JP2023131518A - Halogenated alkene production method - Google Patents
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 56
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 45
- 239000010883 coal ash Substances 0.000 claims abstract description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 22
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010881 fly ash Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical group CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 238000005796 dehydrofluorination reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 40
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 24
- 239000011737 fluorine Substances 0.000 description 24
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010882 bottom ash Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- -1 halogenated butene compound Chemical class 0.000 description 2
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- PFFGXVGPSGJOBV-UHFFFAOYSA-N 1,1,1,3-tetrafluoropropane Chemical compound FCCC(F)(F)F PFFGXVGPSGJOBV-UHFFFAOYSA-N 0.000 description 1
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 description 1
- LKCCQAPPZYBMLN-UHFFFAOYSA-N 1,1,2-trifluorobutane Chemical compound CCC(F)C(F)F LKCCQAPPZYBMLN-UHFFFAOYSA-N 0.000 description 1
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- HHRQYHKSSIGXJV-UHFFFAOYSA-N 1,1,2-trifluoropropane Chemical compound CC(F)C(F)F HHRQYHKSSIGXJV-UHFFFAOYSA-N 0.000 description 1
- GQSMEOJGQJMOHA-UHFFFAOYSA-N 1,1,3-trifluoropropane Chemical compound FCCC(F)F GQSMEOJGQJMOHA-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- CTJAKAQLCQKBTC-UHFFFAOYSA-N 1,1-difluoropropane Chemical compound CCC(F)F CTJAKAQLCQKBTC-UHFFFAOYSA-N 0.000 description 1
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 1
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical class [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
Abstract
Description
本発明は、ハロゲン化アルケンの製造方法に関する。 The present invention relates to a method for producing halogenated alkenes.
ハロゲン化アルケンの製造方法として、複数のハロゲン原子で置換されたハロゲン化アルカンから、ハロゲン化水素を脱離させる製造方法が知られている。例えば、特許文献１には、フルオロアルカンを金属触媒と接触させて、脱フッ化水素反応によってフルオロオレフィンを製造する方法が記載されている。また、特許文献２および特許文献３には、ハロゲン化ブタン化合物を活性炭と接触させて、脱ハロゲン化水素によってハロゲン化ブテン化合物を製造する方法が記載されている。 As a method for producing halogenated alkenes, there is known a production method in which hydrogen halide is eliminated from a halogenated alkane substituted with a plurality of halogen atoms. For example, Patent Document 1 describes a method for producing fluoroolefins through a dehydrofluorination reaction by bringing a fluoroalkane into contact with a metal catalyst. Further, Patent Document 2 and Patent Document 3 describe a method for producing a halogenated butene compound by bringing the halogenated butane compound into contact with activated carbon and dehydrohalogenating the compound.
しかしながら、特許文献１に記載されたフルオロオレフィンを製造する方法、並びに、特許文献２および３に記載されたハロゲン化ブテン化合物を製造する方法は、脱ハロゲン化水素反応の触媒として酸化クロムおよび酸化アルミニウム等の金属触媒、または活性炭が使用されており、触媒に係るコストが嵩むという問題がある。また金属触媒および活性炭はフッ素化することによってより強い活性を示すようになるが、フッ素化するために要するフッ素化剤の使用により、よりコストが嵩むという問題がある。 However, in the method for producing fluoroolefins described in Patent Document 1 and the method for producing halogenated butene compounds described in Patent Documents 2 and 3, chromium oxide and aluminum oxide are used as catalysts for the dehydrohalogenation reaction. etc. or activated carbon are used, and there is a problem in that the cost of the catalyst increases. Furthermore, when metal catalysts and activated carbon are fluorinated, they exhibit stronger activity, but there is a problem in that the cost increases due to the use of fluorinating agents required for fluorination.
さらに発明者らが検討を行った結果、触媒として酸化クロムおよび酸化アルミニウム等を用いると、脱ハロゲン化水素反応の開始直後における選択率が低くなることを見出した。脱ハロゲン化水素反応において、未反応のハロゲン化アルカンを回収し再び原料として反応系に戻すことができるが、選択率が低いと副生成物が製造されてしまうため、再利用するハロゲン化アルカンを得にくいといった問題も生じてくる。そのため、コスト低減の観点から、脱ハロゲン化水素反応の開始直後から選択率の高いハロゲン化アルケンの製造方法が求められている。 Furthermore, as a result of studies conducted by the inventors, it was found that when chromium oxide, aluminum oxide, or the like is used as a catalyst, the selectivity immediately after the start of the dehydrohalogenation reaction becomes low. In the dehydrohalogenation reaction, unreacted halogenated alkanes can be recovered and returned to the reaction system as raw materials, but if the selectivity is low, by-products will be produced, so the halogenated alkanes to be reused are There are also problems that it is difficult to obtain. Therefore, from the viewpoint of cost reduction, there is a need for a method for producing halogenated alkenes that has a high selectivity immediately after the start of the dehydrohalogenation reaction.
本発明は、上述の問題に鑑みてなされたものであり、安価な触媒を使用して、反応開始直後から高選択率でハロゲン化アルケンを得ることを目的とする。 The present invention has been made in view of the above-mentioned problems, and aims to obtain halogenated alkenes with high selectivity immediately after the start of the reaction using an inexpensive catalyst.
本発明者らは上記課題を達成するために、鋭意研究を重ねた結果、触媒として安価な石炭灰を使用することによって、反応開始直後から高選択率でハロゲン化アルケンを製造できることを見出し、本発明を完成させた。 In order to achieve the above object, the present inventors conducted extensive research and discovered that by using inexpensive coal ash as a catalyst, halogenated alkenes could be produced with high selectivity immediately after the start of the reaction. Completed the invention.
本発明の一態様に係るハロゲン化アルケンの製造方法は、フッ素原子を含み炭素数が４以下であるハロゲン化アルカンと、石炭灰と、を接触させて、前記ハロゲン化アルカンを脱ハロゲン化水素させる工程を含むことを特徴とする、ハロゲン化アルケンの製造方法である。 A method for producing a halogenated alkene according to one aspect of the present invention includes contacting a halogenated alkane containing a fluorine atom and having 4 or less carbon atoms with coal ash to dehydrohalogenate the halogenated alkane. A method for producing a halogenated alkene, the method comprising the steps of:
本発明の一態様によれば、安価な触媒を使用して、反応開始直後から高選択率でハロゲン化アルケンを得ることができる。 According to one aspect of the present invention, a halogenated alkene can be obtained with high selectivity immediately after the start of the reaction using an inexpensive catalyst.
以下、本発明の一実施形態について、詳細に説明する。 Hereinafter, one embodiment of the present invention will be described in detail.
本実施形態に係るハロゲン化アルケンの製造方法（以下、「本実施形態の製造方法」と示す場合がある）は、触媒と、フッ素原子を含むハロゲン化アルカンと、を接触させて、ハロゲン化アルカンを脱ハロゲン化水素する工程を含む。以下、当該工程を、「脱ハロゲン化水素工程」と示す場合がある。また、「フッ素原子を含むハロゲン化アルカン」を「含フッ素ハロゲン化アルカン」と示す場合がある。本実施形態の製造方法によって製造されるフッ素原子を含むハロゲン化アルケンについては後述する。 The method for producing a halogenated alkene according to the present embodiment (hereinafter sometimes referred to as "the production method of the present embodiment") includes contacting a catalyst and a halogenated alkane containing a fluorine atom to produce a halogenated alkene. The process includes a step of dehydrohalogenating. Hereinafter, this step may be referred to as a "dehydrohalogenation step." Further, "halogenated alkane containing a fluorine atom" may be referred to as "fluorine-containing halogenated alkane". The halogenated alkene containing a fluorine atom produced by the production method of this embodiment will be described later.
触媒と含フッ素ハロゲン化アルカンとを接触させることによって、フッ素原子を含むハロゲン化アルカンを脱ハロゲン化水素反応させて、ハロゲン化アルケンが得られる。脱ハロゲン化水素反応の例として、脱フッ化水素反応等が挙げられる。 By bringing the catalyst and the fluorine-containing halogenated alkane into contact with each other, the halogenated alkane containing a fluorine atom undergoes a dehydrohalogenation reaction to obtain a halogenated alkene. Examples of dehydrohalogenation reactions include dehydrofluorination reactions and the like.
（触媒）
本実施形態の製造方法において用いられる触媒は、石炭灰である。石炭灰の例として、ボトムアッシュおよびフライアッシュが挙げられる。触媒は、ボトムアッシュおよびフライアッシュの何れかの石炭灰であってもよく、ボトムアッシュおよびフライアッシュの混合物であってもよい。より高い転化率を達成できる点で、触媒はフライアッシュであることが好ましい。
(catalyst)
The catalyst used in the manufacturing method of this embodiment is coal ash. Examples of coal ash include bottom ash and fly ash. The catalyst may be either bottom ash or fly ash, or a mixture of bottom ash and fly ash. Preferably, the catalyst is fly ash, since a higher conversion rate can be achieved.
（石炭灰）
石炭灰は、反応に用いる前に乾燥させてもよく、乾燥させなくてもよい。乾燥させる場合には、２５０℃程度で１時間乾燥させる。水分除去の観点から、減圧下もしくは不活性ガス気流下で乾燥させることが好ましい。
(coal ash)
The coal ash may or may not be dried before being used in the reaction. When drying, dry at about 250° C. for 1 hour. From the viewpoint of moisture removal, it is preferable to dry under reduced pressure or under an inert gas stream.
石炭灰は、反応に用いる前に強熱により揮発性物質を除去してもよく、除去しなくてもよい。強熱する場合には、８００℃程度で３０分以上強熱させる。未燃炭素の除去の観点から、９００℃以上で強熱させることが好ましい。 The coal ash may or may not have volatile substances removed by ignition before being used in the reaction. When igniting, ignite at about 800°C for 30 minutes or more. From the viewpoint of removing unburned carbon, it is preferable to ignite at 900° C. or higher.
フライアッシュは主に、ガラス相（非結晶質（Ａｌ―Ｓｉ））、結晶質シリカ（ＳｉＯ２）、結晶質アルミノケイ酸塩（３Ａｌ２Ｏ３・２ＳｉＯ２）、未燃炭素から構成される。また、フライアッシュは上記以外の化合物が含まれていてもよい。これらの化合物の含有比は特に限定されないが、反応効率および反応器の汚染抑制の観点から、未燃炭素の比率の指標を示す強熱減量は３０％以下であることが好ましく、２０％以下であることがより好ましく、１０％以下であることがさらに好ましい。 Fly ash is mainly composed of a glass phase (amorphous (Al-Si)), crystalline silica (SiO 2 ), crystalline aluminosilicate (3Al 2 O 3 .2SiO 2 ), and unburned carbon. Moreover, the fly ash may contain compounds other than those mentioned above. The content ratio of these compounds is not particularly limited, but from the viewpoint of reaction efficiency and suppression of contamination of the reactor, the loss on ignition, which is an indicator of the proportion of unburned carbon, is preferably 30% or less, and 20% or less. It is more preferable that it be present, and even more preferably that it be 10% or less.
フライアッシュは、直径または長径が０．２ｍｍ以下の球状または不定形の灰粒子である。これらの灰粒子の粒径は特に限定されないが、メディアン径（個数基準）が０．０５ｍｍ以下の微粒子であることが好ましい。 Fly ash is spherical or amorphous ash particles with a diameter or major axis of 0.2 mm or less. Although the particle size of these ash particles is not particularly limited, it is preferable that the particles have a median diameter (number based) of 0.05 mm or less.
ボトムアッシュは、塊状石炭灰であり、反応効率の観点から破砕機などで破砕し、粒度調整したものを用いることが好ましい。 The bottom ash is lumpy coal ash, and from the viewpoint of reaction efficiency, it is preferable to use one that has been crushed with a crusher or the like and whose particle size has been adjusted.
本明細書において、「転化率」は、脱ハロゲン化水素工程において、反応器に供給される含フッ素ハロゲン化アルカンのモル量に対する、反応器出口からの流出ガスに含まれる含フッ素ハロゲン化アルカン以外の化合物の合計モル量の割合（モル％）を示す。また「選択率」は、脱ハロゲン化水素工程において、反応器出口からの流出ガスにおける含フッ素ハロゲン化アルカン以外の化合物の合計モル量に対する、当該流出ガスに含まれるハロゲン化アルケンのモル量の割合（モル％）を指す。 In this specification, "conversion rate" refers to the molar amount of fluorine-containing halogenated alkanes other than fluorine-containing halogenated alkanes contained in the outflow gas from the reactor outlet in the dehydrohalogenation process. The ratio (mol %) of the total molar amount of the compound is shown. In addition, "selectivity" is the ratio of the molar amount of halogenated alkenes contained in the outflow gas to the total molar amount of compounds other than fluorine-containing halogenated alkanes in the outflow gas from the reactor outlet in the dehydrohalogenation process. (mol%).
（含フッ素ハロゲン化アルカン）
含フッ素ハロゲン化アルカンは、炭素数が４以下であるハロゲン化アルカンである。含フッ素ハロゲン化アルカンは炭素数が２であってもよく、炭素数が３であってもよい。含フッ素ハロゲン化アルカンに含まれるハロゲン原子の数は２以上であり、フッ素原子の数が１以上含まれることが好ましい。
(Fluorine-containing halogenated alkane)
The fluorine-containing halogenated alkane is a halogenated alkane having 4 or less carbon atoms. The fluorine-containing halogenated alkane may have two or three carbon atoms. The number of halogen atoms contained in the fluorine-containing halogenated alkane is 2 or more, and it is preferable that the number of fluorine atoms is 1 or more.
含フッ素ハロゲン化アルカンは、下記一般式（１）で示される化合物である。
含フッ素ハロゲン化アルカンとして、例えば、１，１－ジフルオロエタン、１，２－ジフルオロエタン、１，１，１－トリフルオロエタン、１，１，２－トリフルオロエタン、１，１，１，２－テトラフルオロエタン、１，１－ジフルオロプロパン、１，１，１－トリフルオロプロパン、１，１，３－トリフルオロプロパン、１，１，２－トリフルオロプロパン、１，１，１，３－テトラフルオロプロパン、１，１，１，３，３－ペンタフルオロプロパン、１，１，１，３，３，３－ヘキサフルオロプロパン、１，１，１，２，２，３，３－ヘプタフルオロプロパン、１，１，２，２，３，３，３－ヘプタフルオロプロパン、１，１，２－トリフルオロブタン、１－クロロ－１，１－ジフルオロエタン、１－クロロ－２，２－ジフルオロエタン、１，２－ジクロロ―１，１－ジフルオロエタン等が挙げられる。 Examples of the fluorine-containing halogenated alkane include 1,1-difluoroethane, 1,2-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1,2-tetra Fluoroethane, 1,1-difluoropropane, 1,1,1-trifluoropropane, 1,1,3-trifluoropropane, 1,1,2-trifluoropropane, 1,1,1,3-tetrafluoro Propane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,2,2,3,3-heptafluoropropane, 1,1,2,2,3,3,3-heptafluoropropane, 1,1,2-trifluorobutane, 1-chloro-1,1-difluoroethane, 1-chloro-2,2-difluoroethane, 1, Examples include 2-dichloro-1,1-difluoroethane.
（脱ハロゲン化水素工程の詳細および各条件）
脱ハロゲン化水素工程においては、触媒と含フッ素ハロゲン化アルカンとを接触させて、前記含フッ素ハロゲン化アルカンを脱ハロゲン化させる。例えば、反応系に触媒を供給後、含フッ素ハロゲン化アルカンを当該反応系に供給することによって、当該触媒と含フッ素ハロゲン化アルカンとを接触させてもよい。一例として、本実施形態の脱ハロゲン化水素工程では、石炭灰を供給した反応器に、含フッ素ハロゲン化アルカンを通気させることにより石炭灰と含フッ素ハロゲン化アルカンとを接触させる。
(Details and conditions of dehydrohalogenation process)
In the dehydrohalogenation step, the catalyst and the fluorine-containing halogenated alkane are brought into contact to dehalogenate the fluorine-containing halogenated alkane. For example, after supplying the catalyst to the reaction system, the catalyst and the fluorine-containing halogenated alkane may be brought into contact by supplying the fluorine-containing halogenated alkane to the reaction system. As an example, in the dehydrohalogenation step of the present embodiment, the coal ash and the fluorine-containing halogenated alkane are brought into contact by passing the fluorine-containing halogenated alkane into a reactor supplied with the coal ash.
上記反応系内の温度の下限は、より高い転化率を達成できる点で、４００℃以上が好ましく、４５０℃以上がより好ましい。また、当該反応系内の温度の上限は、副生成物の生成を抑制する点で、６００℃以下が好ましく、５５０℃以下がより好ましい。 The lower limit of the temperature in the reaction system is preferably 400°C or higher, more preferably 450°C or higher, from the standpoint of achieving a higher conversion rate. Further, the upper limit of the temperature within the reaction system is preferably 600°C or less, more preferably 550°C or less, from the viewpoint of suppressing the production of by-products.
脱ハロゲン化水素工程において、不活性ガス雰囲気下、触媒と含フッ素ハロゲン化アルカンとを接触させてもよい。不活性ガスとして、例えば、窒素ガス、ヘリウムおよびアルゴン等が挙げられる。 In the dehydrohalogenation step, the catalyst and the fluorine-containing halogenated alkane may be brought into contact under an inert gas atmosphere. Examples of the inert gas include nitrogen gas, helium, and argon.
上記反応系内における、含フッ素ハロゲン化アルカンと触媒の接触時間（Ｗ／Ｆ０）［Ｗ：触媒の重量（ｇ）、Ｆ０：ハロゲン化アルカンの流量（ｍＬ／ｓ）］は、１ｇ・ｓ／ｍＬ以上であることが好ましく、１０ｇ・ｓ／ｍＬ以上であることが好ましい。また、２００ｇ・ｓ／ｍＬ以下であることが好ましく、１５０ｇ・ｓ／ｍＬ以下であることがより好ましい。接触時間が上記範囲内であると、より高い選択率を達成することができる。 The contact time (W/F 0 ) between the fluorine-containing halogenated alkane and the catalyst in the above reaction system [W: weight of catalyst (g), F 0 : flow rate of halogenated alkane (mL/s)] is 1 g. It is preferable that it is s/mL or more, and it is preferable that it is 10 g·s/mL or more. Moreover, it is preferably 200 g·s/mL or less, and more preferably 150 g·s/mL or less. Higher selectivity can be achieved when the contact time is within the above range.
上記反応系で使用する反応器の材質としては、鉄、ニッケル、クロム、モリブテン、これらを主成分とする合金等が挙げられる。 Materials for the reactor used in the above reaction system include iron, nickel, chromium, molybdenum, alloys containing these as main components, and the like.
上記反応器内の圧力は、より効率的に脱ハロゲン化水素反応を進行させて高い選択率でハロゲン化アルケンを得ることができる点から、常圧以上２ＭＰａ・Ｇ以下であることが好ましく、常圧以上１ＭＰａ・Ｇ以下であることがより好ましく、常圧以上０．５ＭＰａ・Ｇ以下であることがさらに好ましい。 The pressure in the reactor is preferably at least normal pressure and at most 2 MPa.G, from the viewpoint of allowing the dehydrohalogenation reaction to proceed more efficiently and obtaining a halogenated alkene with high selectivity. The pressure is more preferably at least 1 MPa.G, and even more preferably the pressure is at least normal pressure and at most 0.5 MPa.G.
上述の通り、触媒と含フッ素ハロゲン化アルカンとを接触させることによって、含フッ素ハロゲン化アルカンが脱ハロゲン化水素反応して、ハロゲン化アルケンが得られる。 As described above, by bringing the catalyst and the fluorine-containing halogenated alkane into contact, the fluorine-containing halogenated alkane undergoes a dehydrohalogenation reaction to obtain a halogenated alkene.
（ハロゲン化アルケン）
本実施形態の製造方法によって製造されるハロゲン化アルケンは、フッ素原子を含むハロゲン化アルケンである。ハロゲン化アルケンの例として、フッ化ビニル（ＶＦ）、フッ化ビニリデン（ＶＤＦ、１，１－ジフルオロエチレン）、１，１，２－トリフルオロエチレン等が挙げられる。
(halogenated alkene)
The halogenated alkene produced by the production method of this embodiment is a halogenated alkene containing a fluorine atom. Examples of halogenated alkenes include vinyl fluoride (VF), vinylidene fluoride (VDF, 1,1-difluoroethylene), 1,1,2-trifluoroethylene, and the like.
本実施形態の製造方法のもっとも好ましい態様の１つは、触媒と１，１，１－トリフルオロエタンとを接触させて、１，１，１－トリフルオロエタンを脱ハロゲン化水素させる工程を含む、ＶＤＦの製造方法である。 One of the most preferred aspects of the production method of the present embodiment includes a step of contacting a catalyst with 1,1,1-trifluoroethane to dehydrohalogenate 1,1,1-trifluoroethane. , a method for manufacturing VDF.
〔まとめ〕
本実施形態に係るハロゲン化アルケンの製造方法は、フッ素原子を含み炭素数が４以下であるハロゲン化アルカンと、石炭灰と、を接触させて、前記ハロゲン化アルカンを脱ハロゲン化水素させる工程を含む。
〔summary〕
The method for producing a halogenated alkene according to the present embodiment includes a step of bringing a halogenated alkane containing a fluorine atom and having a carbon number of 4 or less into contact with coal ash to dehydrohalogenate the halogenated alkane. include.
本実施形態に係るハロゲン化アルケンの製造方法において、前記石炭灰がフライアッシュであってもよい。 In the method for producing a halogenated alkene according to the present embodiment, the coal ash may be fly ash.
本実施形態に係るハロゲン化アルケンの製造方法において、前記石炭灰を供給した反応器に、前記ハロゲン化アルカンを通気させることにより前記石炭灰と前記ハロゲン化アルカンとを接触させるものであって、前記ハロゲン化アルカンと前記石炭灰の接触時間は１０ｇ・ｓ／ｍＬ以上１５０ｇ・ｓ／ｍＬ以下であってもよい。 In the method for producing a halogenated alkene according to the present embodiment, the coal ash and the halogenated alkane are brought into contact by aerating the halogenated alkane into a reactor supplied with the coal ash, the method comprising: The contact time between the halogenated alkane and the coal ash may be 10 g·s/mL or more and 150 g·s/mL or less.
本実施形態に係るハロゲン化アルケンの製造方法において、前記ハロゲン化アルカンは、下記一般式（１）で示される化合物であってもよい。
本実施形態に係るハロゲン化アルケンの製造方法において、前記脱ハロゲン化水素させる工程は脱フッ化水素工程であってもよい。 In the method for producing a halogenated alkene according to the present embodiment, the dehydrohalogenation step may be a dehydrofluorination step.
本実施形態に係るハロゲン化アルケンの製造方法において、前記ハロゲン化アルカンが１，１，１－トリフルオロエタンであってもよい。 In the method for producing a halogenated alkene according to the present embodiment, the halogenated alkane may be 1,1,1-trifluoroethane.
以下に実施例を示し、本発明の実施の形態についてさらに詳しく説明する。もちろん、本発明の以下の実施例に限定されるものではなく、細部については様々な態様が可能であることはいうまでもない。さらに、本発明は上述した実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、それぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。また、本明細書中に記載された文献の全てが参考として援用される。 EXAMPLES Below, embodiments of the present invention will be described in more detail with reference to Examples. Of course, the present invention is not limited to the following embodiments, and it goes without saying that various modifications can be made to the details. Furthermore, the present invention is not limited to the embodiments described above, and various changes can be made within the scope of the claims, and the present invention also includes embodiments obtained by appropriately combining the disclosed technical means. falls within the technical scope of the invention. Additionally, all documents mentioned herein are incorporated by reference.
（実施例１）
触媒としてフライアッシュを１ｇ使用した。触媒を反応管（ＳＵＳ製、外径：１／２インチ）に供給した。反応管を５００℃に昇温させ、窒素雰囲気下、窒素と１，１，１－トリフルオロエタン（Ｒ１４３ａ）との混合ガス（窒素：Ｒ１４３ａ＝９５：５）を２０ｍＬ／分で２０分通気して反応させてＶＤＦを製造した（触媒とＲ１４３ａとの接触時間は２３ｇ・ｓ／ｍＬ）。得られたＶＤＦはガス捕集袋によって回収した。
(Example 1)
1 g of fly ash was used as a catalyst. The catalyst was supplied to a reaction tube (made of SUS, outer diameter: 1/2 inch). The reaction tube was heated to 500°C, and a mixed gas of nitrogen and 1,1,1-trifluoroethane (R143a) (nitrogen: R143a = 95:5) was bubbled through it at 20 mL/min for 20 minutes under a nitrogen atmosphere. The reaction was carried out to produce VDF (the contact time between the catalyst and R143a was 23 g·s/mL). The obtained VDF was collected using a gas collection bag.
（実施例２）
触媒の量を５ｇに変更し、触媒とＲ１４３ａとの接触時間を１１４ｇ・ｓ／ｍＬに変更した以外は、実施例１と同様にして、ＶＤＦを製造した。
(Example 2)
VDF was produced in the same manner as in Example 1, except that the amount of catalyst was changed to 5 g and the contact time between the catalyst and R143a was changed to 114 g·s/mL.
（実施例３）
反応管の昇温温度を６００℃に変更し、触媒とＲ１４３ａとの接触時間を１０１ｇ・ｓ／ｍＬに変更した以外は、実施例２と同様にして、ＶＤＦを製造した。
(Example 3)
VDF was produced in the same manner as in Example 2, except that the heating temperature of the reaction tube was changed to 600° C. and the contact time between the catalyst and R143a was changed to 101 g·s/mL.
（実施例４）
触媒としてボトムアッシュを３ｇ使用し触媒とＲ１４３ａとの接触時間を６０ｇ・ｓ／ｍＬに変更した以外は、実施例１と同様にして、ＶＤＦを製造した。
(Example 4)
VDF was produced in the same manner as in Example 1, except that 3 g of bottom ash was used as a catalyst and the contact time between the catalyst and R143a was changed to 60 g·s/mL.
（実施例５）
触媒としてボトムアッシュを３ｇ使用した以外は、実施例３と同様にして、ＶＤＦを製造した。
(Example 5)
VDF was produced in the same manner as in Example 3, except that 3 g of bottom ash was used as a catalyst.
（比較例１）
触媒をＳｉＯ２／Ａｌ２Ｏ３（シリカアルミナ）に変更した以外は、実施例１と同様にして、ＶＤＦを製造した。
(Comparative example 1)
VDF was produced in the same manner as in Example 1 except that the catalyst was changed to SiO 2 /Al 2 O 3 (silica alumina).
（比較例２）
触媒をゼオライトに変更した以外は、実施例１と同様にして、ＶＤＦを製造した。
(Comparative example 2)
VDF was produced in the same manner as in Example 1, except that the catalyst was changed to zeolite.
（比較例３）
触媒をＣｒＦ３ ｘＨ２Ｏに変更し、触媒とＲ１４３ａとの接触時間を１４ｇ・ｓ／ｍＬに変更した以外は、実施例１と同様にして、ＶＤＦを製造した。
(Comparative example 3)
VDF was produced in the same manner as in Example 1, except that the catalyst was changed to CrF 3 xH 2 O and the contact time between the catalyst and R143a was changed to 14 g·s/mL.
（比較例４）
触媒をＡｌＦ３に変更した以外は、比較例３と同様にして、ＶＤＦを製造した。
(Comparative example 4)
VDF was produced in the same manner as Comparative Example 3 except that the catalyst was changed to AlF3 .
（評価例）
各実施例および比較例について、窒素とＲ１４３ａとの混合ガスを通気し、ガス捕集袋に回収された気体成分を、ガスクロマトグラフィで分析した。ガスクロマトグラフィのカラムはアジレント・テクノロジー社製、ＣＰ－Ｐｏｒａ ＰＬＯＴ Ｑ（登録商標）を使用した。
(Evaluation example)
For each Example and Comparative Example, a mixed gas of nitrogen and R143a was passed through, and the gas components collected in the gas collection bag were analyzed by gas chromatography. The gas chromatography column used was CP-Pora PLOT Q (registered trademark) manufactured by Agilent Technologies.
実施例および比較例で使用した触媒、反応条件（接触条件）、および製造したＶＤＦの評価結果を表１～３および図１に示す。 The catalysts, reaction conditions (contact conditions), and evaluation results of the produced VDF used in Examples and Comparative Examples are shown in Tables 1 to 3 and FIG. 1.
表１～３中、Ｒ１４３ａ転化率（Ｘ）は、下記式（Ａ）から求めた。
Ｘ＝１００×（Ｘａ－Ｘｂ）／Ｘａ・・・（Ａ）
式（Ａ）中、Ｘａは、反応器に供給される含フッ素ハロゲン化アルカンのモル量を示す。また、Ｘｂは、反応器出口からの流出ガスに含まれる含フッ素ハロゲン化アルカンのモル量を示す。
In Tables 1 to 3, the R143a conversion rate (X) was determined from the following formula (A).
X=100×(Xa-Xb)/Xa...(A)
In formula (A), Xa represents the molar amount of the fluorine-containing halogenated alkane supplied to the reactor. Moreover, Xb indicates the molar amount of the fluorine-containing halogenated alkane contained in the gas flowing out from the reactor outlet.
また、選択率Ｙ（％）は、下式（Ｂ）から求めた。
Ｙ＝１００×Ｙａ／（Ｘａ－Ｘｂ）・・・（Ｂ）
式（Ｂ）中、ＸａおよびＸｂは上述の定義の通りである。Ｙａは、反応器出口からの流出ガスに含まれるハロゲン化アルケンのモル量である。
Moreover, the selectivity Y (%) was determined from the following formula (B).
Y=100×Ya/(Xa-Xb)...(B)
In formula (B), Xa and Xb are as defined above. Ya is the molar amount of halogenated alkene contained in the effluent gas from the reactor outlet.
反応器出口からの流出ガスに含まれる含フッ素ハロゲン化アルカンのモル量（Ｘｂ）およびハロゲン化アルケンのモル量（Ｙａ）は、反応器出口からの流出ガスをガスクロマトグラフィで分析した結果から算出した。 The molar amount of fluorine-containing halogenated alkane (Xb) and the molar amount of halogenated alkene (Ya) contained in the gas flowing out from the reactor outlet were calculated from the results of gas chromatography analysis of the gas flowing out from the reactor outlet. .
表１、２に示すように、触媒として、安価な石炭灰を使用することによって、高選択率かつ低コストでハロゲン化アルケンを得ることができた。 As shown in Tables 1 and 2, by using inexpensive coal ash as a catalyst, halogenated alkenes could be obtained with high selectivity and at low cost.
また、図１に示すように、触媒として、石炭灰を使用することによって、反応時間１０分後の時点で約１００％の選択率を示し、さらに６０分後もその高い選択率を維持することができた。これにより、副生成物がほとんど生じないため、未反応のハロゲン化アルカンを回収し、再び原料として使用することができる。 Furthermore, as shown in Figure 1, by using coal ash as a catalyst, the selectivity was approximately 100% after 10 minutes of reaction time, and the high selectivity was maintained even after 60 minutes. was completed. As a result, almost no by-products are produced, so that the unreacted halogenated alkane can be recovered and used again as a raw material.
本発明の製造方法によって得られるハロゲン化アルケンを重合して得られるポリマーは、電気・電子分野、石油ガス分野および自動車分野等、幅広い分野において利用できる。 The polymer obtained by polymerizing the halogenated alkene obtained by the production method of the present invention can be used in a wide range of fields such as electrical and electronic fields, oil and gas fields, and automobile fields.
Claims (6)
石炭灰と、を接触させて、前記ハロゲン化アルカンを脱ハロゲン化水素させる工程を含むことを
特徴とする、ハロゲン化アルケンの製造方法。 A halogenated alkane containing a fluorine atom and having a carbon number of 4 or less,
A method for producing a halogenated alkene, comprising the step of dehydrohalogenating the halogenated alkane by bringing it into contact with coal ash.
前記ハロゲン化アルカンと前記石炭灰の接触時間は１０ｇ・ｓ／ｍＬ以上１５０ｇ・ｓ／ｍＬ以下である、請求項１または２に記載のハロゲン化アルケンの製造方法。 The coal ash and the halogenated alkane are brought into contact by aerating the halogenated alkane into the reactor supplied with the coal ash,
The method for producing a halogenated alkene according to claim 1 or 2, wherein the contact time between the halogenated alkane and the coal ash is 10 g·s/mL or more and 150 g·s/mL or less.
Ｒ１およびＲ３は水素原子を示し、
Ｒ２はフッ素原子を示し、
Ｒ４は、水素原子、フッ素原子、または塩素原子を示し、
Ｒ５およびＲ６は、フッ素原子、塩素原子、水素原子、または、ハロゲン原子で置換されてもよい炭素数１以上２以下のアルカン基を示し、
かつＲ４～Ｒ６の少なくとも１つはフッ素原子または塩素原子である。） The method for producing a halogenated alkene according to any one of claims 1 to 3, wherein the halogenated alkane is a compound represented by the following general formula (1).
R 1 and R 3 represent hydrogen atoms,
R 2 represents a fluorine atom,
R 4 represents a hydrogen atom, a fluorine atom, or a chlorine atom,
R 5 and R 6 represent a fluorine atom, a chlorine atom, a hydrogen atom, or an alkane group having 1 or more and 2 or less carbon atoms that may be substituted with a halogen atom,
And at least one of R 4 to R 6 is a fluorine atom or a chlorine atom. )
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| JP2022036334A JP2023131518A (en) | 2022-03-09 | 2022-03-09 | Halogenated alkene production method |
| PCT/JP2023/005235 WO2023171274A1 (en) | 2022-03-09 | 2023-02-15 | Halogenated alkene production method |
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| JP2022036334A JP2023131518A (en) | 2022-03-09 | 2022-03-09 | Halogenated alkene production method |
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| US2480560A (en) * | 1945-12-06 | 1949-08-30 | Kinetic Chemicals Inc | Method for pyrolyzing polyfluoroalkanes |
| JPS607975B2 (en) * | 1978-03-30 | 1985-02-28 | ダイキン工業株式会社 | Production method of vinylidene fluoride |
| JP6673413B2 (en) * | 2018-05-08 | 2020-03-25 | ダイキン工業株式会社 | Method for producing fluoroolefin |
| JP6933239B2 (en) * | 2019-02-21 | 2021-09-08 | ダイキン工業株式会社 | Method for producing halogenated alkene compound and fluorinated alkyne compound |
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