WO2004087625A1 - イソプレンの製造方法 - Google Patents
イソプレンの製造方法 Download PDFInfo
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- WO2004087625A1 WO2004087625A1 PCT/JP2004/004038 JP2004004038W WO2004087625A1 WO 2004087625 A1 WO2004087625 A1 WO 2004087625A1 JP 2004004038 W JP2004004038 W JP 2004004038W WO 2004087625 A1 WO2004087625 A1 WO 2004087625A1
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- reaction mixture
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- boiling
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- isoprene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/867—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an aldehyde or a ketone
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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
- 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 isoprene.
- the isoprene obtained by the production method of the present invention can be effectively used as a basic chemical raw material for various chemical products and polymer raw materials.
- isobutylene and / or t-butanol As a method for producing isoprene, isobutylene and / or t-butanol (hereinafter, “isobutylene and / or t-butanol” can be abbreviated as “c 4 ”) in a reactor containing an acidic aqueous solution.
- c 4 a method in which formaldehyde and water are supplied continuously or intermittently, and the reaction is carried out while distilling the produced isoprene together with water and other low-boiling components out of the reaction system.
- reaction mixture a part of a mixture of C 4 , formaldehyde, water and an acidic aqueous solution (hereinafter, abbreviated as “reaction mixture”) is used. was removed from the reactor, after it was heated together with at least a portion of the C 4, it is (e.g. is known a manufacturing method of introducing into the reactor again, JP 5 9 1 9 0 9 3 0 No.).
- water may be understood to be included as an aqueous solution such as an acidic aqueous solution
- reaction mixture may contain a product and a by-product of the reaction.
- the isoprene, water, unreacted raw materials and other low-boiling components (hereinafter, referred to as distillate) which are distilled out of the reaction system as a gas.
- the “produced isoprene, water, unreacted raw materials and other low-boiling components” are abbreviated as “reaction distillate gas.”)
- the heat of water is recovered by mainly condensing water in Is used as a heat source for evaporating isobutylene and a heat source for recovering unreacted isobutylene by distillation from the organic layer obtained by condensing the reaction distillate gas and phase-separating it.
- Isoprene production method It is known (see, for example, Japanese Patent Publication No. 60-41838).
- JP-A-59-70623, JP-A-59-19030, and JP-A-59-116326 disclose.
- Simply practicing the production method fluctuates the concentration of high-boiling by-products in the reaction mixture, resulting in unstable acid concentrations in the reaction mixture, which may lead to equipment corrosion and isoprene formation. There is a problem that the reaction performance deteriorates.
- the reaction distillate gas is Although the amount of heat it has can be effectively recovered and reused, it is not satisfactory as a supplement to the amount of heat required for the production of isoprene, and there is still room for improvement for industrial implementation.
- An object of the present invention is to solve the above-mentioned problems and to provide a method for producing isoprene more efficiently than before.
- the present invention achieves the above object by the following features.
- Isobutylene and / or t-butanol, formaldehyde and water are continuously or intermittently fed into an acidic aqueous solution, and isoprene, water, unreacted raw materials and other low boiling points are formed from the reaction mixture.
- a process for producing isoprene by distilling a mixture containing components out of the reaction system and reacting the mixture,
- a reactor containing the reaction mixture is provided with an outlet for the reaction mixture, a part of the reaction mixture is withdrawn from the outlet, and at least at least high-boiling by-products are removed from the reaction mixture. After separating and removing a part, the concentration of the high boiling by-product in the reaction mixture is controlled within the above range by introducing the mixture into the reactor again.
- An outlet for the reaction mixture is provided on the side wall of the reactor, and the height of the outlet is adjusted to the height when the volume of the liquid when the reaction mixture is filled up to the height.
- a mixture containing the produced isoprene, water, unreacted raw materials and other low-boiling components is distilled out of the reaction system as a reaction distillate gas, and water is condensed from the reaction distillate gas.
- the reactor is equipped with a stirring device that is configured so that the stirring blades rotate horizontally in the reaction mixture, and isoprene and / or t-butanol are piped to just below the stirring blades in the reactor.
- the concentration of the high-boiling by-product in the reaction mixture is controlled within the above range by supplying the mixture to the stirring blade from the inlet provided by extending the passage.
- (1) to (5) 3. The method for producing isoprene according to 1.).
- the reactor is provided with a stirring device that is configured so that the stirring blades rotate horizontally in the reaction mixture, and a part of the reaction mixture is withdrawn from the reactor, and this is removed with isobutylene and / or t-butyl acetate.
- the mixture is introduced again into the reactor, and the heated reaction mixture is supplied to the stirring blade from an inlet provided in the reactor.
- FIG. 1 is a schematic diagram of manufacturing equipment for explaining the manufacturing method of the present invention.
- FIG. 2 is a diagram schematically showing a configuration of equipment constructed to carry out the manufacturing method according to the present invention in the embodiment of the present invention.
- the connection inside the heat exchanger is schematically shown by solid lines and broken lines in order to clarify the input / output relationship of piping. However, these do not indicate the internal piping shape.
- FIGS. 1 and 2 The meanings of the reference numerals in FIGS. 1 and 2 are shown below.
- A Reaction mixture
- Pl to P10 Pipeline
- 1 Reactor
- 2, 3, 5, 6, 7, 11, 12 Heat exchanger
- 4 High-boiling by-product separation tank
- 8, 9, 13 Distillation reservoir
- 10, 14 Distillation tower.
- the method for producing isoprene of the present invention is schematically illustrated by the schematic diagram of the production facility shown in FIG.
- a method is used in which a mixture containing isoprene, water, unreacted raw materials, and other low-boiling components is reacted while distilling it out of the reaction system as a reaction distillate gas through a distillation line P2.
- the basic technology of this production method is the same as the conventionally known production technology of isoprene, and is described in JP-A-59-70623 and JP-A-59-190309. Reference may be made to Japanese Unexamined Patent Application Publication No. Sho 60-41838 and Japanese Unexamined Patent Application Publication No. 59-116 1636.
- the concentration of the high-boiling by-product (not shown) generated and accumulated in the reaction mixture A is 0.5.
- the isoprene is produced while controlling the amount to be within the range of 40% by mass.
- Japanese Patent Application Laid-Open No. 59-70623 discloses removal of high-boiling by-products that accumulate during the reaction, and also describes the operation thereof. There is no description of the effect of the concentration on the reaction performance.
- the present invention it has been found that a new action and effect can be obtained by allowing a certain amount of the high-boiling by-product to be present in the reaction mixture, and the concentration is adjusted to 0.5 to 40% by mass. It is characterized in that the operation of removing high-boiling by-products is controlled within the range.
- the high-boiling by-products whose concentration is controlled are usually widely dispersed in the liquid in the reactor, but may be unevenly distributed in the upper or lower part of the reaction mixture depending on the stirring efficiency.
- impurities such as high-boiling organic compounds such as products and by-product multimers in the isoprene production method of the present invention, reaction raw materials, and inorganic substances derived from the reaction apparatus are used. And the like.
- the high-boiling by-product By controlling the concentration of the high-boiling by-product in the reaction mixture within the range of 0.5 to 40% by mass, the high-boiling by-product preferably acts as a heat transfer medium.
- the heating efficiency of the reaction mixture using a heat exchanger or the like can be maintained at a preferable value, and troubles such as clogging of the pipeline by high-boiling by-products do not occur. This Thus, isoprene can be produced more efficiently than in the past.
- the concentration of the high-boiling by-product in the reaction mixture is more preferably in the range of 1 to 30% by mass, and the heat exchange property and the suppression of trapping such as clogging of the pipe are highly enhanced. From the viewpoint of compatibility, it is particularly preferable that the content be in the range of 2 to 20% by mass.
- the concentration of the high-boiling by-product in the reaction mixture is less than 0.5% by mass, the heating efficiency of the reaction mixture decreases, and in the following order, the temperature of the reaction mixture in the reactor decreases, and As a result, the amount of aqueous formaldehyde supplied to the reactor was reduced to maintain the level of the reaction mixture in the reactor at a constant level, and as a result, the amount of isoprene per unit time was reduced. Production volume decreases.
- the amount of heat required for the production of isoprene is considered. The problem is that the use efficiency of the heat exchanger is reduced, high-boiling by-products accumulate in the pipeline, and the pipeline becomes clogged, and the temperature near the heat exchanger surface becomes too high, making it more susceptible to acid corrosion. is there.
- the method for controlling the concentration of the high-boiling by-product in the reaction mixture to be within the above range is not particularly limited.
- a part of the reaction mixture is taken out (hereinafter, the taken out reaction mixture is taken out).
- the taken out reaction mixture is taken out).
- a removal reaction mixture Is sometimes referred to as a “removal reaction mixture”
- a kind of feedback control is a simple control method of returning the mixed solution (hereinafter, sometimes referred to as “reaction mixture after removal”) to the reactor again.
- reaction mixture after removal is a simple control method of returning the mixed solution (hereinafter, sometimes referred to as “reaction mixture after removal”) to the reactor again.
- the reaction mixture is withdrawn from the pipes P 3 and / or P 4, the high-boiling by-product is separated and removed in the high-boiling by-product separation tank 4, and the removed reaction mixture is removed.
- the method for separating and removing high-boiling by-products from the reaction mixture in the high-boiling by-product separation tank 4 is not particularly limited.For example, an extraction method using an organic solvent is preferably used. it can.
- the frequency of withdrawing a part of the reaction mixture in the reactor may be continuous or intermittent.
- the amount of withdrawal may be determined in consideration of the amount of by-products accumulated in the reactor, etc. .
- the concentration of high-boiling by-products in the reaction mixture is determined while continuously withdrawing the reaction mixture at 2 L / hour. Is controlled so as to fall within the range of 0.5 to 40% by mass.
- the method for measuring the concentration of high-boiling by-products in the reaction mixture is not particularly limited.For example, if a part of the reaction mixture is extracted and cooled, the high-boiling by-products are solidified. And measuring the mass to calculate the concentration of the high-boiling by-product in the reaction mixture.
- the concentration of the formaldehyde aqueous solution should be as high as possible from the viewpoint of reducing the amount of heat given to the accompanying water supplied to the reactor as an aqueous solution, that is, the amount of heat required for the production of isoprene. It is good.
- the concentration of the aqueous formaldehyde solution is preferably in the range of 20 to 70% by mass, and more preferably in the range of 25 to 60% by mass.
- the concentration of the aqueous formaldehyde solution is too high, there is a problem that paraformaldehyde is easily precipitated.
- C 4 used in the present invention is 3-methylbutane-1,1,3-diol, 3-methyl-2-buten-1-ol, 3-methyl-1-buten-1-ol, 3-methyl-1-butene-1-ol
- 3-ol methyl isopropyl ketone, 2-methylbutanol, methyl-t-butylformal, 4,4-dimethyl-1,3-dioxane, 4-methyl-5,6-dihydro_2H-pyran, etc. You may go out. It may also contain isobutylene and methyl-t-butyl ether which decomposes into t-butyl under the reaction conditions.
- the acidic aqueous solution used in the present invention is an aqueous solution of an acidic substance such as an inorganic acid, an organic acid, and salts thereof.
- an acidic substance such as an inorganic acid, an organic acid, and salts thereof.
- the acidic substance those having low volatility or non-volatility under the reaction conditions are preferable, for example, inorganic acids (phosphoric acid, sulfuric acid, boric acid, etc.), heteropolyacids (caitungstic acid, phosphotungstic acid, etc.), Organic acids (such as P-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and oxalic acid), and acid salts (such as sodium hydrogen sulfate).
- inorganic acids phosphoric acid, sulfuric acid, boric acid, etc.
- heteropolyacids caitungstic acid, phosphotungstic acid, etc.
- Organic acids such as P-toluenes
- P H of acidic aqueous solution the kind of the acidic substance, the reaction temperature, the feed rate of C 4, but may differ due to the feed rate of Horumua aldehyde, usually, p HO. 5 to 2.
- the production method of the present invention it is possible to carry out the reaction while simultaneously supplying a low-boiling compound or an inert gas which is inert under the reaction conditions to the reactor, if necessary, in addition to the reaction mixture. is there.
- a low-boiling compound or an inert gas which is inert under the reaction conditions to the reactor, if necessary, in addition to the reaction mixture.
- hydrocarbons are preferable, and particularly those having 1 to 10 carbon atoms, for example, n-propane, n-butane, n-hexane, cyclohexane and the like can be mentioned.
- the inert gas nitrogen and the like are preferable.
- the molar ratio of the reactor is supplied c 4 and formaldehyde (hereinafter referred to as "c 4 Horumua aldehyde") is preferably at least 3, and more favorable preferable 5 or more.
- c 4 Horumua aldehyde formaldehyde
- the C 4 / formaldehyde content is preferably 20 or less, more preferably 12 or less. Incidentally, if c 4 7 formaldehyde is less than 3, isoprene yield tends to decrease.
- the unreacted c 4 distilled out of the reaction system has a composition close to the equilibrium composition of isobutylene and t-butanol under the reaction conditions. That is, even if only one of isobutylene and t-butanol is supplied as a starting material to the reactor in the production method of the present invention, unreacted raw materials are separated from the viewpoint of reducing the unit consumption of the raw materials. If separated, collected and reused, a mixture of isobutylene and toluene will be used as a raw material.
- C 4 , formaldehyde and water are supplied continuously or intermittently to an acidic aqueous solution, and from this reaction mixture, the produced isoprene, water, unreacted raw materials and other low-boiling components are removed.
- the reaction is carried out while distilling the mixture containing it out of the reaction system as a reaction distillate gas.
- the pressure in the reactor depends on the reaction temperature. It is preferably in the range of 1.1 to 2.5 times the vapor pressure of the acidic aqueous solution, and more preferably in the range of 1.1 to 2 times.
- the vapor pressure of the acidic aqueous solution at the reaction temperature (hereinafter, abbreviated as Pw) is a physical constant uniquely determined by the type and concentration of the acidic substance contained in the reaction mixture. If the pressure in the reactor exceeds 2.5 times Pw, the yield of isoprene tends to decrease significantly. On the other hand, when the pressure in the reactor is less than 1.1 times Pw, the yield of isoprene does not decrease remarkably, but the conversion of formaldehyde decreases and isoprene in the reaction distillate gas. As the ratio of water to water increases, the amount of heat consumed in the reaction, that is, the amount of heat required to produce isoprene, increases, which is economically disadvantageous.
- the suitable reaction temperature in the present invention is determined in consideration of the acid concentration in the reaction mixture, and is usually preferably in the range of 150 to 220 ° C.
- the reaction temperature is lower than 150 ° C.
- the yield of isoprene tends to decrease even if the concentration of the acidic aqueous solution is increased to maintain the reaction rate at a constant level.
- the reaction temperature exceeded 220 ° C
- the selectivity of isoprene does not decrease remarkably, the reaction conditions under which the conversion of formaldehyde under the condition giving the optimum selectivity decreases and the conversion of formaldehyde increases conversely are selected. It is not beneficial because the sequential reaction from isoprene proceeds to increase by-products, and as a result, the selectivity of isoprene decreases.
- the preferred supply rate of the formaldehyde source (aqueous formaldehyde solution) to the reactor is determined in consideration of the concentration of the acid in the reaction mixture, the reaction temperature and the reaction pressure.
- To increase the supply rate of the formaldehyde source It is necessary to increase the concentration of the acid in the mixture or increase the reaction temperature, in which case the corrosion of the reactor occurs.
- the supply rate of the formaldehyde source is usually preferably in the range of 0.2 to 3 mol hours in terms of formaldehyde per 1 kg of the reaction mixture, and more preferably in the range of 0.5 to 2 mol / hour. More preferred.
- the amount of water supplied to the reactor is usually adjusted so that the amount of the reaction mixture in the reactor is kept constant. That is, the amount is determined by the amount of water distilled from the reactor and the amount of water increased or decreased by the reaction.
- the ratio of the number of moles of water distilled from the reactor to the number of moles of the raw material and product distilled out is determined by the pressure in the reactor.
- the number of moles of starting material and product distilled since approximately equal to the number of moles of C 4 supplied, also the ratio of C 4 supplied with water being distilled may be defined by the pressure in the reactor. Therefore, the amount of water to be supplied, the pressure in the reactor may be determined in consideration of the increase and decrease of water by supply amount and reactivity of c 4.
- high-boiling by-products are generated and accumulated in the reaction mixture as the reaction is performed for a long time. Since the high-boiling by-products are separated and dispersed in the reaction mixture, a part of the reaction mixture in the reactor is continuously or intermittently withdrawn, and a high-boiling by-product separation tank (for example, , Decanter, extraction tower, etc.) Remove at least some of the by-products and control their concentration.
- a high-boiling by-product separation tank for example, Decanter, extraction tower, etc.
- this high-boiling by-product has a small difference in specific gravity with respect to the reaction mixture, and a mixture of large and small specific gravity exists. Therefore, liquid separation operation using a specific gravity difference such as decantation is performed.
- the high-boiling by-product since the high-boiling by-product has a property of solidifying at room temperature, the temperature of the reaction mixture is once lowered to solidify the high-boiling by-product and then separated and removed. However, it is necessary to reheat the reaction mixture. From these points, in order to facilitate the separation of the reaction mixture and the high-boiling by-products, it is preferable to extract and remove using an extraction solvent.
- Such an extraction solvent is preferably a hydrocarbon having a lower boiling point than water, a low solubility in water, and a liquid at normal pressure, such as n-hexane and cyclohexane.
- Compounds contained in the distillation residue include 4-methyl-5,6-dihydro-12H-pyran, methylisopropylketone, 2-methylbutanol, 2,6-dimethyl-2,5-butadiene, 2,6-Dimethyl-1,5-butadiene, 3-methyl-3-buten-2-ol, and the like.
- compounds having various functional groups having 4 to 15 carbon atoms are also available. include.
- a heating device is provided in the reactor itself in order to secure the amount of heat required for producing isoprene and the amount of heat required for distilling isoprene, water, unreacted raw materials and other low-boiling components.
- a suitable auxiliary heating device is preferable.
- a heat exchanger 3 is arranged outside the reactor as an auxiliary heating device, and a reaction between the reactor 1 and the heat exchanger 3 is performed through pipes P7 and P9.
- an embodiment in which the reaction mixture is heated is exemplified.
- the reaction mixture is circulated as it is to an external heat exchanger and heated. Since the amount of isobutylene dissolved in the reaction mixture is small, the boiling point rises in the reactor, and the temperature of the reaction mixture in the heat exchanger rises significantly. An increase in the temperature of the reaction mixture causes an increase in side reactions, which leads to a decrease in isoprene yield. To prevent this, as shown in FIG. 1, the reaction mixture was extracted in conduit P 7 for circulation, adding at least a portion of the C 4 through conduit P 8, the heat exchanger together these A preferred embodiment is that the mixture is heated in the vessel 3 and introduced into the reactor 1 through the line P9.
- t-butyl alcohol prevents the temperature of the reaction mixture from rising due to heating, and is much less effective.
- t - flop evening Nord is by contact with an acidic aqueous solution in the heat exchanger, converted into Isopuchiren, for the first time show the effect described above, as the c 4 be added to the reaction mixture were removed for circulating heating And isobutylene are preferred.
- the calorie of the reaction distillate gas can be recovered and used effectively for the production of isoprene.
- the calorie recovery for example, there is an embodiment in which mainly the water in the reaction distillate gas is condensed to recover the heat of the water (for example, in FIG.shrinking.)
- the heat of the uncondensed reaction distillate gas is used as a heat source for vaporizing isobutylene (for example, in FIG. 2, the heat source is used in the heat exchangers 6 and 7).
- the heat source when unreacted isobutylene in the organic layer obtained by condensing the reaction distillate gas and phase-separating it is recovered by distillation (for example, in Fig. 2, it is used as the heat source in the heat exchanger 11).
- the steam obtained by the heat exchanger 5 may be used as the heating steam in the heat exchanger 11 or the like.
- a part of the reaction mixture is continuously or intermittently controlled in order to control the concentration of the high-boiling by-product in the reaction mixture within the range of 0.5 to 40% by mass.
- an extraction column, etc. remove at least a part of high-boiling by-products from the reaction mixture.
- the present inventors Since the method of removing the high-boiling by-product is the point of the present invention, the present inventors have further studied. As a result, as described above, some of the accumulated high-boiling by-products have a large specific gravity and a small specific gravity with respect to the reaction mixture, and have a specific gravity relative to the reaction mixture in the reactor. It has been found that large high-boiling by-products tend to collect at the bottom of the reaction mixture, that is, at the bottom of the reactor, and high-boiling by-products having a low specific gravity tend to collect at the top of the reaction mixture.
- an outlet for the reaction mixture is provided at least at the bottom of the reactor.
- a sampling line P3 is provided at the center of the bottom of the reactor.
- high-boiling by-products having a higher specific gravity than the reaction mixture are removed outside the reactor when a part of the reaction mixture is continuously or intermittently withdrawn. It is easier to do. It is preferable that such a discharge port is provided at the center of the bottom of the reactor, but the present invention is not limited to this.
- the outlet of the reaction mixture is provided at the side wall of the reactor (reactor).
- the height of the withdrawal port is such that the volume of the liquid when the reaction mixture is filled up to that height is at least 1/2 of the total volume of the reaction mixture to be accommodated at the start of production, and more preferably It is preferable that the height is set to be 2/3 or more (hereinafter, abbreviated as height h).
- reaction mixture outlet is not provided on the side wall of the reactor, the reaction proceeds over a long period of time, and the high-boiling point with a lower specific gravity than the reaction mixture is placed above the reaction mixture.
- concentration of the high-boiling by-product within the range of 0.5 to 40% by mass.
- distilling out of the reaction mixture of isoprene, water, unreacted raw materials and other low-boiling components out of the reactor as a reaction distillate gas is hindered. This raises the problem that the steady state of the reaction cannot be maintained due to the rise, fluctuations in the concentration of the acid in the reaction mixture and the composition ratio of the raw materials.
- the amount of the reaction distillate gas reduced, the amount of aqueous formaldehyde solution supplied to the reactor had to be reduced in order to maintain the level of the reaction mixture in the reactor at a constant level. Production volume decreases.
- a stirrer (an external drive is not shown) is provided so that the stirring blade W rotates horizontally in the reaction mixture in the reactor, and a pipe P 6 for supplying C 4 is connected to the stirring blade in the reactor. extending to just below the., from inlet P 6- 1 to impinge the C 4 to stirring blade, supplied preferably is ejected.
- the distance between the stirring blade and the supply port of C 4 must be strict.
- the distance to the heart tip during the rotation of the stirring blade is 2 m, usually 0. Is preferably a range within 3 m , 0.2 m or less.
- an inlet port P 6- 1 is curved tubes that make up the ring, supplied at appropriate intervals on its circumference
- An embodiment in which a mouth is provided is preferred.
- the radius of curvature of the ring-shaped inlet P6-1 is 50 to 80% of the distance from the rotation center of the stirring blade to the tip.
- the interval between the supply ports provided on the circumference of the ring-shaped inlet port P6-1 is preferably such that the circumference is equally divided by 5 to 100, and is equally divided by 10 to 40. A degree interval is more preferred.
- the reaction mixture heated after the addition of C 4 and then in the heat exchanger 3 is transferred to a pipe P 9.
- a pipe P 9 To the lower part of the reactor, and supply it so as to hit the stirring blade W.
- the lower part of the reactor is not particularly limited as long as the reaction mixture strikes the stirring blade when the reaction mixture is introduced again into the reactor, but the reaction mixture is introduced into the reactor from below the stirring blade. Is preferred.
- reaction mixture returned from the heat exchanger to the reactor is not supplied so as to hit the stirring blade via line P9, the gas and liquid in the reaction mixture in the reactor become insufficiently dispersed.
- the amount of high-boiling by-products increases and accumulates in the reactor, The concentration in the reaction mixture tends to increase.
- water may be decomposed from the reaction distillate gas, and the water thus decomposed may be reused (hereinafter, dewatered from the reaction distillate gas and reused).
- the water used is abbreviated as “recycled water.”)
- the water condensed in the heat exchanger 5 is introduced into the distilling receiving layer 8, supplied to the reactor via the pipe P10-1 and the like, and reused.
- the amount of the reaction mixture in the reactor can be kept constant, and the concentration of the high-boiling by-product in the reaction mixture is 0.5 to 0% by mass. Control within the range becomes easy.
- the temperature of the recycled water is within a range of 120 to 140 ° C (under a pressure of about 1.5 MPa)
- the amount of heat required for producing isoprene can be reduced. If recycled water is not used, i.e. fresh water (typically about 25 ° C) can still control the concentration of high-boiling by-products in the reaction mixture, but until heated to the reaction temperature This is economically disadvantageous because the amount of heat required increases.
- Isoprene can be obtained by fractionating the organic layer of the distillate distilled out of the reaction system by performing the present reaction method.
- steps required until the isoprene is finally fractionated from the distillate distilled from the line P2 in FIG. 1 refer to the known art (for example, Japanese Patent Application Laid-Open No. Sho 60-41838). You may.
- the concentration of the high-boiling by-product in the reaction mixture in the reactor was out of the above range. The significance was confirmed.
- the reactor 1 was prepared tank having an inner volume of 1 2 0 L, this, C 4 inlet conduit P 6, an aqueous formaldehyde solution inlet pipe P 1-1, the water inlet pipe P 1-2, an acidic aqueous solution (phosphate (Aqueous acid solution) Inlet line P1_3, distillate line P2 for products, etc., and reaction mixture withdrawal lines P3 and P4 are connected.
- the reactor is equipped with auxiliary equipment necessary for reaction control, such as a thermometer, a pressure gauge, a stirrer, and a baffle plate.
- reaction from a mixture extraction pipe P 3 branches the conduit P 7, the sampling One reaction mixture from the reactor is mixed with C 4, heating such mixture through the heat exchanger 3, the reactor To return to When returning the reaction mixture heated in the heat exchanger 3 to the inside of the reactor 1, the reaction mixture was jetted toward the stirring blade so as to hit the stirring blade.
- Isoprene generated in the reactor 1 is distilled out of the reactor as a reaction distillate gas through the pipe P2 together with unreacted C 4 , water, formaldehyde and the like. These reaction distillate gases are sent to the heat exchanger 5.
- heat exchange is performed between the reaction distillate gas flowing into the heat exchange pipe and the cooling water flowing into the heat exchanger (that is, the reaction distillate gas is cooled), and the reaction is performed. Water in the distillate gas is fragmented.
- the cooling water that has flowed into the heat exchanger 5 obtains heat from the reaction distillate gas to become steam, and the heat is recovered.
- the water decomposed in the heat exchanger 5 is sent to the distilling tank 8.
- Part of the water in the distilling tank 8 is supplied directly to the reactor through line P 10-1 to be used for adjusting the amount of the reaction mixture in the reactor, and is also connected to line P 10-2. Heat exchange through Is supplied to the vessel 2, it is used to adjust the molar ratio between formaldehyde and C 4, are fed to the reactor 1 by evaporation with C 4. The remainder of the water in distilling tank 8 is sent to distilling tank 9.
- the compounds not condensed in the heat exchanger 5 are condensed in the heat exchangers 6 and 7 and sent to the distillation receiving tank 9, where they are separated into an organic layer and an aqueous layer.
- the organic layer is sent to the heat exchanger 7 where it is heated, and then sent to the distillation column 10 for separating isobutylene.
- the fraction in the distillation column 10 is mainly composed of isobutylene, and is condensed in the heat exchanger 12 and then sent to the distillation receiving tank 13.
- the bottom liquid of the distillation column 10 is mainly composed of isoprene and unreacted t-butanol. By purifying the bottom liquid in the distillation column 14, isoprene is obtained from the top of the column.
- the main component of the bottom liquid of the distillation column 14 is t-butanol, which is separately purified and reused in the production method of the present invention.
- the product is sent to the separation tank 4 and used as an extraction solvent when separating high-boiling by-products from the reaction mixture extracted from the reactor.
- the reaction mixture (including high-boiling by-products) in the reactor 1 is withdrawn from each of the outlets provided near the center of the bottom surface of the reactor and on the side of the reaction mixture on the side wall of the reactor. After being mixed with water, the mixture is sent to a high-boiling by-product separation tank 4, where it is separated into an organic layer (extracting solvent) containing a high-boiling by-product and an aqueous layer.
- the organic layer is effectively used for applications such as fuel, and the aqueous phosphoric acid solution in the aqueous layer is at least partially recycled to the reactor.
- Sampling of the reaction mixture for measuring the concentration of high-boiling by-products in the reaction mixture in the reactor can be performed, for example, by providing outlets in the pipelines P3, P4, and P7. While confirming the concentration of the high-boiling by-product in the reaction mixture, stopping and executing the removal of the reaction mixture from the outlet so that the concentration falls within the range of 0.5 to 40% by mass. Is appropriately performed.
- the reaction conditions in the reactor were a reaction temperature of 175 to 178 ° C, a reaction pressure of 1.52 MPa, and a rotation speed of the stirring blade of 48 to 55 rpm.
- a reactor (internal volume 120L) was charged with 60L of 2.5% phosphoric acid aqueous solution, and under the above reaction conditions, 46% by mass aqueous formaldehyde solution was 3.24 kg / hour, isobutylene was 17.7 kg / hour, The reaction was started by continuously supplying t-butanol at a rate of 6.02 kg / hour and water at a rate of 9.08 kg / hour.
- the concentration of the high-boiling by-products in the reaction mixture is adjusted to a predetermined value as described below by adjusting the removal amount of the high-boiling by-products mainly in the high-boiling by-product separation tank 4. It controlled so that it might become.
- the controlled high-boiling by-product concentrations are as follows:
- Example 1 0.5% by mass (Example 1), 1% by mass (Example 2), 2% by mass (Example 3), 5% by mass (Example 4), 10% by mass (Example 5), 20% by mass (Example 6), 30% by mass (Example 7), 40% by mass (Example 8).
- Example 18 The respective reactions were carried out according to Example 18 and Comparative Example 14.
- concentration of the high-boiling by-product in the reaction mixture was 0.540% by mass (Example 1).
- the steady state of the reaction in the reactor can be maintained, the conversion of formaldehyde is always 98% or more, and the yield of isoprene is always 71% or more. I understand.
- the concentration of high-boiling by-products in the reaction mixture was 0.540 It was found that by maintaining the amount within the range of%, isoprene can be efficiently produced while maintaining the steady state of the reaction.
- the method for producing isoprene of the present invention can be carried out by a known method for producing isoprene (for example, see JP-A-56-79628 and HYDROCARBON PROCESSING, page 167 (January 1971). This is advantageous because the manufacturing process is simpler and the utility can be kept low. The fact that the yield improvement which could not be achieved by this method could be increased by about 2% in the present method is extremely advantageous in the field of the present invention from the viewpoint of production cost. .
- the isoprene obtained by the production method of the present invention is effectively used as a basic chemical raw material for various chemical products and polymer raw materials.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04723001.6A EP1614671B1 (en) | 2003-03-31 | 2004-03-24 | Process for producing isoprene |
US10/551,596 US7442844B2 (en) | 2003-03-31 | 2004-03-24 | Process for producing isoprene |
JP2005504179A JP3917163B2 (ja) | 2003-03-31 | 2004-03-24 | イソプレンの製造方法 |
CN200480008845XA CN1768020B (zh) | 2003-03-31 | 2004-03-24 | 制造异戊二烯的方法 |
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JP2003095152 | 2003-03-31 | ||
JP2003-095152 | 2003-03-31 |
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WO2004087625A1 true WO2004087625A1 (ja) | 2004-10-14 |
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PCT/JP2004/004038 WO2004087625A1 (ja) | 2003-03-31 | 2004-03-24 | イソプレンの製造方法 |
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US (1) | US7442844B2 (ja) |
EP (1) | EP1614671B1 (ja) |
JP (1) | JP3917163B2 (ja) |
CN (1) | CN1768020B (ja) |
RU (1) | RU2320627C2 (ja) |
WO (1) | WO2004087625A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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RU2553823C1 (ru) * | 2014-05-28 | 2015-06-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Способ получения изопрена |
WO2016194983A1 (ja) * | 2015-06-03 | 2016-12-08 | 株式会社クラレ | 共役ジエンの製造方法 |
Families Citing this family (8)
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RU2365574C1 (ru) * | 2008-03-17 | 2009-08-27 | Общество с ограниченной ответственностью "Еврохим-СПб-Трейдинг" | Способ переработки побочных продуктов жидкофазного синтеза изопрена из изобутилена и формальдегида |
BR112012014736B1 (pt) * | 2009-12-18 | 2018-09-18 | Danisco Us Inc | método para purificação de isopreno a partir de um efluente gasoso do fermentador e composição |
CN101880210B (zh) * | 2010-06-25 | 2013-04-24 | 浙江工业大学 | 一种共轭二烯类化合物的制备方法 |
US9115040B2 (en) | 2010-09-24 | 2015-08-25 | Total Research & Technology Feluy | Production of isoprene from iso-butanol |
CN102516009B (zh) * | 2011-11-16 | 2014-05-21 | 万华化学集团股份有限公司 | 一种液相法制备异戊二烯的方法 |
EP3040325A1 (en) | 2014-12-31 | 2016-07-06 | Shell Internationale Research Maatschappij B.V. | Process for preparing ethylene, propylene and isoprene |
CN105152832A (zh) * | 2015-10-13 | 2015-12-16 | 宁波金海晨光化学股份有限公司 | 一种合成异戊二烯的工艺方法 |
CN113582826B (zh) * | 2021-08-18 | 2023-09-12 | 阿拉善经济开发区新鑫化工有限责任公司 | 用酸碱试剂去除甲基异丙基甲酮生产中杂质异戊醛的方法及应用 |
Citations (3)
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JPS5062905A (ja) * | 1973-09-22 | 1975-05-29 | ||
JPS5970623A (ja) * | 1982-10-14 | 1984-04-21 | Kuraray Co Ltd | イソプレンの製造方法 |
JPS604138A (ja) | 1983-06-20 | 1985-01-10 | Kuraray Co Ltd | イソプレンの製造法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CA1215083A (en) * | 1982-10-14 | 1986-12-09 | Yoichi Ninagawa | Process for producing isoprene |
US4511751A (en) * | 1982-10-14 | 1985-04-16 | Kuraray Company, Ltd. | Process for producing isoprene |
US4593145A (en) * | 1984-03-12 | 1986-06-03 | Kuraray Company Limited | Process for producing isoprene |
RU2128637C1 (ru) | 1997-08-20 | 1999-04-10 | Закрытое акционерное общество "Еврохим" | Способ получения изопрена |
RU2177469C1 (ru) * | 2000-09-18 | 2001-12-27 | Общество с ограниченной ответственностью "ЕВРОХИМ - СПб" | Способ получения изопрена |
-
2004
- 2004-03-24 US US10/551,596 patent/US7442844B2/en active Active
- 2004-03-24 JP JP2005504179A patent/JP3917163B2/ja not_active Expired - Lifetime
- 2004-03-24 EP EP04723001.6A patent/EP1614671B1/en not_active Expired - Lifetime
- 2004-03-24 WO PCT/JP2004/004038 patent/WO2004087625A1/ja active Application Filing
- 2004-03-24 RU RU2005133453/04A patent/RU2320627C2/ru active
- 2004-03-24 CN CN200480008845XA patent/CN1768020B/zh not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5062905A (ja) * | 1973-09-22 | 1975-05-29 | ||
JPS5970623A (ja) * | 1982-10-14 | 1984-04-21 | Kuraray Co Ltd | イソプレンの製造方法 |
JPS604138A (ja) | 1983-06-20 | 1985-01-10 | Kuraray Co Ltd | イソプレンの製造法 |
Non-Patent Citations (1)
Title |
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See also references of EP1614671A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2553823C1 (ru) * | 2014-05-28 | 2015-06-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Способ получения изопрена |
WO2016194983A1 (ja) * | 2015-06-03 | 2016-12-08 | 株式会社クラレ | 共役ジエンの製造方法 |
KR20180015632A (ko) | 2015-06-03 | 2018-02-13 | 주식회사 쿠라레 | 공액 디엔의 제조 방법 |
US11198657B2 (en) | 2015-06-03 | 2021-12-14 | Kuraray Co., Ltd. | Method for producing conjugated diene |
Also Published As
Publication number | Publication date |
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EP1614671A4 (en) | 2010-03-24 |
EP1614671A1 (en) | 2006-01-11 |
CN1768020A (zh) | 2006-05-03 |
JP3917163B2 (ja) | 2007-05-23 |
US7442844B2 (en) | 2008-10-28 |
JPWO2004087625A1 (ja) | 2006-06-29 |
RU2005133453A (ru) | 2006-07-10 |
CN1768020B (zh) | 2010-04-21 |
EP1614671B1 (en) | 2015-08-19 |
US20070106104A1 (en) | 2007-05-10 |
RU2320627C2 (ru) | 2008-03-27 |
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