CN115888800B - Shape-selective catalyst for diethylbenzene and preparation method and application thereof - Google Patents

Shape-selective catalyst for diethylbenzene and preparation method and application thereof Download PDF

Info

Publication number
CN115888800B
CN115888800B CN202211157794.3A CN202211157794A CN115888800B CN 115888800 B CN115888800 B CN 115888800B CN 202211157794 A CN202211157794 A CN 202211157794A CN 115888800 B CN115888800 B CN 115888800B
Authority
CN
China
Prior art keywords
catalyst
hzsm
diethylbenzene
rare earth
shape
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.)
Active
Application number
CN202211157794.3A
Other languages
Chinese (zh)
Other versions
CN115888800A (en
Inventor
赵金明
魏永豪
郭文静
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.)
Henan Yongda Chemical Technology Co ltd
Original Assignee
Henan Yongda Chemical Technology Co ltd
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 Henan Yongda Chemical Technology Co ltd filed Critical Henan Yongda Chemical Technology Co ltd
Priority to CN202211157794.3A priority Critical patent/CN115888800B/en
Publication of CN115888800A publication Critical patent/CN115888800A/en
Application granted granted Critical
Publication of CN115888800B publication Critical patent/CN115888800B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

  • Catalysts (AREA)

Abstract

The invention belongs to the field of chemical material preparation, and particularly relates to a shape selective catalyst of p-diethylbenzene, a preparation method and application thereof. The invention provides a shape-selective catalyst for diethylbenzene, which has the advantages that the diethylbenzene selectivity is more than 91% when ethylbenzene ethanol alkylation reaction is carried out, the selectivity is high, the energy consumption is reduced, and the resource waste is reduced. The invention also provides a preparation method of the shape-selective catalyst of the diethylbenzene, which comprises the steps of loading the HZSM-5 molecular sieve with alumina and rare earth elements, and then sequentially carrying out impregnation and activation by adopting silicon, magnesium and phosphorus to prepare the shape-selective catalyst of the diethylbenzene (Si-Mg-P-HZSM-5 catalyst), and the shape-selective catalyst of the diethylbenzene has strong stability, long single-pass reaction period and good activity after continuous reaction.

Description

Shape-selective catalyst for diethylbenzene and preparation method and application thereof
Technical Field
The invention belongs to the field of chemical material preparation, and particularly relates to a shape selective catalyst of p-diethylbenzene, a preparation method and application thereof.
Background
The p-diethylbenzene is used as an important basic organic chemical raw material, and is mainly used as desorber in the process of producing p-xylene by adsorption separation method, and can also be used as cross-linking agent for producing ion exchange resin, paint and synthetic material by dehydrogenation to produce divinylbenzene.
ZSM-5 is a molecular sieve catalyst with excellent performance, and the acid strength and acid distribution of the catalyst can be regulated and controlled in a large range, so ZSM-5 is a molecular sieve material widely adopted in research. However, the acidic centers on the external surface of the ZSM-5 molecular sieve are generally disadvantageous for the shape selective reaction, and in addition, the pore size is slightly larger, so that if the catalyst is directly used for producing p-diethylbenzene, a large amount of isomers can be generated, and the selectivity of the shape selective catalytic reaction of the molecular sieve can be improved by modifying the external surface of the molecular sieve.
In general, the industrial production of p-diethylbenzene adopts a catalyst mainly comprising HZSM-5, and the p-diethylbenzene is synthesized by alkylation reaction of ethylbenzene and ethylene or alkylation reaction of ethylbenzene and ethanol under the gas-solid phase condition. At present, the selectivity of diethylbenzene in a reaction product of a p-diethylbenzene synthesis method is about 60%, the selectivity is low, the material circulation amount is large, the energy consumption is high, the deep alkylation and disproportionation reaction is serious, byproducts such as benzene and heavy aromatic hydrocarbon in the product are more, the resource consumption of high value of ethylbenzene is high, and therefore, the improvement of the selectivity of diethylbenzene in the reaction product is needed.
Disclosure of Invention
The invention aims to provide a shape-selective catalyst of p-diethylbenzene, a preparation method and application thereof. The shape selective catalyst of the p-diethylbenzene provided by the invention is used for ethylbenzene ethanol alkylation reaction, and the diethylbenzene selectivity is high and reaches more than 91%.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a shape-selective catalyst of P-diethylbenzene, which comprises a nano HZSM-5 molecular sieve and an oxide loaded on the nano HZSM-5 molecular sieve, wherein the oxide comprises aluminum oxide, rare earth oxide, mgO, siO 2 and P 2O5, and the rare earth element in the rare earth oxide comprises one or more of lanthanum, cerium and neodymium;
The shape-selective catalyst for the diethylbenzene comprises the following components in percentage by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO, 2-12% of SiO 2 and 2-12% of P 2O5.
Preferably, the molar ratio of SiO 2 to Al 2O3 in the nano HZSM-5 molecular sieve is 20-600:1.
Preferably, the mass ratio of MgO, siO 2 and P 2O5 is 2-12:2-12.
The invention also provides a preparation method of the shape selective catalyst of the p-diethylbenzene, which comprises the following steps:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, rare earth soluble salt and a binder, and sequentially performing molding, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
Carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of tetraethoxysilane, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
Performing second impregnation on the Si-HZSM-5 catalyst and an aqueous solution of magnesium acetate, and sequentially performing third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and an aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst of the p-diethylbenzene.
Preferably, the binder is a nitric acid solution, and the mass fraction of nitric acid in the nitric acid solution is 3-10%.
Preferably, the organic solvent in the organic solution of the ethyl orthosilicate is ethanol or cyclohexane.
Preferably, the time of the first, second and third impregnations is independently 2 to 20 hours.
Preferably, the temperatures of the first drying, the second drying, the third drying and the fourth drying are independently 50-200 ℃ and the time is independently 5-12 h.
Preferably, the temperatures of the first firing, the second firing, the third firing and the fourth firing are independently 500 to 600 ℃ and the time is independently 5 to 12 hours.
The invention also provides application of the shape-selective catalyst of the p-diethylbenzene in preparation of the p-diethylbenzene.
The invention provides a shape-selective catalyst of P-diethylbenzene, which comprises a nano HZSM-5 molecular sieve and an oxide loaded on the nano HZSM-5 molecular sieve, wherein the oxide comprises aluminum oxide, rare earth oxide, mgO, siO 2 and P 2O5, and the rare earth element in the rare earth oxide comprises one or more of lanthanum, cerium and neodymium;
The shape-selective catalyst for the diethylbenzene comprises the following components in percentage by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO, 2-12% of SiO 2 and 2-12% of P 2O5.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a shape-selective catalyst for P-diethylbenzene, mgO, siO 2 and P 2O5 modifier active components are loaded on a nano HZSM-5 molecular sieve, and the diethylbenzene selectivity is more than 91% when ethylbenzene ethanol alkylation reaction is carried out, so that the selectivity is high, the energy consumption is reduced, and the resource waste is reduced.
Furthermore, the shape-selective catalyst of the p-diethylbenzene has strong stability, long single-pass reaction period and good activity after continuous reaction.
The invention also provides a preparation method of the shape-selective catalyst of the P-diethylbenzene, which is characterized in that after the HZSM-5 molecular sieve is loaded with alumina and rare earth elements, silicon, magnesium and phosphorus are sequentially adopted for impregnation and activation, so that the shape-selective catalyst of the P-diethylbenzene (Si-Mg-P-HZSM-5 catalyst) is prepared.
According to the data of the embodiment of the invention, the shape selective catalyst is adopted to carry out ethylbenzene ethanol alkylation reaction, the selectivity of diethylbenzene is more than 91%, the disproportionation and deep alkylation reaction are well controlled, the selectivity of diethylbenzene is more than 97%, the ethylbenzene single pass conversion rate is more than 30%, and the ethylbenzene single pass conversion rate can still be maintained to be more than 25% after the continuous reaction for 1000 hours.
Detailed Description
The invention provides a shape-selective catalyst of P-diethylbenzene, which comprises a nano HZSM-5 molecular sieve and an oxide loaded on the nano HZSM-5 molecular sieve, wherein the oxide comprises aluminum oxide, rare earth oxide, mgO, siO 2 and P 2O5, and the rare earth element in the rare earth oxide comprises one or more of lanthanum, cerium and neodymium;
The shape-selective catalyst for the diethylbenzene comprises the following components in percentage by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 2-12% of MgO, 2-12% of SiO 2 and 2-12% of P 2O5.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
In the invention, the molar ratio of SiO 2 to Al 2O3 in the nano HZSM-5 molecular sieve is preferably 20-600:1, more preferably 30-200:1, and most preferably 30-60:1.
In the invention, the particle size of the nano HZSM-5 molecular sieve is preferably 90-160 nm.
In the invention, the alumina and the rare earth oxide are formed carriers, and the sum of mass fractions of the alumina and the rare earth oxide in the shape selective catalyst of the p-diethylbenzene is preferably 10-30%.
In the present invention, the alumina is preferably a pseudo-boehmite calcined product, and the calcined temperature is preferably 500 to 600 ℃.
In the present invention, the rare earth oxide is preferably a rare earth soluble salt calcined product, the calcined temperature is preferably 500-600 ℃, and the rare earth oxide can increase the stability of the shape selective catalyst.
In the present invention, the rare earth oxide preferably includes one or more of cerium oxide, lanthanum oxide, and neodymium oxide, and the rare earth element in the rare earth oxide is preferably cerium; when the rare earth element in the rare earth oxide preferably includes a plurality of lanthanum, cerium, and neodymium, the present invention has no particular requirement on the kind and proportion of the rare earth element.
In the present invention, the mass fraction of MgO in the shape selective catalyst of p-diethylbenzene is preferably 3 to 5%.
In the invention, the mass fraction of SiO 2 in the shape selective catalyst of the p-diethylbenzene is preferably 2-5%.
In the invention, the mass fraction of P 2O5 in the shape selective catalyst of the P-diethylbenzene is preferably 3-5%.
In the invention, mgO, siO 2 and P 2O5 are active components of the modifier, influence the shape selective effect of the nano HZSM-5 molecular sieve on P-diethylbenzene, and the sum of mass fractions of MgO, siO 2 and P 2O5 in the shape selective catalyst of the P-diethylbenzene is preferably 8-20%.
In the present invention, the mass ratio of MgO, siO 2 and P 2O5 is preferably 2 to 12:2 to 12, more preferably 4:3:4, 2:5:3, 3:4:5 or 5:5:3.
The invention also provides a preparation method of the shape selective catalyst of the p-diethylbenzene, which comprises the following steps:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, rare earth soluble salt and a binder, and sequentially performing molding, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
Carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of tetraethoxysilane, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
Performing second impregnation on the Si-HZSM-5 catalyst and an aqueous solution of magnesium acetate, and sequentially performing third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and an aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst of the p-diethylbenzene.
The invention mixes nano HZSM-5 molecular sieve, pseudo-boehmite, rare earth soluble salt and binder, and then sequentially carries out molding, first drying and first roasting to obtain the Al-rare earth-HZSM-5 catalyst.
The source of the nano HZSM-5 molecular sieve is not particularly limited, and the nano HZSM-5 molecular sieve can be prepared by a method commonly used in the field.
In a specific embodiment of the present invention, the nano HZSM-5 molecular sieve is preferably prepared by a process comprising the steps of: adjusting the pH value by using water glass aqueous solution, aluminum sulfate and concentrated sulfuric acid by taking n-butylamine as a template agent, filtering and washing a product after crystallization synthesis under a hydrothermal condition, and then carrying out fifth drying and fifth roasting to obtain the NaZSM-5 molecular sieve; and carrying out sixth roasting on the NaZSM-5 molecular sieve after adopting ammonium ion exchange to obtain the nano HZSM-5 molecular sieve.
In the present invention, the temperature of the fifth drying is preferably 50 to 200 ℃, and the time is preferably 5 to 12 hours.
In the present invention, the temperature of the fifth firing is preferably 500 to 600 ℃, and the time is preferably 5 to 12 hours.
In the present invention, the pseudo-boehmite is preferably dry-basis pseudo-boehmite.
In the present invention, the rare earth soluble salt is preferably a rare earth nitrate, and the rare earth nitrate is preferably cerium nitrate, lanthanum nitrate or neodymium nitrate, more preferably cerium nitrate.
In the invention, the mass ratio of the nano HZSM-5 molecular sieve, the dry pseudo-boehmite and the rare earth nitrate is preferably 150:51:12.
In the present invention, the molding is preferably extrusion molding, more preferably extrusion molding.
In the invention, the binder is preferably nitric acid solution, the mass fraction of nitric acid in the nitric acid solution is preferably 3-10%, the use amount of the nitric acid solution is not particularly required, and the mixed powder can be formed after being bonded, and the mixed powder is a mixture of nano HZSM-5 molecular sieve, pseudo-boehmite and rare earth soluble salt.
In the present invention, the temperature of the first drying is preferably 50 to 200 ℃, more preferably 150 ℃, and the time is preferably 5 to 12 hours, more preferably 6 hours.
In the present invention, the temperature of the first firing is preferably 500 to 600 ℃, more preferably 550 ℃, and the time is preferably 5 to 12 hours, more preferably 5 hours.
After the Al-rare earth-HZSM-5 catalyst is obtained, the organic solution of the Al-rare earth-HZSM-5 catalyst and tetraethoxysilane is subjected to first impregnation, and then second drying and second roasting are sequentially carried out, so that the Si-HZSM-5 catalyst is obtained.
In the present invention, the organic solvent in the organic solution of ethyl orthosilicate is preferably ethanol or cyclohexane.
In the invention, the first impregnation is preferably equal volume impregnation, the equal volume impregnation refers to equal volume of adsorption quantity of impregnation liquid and molecular sieve, and the mass of the ethyl orthosilicate can be calculated according to the content of the active component of the modifier in the shape-selective catalyst of the p-diethylbenzene.
In the present invention, the time of the first impregnation is preferably 2 to 20 hours, more preferably 15 hours.
In the present invention, the temperature of the second drying is preferably 50 to 200 ℃, more preferably 150 ℃, and the time is preferably 5 to 12 hours, more preferably 6 hours.
In the present invention, the temperature of the second firing is preferably 500 to 600 ℃, more preferably 550 ℃, and the time is preferably 5 to 12 hours, more preferably 5 hours.
After the Si-HZSM-5 catalyst is obtained, the Si-HZSM-5 catalyst and the aqueous solution of magnesium acetate are subjected to second impregnation, and then third drying and third roasting are sequentially carried out, so that the Si-Mg-HZSM-5 catalyst is obtained.
After the Si-Mg-HZSM-5 catalyst is obtained, the Si-Mg-HZSM-5 catalyst and the aqueous solution of ammonium dihydrogen phosphate are subjected to third impregnation, and then fourth drying and fourth roasting are sequentially carried out, so that the shape-selective catalyst of the p-diethylbenzene is obtained.
In the present invention, the second impregnation and the third impregnation are independently preferably equal volume impregnation.
In the present invention, the time of the second impregnation and the third impregnation is preferably the same as that of the first impregnation, and will not be described herein.
In the present invention, the temperature and time of the third drying and the fourth drying are preferably the same as those of the second drying, and will not be described herein.
In the present invention, the temperature and time of the third firing and the fourth firing are preferably the same as those of the second firing, and will not be described herein.
The invention also provides application of the shape-selective catalyst of the p-diethylbenzene in preparation of the p-diethylbenzene.
In the present invention, the application preferably includes: ethanol, ethylbenzene and the shape selective catalyst of the p-diethylbenzene are mixed for alkylation reaction.
In the present invention, the reaction conditions of the alkylation reaction preferably include:
the mol ratio of ethanol to ethylbenzene is 1:5-2:1, the reaction pressure is 0-1.0 MPa, the reaction temperature is 320-420 ℃, the mol ratio of carrier gas to ethylbenzene is 1:1-5:1, and the mass airspeed of ethylbenzene is 0.4-5 h -1.
In the present invention, the carrier gas is preferably nitrogen or water vapor.
In the present invention, the mass space velocity of ethylbenzene is more preferably 0.7h -1.
For further explanation of the present invention, the shape selective catalyst for p-diethylbenzene, its preparation method and application provided in the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The synthesis method of the nanometer HZSM-5 molecular sieve comprises the following steps:
N-butylamine is adopted as a template agent, water glass aqueous solution and aluminum sulfate are used for adjusting the PH value, and the molar ratio of SiO 2/Al2O3 is 30; filtering, washing and drying the product after crystallization synthesis under the hydrothermal condition for 6 hours at 150 ℃, and then transferring the product into a roasting furnace for roasting for 5 hours at 550 ℃ to prepare the Na-ZSM-5 molecular sieve; and then the conventional ammonium ion exchange and roasting method are adopted to obtain the nano HZSM-5 molecular sieve.
Example 2
This example differs from example 1 above only in that the molar ratio of SiO 2/Al2O3 is 60.
Example 3
This example differs from example 1 above only in that the molar ratio of SiO 2/Al2O3 is 200.
Example 4
1) 150G of the nano HZSM-5 molecular sieve (SiO 2/Al2O3 with the mol ratio of 30) obtained in the example 1, 51g of pseudoboehmite on a dry basis and 12g of rare earth cerium nitrate are uniformly mixed, then the mixture is bonded and extruded into strips by dilute nitric acid with the mass concentration of 3%, the strips are molded, dried at 150 ℃ for 6 hours, and then baked at 550 ℃ for 5 hours, so that the molded HZSM-5 catalyst strips are prepared.
2) The molded HZSM-5 catalyst bar obtained in the step 1) was immersed in an ethanol solution of ethyl orthosilicate in an equal volume for 15 hours (4 wt% SiO 2 was contained in the final product catalyst A1), dried at 150℃for 6 hours, and then baked at 550℃for 5 hours, to obtain a molded Si-HZSM-5 catalyst bar.
3) The molded Si-HZSM-5 catalyst bar obtained in the step 2) was immersed in an aqueous solution of magnesium acetate in an equal volume for 15 hours (3 wt% MgO was contained in the final product catalyst A1), dried at 150℃for 6 hours, and then calcined at 550℃for 5 hours to obtain a molded Si-Mg-HZSM-5 catalyst bar.
4) The molded Si-Mg-HZSM-5 catalyst rod obtained in the step 3) was immersed in an aqueous solution of monoammonium phosphate in an equal volume for 15 hours (4 wt% of P 2O5 was contained in the final product catalyst A1), dried at 150℃for 6 hours, and then calcined at 550℃for 5 hours, to obtain a molded Si-Mg-P-HZSM-5 catalyst rod, which was designated as catalyst A1.
Example 5
This example differs from example 4 only in that the final product is made to contain 2% by weight of SiO 2,5wt％MgO,3wt％P2O5, designated catalyst A2.
Example 6
This example differs from example 4 only in that the final product is made to contain 3% by weight of SiO 2,4wt％MgO,5wt％P2O5, designated catalyst A3.
Example 7
This example differs from example 4 only in that the final product is made to contain 5% by weight of SiO 2,5wt％MgO,3wt％P2O5, designated catalyst A4.
Example 8
This example differs from example 4 only in that the nano HZSM-5 molecular sieve obtained in example 2 (molar ratio of SiO 2/Al2O3: 60) was used, and the molded Si-Mg-P-HZSM-5 catalyst strip obtained was designated as catalyst B1.
Example 9
This example differs from example 5 only in that the nano HZSM-5 molecular sieve obtained in example 2 (molar ratio of SiO 2/Al2O3: 60) was used, and the molded Si-Mg-P-HZSM-5 catalyst strip obtained was designated as catalyst B2.
Example 10
This example differs from example 6 only in that the nano HZSM-5 molecular sieve obtained in example 2 (molar ratio of SiO 2/Al2O3: 60) was used, and the molded Si-Mg-P-HZSM-5 catalyst strip obtained was designated as catalyst B3.
Example 11
This example differs from example 7 only in that the nano HZSM-5 molecular sieve obtained in example 2 (molar ratio of SiO 2/Al2O3: 60) was used, and the molded Si-Mg-P-HZSM-5 catalyst strip obtained was designated as catalyst B4.
Example 12
This example differs from example 4 only in that the nano HZSM-5 molecular sieve obtained in example 3 (SiO 2/Al2O3 molar ratio 200) was used and the shaped Si-Mg-P-HZSM-5 catalyst strip obtained was designated catalyst C1.
Example 13
This example differs from example 5 only in that the nano HZSM-5 molecular sieve obtained in example 3 (SiO 2/Al2O3 molar ratio 200) was used and the shaped Si-Mg-P-HZSM-5 catalyst strip obtained was designated catalyst C2.
Example 14
This example differs from example 6 only in that the nano HZSM-5 molecular sieve obtained in example 3 (SiO 2/Al2O3 molar ratio 200) was used and the shaped Si-Mg-P-HZSM-5 catalyst strip obtained was designated catalyst C3.
Example 15
This example differs from example 7 only in that the nano HZSM-5 molecular sieve obtained in example 3 (SiO 2/Al2O3 molar ratio 200) was used and the shaped Si-Mg-P-HZSM-5 catalyst strip obtained was designated catalyst C4.
Application example 1
The shape selective catalysts obtained in examples 4 to 15 were applied to the alkylation reaction of ethylbenzene and ethanol to synthesize p-diethylbenzene, respectively, and the catalytic reaction performance was examined using a fixed bed reactor.
The invention adopts a 316 stainless steel reactor, adopts electric heating and automatically controls the temperature in a plurality of sections. The catalyst is loaded on a fixed bed evaluation device for alkylation reaction of ethylbenzene and ethanol, the loading of the catalyst is 100 g, the molar ratio of the ethylbenzene to the ethanol is 3:2, the mass space velocity is 0.7h -1, the reaction temperature is 350 ℃, the reaction pressure is 0.2MPa, and the molar ratio of carrier gas to the ethylbenzene is 2:1. Liquid and gas phase product analysis was performed on two GC9800 gas chromatographs, respectively.
Experimental data obtained from the reaction were calculated using the following formula, and the reaction results are shown in table 1:
ethylbenzene conversion = [ (ethylbenzene content in feed-ethylbenzene content in product)/ethylbenzene content in feed ] ×100%
Diethylbenzene selectivity= [ mixed diethylbenzene content in product/(total aromatics content in product-ethylbenzene content in product) ]100%
P-diethylbenzene selectivity = (p-diethylbenzene content in product/mixed diethylbenzene content in product) ×100%
TABLE 1 reaction results
As can be seen from the data in Table 1, the shape selective catalyst for para-diethylbenzene of examples 4 to 15 has a diethylbenzene selectivity of 91% or more, a disproportionation reaction and a deep alkylation reaction are well controlled, a para-diethylbenzene selectivity of 97% or more, a ethylbenzene single pass conversion of 30% or more, and a ethylbenzene single pass conversion of 25% or more can be maintained after a continuous reaction for 1000 hours.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the embodiments of the invention without departing from the spirit and scope of the invention.

Claims (8)

1. A shape selective catalyst for preparing P-diethylbenzene by alkylation of ethylbenzene and ethanol, comprising a nano HZSM-5 molecular sieve and an oxide supported on the nano HZSM-5 molecular sieve, wherein the oxide comprises aluminum oxide, rare earth oxide, mgO, siO 2 and P 2O5, and the rare earth element in the rare earth oxide comprises one or more of lanthanum, cerium and neodymium;
The shape-selective catalyst for the diethylbenzene comprises the following components in percentage by mass: 60-80% of nano HZSM-5 molecular sieve, 8-28% of alumina, 2-10% of rare earth oxide, 3-5% of MgO, 2-5% of SiO 2 and 3-5% of P 2O5; the molar ratio of SiO 2 to Al 2O3 in the nano HZSM-5 molecular sieve is 30-200:1;
the preparation method of the shape selective catalyst comprises the following steps:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, rare earth soluble salt and a binder, and sequentially performing molding, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
Carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of tetraethoxysilane, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
Performing second impregnation on the Si-HZSM-5 catalyst and an aqueous solution of magnesium acetate, and sequentially performing third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and an aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst of the p-diethylbenzene.
2. The method for preparing the shape selective catalyst according to claim 1, comprising the steps of:
mixing a nano HZSM-5 molecular sieve, pseudo-boehmite, rare earth soluble salt and a binder, and sequentially performing molding, first drying and first roasting to obtain an Al-rare earth-HZSM-5 catalyst;
Carrying out first impregnation on the Al-rare earth-HZSM-5 catalyst and an organic solution of tetraethoxysilane, and then sequentially carrying out second drying and second roasting to obtain a Si-HZSM-5 catalyst;
Performing second impregnation on the Si-HZSM-5 catalyst and an aqueous solution of magnesium acetate, and sequentially performing third drying and third roasting to obtain the Si-Mg-HZSM-5 catalyst;
and (3) carrying out third impregnation on the Si-Mg-HZSM-5 catalyst and an aqueous solution of ammonium dihydrogen phosphate, and then sequentially carrying out fourth drying and fourth roasting to obtain the shape-selective catalyst of the p-diethylbenzene.
3. The preparation method according to claim 2, wherein the binder is a nitric acid solution, and the mass fraction of nitric acid in the nitric acid solution is 3-10%.
4. The preparation method according to claim 2, wherein the organic solvent in the organic solution of ethyl orthosilicate is ethanol or cyclohexane.
5. The method of claim 2, wherein the first, second and third impregnations are independently performed for a period of 2 to 20 hours.
6. The method according to claim 2, wherein the first, second, third and fourth drying are independently performed at a temperature of 50 to 200 ℃ for a time of 5 to 12 hours.
7. The method according to claim 2, wherein the first firing, the second firing, the third firing, and the fourth firing are independently at a temperature of 500 to 600 ℃ for a time of 5 to 12 hours.
8. Use of a shape selective catalyst according to claim 1 or a shape selective catalyst obtained by a process according to any one of claims 2 to 7 for the preparation of p-diethylbenzene.
CN202211157794.3A 2022-09-22 2022-09-22 Shape-selective catalyst for diethylbenzene and preparation method and application thereof Active CN115888800B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211157794.3A CN115888800B (en) 2022-09-22 2022-09-22 Shape-selective catalyst for diethylbenzene and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211157794.3A CN115888800B (en) 2022-09-22 2022-09-22 Shape-selective catalyst for diethylbenzene and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115888800A CN115888800A (en) 2023-04-04
CN115888800B true CN115888800B (en) 2024-05-24

Family

ID=86492113

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211157794.3A Active CN115888800B (en) 2022-09-22 2022-09-22 Shape-selective catalyst for diethylbenzene and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115888800B (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447666A (en) * 1982-12-30 1984-05-08 Mobil Oil Corporation Para-selective alkylation catalysts and processes
US4849386A (en) * 1987-04-08 1989-07-18 Taiwan Styrene Monomer Corporation Novel silicon-modified catalyst Si/HZSM-5 preparation
US4950835A (en) * 1989-10-24 1990-08-21 Taiwan Styrene Monomer Corporation Novel silicon-modified catalyst Si/HZSM-5, it's preparation, and a process for synthesizing high purity p-dialkyl benzene from monoalkyl benzene by using said catalyst
CN1131060A (en) * 1995-11-27 1996-09-18 南开大学 Catalyst for preparation of high purity para-diethylbenzene by using ethylbenzene disproportionation and its technology
CN1546236A (en) * 2003-11-28 2004-11-17 大连理工大学 Preparation and use of nano HZSM-5 zeolite metallic ion composite modified catalyst
CN101618335A (en) * 2009-08-06 2010-01-06 上海卓悦化工科技有限公司 Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol
CN103406142A (en) * 2013-07-16 2013-11-27 常州大学 Preparation method of P2O5 modified micro-porous molecular sieve shape-selective catalyst
CN105749961A (en) * 2016-03-22 2016-07-13 河南永大化工有限公司 Shape-selective catalyst for preparing p-xylene as well as preparation and application thereof
CN107213666A (en) * 2016-03-22 2017-09-29 河南永大化工有限公司 The separator of benzene in a kind of alkylation of toluene methanol reaction product
CN107913727A (en) * 2017-10-31 2018-04-17 中海油天津化工研究设计院有限公司 A kind of ethylbenzene is efficiently alkylated the preparation method of p-Diethylbenzene catalyst processed
CN109590019A (en) * 2017-09-30 2019-04-09 株式会社模范 Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas
CN110721737A (en) * 2019-11-11 2020-01-24 湘潭大学 Shape-selective catalyst for efficient alkylation of light aromatic hydrocarbon and methanol

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447666A (en) * 1982-12-30 1984-05-08 Mobil Oil Corporation Para-selective alkylation catalysts and processes
US4849386A (en) * 1987-04-08 1989-07-18 Taiwan Styrene Monomer Corporation Novel silicon-modified catalyst Si/HZSM-5 preparation
US4950835A (en) * 1989-10-24 1990-08-21 Taiwan Styrene Monomer Corporation Novel silicon-modified catalyst Si/HZSM-5, it's preparation, and a process for synthesizing high purity p-dialkyl benzene from monoalkyl benzene by using said catalyst
CN1131060A (en) * 1995-11-27 1996-09-18 南开大学 Catalyst for preparation of high purity para-diethylbenzene by using ethylbenzene disproportionation and its technology
CN1546236A (en) * 2003-11-28 2004-11-17 大连理工大学 Preparation and use of nano HZSM-5 zeolite metallic ion composite modified catalyst
CN101618335A (en) * 2009-08-06 2010-01-06 上海卓悦化工科技有限公司 Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol
CN103406142A (en) * 2013-07-16 2013-11-27 常州大学 Preparation method of P2O5 modified micro-porous molecular sieve shape-selective catalyst
CN105749961A (en) * 2016-03-22 2016-07-13 河南永大化工有限公司 Shape-selective catalyst for preparing p-xylene as well as preparation and application thereof
CN107213666A (en) * 2016-03-22 2017-09-29 河南永大化工有限公司 The separator of benzene in a kind of alkylation of toluene methanol reaction product
CN109590019A (en) * 2017-09-30 2019-04-09 株式会社模范 Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas
CN107913727A (en) * 2017-10-31 2018-04-17 中海油天津化工研究设计院有限公司 A kind of ethylbenzene is efficiently alkylated the preparation method of p-Diethylbenzene catalyst processed
CN110721737A (en) * 2019-11-11 2020-01-24 湘潭大学 Shape-selective catalyst for efficient alkylation of light aromatic hydrocarbon and methanol

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Para-selective methylation of toluene with methanol over nano-sized ZSM-5 catalysts: Synergistic effects of surface modifications with SiO2, P2O5 and MgO;Wei Tan et al.;《Microporous and Mesoporous Materials》;20140505;第196卷;18-30 *
硅磷镁改性对纳米HZSM-5催化苯和甲醇烷基化反应的影响;赵博 等;《石油学报（石油加工）》;20130825;第29卷(第4期);摘要、第1.1节、第1.3节 *

Also Published As

Publication number Publication date
CN115888800A (en) 2023-04-04

Similar Documents

Publication Publication Date Title
CN101485994B (en) Nano molecular sieve catalyst for synthesizing paraxylene and preparation method thereof
CN101885662B (en) Toluene methanol alkylation method
EP2803407B1 (en) Process for preparing paraxylene by concomitant conversion of methyl alcohol and/or dimethyl ether and c4 liquefied gas with a bimetal- and siloxane-modified zeolite catalyst
CN101884935A (en) Catalyst material and preparation method thereof
CN110756218A (en) Synthetic method and application of catalyst for producing durene
CN103638963A (en) P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof
CN101885663B (en) Method for converting heavy aromatics to light aromatics and transferring alkyl radical
CN104117385A (en) Modified IM-5 molecular sieve and catalyst as well as application
CN107970989B (en) Preparation method of xylene isomerization catalyst
CN106925339A (en) Preparation method of hierarchical pore molecular sieve catalyst for xylene isomerization reaction in carbon octaarene
CN110227546B (en) Catalyst for preparing p-xylene by methanol conversion and preparation method thereof
CN102616801A (en) Method for modification of zeolite NU-85 and aromatic isomerization catalyst containing modified zeolite NU-85
CN108786910B (en) C8Aromatic hydrocarbon isomerization catalyst and preparation method thereof
CN107955639B (en) Method for cracking hexaalkane
CN115888800B (en) Shape-selective catalyst for diethylbenzene and preparation method and application thereof
CN112299433B (en) Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application
CN107262140B (en) 2, 6-dimethylnaphthalene catalyst prepared from 2-methylnaphthalene, preparation and application thereof
CN109569703B (en) Catalyst for producing gasoline component from naphtha and methanol, preparation method and application
CN114192184B (en) Cracking catalyst and preparation method and application thereof
CN107445788B (en) Method for liquid-phase transalkylation of polyethylbenzene and benzene
JP3302553B2 (en) Catalyst for converting heavy aromatics to light aromatics and method for converting the same
CN108970636B (en) Preparation method of benzene alkylation catalyst
CN104230633A (en) Liquid phase alkyl transfer method
CN103664477A (en) Toluene shape-selective disproportionation method
CN102373069A (en) Method used for C6-alkane cracking

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