CN112138724B - Hydroalkylation catalyst and method thereof - Google Patents

Hydroalkylation catalyst and method thereof Download PDF

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CN112138724B
CN112138724B CN201910558908.7A CN201910558908A CN112138724B CN 112138724 B CN112138724 B CN 112138724B CN 201910558908 A CN201910558908 A CN 201910558908A CN 112138724 B CN112138724 B CN 112138724B
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hydroalkylation catalyst
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hydroalkylation
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王高伟
高焕新
魏一伦
胥明
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Sinopec Shanghai Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention relates to a hydroalkylation catalyst and a method thereof. The catalyst comprises the following components in parts by weight: a) 10-60 parts of an oxide carrier; b) 40-90 parts of microporous zeolite; the microporous zeolite has the formula (1/n) Al 2 O 3 :SiO 2 :(m/n)R 1 "schematic chemical composition shown; and the microporous zeolite framework structure has-Si-R therein 1 -Si-units; wherein n=5 to 500; m=0.01 to 50; r is R 1 Is C 1‑20 Alkylene group, C 2‑20 Alkenylene of C 2‑20 Alkynylene or phenylene of (a).

Description

Hydroalkylation catalyst and method thereof
Technical Field
The invention relates to a hydroalkylation catalyst and a method thereof.
Background
Cyclohexylbenzene is an important intermediate for fine chemical engineering, has a high boiling point and a condensation point close to room temperature, and has special physical and chemical properties. Cyclohexylbenzene has been widely used in the battery industry as an additive in lithium ion battery electrolytes, has overcharge preventing properties, and can improve the safety performance of batteries. In addition, cyclohexylbenzene can also be used for synthesizing liquid crystal materials.
The peroxidation of cyclohexylbenzene can produce phenol and cyclohexanone. Phenol plays an important role as an important product in the chemical industry. At present, phenol is mainly prepared by peroxidation of cumene, but a large amount of acetone is by-produced in the reaction process. Compared with the process for preparing phenol by the cumene oxidation method, the oxidation products of the cyclohexylbenzene are phenol and cyclohexanone. The latter is an important raw material for the production of caprolactam and nylon, and thus there is no problem of utilization of by-products.
Patent US5053571 discloses a process for the preparation of cyclohexylbenzene by hydroalkylation of benzene on Ru and Ni loaded Beta molecular sieves. Patent US5146024 discloses aA process for preparing cyclohexylbenzene by benzene hydroalkylation, namely, loading metal Pd on an X or Y molecular sieve, wherein the catalyst is modified by alkali metal or rare earth metal. Patent US20120157718 discloses a process for preparing cyclohexyl by benzene hydroalkylation reaction using a Y molecular sieve to alkylate benzene and cyclohexene, and loading the Y molecular sieve with a hydrogenation metal (palladium, platinum, nickel and ruthenium). The catalytic systems of the exxonmobil company in patents US6037513, US7579511, US7847128, US7910778, US8084648, US8106243, US8178728, US8329956, US8519194, US20100191017, US20110015457, US20110288341, US20120178969 and patents CN101687728, CN101754940, CN101796000, CN101925561, CN101998942, CN101998942, CN102015589, CN102177109 and CN103261126 using molecular sieves of the MCM-22 family and at least one hydrogenating metal (palladium, platinum, nickel and ruthenium) are used for the hydroalkylation reaction under a hydrogen atmosphere. The reaction conditions are as follows: the temperature is about 140-175 ℃, the pressure is about 931-1207 KPa, the molar ratio of hydrogen to benzene is about 0.3-0.65 and about 0.26-1.05 hr -1 Weight hourly space velocity of benzene. The highest yield of cyclohexylbenzene was about 40%.
Document CN201410428951.9 discloses a process for preparing cyclohexylbenzene by liquid phase alkylation, the catalyst comprising, in weight percent, 0.1 to 1% of a metal active component, 40 to 90% of a silicone microporous zeolite and 10 to 60% of a binder. The organosilicon microporous zeolite is synthesized by using organosilane to obtain organosilicon hybridized microporous zeolite. However, since the silane used is-O-Si-R, the organic functional groups can only be located on the outermost surface of the zeolite framework structure. The microporous zeolite inevitably needs to be calcined and activated during the preparation and use processes, so that the organic functional groups on the outer surface are oxidized during the calcination and activation processes, resulting in unsatisfactory catalyst stability and cyclohexylbenzene yield.
Disclosure of Invention
The inventor of the present invention has found a new structure of microporous zeolite with skeleton containing organic functional group through diligent research based on the prior art, and compared with the prior art, the microporous zeolite with skeleton containing organic functional group as the acid component of benzene hydroalkylation catalyst has at least the characteristics of good catalyst stability and high cyclohexylbenzene yield, and the present invention is completed based on the discovery.
Specifically, the present invention relates to the following:
1. the hydroalkylation catalyst comprises the following components in parts by weight:
a) 10-60 parts of an oxide carrier;
b) 40-90 parts of microporous zeolite;
the microporous zeolite has the formula (1/n) Al 2 O 3 :SiO 2 :(m/n)R 1 "schematic chemical composition shown; and the microporous zeolite framework structure has-Si-R therein 1 -Si-units;
wherein n=5 to 500; m=0.01 to 50; r is R 1 Is C 1-20 Alkylene group, C 2-20 Alkenylene of C 2-20 Alkynylene or phenylene of (C) is preferred 1-10 Alkylene group, C 2-10 Alkenylene of C 2-10 Alkynylene or phenylene of (C) is more preferred 1-5 Alkylene group, C 2-5 Alkenylene of C 2-5 Alkynylene or phenylene of (C) is more preferred 1-2 Alkylene group, C 2-3 Alkenylene of C 2-3 Alkynylene or phenylene of (a).
2. The hydroalkylation catalyst of claim 1, wherein the microporous zeolite Si 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak.
3. The hydroalkylation catalyst of claim 2, wherein the microporous zeolite, in its as-synthesized or calcined form, is Si 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak.
4. A hydroalkylation catalyst according to any of claims 1-3, wherein the microporous zeolite has an X-ray diffraction pattern with d-spacing maxima at 12.4±0.2, 11.0±0.3,9.3±0.3,6.8±0.2,6.1±0.2,5.5±0.2,4.4±0.2,4.0±0.2 and 3.4±0.1 angstrom.
5. The hydroalkylation catalyst of any of claims 1-4, wherein the synthesis process of the microporous zeolite comprises the step of crystallizing a mixture comprising or formed from an inorganic silicon source, a silicone source, an aluminum source, a base, an organic amine templating agent, and water to obtain the microporous zeolite; and optionally, a step of calcining the obtained microporous zeolite;
wherein the organosilicon source has the structure of formula I:
Figure SMS_1
preferably having the structure of formula II:
Figure SMS_2
wherein R is 1 Is C 1-20 Alkylene group, C 2-20 Alkenylene of C 2-20 Alkynylene or phenylene of (C) is preferred 1-10 Alkylene group, C 2-10 Alkenylene of C 2-10 Alkynylene or phenylene of (C) is more preferred 1-5 Alkylene group, C 2-5 Alkenylene of C 2-5 Alkynylene or phenylene of (C) is more preferred 1-2 Alkylene group, C 2-3 Alkenylene of C 2-3 Alkynylene or phenylene of (a);
R 2 each independently is H, halogen OR alkoxy OR 3 Preferably H, cl OR alkoxy OR 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 3 Is C 1-20 Alkyl, C of (2) 2-20 Alkenyl or C of (2) 2-20 Alkynyl of (C) is preferred 1-10 Alkyl, C of (2) 2-10 Alkenyl or C of (2) 2-10 More preferably C 1-5 Alkyl, C of (2) 2-5 Alkenyl or C of (2) 2-5 More preferably C 1-2 Alkyl, C of (2) 2-3 Alkenyl or C of (2) 2-3 Is an alkynyl group of (c).
6. The hydroalkylation catalyst according to any of claims 1-5, wherein,
the inorganic silicon source is at least one selected from the group consisting of silica sol, solid silica, silica gel, sodium silicate, diatomaceous earth, and water glass;
the aluminum source is at least one selected from the group consisting of sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, aluminum oxide, kaolin and montmorillonite;
the base is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide;
the organic amine template is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, piperidine, butylamine, hexylamine, octylamine, quinine, dodecylamine, hexadecylamine, and octadecylamine;
In the form of SiO in an inorganic silicon source 2 Based on the mixture, siO 2 /Al 2 O 3 The molar ratio of the organic silicon source/SiO is 5-500 2 Molar ratio of 0.001 to 1, OH - /SiO 2 The molar ratio of H is 0.01-5.0 2 O/SiO 2 The molar ratio of the organic amine template agent/SiO is 5-100 2 The molar ratio of (2) is 0-2.0; preferably SiO 2 /Al 2 O 3 The molar ratio of the organic silicon source/SiO is 10-250 2 In a molar ratio of 0.005 to 0.5, OH - /SiO 2 The molar ratio of H is 0.05-1.0 2 O/SiO 2 The molar ratio of the organic amine template agent/SiO is 10-80 2 The molar ratio of (2) is 0 to 1.0.
7. The hydroalkylation catalyst of any of claims 1-6, wherein the crystallization conditions comprise: the crystallization temperature is 90-250 ℃ and the crystallization time is 1-300 hours; preferably, the crystallization temperature is 100-210 ℃ and the crystallization time is 2-200 hours.
8. The hydroalkylation catalyst of any of claims 1-7, wherein the process comprises an aging step prior to crystallization; the aging conditions include: the aging temperature is 10-80 ℃ and the aging time is 2-100 hours.
9. The hydroalkylation catalyst of any one of claims 1-8, wherein the oxide support is selected from at least one of the group consisting of alumina, silica, iron oxide, zinc oxide, magnesium oxide, cerium oxide, zirconium oxide, and titanium oxide; preferably at least one selected from the group consisting of alumina and silica.
10. Hydroalkylation catalyst according to any of claims 1 to 9, wherein the catalyst further comprises 0.05 to 3 parts (preferably 0.1 to 2 parts) of a hydrogenation metal.
11. The hydroalkylation catalyst of claim 10, wherein the hydrogenation metal is selected from at least one of the group consisting of palladium, ruthenium, platinum, nickel, iron, copper, and cobalt.
12. Hydroalkylation catalyst according to any of claims 1-9, wherein at least 50 wt% (preferably at least 75 wt%, more preferably substantially all) of the hydrogenation metal is supported on the oxide support.
13. A process for the hydroalkylation of benzene comprising the step of contacting benzene under hydroconditions with a hydroalkylation catalyst of any one of claims 1-12.
14. The benzene hydroalkylation process of claim 13, wherein the contacting temperature is 100 to 300 ℃, the pressure is 0.5 to 5.0MPa, the hydrogen/benzene molar ratio is 0.1 to 5, and the benzene weight space velocity is 0.1 to 10 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the contact temperature is 150-250 ℃, the pressure is 1.0-4.0 MPa, the molar ratio of hydrogen to benzene is 0.2-2, and the weight space velocity of benzene is 0.2-5 hours -1 。
The invention has the beneficial effects that:
According to the present invention, the framework structure of the microporous zeolite concerned has never been obtained before in the art.
According to the present invention, the microporous zeolite is concerned, and the organic functional groups in the framework structure of the microporous zeolite can exist stably.
According to the invention, when the microporous zeolite is used for providing an acid site for benzene hydroalkylation reaction, the affinity of reactants and the microporous zeolite catalyst can be effectively improved, and the diffusion of benzene molecules in the microporous zeolite in the framework can be improved, so that the selectivity of a target product cyclohexylbenzene can be improved, and the activity and stability of the catalyst can be improved.
According to the invention, the hydrogenation metal is loaded on the oxide carrier as much as possible, preferably substantially all, so that the coverage of the metal component on the acid site of the molecular sieve and the influence on the pore channel structure can be effectively reduced, and the stability of the catalyst and the selectivity of the target product cyclohexylbenzene are obviously improved.
Drawings
FIG. 1 is a schematic representation of the as-synthesized molecular structure of a sample of synthesized zeolite [ example 2 ].
FIG. 2 is a schematic representation of the molecular structure of a calcined zeolite sample synthesized [ example 2 ].
FIG. 3 is a schematic representation of the as-synthesized molecular structure of a sample of the zeolite synthesized [ comparative example 1 ].
FIG. 4 is a schematic representation of the molecular structure of the calcined zeolite sample synthesized [ comparative example 1 ].
[ example 2 ] to have
Figure SMS_3
Structural silicones, such as bis (triethoxysilyl) ethane, are the silicone source and are of the formula:
Figure SMS_4
as can be seen from FIGS. 1 and 2, the organic group-R is located on the outer surface 1 -R in the framework, although possibly baked out 1 Can be present stably.
[ comparative example 1 ] to have
Figure SMS_5
Structural silicones, such as dimethyldiethoxysilane, are the silicone source and are of the formula:
Figure SMS_6
as can be seen from fig. 3 and 4, the silicon of dimethyldiethoxysilane can only be located on the outermost surface of the skeleton structure due to the action of two methyl groups, and is extremely easily oxidized during baking.
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art at the time of the application, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
It is specifically noted that two or more aspects (or embodiments) disclosed in the context of this specification may be arbitrarily combined with each other, and the resulting solution (such as a method or system) is part of the original disclosure of this specification, while also falling within the scope of the invention.
In the context of the present specification, the term "as synthesized, as synthesized or as synthesized zeolite" refers to the state of the microporous zeolite after the synthesis has ended. As the synthesis state, for example, a state directly presented after the completion of synthesis is specifically possible. In view of this, in the synthesized state, the microporous zeolite may contain water and/or may contain organic matter (particularly an organic templating agent).
In the context of the present specification, the term calcined, calcined form or calcined zeolite refers to the state of the microporous zeolite after calcination. As the calcined state, specifically, for example, a state may be presented after the synthetic microporous zeolite is further freed of organic matter (particularly, organic template agent) and water, etc. possibly present in its pore channels by calcination. The conditions for the calcination here include in particular: roasting for 6 hours in an air atmosphere at 550 ℃.
In the context of the present specification, whether or not the microporous zeolite framework structure contains organic functional groups is defined by Si 29 And (3) determining the NMR solid nuclear magnetic spectrum. Microporous zeolite containing organic functional group, si thereof 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak. Si of the microporous zeolite 29 NMR solid nuclear magnetic patterns were performed on a Varian 400MHz solid nuclear magnetic resonance spectrometer. Si (Si) 29 The resonance frequency was 79.49MHz, the chemical shift was referenced to TMS (tetramethylsilane), and the pulse waiting times were 5 seconds (cross polarization) and 30 seconds, respectively.
In the context of the present specification, the structure of a microporous zeolite is determined by X-ray diffraction patterns (XRD) of the molecular sieve, as determined by an X-ray powder diffractometer, using a Cu-ka radiation source, ka 1 wavelength λ= 1.5405980 angstroms
Figure SMS_7
A nickel filter.
In the context of the present specification, the content of hydrogenation metal in the catalyst is determined by inductively coupled plasma-emission spectrometry (ICP-AES) and its wavelength ranges from 175 to 785nm.
Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.
All pressures mentioned in this specification are referred to as gauge pressures unless explicitly indicated.
The present invention relates to a hydroalkylation catalyst. The catalyst comprises the following components in parts by weight: a) 10-60 parts of an oxide carrier; b) 40-90 parts of microporous zeolite.
According to the present invention, the framework structure of the microporous zeolite has never been obtained before in the art. The microporous zeolite has the formula (1/n) Al 2 O 3 :SiO 2 :(m/n)R 1 "schematic chemical composition shown. It is known that a certain amount of moisture is sometimes contained in a microporous zeolite (especially immediately after synthesis), but the present invention recognizes that it is not necessary to specify the amount of moisture because the presence or absence of the moisture does not substantially affect the XRD spectrum of the microporous zeolite. In view of this, the schematic chemical composition is in fact representative of the anhydrous chemical composition of the microporous zeolite. Moreover, it is evident that the schematic chemical composition represents the framework chemical composition of the microporous zeolite.
According to the invention, in the illustrative chemical composition "(1/n) Al 2 O 3 :SiO 2 :(m/n)R 1 In "n=5 to 500, m=0.01 to 50.
In accordance with the present invention, the microporous zeolite may further contain organic matters (particularly, organic templates) and water or the like, such as those filled in its pore channels, in general, in the composition immediately after synthesis. The microporous zeolite at this time may be referred to as "as synthesized" microporous zeolite. Here, any organic template agent and water or the like present in the pore channels thereof can be removed by firing to obtain the (1/n) Al having the schematic chemical composition 2 O 3 :SiO 2 :(m/n)R 1 "microporous zeolite. In addition, the calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 300 to 750 ℃, preferably 400 to 600 ℃, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere. In view of this, the schematic chemical composition is sometimes also referred to as post-bake schematic chemical composition.
According to the invention, in the illustrative chemical composition "(1/n) Al 2 O 3 :SiO 2 :(m/n)R 1 "wherein R is 1 Is C 1-20 Alkylene of (C)Radical, C 2-20 Alkenylene of C 2-20 Alkynylene or phenylene of (C) is preferred 1-10 Alkylene group, C 2-10 Alkenylene of C 2-10 Alkynylene or phenylene of (C) is more preferred 1-5 Alkylene group, C 2-5 Alkenylene of C 2-5 Alkynylene or phenylene of (C) is more preferred 1-2 Alkylene group, C 2-3 Alkenylene of C 2-3 Alkynylene or phenylene of (a).
According to the invention, in the framework structure of the microporous zeolite, O in Si-O-Si-units is replaced by an organic functional group R 1 Substituted so as to have-Si-R 1 -Si-units.
According to the invention, si of the microporous zeolite 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak, i.e. Si 29 Nuclear magnetic resonance spectrum peak can be used for representing whether the microporous zeolite framework has-Si-R 1 -Si-units. In particular, the microporous zeolite, whether in its as-synthesized or calcined form, has Si 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak.
According to the invention, an organofunctional group R 1 Exist in a TO with rigidity three-dimensional 4 (SiO 4 、AlO 4 ) Unit structure, TO 4 In microporous zeolites that share oxygen atoms in a tetrahedral manner. The microporous zeolite has an MWW structure, and has an X-ray diffraction pattern with d-spacing maxima at 12.4+ -0.2, 11.0+ -0.3, 9.3+ -0.3, 6.8+ -0.2, 6.1+ -0.2, 5.5+ -0.2, 4.4+ -0.2, 4.0+ -0.2 and 3.4+ -0.1 Angstrom.
According to the present invention, the microporous zeolite can be synthesized by the following method. The method includes the step of crystallizing a mixture (hereinafter collectively referred to as a mixture) containing or formed from an inorganic silicon source, an organic silicon source, an aluminum source, a base, an organic amine template, and water to obtain the microporous zeolite.
According to the invention, in the synthesis method of the microporous zeolite, the organosilicon source has the structure of formula I:
Figure SMS_8
Preferably having the structure of formula II:
Figure SMS_9
by using such silanes of structure I, in particular structure II, organic functional groups can be introduced into the framework of the microporous zeolite, thereby enabling a stable presence of organic functional groups during subsequent microporous zeolite treatment processes, such as drying, calcination, activation.
In the organosilicon source with the structure I and the structure II, R 1 Is C 1-20 Alkylene group, C 2-20 Alkenylene of C 2-20 Alkynylene or phenylene of (C) is preferred 1-10 Alkylene group, C 2-10 Alkenylene of C 2-10 Alkynylene or phenylene of (C) is more preferred 1-5 Alkylene group, C 2-5 Alkenylene of C 2-5 Alkynylene or phenylene of (C) is more preferred 1-2 Alkylene group, C 2-3 Alkenylene of C 2-3 Alkynylene or phenylene of (a).
In the organosilicon source with the structure I and the structure II, R 2 Each independently is H, halogen OR alkoxy OR 3 Preferably H, cl OR alkoxy OR 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 3 Is C 1-20 Alkyl, C of (2) 2-20 Alkenyl or C of (2) 2-20 Alkynyl of (C) is preferred 1-10 Alkyl, C of (2) 2-10 Alkenyl or C of (2) 2-10 More preferably C 1-5 Alkyl, C of (2) 2-5 Alkenyl or C of (2) 2-5 More preferably C 1-2 Alkyl, C of (2) 2-3 Alkenyl or C of (2) 2-3 Is an alkynyl group of (c).
According to the present invention, the organosilicon source may be selected from the group consisting of bis (trimethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) benzene, 1, 2-bis (trichlorosilane) ethane, bis (dichlorosilyl) methane, bis (trichlorosilyl) methane, and bis (chlorodimethylsilyloxy) ethane. These silicone sources may be used alone or in combination of plural kinds in a desired ratio.
According to the present invention, in the synthesis method of the microporous zeolite, the crystallization step may be performed in any manner conventionally known in the art, for example, a method of mixing the inorganic silicon source, the organic silicon source, the aluminum source, the base, the organic amine template agent, and water in a predetermined ratio and subjecting the obtained mixture to hydrothermal crystallization under the crystallization conditions may be exemplified. May be in the presence of agitation as desired.
In the synthesis method of the microporous zeolite according to the present invention, as the inorganic silicon source, any inorganic silicon source conventionally used for this purpose in the art may be used. Examples thereof include silica sol, solid silica, silica gel, sodium silicate, diatomaceous earth and water glass. These inorganic silicon sources may be used singly or in combination of plural kinds in a desired ratio.
In the synthesis method of the microporous zeolite according to the present invention, as the aluminum source, any aluminum source conventionally used for this purpose in the art may be used. Examples thereof include sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, aluminum oxide, kaolin and montmorillonite. These aluminum sources may be used singly or in combination of plural kinds in a desired ratio.
In the synthesis method of the microporous zeolite according to the present invention, as the base, any base conventionally used for this purpose in the art may be used. Examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. These bases may be used singly or in combination of plural kinds in a desired ratio.
In the synthesis method of the microporous zeolite according to the present invention, as the organic amine template, any organic amine template conventionally used for this purpose in the art may be used. Examples thereof include ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, piperidine, butylamine, hexylamine, octylamine, quinine, dodecylamine, hexadecylamine and octadecylamine. These organic amine templates may be used singly or in combination of plural kinds in a desired ratio.
According to the invention, in the synthesis method of the microporous zeolite, siO in an inorganic silicon source is used 2 Based on the mixture, siO 2 /Al 2 O 3 The molar ratio of the organic silicon source/SiO is 5-500 2 Molar ratio of 0.001 to 1, OH - /SiO 2 The molar ratio of H is 0.01-5.0 2 O/SiO 2 The molar ratio of the organic amine template agent/SiO is 5-100 2 The molar ratio of (2) is 0-2.0; preferably SiO 2 /Al 2 O 3 The molar ratio of the organic silicon source/SiO is 10-250 2 In a molar ratio of 0.005 to 0.5, OH - /SiO 2 The molar ratio of H is 0.05-1.0 2 O/SiO 2 The molar ratio of the organic amine template agent/SiO is 10-80 2 The molar ratio of (2) is 0 to 1.0.
According to the present invention, in the synthesis method of the microporous zeolite, the crystallization conditions include: the crystallization temperature is 90-250 ℃ and the crystallization time is 1-300 hours; preferably, the crystallization temperature is 100-210 ℃ and the crystallization time is 2-200 hours.
According to the present invention, in the synthesis method of the microporous zeolite, an aging step before crystallization is included; the aging conditions include: the aging temperature is 10-80 ℃ and the aging time is 2-100 hours.
According to the present invention, in the synthesis method of the microporous zeolite, after the completion of the crystallization, the microporous zeolite may be separated from the obtained reaction mixture by any conventionally known separation means as a product, and thus obtained microporous zeolite is also referred to as a microporous zeolite in a synthesized form. Examples of the separation method include a method of filtering, washing and drying the obtained reaction mixture.
In the synthesis method of the microporous zeolite according to the present invention, the filtration, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained reaction mixture may be simply suction-filtered. The washing may be performed using deionized water, for example. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be performed under normal pressure or under reduced pressure.
According to the present invention, in the method for synthesizing a microporous zeolite, the microporous zeolite obtained by crystallization may be calcined as needed to remove the organic amine template, moisture which may be present, and the like, thereby obtaining a calcined microporous zeolite, also referred to as a calcined form of microporous zeolite. The calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 300 to 800 ℃, preferably 400 to 650 ℃, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
According to the present invention, the oxide support is not narrowly defined as long as it is stable and inert under hydroalkylation reaction conditions. Suitable oxide supports may be selected from the group consisting of alumina, silica, iron oxide, zinc oxide, magnesium oxide, cerium oxide, zirconium oxide and titanium oxide; alumina and silica are preferable. These oxide supports may be used alone or in combination of plural kinds in a desired ratio.
According to the invention, preferably, the catalyst may further comprise a hydrogenation metal. Any known hydrogenation metal may be used in the catalyst. However, suitable metals, including palladium, ruthenium, platinum, nickel, iron, copper and cobalt are advantageous. The amount of hydrogenation metal present in the catalyst is 0.05 to 3 parts by weight, preferably 0.1 to 2 parts by weight.
According to the invention, the hydrogenation metal is present in the catalyst in such a way that at least 50% by weight, for example at least 75% by weight, preferably substantially all, even 100% by weight, of the hydrogenation metal is supported on the oxide support.
According to the present invention, the hydrogenation metal may be supported on the oxide support using an isovolumetric impregnation method, a precipitation, co-precipitation or a sol-gel method, which are well known in the art.
According to the present invention, the catalyst can be obtained by mixing and molding an oxide carrier carrying a hydrogenation metal and a microporous zeolite by a method known in the art as tabletting granulation or extrusion. According to the requirement, before the microporous zeolite is formed, the microporous zeolite in the hydrogen form can be obtained through ammonium nitrate solution exchange, washing and drying.
According to the invention, the catalyst may be shaped to take any physical form, such as powder, granules or molded articles (such as strips, clover, etc.). These physical forms may be obtained in any manner conventionally known in the art, and are not particularly limited.
The invention also relates to the use of the hydroalkylation catalyst. It can be used as a catalyst for preparing cyclohexylbenzene by benzene hydroalkylation.
According to the present invention, a benzene hydroalkylation process comprises the step of contacting benzene under hydroconditions with the aforementioned hydroalkylation catalyst.
According to the present invention, hydroalkylation conditions include: the temperature is 100-300 ℃, the pressure is 0.5-5.0 MPa, the molar ratio of hydrogen to benzene is 0.1-5, and the weight space velocity of benzene is 0.1-10 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably at 150-250 deg.C, under 1.0-4.0 MPa, with a hydrogen/benzene molar ratio of 0.2-2 and a benzene weight space velocity of 0.2-5 hours -1 。
The invention is further illustrated by the following examples.
[ example 1 ]
Sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
bis (triethoxysilyl) methane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 150℃for 50 hours with stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
Roasting the dried sample to obtain Si 29 The solid nuclear magnetic resonance spectrum showed a nuclear magnetic resonance spectrum peak at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 1.
TABLE 1
Figure SMS_10
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample.
Taking active alumina, drying and then adding RuCl 3 0.5wt% Ru/Al was obtained using an isovolumetric impregnation method 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, mixing 12 g of hydrogen type molecular sieve, tabletting and granulating, and taking 40-60 mesh particles for evaluation. Catalyst No. 100% Ru/Al 2 O 3 +MWW-R1, composition is shown in Table 10.
[ example 2 ]
Sodium aluminate (Al) 2 O 3 42.0 wt.%) 3.5 g of said catalyst is dissolved in 540 g of water, 8.0 g of sodium hydroxide is added to make it dissolve, then 30 g of hexamethyleneimine is added under stirring, 60 g of solid silicon oxide and 7.1 g of bis (triethoxysilyl) ethane are added, and the material ratio (mole) of the reactantRatio) is:
SiO 2 /Al 2 O 3 ＝70
NaOH/SiO 2 ＝0.2
bis (triethoxysilyl) ethane/SiO 2 ＝0.02
hexamethyleneimine/SiO 2 ＝0.3
H 2 O/SiO 2 ＝30
After the reaction mixture is stirred uniformly, transferring the mixture into a stainless steel reaction kettle, and crystallizing the mixture at 135 ℃ for 35 hours under the condition of stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 68.5.
Roasting the dried sample to obtain Si 29 NMR solid Nuclear magnetic Spectrometry A nuclear magnetic resonance Spectrometry peak appears at-60.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 2.
TABLE 2
Figure SMS_11
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample.
Taking active alumina, drying and then adding RuCl 3 0.5wt% Ru/Al was obtained using an isovolumetric impregnation method 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, mixing 12 g of hydrogen type molecular sieve, tabletting and granulating, and taking 40-60 mesh particles for evaluation. Catalyst No. 100% Ru/Al 2 O 3 +MWW-R2, composition is shown in Table 10.
[ example 3 ]
Sodium aluminate (Al) 2 O 3 42.0 wt.%) 2.4 g of the obtained product was dissolved in 900 g of water, 4.0 g of sodium hydroxide was added to dissolve the obtained product, and then 20 g of hexamethyleneimine was added with stirring, followed by addition of solid60 g of bulk silicon oxide, 5.4 g of bis (trimethoxysilyl) ethane, and the material ratio (molar ratio) of reactants is as follows:
SiO 2 /Al 2 O 3 ＝100
NaOH/SiO 2 ＝1.0
bis (trimethoxysilyl) ethane/SiO 2 ＝0.02
hexamethyleneimine/SiO 2 ＝0.2
H 2 O/SiO 2 ＝50
After the reaction mixture is stirred uniformly, transferring the mixture into a stainless steel reaction kettle, and crystallizing the mixture at 135 ℃ for 35 hours under the condition of stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 105.3.
Roasting the dried sample to obtain Si 29 NMR solid Nuclear magnetic Spectrometry A nuclear magnetic resonance Spectrometry peak appears at-60.5 ppm.
The X-ray diffraction data of the dried sample are shown in Table 3.
TABLE 3 Table 3
Figure SMS_12
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample.
Taking active alumina, drying and then adding RuCl 3 0.5wt% Ru/Al was obtained using an isovolumetric impregnation method 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, mixing 12 g of hydrogen type molecular sieve, tabletting and granulating, and taking 40-60 mesh particles for evaluation. Catalyst No. 100% Ru/Al 2 O 3 +MWW-R3, composition is shown in Table 10.
[ example 4 ]
The synthesis of the microporous zeolite was performed according to the formulation of the microporous zeolite synthesis of [ example 1 ], except that,the oxide carrier is SiO 2 The method comprises the following specific steps:
sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
Bis (triethoxysilyl) methane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 150℃for 50 hours with stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
The dried sample was characterized for Si 29 The solid nuclear magnetic resonance spectrum showed a nuclear magnetic resonance spectrum peak at-61.1 ppm. The X-ray diffraction data of the dried sample are shown in Table 4.
TABLE 4 Table 4
Figure SMS_13
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample.
Taking silicon oxide, drying and then adding RuCl 3 0.5wt% Ru/SiO was obtained using an isovolumetric impregnation method 2 (based on SiO) 2 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/SiO is taken 2 8 g of sample, mixing 12 g of hydrogen type molecular sieve, tabletting and granulating, and taking 40-60 mesh particles for evaluation. The catalyst number is 100% Ru/SiO 2 +MWW-R1, composition is shown in Table 10.
[ example 5 ]
The synthesis of microporous zeolite was performed according to the formulation of microporous zeolite synthesis of [ example 1 ], except that the supported metal was Pd, as follows:
sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
Bis (triethoxysilyl) methane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 150℃for 50 hours with stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
Roasting the dried sample to obtain Si 29 The solid nuclear magnetic resonance spectrum showed a nuclear magnetic resonance spectrum peak at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 5.
TABLE 5
Figure SMS_14
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample.
Taking active alumina, drying and adding PdCl 2 0.5wt% Pd/Al was obtained using an isovolumetric impregnation method 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Pd/Al is taken 2 O 3 8 g of sample, mixing 12 g of hydrogen type molecular sieve, tabletting and granulating, and taking 40-60 mesh particles for evaluation. Catalyst No. 100% Pd/Al 2 O 3 +MWW-R1, composition is shown in Table 10.
[ example 6 ]
The synthesis of microporous zeolite was performed according to the formulation of microporous zeolite synthesis of [ example 1 ], except that 80% of Ru was supported on alumina and 20% of Ru was supported on H-type molecular sieve during the preparation process, as follows:
Sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
bis (triethoxysilyl) methane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 150℃for 50 hours with stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
Roasting the dried sample to obtain Si 29 The solid nuclear magnetic resonance spectrum showed a nuclear magnetic resonance spectrum peak at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 6.
TABLE 6
Figure SMS_15
12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample is taken, and 0.0667wt% of Ru/MWW-R1 (based on the weight of the H-type molecular sieve) is obtained by using an isovolumetric impregnation method.
Taking active alumina, drying and then adding RuCl 3 0.4wt% Ru/Al was obtained by isovolumetric impregnation 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, and 12 g of Ru/MWW-R1 are mixed for tabletting and granulating, and 40-60 meshes of particles are taken for evaluation. Catalyst number is 80% Ru/Al 2 O 3 The composition of +20% Ru-MWW-R1 is shown in Table 10.
[ example 7 ]
The synthesis of microporous zeolite was performed according to the formulation of microporous zeolite synthesis of [ example 1 ], except that 60% Ru was supported on alumina and 40% Ru was supported on molecular sieve during the preparation.
Sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
bis (triethoxysilyl) methane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 150℃for 50 hours with stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
Roasting the dried sample to obtain Si 29 The solid nuclear magnetic resonance spectrum showed a nuclear magnetic resonance spectrum peak at-61.1 ppm.
The X-ray diffraction data of the dried sample are shown in Table 7.
TABLE 7
Figure SMS_16
The dried molecular sieve sample is taken, 12 g of H-shaped molecular sieve sample is obtained after roasting, exchanging and activating, and 0.133wt% of Ru/MWW-R1 (based on the weight of the H-shaped molecular sieve) is obtained by using an isovolumetric impregnation method.
Taking active alumina, drying and then adding RuCl 3 0.3wt% Ru/Al was obtained by isovolumetric impregnation 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, and 12 g of Ru/MWW-R1 are mixed for tabletting and granulating, and 40-60 meshes of particles are taken for evaluation. Catalyst number is 60% Ru/Al 2 O 3 The composition of +40% Ru-MWW-R1 is shown in Table 10.
[ comparative example 1 ]
The synthesis of molecular sieves was performed according to the formulation of molecular sieve synthesis of [ example 1 ], except that the organosilicon source (having the structure-O-Si-R) was replaced in the feedstock. The synthesis steps are as follows:
sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 2.8 g of dimethyldiethoxysilane were added, and the material ratios (molar ratios) of the reactants were:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
Dimethyldiethoxysilane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
To be reversedAfter the mixture is stirred uniformly, the mixture is transferred into a stainless steel reaction kettle and crystallized for 50 hours at 150 ℃ under stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
Roasting the dried sample to obtain Si 29 The solid nuclear magnetic spectrum showed a nuclear magnetic resonance spectrum peak at-16.2 ppm.
The X-ray diffraction data of the dried sample are shown in Table 8.
TABLE 8
Figure SMS_17
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample.
Taking active alumina, drying and then adding RuCl 3 0.5wt% Ru/Al was obtained using an isovolumetric impregnation method 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, mixing 12 g of hydrogen type molecular sieve, tabletting and granulating, and taking 40-60 mesh particles for evaluation. Catalyst No. 100% Ru/Al 2 O 3 +MWW-1, composition is shown in Table 10.
[ comparative example 2 ]
The synthesis of microporous zeolite was performed according to the formulation of microporous zeolite synthesis of [ example 1 ], except that 20% of the metal was loaded on the microporous zeolite and 80% of the metal was loaded on the molecular sieve, as follows:
sodium aluminate (Al) 2 O 3 42.0 wt.%) 6.1 g of the catalyst was dissolved in 288.0 g of water, 1.0 g of sodium hydroxide was added to dissolve the catalyst, then 34.0 g of piperidine was added to the solution under stirring, and then 60.0 g of solid silica and 6.8 g of bis (triethoxysilyl) methane were added, and the mixture ratio (molar ratio) of the reactants was:
SiO 2 /Al 2 O 3 ＝40
NaOH/SiO 2 ＝0.025
bis (triethoxysilyl) methane/SiO 2 ＝0.02
hexahydropyridine/SiO 2 ＝0.50
H 2 O/SiO 2 ＝16
After the reaction mixture was stirred uniformly, it was transferred to a stainless steel reaction vessel and crystallized at 150℃for 50 hours with stirring. Taking out, filtering, washing and drying. Chemical analysis to obtain SiO 2 /Al 2 O 3 The molar ratio was 42.1.
The dried sample was characterized for Si 29 The solid nuclear magnetic resonance spectrum showed a nuclear magnetic resonance spectrum peak at-61.1 ppm.
TABLE 9
Figure SMS_18
Taking 12 g of H-type molecular sieve sample obtained by roasting, exchanging and activating the dried molecular sieve sample, taking active alumina, drying, adding RuCl3 solution, and obtaining 0.267wt% Ru/MWW-R1 (based on the weight of the H-type molecular sieve) by using an isovolumetric impregnation method.
Taking active alumina, drying and then adding RuCl 3 0.1wt% Ru/Al was obtained by isovolumetric impregnation 2 O 3 (based on Al 2 O 3 Is dried at 120 ℃ for 12 hours and baked at 500 ℃ for 6 hours.
Ru/Al is taken 2 O 3 8 g of sample, mixing 12 g of Ru/MWW-R1, tabletting and granulating, and taking 40-60 mesh particles for evaluation. Catalyst No. 20% Ru/Al 2 O 3 The composition of +80% Ru-MWW-R1 is shown in Table 10.
Examples 8 to 14
5 g of the catalyst synthesized according to examples 1 to 7 are packed in a fixed-bed tubular reactor, in H 2 /N 2 Reducing for 2H at 200 ℃ in the mixed gas of (2) wherein H 2 The flow rate is 40ml/min, N 2 The flow rate was 60ml/min. After reduction with N 2 Purging is carried outAnd cooling. Then introducing benzene and hydrogen to carry out hydroalkylation reaction, and after the reaction, carrying out gas-liquid separation and then analyzing the liquid phase composition by using on-line chromatography.
The reaction conditions are as follows: benzene weight space velocity of 0.8h -1 The molar ratio of hydrogen to benzene is 0.5, the reaction temperature is 150 ℃, and the reaction pressure is 1.0MPa.
The reaction results are shown in Table 11 after 50 hours of continuous operation.
[ comparative examples 3 to 4 ]
The performance of the catalysts prepared in accordance with examples 8-14 was examined in comparison with examples 1-2. The results are shown in Table 11.
Table 10
Figure SMS_19
* The metal loading degree refers to the degree to which the hydrogenation metal is loaded on the oxide support.
TABLE 11
Figure SMS_20

Claims (29)

1. The hydroalkylation catalyst comprises the following components in parts by weight:
a) 10-60 parts of an oxide carrier;
b) 40-90 parts of microporous zeolite;
the microporous zeolite has the formula (1/n) Al 2 O 3 :SiO 2 :(m/n)R 1 "schematic chemical composition shown; and the microporous zeolite framework structure has-Si-R therein 1 -Si-units;
wherein n=5 to 500; m=0.01 to 50; r is R 1 Is C 1-20 Alkylene group, C 2-20 Alkenylene of C 2-20 Alkynylene or C of (C) 6 Phenylene group of (a).
2. Hydroalkylation catalyst according to claim 1, wherein R1 is C 1-10 Alkylene group, C 2-10 Alkenylene of C 2-10 Alkynylene or C of (C) 6 Phenylene group of (a).
3. Hydroalkylation catalyst according to claim 2, wherein R1 is C 1-5 Alkylene group, C 2-5 Alkenylene of C 2-5 Alkynylene or C of (C) 6 Phenylene group of (a).
4. A hydroalkylation catalyst according to claim 3, wherein R1 is C 1-2 Alkylene group, C 2-3 Alkenylene of C 2-3 Alkynylene or C of (C) 6 Phenylene group of (a).
5. The hydroalkylation catalyst of claim 1, wherein the microporous zeolite Si 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak.
6. The hydroalkylation catalyst of claim 5, wherein the microporous zeolite in its as-synthesized or calcined form is Si 29 The NMR solid nuclear magnetic spectrum at least comprises one Si between-80 and +50ppm 29 Nuclear magnetic resonance spectrum peak.
7. The hydroalkylation catalyst of claim 1, wherein the microporous zeolite has an X-ray diffraction pattern with d-spacing maxima at 12.4±0.2, 11.0±0.3,9.3±0.3,6.8±0.2,6.1±0.2,5.5±0.2,4.4±0.2,4.0±0.2, and 3.4±0.1 angstroms.
8. The hydroalkylation catalyst of claim 1, wherein the synthesis process of the microporous zeolite comprises the step of crystallizing a mixture comprising or formed from an inorganic silicon source, an organosilicon source, an aluminum source, a base, an organic amine templating agent, and water to obtain the microporous zeolite; and optionally, a step of calcining the obtained microporous zeolite;
wherein the organosilicon source has the structure of formula I:
Figure FDA0004044405690000021
wherein R is 1 Is C 1-20 Alkylene group, C 2-20 Alkenylene of C 2-20 Alkynylene or C of (C) 6 Phenylene of (a);
R 2 each independently is H, halogen OR alkoxy OR 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 3 Is C 1-20 Alkyl, C of (2) 2-20 Alkenyl or C of (2) 2-20 Is an alkynyl group of (c).
9. The hydroalkylation catalyst of claim 8, wherein the organosilicon source has the structure of formula II:
Figure FDA0004044405690000022
10. the hydroalkylation catalyst of claim 8, wherein R 2 Each independently is H, cl OR alkoxy OR 3 。
11. The hydroalkylation catalyst of claim 8, wherein R1 is C 1-10 Alkylene group, C 2-10 Alkenylene of C 2-10 Alkynylene or C of (C) 6 Phenylene of (a); r3 is C 1-10 Alkyl, C of (2) 2-10 Alkenyl or C of (2) 2-10 Is an alkynyl group of (c).
12. Hydroalkylation catalyst according to claim 11, wherein R1 is C 1-5 Alkylene group, C 2-5 Alkenylene of C 2-5 Alkynylene or (V)C 6 Phenylene of (a); r3 is C 1-5 Alkyl, C of (2) 2-5 Alkenyl or C of (2) 2-5 Is an alkynyl group of (c).
13. Hydroalkylation catalyst according to claim 12, wherein R1 is C 1-2 Alkylene group, C 2-3 Alkenylene of C 2-3 Alkynylene or C of (C) 6 Phenylene of (a); r3 is C 1-2 Alkyl, C of (2) 2-3 Alkenyl or C of (2) 2-3 Is an alkynyl group of (c).
14. The hydroalkylation catalyst of claim 8, wherein the hydroalkylation catalyst is,
the inorganic silicon source is at least one selected from the group consisting of silica sol, solid silica, silica gel, sodium silicate, diatomaceous earth, and water glass;
the aluminum source is at least one selected from the group consisting of sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, aluminum oxide, kaolin and montmorillonite;
the base is at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide;
the organic amine template is at least one selected from the group consisting of ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, piperidine, butylamine, hexylamine, octylamine, quinine, dodecylamine, hexadecylamine, and octadecylamine;
In the form of SiO in an inorganic silicon source 2 Based on the mixture, siO 2 /Al 2 O 3 The molar ratio of the organic silicon source/SiO is 5-500 2 Molar ratio of 0.001 to 1, OH - /SiO 2 The molar ratio of H is 0.01-5.0 2 O/SiO 2 The molar ratio of the organic amine template agent/SiO is 5-100 2 The molar ratio of (2) is 0 to 2.0.
15. The hydroalkylation catalyst of claim 14, wherein the SiO in the inorganic silicon source is 2 As a reference to this, the reference,in the mixture, siO 2 /Al 2 O 3 The molar ratio of the organic silicon source/SiO is 10-250 2 In a molar ratio of 0.005 to 0.5, OH - /SiO 2 The molar ratio of H is 0.05-1.0 2 O/SiO 2 The molar ratio of the organic amine template agent/SiO is 10-80 2 The molar ratio of (2) is 0 to 1.0.
16. The hydroalkylation catalyst of claim 8, wherein the crystallization conditions comprise: the crystallization temperature is 90-250 ℃ and the crystallization time is 1-300 hours.
17. The hydroalkylation catalyst of claim 16, wherein the crystallization conditions comprise: the crystallization temperature is 100-210 ℃ and the crystallization time is 2-200 hours.
18. The hydroalkylation catalyst of claim 8, wherein the process comprises an aging step prior to crystallization; the aging conditions include: the aging temperature is 10-80 ℃ and the aging time is 2-100 hours.
19. The hydroalkylation catalyst of claim 1, wherein the oxide support is selected from at least one of the group consisting of alumina, silica, iron oxide, zinc oxide, magnesium oxide, cerium oxide, zirconium oxide, and titanium oxide.
20. The hydroalkylation catalyst of claim 19, wherein the oxide support is selected from at least one of the group consisting of alumina and silica.
21. The hydroalkylation catalyst of claim 1, wherein the catalyst comprises 0.05 to 3 parts of hydrogenation metal.
22. The hydroalkylation catalyst of claim 21, wherein the catalyst comprises 0.1 to 2 parts of hydrogenation metal.
23. The hydroalkylation catalyst of claim 21, wherein the hydrogenation metal is selected from at least one of the group consisting of palladium, ruthenium, platinum, nickel, iron, copper, and cobalt.
24. The hydroalkylation catalyst of claim 21, wherein at least 50 wt% of the hydrogenation metal is supported on the oxide support.
25. The hydroalkylation catalyst of claim 24, wherein at least 75 wt% of the hydrogenation metal is supported on the oxide support.
26. The hydroalkylation catalyst of claim 25, wherein all of the hydrogenation metal is supported on the oxide support.
27. A process for the hydroalkylation of benzene comprising the step of contacting benzene under hydroconditions with the hydroalkylation catalyst of any one of claims 1-26.
28. The benzene hydroalkylation process of claim 27, wherein the contacting temperature is 100 to 300 ℃, the pressure is 0.5 to 5.0MPa, the hydrogen/benzene molar ratio is 0.1 to 5, and the benzene weight space velocity is 0.1 to 10 hours -1 。
29. The benzene hydroalkylation process of claim 28, wherein the contacting temperature is 150 to 250 ℃, the pressure is 1.0 to 4.0MPa, the hydrogen/benzene molar ratio is 0.2 to 2, and the benzene weight space velocity is 0.2 to 5 hours -1 。
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