CN114797961B - Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene - Google Patents

Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene Download PDF

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CN114797961B
CN114797961B CN202110065830.2A CN202110065830A CN114797961B CN 114797961 B CN114797961 B CN 114797961B CN 202110065830 A CN202110065830 A CN 202110065830A CN 114797961 B CN114797961 B CN 114797961B
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刘盛林
董忠文
杨传禹
赵东璞
王玉忠
辛文杰
徐龙伢
朱向学
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Dalian Institute of Chemical Physics of CAS
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    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38Type ZSM-5
    • C01B39/40Type ZSM-5 using at least one organic template directing agent
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    • C07C2/862Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65

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Abstract

The invention provides a synthesis method of ZSM5/ZSM11 co-crystallized molecular sieve catalyst for alkylation reaction of ethanol and benzene, which comprises the following steps: the method takes USY, 1, 6-Hexamethylenediamine (HMDA), deionized water and inorganic base as raw materials, and the molar ratio of the initial raw materials is as follows: siO (SiO) 2 /Al 2 O 3 =50‑160、Na 2 O/SiO 2 =0.025‑0.1、HMDA/SiO 2 =0.05‑0.5、H 2 O/SiO 2 The initial raw material mixture is crystallized for 10-24 hours under the conditions of autogenous pressure and crystallization temperature of 130-150 ℃, ZSM5/ZSM11 co-crystallized zeolite is synthesized by hydrothermal synthesis, then 0.5-1.0 mol/L ammonium nitrate solution is used for exchange at 70-90 ℃, and HZSM5/ZSM11 co-crystallized zeolite catalyst in hydrogen form is prepared after drying and roasting. The synthesis time of the invention can be greatly shortened, and the stability of the benzene conversion rate on the catalyst can be further improved.

Description

Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene
Technical Field
The invention belongs to the field of molecular sieve catalysts, and particularly relates to a synthesis method of a ZSM5/ZSM11 co-crystallized zeolite catalyst for an alkylation reaction of ethanol and benzene.
Background
Ethylbenzene is an important petrochemical raw material, and is mainly used for producing styrene, which is an important raw material for producing polystyrene and other copolymer resins. Ethylbenzene can be produced by various different processes, mainly including a traditional AlCl3 liquid phase alkylation process and a molecular sieve alkylation process, wherein the molecular sieve alkylation production process has been greatly successful, and at present, the ethylbenzene production mainly includes an ethylene (dry gas) process, a benzene gas phase process and a liquid phase process.
The processes for preparing ethylbenzene by gas phase alkylation using ZSM-5 zeolite as catalyst are disclosed in U.S. Pat. Nos. 5,172, 3751506, 5,83 and 4547605, which have the advantages of no corrosion, no pollution, simple process and high recovery rate of heat energy. Patents US4891458, US5227558 and ZL02151177.2 disclose a process for the liquid phase alkylation of molecular sieves to produce ethylbenzene which uses beta and Y-type molecular sieves as catalysts and has the advantages of low reaction temperature, simple operation and few by-products.
The alkylating agents disclosed in the above patents are all ethylene and cannot be implemented in areas lacking ethylene resources. Ethanol is also a good alkylating agent, and is currently mainly derived from grain fermentation. Recently, domestic ethanol production from synthesis gas, ethanol production from acetic acid and acetate hydrogenation, and ethanol production from dimethyl ether carbonylation/hydrogenation are sequentially put into production, and in addition, important progress is made in biomass to produce cellulosic ethanol, so that more possibilities are provided for further utilization of ethanol. For example, the ethanol and benzene are synthesized into ethylbenzene by a one-step gas phase method, so that the investment and the operation cost of an ethanol dehydration device are saved, and the ethylbenzene is effectively supplemented. In addition, ethanol is adopted as an alkylating reagent, so that the method has the advantages of convenient raw material transportation and storage and simple operation.
Patent CN102274746 of Shanghai petrochemical institute discloses a catalyst obtained by roasting nano ZSM-5 after being treated with rare earth loaded, steam and phosphoric acid. At 390 ℃,1.2 MPa, the weight space velocity of ethanol is 0.8 h -1 Under the condition of benzene/ethanol mole ratio of 6.5, the ethanol conversion rate can reach 99.9%, the ethyl selectivity can reach 99.0%, the xylene content in the ethylbenzene product is below 800 ppm, and the catalyst regeneration period reaches half a year.
Pan Lvrang et al [ Pan Lvrang, li Hexuan ] university chemical school journal 1990,11 (6): 617] studied the change rule of the surface acidity of MgO, caO and BaO modified HZSM-5, and examined the activity and selectivity of the catalyst by reacting ethanol with benzene alkyl to ethylbenzene. The results show that both catalyst activity and selectivity decrease with increasing oxide content.
Sun Linping (Sun Linping) research on alkylation of coked benzene on a nano ZSM-5 molecular sieve to ethylbenzene (D), university of Dai's company, 2010] research on alkylation of coked benzene on a nano ZSM-5 molecular sieve to ethylbenzene. The activity and stability of the catalyst can be obviously improved after the catalyst is subjected to high-temperature roasting after being subjected to hydrothermal treatment and lanthanum oxide loading. Reducing the acid amount, acid strength, B/L value and pore formation on the surface of the nano ZSM-5 is an important factor for enhancing the stability of the catalyst. Nanometer ZSM-5 is used as a catalyst parent body, hydrothermal treatment and lanthanum oxide loading modification are carried out on the catalyst parent body, so that the sulfur-resistant industrial catalyst La-C-HT-HZSM-5 suitable for the reaction system is obtained, the alkylation reaction of coking benzene and ethylene is stably catalyzed for at least 1500 hours under the industrial production condition, and the ethylbenzene yield is more than 14%. Under the same conditions, the catalyst is used for alkylation reaction of coked benzene and ethanol, the ethylbenzene selectivity can reach 97%, but after 140 hours of operation, the activity starts to be reduced.
Since the development of zeolite materials, the zeolite materials have been widely used in the fields of adsorption, separation, catalytic reactions, and the like due to their regular pore structure, proper acidity, and good stability. In general, crystallization of zeolites requires specific organic molecules as templates that are directed to the formation of zeolites of specific structure by interaction with the silica-alumina species and binding to the zeolite framework. The molecular sieve can be synthesized by inorganic silicon-aluminum source or by crystal transformation (isomorphous or heteromorphous). Isomorphous guiding can accelerate the synthesis of molecular sieves, but the morphology is generally unchanged, and isomorphous guiding affects the synthesis speed of molecular sieves and the morphology and catalytic performance of molecular sieves. Therefore, development of a zeolite synthesis method by isomorphous transformation has important significance.
In 1980, the company Mobil synthesized ZSM5/ZSM11 co-crystallized zeolite with ZSM-5 and ZSM-11 intermediaries using quaternary ammonium salt as a template (USP 4229424), and further reported the catalytic applications of the zeolite in processes such as methanol to gasoline, olefin oligomerization, aromatic hydrocarbon alkylation, xylene isomerization, and hydrocarbon catalytic cracking (USP 4289607). CN 1137022, USP 5869021 and USP 6093866 disclose rare earth-ZSM 5/ZSM11 co-crystallized zeolite which is synthesized by taking C2-C8 diamine as a template agent and can be applied to catalytic processes of alkylation of dilute ethylene and benzene, aromatization of low-carbon alkane, preparation of low-carbon olefin from methanol and the like. At present, ZSM5/ZSM11 co-crystallized zeolite has successfully realized the industrial application of alkylation of ethylene and benzene in catalytic cracking dry gas, the required raw material dry gas can react with benzene to prepare ethylbenzene without special refining, and the catalyst developed by utilizing the co-crystallized zeolite is the key of the technology. However, the method for synthesizing ZSM5/ZSM11 co-crystallized zeolite by using USY isomorphous is not reported yet.
Disclosure of Invention
The invention aims to provide a synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene, which has simple operation process, good crystallization quality of the obtained product and wide application prospect. Compared with the conventional amorphous silicon-aluminum source synthesized ZSM5/ZSM11 co-crystallized zeolite, the synthesis time can be greatly shortened, the morphology is different, and the stability of the benzene conversion rate on the catalyst can be further improved.
The invention specifically provides a synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene, which takes USY, 1, 6-Hexamethylenediamine (HMDA), deionized water and inorganic base as raw materials, and the mole ratio of the initial raw materials is as follows: the preparation method comprises the steps of crystallizing an initial raw material mixture for reaction for 10-24 hours under the conditions of autogenous pressure and crystallization temperature of 130-150 ℃ under the conditions of 50-160 of SiO2/Al2O3 = 50-160, (Li2O+Na2O)/SiO2 = 0.025-0.1, MDA+/SiO2 = 0.05-0.5 and H2O/SiO2 = 5-15, hydrothermally synthesizing ZSM5/ZSM11 co-crystallized zeolite, exchanging with 0.5-1.0 mol/L ammonium nitrate solution at 70-90 ℃, drying and roasting to prepare the hydrogen-type HZSM5/ZSM11 molecular sieve catalyst.
According to the synthesis method of the ZSM5/ZSM11 co-crystallized zeolite catalyst for the alkylation reaction of ethanol and benzene, disclosed by the invention, the alkalinity of a system is regulated by using inorganic alkali, wherein the inorganic alkali is sodium hydroxide and/or lithium hydroxide, and the molar ratio of Li2O and/or Na2O to SiO2 is 0.05-0.08.
The invention provides a synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene, wherein the molar ratio of HMDA to SiO2 is 0.075-0.3.
The invention provides a synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene, wherein the roasting temperature is 500-600 ℃, and the roasting time is 4-8 hours.
The Na2O content in the ZSM5/ZSM11 cocrystallized zeolite catalyst prepared by the invention is less than or equal to 0.05 and wt percent.
The invention provides an application of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene, which is characterized in that the prepared ZSM5/ZSM11 co-crystallized zeolite catalyst is used for alkylation reaction of ethanol and benzene, and specifically comprises the following steps: the catalyst is put in N 2 (60 ml/min) in-situ pretreatment of 2h at 400 ℃ in the presence of ethanol and benzene as raw materials under the following reaction conditions: 1.5 MPa,380DEG C, ethanol weight space velocity 10h -1 Ethanol/benzene molar ratio=1/2.
Compared with the conventional amorphous silicon-aluminum source synthesized ZSM5/ZSM11 co-crystallized zeolite catalyst, the synthesis time can be greatly shortened, the morphology is different, and the stability of the benzene conversion rate on the catalyst is obviously improved.
Drawings
FIG. 1X-ray diffraction (XRD) patterns of the products obtained in comparative example 1 and example 1
FIG. 2 Scanning Electron Microscope (SEM) pictures of the products obtained in comparative example 1 and example 1
FIG. 3 comparative example 1 and examples 1 to 4 reaction evaluation
Detailed Description
The following examples further illustrate the invention, but are not intended to limit it.
Comparative example 1:
5.11g of chromatography silica gel (98 wt.% SiO 2), 0.93g of aluminum sulfate octadecanoate (99 wt wt.% Al2 (SO 4) 3.18H2O), 0.35g of sodium hydroxide (99 wt.% NaOH), 3.91g of 1, 6-hexamethylenediamine (99 wt.% HMDA) and 14.56g of deionized water were added to the reaction vessel in this order with stirring. The molar composition of the raw material mixture is: siO 2/ai 2 o3=60, na 2O/sio2=0.05, mda+/sio2=0.4, H2O/sio2=10. Stirring for 30min to fully and uniformly mix, sealing the synthesis kettle, and heating to 150 ℃ for dynamic (60 r/min) crystallization for 60h (crystallization for 24h, XRD spectrum shows that the solid is amorphous). Quenching reaction with tap water, centrifugal separation to obtain solid product and drying to obtain molecular sieve powder. The prepared molecular sieve was exchanged with 0.8 mol/L ammonium nitrate solution three times (2 hours/time), washed three times (1 hour/time), dried at 120℃and calcined at 540℃for 3 hours to prepare catalyst Cat-A. Wherein the ammonium nitrate exchange and water washing temperatures were 80 ℃. The obtained catalyst Cat-A has Na2O less than 0.05 and wt% detected by XRF. The XRD spectrum of the product Cat-A is shown in figure 1 and is a typical ZSM5/ZSM11 spectrum, and the SEM picture is shown in figure 2 and consists of irregular diamond shapes, similar triangles and the like. The prepared catalyst is used for the raw material benzene in the alkylation reaction of ethanol and benzene, and the change of the raw material benzene along with the reaction time is shown in figure 3.
Comparative example 2:
6.04g USY (SiO 2/Al2 O3=60), 0.35g sodium hydroxide and 14.56g deionized water were added to the reaction vessel in this order with stirring. The molar composition of the raw material mixture is: siO 2/ai 2 o3=60, na 2O/sio2=0.05, H2O/sio2=10. Stirring for 30min to fully and uniformly mix, sealing the synthesis kettle, heating to 150 ℃ for dynamic (60 r/min) crystallization for 100h, quenching reaction with tap water, centrifuging to obtain a solid product, and drying to obtain molecular sieve raw powder. XRD spectra showed that the solid had ZSM-5 diffraction peaks, and was very low in crystallinity, containing many amorphous materials.
Example 1:
6.04g USY (SiO 2/Al2 O3=60), 0.35g sodium hydroxide, 3.91g1, 6-hexamethylenediamine and 14.56g deionized water were added to the reaction vessel in this order with stirring. The molar composition of the raw material mixture is: siO 2/ai 2 o3=60, na 2O/sio2=0.05, mda+/sio2=0.4, H2O/sio2=10. Stirring for 30min to fully and uniformly mix, sealing the synthesis kettle, and heating to 150 ℃ for dynamic (60 rpm) crystallization for 24h. Quenching reaction with tap water, centrifugal separation to obtain solid product and drying to obtain molecular sieve powder. The prepared molecular sieve was exchanged with 0.8 mol/L ammonium nitrate solution three times (2 hours/time), washed three times (1 hour/time), dried at 120℃and calcined at 540℃for 3 hours to prepare catalyst Cat-B. Wherein the ammonium nitrate exchange and water washing temperatures were 80 ℃. The obtained catalyst Cat-B has Na2O less than 0.05 and wt% detected by XRF. XRD spectra of the obtained product Cat-B are shown in figure 1, typical ZSM5/ZSM11, and SEM pictures are shown in figure 2, and are spherical aggregates. The prepared catalyst is used for the raw material benzene in the alkylation reaction of ethanol and benzene, and the change of the raw material benzene along with the reaction time is shown in figure 3.
The implementation is as follows:
6.04g USY (SiO 2/Al2 O3=50), 0.36g lithium hydroxide (99 wt.% LiOH), 0.35g sodium hydroxide, 4.89g1, 6-hexamethylenediamine and 7.28g deionized water were added to the reaction vessel in this order with stirring. The molar ratio of the raw material mixture is as follows: siO 2/ai 2 o3=50, (li2o+na2o)/sio2=0.1, mda+/sio2=0.5, h2o/sio2=5. Stirring for 30min to fully and uniformly mix, sealing the synthesis kettle, and heating to 145 ℃ for dynamic (60 r/min) crystallization for 10h. Quenching reaction with tap water, centrifugal separation to obtain solid product and drying to obtain molecular sieve powder. The prepared molecular sieve is exchanged with 0.5 mol/L ammonium nitrate solution for three times (2 hours/time), washed with water for three times (1 hour/time), dried at 120 ℃, and baked at 500 ℃ for 8 hours to prepare the catalyst Cat-C. Wherein the ammonium nitrate exchange and water washing temperatures are 90 ℃. The catalyst Cat-C has Li2O less than 0.05 and wt% detected by XRF. XRD patterns and SEM of the resulting product Cat-C were similar to those of example 1. The prepared catalyst is used for the raw material benzene in the alkylation reaction of ethanol and benzene, and the change of the raw material benzene along with the reaction time is shown in figure 3.
The implementation is as follows:
6.04g USY (SiO 2/Al2 O3=160), 0.18g sodium hydroxide, 0.75 g1, 6-hexamethylenediamine and 21.84g deionized water were added to the reaction vessel in this order with stirring. The molar ratio of the raw material mixture is as follows: siO 2/ai 2 o3=160, na 2O/sio2=0.025, mda+/sio2=0.05, H2O/sio2=15. Stirring for 30min to fully and uniformly mix, sealing the synthesis kettle, and heating to 140 ℃ for dynamic (60 rpm) crystallization for 15h. Quenching reaction with tap water, centrifugal separation to obtain solid product and drying to obtain molecular sieve powder. The prepared molecular sieve was exchanged with 1.0mol/L ammonium nitrate solution three times (2 hours/time), washed three times (1 hour/time), dried at 120℃and calcined at 600℃for 4 hours to prepare catalyst Cat-D. Wherein the ammonium nitrate exchange and water washing temperatures were 70 ℃. The obtained catalyst Cat-D has Na2O less than 0.05 and wt% detected by XRF. XRD pattern and SEM of the resulting product Cat-D were similar to those of example 1. The prepared catalyst is used for the raw material benzene in the alkylation reaction of ethanol and benzene, and the change of the raw material benzene along with the reaction time is shown in figure 3.
The implementation is as follows:
6.04g USY (SiO 2/Al2 O3=100), 0.35g sodium hydroxide, 0.24g1, 6-hexamethylenediamine and 14.56g deionized water were added to the reaction vessel in this order with stirring. The molar ratio of the raw material mixture is as follows: siO 2/ai 2 o3=100, na 2O/sio2=0.05, mda+/sio2=0.025, H2O/sio2=10. Stirring for 30min to fully and uniformly mix, sealing the synthesis kettle, and heating to 150 ℃ for dynamic (60 rpm) crystallization for 12h. Quenching reaction with tap water, centrifugal separation to obtain solid product and drying to obtain molecular sieve powder. The prepared molecular sieve is exchanged with 0.8 mol/L ammonium nitrate solution for three times (2 hours/time), washed with water for three times (1 hour/time), dried at 120 ℃, and baked at 550 ℃ for 6 hours to prepare the catalyst Cat-D. Wherein the ammonium nitrate exchange and water washing temperatures were 80 ℃. The obtained catalyst Cat-E has Na2O less than 0.05 and wt% detected by XRF. XRD patterns and SEM of the resulting product Cat-E were similar to those of example 1. The prepared catalyst is used for the raw material benzene in the alkylation reaction of ethanol and benzene, and the change of the raw material benzene along with the reaction time is shown in figure 3.
Comparative example 1 and examples 1 to 4 reaction evaluation:
the reaction performance evaluation was performed on a fixed bed reactor with 0.5. 0.5 g catalyst placed in the middle constant temperature zone of a stainless steel reactor (inside diameter 12 mm, length 32 cm). Pre-reaction catalyst in N 2 (60 ml/min) atmosphere at 400 ℃ in situ pretreatment 2h, then adjusting to a given temperature, wherein the raw materials are ethanol and benzene, and the reaction conditions are as follows: 1.5 MPa,380 ℃, ethanol weight space velocity 10h -1 Ethanol (ethanol)Benzene molar ratio = 1/2. The analysis was sampled at regular time intervals, each sampling being a 1 hour cumulative sample. The generated product is separated into gas and liquid by a gas-liquid separator, the liquid is further dehydrated, the gas and dehydrated liquid products are all analyzed and formed by an Agilent 7890A chromatographic system, and the dehydrated liquid products adopt a PONA capillary column and a hydrogen flame ion detector. And normalizing the analysis result to obtain the composition of dry gas, liquefied gas and liquid products. The percentages adopted by the invention are weight percentages.
Experimental results show that the conversion rate of ethanol on the series of ZSM5/ZSM11 cocrystallized zeolite catalysts is more than 98%, the selectivity of ethylbenzene, diethylbenzene and other products is not obvious (not shown), and the conversion rate of benzene on the catalysts synthesized by different silicon-aluminum precursors changes with time as shown in figure 3. As can be seen from the results in the figure, the stability of benzene conversion on ZSM5/ZSM11 co-crystallized zeolite catalyst (Cat-B, cat-C, cat-D, cat-E) synthesized by USY transcrystalline can be further improved compared with conventional amorphous silica alumina source synthesized ZSM5/ZSM11 co-crystallized zeolite catalyst (Cat-A).

Claims (7)

1. A synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene is characterized in that: the method is characterized by taking USY, 1, 6-hexamethylenediamine HMDA, deionized water and inorganic alkali as raw materials, wherein the inorganic alkali is sodium hydroxide and/or lithium hydroxide, and the molar ratio of the initial raw materials is as follows: siO (SiO) 2 /Al 2 O 3 =50~160、Na 2 O and/or Li 2 O content and SiO 2 The molar ratio of HMDA/SiO is 0.05 to 0.08 2 =0.05~0.5、H 2 O/SiO 2 And (2) crystallizing the initial raw material mixture for 10-24 hours under the conditions of autogenous pressure and crystallization temperature of 130-150 ℃, hydrothermally synthesizing ZSM5/ZSM11 co-crystallizing zeolite, exchanging with 0.5-1.0 mol/L ammonium nitrate solution at 70-90 ℃, drying and roasting to prepare the hydrogen HZSM5/ZSM11 co-crystallizing zeolite catalyst.
2. A process for the synthesis of a ZSM5/ZSM11 co-crystallized zeolite catalyst according to claim 1 for the alkylation of ethanol with benzene,the method is characterized in that: the silicon-aluminum sources in the initial raw materials are all from USY, siO 2 /Al 2 O 3 The molar ratio of (2) is 60-100.
3. A process for synthesizing a ZSM5/ZSM11 co-crystallized zeolite catalyst for the alkylation of ethanol with benzene as claimed in claim 1, wherein: HMDA and SiO 2 The molar ratio of (2) is 0.075-0.3.
4. A process for synthesizing a ZSM5/ZSM11 co-crystallized zeolite catalyst for the alkylation of ethanol with benzene as claimed in claim 1, wherein: the roasting temperature is 500-600 ℃, and the roasting time is 4-8 hours.
5. A ZSM5/ZSM11 co-crystallized zeolite catalyst synthesized according to the process of any of claims 1-4 for the alkylation of ethanol with benzene.
6. A ZSM5/ZSM11 co-crystallized zeolite catalyst for the alkylation of ethanol with benzene as claimed in claim 5, wherein: na in the ZSM5/ZSM11 cocrystallized zeolite catalyst 2 The O content is less than or equal to 0.05 and wt percent.
7. The application of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene is characterized in that the ZSM5/ZSM11 co-crystallized zeolite catalyst synthesized by adopting the method of claim 1 is used for alkylation reaction of ethanol and benzene, and specifically comprises the following steps: the catalyst was added to 60mL/min of N 2 2h is pretreated in situ at 400 ℃ in the atmosphere, the raw materials are ethanol and benzene, and the reaction conditions are as follows: 1.5 MPa,380 ℃, ethanol weight space velocity 10h -1 Ethanol/benzene molar ratio=1/2.
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