WO2012053656A1 - ポリクロロプロパンを製造するための連続バッチ反応方法 - Google Patents

ポリクロロプロパンを製造するための連続バッチ反応方法 Download PDF

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WO2012053656A1
WO2012053656A1 PCT/JP2011/074596 JP2011074596W WO2012053656A1 WO 2012053656 A1 WO2012053656 A1 WO 2012053656A1 JP 2011074596 W JP2011074596 W JP 2011074596W WO 2012053656 A1 WO2012053656 A1 WO 2012053656A1
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reaction
batch
gas phase
substituted
chlorine
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PCT/JP2011/074596
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English (en)
French (fr)
Japanese (ja)
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俊輔 保坂
康尚 小松
聡洋 齋藤
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株式会社トクヤマ
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Priority claimed from JP2010237273A external-priority patent/JP5642495B2/ja
Priority claimed from JP2010254626A external-priority patent/JP5783707B2/ja
Application filed by 株式会社トクヤマ filed Critical 株式会社トクヤマ
Priority to KR1020137003021A priority Critical patent/KR20130122617A/ko
Priority to CN2011800462081A priority patent/CN103119006A/zh
Publication of WO2012053656A1 publication Critical patent/WO2012053656A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

Definitions

  • the present invention relates to a continuous batch reaction method for producing polychloropropane. More specifically, the present invention relates to a method capable of stably controlling the reaction rate and selectivity of each batch when producing polychloropropane by a system in which batch reactions are repeated.
  • Chlorinated hydrocarbons are important as raw materials or intermediates for producing various products such as agricultural chemicals, pharmaceuticals, and CFC substitute materials. For example, starting from 1,1,1,2,3-pentachloropropane and via 1,1,2,3-tetrachloropropene, trichloroallyldiisopropylthiocarbamate useful as a herbicide can be produced.
  • a method for producing such a chlorinated hydrocarbon for example, a first reaction for obtaining chloropropane by adding carbon tetrachloride to an unsaturated compound having 2 carbon atoms (unsubstituted or chlorine-substituted ethylene), A second reaction to dehydrochlorinate the chloropropane to obtain chloropropene; A three-stage reaction comprising a third reaction in which chlorine is further added to the chloropropene to obtain the desired chloropropane is known.
  • the first reaction among them for example, in Japanese Patent Publication No. 2-47969, an addition reaction of ethylene and carbon tetrachloride is carried out in the presence of a phase transfer catalyst composed of metallic iron and a phosphoryl compound.
  • a phase transfer catalyst composed of metallic iron and a phosphoryl compound.
  • Such a first reaction is often performed in a batch system in a reaction system composed of a liquid phase composed of carbon tetrachloride and a gas phase mainly composed of an unsaturated compound having 2 carbon atoms.
  • a batch reaction is carried out industrially, after completion of each batch reaction, after the reaction mixture is discharged from the reactor, new carbon tetrachloride is charged without washing the reactor, and the catalyst and carbon number The production efficiency is higher when the unsaturated compound 2 is supplied and the reaction of the next batch is performed.
  • the addition reaction activity may decrease or the reaction selectivity may vary as the number of batches increases. It was.
  • the present invention has been made in view of the fact that the above-described problems exist in the prior art, and its purpose is to produce polychloropropane by a method in which batch reaction is repeated.
  • the object is to provide a method capable of stably controlling the reaction rate and selectivity of each batch. Further objects and advantages of the present invention will become apparent from the following description.
  • the present inventors have conducted batch reaction when an addition reaction between carbon tetrachloride and an unsaturated compound having 2 carbon atoms is carried out by repeating the batch reaction. It has been found that the composition of the gas phase part gradually changes as the number passes.
  • the above problems in the prior art are as follows:
  • an addition reaction in which carbon tetrachloride is added to unsubstituted or chlorine-substituted ethylene to obtain polychloropropane is not substituted in a batch reactor in which a liquid phase and a gas phase exist.
  • it is carried out in a batch system while supplying ethylene substituted with chlorine, and after completion of the batch reaction, the reaction mixture is discharged from the reactor, and subsequently, the raw material for the next batch reaction is supplied to the reactor, and the addition reaction is performed.
  • FIG. 1 is a graph showing the results of continuous batch reactions in Experimental Example A-1 and Example B-1.
  • FIG. 2 is a graph showing the results of continuous batch reaction in Experimental Example A-2 and Example C-1.
  • FIG. 3 is a graph showing the ethylene partial pressure before the start of each batch reaction in Experimental Example A-2 and Example C-1.
  • the method of the present invention as described above can be realized by the following two specific methods, for example.
  • the first method for carrying out the present invention is as follows: When the reaction mixture is discharged from the reactor after the reaction of the previous batch is completed, and then the raw material for the next batch reaction is supplied to the reactor, First, carbon tetrachloride was charged into the reactor, After supplying one or more pressurization / depressurization operations to reduce the gas phase pressure by supplying ethylene with non-substituted or chlorine-substituted ethylene to the gas phase and then evacuating it, the gas phase is further non-substituted Alternatively, a method of performing the next batch reaction after adjusting the partial pressure of unsubstituted or chlorine-substituted ethylene existing in the gas phase by supplying ethylene pressurized with chlorine and adjusting the pressure to the above range (hereinafter, It is also referred to as “Method 1”.
  • the second method for carrying out the present invention is: When the reaction mixture is discharged from the reactor after the reaction of the previous batch is completed, and then the raw material for the next batch reaction is supplied to the reactor, First, carbon tetrachloride was charged into the reactor, The partial pressure of the non-substituted or chlorine-substituted ethylene present in the gas phase part is adjusted to the above range by supplying ethylene that is unsubstituted or substituted with chlorine to the gas phase part and pressurizing the gas phase part.
  • a method in which the total pressure is set to the total pressure of the partial pressure of ethylene that is unsubstituted or substituted with chlorine and the partial pressure of a gas other than ethylene that is unsubstituted or substituted with chlorine present in the gas phase (Hereinafter also referred to as “method 2”).
  • method 2 A method in which the total pressure is set to the total pressure of the partial pressure of ethylene that is unsubstituted or substituted with chlorine and the partial pressure of a gas other than ethylene that is unsubstituted or substituted with chlorine present in the gas phase.
  • Unsubstituted or chlorine-substituted ethylene used as a raw material in the present invention includes ethylene, vinyl chloride, 1,1-dichloroethylene, 1,2-dichloroethylene. 1,1,2-trichloroethylene and perchloroethylene are included, and among these, ethylene or vinyl chloride which is a gas at normal temperature and normal pressure is preferable from the viewpoint of easy implementation of the present method.
  • ethylene or vinyl chloride which is a gas at normal temperature and normal pressure is preferable from the viewpoint of easy implementation of the present method.
  • each batch reaction of the continuous batch reaction in the present invention proceeds in a liquid phase reaction system in a batch reactor in which a liquid phase and a gas phase exist.
  • the unsaturated compound having 2 carbon atoms which is a raw material compound, is supplied to the reaction system, then dissolved in the liquid phase, and subjected to an addition reaction with carbon tetrachloride.
  • the raw material compound corresponding to the consumed amount is added to the gas phase as needed, so that the pressure in the gas phase part is maintained almost constant during the batch reaction.
  • the unsaturated compound having 2 carbon atoms may be supplied to the gas phase part, for example, may be supplied to the liquid phase part by bubbling, or both of them may be supplied. You may do it at the same time. However, for reasons such as ensuring a stable progress of the reaction and bubbling into the liquid requires a larger pressure than supplying to the gas phase portion, the unsaturated compound having 2 carbon atoms is in the gas phase portion. It is preferable to supply to.
  • the addition reaction in the present invention is preferably carried out in the presence of a suitable catalyst.
  • Examples of the catalyst that can be used here include an iron-phosphate ester catalyst, an iron-aprotic polar solvent catalyst, a copper-amine catalyst, and the like. Among these, an iron-phosphate ester catalyst is preferable. .
  • the addition reaction is preferably carried out in the presence of an iron-phosphate ester catalyst in the liquid phase.
  • This iron-phosphate ester catalyst is prepared by contacting a predetermined amount of iron and a predetermined amount of phosphate ester in a liquid phase reaction system (that is, in liquid carbon tetrachloride).
  • the contact between iron and phosphate ester is based on a method in which the total amount of each of iron and phosphate ester is put into the reaction system at one time before starting the reaction, Alternatively, the total amount of iron and a part of the phosphate ester can be added before starting the reaction, and the phosphate ester can be additionally added during the progress of the addition reaction.
  • “before the reaction” means that the temperature of the reaction system is raised to a temperature at which carbon tetrachloride and the unsaturated compound having 2 carbons substantially react (hereinafter referred to as “minimum reaction temperature”).
  • the minimum reaction temperature when the iron-phosphate ester catalyst is used is 90 ° C. Therefore, the total amount of iron and all or part of the phosphate ester are preferably added when the reaction system is below 90 ° C., and more preferably added at room temperature.
  • the iron used here include metallic iron, pure iron, soft iron, carbon steel, ferrosilicon steel, and an alloy containing iron (for example, stainless steel).
  • the shape of iron for example, it can be any shape such as powder, granule, lump, rod, sphere, plate, fiber, etc., and metal pieces that are further processed using these, distillation filling A thing etc. may be sufficient.
  • Examples of the processed metal piece include a coil, a net, steel wool, and other irregularly shaped pieces; examples of the distillation filling include a Raschig ring and a helix. Any of these forms can be used, but from the viewpoint of ensuring a sufficient contact area with the phosphate ester and the reactant, it is preferably in the form of powder or fiber. From the same viewpoint, the specific surface area of iron measured by the BET method using nitrogen as an adsorbate is 0.001 to 5 m. 2 / G is preferable.
  • the amount of iron used in the case where phosphoric acid esters are added all at once before the start of the reaction is 0 with respect to 1 mol of carbon tetrachloride used from the viewpoint of achieving both high reaction conversion and high selectivity.
  • the amount is preferably 0.001 mol or more, more preferably 0.005 mol or more, and particularly preferably 0.01 mol or more.
  • the upper limit of the amount of iron used is not particularly limited. Increasing the amount of iron used has little effect on activity and selectivity, but the amount of raw material that can be introduced into the reactor is reduced by an amount corresponding to the iron volume, resulting in poor reaction efficiency. This is also economically disadvantageous in that the amount of wasted iron that is not involved in the reaction increases.
  • the amount of iron used is preferably 10 mol or less, more preferably 5 mol or less, and even more preferably 1 mol or less, with respect to 1 mol of carbon tetrachloride used. In particular, it is preferably 0.1 mol or less.
  • the phosphate ester include the following general formula (1).
  • R 1 Is a phenyl group or an alkyl group having 1 to 4 carbon atoms
  • R 2 And R 3 Are each independently a hydrogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms.
  • Specific examples thereof include, for example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, diethyl phosphate, dibutyl phosphate, monophenyl phosphate, monobutyl phosphate, Examples thereof include dimethylphenyl phosphate, diethylphenyl phosphate, dimethylethyl phosphate, and phenylethylmethyl phosphate.
  • R 1 , R 2 And R 3 Trialkyl phosphates, all of which are alkyl groups having 1 to 4 carbon atoms, are preferred, and trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate are particularly preferred.
  • the amount of phosphate ester used is preferably 0.001 mol or more, particularly 0.002 mol, relative to 1 mol of carbon tetrachloride used. The above is preferable.
  • the upper limit of the amount of phosphate ester used is not particularly limited, but if the amount used is excessively large, it becomes difficult to control the reaction due to heat generation, and the amount of phosphate ester that is wasted without being involved in the reaction increases. Economic disadvantage. From this point of view, the amount of phosphate ester used is preferably 1 mol or less, more preferably 0.1 mol or less, and 0.05 mol or less with respect to 1 mol of carbon tetrachloride. May be.
  • the reaction temperature of the addition reaction is preferably a temperature equal to or higher than the minimum reaction temperature in order to make the reaction proceed reliably, and more preferably 90 to 160 ° C. in order to achieve both high conversion and high selectivity.
  • the temperature is 105 to 130 ° C.
  • the reaction pressure may be any pressure that allows the reaction system to maintain a liquid phase at the reaction temperature.
  • the reaction pressure converted to 25 ° C. is preferably 0.13 to 0.54 MPa (abs), and more preferably 0.17 to 0.37 MPa (abs).
  • the reaction pressure can be set to 0.40 to 0.90 MPa (abs), preferably 0.45 to 0. 70 MPa (abs).
  • the partial pressure of the unsaturated compound having 2 carbon atoms in the gas phase is preferably 0.11 to 0.52 MPa (abs) as a value converted to 25 ° C., and preferably 0.15 to 0.35 MPa (abs).
  • the above preferable range is 0.15 to 0.65 MPa (abs), and the more preferable range is 0.20 to 0.45 MPa (abs). . If the partial pressure of the unsaturated compound having 2 carbon atoms converted to 25 ° C. is less than 0.11 MPa, the concentration of the raw material compound (unsaturated compound having 2 carbon atoms) in the liquid phase becomes too low, and the reaction addition rate is insufficient. On the other hand, when the pressure exceeds 0.52 MPa, the ratio of the multimer formation increases and the selectivity may be impaired, which is not preferable.
  • the reaction pressure is a value obtained by summing the partial pressures of unsaturated compounds having 2 carbon atoms and the partial pressures of other gases.
  • carbon tetrachloride which is a liquid having only a small vapor pressure at 25 ° C., also has a significant vapor pressure at the reaction temperature.
  • the vapor pressure of carbon tetrachloride is only about 0.02 MPa at 25 ° C., but shows a significantly high value of 0.25 MPa at 110 ° C.
  • the partial pressure of the unsaturated compound having 2 carbon atoms and the partial pressure of the other gas can be determined from the analysis result of the gas phase portion by gas chromatography and the total pressure of the gas phase portion.
  • all of the above pressures are absolute pressures at a set or specially specified temperature.
  • the total amount of iron and a part of the phosphate ester are added before the start of the reaction, and the phosphate ester is additionally added during the addition reaction. It is preferable that the controllability of the reaction is good, the conversion rate and the selectivity are increased, and the amount of iron and phosphate used can be reduced.
  • the amount of iron that is added all at once before the start of the reaction can be made smaller than the above-described value as the lower limit of the amount of iron used when the phosphate ester is added all at once before the start of the reaction.
  • the amount of iron used is more preferably 0.0005 mol or more, further preferably 0.001 mol or more, especially 0.005 mol with respect to 1 mol of carbon tetrachloride used.
  • the above is preferable.
  • the upper limit of iron usage is set from an economic point of view.
  • the amount of iron used is preferably 1 mol or less, more preferably 0.1 mol or less, and 0.05 mol or less with respect to 1 mol of carbon tetrachloride used. Is more preferable.
  • the addition of the phosphate ester may be performed only once, may be divided into several times, or may be performed continuously.
  • the number of additional additions in the case of dividing into several times is preferably 2 to 10 times, and preferably 2 to 6 times.
  • the total amount of phosphate ester used (total amount in one batch of addition before starting reaction and additional addition) is preferably 0.001 mol or more with respect to 1 mol of carbon tetrachloride used, In particular, the amount is preferably 0.002 mol or more.
  • the total amount of phosphate ester added in the case of additional addition is not particularly limited.
  • the total amount of phosphate ester added is preferably 1 mol or less, more preferably 0.1 mol or less, based on 1 mol of carbon tetrachloride. .01 mol or less may be used.
  • the target compound is converted to a higher level.
  • the addition reaction proceeds even when the phosphate ester is added after raising the temperature of the reaction system to the minimum reaction temperature.
  • the addition amount of the phosphoric acid ester before the start of the reaction is preferably 0.0001 mol or more, more preferably 0.0005 mol or more with respect to 1 mol of carbon tetrachloride to be used.
  • the upper limit of the phosphate ester added before the start of the reaction is independent of the mode of additional addition (whether the additional addition is performed once, divided into several times, or performed continuously), and In the case of additional addition divided into several times, regardless of the number of additions, it is preferably 80% or less, more preferably 70% or less of the total amount of phosphate ester used.
  • This continuous monitoring of the consumption rate of unsaturated compounds is performed, for example, by examining the amount of unsaturated compounds supplied to the gas phase in order to maintain an appropriate reaction pressure in a liquid phase batch reaction in the presence of the gas phase. be able to.
  • the consumption rate of the unsaturated compound is preferably 5 to 50%, more preferably 10 to 40% of the average consumption rate in 60 minutes after the start of the reaction.
  • the entire remaining amount of phosphate ester is added.
  • the consumption rate is preferably 5 to 50%, more preferably 10 to 40% of the average consumption rate in 60 minutes after the start of the reaction.
  • the first addition of phosphate ester is performed.
  • the consumption rate of the unsaturated compound once reduced is recovered, and thereafter, the consumption rate gradually decreases again.
  • the second and subsequent additions of phosphate ester are added. Addition is performed. With this additional addition, the consumption rate of the unsaturated compound is restored again.
  • the consumption rate of the unsaturated compound having 2 carbon atoms can be continuously monitored, and the phosphate ester can be additionally added a predetermined number of times.
  • each divided addition amount is preferably set equal to the addition amount for each time or gradually increased as the number of times is increased.
  • the addition of phosphate ester is continuously performed, it may be performed immediately after the start of the reaction, or the consumption rate is preferably 5 to 50% of the average consumption rate in 60 minutes after the start of the reaction, more preferably 10 to Additional addition of phosphate ester may be initiated when 40% is reached.
  • the phosphoric acid ester 1.3 ⁇ 10 4 per 1 mol of carbon tetrachloride. -6 ⁇ 6.6 ⁇ 10 -3 Preferably it is performed at a rate of mol / min, 6.6 ⁇ 10 -6 ⁇ 6.6 ⁇ 10 -4 More preferably, it is carried out at a rate of mol / min.
  • the phosphate ester 1 is added to 1 mol of carbon tetrachloride. .3x10 -6 ⁇ 6.6 ⁇ 10 -3 mol / min, more preferably 6.6 ⁇ 10 -6 ⁇ 6.6 ⁇ 10 -4
  • the rate of the above continuous addition may be increased from the middle in the range of mol / min. This continuous addition is preferably continued until the carbon tetrachloride conversion rate is 30 to 100%, more preferably 80 to 98%.
  • the conversion rate of carbon tetrachloride can be judged from the consumption of unsaturated compounds having 2 carbon atoms.
  • the total reaction time is preferably 1 to 12 hours, and more preferably 2 to 10 hours. Since the reaction mixture obtained by such a method contains the target product converted into the target product with high conversion and high selectivity, unreacted carbon tetrachloride contained therein (the content is small) )), The iron-phosphate ester catalyst residue, by-products and excess unsaturated compound having 2 carbon atoms can be separated and used as a product in many cases.
  • the purification method may be very simple, and for example, a high-purity product can be obtained by simple distillation purification having about 2 to 10 theoretical plates.
  • the liquid phase part decreases and the gas phase part increases as the reaction mixture is discharged.
  • the pressure in the gas phase part is reduced. It is preferable to maintain.
  • an unsaturated compound having 2 carbon atoms it is preferable to use an unsaturated compound having 2 carbon atoms.
  • an iron-phosphate ester catalyst is used as the catalyst, unreacted iron usually remains in the reactor, depending on the amount of iron used in the first batch. Since this unreacted iron can be used as it is as the catalyst component in the second batch or later, it is not necessary to take it out (rather, such unreacted solid iron has higher surface activity than new iron, It is preferable to leave in the reactor positively).
  • the amount of iron to be newly added may be reduced in consideration of the amount of iron remaining in the reactor.
  • the reaction mixture of the previous batch does not discharge the entire amount, and is 0.5 to 20% by volume, preferably 2 to 10% by volume, more preferably It is preferable that about 3 to 5% by volume is left in the reactor because the initial reaction rate after the next batch can be improved. This is presumed to be because the iron-phosphate ester catalyst is dissolved in the reaction mixture of the previous batch, and this acts immediately and effectively as a catalyst at the initial stage of the reaction.
  • Method 1 When the method of the present invention is performed according to Method 1, in the second batch of the continuous batch reaction, the reaction mixture is discharged from the reactor after the completion of the addition reaction of the previous batch, and then the next batch reaction is performed in the reactor.
  • carbon tetrachloride was charged into the reactor, After supplying and pressurizing an unsaturated compound having 2 carbon atoms to the gas phase portion and then performing one or more pressurization / depressurization operations for evacuating and lowering the gas phase pressure, the gas phase portion further has 2 carbon atoms.
  • Method 1 After supplying and pressurizing an unsaturated compound to adjust the partial pressure of the unsubstituted or chlorine-substituted ethylene present in the gas phase part to the above range, that is, 0.11 to 0.52 MPa (abs). Perform each batch reaction.
  • the biggest feature of Method 1 is that, after discharging the reaction mixture, when supplying the raw material for the next batch reaction to the reactor, carbon tetrachloride is first charged in the reactor, and then in the gas phase part. After supplying and pressurizing an unsaturated compound having 2 carbon atoms and then performing one or more pressurization / depressurization operations to exhaust and lower the gas phase pressure, an unsaturated compound having 2 carbon atoms is further added to the gas phase portion.
  • the reaction rate of the addition reaction after the second batch is maintained at the same level or higher as that of the first batch. That is, in the gas phase part after the second batch, as described above, in addition to the unsaturated compound having 2 carbon atoms, air (nitrogen, oxygen, carbon dioxide, etc.) dissolved in the raw material carbon tetrachloride, Impurities and the like contained in a small amount in the unsaturated compound having 2 carbon atoms remain and accumulate without being completely removed after completion of the batch.
  • air nitrogen, oxygen, carbon dioxide, etc.
  • the partial pressure of the unsaturated compound having 2 carbon atoms which is the raw material compound, is lower than the total pressure in the gas phase portion, which lowers the concentration of the raw material compound in the liquid phase portion.
  • the reaction rate when reacting gradually decreases as the number of batches increases.
  • examples of impurities contained in a small amount in the unsaturated compound having 2 carbon atoms include ethane, methane and the like when the unsaturated compound having 2 carbon atoms is ethylene. Therefore, the gas phase partial pressure of the unsaturated compound having 2 carbon atoms is changed by the pressure / depressurization operation as described above by replacing the gas phase portion with the unsaturated compound having 2 carbon atoms at least once.
  • the medium concentration is also made equal between batches, thereby maintaining the reaction rate.
  • a raw material compound (unsaturated compound having 2 carbon atoms) is introduced into the gas phase part at room temperature (25 ° C.) until it exceeds the desired total pressure, and then this is evacuated to remove the gas phase part. Since it is intended to be replaced with a raw material compound, it is not necessary to strictly control the temperature at the time of replacement, the pressurized pressure, and the pressure after exhaust, respectively. However, excessive pressurization and decompression lead to meaningless consumption of the raw material compound.
  • the pressure when supplying and pressurizing the unsaturated compound having 2 carbon atoms to the gas phase is 0.11 to 2.1 MPa (abs). More preferably, the pressure is 0.15 to 1.0 MPa (abs). From the same viewpoint, the pressure after exhausting is preferably 0.10 to 0.3 MPa (asb), more preferably 0.10 to 0.15 MPa (abs).
  • the time for maintaining the system in a pressurized state is arbitrary, but may be, for example, 1 to 120 seconds, preferably 2 to 30 seconds.
  • This pressurizing / depressurizing operation is performed once or more, and the number of times is preferably 1 to 10 times, more preferably 1 to 2 times. Thereafter, the raw material compound is supplied again, and the total pressure in the gas phase is set within the preferable reaction pressure range described above for the first batch, and the addition reaction is started. It is preferable that the partial pressure of the unsaturated compound having 2 carbon atoms in the gas phase during the addition reaction after the second batch is within the preferred range described above for the first batch. That is, the 25 ° C. converted value is preferably 0.11 to 0.52 MPa (abs), and preferably 0.15 to 0.35 MPa (abs).
  • the addition of the catalyst component (especially phosphate ester) for the second batch or later may be performed before or after the pressurization / depressurization operation with the unsaturated compound having 2 carbon atoms. Also good.
  • Such a continuous batch method according to Method 1 can be repeated a plurality of times, for example, 2 to 300 times.
  • the reaction rate and selectivity of each batch can be stably controlled. It should be noted that the same effect can be obtained if the unsaturated compound having 2 carbon atoms is supplied and exhausted before carbon tetrachloride is charged into the reactor.
  • the partial pressure of the non-substituted or chlorine-substituted ethylene present in the gas phase portion is supplied by pressurizing and supplying ethylene that is unsubstituted or substituted with chlorine to the gas phase portion in the above range, that is, 0.11 to 0.
  • the total pressure in the gas phase part is adjusted to 52 MPa (abs), and the partial pressure of ethylene which is unsubstituted or substituted with chlorine and the gas other than ethylene which is present in the gas phase part and which is not substituted or substituted with chlorine.
  • Each batch reaction is carried out with the pressure set to the total pressure.
  • Method 2 The greatest feature of Method 2 is that, in the second batch and subsequent batches of the continuous batch reaction, the total pressure in the gas phase part is changed to the desired partial pressure of the unsaturated compound having 2 carbon atoms and the carbon number 2 existing in the gas phase part. It is to set to the total pressure with the partial pressure of gas other than an unsaturated compound. By performing such setting, the reaction rate of the addition reaction after the second batch is maintained at the same level as the first batch.
  • the partial pressure of the unsaturated compound having 2 carbon atoms which is the raw material compound, is lower than the total pressure in the gas phase portion, which lowers the concentration of the raw material compound in the liquid phase portion.
  • the reaction rate when reacting gradually decreases as the number of batches passes.
  • the total pressure in the gas phase is set to the total pressure of the desired partial pressure of the unsaturated compound having 2 carbon atoms and the partial pressure of a gas other than the unsaturated compound having 2 carbon atoms existing in the gas phase.
  • the partial pressure of the gas phase of the unsaturated compound having 2 carbon atoms (and hence the concentration in the liquid phase) is made equal between the batches, thereby maintaining the reaction temperature.
  • the types of components other than the unsaturated compound having 2 carbon atoms and the partial pressures in the gas phase can be easily known by gas chromatography. As the batch reaction is repeated, the partial pressures of these components accumulate in the gas phase and gradually increase. At a certain point, the gas phase composition and the exhaust gas composition coincide with each other and reach equilibrium.
  • the type of each component other than the unsaturated compound having 2 carbon atoms and the partial pressure after accumulating in each batch or reaching the equilibrium are determined by the filling rate of carbon tetrachloride, the purity of the raw material compound used, etc. Dependent.
  • the desired partial pressure of the saturated compound may be applied to set the gas phase total pressure.
  • the total partial pressure of gases other than unsaturated compounds having 2 carbon atoms in the gas phase for each batch depends on the number of repeated batches. Can be estimated to be the same between series.
  • the gas phase total pressure may be set using a value measured after each batch in a series of repeated reactions as an estimated value in each batch of another series. It is preferable that the partial pressure of the unsaturated compound having 2 carbon atoms in the gas phase during the addition reaction after the second batch is within the preferable range described above for the first batch. That is, the 25 ° C. converted value is preferably 0.11 to 0.52 MPa (abs), and preferably 0.15 to 0.35 MPa (abs).
  • Such a continuous batch method according to Method 2 can be repeated a plurality of times, for example, 2 to 300 times. Method 2 as described above is capable of stably controlling the reaction rate and selectivity of each batch when producing polychloropropane by a system in which batch reactions are repeated.
  • Reference example (first batch addition reaction) Filled with SUS autoclave (internal volume 1,500 mL) with stirrer, ethylene gas inlet and gas outlet, carbon tetrachloride and iron addition port, phosphate ester addition port and liquid discharge port It was.
  • An autoclave was charged with 1,560 g of carbon tetrachloride, 2.0 g of triethyl phosphate, and 4.0 g of K100 (manufactured by JFE Steel Corporation, coke reduced iron powder), the temperature was set to 110 ° C., and the total pressure of the gas phase
  • the addition reaction was performed by supplying ethylene so that the pressure became 0.5 MPa (abs).
  • the ethylene partial pressure in the gas phase immediately after the total pressure in the gas phase reached 0.5 MPa (abs) was 0.25 MPa. From the time when the temperature reached 110 ° C. and the total pressure in the gas phase reached 0.5 MPa (abs), triethyl phosphate was continuously added at 0.02 ml / min until the end of the reaction. During the reaction, ethylene is supplied so that the total pressure in the gas phase is maintained at 0.5 MPa (abs), and the ethylene consumption rate (additional supply rate) is 0.1% of the initial amount of carbon tetrachloride. The reaction was judged to be complete when it reached mol% / min (200 ml / min), and the first batch addition reaction was completed.
  • reaction time was 600 minutes, the amount of triethyl phosphate used was 14.5 g, the conversion of carbon tetrachloride was 94%, and the selectivity for 1,1,1,3-tetrachloropropane was 97%.
  • Experimental Example A-1 (Comparative example showing the method of the prior art) The addition reaction of the first batch was performed as in the above reference example. After completion of the addition reaction in the first batch, the gas phase is pressurized with ethylene, and 95% by volume of the liquid phase reaction mixture is discharged from the liquid discharge port and left as it is (without washing the autoclave, 5 in the reactor).
  • the temperature was set to 110 ° C., and ethylene was supplied again so that the gas phase total pressure was 0.5 MPa (abs) to start the addition reaction.
  • the ethylene partial pressure in the gas phase at the start of the reaction was 0.25 MPa.
  • additional triethyl phosphate was continuously added at a rate of 0.02 mL / min until the end of the reaction.
  • ethylene was supplied while maintaining the total pressure in the gas phase at 0.5 MPa (abs). Triethyl phosphate was added continuously in the same manner as in the first batch, and the reaction was terminated on the same basis as in the first batch.
  • Experimental Examples B-2 to B-5 the relationship between the gas phase pressure (reaction pressure) during the reaction and the reaction results was examined.
  • Experimental Example B-2 (Example of Method 1)
  • the addition reaction of the first batch was performed as in the above reference example.
  • the batch reaction after charging the raw material for the next batch without washing the autoclave after completion of the previous batch and performing pressure / depressurization operation with ethylene.
  • the reaction pressure of the second batch and the third batch is 0.50 MPa (abs) at the reaction temperature, which corresponds to 0.21 MPa (abs) when converted to a pressure at 25 ° C.
  • Table 2 shows the reaction time, reaction conversion rate, and selectivity of 1,1,1,3-tetrachloropropane in the third batch.
  • Experimental Example B-3 Example of Method 1
  • the addition reaction of the first batch was performed as in the above reference example.
  • the batch reaction after charging the raw material for the next batch without washing the autoclave after completion of the previous batch and performing pressure / depressurization operation with ethylene.
  • Experimental Example B-4 (Example of Method 1) The addition reaction of the first batch was performed as in the above reference example. Subsequently, as in the sixth batch of Experimental Example B-1, the addition reaction of the second batch was performed as a batch reaction after the pressure / depressurization operation with ethylene. Next, as in the sixth batch of Experimental Example B-1, except that the reaction pressure was changed, raw materials for the next batch were charged without washing the autoclave after completion of the previous batch, and pressure / decompression operation with ethylene was performed.
  • Experimental Example A-2 (Comparative example showing the method of the prior art) The addition reaction of the first batch was performed as in the above reference example. After completion of the addition reaction of the first batch, the gas phase was pressurized with ethylene, 95 volume% of the liquid phase reaction mixture was discharged from the liquid outlet, and left as it was (without washing the autoclave, 5 volumes in the reactor). % Of carbon tetrachloride, 560 g of triethyl phosphate, 2.0 g of triethyl phosphate and 3.0 g of K100 are set again, the temperature is set to 110 ° C., and the total pressure in the gas phase is 0.5 MPa. The addition reaction was started by supplying ethylene so as to be (abs).
  • Experimental Example C-1 (Example of Method 2) The addition reaction of the first batch was performed as in the above reference example. This experiment was performed as an addition reaction after the eighth batch, following the experiment A-2. After completion of the addition reaction in the seventh batch in Experimental Example A-2, the gas phase was pressurized with ethylene, and 95% by volume of the liquid phase reaction mixture was discharged from the liquid discharge port as it was (without washing the autoclave).
  • Reaction time determined according to the above criteria for the eighth, twelfth, fifteenth, eighteenth, twentieth, twenty-sixth, twenty-sixth, twenty-ninth and thirtieth batches of the eighth to thirty batches.
  • the reaction conversion rate and the ethylene partial pressure before the start of the reaction are shown in FIGS. 2 and 3 in succession to the results of Experimental Example A-2.
  • ethylene was supplied to the reaction system, and the gas phase part immediately after the gas phase pressure became 0.6 MPa was measured by GC, as shown in Table 4 below. (Unit is mol%. Carbon tetrachloride is the same as in Table 3).

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106934A (ja) * 2010-11-15 2012-06-07 Tokuyama Corp ポリクロロプロパンを製造するための連続バッチ反応方法
US20160107955A1 (en) * 2014-10-16 2016-04-21 Spolek Pro Chemickou A Hutni Vyrobu A.S. Process for producing a chlorinated c3-6 alkane

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2889073T3 (es) * 2014-10-16 2022-01-11 Spolek Pro Chemickou A Hutni Vyrobu As Un proceso controlado y continuo para producir 1,1,1,2,3-pentacloropropano

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61271248A (ja) * 1985-05-28 1986-12-01 Mitsui Toatsu Chem Inc ２−ヒドロキシアルキル（メタ）アクリレ−トの製造方法
JPS62263134A (ja) * 1982-04-01 1987-11-16 ヘイロウカ−ボン　プロダクツ　コ−ポレイシヨン １，１，１，３−テトラクロロプロパンの製法
JPH0247969B2 (zh) * 1983-07-06 1990-10-23 Monsanto Co
JP2001213820A (ja) * 2000-01-31 2001-08-07 Central Glass Co Ltd １，１，１，３，３−ペンタクロロプロパンの製造方法
JP2004524272A (ja) * 2000-09-29 2004-08-12 バルカン・マテリアルズ・カンパニー １，１，１，３，３−ペンタクロロプロパンの製法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4605802A (en) * 1982-04-01 1986-08-12 Halocarbon Products Corp. Production of 1,1,1,3-tetrachloropropane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62263134A (ja) * 1982-04-01 1987-11-16 ヘイロウカ−ボン　プロダクツ　コ−ポレイシヨン １，１，１，３−テトラクロロプロパンの製法
JPH0247969B2 (zh) * 1983-07-06 1990-10-23 Monsanto Co
JPS61271248A (ja) * 1985-05-28 1986-12-01 Mitsui Toatsu Chem Inc ２−ヒドロキシアルキル（メタ）アクリレ−トの製造方法
JP2001213820A (ja) * 2000-01-31 2001-08-07 Central Glass Co Ltd １，１，１，３，３−ペンタクロロプロパンの製造方法
JP2004524272A (ja) * 2000-09-29 2004-08-12 バルカン・マテリアルズ・カンパニー １，１，１，３，３−ペンタクロロプロパンの製法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012106934A (ja) * 2010-11-15 2012-06-07 Tokuyama Corp ポリクロロプロパンを製造するための連続バッチ反応方法
US20160107955A1 (en) * 2014-10-16 2016-04-21 Spolek Pro Chemickou A Hutni Vyrobu A.S. Process for producing a chlorinated c3-6 alkane
US9896400B2 (en) * 2014-10-16 2018-02-20 Spolek Pro Chemickou A Hutni Vyrobu A.S. Process for producing a chlorinated C3-6 alkane
US10294179B2 (en) 2014-10-16 2019-05-21 Spolek Pro Chemickou A Hutni Vyrobu A.S. Process for producing a chlorinated C3-6 alkane
US10934232B2 (en) 2014-10-16 2021-03-02 Spolek Pro Chemickou A Hutni Vyrobu A.S. Composition comprising 1,1,1,3-tetrachloropropane and a process for producing the composition thereof
US11325876B2 (en) 2014-10-16 2022-05-10 Spolchemie Zebra, A.S. Process for producing a chlorinated C3-6 alkane

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