CN114797961A - Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction - Google Patents
Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction Download PDFInfo
- Publication number
- CN114797961A CN114797961A CN202110065830.2A CN202110065830A CN114797961A CN 114797961 A CN114797961 A CN 114797961A CN 202110065830 A CN202110065830 A CN 202110065830A CN 114797961 A CN114797961 A CN 114797961A
- Authority
- CN
- China
- Prior art keywords
- zsm11
- ethanol
- zsm5
- benzene
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline 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
- C01B39/04—Crystalline 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
- C07C2/862—Preparation 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
- C07C2/864—Preparation 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
Abstract
The invention provides a synthesis method of a ZSM5/ZSM11 co-crystallized molecular sieve catalyst for alkylation reaction of ethanol and benzene, which comprises the following specific steps: USY, 1, 6-hexamethylene diamine (HMDA), deionized water and inorganic base are used as raw materials, and the molar ratio of the initial raw materials is as follows: SiO 2 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 5-15, crystallizing the initial raw material mixture for 10-24 hours under the conditions of autogenous pressure and crystallization temperature of 130-150 DEG CIn the process, ZSM5/ZSM11 cocrystallized zeolite is hydrothermally synthesized, then 0.5-1.0 mol/L ammonium nitrate solution is used for exchange at 70-90 ℃, and the catalyst is roasted after being dried to prepare the hydrogen type HZSM5/ZSM11 cocrystallized zeolite catalyst. 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
Technical Field
The invention belongs to the field of molecular sieve catalysts, and particularly relates to a synthesis method of a ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction.
Background
Ethylbenzene is an important petrochemical raw material and is mainly used for producing styrene, and the styrene is an important raw material for producing polystyrene and other copolymer resins. Ethylbenzene can be produced by various processes, mainly by conventional AlCl 3 Liquid phase alkylation and molecular sieve alkylation, wherein molecular sieve alkylation has been used with great success, and at present, ethylbenzene production mainly comprises gas phase and liquid phase processes of ethylene (dry gas) and benzene.
U.S. Pat. Nos. 3751504, 3751506, 4016218 and 4547605 disclose a process for preparing ethylbenzene by gas phase alkylation using ZSM-5 zeolite as catalyst, which has the advantages of no corrosion, no pollution, simple process and high heat recovery rate. Patents US4891458, US5227558 and ZL02151177.2 disclose a process for the liquid phase alkylation of molecular sieves to ethylbenzene which uses beta and Y type molecular sieves as catalysts, and has the advantages of low reaction temperature, simple operation and less 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 mainly derived from grain fermentation at present. Recently, domestic synthesis gas is used for preparing ethanol, acetic acid and acetic ester are hydrogenated to prepare ethanol, and dimethyl ether carbonylation/hydrogenation is used for preparing ethanol in a continuous mode. For example, the method for synthesizing the ethylbenzene by the ethanol and the benzene one-step gas phase method saves the investment and the operation cost of an ethanol dehydration device, and is an effective supplement for the ethylbenzene source. In addition, the ethanol is adopted as the alkylating reagent, and the method also has the advantages of convenient transportation and storage of raw materials and simple operation.
Patent CN102274746 of Shanghai oil chemical research institute discloses a catalyst obtained by roasting nanometer ZSM-5 after rare earth loading, water vapor and phosphoric acid treatment. At 390 ℃, 1.2MPa and the weight space velocity of ethanol of 0.8h -1 Under the condition of benzene/ethanol molar ratio of 6.5, the conversion rate of ethanol can reach 99.9%, the ethyl selectivity can reach 99.0%, the content of xylene in the product ethylbenzene is below 800ppm, and the regeneration period of the catalyst can reach half a year.
Pan Pao et al [ Pan Pao, Li He bro, advanced school chemistry, 1990,11(6):617] studied the law of changes in the acidity of MgO, CaO and BaO modified HZSM-5 surface, and examined the activity and selectivity of the catalyst by the alkylation reaction of ethanol with benzene to synthesize ethylbenzene. The results show that as the oxide content increases, both the catalyst activity and selectivity decrease.
Research on synthesis of ethylbenzene by alkylation of coking benzene on nano ZSM-5 molecular sieve was carried out on synthesis of ethylbenzene by alkylation of coking benzene on nano ZSM-5 molecular sieve (D), university of Oncorhynchs, 2010). After hydrothermal treatment and high-temperature roasting between the catalyst and the loaded lanthanum oxide, the activity and stability of the catalyst can be obviously improved. The reduction of the acid amount, the acid strength, the B/L value and the pore-forming of the surface of the nano ZSM-5 are important factors for enhancing the stability of the catalyst. Nano ZSM-5 is used as a catalyst matrix, hydrothermal treatment and loaded lanthanum oxide modification are carried out on the nano ZSM-5 to obtain the sulfur-resistant industrial catalyst La-C-HT-HZSM-5 suitable for the reaction system, the coking benzene and the ethylene alkylation reaction are 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 the alkylation reaction of coking benzene and ethanol, the ethylbenzene selectivity can reach 97%, but the activity begins to decline after running for 140 hours.
Since the development of zeolite materials, the zeolite materials are widely applied to the fields of adsorption, separation, catalytic reaction and the like due to the regular pore channel structure, proper acidity and better stability. In general, crystallization of zeolites requires a specific organic molecule as a templating agent that directs the formation of a zeolite of a specific structure through interaction with the silica-alumina species and binding to the zeolite framework. In terms of synthesis mode, the molecular sieve can be synthesized by an inorganic silica-alumina source, and can also be synthesized by a crystal transformation (isomorphous or heteromorphic) mode. Isomorphous orientation can accelerate the synthesis of the molecular sieve, but the morphology is generally unchanged, while isomorphous orientation influences the synthesis speed of the molecular sieve and also possibly influences the morphology and catalytic performance of the molecular sieve. Therefore, the development of a heteromorphic crystal transition zeolite synthesis method has important significance.
In 1980, Mobil corporation used quaternary ammonium salt as template to synthesize ZSM5/ZSM11 co-crystallized zeolite (USP 4229424) with intermediate structure of ZSM-5 and ZSM-11, and further reported the catalytic application of the zeolite in processes of methanol-to-gasoline, olefin oligomerization, aromatic alkylation, xylene isomerization and hydrocarbon catalytic cracking (USP 4289607). CN 1137022, USP 5869021 and USP 6093866 disclose a rare earth-ZSM 5/ZSM11 cocrystallized zeolite, which is synthesized by using C2-C8 diamine as a template agent and can be applied to catalytic processes such as 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 cocrystallized zeolite has successfully realized the industrial application of the alkylation of ethylene and benzene in the 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 cocrystallized zeolite is the key of the technology. However, the method for synthesizing ZSM5/ZSM11 cocrystallized zeolite by USY isomorphous has not been reported yet.
Disclosure of Invention
The invention aims to provide a synthetic method of a ZSM5/ZSM11 cocrystallization zeolite catalyst for ethanol and benzene alkylation reaction, 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 particularly provides a ZSM5/ZSM11 cocrystallization boiling point for alkylation reaction of ethanol and benzeneThe synthesis method of the stone catalyst takes USY, 1, 6-hexamethylene diamine (HMDA), deionized water and inorganic base as raw materials, and the molar ratio of the initial raw materials is as follows: SiO 2 2 /Al 2 O 3 ＝50～160、(Li 2 O+Na 2 O)/SiO 2 ＝0.025～0.1、MDA + /SiO 2 ＝0.05～0.5、H 2 O/SiO 2 And (2) crystallizing the initial reaction raw material mixture for 10-24 hours under the conditions of autogenous pressure and crystallization temperature of 130-150 ℃, hydrothermally synthesizing ZSM5/ZSM11 cocrystallized zeolite, exchanging at 70-90 ℃ by using 0.5-1.0 mol/L ammonium nitrate solution, drying, and roasting to prepare the hydrogen type HZSM5/ZSM11 molecular sieve catalyst.
The invention provides a synthesis method of a ZSM5/ZSM11 co-crystallization zeolite catalyst for ethanol and benzene alkylation reaction, which adjusts the alkalinity of a system by using inorganic alkali, wherein the inorganic alkali is sodium hydroxide and/or lithium hydroxide, and Li 2 O and/or Na 2 O and SiO 2 The molar ratio of (A) to (B) is 0.05 to 0.08.
The invention provides a synthetic method of a ZSM5/ZSM11 cocrystallized zeolite catalyst for alkylation of ethanol and benzene, HMDA and SiO 2 The molar ratio of (A) to (B) is 0.075-0.3.
The invention provides a synthesis method of a ZSM5/ZSM11 co-crystallization zeolite catalyst for ethanol and benzene alkylation reaction, wherein the roasting temperature is 500-600 ℃, and the roasting time is 4-8 hours.
Na in ZSM5/ZSM11 cocrystallized zeolite catalyst prepared by the invention 2 The O content is less than or equal to 0.05 wt%.
The invention provides an application of ZSM5/ZSM11 cocrystallized zeolite catalyst for alkylation reaction of ethanol and benzene, which is characterized in that the ZSM5/ZSM11 cocrystallized zeolite catalyst prepared by the method in claim 1 is used for alkylation reaction of ethanol and benzene, and specifically comprises the following steps: the catalyst is added in N 2 (60ml/min) in-situ pretreatment is carried out for 2h at 400 ℃, the raw materials are ethanol and benzene, and the reaction conditions are as follows: 1.5MPa, 380 ℃ and the ethanol weight space velocity of 10h -1 The molar ratio of ethanol to benzene was 1/2.
The ZSM5/ZSM11 co-crystallization zeolite catalyst synthesized by USY crystal transformation is used for the alkylation reaction of ethanol and benzene, compared with the conventional amorphous ZSM5/ZSM11 co-crystallization zeolite catalyst synthesized by a silicon-aluminum source, 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 reaction evaluation of comparative example 1 and examples 1 to 4
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Comparative example 1:
under stirring, 5.11g of chromatography silica gel (98 wt.% SiO) 2 ) 0.93g of aluminum sulfate octadecahydrate (99 wt.% Al) 2 (SO 4 ) 3 ·18H 2 O), 0.35g sodium hydroxide (99 wt.% NaOH), 3.91g1, 6-hexanediamine (99 wt.% HMDA), and 14.56g deionized water were added to the reaction kettle in that order. The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝60，Na 2 O/SiO 2 ＝0.05，MDA + /SiO 2 ＝0.4，H 2 O/SiO 2 10. Stirring for 30min to mix thoroughly, sealing the synthesis kettle, heating to 150 deg.C, dynamically crystallizing at 60 rpm for 60 hr (crystallizing for 24 hr, XRD spectrum shows that the solid is amorphous). Quenching the reaction with tap water, centrifugally separating to obtain a solid product, and drying to obtain the molecular sieve raw powder. The prepared molecular sieve is exchanged for three times (2 hours/time) by using 0.8mol/L ammonium nitrate solution, washed for three times (1 hour/time), dried at 120 ℃, and roasted for 3 hours at 540 ℃ to prepare the catalyst Cat-A. Wherein the ammonium nitrate exchange and water washing temperature is 80 ℃. The obtained catalyst Cat-A is detected by XRF, and Na in the catalyst is detected 2 O is less than 0.05 wt%. The XRD spectrum of the obtained product Cat-A is shown in figure 1, and is the spectrum of typical ZSM5/ZSM11, and the SEM picture is shown in figure 2 and consists of irregular diamonds, triangles and the like. The prepared catalyst is used for ethanolAnd benzene alkylation the feed benzene as a function of reaction time is shown in figure 3.
Comparative example 2:
under stirring, 6.04g USY (SiO) 2 /Al 2 O 3 60), 0.35g sodium hydroxide and 14.56g deionized water were added to the reaction kettle in that order. The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝60，Na 2 O/SiO 2 ＝0.05，H 2 O/SiO 2 10. Stirring for 30min to mix thoroughly, sealing the synthesis kettle, heating to 150 deg.C for dynamic (60 r/min) crystallization for 100h, quenching with tap water, centrifuging to obtain solid product, and drying to obtain molecular sieve powder. The XRD pattern showed that the solid had ZSM-5 diffraction peak and very low crystallinity, containing many amorphous substances.
Example 1:
under stirring, 6.04gUSY (SiO) 2 /Al 2 O 3 60), 0.35g of sodium hydroxide, 3.91g of 1, 6-hexanediamine and 14.56g of deionized water were added to the reaction vessel in this order. The molar composition of the raw material mixture is: SiO 2 2 /Al 2 O 3 ＝60，Na 2 O/SiO 2 ＝0.05，MDA + /SiO 2 ＝0.4，H 2 O/SiO 2 10. Stirring for 30min to mix thoroughly, sealing the synthesis kettle, and dynamically crystallizing at 150 deg.C (60 r/min) for 24 h. Quenching the reaction with tap water, centrifugally separating to obtain a solid product, and drying to obtain the molecular sieve raw powder. The prepared molecular sieve is exchanged for three times (2 hours/time) by using 0.8mol/L ammonium nitrate solution, washed for three times (1 hour/time), dried at 120 ℃, and roasted for 3 hours at 540 ℃ to prepare the catalyst Cat-B. Wherein the ammonium nitrate exchange and water washing temperature is 80 ℃. The obtained catalyst Cat-B, detected by XRF, contains Na 2 O is less than 0.05 wt%. The XRD spectrum of the obtained product Cat-B is shown in figure 1, and is the spectrum of typical ZSM5/ZSM11, and the SEM picture is shown in figure 2 and is spherical aggregate. The catalyst prepared was used in the alkylation of ethanol with benzene as a function of the reaction time for the feed benzene as shown in FIG. 3.
Example 2:
under stirring, 6.04gUSY (SiO) 2 /Al 2 O 3 50), 0.36g of lithium hydroxide (99 wt.% LiOH), 0.35g of sodium hydroxide, 4.89g of 1, 6-hexanediamine and 7.28g of deionized water were added to the reaction kettle in that order. The molar ratio of the raw material mixture is as follows: SiO 2 2 /Al 2 O 3 ＝50、(Li 2 O+Na 2 O)/SiO 2 ＝0.1、MDA + /SiO 2 ＝0.5、H 2 O/SiO 2 5. Stirring for 30min to mix thoroughly, sealing the synthesis kettle, and dynamically crystallizing at 145 deg.C (60 r/min) for 10 h. Quenching reaction with tap water, centrifugally separating to obtain solid product and drying to obtain molecular sieve powder. And exchanging the prepared molecular sieve with 0.5mol/L ammonium nitrate solution for three times (2 hours/time), washing with water for three times (1 hour/time), drying at 120 ℃, and roasting at 500 ℃ for 8 hours to obtain the catalyst Cat-C. Wherein the ammonium nitrate exchange and water wash temperature is 90 ℃. The obtained catalyst Cat-C is detected by XRF, and Li in the catalyst 2 O is less than 0.05 wt%. The XRD pattern and SEM of the resulting product Cat-C were similar to those of example 1. The catalyst prepared was used in the alkylation of ethanol with benzene as a function of the reaction time for the feed benzene as shown in FIG. 3.
Example 3:
under stirring, 6.04gUSY (SiO) 2 /Al 2 O 3 160), 0.18g of sodium hydroxide, 0.755g of 1, 6-hexanediamine and 21.84g of deionized water were added to the reaction vessel in this order. The molar ratio of the raw material mixture is as follows: SiO 2 2 /Al 2 O 3 ＝160、Na 2 O/SiO 2 ＝0.025、MDA + /SiO 2 ＝0.05、H 2 O/SiO 2 15. Stirring for 30min to mix thoroughly, sealing the synthesis kettle, and dynamically crystallizing at 140 deg.C (60 r/min) for 15 h. Quenching the reaction with tap water, centrifugally separating to obtain a solid product, and drying to obtain the molecular sieve raw powder. The prepared molecular sieve is exchanged for three times (2 hours/time) by using 1.0mol/L ammonium nitrate solution, washed for three times (1 hour/time), dried at 120 ℃, and roasted for 4 hours at 600 ℃ to prepare the catalyst Cat-D. Wherein the ammonium nitrate exchange and water wash temperature is 70 ℃. The obtained catalyst Cat-D was detected by XRFNa in the catalyst 2 O is less than 0.05 wt%. The XRD pattern and SEM of the resulting product, Cat-D, were similar to those of example 1. The catalyst prepared was used in the alkylation of ethanol with benzene as a function of the reaction time for the feed benzene as shown in FIG. 3.
Example 4:
under stirring, 6.04gUSY (SiO) 2 /Al 2 O 3 100), 0.35g sodium hydroxide, 0.24g1, 6-hexanediamine and 14.56g deionized water were added to the reaction kettle in that order. The molar ratio of the raw material mixture is as follows: SiO 2 2 /Al 2 O 3 ＝100、Na 2 O/SiO 2 ＝0.05、MDA + /SiO 2 ＝0.025、H 2 O/SiO 2 10. Stirring for 30min to mix thoroughly, sealing the synthesis kettle, and dynamically crystallizing at 150 deg.C (60 r/min) for 12 h. Quenching the reaction with tap water, centrifugally separating to obtain a solid product, and drying to obtain the molecular sieve raw powder. The prepared molecular sieve is exchanged for three times (2 hours/time) by using 0.8mol/L ammonium nitrate solution, washed for three times (1 hour/time), dried at 120 ℃, and roasted for 6 hours at 550 ℃ to prepare the catalyst Cat-D. Wherein the ammonium nitrate exchange and water washing temperature is 80 ℃. The resulting catalyst, Cat-E, was examined by XRF for Na 2 O is less than 0.05 wt%. The XRD pattern and SEM of the resulting product Cat-E were similar to those of example 1. The catalyst prepared was used in the alkylation of ethanol with benzene as a function of the reaction time for the feed benzene as shown in FIG. 3.
Comparative example 1 and examples 1 to 4 reaction evaluation:
the evaluation of the reaction properties was carried out on a fixed-bed reactor, 0.5g of the catalyst being placed in a constant temperature zone in the middle of a stainless steel reactor (internal diameter 12mm, length 32 cm). Catalyst before reaction in N 2 Pretreating in situ for 2h at 400 ℃ in the atmosphere of 60ml/min, then adjusting to a given temperature, wherein the raw materials are ethanol and benzene, and the reaction conditions are as follows: 1.5MPa, 380 ℃ and the ethanol weight space velocity of 10h -1 The molar ratio of ethanol to benzene was 1/2. Samples were taken at regular intervals for analysis, each sample being a 1 hour cumulative sample. Separating the resultant product into gas and liquid by gas-liquid separator, further dehydrating the liquid, and using Agilent 7890A to separate the gas and the dehydrated liquid productThe chromatographic system is used for analyzing the composition, and the dehydrated liquid product adopts a PONA capillary column and a hydrogen flame ion detector. The analysis result is normalized to obtain the composition of dry gas, liquefied gas and liquid product. The percentage adopted by the invention is weight percentage.
The experimental results show that the conversion rates of ethanol on the series of ZSM5/ZSM11 cocrystallized zeolite catalysts are all larger than 98%, the selectivity differences of products such as ethylbenzene, diethylbenzene and the like are not obvious (not shown), and the conversion rates of benzene on the catalysts synthesized by different silicon-aluminum precursors are changed along with time as shown in figure 3. From the results in the figure, it can be seen that the stability of benzene conversion rate on the USY crystal-transformed ZSM5/ZSM11 cocrystallized zeolite catalyst (Cat-B, Cat-C, Cat-D, Cat-E) can be further improved compared with the conventional amorphous silica-alumina source synthesized ZSM5/ZSM11 cocrystallized zeolite catalyst (Cat-A).
Claims (8)
1. A synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction is characterized in that: USY, 1, 6-hexamethylene diamine (HMDA), deionized water and inorganic base are used as raw materials, and the molar ratio of the initial raw materials is as follows: SiO 2 2 /Al 2 O 3 ＝50～160、(Li 2 O+Na 2 O)/SiO 2 ＝0.025～0.1、MDA + /SiO 2 ＝0.05～0.5、H 2 O/SiO 2 And (2) crystallizing the initial reaction raw material mixture for 10-24 hours under the conditions of autogenous pressure and crystallization temperature of 130-150 ℃, hydrothermally synthesizing ZSM5/ZSM11 co-crystallized zeolite, exchanging at 70-90 ℃ by using 0.5-1.0 mol/L ammonium nitrate solution, drying, and roasting to prepare the hydrogen type HZSM5/ZSM11 co-crystallized zeolite catalyst.
2. A process for the synthesis of a ZSM5/ZSM11 co-crystallized zeolite catalyst for use in the alkylation of ethanol with benzene as claimed in claim 1 wherein: the silicon-aluminum source in the initial raw material is all from USY, SiO 2 /Al 2 O 3 The molar ratio of (A) to (B) is 60 to 100.
3. A process according to claim 1 for the alkylation of ethanol with benzeneThe synthesis method of the reaction ZSM5/ZSM11 cocrystallization zeolite catalyst is characterized in that: the inorganic alkali is sodium hydroxide and/or lithium hydroxide, Na 2 O and/or Li 2 O content and SiO 2 The molar ratio of (A) to (B) is 0.05 to 0.08.
4. A process for the synthesis of a ZSM5/ZSM11 co-crystallized zeolite catalyst for use in the alkylation of ethanol with benzene as claimed in claim 1 wherein: HMDA and SiO 2 The molar ratio of (A) to (B) is 0.075-0.3.
5. A process for the synthesis of a ZSM5/ZSM11 co-crystallized zeolite catalyst for use in 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.
6. A ZSM5/ZSM11 co-crystallized zeolite catalyst for the alkylation of ethanol with benzene synthesized by the method of any one of claims 1-5.
7. A ZSM5/ZSM11 co-crystallized zeolite catalyst for ethanol and benzene alkylation in accordance with claim 6, wherein: na in the ZSM5/ZSM11 co-crystallized zeolite catalyst 2 The content of O is less than or equal to 0.05wt percent.
8. Use of a ZSM5/ZSM11 co-crystallized zeolite catalyst for ethanol and benzene alkylation, characterized in that a ZSM5/ZSM11 co-crystallized zeolite catalyst prepared according to claim 1 is used for ethanol and benzene alkylation, and specifically: the catalyst is added in N 2 (60ml/min) in-situ pretreatment is carried out for 2h at 400 ℃, the raw materials are ethanol and benzene, and the reaction conditions are as follows: 1.5MPa, 380 ℃ and the ethanol weight space velocity of 10h -1 The molar ratio of ethanol to benzene was 1/2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110065830.2A CN114797961B (en) | 2021-01-19 | 2021-01-19 | Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110065830.2A CN114797961B (en) | 2021-01-19 | 2021-01-19 | Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114797961A true CN114797961A (en) | 2022-07-29 |
| CN114797961B CN114797961B (en) | 2023-09-26 |
Family
ID=82524396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110065830.2A Active CN114797961B (en) | 2021-01-19 | 2021-01-19 | Synthesis method of ZSM5/ZSM11 co-crystallized zeolite catalyst for alkylation reaction of ethanol and benzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114797961B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000022155A (en) * | 1996-06-24 | 2000-04-25 | 후순 페트로-케미컬 콤파니, 시노펙 | Alkylation catalyst and the application thereof |
| CN101717095A (en) * | 2009-12-23 | 2010-06-02 | 中国科学院大连化学物理研究所 | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite |
| CN102372282A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院大连化学物理研究所 | Amine-free synthesis method for ZSM5/ZSM11 co-crystallized zeolite |
| CN102389830A (en) * | 2011-10-31 | 2012-03-28 | 中国科学院大连化学物理研究所 | Preparation method of superfine cocrystallized molecular sieve catalyst |
| CN102745715A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of small crystal grain ZSM-5/ZSM-11 composite zeolite |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN105381814A (en) * | 2015-10-09 | 2016-03-09 | 江苏常青树新材料科技有限公司 | Catalyst used in alkylation reaction of ethylbenzene and ethanol and preparation method thereof |
| CN106466625A (en) * | 2015-08-19 | 2017-03-01 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of binder free phosphorus rare earth-ZSM5/ZSM11 molecular sieve catalyst |
| CN106673002A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Synthesis method of ZSM-11/ZSM-5 composite molecular sieve and composite molecular sieve synthesized through same |
| CN110422856A (en) * | 2019-07-05 | 2019-11-08 | 中节能万润股份有限公司 | Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR |
-
2021
- 2021-01-19 CN CN202110065830.2A patent/CN114797961B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000022155A (en) * | 1996-06-24 | 2000-04-25 | 후순 페트로-케미컬 콤파니, 시노펙 | Alkylation catalyst and the application thereof |
| CN101717095A (en) * | 2009-12-23 | 2010-06-02 | 中国科学院大连化学物理研究所 | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite |
| CN102372282A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院大连化学物理研究所 | Amine-free synthesis method for ZSM5/ZSM11 co-crystallized zeolite |
| CN102745715A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of small crystal grain ZSM-5/ZSM-11 composite zeolite |
| CN102389830A (en) * | 2011-10-31 | 2012-03-28 | 中国科学院大连化学物理研究所 | Preparation method of superfine cocrystallized molecular sieve catalyst |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN106466625A (en) * | 2015-08-19 | 2017-03-01 | 中国科学院大连化学物理研究所 | A kind of preparation method and application of binder free phosphorus rare earth-ZSM5/ZSM11 molecular sieve catalyst |
| CN105381814A (en) * | 2015-10-09 | 2016-03-09 | 江苏常青树新材料科技有限公司 | Catalyst used in alkylation reaction of ethylbenzene and ethanol and preparation method thereof |
| CN106673002A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Synthesis method of ZSM-11/ZSM-5 composite molecular sieve and composite molecular sieve synthesized through same |
| CN110422856A (en) * | 2019-07-05 | 2019-11-08 | 中节能万润股份有限公司 | Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114797961B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2607633C2 (en) | Moulded catalyst for converting methanol into aromatic hydrocarbons and method of producing said catalyst | |
| CN112657547B (en) | Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve | |
| CN108726535B (en) | Preparation method of phosphorus modified ZSM-5 molecular sieve with hierarchical pores | |
| NO164830B (en) | NEW CRYSTALLINE ALUMINUM SILICATES. | |
| Akhtar et al. | Aromatization of alkanes over Pt promoted conventional and mesoporous gallosilicates of MEL zeolite | |
| CN111054430B (en) | Core-shell structure HZSM-5 molecular sieve for reaction of preparing aromatic hydrocarbon from methanol and preparation method thereof | |
| US11434183B2 (en) | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof | |
| JP7467475B2 (en) | Catalyst for producing light olefins from C4-C7 hydrocarbons | |
| US20070032379A1 (en) | Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst | |
| CN106215970A (en) | The modification processing method of HZSM 5 molecular sieve catalyst and application | |
| CN112645349A (en) | Preparation method and application of mordenite molecular sieve | |
| CN105102374A (en) | Dehydration-hydrolysis processes and catalysts therefor | |
| LI et al. | Effect of ZSM-5 acid modification on aromatization performance of methanol | |
| EP2773603A1 (en) | Catalyst and process for hydrocarbon conversion | |
| CN104475150B (en) | One-step synthesis method for B-EU-1/ZSM-5 composite molecular sieve | |
| CN102502682A (en) | Mordenite preparation method | |
| JPS62114656A (en) | Catalyst for inverting hydrocarbon, manufacture thereof and inversion reaction method of hydrocarbon | |
| CN101549302A (en) | Faujasite/Al2O3 composite material and preparation method thereof | |
| CN108435246B (en) | Preparation method of hierarchical pore isomorphous substituted Ga-ZSM-5 molecular sieve catalyst | |
| CN107262140B (en) | 2, 6-dimethylnaphthalene catalyst prepared from 2-methylnaphthalene, preparation and application thereof | |
| CN107955639B (en) | Method for cracking hexaalkane | |
| WO2019228132A1 (en) | Process for preparation of aromatic compound from biomass | |
| CN114797961A (en) | Synthetic method of ZSM5/ZSM11 cocrystallized zeolite catalyst for ethanol and benzene alkylation reaction | |
| Aloise et al. | Catalytic behavior in propane aromatization using GA-MFI catalyst | |
| Heng et al. | Facile preparation of hierarchically porous IM-5 zeolite with enhanced catalytic performance in methane aromatization |
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 |