WO2016009774A1 - クロロプロペンの製造方法及び2,3,3,3-テトラフルオロプロペンの製造方法 - Google Patents
クロロプロペンの製造方法及び2,3,3,3-テトラフルオロプロペンの製造方法 Download PDFInfo
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- WO2016009774A1 WO2016009774A1 PCT/JP2015/067326 JP2015067326W WO2016009774A1 WO 2016009774 A1 WO2016009774 A1 WO 2016009774A1 JP 2015067326 W JP2015067326 W JP 2015067326W WO 2016009774 A1 WO2016009774 A1 WO 2016009774A1
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- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- 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
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- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
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- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
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- C01B7/195—Separation; Purification
- C01B7/196—Separation; Purification by distillation
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- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C07—ORGANIC CHEMISTRY
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- C07C21/04—Chloro-alkenes
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- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- 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
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- 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
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- 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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a method for producing 2,3,3,3-tetrafluoropropene that can be used for refrigerant applications and the like, and production of chloropropene that can be used to produce 2,3,3,3-tetrafluoropropene. Regarding the method.
- HFO-1234yf (CF 3 CF ⁇ CH 2 ), which is an olefin HFC with a low global warming potential, has attracted attention as a substance that solves these problems.
- HFO-1234yf by itself or as a mixture of other hydrofluorocarbons (HFC), hydrofluoroolefins (HFO), hydrochlorofluoroolefins (HCFO), etc., as well as refrigerant applications, other blowing agents, propellants, fire extinguishing Application to agents is expected.
- HFO-1234yf Various methods for producing HFO-1234yf are known. For example, a method in which CCl 3 CF 2 CH 3 is used as a starting material and hydrogen fluoride (HF) exceeding the stoichiometric amount is reacted thereto (Patent Document 1), or represented by CF 3 CFHCHF 2 A method of performing dehydrofluorination treatment on a fluorocarbon (Patent Document 2) has been proposed.
- HF hydrogen fluoride
- the conversion rate of HCFO-1233xf to HFO-1234yf is as low as 20% or less.
- the effluent from the reactor includes not only the target product HFO-1234yf but also a mixture containing unreacted HCFO-1233xf and an amount of HF equal to or higher than that. Therefore, by distillation, the target HFO-1234yf is extracted from the top of the distillation column, the other HF and HCFO-1233xf are extracted from the bottom of the distillation column, and recycled by feeding HF and HCFO-1233xf back into the reactor. Things are also done.
- the present invention has been made in view of the above, and in producing 2,3,3,3-tetrafluoropropene, the catalyst is lost by distilling and reusing unreacted substances without separating them.
- An object of the present invention is to provide a method for producing 2,3,3,3-tetrafluoropropene stably while suppressing activity.
- An object of the present invention is to provide a method for producing chloropropene stably over a long period of time by suppressing the deactivation of the catalyst by distilling and reusing without separating the liquid.
- the present inventor obtained by distilling an unreacted substance mainly composed of hydrogen fluoride and an organic substance such as HCFO-1233xf under the condition of not separating the liquid. The inventors have found that the object can be achieved and have completed the present invention.
- the present invention relates to the following chloropropene production method and 2,3,3,3-tetrafluoropropene production method.
- the molar ratio of the hydrogen fluoride to the starting material is 15 or more, and the pressure in the distillation column in which the distillation of the step (b) is performed is 0 MPa or more and 1 MPa or less.
- Item 2 The method according to Item 1.
- the chloropropene represented by the general formula (II) is 2-chloro-3,3,3-trifluoropropene
- the pressure in the distillation column in which the distillation in the step (e) is performed is Y and the molar ratio of the hydrogen fluoride to the organic substance is X, the following formula (1) (Expression 1) Y ⁇ ⁇ 0.00004X 5 + 0.0026X 4 ⁇ 0.0653X 3 + 0.8224X 2 ⁇ 5.3282X + 14.787 (1)
- Item 4 The production method according to Item 3, wherein the distillation in the step (e) is performed under a condition that satisfies the above relationship.
- Item 5 The method according to Item 4, wherein the molar ratio X is 10 or more, and the pressure Y is 0 MPa or more and 1 MPa or less.
- the second stage includes the following (d) to (f): (D) reacting the chloropropene of the general formula (II) with hydrogen fluoride in the presence of a catalyst; (E) The reaction mixture obtained in the step (d) is subjected to distillation to obtain a first stream mainly composed of 2,3,3,3-tetrafluoropropene and an unreacted general formula (II) Separating the organic substance containing chloropropene represented into the second stream mainly composed of unreacted hydrogen fluoride; (F) Recycling the second stream separated in the step (e) into the reaction of the step (d), Have The distillation in the step (b) is performed under the condition that the unreacted starting material and the unreacted hydrogen fluoride are not separated, and / or the distillation in the step (e) is performed in the unreacted general formula.
- the manufacturing method characterized by
- the chloropropene represented by the general formula (II) is 2-chloro-3,3,3-trifluoropropene
- the pressure in the distillation column in which the distillation in the step (e) is performed is Y and the molar ratio of the hydrogen fluoride to the organic substance is X, the following formula (1) (Expression 1) Y ⁇ ⁇ 0.00004X 5 + 0.0026X 4 ⁇ 0.0653X 3 + 0.8224X 2 ⁇ 5.3282X + 14.787 (1)
- Item 7 The production method according to Item 6, wherein the distillation in the step (e) is performed under conditions satisfying the relationship.
- the starting material is 1,1,1,2,3-pentachloropropane;
- the molar ratio of the hydrogen fluoride to the 1,1,1,2,3-pentachloropropane is 15 or more, and the inside of the distillation column in which the distillation of the step (b) is performed Item 9.
- the production method according to any one of Items 6 to 8, wherein the pressure is 0 MPa or more and 1 MPa or less.
- the mixture containing unreacted raw material and unreacted hydrogen fluoride remaining after reacting the raw materials is distilled under conditions that do not separate liquids.
- the distillate obtained is used again for the reaction. Therefore, it becomes possible to suppress the deactivation of the catalyst in the reaction system, and as a result, 2,3,3,3-tetrafluoropropene can be produced stably over a long period of time.
- Chloropropene is represented by the general formula (II) CX 3 CCl ⁇ CH 2 (in formula (II), at least one of each X is F, the other is Cl or F, and each X may be the same or different). It is represented by This chloropropene has the general formula (Ia) CX 3 CClYCH 2 Y (in the formula (Ia), X is Cl or F, each X may be the same or different, and Y is H, F or Cl.
- each Y may be the same or different) and / or the general formula (Ib) CY 3 CCl ⁇ CZ 2 (wherein Y is H or Cl, Each Y may be the same or different, Z may be H, F or Cl, and each Z may be the same or different).
- chloropropane represented by the general formula (Ia) is represented by “raw chloropropane”
- chloropropene represented by the general formula (Ib) is represented by “raw chloropropene”
- the general formula (II) Chloropropene may be abbreviated as “chloropropene intermediate”.
- “Raw material chloropropane” and “raw material chloropropene” are collectively abbreviated as “starting raw material”. This “starting material” means one or both of “raw material chloropropane” and “raw material chloropropene”.
- first step the step of producing the chloropropene (chloropropene intermediate) represented by the general formula (II) from the above starting material is referred to as “first step”.
- raw material chloropropane of the general formula (Ia) include CCl 3 CHClCH 2 Cl (hereinafter sometimes referred to as “240db”) and CF 3 CHClCH 2 Cl (hereinafter referred to as “243db”). ), CF 3 CClFCH 3 (hereinafter sometimes referred to as “244bb”), CF 3 CHClCH 2 F (hereinafter sometimes referred to as “244db”), CFCl 2 CHClCH 2 Cl (hereinafter referred to as “241db”) CF 2 ClCHClCH 2 Cl (hereinafter also referred to as “242dc”) and the like.
- raw material chloropropane can be used individually by 1 type or in mixture of 2 or more types.
- the first stage includes the following steps (a) to (c).
- C A step of recycling the second stream separated in the step (b) to the reaction of the step (a).
- the distillation in the above step (b) is performed under the condition that the unreacted starting material and the unreacted hydrogen fluoride are not separated at the second stream extraction portion of the distillation column.
- step (a) a product containing a chloropropene intermediate can be obtained by reacting the starting material with hydrogen fluoride.
- the product containing this chloropropene intermediate is a compound that becomes an intermediate in the production of 2,3,3,3-tetrafluoropropene.
- the method for reacting the starting material with hydrogen fluoride in the presence of a catalyst is not particularly limited.
- the starting material and hydrogen fluoride can be reacted in a gas phase state, as long as the starting material and hydrogen fluoride can be contacted in a gas state in the reaction temperature range described below.
- the starting material is liquid at normal temperature and normal pressure, it can be vaporized in advance with a vaporizer and supplied into the reactor in which the reaction of step (a) is carried out.
- Hydrogen fluoride can usually be supplied to the reactor in a gas phase together with the starting materials.
- the supply amount of hydrogen fluoride is usually about 1 to 100 mol, preferably about 5 to 50 mol, and preferably about 15 to 40 mol with respect to 1 mol of the starting material. It is more preferable. By setting the amount within these ranges, the conversion rate of the starting material can be maintained within a good range. In addition, it is particularly preferable that the supply amount of hydrogen fluoride is 15 mol or more with respect to 1 mol of the starting material because the deactivation of the catalyst can be suppressed.
- the molar ratio of hydrogen fluoride to the starting material can be adjusted by the amount supplied to both reactors. Therefore, instead of recycling, the stream for supplying the main raw material to the reactor and the second stream are supplied with additional hydrogen fluoride and starting raw materials, or withdrawing these from the reactor. Can be adjusted.
- an inert gas such as nitrogen, helium, or argon and a gas inert to the catalyst may coexist.
- concentration of the inert gas is based on the total amount of the starting material introduced into the reactor, the raw material containing hydrogen fluoride and the inert gas, and the total amount of oxygen gas described later when added. As 0 to 10 mol%.
- the starting material may be accompanied by oxygen or chlorine and supplied to the reactor of step (a).
- the supply amount of oxygen or chlorine is 0. 0, based on the total amount of the raw material and oxygen or the total amount of the raw material and chlorine, plus the total amount when an inert gas is used. It can be about 1 to 50 mol%.
- the supply amount of oxygen or chlorine is increased, a side reaction such as an oxidation reaction occurs and the selectivity is not preferable.
- a known material conventionally used for this reaction can be used, and the type thereof is not particularly limited.
- a known catalyst that can be used in the dehydrohalogenation reaction can be used, and examples thereof include transition metals, halides such as group 14 elements and group 15 elements, and oxides.
- Specific examples of the transition element include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Ta, and W.
- Specific examples of the group 14 element include Sn and Pb.
- Specific examples of the group 15 element include Sb and Bi.
- halides of these elements include fluorides and chlorides.
- the carrier is not particularly limited, and examples thereof include porous alumina silicate represented by zeolite, aluminum oxide, silicon oxide, activated carbon, titanium oxide, zirconia oxide, zinc oxide, aluminum fluoride, and the like. Of these, a mixture of one or two or more, or a composite of them can be used.
- the reactor is preferably a tubular reactor, and the contact method with the catalyst is preferably a fixed bed type.
- the reactor is preferably made of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy (registered trademark), Inconel (registered trademark), and Monel (registered trademark).
- the reaction temperature of the reaction in the above step (a) is not particularly limited, and is usually preferably about 200 ° C. to 550 ° C. If it is this temperature range, the conversion rate of a starting raw material will become favorable, and generation
- a more preferable reaction temperature is about 300 ° C. to 450 ° C.
- the pressure during the reaction in the step (a) is not particularly limited, and the reaction can be performed under reduced pressure, normal pressure or increased pressure. Usually, it may be carried out under a pressure in the vicinity of atmospheric pressure (0.1 MPa), but the reaction can proceed smoothly even under a reduced pressure of less than 0.1 MPa. Further, the reaction may be performed under a pressure that does not liquefy the raw material.
- the reaction time is not limited.
- the ratio of the catalyst filling amount W (g) to the total flow rate F0 of the gas components flowing through the reaction system (flow rate at 0 ° C. and 0.1 MPa: cc / sec): W
- the contact time represented by / F0 is preferably about 0.1 to 90 g ⁇ sec / cc, and preferably about 1 to 50 g ⁇ sec / cc.
- the total flow rate of the gas components is a total flow rate obtained by adding these flow rates when an inert gas, oxygen, or the like is further used in addition to the total flow rate of the starting material and hydrogen fluoride.
- step (a) a reaction mixture containing unreacted starting materials and unreacted hydrogen fluoride is obtained in addition to the main component containing the product chloropropene intermediate.
- step (b) the reaction mixture obtained in step (a) is distilled.
- the extraction portion may be either the distillation column still or the middle of the distillation column. Distillation can be performed by a commonly used distillation column or the like.
- the liquid separation referred to in this specification is not a state in which two or more liquids are mixed in a single liquid phase, but two or more liquids (for example, a liquid phase of chloropropane and a liquid phase of hydrogen fluoride). ) And are separated into two phases.
- the molar ratio of hydrogen fluoride to the unreacted starting material present in the distillation column that is, [number of moles of hydrogen fluoride] / [mol of unreacted starting material]
- pressure in the distillation column refers to gauge pressure (that is, pressure notation with the atmospheric pressure set to 0), unless otherwise specified.
- distillation under conditions where liquid separation is not performed include adjustment of the pressure in the distillation column.
- the pressure in the distillation column can be adjusted by changing the temperature in the distillation column, and the reaction mixture, starting material, hydrogen fluoride, and other inert gases can be supplied to or discharged from the distillation column. You can adjust the pressure.
- the presence or absence of separation in the distillation column can be determined from the liquid density of the stream when it is extracted from the distillation column. That is, when liquid separation occurs in the second stream extraction portion of the distillation column, the lower organic layer (the layer containing the starting material) is mainly extracted from the distillation column, and therefore is extracted from the distillation column.
- the liquid density of the stream rises from the case where the liquid is not separated and becomes a value close to the liquid density of the starting raw material alone. If such a change in liquid density is observed, it can be determined that liquid separation has occurred.
- the pressure in the distillation tower is not particularly limited.
- the pressure in the distillation column can be 0 to 1 MPa.
- distillation is performed under the condition that the unreacted starting material and the hydrogen fluoride are not separated, and the unreacted starting material and the second stream of unreacted hydrogen fluoride are extracted from the distillation column.
- the temperature of the still can be heated to 33 ° C. or higher when the pressure is 0.34 MPa (absolute pressure) in the liquid-liquid separation curve of 1233xf-HF, for example. In this case, separation can be made more difficult.
- the temperature is particularly preferably 50 ° C. or higher.
- step (c) the second stream extracted from the distillation tower is sent into the reactor in which the reaction in step (a) is performed. Thereby, unreacted starting materials and hydrogen fluoride can be reused in the reaction of step (a).
- the second stream can be sent into the reactor while being pressurized by, for example, a pump or a compressor.
- distillation conditions can be set as follows.
- the pressure in the distillation column in which the distillation in the step (b) is performed is Y 1 (MPa; gauge pressure), and the molar ratio of hydrogen fluoride to unreacted starting material (ie, [number of moles of hydrogen fluoride] / the number of moles of unreacted starting material] and X 1, plotting the relationship between X 1 and Y 1. for example, the Y 1 range of 0 ⁇ 1 MPa, the X 1 in the range of 5 ⁇ 25 X 1 and plotted points 10-50 the relationship between Y 1. since the is X-Y curve by plotting drawn, calculating the relational expression indicating the Y 1 as a function of X 1 from the curve.
- the Automatic calculation software may be used to calculate the relational expression.
- step (b) by extracting the second stream without separating the liquid, it is possible to prevent the concentration of the unreacted starting material in the second stream from being increased, As a result, deactivation of the catalyst used in the reaction of step (a) can be suppressed. If the liquid is separated and separated into two phases, the lower phase is an unreacted starting material having a large specific gravity. Therefore, when the second stream is extracted in a separated state, the unreacted starting material is It is recycled to the reactor in a high concentration state. When such an organic substance (unreacted starting material) becomes too much in the reaction system, it becomes easy to coat the catalyst, thereby deactivating the catalyst.
- step (b) if the second stream is extracted without being separated in step (b), as described above, it is possible to prevent high concentration unreacted starting materials from being fed into the reactor, As a result, the deactivation of the catalyst can be made difficult to occur. Thereby, it becomes possible to produce a chloropropene intermediate stably over a long period of time.
- HFO-1234yf 2,3,3,3-tetrafluoropropene> 2,3,3,3-tetrafluoropropene (hereinafter sometimes referred to as “HFO-1234yf” or “1234yf”) is represented by the general formula (II) CX 3 CCl ⁇ CH 2 (in the formula (II): At least one of each X is F, the other is Cl or F, and each X may be the same or different) (ie, corresponding to the first stage chloropropene intermediate) It is manufactured by using as.
- second step the step of producing HFO-1234yf from the chloropropene intermediate.
- the second stage includes the following steps (d) to (f).
- the distillation in the above step (e) is performed under the condition that the unreacted chloropropene intermediate and the unreacted hydrogen fluoride are not separated at the second stream extraction portion of the distillation column.
- step (d) the target product, HFO-1234yf (2,3,3,3-tetrafluoropropene) can be obtained by reacting the chloropropene intermediate with hydrogen fluoride.
- the method for reacting the chloropropene intermediate with hydrogen fluoride in the presence of a catalyst is not particularly limited.
- An example of a specific embodiment is a method of introducing a chloropropene intermediate used as a raw material and hydrogen fluoride into a reactor by using a tubular flow reactor and filling the catalyst therewith. Can do.
- the chloropropene intermediate and hydrogen fluoride can be reacted in a gas phase, but it is sufficient that the chloropropene intermediate and hydrogen fluoride can be contacted in a gas state in the reaction temperature range described below. Further, when the chloropropene intermediate is in a liquid state at normal temperature and normal pressure, it can be vaporized in advance with a vaporizer and supplied into the reactor in which the reaction of step (d) is carried out.
- Hydrogen fluoride can be supplied to the reactor by the same method as in step (a), for example, and the method is not particularly limited.
- the supply amount of hydrogen fluoride is usually about 1 to 100 mol and preferably about 5 to 50 mol with respect to 1 mol of the chloropropene intermediate. By setting it as the range of these usage-amounts, the conversion ratio of a chloropropene intermediate can be maintained in a favorable range.
- the supply amount of hydrogen fluoride is 10 mol or more with respect to 1 mol of the chloropropene intermediate, it is particularly preferable in that the deactivation of the catalyst can be suppressed.
- the molar ratio of hydrogen fluoride and chloropropene intermediate can be adjusted by the amount supplied to both reactors. Therefore, for the main feed stream and second stream for the reactor, the flow rate can be adjusted by supplying additional hydrogen fluoride and starting materials, or withdrawing them from the reactor. can do.
- a gas inert to the raw material and the catalyst such as nitrogen, helium, and argon may coexist.
- the concentration of the inert gas is the total amount of the raw material containing the chloropropene intermediate and hydrogen fluoride introduced into the reactor and the inert gas. As a reference, it can be about 0 to 80 mol%.
- oxygen may be entrained in the chloropropene intermediate and supplied to the reactor in step (d).
- the supply amount of oxygen can be set to about 0.1 to 50 mol% on the basis of the total amount of the above raw material and oxygen plus the addition amount of the inert gas when used.
- an increase in the amount of oxygen supplied is not preferable because side reactions such as oxidation reactions occur and the selectivity decreases.
- the catalyst a known material conventionally used for this reaction can be used, and the type thereof is not particularly limited.
- a catalyst that can be used in the above-described step (a) can also be used in step (d).
- the reactor is preferably a tubular reactor, and the contact method with the catalyst is preferably a fixed bed type.
- the reactor is preferably made of a material that is resistant to the corrosive action of hydrogen fluoride, such as Hastelloy (registered trademark), Inconel (registered trademark), and Monel (registered trademark).
- the reaction temperature of the reaction in the above step (d) is not particularly limited, and is usually preferably about 200 ° C. to 550 ° C. If it is this temperature range, the conversion rate of the chloropropene intermediate to the target object will become favorable, and generation
- a more preferable reaction temperature is about 300 ° C. to 450 ° C.
- the pressure during the reaction in the above step (d) is not particularly limited, and the reaction can be performed under reduced pressure, normal pressure or increased pressure. Usually, it may be carried out under a pressure in the vicinity of atmospheric pressure (0.1 MPa), but the reaction can proceed smoothly even under a reduced pressure of less than 0.1 MPa. Further, the reaction may be performed under a pressure that does not liquefy the raw material.
- the reaction time is not limited.
- the ratio of the catalyst filling amount W (g) to the total flow rate F0 of the gas components flowing through the reaction system (flow rate at 0 ° C. and 0.1 MPa: cc / sec): W
- the contact time represented by / F0 is preferably about 0.1 to 90 g ⁇ sec / cc, and preferably about 1 to 50 g ⁇ sec / cc.
- the total flow rate of the gas component is the total flow rate of the total flow rate of the chloropropene intermediate and hydrogen fluoride plus the addition of these flow rates when an inert gas, oxygen, or the like is used. is there.
- the product obtained in the first stage may be supplied as it is to the reactor of the step (d), but may be supplied after removing hydrogen chloride contained in the product. preferable.
- the method for removing hydrogen chloride from the first-stage product is not particularly limited. For example, according to distillation in step (e) after step (d), hydrogen chloride can be easily used as a top component. Can be removed.
- reaction mixture containing unreacted chloropropene intermediate and unreacted hydrogen fluoride in addition to the main component containing the target product HFO-1234yf is obtained.
- this reaction mixture contains hydrogen chloride (HCl) produced as a by-product in the reaction.
- step (e) the reaction mixture obtained in step (d) is distilled.
- Distillation can be performed by a commonly used distillation column or the like. By this distillation, it is possible to separate the first stream mainly composed of HFO-1234yf and the second stream mainly composed of an organic substance containing at least unreacted chloropropene intermediate and unreacted hydrogen fluoride. .
- the extraction portion may be either the distillation column still or the middle of the distillation column.
- the “organic substance containing a chloropropene intermediate” contained in the second stream usually contains 90% or more of the chloropropene intermediate, and other organic compounds although it is less than 10%. Examples of the other organic compounds include 1233zd (1-chloro-3,3,3-trifluoropropene), 1223xd (1,2-dichloro-3,3,3-trifluoropropene) and the like. .
- the first stream is mainly composed of HFO-1234yf, which is the target product, in addition to hydrogen chloride, 1,1,1,2,2-pentafluoropropane (hereinafter referred to as “by-product” produced in the reaction of step (d)).
- by-product produced in the reaction of step (d)
- 245cb Abbreviation "245cb”
- the obtained HFO-1234yf can be further made into a final product through a crude process and a purification process.
- Specific methods of the crude process and the purification process are not particularly limited. For example, means such as water washing, dehydration (drying), distillation, and liquid separation can be applied.
- the molar ratio of hydrogen fluoride to 1 mol of organic substance present in the distillation column that is, [number of moles of hydrogen fluoride] / [number of moles of organic substance]
- the pressure in the distillation column is not particularly limited, but may be, for example, 0 to 1 MPa.
- Other methods of distillation under conditions where liquid separation is not performed include adjustment of the pressure in the distillation column.
- the pressure in the distillation column can be adjusted by changing the temperature in the distillation column, and the pressure in the distillation column can be adjusted by supplying or discharging a reaction mixture, hydrogen fluoride, or other inert gas into the distillation column. Can be adjusted.
- the presence or absence of liquid separation in the distillation column can be judged from the liquid density of the stream when it is extracted from the still of the distillation column. That is, when liquid separation occurs in the second stream extraction portion of the distillation column, the lower organic layer (the layer containing the starting material) is mainly extracted from the distillation column, and therefore is extracted from the distillation column.
- the liquid density of the stream rises from the case where the liquid is not separated and becomes a value close to the liquid density of the starting raw material alone. If such a change in liquid density is observed, it can be determined that liquid separation has occurred.
- distillation is performed under the condition that the chloropropene intermediate and hydrogen fluoride are not separated, and the second stream of chloropropene intermediate and hydrogen fluoride is extracted from the distillation column. If the second stream is extracted from the still of the distillation column, the temperature of the still can be heated to, for example, 33 ° C. or higher, and is preferably 50 ° C. or higher, from the viewpoint that liquid separation is less likely to occur.
- distillation conditions can be set as follows.
- the pressure in the distillation column in which the distillation in the step (e) is performed is Y 2 (MPa; gauge pressure), the molar ratio of hydrogen fluoride to 1 mol of organic matter (ie, [number of moles of hydrogen fluoride] / [organic matter)
- the number of moles of X] is X 2 and the relationship between X 2 and Y 2 is plotted, where the organic substance is a chloropropene intermediate, in the same range as in the distillation in the first stage, Since the XY curve is drawn by plotting the relationship between X 2 and Y 2 at 10 to 50 points, a relational expression expressing Y 2 as a function of X 2 is calculated. May be used.
- FIG. 2 is a curve (separation curve) derived from the relationship between Y 2 and X 2 by the above method when the chloropropene intermediate is 2-chloro-3,3,3-trifluoropropene. is there.
- the chloropropene intermediate is 2-chloro-3,3,3-trifluoropropene
- the relationship between Y 2 and X 2 is derived from the separation curve of FIG.
- step (f) the second stream extracted from the distillation tower is sent into the reactor in which the reaction in step (d) is performed.
- a chloropropene intermediate and hydrogen fluoride can be reused for the reaction of the step (d).
- the second stream can be sent into the reactor while being pressurized by, for example, a pump or a compressor.
- the concentration of the chloropropene intermediate in the second stream is increased by extracting the second stream without being separated by distillation in the step (e), and as a result.
- the deactivation of the catalyst used in the reaction of step (d) can be suppressed. If the liquid phase is separated and separated into two phases, the lower phase is a chloropropene intermediate having a large specific gravity. Therefore, when the second stream is extracted in a liquid-separated state, the concentration of the chloropropene intermediate is high. It will be sent to the reactor in the state of. When the amount of organic substances such as chloropropene intermediates is too large in the reaction system, the catalyst is easily coated, which deactivates the catalyst.
- step (e) if the second stream is extracted without being separated in step (e), it is possible to prevent the high concentration chloropropene intermediate from being fed into the reactor, and as a result, the catalyst is lost. It can make life less likely to occur. This makes it possible to manufacture HFO-1234yf stably over a long period of time.
- HFO-1234yf can also be manufactured by combining the first stage and the second stage. That is, first, a chloropropene intermediate of the general formula (II) is produced from a starting material containing the general formula (Ia) and / or the general formula (Ib) in the first step, and then the first chloropropene intermediate in the second step. HFO-1234yf can also be prepared from the chloropropene intermediate obtained in the step.
- the HFO-1234yf is manufactured by combining the first stage and the second stage as described above, in the first stage, the above-described steps (a), (b) and (c), The two stages include the above-described step (d), step (e) and step (f).
- the distillation in the step (b) is carried out under the condition that the unreacted starting material and the unreacted hydrogen fluoride are not separated, or the distillation in the step (e) is performed with the unreacted chloropropene intermediate.
- the reaction is performed under the condition that the organic matter contained and unreacted hydrogen fluoride are not separated.
- the distillation in the step (b) is performed under the condition that the unreacted starting material and the unreacted hydrogen fluoride are not separated, and the distillation in the step (e) includes an unreacted chloropropene intermediate.
- the reaction is performed under the condition that the organic substance and unreacted hydrogen fluoride are not separated.
- catalyst deactivation can be made difficult to occur in the first stage and / or the second stage, and the first stage chloropropene intermediate and the second stage HFO-1234yf can be stably produced over a long period of time. It becomes possible.
- FIG. 1 shows a schematic flow diagram for explaining an example of the manufacturing flow of HFO-1234yf.
- HFO-1234yf is produced on a production line including a first reactor 1a, a second reactor 1b, a first distillation column 2a, a second distillation column 2b, and the like.
- first reactor 1a the reaction in the step (a) in the first stage can be performed, and in the second reactor 1b, the reaction in the step (d) in two stages can be performed.
- the starting material is supplied together with hydrogen fluoride from the inlet side 10a of the first reactor 1a and reacted in the presence of a catalyst.
- the reaction product is extracted from the outlet side 11a of the first reactor 1a, and the reaction mixture containing the product chloropropene intermediate and the unreacted raw material chloropropane and hydrogen fluoride is subjected to step (b). Supply to the first distillation column 2a.
- the product chloropropene intermediate is extracted as a first stream from the top 20a of the first distillation column 2a and supplied to the second reactor 1b.
- unreacted raw material chloropropane and unreacted hydrogen fluoride are withdrawn from the still 21a of the first distillation column 2a as a second stream and supplied again to the first reactor 1a for the reaction of step (a). Use.
- the distillation is performed under the condition that the unreacted starting material and the unreacted hydrogen fluoride are not separated.
- the chloropropene intermediate supplied to the second reactor 1b is reacted with hydrogen fluoride in the presence of a catalyst. What is necessary is just to supply separately the hydrogen fluoride used here to the 2nd reactor 1b.
- the reaction product is extracted from the outlet side 11b of the second reactor 1b, and a reaction mixture containing unreacted chloropropene intermediate and hydrogen fluoride in addition to the main component containing the target product, HFO-1234yf, is obtained in the step ( It supplies to the 2nd distillation column 2b in which e) is performed.
- the HFO-1234yf supplied to the second distillation column 2b is extracted from the top 20b of the second distillation column 2b by distillation, and then hydrogen chloride and the like are removed by a treatment such as purification.
- the chloropropene intermediate and unreacted hydrogen fluoride are extracted from the still 21b of the second distillation column 2b, supplied again to the second reactor 1b, and used for the reaction in the step (d).
- the distillation is performed under the condition that the unreacted chloropropene intermediate and the unreacted hydrogen fluoride are not separated.
- the above manufacturing flow is an example for manufacturing HFO-1234yf, and may be manufactured by a manufacturing line other than FIG.
- Example 1 According to the manufacturing flow of FIG. 1, HFO-1234yf was manufactured.
- the reactor is made of Hastelloy C22 and the shape is a cylinder type, and the distillation column is a Hastelloy C22 material and a cylinder type packed tower is applied, the packing is CMR No2.5, the column diameter is 500 A, the packing length is 10000 mm ⁇ 2.
- 240 db (1,1,1,2,3-pentachloropropane) was used as the starting material in step (a) of the first stage.
- This mixed gas of 240 db and hydrogen fluoride was continuously supplied to the first reactor 1a at a flow rate of 7000 m 3 / hr (converted to a standard state of gas).
- the internal temperature of the first reactor 1a was 300 ° C.
- the pressure was 0.75 MPa (gauge pressure)
- the molar ratio of hydrogen fluoride to 240 db was 20 in this reaction.
- Cr oxide catalyst (Cr 2 O 3 ) 24.8 t was previously supplied to the first reactor 1a as a catalyst.
- the reaction product was extracted from the first reactor 1a, sent to the first distillation column 2a, and subjected to distillation. Unreacted 240 db and unreacted hydrogen fluoride were extracted from the still of the first distillation column 2a, and these were again sent to the first reactor 1a to be reused as reaction raw materials.
- the product 1233xf (2-chloro-3,3,3-trifluoropropene) is extracted from the top of the first distillation column 2a, and the second reactor 1b in which the next second-stage reaction is performed. I was sent to. In the above reaction, the conversion rate from 240 db to 1233xf was 50 to 99%.
- FIG. 3 is a schematic flow diagram for explaining in detail the steps from reaction to distillation.
- the material of the vaporizer 3 and the cooler 4 in FIG. 3 is Hastelloy C22.
- the 1233xf sent from the first distillation column 2a was sent through the line S1 in FIG. 3, and hydrogen fluoride was supplied from the line S2 and merged in the line S3.
- a mixed gas of 1233xf and hydrogen fluoride was continuously supplied to the reactor 1 at a flow rate of 21000 m 3 / hr (converted into a gas standard state).
- 1233xf and hydrogen fluoride were reacted in the presence of 49.6 t of a Cr oxide catalyst (Cr 2 O 3 ) as a catalyst.
- the internal temperature of the reactor 1 was 365 ° C.
- the pressure was 0.75 MPa (gauge pressure)
- the molar ratio of hydrogen fluoride to 1233xf was 10 in this reaction.
- the obtained reaction mixture was sent from the reactor 1 to the distillation column 2.
- 1,1,1,2,2-pentafluoropropane (245cb) was by-produced.
- Distillation in the distillation tower 2 was performed under the conditions of a tower top temperature of 33 ° C., a tower bottom temperature of 70 ° C., a pressure of 0.75 MPa, and a reflux ratio of 3.4.
- the reflux ratio here refers to the molar flow rate ratio between the reflux liquid and the distillate (reflux liquid / distillate).
- a mixture containing HCl and the target product HFO-1234yf was extracted from the top of the column, and a mixture containing unreacted hydrogen fluoride and unreacted 1233xf was extracted from the still (bottom).
- Table 1 shows the gas flow rates of the lines S1 to S8 in FIG.
- Example 2 According to the manufacturing flow shown in FIG. 3, 1233xf was manufactured from 240 db.
- 240db is sent through the S1 line
- hydrogen fluoride is sent through the S2 line and merged in the S3 line
- the mixed gas of 240db and hydrogen fluoride is flowed at a flow rate of 7000 m 3 / hr (standard state conversion of gas). 1 was fed continuously.
- the internal temperature of the reactor 1 was 300 ° C.
- the pressure was 0.75 MPa (gauge pressure)
- the molar ratio of hydrogen fluoride to 240 db was 20 in this reaction.
- Cr oxide catalyst (Cr 2 O 3 ) 24.8 t was previously supplied to the reactor 1 as a catalyst.
- the reaction mixture was extracted from the reactor 1, sent to the distillation column 2, and subjected to distillation.
- the reactor 1, distillation column 2, vaporizer 3 and cooler 4 used were the same as in Example 1.
- Distillation in the distillation tower 2 was performed under the conditions of a tower top temperature of 6.63 ° C., a tower bottom temperature of 93.6 ° C., a pressure of 0.75 MPa, and a reflux ratio of 5. And the mixture containing 1233xf was extracted from the tower top part, and the mixture of unreacted hydrogen fluoride and 240db was extracted from the still (column bottom part). Unreacted 240 db and hydrogen fluoride extracted from the still were sent again to the reactor 1 and reused as reaction raw materials. In performing this distillation, the fluoride flowing through the lines S1, S2 and S7 in FIG. 3 is maintained so that hydrogen fluoride and 240db are not separated in the distillation column 2 and a single-phase state is maintained. The molar ratio of hydrogen to 240 db, flow rate and pressure were adjusted.
- Table 2 shows the gas flow rates of the lines S1 to S8 in FIG.
- 1233xf was produced from 1230xa (1,1,2,3-tetrachloropropene).
- 1230xa is sent through the S1 line
- hydrogen fluoride is sent through the S2 line and merged in the S3 line
- the mixed gas of 1230xa and hydrogen fluoride is reacted at a flow rate of 7000 m 3 / hr (converted into a gas standard state).
- 1 was fed continuously.
- the internal temperature of the reactor 1 was 300 ° C.
- the pressure was 0.75 MPa
- the molar ratio of hydrogen fluoride to 1230xa was 20 in this reaction.
- Distillation in the distillation tower 2 was performed under the conditions of a tower top temperature of ⁇ 13.2 ° C., a tower bottom temperature of 89.6 ° C., a pressure of 0.75 MPa, and a reflux ratio of 4. And the mixture containing 1233xf was extracted from the tower top part, and the mixture of unreacted hydrogen fluoride and 1230xa was extracted from the still (column bottom part).
- hydrogen fluoride flowing through the lines S1, S2 and S7 in FIG. 3 is maintained so that hydrogen fluoride and 1230xa are not separated in the distillation column 2 and a one-phase state is maintained. And 1230xa molar ratio, flow rate and pressure were adjusted.
- Table 3 shows the gas flow rates of the lines S1 to S8 in FIG.
- Example 4 According to the production flow shown in FIG. 3, 1233xf was produced from 243db (2,3-dichloro-1,1,1-trifluoropropane).
- 243db is sent through the S1 line
- hydrogen fluoride is sent through the S2 line and merged in the S3 line
- the mixed gas of 243db and hydrogen fluoride is reacted at a flow rate of 7000 m 3 / hr (converted into a gas standard state). 1 was fed continuously.
- the internal temperature of the reactor 1 was 300 ° C.
- the pressure was 0.75 MPa
- the molar ratio of hydrogen fluoride to 243 db was 20.
- Distillation in the distillation tower 2 was performed under the conditions of a tower top temperature of 1.24 ° C., a tower bottom temperature of 81.1 ° C., a pressure of 0.75 MPa, and a reflux ratio of 5. And the mixture containing 1233xf was extracted from the tower top part, and the mixture of unreacted hydrogen fluoride and unreacted 243db was extracted from the still (bottom part). Unreacted 243db and hydrogen fluoride extracted from the still were sent again to the reactor 1 and reused as reaction raw materials. In performing this distillation, the fluoride flowing through the lines S1, S2 and S7 in FIG. 3 is maintained so that hydrogen fluoride and 243db are not separated in the distillation column 2 and a single-phase state is maintained. The molar ratio of hydrogen and 243 db, the flow rate and the pressure were adjusted.
- Table 4 shows the gas flow rates of the lines S1 to S8 in FIG.
- 1233xf was produced from 244bb (2-chloro-1,1,1,2-tetrafluoropropane).
- 244bb was sent through the S1 line, and a mixed gas of 244bb and hydrogen fluoride was continuously supplied to the reactor 1 at a flow rate of 7000 m 3 / hr (converted into a gas standard state).
- hydrogen fluoride is released from the raw material 244bb, so hydrogen fluoride is not supplied from the S2 line.
- the internal temperature of the reactor 1 was 300 ° C., the pressure was 0.75 MPa, and the molar ratio of hydrogen fluoride to 244bb was 20 in this reaction.
- Distillation in the distillation tower 2 was performed under the conditions of a tower top temperature of 6.63 ° C., a tower bottom temperature of 93.6 ° C., a pressure of 0.75 MPa, and a reflux ratio of 4. And the mixture containing 1233xf was extracted from the tower top part, and the mixture of unreacted hydrogen fluoride and unreacted 244bb was extracted from the still (bottom part). Unreacted 244bb and hydrogen fluoride extracted from the still were sent again to the reactor 1 and used as reaction raw materials. In performing this distillation, hydrogen fluoride and 244bb are not separated in the distillation column 2, and hydrogen fluoride flowing through the lines S1, S2, and S7 in FIG. 3 is maintained so as to maintain a single-phase state. And 244bb molar ratio, flow rate and pressure were adjusted.
- Table 5 shows the gas flow rates of the lines S1 to S8 in FIG.
- Distillation in the distillation tower 2 was performed under the conditions of a tower top temperature of 33 ° C., a tower bottom temperature of 70 ° C., a pressure of 0.1 MPa, and a reflux ratio of 3.4.
- a mixture of HCl and the target product HFO-1234yf was extracted from the top of the column, and a mixture of unreacted hydrogen fluoride and unreacted 1233xf was extracted from the still.
- hydrogen fluoride and 1233xf flowing through the lines at S1, S2 and S7 in FIG. 3 are used so that hydrogen fluoride and 1233xf are separated in the distillation column 2.
- the molar ratio, flow rate and pressure were adjusted.
- the mixture of unreacted hydrogen fluoride and unreacted 1233xf extracted from the still was recycled again to the second reactor.
- FIG. 4 is a graph plotting the relationship between the conversion rate (conversion) from 1233xf to 1234yf and the reaction time in Example 1, and in the second stage reaction of Example 1, hydrogen fluoride with respect to 1233xf.
- the molar ratio is changed to 6.4 and 16 (the pressure in the distillation column is both 0.75 MPa)
- the respective results are also shown.
- the molar ratio is 6.4
- it is a condition that does not satisfy the above-mentioned formula (1) (see also FIG. 2).
- the conversion rate further decreases with time.
- the catalyst deactivation is suppressed, so the conversion rate is high and the reaction time has elapsed. It can also be seen that the degree of decrease in the conversion rate is suppressed as compared with the molar ratio of 6.4.
- FIG. 5 plots the relationship between the reaction time in the second stage reaction of Example 1 and the reaction yield of HFO-1234yf, and the relationship between the reaction time in the reaction of the comparative example and the reaction yield of HFO-1234yf. It is a graph.
- the reaction yield decreased as the reaction time passed, whereas in Example 1, the reaction yield did not decrease even after 200 hours passed from the start of the reaction.
- Comparative Example 1 since distillation is performed under conditions where hydrogen fluoride and 1233xf are separated, a large amount of organic matter is returned to the reactor during the reflux. For this reason, the catalyst is deactivated by the action of organic substances, and this causes a decrease in the reaction yield.
- Example 1 the hydrogen fluoride and 1233xf were distilled under the condition that they were not separated, so that the catalyst was hardly deactivated even when refluxed, resulting in a stable reaction over a long period of time. It is possible.
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Abstract
Description
一般式(Ib)CY3CCl=CZ2(式(Ib)中、YはH又はClであって、各Yは同一又は異なっていてよく、ZはH,F又はClであって、各Zは同一又は異なっていてよい)で表されるクロロプロペンを含む出発原料から、一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表されるクロロプロペンを製造する方法であって、
下記(a)~(c);
(a)前記出発原料を、触媒の存在下、フッ化水素と反応させる工程と、
(b)前記工程(a)で得た反応混合物を蒸留に付して、前記一般式(II)のクロロプロペンを主成分とする第1ストリーム及び未反応の前記出発原料と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(c)前記工程で分離させた第2ストリームを工程(a)の反応にリサイクルする工程、
を有し、
前記工程(b)の蒸留を、未反応の前記出発原料と未反応の前記フッ化水素とが蒸留塔の前記第2ストリーム抜き出し部分で分液しない条件で行うことを特徴とするクロロプロペンの製造方法。
下記(d)~(f);
(d)前記一般式(II)のクロロプロペンを、触媒の存在下、フッ化水素と反応させる工程と、
(e)前記工程(d)で得た反応混合物を蒸留に付して、2,3,3,3-テトラフルオロプロペンを主成分とする第1ストリーム及び未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(f)前記工程(e)で分離させた第2ストリームを工程(d)の反応にリサイクルする工程、
を有し、
前記工程(e)の蒸留を、未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とが蒸留塔の前記第2ストリーム抜き出し部分で分液しない条件で行うことを特徴とする2,3,3,3-テトラフルオロプロペンの製造方法。
前記工程(e)の蒸留が行われる蒸留塔内の圧力をY、前記有機物に対する前記フッ化水素のモル比をXとした場合に、下記の(1)式
(数1)
Y≧-0.00004X5+0.0026X4-0.0653X3
+0.8224X2-5.3282X+14.787 (1)
の関係を満たす条件で前記工程(e)の蒸留を行う、上記項3に記載の製造方法。
各Xは同一又は異なっていてよく、YはH,F又はClであって、各Yは同一又は異なっていてもよい)で表されるクロロプロパン、及び/又は、
一般式(Ib)CY3CCl=CZ2(式(Ib)中、YはH又はClであって、各Yは同一又は異なっていてよく、ZはH,F又はClであって、各Zは同一又は異なっていてよい)で表されるクロロプロペンを含む出発原料から、一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表されるクロロプロペンを得る第1段階と、前記一般式(II)のクロロプロペンから2,3,3,3-テトラフルオロプロペンを得る第2段階とで構成される2,3,3,3-テトラフルオロプロペンの製造方法であって、
前記第1段階は、下記(a)~(c);
(a)前記出発原料を、触媒の存在下、フッ化水素と反応させる工程と、
(b)前記工程(a)で得た反応混合物を蒸留に付して、前記一般式(II)のクロロプロペンを主成分とする第1ストリーム及び未反応の前記出発原料と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(c)前記工程(b)で分離させた第2ストリームを工程(a)の反応にリサイクルする工程、
を有し、
前記第2段階は、下記(d)~(f);
(d)前記一般式(II)のクロロプロペンを、触媒の存在下、フッ化水素と反応させる工程と、
(e)前記工程(d)で得た反応混合物を蒸留に付して、2,3,3,3-テトラフルオロプロペンを主成分とする第1ストリーム及び未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(f)前記工程(e)で分離させた第2ストリームを工程(d)の反応にリサイクルする工程、
を有し、
前記工程(b)の蒸留を、未反応の前記出発原料と未反応の前記フッ化水素とが分液しない条件で行う、及び/又は
前記工程(e)の蒸留を、未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とが分液しない条件で行うことを特徴とする製造方法。
前記工程(e)の蒸留が行われる蒸留塔内の圧力をY、前記有機物に対する前記フッ化水素のモル比をXとした場合に、下記の(1)式
(数1)
Y≧-0.00004X5+0.0026X4-0.0653X3
+0.8224X2-5.3282X+14.787 (1)
の関係を満たす条件で前記工程(e)の蒸留を行う、上記項6に記載の製造方法。
前記工程(b)の蒸留において、前記1,1,1,2,3-ペンタクロロプロパンに対する前記フッ化水素のモル比が15以上であり、前記工程(b)の蒸留が行われる蒸留塔内の圧力が0MPa以上、1MPa以下である、上記項6~8のいずれか1項の記載の製造方法。
クロロプロペンは、一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表される。このクロロプロペンは、一般式(Ia)CX3CClYCH2Y(式(Ia)中、XはCl又はFであって、各Xは同一又は異なっていてよく、YはH,F又はClであって、各Yは同一又は異なっていてもよい)で表されるクロロプロパン、及び/又は、一般式(Ib)CY3CCl=CZ2(式(Ib)中、YはH又はClであって、各Yは同一又は異なっていてよく、ZはH,F又はClであって、各Zは同一又は異なっていてよい)で表されるクロロプロペンを含む出発原料から製造される。
(a)前記出発原料を、触媒の存在下、フッ化水素と反応させる工程と、
(b)前記工程(a)で得た反応混合物を蒸留に付して、前記一般式(II)のクロロプロペンを主成分とする第1ストリーム及び未反応の前記出発原料と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(c)前記工程(b)で分離させた第2ストリームを工程(a)の反応にリサイクルする工程。
2,3,3,3-テトラフルオロプロペン(以下、「HFO-1234yf」又は「1234yf」と記載することもある)は、一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表されるクロロプロペン(すなわち、第1段階のクロロプロペン中間体に相当)を原料として用いることで製造される。
(d)前記一般式(II)のクロロプロペンを、触媒の存在下、フッ化水素と反応させる工程と、
(e)前記工程(d)で得た反応混合物を蒸留に付して、2,3,3,3-テトラフルオロプロペンを主成分とする第1ストリーム及び未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(f)前記工程(e)で分離させた第2ストリームを工程(d)の反応にリサイクルする工程。
(数1)
Y2≧-0.00004X2 5+0.0026X2 4-0.0653X2 3
+0.8224X2 2-5.3282X2+14.787 (1)
クロロプロペン中間体が2-クロロ-3,3,3-トリフルオロプロペンである場合は、上記(1)式の関係を満たすように、X2とY2を決定して蒸留を行えば、クロロプロペン中間体とを含む有機物とフッ化水素との分液を防止することができる。特に、図2において、X≧10の領域であって、Y2≧f(X2)の領域であれば、触媒の失活がより抑制される。
図1の製造フローに従い、HFO-1234yfの製造を行った。反応器は、材質がハステロイC22、形状は寸胴式とし、蒸留塔は、材質をハステロイC22として寸胴式の充填塔を適用し、充填物はCMRNo2.5、塔径は500A、充填長は10000mm×2とした。
図3に示す製造フローに従って、240dbから1233xfを製造した。まず、S1ラインを通じて240dbを、S2ラインを通じてフッ化水素を送流してS3ラインで合流させ、この240db及びフッ化水素の混合ガスを7000m3/hr(気体の標準状態換算)の流量で反応器1に連続的に供給した。反応器1の内部温度は300℃、圧力は0.75MPa(ゲージ圧)とし、さらに、この反応において、240dbに対するフッ化水素のモル比を20とした。また、反応器1には、触媒としてあらかじめCr酸化物触媒(Cr2O3)24.8tを供給しておいた。反応後、反応器1から反応混合物を抜き出して、蒸留塔2へ送流させ、蒸留に付した。尚、使用した反応器1、蒸留塔2、気化器3及び冷却器4は実施例1と同様とした。
図3に示す製造フローに従って、1230xa(1,1,2,3-テトラクロロプロペン)から1233xfを製造した。まず、S1ラインを通じて1230xaを、S2ラインを通じてフッ化水素を送流してS3ラインで合流させ、この1230xa及びフッ化水素の混合ガスを7000m3/hr(気体の標準状態換算)の流量で反応器1に連続的に供給した。反応器1の内部温度は300℃、圧力は0.75MPaとし、さらに、この反応において、1230xaに対するフッ化水素のモル比を20とした。また、反応器1には、触媒としてあらかじめCr酸化物触媒(Cr2O3)24.8tを供給しておいた。反応後、反応器1から反応混合物を抜き出して、蒸留塔2へ送流させ、蒸留に付した。蒸留塔2のスチルからは、未反応の1230xa及び未反応のフッ化水素を抜き出し、これらを再度、反応器1へ送り込んで反応用の原料として再利用した。尚、使用した反応器1、蒸留塔2、気化器3及び冷却器4は実施例1と同様とした。
図3に示す製造フローに従って、243db(2,3-ジクロロ-1,1,1-トリフルオロプロパン)から1233xfを製造した。まず、S1ラインを通じて243dbを、S2ラインを通じてフッ化水素を送流してS3ラインで合流させ、この243db及びフッ化水素の混合ガスを7000m3/hr(気体の標準状態換算)の流量で反応器1に連続的に供給した。反応器1の内部温度は300℃、圧力は0.75MPaとし、さらに、この反応において、243dbに対するフッ化水素のモル比を20とした。また、反応器1には、触媒としてあらかじめCr酸化物触媒(Cr2O3)24.8tを供給しておいた。反応後、反応器1から反応混合物を抜き出して、蒸留塔2へ送流させ、蒸留に付した。尚、使用した反応器1、蒸留塔2、気化器3及び冷却器4は実施例1と同様とした。
図3に示す製造フローに従って、244bb(2-クロロ-1,1,1,2-テトラフルオロプロパン)から1233xfを製造した。まず、S1ラインを通じて244bbを送流し、この244bb及びフッ化水素の混合ガスを7000m3/hr(気体の標準状態換算)の流量で反応器1に連続的に供給した。尚、この反応では、原料の244bbからフッ化水素が放出されるので、S2ラインからフッ化水素の供給は行っていない。反応器1の内部温度は300℃、圧力は0.75MPaとし、さらに、この反応において、244bbに対するフッ化水素のモル比を20とした。また、反応器1には、触媒としてあらかじめ0.75MPa24.8tを供給しておいた。反応後、反応器1から反応混合物を抜き出して、蒸留塔2へ送流させ、蒸留に付した。尚、使用した反応器1、蒸留塔2、気化器3及び冷却器4は実施例1と同様とした。
実施例1と同様の条件で、第1段階での反応により、240dbから1233xfを製造した。次いで、この得られた1233xfを第1蒸留塔2aの塔頂から抜き出し、第2段階の反応が行われる第2反応器1bへ送流した。具体的には、図3に示す製造フローに従い、1233xfをS1のラインを通じて送流させ、また、フッ化水素はS2のラインから供給させて、S3のラインで合流させるようにした。このS3のラインを通じて1233xfと、フッ化水素の混合ガスを、21000m3/hr(気体の標準状態換算)の流量で反応器1へ連続的に供給させた。反応器1では、触媒であるCr酸化物触媒(Cr2O3)49.6tの存在下、1233xfとフッ化水素とを反応させた。反応器1の内部温度は365℃、圧力は0.1MPa(ゲージ圧)とし、さらに、この反応において、1233xfに対するフッ化水素のモル比を10、W/F0を10とした。反応後、得られた反応混合物を反応器1から蒸留塔2へ送流した。
図4は、実施例1において、1233xfから1234yfへの転化率(Conversion)と反応時間との関係をプロットした図であり、また、実施例1の第2段階の反応において、1233xfに対するフッ化水素のモル比を6.4及び16に変更した場合(蒸留塔内の圧力はいずれも0.75MPa)のそれぞれの結果も併せて示している。この図において、モル比が6.4の場合は、上述の(1)式を満たさない条件であるため(図2も参照)、触媒が失活したことで転化率が低くなっており、反応時間と共にさらに転化率の低下が起こっている。一方、モル比が10及び16の場合は、(1)式を満たす条件であるため(図2も参照)、触媒の失活が抑制されているので転化率が高く、反応時間が経過しても転化率の低下の度合いが、モル比6.4の場合に比べて抑制されていることがわかる。
1a 第1反応器
1b 第2反応器
2 蒸留塔
2a 第1蒸留塔
2b 第2蒸留塔
3 気化器
4 冷却器
Claims (9)
- 一般式(Ia)CX3CClYCH2Y(式(Ia)中、XはCl又はFであって、各Xは同一又は異なっていてよく、YはH,F又はClであって、各Yは同一又は異なっていてもよい)で表されるクロロプロパン、及び/又は、
一般式(Ib)CY3CCl=CZ2(式(Ib)中、YはH又はClであって、各Yは同一又は異なっていてよく、ZはH,F又はClであって、各Zは同一又は異なっていてよい)で表されるクロロプロペンを含む出発原料から、一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表されるクロロプロペンを製造する方法であって、
下記(a)~(c);
(a)前記出発原料を、触媒の存在下、フッ化水素と反応させる工程と、
(b)前記工程(a)で得た反応混合物を蒸留に付して、前記一般式(II)のクロロプロペンを主成分とする第1ストリーム及び未反応の前記出発原料と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(c)前記工程(b)で分離させた第2ストリームを工程(a)の反応にリサイクルする工程、
を有し、
前記工程(b)の蒸留を、未反応の前記出発原料と未反応の前記フッ化水素とが蒸留塔の前記第2ストリーム抜き出し部分で分液しない条件で行うことを特徴とするクロロプロペンの製造方法。 - 前記工程(b)の蒸留において、前記出発原料に対する前記フッ化水素のモル比が15以上であり、前記工程(b)の蒸留が行われる蒸留塔内の圧力が0MPa以上、1MPa以下である、請求項1に記載の製造方法。
- 一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表されるクロロプロペンから2,3,3,3-テトラフルオロプロペンを製造する方法であって、
下記(d)~(f);
(d)前記一般式(II)のクロロプロペンを、触媒の存在下、フッ化水素と反応させる工程と、
(e)前記工程(d)で得た反応混合物を蒸留に付して、2,3,3,3-テトラフルオロプロペンを主成分とする第1ストリーム及び未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(f)前記工程(e)で分離させた第2ストリームを工程(d)の反応にリサイクルする工程、
を有し、
前記工程(e)の蒸留を、未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とが蒸留塔の前記第2ストリーム抜き出し部分で分液しない条件で行うことを特徴とする2,3,3,3-テトラフルオロプロペンの製造方法。 - 前記一般式(II)で表されるクロロプロペンが2-クロロ-3,3,3-トリフルオロプロペンであり、
前記工程(e)の蒸留が行われる蒸留塔内の圧力をY、前記有機物に対する前記フッ化水素のモル比をXとした場合に、下記の(1)式
(数1)
Y≧-0.00004X5+0.0026X4-0.0653X3
+0.8224X2-5.3282X+14.787 (1)
の関係を満たす条件で前記工程(e)の蒸留を行う、請求項3に記載の製造方法。 - 前記モル比Xが10以上であり、前記圧力Yが0MPa以上、1MPa以下である、請求項4に記載の製造方法。
- 一般式(Ia)CX3CClYCH2Y(式(Ia)中、XはCl又はFであって、各Xは同一又は異なっていてよく、YはH,F又はClであって、各Yは同一又は異なっていてもよい)で表されるクロロプロパン、及び/又は、
一般式(Ib)CY3CCl=CZ2(式(Ib)中、YはH又はClであって、各Yは同一又は異なっていてよく、ZはH,F又はClであって、各Zは同一又は異なっていてよい)で表されるクロロプロペンを含む出発原料から、一般式(II)CX3CCl=CH2(式(II)中、各Xの少なくとも一つはF、他はCl又はFであって、各Xは同一又は異なっていてよい)で表されるクロロプロペンを得る第1段階と、前記一般式(II)のクロロプロペンから2,3,3,3-テトラフルオロプロペンを得る第2段階とで構成される2,3,3,3-テトラフルオロプロペンの製造方法であって、
前記第1段階は、下記(a)~(c);
(a)前記出発原料を、触媒の存在下、フッ化水素と反応させる工程と、
(b)前記工程(a)で得た反応混合物を蒸留に付して、前記一般式(II)のクロロプロペンを主成分とする第1ストリーム及び未反応の前記出発原料と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(c)前記工程(b)で分離させた第2ストリームを工程(a)の反応にリサイクルする工程、
を有し、
前記第2段階は、下記(d)~(f);
(d)前記一般式(II)のクロロプロペンを、触媒の存在下、フッ化水素と反応させる工程と、
(e)前記工程(d)で得た反応混合物を蒸留に付して、2,3,3,3-テトラフルオロプロペンを主成分とする第1ストリーム及び未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とを主成分とする第2ストリームに分離する工程と、
(f)前記工程(e)で分離させた第2ストリームを工程(d)の反応にリサイクルする工程、
を有し、
前記工程(b)の蒸留を、未反応の前記出発原料と未反応の前記フッ化水素とが分液しない条件で行う、及び/又は
前記工程(e)の蒸留を、未反応の前記一般式(II)で表されるクロロプロペンを含む有機物と未反応の前記フッ化水素とが分液しない条件で行うことを特徴とする製造方法。 - 前記一般式(II)で表されるクロロプロペンが2-クロロ-3,3,3-トリフルオロプロペンであり、
前記工程(e)の蒸留が行われる蒸留塔内の圧力をY、前記有機物に対する前記フッ化水素のモル比をXとした場合に、下記の(1)式
(数1)
Y≧-0.00004X5+0.0026X4-0.0653X3
+0.8224X2-5.3282X+14.787 (1)
の関係を満たす条件で前記工程(e)の蒸留を行う、請求項6に記載の製造方法。 - 前記モル比Xが10以上であり、前記圧力Yが0MPa以上、1MPa以下である、請求項7に記載の製造方法。
- 前記出発原料が1,1,1,2,3-ペンタクロロプロパンであり、
前記工程(b)の蒸留において、前記1,1,1,2,3-ペンタクロロプロパンに対する前記フッ化水素のモル比が15以上であり、前記工程(b)の蒸留が行われる蒸留塔内の圧力が0MPa以上、1MPa以下である、請求項6~8のいずれか1項の記載の製造方法。
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JP2017122063A (ja) * | 2016-01-06 | 2017-07-13 | ダイキン工業株式会社 | 2,3,3,3−テトラフルオロプロペンの製造方法 |
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US10173952B2 (en) | 2019-01-08 |
EP3170804B1 (en) | 2019-05-01 |
KR20170015474A (ko) | 2017-02-08 |
CN106536463A (zh) | 2017-03-22 |
US20170217859A1 (en) | 2017-08-03 |
CN106536463B (zh) | 2019-06-11 |
JP2016020319A (ja) | 2016-02-04 |
JP5939283B2 (ja) | 2016-06-22 |
EP3170804A1 (en) | 2017-05-24 |
KR101928224B1 (ko) | 2018-12-11 |
EP3170804A4 (en) | 2018-03-14 |
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