CN106179459A - The preparation of a kind of high-performance Benzyl Side-Chain alkylation catalyst and application thereof - Google Patents
The preparation of a kind of high-performance Benzyl Side-Chain alkylation catalyst and application thereof Download PDFInfo
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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
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/082—X-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/073—Ethylbenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
- C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
- C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
- C07C15/46—Styrene; Ring-alkylated styrenes
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- 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
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
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- 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
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/88—Growth and elimination reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
Abstract
The invention provides preparation and the application thereof of a kind of high-performance Benzyl Side-Chain alkylation catalyst.This catalyst is in methylbenzene methanol side chain alkylation reaction system, and the selectivity that styrene is higher in keeping product simultaneously, can increase substantially toluene conversion.Described catalyst, it is characterised in that include alkaline molecular sieve and loading type alkali metal oxide;Wherein, described alkaline molecular sieve is the alkali metal type molecular sieve with FAU structure;Described loading type alkali metal oxide includes carrier and the alkali metal oxide being supported on carrier.Present invention also offers the application in toluene reacts of the above-mentioned catalyst with methanol preparation of styrene and ethylbenzene.
Description
Technical field
The present invention relates to a kind of bifunctional catalyst, its preparation method and anti-at methylbenzene methanol preparation of styrene coproduction ethylbenzene
Application in Ying.
Background technology
Styrene can be used for producing SBR rubber, ABS plastic, SBN resin etc., is the important of synthetic rubber and plastics industry
Raw material.The production of styrene route of main flow is ethylbenzene dehydrogenation method at present, and it is big that this technique exists equipment investment, and side reaction is many, energy consumption
The problems such as height, therefore people have keen interest to the exploitation of new styrene Production.
Within 1967, first reported a kind of technique by methylbenzene methanol side chain alkylation preparation of styrene, this technique is considered to have
Important industrial application value.This reaction had both needed catalyst to provide acidity, it is also desirable to catalyst provides alkalescence, at numerous kinds
In the catalyst of class, the molecular sieve of alkali metal ion exchange is considered there is preferable activity, the CsX molecule that wherein degree of depth is modified
Sieve is the emphasis of research at present.Although CsX molecular sieve has best catalysis active in similar catalyst, but the conversion of toluene
Rate is the most on the low side, is the principal element limiting the application of methylbenzene methanol side chain alkylation process industry.
Summary of the invention
It is an object of the invention to provide a kind of catalyst, this catalyst, can in methylbenzene methanol side chain alkylation system
Increase substantially toluene conversion, meanwhile, styrene in product can be kept to have higher selectivity.
Described catalyst, it is characterised in that include alkaline molecular sieve and loading type alkali metal oxide;
Wherein, described alkaline molecular sieve is the alkali metal type molecular sieve with FAU structure;
Described loading type alkali metal oxide includes carrier and the alkali metal oxide being supported on carrier.
Preferably, described alkaline molecular sieve is X molecular sieve and/or the Y molecular sieve of alkali metal type of alkali metal type.Further
Preferably, at least one in Na, K, Rb, Cs of the alkali metal in described alkaline molecular sieve.
Preferably, the silica alumina ratio in described alkaline molecular sieve is Si/Al=1~10.It is further preferred that described alkali
Silica alumina ratio in property molecular sieve is Si/Al=1~3.
Preferably, described carrier is selected from SiO2、α-Al2O3, activated carbon, SiC, ZrO2、TiO2In at least one.
Preferably, the alkali metal oxide being supported on carrier is selected from the oxide of sodium, the oxide of potassium, the oxidation of rubidium
Thing, caesium oxide at least one.
Preferably, in loading type alkali metal oxide, alkali metal oxide mass loading amount is 5~25%.
Preferably, described alkaline molecular sieve is 0.5~10:1 with the mass ratio of loading type alkali metal oxide.
Preferably, the preparation method of above-mentioned any catalyst comprises the steps of
(a) alkaline molecular sieve:
The preparation of loading type alkali metal oxide: carrier is carried out incipient impregnation with the impregnation liquid containing alkali metal ion
After, drying, roasting obtain loading type alkali metal oxide;
B loading type alkali metal oxide that step (a) is obtained by () and alkaline molecular sieve according in following 3 kinds of modes extremely
Few one, prepares catalyst:
Mode (1): after the molding respectively of loading type alkali metal oxide and alkaline molecular sieve, uniform through mechanical mixture;
Mode (2): loading type alkali metal oxide and alkaline molecular sieve are ground or ball mill ball milling respectively, blended all
After even, then carry out shaping of catalyst;
After loading type alkali metal oxide and alkaline molecular sieve are mixed by mode (3), ground or ball mill ball milling enters again
Row shaping of catalyst.
Preferably, at least one in potassium ion, rubidium ion, cesium ion of described alkali metal ion.
A further object of the present invention there are provided the application of a kind of described catalyst, it is characterised in that described catalyst
Reaction for methylbenzene methanol preparation of styrene coproduction ethylbenzene.
Preferably, in the reactor feed gas of methylbenzene methanol preparation of styrene coproduction ethylbenzene, toluene and methanol molar ratio be 0.5~
10:1;The mass space velocity WHSV of toluene is 0.2~6h-1;Reaction pressure is 0.1~20MPa;Reaction temperature 370~500 DEG C.
Beneficial effects of the present invention includes but not limited to:
(1) catalyst provided by the present invention, in the reaction of methylbenzene methanol preparation of styrene co-production ethylbenzene, has first
Benzene conversion ratio is high, selectivity of styrene high in product.
(2) catalyst stability provided by the present invention is good, on fixed bed reactors, runs there are no of 500h continuously
Significantly deactivation phenomenom.
(3) method of methylbenzene methanol preparation of styrene coproduction ethylbenzene provided by the present invention, under the conditions of high toluene conversion,
Effectively inhibit styrene in product to convert to ethylbenzene, thus maintain higher selectivity of styrene.
(4) method of methylbenzene methanol preparation of styrene coproduction ethylbenzene provided by the present invention, easy and simple to handle, meets commercial Application
Requirement, it is simple to carry out large-scale industrial production.
Detailed description of the invention
Below in conjunction with embodiment in detail the present invention is described in detail, but the invention is not limited in these embodiments.Embodiment is simply simultaneously
Provide realization and prepare cinnamic partial condition, but be not meant to that must being fulfilled for these conditions just can reach this purpose.
If no special instructions, employed in embodiment, raw material is all from commercially available, and instrument and equipment uses manufacturer's recommended
Parameter is arranged.
In embodiment, the Axios 2.4KW type X-ray of the elementary composition employing PANAbalytical company of catalyst is glimmering
Light analyser (XRF) measures.
In embodiment, product uses Agilent 7890A on-line chromatographic analysis.Hydrocarbon component uses Agilent CP-WAX
25m × 32 μ m 1.2 μm capillary column separates, and fid detector detects, Porapark Q 4m × 1/8 " packed column separation CO,
CO2And H2, TCD detector detects.
In embodiment, toluene conversion XToluene, selectivity of styrene SStyrene, ethylbenzene selectivity SEthylbenzeneIt is defined as follows:
The preparation of embodiment 1 alkaline molecular sieve sample
Alkali metal type molecular sieve employed in embodiment is all from commercially available.
Alkali metal X-type molecular sieve:
Take the NaX molecular sieve that 80g silica alumina ratio (Si/Al) is 1.17, be divided into four parts by quality, respectively with 0.5mol/L
CsOH solution 100ml, exchanges 1~4 time at 80 DEG C, is washed with deionized sucking filtration is neutrality to filter liquor, 120 DEG C of bakings
Doing overnight, roasting 4h in 550 DEG C of air, the sample exchanging 1~4 time is designated as Z-1 respectively#、Z-2#、Z-3#、Z-4#。
Alkali metal Y type molecular sieve:
Taking silica alumina ratio (Si/Al) is NaY molecular sieve 20g of 2.13, with 0.5mol/L CsOH solution 100ml, at 80 DEG C of bars
Exchanging under part 3 times, dry overnight for 120 DEG C, 550 DEG C of roasting 4h, sample is designated as Z-5#。
Take each 20g of NaY molecular sieve that silica alumina ratio (Si/Al) is 2.89, respectively with 0.5mol/L CsOH solution 100ml,
0.5mol/L KOH solution 100ml, 0.5mol/L RbOH solution 100ml, exchange 3 times under the conditions of 80 DEG C, dried for 120 DEG C
At night, 550 DEG C of roasting 4h, sample is designated as Z-6 respectively#、Z-7#、Z-8#。
Gained sample number into spectrum, ion exchange liquid kind and concentration and ion-exchange degree are as shown in table 1.Use XRF element
Analyzing and gained sample is carried out elementary analysis, ion-exchange degree calculates according to the sodium content in sample before and after exchange.
Table 1
The preparation of embodiment 2 metal oxide samples
Equi-volume impregnating:
First by carrier evacuation to be impregnated, then the carrier saturated extent of adsorption to deionized water is measured with deionized water.
Calculate the quality of required dipping predecessor by load capacity, the predecessor of respective quality is dissolved in quality needed for the saturated absorption of carrier
Deionized water in, stir, make impregnation liquid.At room temperature incipient impregnation is after 24 hours, through 120 DEG C of drying, and 550 DEG C
In air, roasting 4h is standby.Load oxide is as shown in table 2 with the kind of load predecessor and load capacity.
Table 2
Sample | Carrier * | Dipping presoma | Load oxide | Load capacity (quality) |
AC-1# | Type B SiO2 | Sodium acetate | Sodium oxide | 10% |
AC-2# | Type B SiO2 | Potassium acetate | Potassium oxide | 10% |
AC-3# | Type B SiO2 | Cesium acetate | Cs2O | 5% |
AC-4# | Type B SiO2 | Cesium acetate | Cs2O | 10% |
AC-5# | Type B SiO2 | Cesium acetate | Cs2O | 25% |
AC-6# | α-Al2O3 | Cesium acetate | Cs2O | 10% |
AC-7# | Activated carbon | Cesium acetate | Cs2O | 10% |
AC-8# | SiC | Cesium acetate | Cs2O | 10% |
AC-9# | ZrO2 | Cesium acetate | Cs2O | 10% |
AC-10# | TiO2 | Cesium acetate | Cs2O | 10% |
*: the Type B SiO in carrier2Refer to Type B silica gel.
The preparation of embodiment 3 catalyst sample
The alkaline molecular sieve sample Z-1 that embodiment 1 is prepared#~Z-8#In at least one and metal-oxide sample
Product AC-1#~AC-10#In at least one mixing, take 20~40 mesh, the catalyst obtained is designated as CAT-1#~CAT-13#.Its
Middle CAT-1#~CAT-14#Ball milling 20h on QM-3SP2 type ball mill;CAT-15#Uniform by mechanical mixture;CAT-16#Point
Do not grind, by evenly mixing after, then carry out shaping of catalyst.
The numbering of gained bifunctional catalyst sample and alkaline molecular sieve sample and metal oxide samples kind contained by it
As shown in table 3 with the relation of mass ratio.
Table 3
Sample | Alkaline molecular sieve sample and the kind of metal oxide samples and mass ratio |
CAT-1# | Z-1#: AC-4#:=4:1 |
CAT-2# | Z-2#: AC-4#:=4:1 |
CAT-3# | Z-3#: AC-4#:=4:1 |
CAT-4# | Z-4#: AC-4#:=4:1 |
CAT-5# | Z-5#: AC-6#:=4:1 |
CAT-6# | Z-6#: AC-7#:=4:1 |
CAT-7# | Z-7#: AC-8#:=4:1 |
CAT-8# | Z-8#: AC-9#:=4:1 |
CAT-9# | Z-3#: AC-10#:=4:1 |
CAT-10# | Z-3#: AC-1#:=4:1 |
CAT-11# | Z-3#: AC-2#:=4:1 |
CAT-12# | Z-3#: AC-3#:=4:1 |
CAT-13# | Z-3#: AC-5#:#=4:1 |
CAT-14# | Z-3#: AC-4#:=1:2 |
CAT-15# | Z-3#: AC-4#:=2:1 |
CAT-16# | Z-3#: AC-4#:=10:1 |
Prepared by comparative example 1 catalyst
The Z-3 obtained by embodiment 1#And Z-4#Molecular sieve, directly as catalyst, is designated as CAT-D1#And CAT-D2#。
Prepared by comparative example 2 catalyst
The Z-3 obtained by embodiment 1#And Z-4#Molecular sieve is directly as carrier loaded, by equi-volume impregnating, load
Cs2O, the mass loading amount of Cs2O is 2%, and the catalyst obtained is designated as CAT-D3#And CAT-D4#。
Embodiment 4 evaluating catalyst
The catalyst tabletting that respectively catalyst in table 3 and comparative example 1, comparative example 2 obtained, broken and sieve as 20-
40 mesh, respectively take 1g and load in small fixed reactor, and catalyst two ends filling quartz sand, first catalyst flows at 40ml/min
The lower 550 DEG C of activation 1h of helium atmosphere of speed, are then cooled to reaction temperature, are passed through raw material methylbenzene methanol, first with trace feed pump
Benzyl alcohol molar feed ratio, air speed, reaction pressure, reaction temperature are shown in Table 4.Product is entered by Agilent 7890A gas chromatograph
Row detection, reaction result is listed in table 4.
Table 4
The above, be only several embodiments of the present invention, and the present invention not does any type of restriction, although this
Bright with preferred embodiment disclose as above, but and be not used to limit the present invention, any those skilled in the art, do not taking off
In the range of technical solution of the present invention, utilize the technology contents of the disclosure above to make a little variation or modification is all equal to
Effect case study on implementation, in the range of belonging to technical solution of the present invention.
Claims (10)
1. a catalyst, it is characterised in that include alkaline molecular sieve and loading type alkali metal oxide;
Wherein, described alkaline molecular sieve is the alkali metal type molecular sieve with FAU structure;
Described loading type alkali metal oxide includes carrier and the alkali metal oxide being supported on carrier.
Catalyst the most according to claim 1, it is characterised in that described alkaline molecular sieve is the X molecular sieve of alkali metal type
And/or the Y molecular sieve of alkali metal type.
Catalyst the most according to claim 1, it is characterised in that described carrier is selected from SiO2、α-Al2O3, activated carbon,
SiC、ZrO2、TiO2In at least one.
Catalyst the most according to claim 1, it is characterised in that the alkali metal oxide being supported on carrier is selected from sodium
Oxide, the oxide of potassium, the oxide of rubidium, caesium oxide at least one.
Catalyst the most according to claim 1, it is characterised in that in loading type alkali metal oxide, alkali metal oxide
Mass loading amount be 5%~25%.
Catalyst the most according to claim 1, it is characterised in that described alkaline molecular sieve and loading type alkali metal oxide
Mass ratio be 0.5~10:1.
7. according to catalyst described in any one of claim 1 to 6, it is characterised in that preparation method comprises the steps of
The preparation of (a) loading type alkali metal oxide: carrier is carried out incipient impregnation with the impregnation liquid containing alkali metal ion
After, drying, roasting obtain loading type alkali metal oxide;
B loading type alkali metal oxide that step (a) is obtained by () and alkaline molecular sieve are according at least in following 3 kinds of modes
Kind, prepare catalyst:
Mode (1): after the molding respectively of loading type alkali metal oxide and alkaline molecular sieve, uniform through mechanical mixture;
Mode (2): loading type alkali metal oxide and alkaline molecular sieve are ground or ball mill ball milling respectively, by evenly mixing
After, then carry out shaping of catalyst;
After loading type alkali metal oxide and alkaline molecular sieve are mixed by mode (3), ground or ball mill ball milling is urged again
Agent molding.
Catalyst the most according to claim 7, it is characterised in that described alkaline molecular sieve is aoxidizing with loading type alkali metal
Before thing mixing, first carry out ion exchange with the solution containing alkali metal ion;Described alkali metal ion selected from potassium ion, rubidium from
At least one in son, cesium ion.
9. the application in methylbenzene methanol preparation of styrene coproduction ethylbenzene reacts of the catalyst described in any one of claim 1 to 8.
Application the most according to claim 9, it is characterised in that described raw material toluene and methanol molar ratio are 0.5~10:
1;The mass space velocity WHSV of toluene is 0.2~6h-1;Reaction pressure is 0.1~20MPa;Reaction temperature 350~500 DEG C.
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PCT/CN2016/106953 WO2018010360A1 (en) | 2016-07-15 | 2016-11-23 | Preparation and application of high-performance toluene side-chain alkylation catalyst |
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CN109675610A (en) * | 2018-11-29 | 2019-04-26 | 中国科学院大连化学物理研究所 | Composite catalyst, styrene preparation method for methylbenzene methanol side chain alkylation reaction preparation of styrene |
CN109847789A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | The method that bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene |
CN109847788A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | The method that bifunctional catalyst and preparation method thereof, toluene and methanol side chain alkylation prepare styrene |
CN109851469A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of method that methanol anaerobic dehydrogenation prepares styrene with Benzyl Side-Chain alkylation coupling reaction |
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CN111215126B (en) * | 2018-11-26 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst |
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CN112844448B (en) * | 2019-11-28 | 2023-07-04 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylbenzene by directly converting catalytic synthesis gas and toluene and application thereof |
CN114456034A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene and xylene from oxygen-containing compound |
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