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WO2016099408A1 - A process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alchol - Google Patents

A process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alchol Download PDF

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Publication number
WO2016099408A1
WO2016099408A1 PCT/TH2015/000090 TH2015000090W WO2016099408A1 WO 2016099408 A1 WO2016099408 A1 WO 2016099408A1 TH 2015000090 W TH2015000090 W TH 2015000090W WO 2016099408 A1 WO2016099408 A1 WO 2016099408A1
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Prior art keywords
zeolite catalyst
catalyst
benzene
cumene
alkylation
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French (fr)
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Sitthiphong PENGPANICH
Takul LOSIRIWAT
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PTT Global Chemical PCL
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PTT Global Chemical PCL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • 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
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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

Definitions

  • This invention intends to improve stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol, comprising contacting zeolite catalyst with silane compound wherein the ratio of millimole of silane compound to gram of catalyst is in a range of 0.01 to 1 , in a temperature range of room temperature but not higher than boiling point of the silane compound, for 0.5 to 48 hours.
  • the aim of the process according to this invention is to treat surface of zeolite catalyst without changing structure of the catalyst, resulting in that the catalyst is more stable to water which is by-product of the reaction, and the lifetime of catalyst is longer.
  • This invention relates to a chemical mixture and s chemical process, especially in the process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol.
  • cumene or isopropylbenzene an alkyl aromatic substance obtained from alkylation reaction of benzene
  • is an important precursor for phenol production More than 90% of phenol production uses cumene as precursor.
  • phenol production usually obtains acetone as a by-product, which is cheap and has low market demand.
  • acetone has an advantage in its ability of being used as a precursor for cumene production. Therefore, reaction of acetone for converting to cumene has high commercial interest.
  • the production of cumene from acetone can be divided into two stages which are the hydrogenation of acetone to be isopropyl alcohol (IPA) or isopropanol, and then the alkylation of the obtained isopropyl alcohol to cumene as the following reactions.
  • IPA isopropyl alcohol
  • isopropanol isopropanol
  • US Patent No. 5015786 discloses cumene production by the alkylation of benzene with isopropyl alcohol using Y-zeolite as a catalyst. Cumene obtained from said reaction has a production yield of 17.7%.
  • US Patent No. 6512153B1 discloses cumene production by the alkylation of benzene with isopropyl alcohol using zeolite catalysts which are ZSM-5, ZSM-12, dealuminated H- mordenite, Y-zeolite, and ⁇ -zeolite. The results show that ⁇ -zeolite exhibits the highest activity of cumene selectivity of 85%,.
  • US Patent No. 6841704B2 discloses cumene production by the alkylation of benzene with isopropyl alcohol using ⁇ -zeolite catalyst supported on silica alumina (Si0 2 /Al 2 03) in the ratio of 70:1 to 200:1.
  • the selectivity of cumene could be up to 93.1%.
  • US Patent No. 7524788B2 discloses cumene production in one step by feeding acetone, benzene and hydrogen to be reacted together.
  • the catalysts are combined in hydrogenation and alkylation processes.
  • the catalyst used in the alkylation reaction is ⁇ - zeolite which has cumene selectivity of 80%.
  • US Patent No. 7790936B2 discloses cumene production from acetone in one step.
  • catalyst used is ⁇ -zeolite or MCM-22.
  • the selectivity of cumene could be up to 70 to 80%.
  • US Patents No. 8212096B2, WO2010014404 Al, CA2729173, and CA2729266C disclose the steps of reacting zeolite catalyst with silicone, siloxane, polysiloxane, or silane compounds for the improvement of zeolite catalyst structure for alkylation reaction of benzene or aromatic compounds in the production of alkylated aromatic compounds.
  • these patents do not disclose the surface treatment or increasing of stability of zeolite catalyst.
  • this invention aims to improve stability of zeolite catalyst for the production of cumene from alkylation reaction of benzene with isopropyl alcohol.
  • Figure 1 shows cumene selectivity comparing between modified zeolite catalyst according to this invention to the compared catalyst.
  • Figure 2 shows aromatic selectivity comparing between modified zeolite catalyst according to this invention to the compared catalyst.
  • Figure 3 shows x-ray diffraction (XRD) pattern of compared MCM-22 catalyst and modified MCM-22 catalyst according to this invention, comparing between before and after being used.
  • XRD x-ray diffraction
  • This invention discloses a process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol, comprising contacting zeolite catalyst with silane compound in a certain condition, making the surface of zeolite catalyst more hydrophobic without affecting its structure. Said improvement makes the catalyst more stable to water which is the by-product produced during alkylation reaction of benzene with isopropyl alcohol, and longer lifetime of the catalyst.
  • the improving process can be explained according to the specification as the following.
  • Equipment, apparatus, methods, or chemicals mentioned here means equipment, apparatus, processes or chemicals commonly operated or used by those skilled in the art, unless explicitly stated otherwise that they are equipment, apparatus, methods, or chemicals specifically used in this invention.
  • compositions and/or processes disclosed and claimed are aimed to include aspects of the invention from actions, operation, modifications, or changing of any parameters without performing significantly different experiments from this invention, and obtaining similar objects with same utilities and results of the present invention according to persons skilled in the art although without mentions in claims specifically. Therefore, substitution or similar objects to the present invention including minor modifications or change which clearly seen to persons skilled in the art should be considered with scope, spirit, and concept of the invention as appended claims.
  • This invention relates to a process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol.
  • Said process comprises contacting zeolite catalyst with silane compound wherein the ratio of millimole of silane compound to gram of catalyst is in a range of 0.01 to 1, in a temperature range of room temperature but not higher than boiling point of the silane compound, for 0.5 to 48 hours.
  • the ratio of millimole of silane compound to gram of catalyst is in the range of 0.01 to 1, and preferable is in the range of 0.3 to 0.5.
  • the temperature is between room temperature but not higher than boiling point of silane compound.
  • the temperature is from room temperature to 100 °C.
  • the contacting time for improving stability of zeolite catalyst is from 0.5 to 48 hours.
  • the contacting time for improving zeolite catalyst is from 20 to 24 hours.
  • the silane compound may be selected from dimethyldichlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, trichloro(phenyl)silane, or a mixture thereof.
  • the silane compound is dimethyldichlorosilane.
  • the zeolite catalyst that can be improved stability by the process according to this invention may be selected from, but not limited to MCM-22, MCM-36, TNU-9, ZSM-5, ZSM-12, ITQ-39, Y-zeolite, ⁇ -zeolite catalyst.
  • the zeolite catalyst is MCM-22.
  • organic solvent may be selected from, but not limited to aromatic hydrocarbon, aliphatic hydrocarbon, cyclic hydrocarbon, normally are toluene, benzene, ethylbenzene, xylene, hexane, cyclohexane, cyclohexene, and heptane.
  • Said improving process of catalyst may further comprise a step of drying if necessary.
  • Said step may be selected from, but not limited to stirring, evaporation, and vacuum drying.
  • the invention involves using of modified zeolite catalyst according to the invention in a cumene production process by alkylation of benzene with isopropyl alcohol wherein said catalyst may be used in liquid, semi-liquid, or solid form.
  • the process for producing cumene by alkylation reaction of benzene with isopropyl alcohol may be performed in reactor but not limited to fixed-bed reactor.
  • the process can be performed in batch or continuous process.
  • the synthesis of compared catalyst MCM-22 started from adding 6 g of sodium hydroxide (NaOH) into about 60.5 g of distilled water. Then, gradually added 12.4 g of hexamethyleneimine (HMI) into the solution and stirred. Then, dropped 50.7 g of 30 % by weight slurry silica into prepared solution and stirred for about 15 minutes. Then, dropped obtained solution into aluminium sulphate solution containing 3.5 g of aluminium sulphate (A1 2 (S0 4 ) 3 .18H 2 0) in 87.5 g of distilled water and stirred for about 30 minutes. Then, dropped about 4.5 g of concentrated sulfuric acid (96 % wt) into above solution and stirred for about 30 minutes.
  • NaOH sodium hydroxide
  • HMI hexamethyleneimine
  • the catalyst according to the invention can be prepared by contacting compared catalyst MCM-22 prepared from above process with silane compound in the following steps.
  • the compared catalyst MCM-22 was dispersed in toluene at a ratio about 20 mL/g of catalyst in ultrasonic bath. Then, dimethyldichlorosilane solution was added into toluene at a ratio about 0.5 mmol/g of catalyst and stirred continuously for about 24 hours. The obtained solid was filtered and washed with ethanol and then dried at the temperature of at least 100 °C.
  • the catalyst was pretreated with nitrogen gas at the flow rate of 10 mL/min at about
  • Cumene selectivity mol of cumene produced
  • Aromatic compounds selectivity mol of aromatic compounds produced mol of isopropyl alcohol used in the reaction
  • Figure 1 and 2 show results of cumene selectivity and aromatic selectivity of modified zeolite catalyst according to this invention comparing to the compared catalyst MCM-22.
  • the modified zeolite catalyst according to this invention gives higher production selectivity and higher stability of cumene and aromatic compounds when time passes.
  • Figure 3 shows crystal characteristics of compared MCM-22 catalyst and MCM-22 catalyst modified with the silane compound according to this invention. Both catalysts were compared before and after being used. The results show that the process for improving stability of zeolite catalyst according to the invention using silane compound has no effect on the structure of MCM-22 catalyst. Moreover, although modified MCM-22 catalyst according to this invention was used in alkylation reaction of benzene with isopropyl alcohol, said catalyst still remains intact as MCM-22 catalyst with no change in its structure.

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Abstract

The present invention relates to a process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol comprising contacting zeolite catalyst with silane compound in a certain condition. This results in the zeolite catalyst which is stable to water which is by-product of the reaction, providing longer ability to catalyze alkylation reaction.

Description

A PROCESS FOR IMPROVING STABILITY OF ZEOLITE CATALYST TO USE IN CUMENE PRODUCTION BY ALKYLATION OF BENZENE WITH
ISOPROPYL ALCHOL Summary of the Invention
This invention intends to improve stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol, comprising contacting zeolite catalyst with silane compound wherein the ratio of millimole of silane compound to gram of catalyst is in a range of 0.01 to 1 , in a temperature range of room temperature but not higher than boiling point of the silane compound, for 0.5 to 48 hours. The aim of the process according to this invention is to treat surface of zeolite catalyst without changing structure of the catalyst, resulting in that the catalyst is more stable to water which is by-product of the reaction, and the lifetime of catalyst is longer.
Field of the Invention
This invention relates to a chemical mixture and s chemical process, especially in the process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol.
Background of the Invention
It has been known that cumene or isopropylbenzene, an alkyl aromatic substance obtained from alkylation reaction of benzene, is an important precursor for phenol production. More than 90% of phenol production uses cumene as precursor. However, such phenol production usually obtains acetone as a by-product, which is cheap and has low market demand. Nevertheless, acetone has an advantage in its ability of being used as a precursor for cumene production. Therefore, reaction of acetone for converting to cumene has high commercial interest.
The production of cumene from acetone can be divided into two stages which are the hydrogenation of acetone to be isopropyl alcohol (IPA) or isopropanol, and then the alkylation of the obtained isopropyl alcohol to cumene as the following reactions.
Figure imgf000003_0001
US Patent No. 5015786 discloses cumene production by the alkylation of benzene with isopropyl alcohol using Y-zeolite as a catalyst. Cumene obtained from said reaction has a production yield of 17.7%.
US Patent No. 6512153B1 discloses cumene production by the alkylation of benzene with isopropyl alcohol using zeolite catalysts which are ZSM-5, ZSM-12, dealuminated H- mordenite, Y-zeolite, and β-zeolite. The results show that β-zeolite exhibits the highest activity of cumene selectivity of 85%,.
US Patent No. 6841704B2 discloses cumene production by the alkylation of benzene with isopropyl alcohol using β-zeolite catalyst supported on silica alumina (Si02/Al203) in the ratio of 70:1 to 200:1. The selectivity of cumene could be up to 93.1%.
US Patent No. 7524788B2 discloses cumene production in one step by feeding acetone, benzene and hydrogen to be reacted together. The catalysts are combined in hydrogenation and alkylation processes. The catalyst used in the alkylation reaction is β- zeolite which has cumene selectivity of 80%.
US Patent No. 7790936B2 discloses cumene production from acetone in one step. In alkylation step of benzene and isopropyl alcohol, catalyst used is β-zeolite or MCM-22. The selectivity of cumene could be up to 70 to 80%.
US Patents No. 8212096B2, WO2010014404 Al, CA2729173, and CA2729266C disclose the steps of reacting zeolite catalyst with silicone, siloxane, polysiloxane, or silane compounds for the improvement of zeolite catalyst structure for alkylation reaction of benzene or aromatic compounds in the production of alkylated aromatic compounds. However, these patents do not disclose the surface treatment or increasing of stability of zeolite catalyst.
As in alkylation step of benzene and isopropyl alcohol, apart from cumene obtained as primary product, water is also produced as by-product. Water obtained in this reaction is poison to the zeolite catalyst which deactivating catalyst and reducing the selectivity of cumene production. As a result, this invention aims to improve stability of zeolite catalyst for the production of cumene from alkylation reaction of benzene with isopropyl alcohol.
Brief Description of the Drawings
Figure 1 shows cumene selectivity comparing between modified zeolite catalyst according to this invention to the compared catalyst.
Figure 2 shows aromatic selectivity comparing between modified zeolite catalyst according to this invention to the compared catalyst.
Figure 3 shows x-ray diffraction (XRD) pattern of compared MCM-22 catalyst and modified MCM-22 catalyst according to this invention, comparing between before and after being used.
Detailed Description of the Invention
This invention discloses a process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol, comprising contacting zeolite catalyst with silane compound in a certain condition, making the surface of zeolite catalyst more hydrophobic without affecting its structure. Said improvement makes the catalyst more stable to water which is the by-product produced during alkylation reaction of benzene with isopropyl alcohol, and longer lifetime of the catalyst. The improving process can be explained according to the specification as the following.
Any aspect showed here aims to include every application of other aspects of this invention unless stated otherwise.
Technical terms or scientific terms used herein, have definitions as understood by those having an ordinary skill in the art, unless stated otherwise.
Equipment, apparatus, methods, or chemicals mentioned here means equipment, apparatus, processes or chemicals commonly operated or used by those skilled in the art, unless explicitly stated otherwise that they are equipment, apparatus, methods, or chemicals specifically used in this invention.
The use of the singular or plural nouns with the term "comprising" in the claims or in the specification refers to "one" and also "one or more", "at least one", and "one or more than one".
All compositions and/or processes disclosed and claimed are aimed to include aspects of the invention from actions, operation, modifications, or changing of any parameters without performing significantly different experiments from this invention, and obtaining similar objects with same utilities and results of the present invention according to persons skilled in the art although without mentions in claims specifically. Therefore, substitution or similar objects to the present invention including minor modifications or change which clearly seen to persons skilled in the art should be considered with scope, spirit, and concept of the invention as appended claims.
Throughout this application, the term "about" is used to indicate that any value presented herein may potentially vary or deviate. Such variation or deviation may result from errors of apparatus, methods used in calculation or from individual operator implementing apparatus or methods. These include variations or deviations caused by the changes of physical properties.
The following shows detailed description of the invention without any intention to limit the scope of the invention.
This invention relates to a process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol. Said process comprises contacting zeolite catalyst with silane compound wherein the ratio of millimole of silane compound to gram of catalyst is in a range of 0.01 to 1, in a temperature range of room temperature but not higher than boiling point of the silane compound, for 0.5 to 48 hours.
In one aspect of the invention, the ratio of millimole of silane compound to gram of catalyst is in the range of 0.01 to 1, and preferable is in the range of 0.3 to 0.5.
In one aspect of the invention, the temperature is between room temperature but not higher than boiling point of silane compound. Preferably, the temperature is from room temperature to 100 °C.
In one aspect of the invention, the contacting time for improving stability of zeolite catalyst is from 0.5 to 48 hours. Preferably, the contacting time for improving zeolite catalyst is from 20 to 24 hours.
In one aspect of the invention, the silane compound may be selected from dimethyldichlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, trichloro(phenyl)silane, or a mixture thereof. Preferably, the silane compound is dimethyldichlorosilane. The zeolite catalyst that can be improved stability by the process according to this invention may be selected from, but not limited to MCM-22, MCM-36, TNU-9, ZSM-5, ZSM-12, ITQ-39, Y-zeolite, β-zeolite catalyst. Preferably, the zeolite catalyst is MCM-22.
In each step of the improving stability of catalyst described in this invention, unless being stated specifically, organic solvent may be selected from, but not limited to aromatic hydrocarbon, aliphatic hydrocarbon, cyclic hydrocarbon, normally are toluene, benzene, ethylbenzene, xylene, hexane, cyclohexane, cyclohexene, and heptane.
Said improving process of catalyst may further comprise a step of drying if necessary. Said step may be selected from, but not limited to stirring, evaporation, and vacuum drying.
In one aspect, the invention involves using of modified zeolite catalyst according to the invention in a cumene production process by alkylation of benzene with isopropyl alcohol wherein said catalyst may be used in liquid, semi-liquid, or solid form.
In one aspect, the process for producing cumene by alkylation reaction of benzene with isopropyl alcohol may be performed in reactor but not limited to fixed-bed reactor. The process can be performed in batch or continuous process.
Hereafter, examples of the invention are shown without any purpose to limit any scope of the invention.
Preparation of compared catalyst
The synthesis of compared catalyst MCM-22 started from adding 6 g of sodium hydroxide (NaOH) into about 60.5 g of distilled water. Then, gradually added 12.4 g of hexamethyleneimine (HMI) into the solution and stirred. Then, dropped 50.7 g of 30 % by weight slurry silica into prepared solution and stirred for about 15 minutes. Then, dropped obtained solution into aluminium sulphate solution containing 3.5 g of aluminium sulphate (A12(S04)3.18H20) in 87.5 g of distilled water and stirred for about 30 minutes. Then, dropped about 4.5 g of concentrated sulfuric acid (96 % wt) into above solution and stirred for about 30 minutes. The obtained solution was autoclaved at 150 °C at 40 rpm for 4 days, then quenched in water. The obtained solid was filtered and washed with distilled water till neutral and dried at about 100 °C for at least 8 hours. The obtained dried powder was calcinated at about 580 °C for 5 hours. Crystal structure was confirmed by x-ray diffraction (XRD) technique. Preparation of catalyst according to the invention
The catalyst according to the invention can be prepared by contacting compared catalyst MCM-22 prepared from above process with silane compound in the following steps.
The compared catalyst MCM-22 was dispersed in toluene at a ratio about 20 mL/g of catalyst in ultrasonic bath. Then, dimethyldichlorosilane solution was added into toluene at a ratio about 0.5 mmol/g of catalyst and stirred continuously for about 24 hours. The obtained solid was filtered and washed with ethanol and then dried at the temperature of at least 100 °C.
Cumene selectivity test
The catalyst was pretreated with nitrogen gas at the flow rate of 10 mL/min at about
200 °C for 1 hour. Then, the temperature was reduced to 190 °C. Cumene selectivity of the catalyst was tested in a fixed-bed reactor fed with benzene and isopropyl alcohol (a mole ratio of benzene to isopropyl alcohol is 3:1) into a heated vessel with controlled temperature at about 70 °C before entered to the reactor which heated by vessel heater with a space velocity of 4 per hour. The catalyst was contained in the reactor. The obtained product was analyzed for its chemical composition using gas chromatography technique. The production selectivity of cumene and aromatic were calculated from the following formula.
Cumene selectivity = mol of cumene produced
mol of isopropyl alcohol used in the reaction
Aromatic compounds selectivity = mol of aromatic compounds produced mol of isopropyl alcohol used in the reaction
Figure 1 and 2 show results of cumene selectivity and aromatic selectivity of modified zeolite catalyst according to this invention comparing to the compared catalyst MCM-22. When considering the weight of cumene produced to the weight of catalyst at each times (x-axis) which means the reaction rate at each interval, it is found that the modified zeolite catalyst according to this invention gives higher production selectivity and higher stability of cumene and aromatic compounds when time passes.
Figure 3 shows crystal characteristics of compared MCM-22 catalyst and MCM-22 catalyst modified with the silane compound according to this invention. Both catalysts were compared before and after being used. The results show that the process for improving stability of zeolite catalyst according to the invention using silane compound has no effect on the structure of MCM-22 catalyst. Moreover, although modified MCM-22 catalyst according to this invention was used in alkylation reaction of benzene with isopropyl alcohol, said catalyst still remains intact as MCM-22 catalyst with no change in its structure.
Best Mode of the Invention
Best mode of the invention is as disclosed in the detailed description.

Claims

Claims
1. A process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alcohol, comprising contacting zeolite catalyst with silane compound wherein a ratio of millimole of silane compound to gram of catalyst is in a range of 0.01 to 1, in a temperature range of room temperature but not higher than boiling point of the silane compound, for 0.5 to 48 hours.
2. The process for improving stability of zeolite catalyst according to claim 1 wherein the ratio of millimole of the silane compound to gram of the catalyst is in the range of 0.3 to 0.5.
3. The process for improving stability of zeolite catalyst according to claim 1 wherein the temperature is in the range of room temperature to 100 °C.
4. The process for improving stability of zeolite catalyst according to claim 1 wherein the contacting time is between 20 to 24 hours.
5. The process for improving stability of zeolite catalyst according to claim 1 wherein the zeolite catalyst is selected from MCM-22, MCM-36, TNU-9, ZSM-5, ZSM-12,
ITQ-39, Y-zeolite, β-zeolite catalyst, or a mixture thereof.
6. The process for improving stability of zeolite catalyst according to claim 5 wherein the zeolite catalyst is MCM-22.
7. The process for improving stability of zeolite catalyst according to claim 1 wherein the silane compound is selected from dimethyldichlorosilane, octyltrichlorosilane, octadecyltrichlorosilane, trichloro(phenyl) silane, or a mixture thereof.
8. The process for improving zeolite catalyst according to claim 7 wherein the silane compound is dimethyldichlorosilane.
PCT/TH2015/000090 2014-12-16 2015-12-16 A process for improving stability of zeolite catalyst to use in cumene production by alkylation of benzene with isopropyl alchol Ceased WO2016099408A1 (en)

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CN110465326A (en) * 2018-05-09 2019-11-19 中国科学院大连化学物理研究所 A kind of method of modifying for ethyl alcohol and benzene alkylation reaction ZSM-11 molecular sieve catalyst
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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
CN110743605B (en) * 2018-07-23 2021-07-27 中国科学院大连化学物理研究所 A kind of catalyst for preparing ethylbenzene from ethanol and benzene and its preparation and application
US11434183B2 (en) 2018-07-23 2022-09-06 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof
US12383891B2 (en) 2018-11-15 2025-08-12 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparation of hierarchical TS-1 molecular sieve
US12384686B2 (en) 2018-11-15 2025-08-12 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing TS-1 molecular sieve with hierarchical pores

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