propylene
CN106607078B (en) The catalyst of oxygenatedchemicals paraxylene and propylene, preparation method and applications
CN104230632B (en) The method producing ethyltoluene
CN103030501A (en) Method for producing propylene
CN105582982B (en) A kind of in-situ pretreatment method of toluene and ethylene selectivity alkylation catalyst
CN114534777B (en) Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene
CN105214643B (en) Catalyst for metathesis reaction
CN102909067B (en) Two zeolite-containing catalyst for ethene and benzene alkylation, and preparation method and application thereof
CN101239879B (en) Method for producing propylene
CN105367373A (en) Method for producing methyl-ethyl benzene by means of methylbenzene and ethyl alcohol
CN102909062B (en) Composite zeolites-containing ethylene and benzene alkylation catalyst, a preparation method and applications thereof
CN102909052B (en) Mordenite-containing catalyst, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant