CN114057538B - Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene - Google Patents

Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene Download PDF

Info

Publication number
CN114057538B
CN114057538B CN202010755137.3A CN202010755137A CN114057538B CN 114057538 B CN114057538 B CN 114057538B CN 202010755137 A CN202010755137 A CN 202010755137A CN 114057538 B CN114057538 B CN 114057538B
Authority
CN
China
Prior art keywords
ethylene
molecular sieve
benzene
aluminum
reaction
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
CN202010755137.3A
Other languages
Chinese (zh)
Other versions
CN114057538A (en
Inventor
翟云平
梁世航
王永睿
罗一斌
舒兴田
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.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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 Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN202010755137.3A priority Critical patent/CN114057538B/en
Publication of CN114057538A publication Critical patent/CN114057538A/en
Application granted granted Critical
Publication of CN114057538B publication Critical patent/CN114057538B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • 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

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a preparation method of ethylbenzene, which is characterized in that the method is characterized in that ethylbenzene is obtained by gas phase alkylation reaction carried out by contacting ethylene-containing gas with benzene under the conditions of 260-360 ℃ and 0.3-2.0MPa in the presence of a catalyst taking TUN structure molecular sieve as an active component. The method can effectively reduce the reaction temperature, has less side reaction and high ethylbenzene quality.

Description

Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene
Technical Field
The invention relates to a method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene
Background
Ethylbenzene is an important petrochemical raw material and is mainly used for the production of styrene. Styrene is an important monomer for synthesizing high molecular materials such as polystyrene and copolymer ABS resin. The increasing demand for high quality styrene has driven an increase in the demand for ethylbenzene.
At present, ethylbenzene is mainly produced by alkylation of benzene with ethylene. The process for preparing ethylbenzene by gas phase alkylation has the characteristics of wide sources of ethylene raw materials and flexible operation of devices. Pure ethylene, dilute ethylene or concentrated ethylene can be used as the reaction raw material. Dilute ethylene refers to ethylene in the catalytically cracked dry gas, which is present in an amount of about 12 to 25%. The concentrated ethylene refers to ethylene contained in the gas produced in the process of preparing olefin from methanol, and the content of the ethylene is about 60-95%. Compared with pure ethylene, the method for synthesizing ethylbenzene by using dilute ethylene in catalytic dry gas or concentrated ethylene generated in the process of preparing olefin from methanol as reaction raw materials can save raw material cost and has better economic benefit.
The traditional ethylbenzene production process mostly uses inorganic acids such as aluminum trichloride, solid phosphoric acid and the like as catalysts. The inorganic acid catalyst has serious corrosion to equipment pipelines and cannot be regenerated and used, so that the traditional process has large investment and more three wastes. At present, molecular sieves are used as catalysts in the ethylbenzene production process. US3751504 and US3751506 disclose a process for preparing ethylbenzene by gas phase alkylation of pure ethylene and benzene using a ZSM-5 molecular sieve as catalyst at a reaction temperature of 380-450 ℃ and a xylene content of higher than 2000ppm; US4107224 reports a method for preparing ethylbenzene by gas phase alkylation of dilute ethylene and benzene with a ZSM-5 molecular sieve as a catalyst, wherein the reaction temperature is 370 ℃, and the reaction raw materials need to be strictly refined to remove impurities such as hydrogen sulfide and water, and the operation is complex; CN1031072a discloses a rare earth element-containing Pentasil type aluminosilicate zeolite catalyst and a process for preparing ethylbenzene by alkylation reaction of benzene and low concentration ethylene, wherein the temperature is 375-425 ℃; CN106881146a reports a method of using F-ZSM-11 molecular sieve for the production of ethylbenzene from dry gas and phenylalkyl, in the examples the reaction temperature is 340 ℃ and the xylene content is >750ppm.
In summary, the prior art generally has the problems of high reaction temperature and high content of byproduct dimethylbenzene. The separation of the dimethylbenzene and the ethylbenzene is difficult because the boiling points of the dimethylbenzene and the ethylbenzene are not different, and the quality of ethylbenzene products is affected. The mesoporous molecular sieve adopted in the process has a pore diameter close to the diameters of benzene and alkylbenzene, and has a certain limit on the diffusion of reactant and product molecules in micropores while providing good shape selectivity, so that a higher reaction temperature (such as 360-480 ℃) is required to promote the molecular diffusion. However, at higher reaction temperatures, the side reactions of ethylbenzene isomerization to xylenes are exacerbated, resulting in higher xylenes content in the product.
Disclosure of Invention
The invention aims at solving the problems of high reaction temperature and high xylene content, and provides a method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas with low xylene content and benzene, which reduces the reaction temperature.
The method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene is characterized in that the method is a gas phase alkylation reaction carried out by contacting the ethylene-containing gas and benzene under the conditions of 260-360 ℃ and 0.3-2.0MPa in the presence of a catalyst taking TUN structure molecular sieve as an active component.
In the invention, the catalyst comprises the following components: 60-90wt% TUN structure molecular sieve and 10-40wt% aluminum-containing oxide; preferably, the catalyst consists of 60-90wt% TUN structure molecular sieve and 10-40wt% aluminum-containing oxide.
The invention adopts TUN structure molecular sieve with larger diameter than ZSM-5 or ZSM-5/ZSM-11 molecular sieve pore canal as catalyst active component, and can realize gas phase alkylation reaction of ethylene and benzene under the reaction temperature condition of 360 ℃ and below. TUN structure molecular sieves (J.am.chem.Soc.2007, 129, 10870-10885) have two 10-membered ring channels independent of each other, the diameters of which are 0.52x 0.60nm and 0.55x 0.60nm, respectively, the channels being connected by other 10-membered rings (0.54 x 0.55 nm). The TUN structure molecular sieve SiO 2 /Al 2 O 3 The molar ratio is 20 to 300, preferably 40 to 200, more preferably 60 to 150, most preferably 80 to 120.
In the present invention, the preferred TUN structure molecular sieve is TNU-9. The TNU-9 molecular sieve is prepared by crystallizing a mixture of a silicon source, an aluminum source, a template agent R, alkali and water at 100-200 ℃ for 2-14 days and recycling; wherein the mixture is SiO in mole ratio 2 /A1 2 O 3 ＝30-300,H 2 O/SiO 2 ＝10-70,R/SiO 2 ＝0.10-0.30,NaOH/SiO 2 =0.4-1.0; the template agent R is 1, 4-diazamethylpyrrolidine butane bromide; the silicon source is at least one of white carbon black, amorphous silicon dioxide, silica sol, silica gel, diatomite or water glass; the aluminum source is at least one of aluminum hydroxide, aluminum isopropoxide, aluminum sec-butoxide, sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride or aluminum oxide, and the alkali is inorganic alkali and at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.
In the invention, the preparation method of the catalyst comprises the following steps: and carrying out ammonium exchange, washing, drying and roasting on the synthesized TNU-9 molecular sieve under the conditions known to those skilled in the art to obtain the hydrogen TNU-9 molecular sieve, namely HTNU-9 molecular sieve. The HTNU-9 molecular sieve and the aluminum-containing oxide binder are kneaded, molded and dried to prepare a catalyst precursor, and in order to ensure that the sodium ion content is less than 0.1wt percent, more preferably less than or equal to 0.05wt percent, the sodium ions in the catalyst precursor are optionally exchanged by an ammonium salt solution, and finally, the catalyst precursor is dried and roasted to obtain the catalyst finished product.
In the present invention, the aluminum-containing oxide is one or more of aluminum oxide, aluminum sol or aluminum oxide-silicon oxide mixture. Preferably, the aluminum-containing oxide is aluminum oxide.
In the invention, the conditions also comprise a benzene/ethylene molar ratio of 2:1-10:1 and an ethylene weight space velocity of 0.2-10.0h -1 . The preferable conditions are 285-330 ℃, 0.6-1.0MPa, the mol ratio of benzene to ethylene is 4-8:1, and the weight space velocity of ethylene is 0.5-5.0h -1 More preferably at 290-330 deg.C, 0.7-0.9MPa, benzene/ethylene molar ratio of 5-7:1, ethylene weight space velocity of 0.8-4.0h -1 。
In the present invention, the ethylene-containing gas is at least one selected from the group consisting of dilute ethylene, concentrated ethylene and pure ethylene, preferably dilute ethylene. The volume content of ethylene in the dilute ethylene is 12-95%.
The method adopts TNU-9 molecular sieve as an active component of the catalyst, and can effectively reduce the reaction temperature, reduce side reaction and improve the quality of ethylbenzene products when being used for the gas phase alkylation reaction of ethylene-containing gas and benzene due to the larger aperture diameter.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the examples and comparative examples, the ethylene concentration in the dilute ethylene feed was 20% by volume and was formulated using pure ethylene and nitrogen.
Example 1-1
1.55g sodium metaaluminate (8.21 wt% Al) was placed in a Teflon vessel 2 O 3 ，16.89wt％NaOH，74.90wt％H 2 O, hereinafter the same), 3.06g of sodium hydroxide (96.00% by weight, hereinafter the same) 20.00g of silica sol (30% by weight of SiO) 2 ，0.05wt％Na 2 O，69.95wt％H 2 O), 2.96g of template agent 1, 4-bis (nitrogen methyl pyrrolidine) butane bromine salt and a proper amount of water are added according to the sequence and mixed evenly, and the metering is carried outAdding the rest deionized water to obtain the components with the mol ratio of SiO 2 /A1 2 O 3 ＝80，H 2 O/SiO 2 ＝30，R/SiO 2 ＝0.10，NaOH/SiO 2 A mixture of =0.80; transferring the mixture into a crystallization kettle, crystallizing for 12 days at 150 ℃ under a closed condition, cooling the crystallization kettle to room temperature, taking out crystallization liquid, washing, filtering, putting the product into an oven, and drying for 8 hours at 120 ℃ to obtain the TNU-9 molecular sieve with the number of Zeo-A.
Sample Zeo-A is subjected to 3 times of ion exchange with ammonium chloride solution at 80 ℃ for 2 hours each time, the sodium content of the molecular sieve after treatment is less than 0.5 weight percent, and the sample is subjected to filtration, washing and drying, and roasting for 4 hours at 550 ℃ in air, so as to obtain the HTNU-9 molecular sieve. Mixing HTNU-9 molecular sieve and alumina according to the proportion of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 5 hours at 550 ℃ in air to obtain the catalyst, wherein the number is Cat-A.
2.0 g of catalyst Cat-A was charged in a fixed bed reactor, and a mixture of dilute ethylene and benzene was introduced. The reaction conditions are as follows: the reaction temperature is 315 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours. The reaction results are shown in Table 1.
Examples 1 to 2
The catalyst Cat-A in example 1-1 was used to evaluate the alkylation reaction performance of dilute ethylene and benzene.
The reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours, and the reaction results are shown in Table 1.
Examples 1 to 3
The catalyst Cat-A in example 1-1 was used to evaluate the alkylation reaction performance of dilute ethylene and benzene.
The reaction conditions are as follows: the reaction temperature is 360 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours, and the reaction results are shown in Table 1.
Comparative examples 1 to 1
Mixing an HZSM-5 molecular sieve with 80 silicon aluminum and alumina according to the mass ratio of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 6 hours at 550 ℃ in air to prepare a comparative catalyst, wherein the number is DB-1.
The reaction conditions were the same as in example 1-1, and the reaction results are shown in Table 1.
Comparative examples 1 to 2
The same as comparative examples 1 to 1 except that the reaction temperature was changed to 360℃in the reaction conditions. The reaction results are shown in Table 1.
Example 2
Adding 2.07g sodium metaaluminate, 2.57g sodium hydroxide, 6.00g white carbon black, 2.55g template agent 1, 4-bis (nitrogen methyl pyrrolidine) butane bromine salt and a proper amount of water into a Teflon container, uniformly mixing, adding the rest deionized water according to a metering ratio, and obtaining the SiO molar ratio of each component 2 /A1 2 O 3 ＝60，H 2 O/SiO 2 ＝35，R/SiO 2 ＝0.12，NaOH/SiO 2 A mixture of =0.73; transferring the mixture into a crystallization kettle, crystallizing for 10 days at 160 ℃ under a closed condition, cooling the crystallization kettle to room temperature, taking out crystallization liquid, washing, filtering, putting the product into an oven, and drying for 8 hours at 120 ℃ to obtain the TNU-9 molecular sieve with the number of Zeo-B.
And (3) carrying out ion exchange on the synthesized TNU-9 molecular sieve with an ammonium chloride solution at 80 ℃ for 3 times, wherein the sodium content of the molecular sieve after treatment is less than 0.5 weight percent each time for 2 hours, and roasting the molecular sieve in air at 550 ℃ for 4 hours after filtering, washing and drying to obtain the HTNU-9 molecular sieve. Mixing HTNU-9 molecular sieve and alumina according to the proportion of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 5 hours at 550 ℃ in air to obtain the catalyst, wherein the number is Cat-B.
2.0 g of catalyst Cat-B is filled in a fixed bed reactor, and a mixture of dilute ethylene and benzene is introduced. Reverse-rotationThe conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours. The reaction results are shown in Table 1.
Example 3
Aluminum nitrate 0.47g (Al (NO) 3 ) 3 .9H 2 O,98.00wt percent, the following are the same), 2.92 sodium hydroxide, 20.00g silica sol, 2.96g template agent 1, 4-bis (nitrogen methyl pyrrolidine) butane bromine salt and a proper amount of water are added and mixed uniformly, and the rest deionized water is added according to the metering ratio to obtain the SiO with the mole ratio of each component 2 /A1 2 O 3 ＝40，H 2 O/SiO 2 ＝40，R/SiO 2 ＝0.10，NaOH/SiO 2 A mixture of =0.70; transferring the mixture into a crystallization kettle, crystallizing for 10 days at 165 ℃ under a closed condition, cooling the crystallization kettle to room temperature, taking out crystallization liquid, washing, filtering, putting the product into an oven, and drying at 120 ℃ for 8 hours to obtain the TNU-9 molecular sieve with the number of Zeo-C.
And (3) carrying out ion exchange on the synthesized TNU-9 molecular sieve with an ammonium chloride solution at 80 ℃ for 3 times, wherein the sodium content of the molecular sieve after treatment is less than 0.5 weight percent each time for 2 hours, and roasting the molecular sieve in air at 550 ℃ for 4 hours after filtering, washing and drying to obtain the HTNU-9 molecular sieve. Mixing HTNU-9 molecular sieve and alumina according to the proportion of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 5 hours at 550 ℃ in air to obtain the catalyst, wherein the number is Cat-C.
Catalyst Cat-C2.0 g was packed in a fixed bed reactor and a mixture of dilute ethylene and benzene was introduced. The reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours. The reaction results are shown in Table 1.
Example 4-1
In a Teflon container, 0.31g of aluminum isopropoxide, 3.25g of sodium hydroxide, 6g of white carbon black, 4.74 template 1, 4-bis (nitrogen methyl pyrrolidine) butane bromine and a proper amount of water are added and mixed in turnAdding the rest deionized water according to the metering ratio to obtain the components with the mol ratio of SiO 2 /A1 2 O 3 ＝130，H 2 O/SiO 2 ＝35，R/SiO 2 ＝0.16，NaOH/SiO 2 A mixture of =0.78; transferring the mixture into a crystallization kettle, crystallizing for 10 days at 165 ℃ under a closed condition, cooling the crystallization kettle to room temperature, taking out crystallization liquid, washing, filtering, putting the product into an oven, and drying at 120 ℃ for 8 hours to obtain the TNU-9 molecular sieve with the number of Zeo-D.
And (3) carrying out ion exchange on the synthesized TNU-9 molecular sieve with an ammonium chloride solution at 80 ℃ for 3 times, wherein the sodium content of the molecular sieve after treatment is less than 0.5 weight percent each time for 2 hours, and roasting the molecular sieve in air at 550 ℃ for 4 hours after filtering, washing and drying to obtain the HTNU-9 molecular sieve. Mixing HTNU-9 molecular sieve and alumina according to the proportion of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using ammonium chloride aqueous solution, drying, and roasting for 5 hours at 550 ℃ in air to obtain the catalyst, with the number Cat-D.
Catalyst Cat-D2.0 g was packed in a fixed bed reactor and a mixture of dilute ethylene and benzene was introduced. The reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours. The reaction results are shown in Table 1.
Example 4-2
The performance evaluation of the alkylation reaction of dilute ethylene with benzene was carried out with catalyst Cat-D in example 4-1.
The reaction conditions are as follows: the reaction temperature is 315 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours, and the reaction results are shown in Table 1.
Comparative example 4-1
Mixing HZSM-5 molecular sieve with 130 silicon aluminum and alumina according to the mass ratio of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 6 hours at 550 ℃ in air to obtain a comparative catalyst, the number of which is DB-2.
The reaction conditions were the same as in example 4-1, and the reaction results are shown in Table 1.
Comparative example 4-2
The same as in comparative example 4-1 was found except that the reaction temperature was changed to 315℃in the reaction conditions. The reaction results are shown in Table 1.
Example 5-1
Adding 0.59g sodium metaaluminate, 3.64g sodium hydroxide, 6.10g silica gel (98.50 wt%) and 5.92 template agent 1, 4-bis (nitrogen methyl pyrrolidine) butane bromide and proper quantity of water into a Teflon container, uniformly mixing them, adding the rest deionized water according to the above-mentioned metering ratio so as to obtain the invented product with the mole ratio of each component being SiO 2 /A1 2 O 3 ＝210，H 2 O/SiO 2 ＝60，R/SiO 2 ＝0.2，NaOH/SiO 2 =0.9; transferring the mixture into a crystallization kettle, crystallizing at 170 ℃ for 10 days under a closed condition, cooling the crystallization kettle to room temperature, taking out crystallization liquid, washing, filtering, putting the product into an oven, and drying at 120 ℃ for 8 hours to obtain the TNU-9 molecular sieve with the number of Zeo-E.
And (3) carrying out ion exchange on the synthesized TNU-9 molecular sieve with an ammonium chloride solution at 80 ℃ for 3 times, wherein the sodium content of the molecular sieve after treatment is less than 0.5 weight percent each time for 2 hours, and roasting the molecular sieve in air at 550 ℃ for 4 hours after filtering, washing and drying to obtain the HTNU-9 molecular sieve. Mixing HTNU-9 molecular sieve and alumina according to the proportion of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 5 hours at 550 ℃ in air to obtain the catalyst, wherein the number is Cat-E.
Catalyst Cat-E2.0 g was packed in a fixed bed reactor and a mixture of dilute ethylene and benzene was introduced. The reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours. The reaction results are shown in Table 1.
Example 5-2
Catalyst Cat-E was the same as in example 5-1 except that the reaction temperature was 315 ℃. The reaction results are shown in Table 1.
Example 6-1
Aluminum sulfate (Al) was added to a Teflon container at 0.12 2 (SO 4 ) 3 .18H 2 O), 4.17g of sodium hydroxide, 6.10g of silica gel, 4.44g of template agent 1, 4-bis (nitrogen methyl pyrrolidine) butane bromine salt and a proper amount of water are added and mixed uniformly according to the sequence, and the rest deionized water is added according to the metering ratio to obtain the SiO with the mole ratio of each component 2 /A1 2 O 3 ＝270，H 2 O/SiO 2 ＝35，R/SiO 2 ＝0.15，NaOH/SiO 2 A mixture of =1.0; transferring the mixture into a crystallization kettle, crystallizing for 10 days at 155 ℃ under a closed condition, cooling the crystallization kettle to room temperature, taking out crystallization liquid, washing, filtering, putting the product into an oven, and drying at 120 ℃ for 8 hours to obtain the TNU-9 molecular sieve with the number of Zeo-F.
And (3) carrying out ion exchange on the synthesized TNU-9 molecular sieve with an ammonium chloride solution at 80 ℃ for 3 times, wherein the sodium content of the molecular sieve after treatment is less than 0.5 weight percent each time for 2 hours, and roasting the molecular sieve in air at 550 ℃ for 4 hours after filtering, washing and drying to obtain the HTNU-9 molecular sieve. Mixing HTNU-9 molecular sieve and alumina according to the proportion of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using an ammonium chloride aqueous solution, drying, and roasting for 5 hours at 550 ℃ in air to obtain the catalyst, wherein the number is Cat-F.
Catalyst Cat-F2.0 g was packed in a fixed bed reactor and a mixture of dilute ethylene and benzene was introduced. The reaction conditions are as follows: the reaction temperature is 330 ℃, the reaction pressure is 0.8MPa, the mol ratio of benzene to ethylene is 5:1, and the weight space velocity of ethylene is 1.0h -1 The reaction was continued for 12 hours. The reaction results are shown in Table 1.
Example 6-2
Catalyst Cat-F of example 6-1 was used except that the reaction temperature was 315 ℃. The reaction results are shown in Table 1.
Comparative example 6-1
Mixing HZSM-5 molecular sieve with 270 silicon aluminum and alumina according to the mass ratio of 70:30, adding dilute nitric acid into the mixed powder, kneading, forming, drying, carrying out ion exchange on the formed sample by using ammonium chloride aqueous solution, drying, and roasting at 550 ℃ for 6 hours in air to obtain a comparative catalyst, the number of which is DB-3.
The reaction conditions were the same as in example 6-1, and the reaction results are shown in Table 1.
Comparative example 6-2
The same as in comparative example 6-1 except that the reaction temperature was changed to 315℃in the reaction conditions. The reaction results are shown in Table 1.
TABLE 1
In the method, because TNU-9 molecular sieve is adopted as an active component of the catalyst, the aperture diameter is larger, the diffusion rate of reactants and products is accelerated, the occurrence of side reaction is reduced, and when the method is used for the gas phase alkylation reaction of ethylene-containing gas and benzene, the reaction temperature can be effectively reduced, and the xylene content is reduced.
Specifically, as is apparent from the results of examples 1-1 and comparative examples 1-1, it was possible to achieve a reaction temperature of 315℃and a reaction pressure of 0.8MPa, a benzene/ethylene molar ratio of 5:1, and an ethylene weight space velocity of 1.0h using a TNU-9 molecular sieve catalyst -1 Under the condition of (2) the conversion rate of ethylene can reach 99.5 percent, and the xylene content is 596 ppm. Under the same reaction conditions, when a ZSM-5 molecular sieve catalyst was used, the ethylene conversion was 99.1% and the xylene content was 1761ppm.
As is clear from the results of examples 1-3 and comparative examples 1-2, when TNU-9 molecular sieve catalyst was used, the reaction pressure was 0.8MPa, the benzene/ethylene molar ratio was 5:1, and the ethylene weight space velocity was 1.0h, even though the reaction temperature was 360 ℃ (relatively high reaction temperature) -1 Under the condition of (2) the ethylene conversion rate can reach 99.7 percent, and the xylene content is 547 ppm. Under the same reaction conditions, the ethylene conversion was 99.4% and the xylene content was 3128ppm with a ZSM-5 molecular sieve catalyst.
It can be further seen from the results of examples 1-1 to 1-3 of the present invention that the TNU-9 molecular sieve catalyst provided by the present invention is used for catalyzing the gas phase alkylation reaction of dilute ethylene-containing gas and benzene, and can further reduce the reaction temperature and reduce the xylene content on the premise of maintaining the ethylene conversion rate not lower than 99.5%.
As can be further seen from the results of examples 1-1 and comparative examples 1-1, examples 1-3 and comparative examples 1-2, examples 4-1 and comparative examples 4-1, examples 4-2 and comparative examples 4-2, examples 6-1 and comparative examples 6-1, examples 6-2 and comparative examples 6-2 according to the present invention, the TNU-9 molecular sieve catalyst provided by the present invention has a reaction effect superior to that of ZSM-5 molecular sieve catalyst in all ranges of silica-alumina ratio.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (6)

1. A preparation method of ethylbenzene is characterized in that the method is characterized in that the catalyst with TUN structure molecular sieve as active component exists at 260-360 ℃, the mol ratio of benzene to ethylene is 2:1-10:1, and the weight space velocity of ethylene is 0.2-10.0h -1 A gas phase alkylation reaction carried out by contacting an ethylene-containing gas with benzene; the catalyst consists of 60-90wt% of TUN structure molecular sieve and 10-40wt% of alumina; the TUN structure molecular sieve is a TNU-9 structure molecular sieve; the TNU-9 structure molecular sieve is prepared by crystallizing a mixture of a silicon source, an aluminum source, a template agent R, alkali and water at 100-200 ℃ for 2-14 days and recycling; wherein the mixture is SiO in mole ratio 2 /A1 2 O 3 =30-300, H 2 O/SiO 2 =10-70, R/SiO 2 =0.10-0.30, NaOH/SiO 2 =0.4-1.0; the template agent R is 1, 4-diazamethylpyrrolidine butane bromide; the silicon source is at least one of white carbon black, amorphous silicon dioxide, silica sol, silica gel, diatomite or water glass; the aluminum source is selected from aluminum hydroxide, aluminum isopropoxide and aluminum sec-butoxideAt least one of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum chloride or aluminum oxide, wherein the alkali is inorganic alkali and is at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.
2. The process according to claim 1, wherein the conditions are 285 to 340 ℃, 0.6 to 1.0MPa, a benzene/ethylene molar ratio of 4 to 8:1, and an ethylene weight space velocity of 0.5 to 5.0h -1 。
3. The process according to claim 2, wherein the conditions are 290-330 ℃, 0.7-0.9MPa, a benzene/ethylene molar ratio of 5-7:1, an ethylene weight space velocity of 0.8-4.0h -1 。
4. The method of claim 1, wherein the ethylene-containing gas is selected from at least one of dilute ethylene, concentrated ethylene, and pure ethylene.
5. The method of claim 1, wherein the ethylene-containing gas is dilute ethylene.
6. The process according to claim 5, wherein the ethylene content of the dilute ethylene is from 12 to 30% by volume.
CN202010755137.3A 2020-07-31 2020-07-31 Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene Active CN114057538B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010755137.3A CN114057538B (en) 2020-07-31 2020-07-31 Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010755137.3A CN114057538B (en) 2020-07-31 2020-07-31 Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene

Publications (2)

Publication Number Publication Date
CN114057538A CN114057538A (en) 2022-02-18
CN114057538B true CN114057538B (en) 2023-11-10

Family

ID=80227893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010755137.3A Active CN114057538B (en) 2020-07-31 2020-07-31 Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene

Country Status (1)

Country Link
CN (1) CN114057538B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101584993A (en) * 2009-06-19 2009-11-25 中国科学院大连化学物理研究所 Catalyst for preparing phenylethane from dilute ethylene and benzene alkylation and method for preparing same
CN104169242A (en) * 2011-12-08 2014-11-26 Gtc科技美国有限责任公司 Production of xylenes by methylation of aromatic compounds
CN104379505A (en) * 2011-12-22 2015-02-25 环球油品公司 UZM-39 aluminosilicate zeolite
CN106881146A (en) * 2017-03-02 2017-06-23 中国科学院大连化学物理研究所 It is a kind of for dry gas and the preparation method of the molecular sieve catalysts of benzene alkylation reaction F ZSM 11
CN110743605A (en) * 2018-07-23 2020-02-04 中国科学院大连化学物理研究所 Catalyst for preparing ethylbenzene from ethanol and benzene and preparation and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7651603B2 (en) * 2006-06-08 2010-01-26 Chevron U.S.A. Inc. Hydrocarbon conversion using molecular sieve SSZ-75
WO2015047085A1 (en) * 2013-09-26 2015-04-02 Biobtx B.V. Process for the preparation of aromatic compounds
US20150273453A1 (en) * 2014-03-25 2015-10-01 Uop Llc Bismuth-modified molecular sieves and methods for preparing and using bismuth-modified molecular sieves

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101584993A (en) * 2009-06-19 2009-11-25 中国科学院大连化学物理研究所 Catalyst for preparing phenylethane from dilute ethylene and benzene alkylation and method for preparing same
CN104169242A (en) * 2011-12-08 2014-11-26 Gtc科技美国有限责任公司 Production of xylenes by methylation of aromatic compounds
CN104379505A (en) * 2011-12-22 2015-02-25 环球油品公司 UZM-39 aluminosilicate zeolite
CN106881146A (en) * 2017-03-02 2017-06-23 中国科学院大连化学物理研究所 It is a kind of for dry gas and the preparation method of the molecular sieve catalysts of benzene alkylation reaction F ZSM 11
CN110743605A (en) * 2018-07-23 2020-02-04 中国科学院大连化学物理研究所 Catalyst for preparing ethylbenzene from ethanol and benzene and preparation and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
分子筛限域孔道中的酸碱特性表征与反应机理研究;易先锋;《中国博士学位论文全文数据库工程科技Ⅰ辑》(第11期);第B014-177页 *

Also Published As

Publication number Publication date
CN114057538A (en) 2022-02-18

Similar Documents

Publication Publication Date Title
CN108745410B (en) Preparation method of phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve
CN107282096B (en) SSZ-13 molecular sieve catalyst and preparation method and application thereof
CN108726535B (en) Preparation method of phosphorus modified ZSM-5 molecular sieve with hierarchical pores
RU2607633C2 (en) Moulded catalyst for converting methanol into aromatic hydrocarbons and method of producing said catalyst
WO1996020891A1 (en) Rare earth-zsm-5/zsm-11 cocrystalline zeolite
CN105817260B (en) Method for synthesizing FER/MOR eutectic molecular sieve
CN111167504B (en) Light gasoline cracking catalyst, preparation method thereof and catalytic cracking method
JPH0214286B2 (en)
KR101098495B1 (en) - Process for the manufacture of catalysts used for producing para-xylene by toluene shape selective alkylation
CN101554592A (en) Preparation method of high silica alumina ratio MCM-22 molecular sieve catalyst
CN111167509A (en) Carbon tetraolefin cracking catalyst, preparation method thereof and catalytic cracking method
CN102746096A (en) Method for liquid phase transalkylation of polyethylbenzene and benzene
CN114057538B (en) Method for preparing ethylbenzene by gas phase alkylation of ethylene-containing gas and benzene
JPH0238571B2 (en)
CN101941710B (en) porous material and synthesis method thereof
CN102373069B (en) Method used for C6-alkane cracking
CN114054078B (en) Catalyst for synthesizing ethylbenzene from ethylene-containing gas and application thereof
CN104230633A (en) Liquid phase alkyl transfer method
CN102335622A (en) Catalyst for toluene alkylation reaction, and preparation method thereof
JPH08253313A (en) Synthetic zeolite substance
CN116265106A (en) Preparation method of catalytic cracking catalyst for high yield of low carbon olefin
CN105712818B (en) A kind of method that MTBE and TBA compounds prepare isobutene
CN105712830B (en) A kind of preparation method of isobutene
CN114180596A (en) NaY molecular sieve containing mesopores, and preparation method and application thereof
CA2969359A1 (en) Catalyst and preparation method thereof, and method for preparing isobutylene by applying the same

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