WO2013081034A1 - Catalyseur d'halogénation et son procédé de fabrication - Google Patents

Catalyseur d'halogénation et son procédé de fabrication Download PDF

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WO2013081034A1
WO2013081034A1 PCT/JP2012/080866 JP2012080866W WO2013081034A1 WO 2013081034 A1 WO2013081034 A1 WO 2013081034A1 JP 2012080866 W JP2012080866 W JP 2012080866W WO 2013081034 A1 WO2013081034 A1 WO 2013081034A1
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reaction
catalyst
halogenated
halogenated catalyst
oxide
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PCT/JP2012/080866
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Japanese (ja)
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勇太 仁科
佳志 高見
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国立大学法人岡山大学
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • 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
    • B01J29/88—Ferrosilicates; Ferroaluminosilicates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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

Definitions

  • the present invention relates to a halogenation catalyst for halogenating an aromatic ring and a method for producing the same.
  • the present invention also relates to a method for producing a halogen compound using a halogenated catalyst.
  • Non-Patent Document 1 describes a method of synthesizing bromobenzene by reacting benzene and bromine in the presence of mercury oxide and sulfuric acid.
  • this method it is necessary to add mercury oxide in a stoichiometric amount or more.
  • this method has a problem that a neutralization step is required after the reaction because the reaction is performed under acidic conditions.
  • Patent Document 1 describes a method of synthesizing bromobenzene by reacting benzene and bromine using sodium lauryl sulfate as a catalyst.
  • this method has a problem that the reaction time is long and a neutralization step is required after the reaction because an aqueous sulfuric acid solution is used as a solvent.
  • Non-Patent Document 2 describes a method of synthesizing 1,2,4,5-tetrabromobenzene by reacting benzene and bromine using aluminum bromide as a catalyst.
  • Patent Document 2 describes a method of synthesizing 2-bromo-1,4-difluorobenzene by reacting 1,4-difluorobenzene and bromine using iron powder as a catalyst.
  • these catalysts are uniformly dissolved in the reaction solution, it is difficult to separate from the product after the reaction, and there is a problem that the catalyst cannot be reused.
  • Non-Patent Document 3 describes a method of synthesizing bromobenzene by reacting benzene and bromine in the presence of zeolite.
  • this synthesis method has a problem that an excessive amount of zeolite is required with respect to the amount of bromobenzene and bromine.
  • the present invention has been made to solve the above problems, and provides a halogenation catalyst for halogenating an aromatic ring, which can obtain a halogen compound in a high yield and can be easily recovered. It is intended. Moreover, it aims at providing the manufacturing method of such a halogenated catalyst. Furthermore, it aims at providing the method of manufacturing a halogen compound using such a halogenated catalyst.
  • a halogenation catalyst for halogenating an aromatic ring wherein iron oxide or zinc oxide is supported on a support composed of a composite oxide containing silicon and aluminum.
  • the halogenation catalyst is preferably a bromination catalyst for brominating an aromatic ring. It is also preferable to contain 0.1 to 10 mmol of iron element or zinc element with respect to 1 g of the composite oxide. It is also preferable that iron oxide is supported on the carrier made of the composite oxide.
  • the ratio (Si / Al) of silicon atoms to aluminum atoms in the composite oxide is 1 to 1000. It is also preferable that the composite oxide is zeolite.
  • the said subject is a manufacturing method of the said halogenated catalyst, Comprising: The 1st process which mixes the complex oxide containing a silicon and aluminum, and an iron salt or a zinc salt in a solvent, and obtained by the said 1st process.
  • a method for producing a halogenated catalyst comprising: a second step of removing the solvent from the obtained mixture; and a third step of heating the mixture from which the solvent has been removed in the second step in an oxidizable atmosphere. It is also solved by providing.
  • the subject is a method for producing a halogen compound using the halogenated catalyst; and a method for producing a halogen compound comprising reacting a compound having an aromatic ring with halogen in the presence of the halogenated catalyst. It is also solved by providing.
  • a halogen compound can be obtained in a high yield.
  • the halogenated catalyst of the present invention is easily separated from the reaction system and easily recovered. According to the production method of the present invention, such a halogenated catalyst can be easily obtained. If the halogenated catalyst of the present invention is used, a halogen compound can be easily produced.
  • FIG. 6 is a diagram showing the results of analysis by powder X-ray diffraction of Na- ⁇ zeolite and Na- ⁇ zeolite supporting iron oxide.
  • the halogenation catalyst of the present invention is a catalyst for halogenating an aromatic ring, and iron oxide or zinc oxide is supported on a support made of a composite oxide containing silicon and aluminum.
  • the reaction system becomes a so-called heterogeneous system, and the catalyst can be easily separated and recovered from the reaction system.
  • the composite oxide used in the present invention contains at least silicon (Si), aluminum (Al), and oxygen (O). Specifically, it is a composite oxide containing a silicon oxide and an aluminum oxide, in which at least a part of silicon atoms and aluminum atoms are chemically bonded through oxygen.
  • the ratio of silicon atom to aluminum atom (Si / Al) in the composite oxide is preferably 1 to 1000, more preferably 2 to 500, and 5 to 300. Further preferred.
  • Specific examples of the complex oxide used in the present invention preferably include zeolite, silica alumina, and aluminosilicate, and more preferably zeolite.
  • iron element or zinc element it is preferable that 0.1 to 10 mmol of iron element or zinc element is contained with respect to 1 g of the composite oxide. If the content of the iron element or zinc element relative to 1 g of the composite oxide is less than 0.1 mmol, the reactivity of the halogenation reaction may be lowered, more preferably 0.2 mmol or more, and even more preferably 0. .5 mmol or more. On the other hand, when the content of the iron element or zinc element with respect to 1 g of the composite oxide exceeds 10 mmol, the production cost may increase, more preferably 8 mmol or less, and further preferably 5 mmol or less.
  • the iron element and the zinc element are supported in an oxide state on a support made of a composite oxide containing silicon and aluminum.
  • iron oxide is supported on a support made of a composite oxide containing silicon and aluminum.
  • the iron oxide supported on the carrier is preferably hematite.
  • a preferred method for producing the halogenated catalyst of the present invention comprises a first step of mixing a composite oxide containing silicon and aluminum, an iron salt or a zinc salt in a solvent, and a mixture obtained in the first step. A second step of removing the solvent and a third step of heating the mixture from which the solvent has been removed in the second step in an oxidizable atmosphere.
  • the iron salt or zinc salt used in the first step is not particularly limited as long as it is a metal salt that becomes an oxide when heated.
  • the metal salts include iron chloride, iron nitrate, iron sulfate, iron acetate, iron acetylacetonate, zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, zinc acetylacetonate, etc., which are inexpensive and easily available. Can do.
  • the solvent used in the first step is not particularly limited as long as the metal salt is dissolved and can be easily distilled off, and examples thereof include polar organic solvents such as alcohol and water. Of these, alcohols having 3 or less carbon atoms, particularly methanol, are preferred.
  • the mixing operation in the first step is not particularly limited.
  • the complex oxide may be added to and mixed with the metal salt solution, or the metal salt may be added and dissolved in a mixture of the complex oxide and the solvent.
  • the method for removing the solvent in the second step is not particularly limited, and methods such as reduced pressure and heating can be employed.
  • the mixture from which the solvent has been removed is heated in an oxidizable atmosphere.
  • the oxidizable atmosphere here means an atmosphere in which the metal salt contained in the mixture can be oxidized by heating. Therefore, the atmosphere for heating may be an atmosphere containing oxygen, and heating in the air is simple and preferable.
  • the heating temperature is preferably 150 to 500 ° C.
  • the heating time is set in relation to the heating temperature, but may be set as appropriate so that the metal salt contained in the mixture becomes an oxide.
  • the heating method is not particularly limited, and examples thereof include a method of heating in an oven and a method of heating using a heater.
  • a halogen compound can be produced by reacting a compound having an aromatic ring with halogen.
  • a hydrogen atom on the aromatic ring is substituted with a halogen atom by an aromatic electrophilic substitution reaction.
  • a halogen compound can be obtained with a sufficient yield.
  • the compound having an aromatic ring may be a compound having an aromatic ring and at least one of the atoms bonded to the carbon atom of the aromatic ring being a hydrogen atom.
  • the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and biphenyl. Further, it may be a 5-membered heteroaromatic ring such as a thiophene ring, a pyrrole ring or a furan ring, or a 6-membered heteroaromatic ring such as a pyridine ring or a pyrimidine ring. Moreover, the compound which these aromatic rings condensed may be sufficient. Examples of the substituent introduced into these aromatic rings include halogen, amino group, hydroxy group, alkoxy group, alkyl group, aryl group, cyano group, nitro group and the like. A plurality of such substituents may be introduced.
  • the reaction temperature when producing the halogen compound is usually room temperature to 150 ° C., and the reaction time is appropriately set in relation to the reaction temperature.
  • the molar ratio of the starting compound having an aromatic ring and the halogen is not particularly limited. It may be equivalent, or one may be in excess.
  • the amount of the halogenated catalyst is not particularly limited.
  • the amount of the halogenated catalyst used per 1 mol of the raw material is preferably 0.5 mol or less, and more preferably 0.1 mol or less, as the number of mols of iron element or zinc element.
  • the usage-amount of the halogenated catalyst with respect to 1 mol of raw materials is 0.001 mol or more normally as a mol number of an iron element or a zinc element.
  • the halogenation catalyst is preferably a bromination catalyst for brominating an aromatic ring.
  • the halogen used in the halogenation reaction in the present invention include chlorine, bromine and iodine. Among these, when the halogenated catalyst of the present invention is used for bromination reaction, the reaction proceeds efficiently.
  • a preferred embodiment of the present invention is to separate the halogenated catalyst from the reaction system after completion of the reaction. More preferably, the separated halogenated catalyst is reused. Since the halogenated catalyst of the present invention is a so-called heterogeneous catalyst, the halogenated catalyst can be separated by a simple method such as centrifugation or filtration after completion of the halogenation reaction. At this time, the halogenated catalyst separated from the reaction system is preferably reused after being heated. As the heating conditions, the same conditions as in the third step in the method for producing a halogenated catalyst are preferably employed. Thus, even when the halogenated catalyst of the present invention is separated and reused, a halogen compound can be obtained in high yield. Therefore, the halogenated catalyst of the present invention is excellent in terms of environment and cost.
  • Example 1 (Examination of metal species supported on a carrier)
  • Example 1 is an example in which the reactivity of the halogenation reaction was examined when the metal species supported on the carrier was changed. Specifically, halogenation catalysts each having iron, zinc, manganese, copper, chromium, and cobalt supported on a carrier were prepared, and the reactivity of bromination reaction and chlorination reaction using these catalysts was examined. Further, the halogenated catalyst used in Reaction Example 1-1 was analyzed by a powder X-ray diffraction method.
  • Reaction Example 1-2 0.14 g (1 mmol) of zinc chloride (ZnCl 2 ) was used as the metal salt, and in Reaction Example 1-3, manganese (II) chloride tetrahydrate was used as the metal salt.
  • Reaction Examples 1-1 to 8 (bromination reaction) Under an argon atmosphere (1 atm), the halogenated catalyst shown in Table 1 (0.01 g), benzene (1 mL) and bromine (0.08 g, 0.5 mmol) were added to a test tube using dichloromethane as a solvent. The mixture was heated and stirred for 1.5 hours. Thereafter, the reaction mixture was treated with an aqueous sodium thiosulfate solution, and organic substances were extracted with hexane. The organic phase was analyzed by gas chromatography to determine the yield of bromobenzene.
  • the hematite used in Reaction Example 1-8 is iron (III) oxide manufactured by Wako Pure Chemical Industries, Ltd. The results are shown in Table 1.
  • the reaction formula is as shown in the following formula (I).
  • Reaction Example 1-9 (bromination reaction) Under an argon atmosphere (1 atm), the halogenated catalyst of Reaction Example 1-1 (0.05 g), benzene (6 mL) and bromine (3.2 g, 20 mmol) were added to a 50 mL eggplant flask, and the top of the eggplant flask was added. A balloon filled with argon was attached. After stirring with heating at 40 ° C. for 2 hours, the reaction mixture was treated with an aqueous sodium thiosulfate solution, and organic substances were extracted with hexane. The organic phase was analyzed by gas chromatography to determine the yield of bromobenzene. The yield of bromobenzene was 87%.
  • the reaction formula is as shown in the following formula (II).
  • Reaction Example 1-10 (chlorination reaction)
  • the halogenated catalyst (0.01 g) and benzene (1 mL) of Reaction Example 1-1 were put in a test tube, and the air in the test tube was replaced with chlorine and sealed, and a chlorine atmosphere (1 atm) was obtained. At this time, the chlorine added to the test tube was 2 mmol.
  • the reaction mixture was treated with an aqueous sodium thiosulfate solution, and organic substances were extracted with hexane. The organic phase was analyzed by gas chromatography to determine the yield of chlorobenzene. The yield of chlorobenzene was 77%.
  • the reaction formula is as shown in the following formula (III).
  • Example 2 is an example in which the reactivity of the halogenation reaction when the carrier was changed was examined. Specifically, except that the support was changed as shown in Table 2, a halogenated catalyst was prepared in the same manner as when the halogenated catalyst of Reaction Example 1-1 was prepared, and the reactivity of the bromination reaction was examined. .
  • the halogenation catalyst of Reaction Example 1-1 that is, the halogenation catalyst in which iron oxide is supported on a zeolite carrier was used.
  • a halogenated catalyst was prepared using aluminum oxide as a carrier that is not a complex oxide, and in Reaction Example 2-5, silicon dioxide was used as a carrier that was not a complex oxide. is there.
  • Example 3 (Examination of reusability)
  • Example 3 is an example of examining whether or not the halogenated catalyst can be separated from the reaction system and reused.
  • the bromination reaction of benzene was performed using the halogenation catalyst of Reaction Example 1-1, that is, the halogenation catalyst in which iron oxide is supported on a zeolite carrier.
  • the reaction solution was filtered through a membrane filter to recover the halogenated catalyst, washed with a very small amount of hexane, and then heated in the atmosphere at 300 ° C. for 1 hour using an electric furnace.
  • the halogenated catalyst thus recovered was reused in the next reaction.
  • the reactivity of the bromination reaction when this operation was repeated was examined.
  • the conditions for the bromination reaction are the same as in Reaction Example 1-1 of Example 1, except that 3 mL of benzene and 0.24 g (1.5 mmol) of bromine were used and the reaction time was 2 hours. The results are shown in Table 3.
  • Example 4 is an example in which the reactivity of the bromination reaction when the reaction substrate was changed was examined. Specifically, bromination reaction was carried out using the reaction substrate shown in Table 4 using the halogenation catalyst used in Reaction Example 1-1, that is, the halogenation catalyst in which iron oxide was supported on a zeolite carrier. The conditions for the bromination reaction are as shown in Table 4.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
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Abstract

L'invention concerne un catalyseur d'halogénation pour halogéner un cycle aromatique, qui est caractérisé comme étant obtenu en ayant de l'oxyde de fer ou de l'oxyde de zinc supporté par un support qui est formé d'un oxyde complexe qui contient du silicium et de l'aluminium. A cet égard, il est préférable que le catalyseur d'halogénation soit un catalyseur de bromination pour bromer un cycle aromatique. Il est également préférable que 0,1-10 mmol de fer élémentaire ou de zinc élémentaire soit contenu pour 1 g de l'oxyde complexe. Il est également préférable que le rapport des atomes de silicium aux atomes d'aluminium dans l'oxyde complexe, à savoir Si/Al soit de 1-1 000. En conséquence, un halogénure est capable d'être obtenu avec un rendement élevé.
PCT/JP2012/080866 2011-12-01 2012-11-29 Catalyseur d'halogénation et son procédé de fabrication WO2013081034A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566183A (zh) * 2016-03-21 2016-05-11 太原理工大学 一种4,4’-二巯基二苯硫醚的制备方法
CN115141079A (zh) * 2022-08-11 2022-10-04 安徽东至广信农化有限公司 一种氯化苯生产中降低杂质二氯苯的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112194562A (zh) * 2020-09-03 2021-01-08 潍坊摩根化工有限公司 一种溴代苯的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01503066A (ja) * 1987-03-25 1989-10-19 イーストマン コダック カンパニー 芳香族化合物の改良蒸気相臭素化
JPH07330665A (ja) * 1994-06-03 1995-12-19 Mitsubishi Chem Corp ハロゲン化芳香族化合物の製造法
EP0866046A1 (fr) * 1997-03-20 1998-09-23 Contract Chemicals Limited Procédé catalytique de bromation d'aromatiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01503066A (ja) * 1987-03-25 1989-10-19 イーストマン コダック カンパニー 芳香族化合物の改良蒸気相臭素化
JPH07330665A (ja) * 1994-06-03 1995-12-19 Mitsubishi Chem Corp ハロゲン化芳香族化合物の製造法
EP0866046A1 (fr) * 1997-03-20 1998-09-23 Contract Chemicals Limited Procédé catalytique de bromation d'aromatiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. ZABICKY ET AL.: "Molecular sieves as catalysts for aromatic bromination", ZEOLITES, vol. 7, no. 6, 1987, pages 499 - 502, XP055070942 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566183A (zh) * 2016-03-21 2016-05-11 太原理工大学 一种4,4’-二巯基二苯硫醚的制备方法
CN115141079A (zh) * 2022-08-11 2022-10-04 安徽东至广信农化有限公司 一种氯化苯生产中降低杂质二氯苯的方法

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