CN107721810A - A kind of method for synthesizing extinguishing chemical octafluorocyclobutane - Google Patents

A kind of method for synthesizing extinguishing chemical octafluorocyclobutane Download PDF

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Publication number
CN107721810A
CN107721810A CN201711081489.XA CN201711081489A CN107721810A CN 107721810 A CN107721810 A CN 107721810A CN 201711081489 A CN201711081489 A CN 201711081489A CN 107721810 A CN107721810 A CN 107721810A
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octafluorocyclobutane
hydrogen fluoride
dichloro
catalyst
chlorine
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CN107721810B (en
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周晓猛
周彪
赵洪海
张青松
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Tianjin Hangda Yian Technology Development Co.,Ltd.
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Civil Aviation University of China
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    • 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
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/864—Cobalt and chromium
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons

Abstract

The present invention relates to " a kind of method for synthesizing extinguishing chemical octafluorocyclobutane ", belong to organic chemical synthesis field.This synthesis octafluorocyclobutane method, it is characterised in that：Dichloro-tetrafluoro cyclobutane and hydrogen fluoride, chlorine generate octafluorocyclobutane under fluorination catalyst effect.

Description

A kind of method for synthesizing extinguishing chemical octafluorocyclobutane
Technical field
The invention belongs to organic chemical synthesis technical field, particularly a kind of method for synthesizing extinguishing chemical octafluorocyclobutane.
Background technology
Octafluorocyclobutane has very high industrial value, is a kind of very important fluorine-containing extinguishing chemical.
Study on the synthesis about octafluorocyclobutane, relevant report are less.A kind of conjunction is reported in patent (US 6710215) Into octafluorocyclobutane method, this method under conditions of HTHP by tetrafluoroethene and water by synthesizing octafluorocyclobutane.But The condition of this method HTHP limits its industrialized production.A kind of synthesis octafluoro ring fourth is reported in patent (US2404374) Alkane method, this method synthesize octafluorocyclobutane by high temperature high pressure process tetrafluoroethene.But the shortcomings that this method is cost of material Costliness, high-pressure process is dangerous, and reaction yield is low.Document (Bardin, V.V.；Avramenko,A.A.；Furin,G.G.； Krasilnikov,V.A.；Karelin,A.I.；et al.；Journal of Fluorine Chemistry；vol.49； nb.3；(1990)；P.385-400 a kind of synthesis octafluorocyclobutane method is reported in), this method passes through hexafluoro cyclobutane and five Vanadium fluoride reaction synthesis octafluorocyclobutane.This method expensive raw material price, limit its industrialized production.
It can be seen from more than when preparing octafluorocyclobutane, there are severe reaction conditions, raw material, which is not easy to prepare, etc. lacks Point, these all limit the industrialized production of octafluorocyclobutane.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of method for synthesizing extinguishing chemical octafluorocyclobutane.
In order to achieve the above object, the method for synthesis octafluorocyclobutane provided by the invention includes being with dichloro-tetrafluoro ring fourth Alkene, as raw material, carries out gas phase fluorination generation octafluorocyclobutane with hydrogen fluoride, chlorine under fluorination catalyst effect.
Described fluorination catalyst is selected from Cr, Ni, Cu, Zn, Mg, at least one of Co, In.
The temperature of described gas phase fluorination is 100-600 DEG C.
The time of described gas phase fluorination is 0.1-20s.
The mol ratio of described dichloro-tetrafluoro cyclobutane and hydrogen fluoride, chlorine is 1: 5~30: 2.5~5.
The method of synthesis extinguishing chemical octafluorocyclobutane provided by the invention has the beneficial effect that：
1. raw material of the present invention is cheap, source facility.
2. three industrial wastes are less.
3. product yield is high, product separating-purifying is simple.
4. building-up process is safe, it is suitable for industrialized production.
Embodiment
The method of synthesis extinguishing chemical octafluorocyclobutane provided by the invention is carried out in detail with reference to specific embodiment Explanation.
Embodiment 1
(1) preparation of fluorination catalyst：It is as follows using coprecipitation, step：By CrCl3、In(NO3)3、Zn(NO3)2Solution With 90: 5: 5 mixed in molar ratio into mixed liquor, then the ammoniacal liquor for accounting for the weight of mixed liquor 30% is added drop-wise in above-mentioned mixed liquor, The pH value of mixed liquor is adjusted to 9.0, by precipitation aging in 24 hours, precipitation filtering, is washed with deionized, dries, be pressed into Type, so as to obtain Cr-In-Zn catalyst.
The drying process of Cr-In-Zn catalyst：20ml Cr-In-Zn catalyst is loaded into fixed bed reactors, Ran Houyong Open-type pipe heats stove heat fixed bed reactors.Make Cr-In-Zn catalyst under the protection of 50m/minl nitrogen, first with 10 DEG C/min speed rises to 400 DEG C of temperature and dries 10 hours, then, temperature is reduced to 200 DEG C, thus complete Cr-In-Zn and urge The drying process of agent.
The activation process of Cr-In-Zn catalyst：Fixed bed reactors are heated to 200 DEG C, first with 100ml/min Nitrogen carries out activating catalytic 4 hours with 20ml/min hydrogen fluoride；Then entered using 100ml/min nitrogen and 50ml/min hydrogen fluoride Row activating catalytic 4 hours；Afterwards activating catalytic is carried out using 50ml/min nitrogen and 100ml/min hydrogen fluoride 4 hours；Recycle The pure hydrogen fluoride of 100ml/min carries out activating catalytic 4 hours；Temperature is raised to 400 DEG C, finally utilizes the pure hydrogen fluoride of 100ml/min Carry out activating catalytic 4 hours, thus complete the activation process of Cr-In-Zn catalyst.
Above-mentioned fluorination catalyst participates in course of reaction：By mixed gas, (dichloro-tetrafluoro cyclobutane, hydrogen fluoride, chlorine rub Your ratio=1: 5: 400 DEG C of fixed bed reactors equipped with Cr-In-Zn catalyst 3) are passed through with 250ml/min speed.It Afterwards, surge flask, washing bottle, concentrated base absorber, cooling collector are passed through.After experiment terminates, product is mainly distributed on cooling and collected In device.Collect the product in cooling collector and carry out GC analyses.GC results are shown, are collected in product and are contained 8% octafluoro ring fourth Alkane, 12% dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane, 16% trichloro-monofluoro cyclobutane, 62% dichloro-tetrafluoro cyclobutane.
Embodiment 2
(1) preparation of fluorination catalyst：It is as follows using coprecipitation, step：By CrCl3、Co(NO3)2、Mg(NO3)2Solution With 90: 5: 5 mixed in molar ratio into mixed liquor, then the ammoniacal liquor for accounting for the weight of mixed liquor 30% is added drop-wise in above-mentioned mixed liquor, The pH value of mixed liquor is adjusted to 9.0, by precipitation aging in 24 hours, precipitation filtering, is washed with deionized, dries, be pressed into Type, so as to obtain Cr-Co-Mg catalyst.
The drying process of Cr-Co-Mg catalyst：20ml Cr-Co-Mg catalyst is loaded into fixed bed reactors, Ran Houyong Open-type pipe heats stove heat fixed bed reactors.Make Cr-Co-Mg catalyst under the protection of 50m/minl nitrogen, first with 10 DEG C/min speed rises to 400 DEG C of temperature and dries 10 hours, then, temperature is reduced to 200 DEG C, thus complete Cr-Co-Mg and urge The drying process of agent.
The activation process of Cr-Co-Mg catalyst：Fixed bed reactors are heated to 200 DEG C, first with 100ml/min Nitrogen carries out activating catalytic 4 hours with 20ml/min hydrogen fluoride；Then entered using 100ml/min nitrogen and 50ml/min hydrogen fluoride Row activating catalytic 4 hours；Afterwards activating catalytic is carried out using 50ml/min nitrogen and 100ml/min hydrogen fluoride 4 hours；Recycle The pure hydrogen fluoride of 100ml/min carries out activating catalytic 4 hours；Temperature is raised to 400 DEG C, finally utilizes the pure hydrogen fluoride of 100ml/min Carry out activating catalytic 4 hours, thus complete the activation process of Cr-Co-Mg catalyst.
Above-mentioned fluorination catalyst participates in course of reaction：By mixed gas, (dichloro-tetrafluoro cyclobutane, hydrogen fluoride, chlorine rub Your ratio=1: 20: 490 DEG C of fixed bed reactors equipped with Cr-Co-Mg catalyst 3) are passed through with 250ml/min speed.It Afterwards, surge flask, washing bottle, concentrated base absorber, cooling collector are passed through.After experiment terminates, product is mainly distributed on cooling and collected In device.Collect the product in cooling collector and carry out GC analyses.GC results are shown, are collected in product and are contained 12% octafluoro ring fourth Alkane, 15% dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane, 21% trichloro-monofluoro cyclobutane, 45% dichloro-tetrafluoro cyclobutane.

Claims (5)

  1. A kind of 1. method for synthesizing extinguishing chemical octafluorocyclobutane, it is characterised in that：Dichloro-tetrafluoro cyclobutane exists with hydrogen fluoride, chlorine Under fluorination catalyst effect, octafluorocyclobutane is generated.
  2. 2. according to the method for claim 1, it is characterised in that：Dichloro-tetrafluoro cyclobutane is urged with hydrogen fluoride, chlorine in fluorination The lower generation octafluorocyclobutane of agent effect, the catalyst is Cr, Ni, Cu, Zn, Mg, Co, one or more complex groups in In Divided catalyst.
  3. 3. according to the method for claim 1, it is characterised in that：Dichloro-tetrafluoro cyclobutane is urged with hydrogen fluoride, chlorine in fluorination The lower generation octafluorocyclobutane of agent effect, the reaction temperature is 100-600 DEG C.
  4. 4. according to the method for claim 1, it is characterised in that：Dichloro-tetrafluoro cyclobutane is urged with hydrogen fluoride, chlorine in fluorination Generation octafluorocyclobutane, the time of contact of the reaction are under agent effect：0.1—20s.
  5. 5. according to the method for claim 1, it is characterised in that：Dichloro-tetrafluoro cyclobutane and hydrogen fluoride, chlorine are urged in fluorination The lower generation octafluorocyclobutane of agent effect, the molar ratio of material of the reaction：Dichloro-tetrafluoro cyclobutane：Hydrogen fluoride：Chlorine=1：5 ~30：2.5~5.
CN201711081489.XA 2017-11-07 2017-11-07 Method for synthesizing extinguishing agent octafluorocyclobutane Active CN107721810B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020137825A1 (en) * 2018-12-27 2020-07-02 ダイキン工業株式会社 Method for producing cyclobutene
WO2020145088A1 (en) * 2019-01-09 2020-07-16 ダイキン工業株式会社 Method for producing cyclobutane
CN114956950A (en) * 2022-07-14 2022-08-30 中船(邯郸)派瑞特种气体股份有限公司 Method for synthesizing octafluorocyclobutane by using fluorine-chlorine exchange reaction
RU2784315C1 (en) * 2018-12-27 2022-11-23 Дайкин Индастриз, Лтд. Method for production of cyclobutene

Citations (1)

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CN103570490A (en) * 2012-07-21 2014-02-12 北京宇极神光科技有限公司 Method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020137825A1 (en) * 2018-12-27 2020-07-02 ダイキン工業株式会社 Method for producing cyclobutene
JP2020105114A (en) * 2018-12-27 2020-07-09 ダイキン工業株式会社 Method for producing cyclobutene
RU2784315C1 (en) * 2018-12-27 2022-11-23 Дайкин Индастриз, Лтд. Method for production of cyclobutene
WO2020145088A1 (en) * 2019-01-09 2020-07-16 ダイキン工業株式会社 Method for producing cyclobutane
JP2020111520A (en) * 2019-01-09 2020-07-27 ダイキン工業株式会社 Production method of cyclobutane
TWI798518B (en) * 2019-01-09 2023-04-11 日商大金工業股份有限公司 The production method of cyclobutane
RU2807184C2 (en) * 2019-01-09 2023-11-10 Дайкин Индастриз, Лтд. Method for obtaining cyclobutene
RU2807184C9 (en) * 2019-01-09 2024-01-17 Дайкин Индастриз, Лтд. Method for obtaining cyclobutane
CN114956950A (en) * 2022-07-14 2022-08-30 中船(邯郸)派瑞特种气体股份有限公司 Method for synthesizing octafluorocyclobutane by using fluorine-chlorine exchange reaction
CN114956950B (en) * 2022-07-14 2023-05-02 中船(邯郸)派瑞特种气体股份有限公司 Method for synthesizing octafluorocyclobutane by utilizing fluorine-chlorine exchange reaction

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