WO2023190038A1 - 第三級ブチルアルコールの製造方法 - Google Patents

第三級ブチルアルコールの製造方法 Download PDF

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WO2023190038A1
WO2023190038A1 PCT/JP2023/011523 JP2023011523W WO2023190038A1 WO 2023190038 A1 WO2023190038 A1 WO 2023190038A1 JP 2023011523 W JP2023011523 W JP 2023011523W WO 2023190038 A1 WO2023190038 A1 WO 2023190038A1
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Prior art keywords
reactor
tertiary butyl
butyl alcohol
isobutylene
raw material
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PCT/JP2023/011523
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English (en)
French (fr)
Japanese (ja)
Inventor
隼輔 橋本
貴史 豊田
祐吾 溝越
篤史 柳楽
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to KR1020247033298A priority Critical patent/KR20240158324A/ko
Priority to CN202380030871.5A priority patent/CN118973987A/zh
Priority to JP2024512271A priority patent/JPWO2023190038A1/ja
Publication of WO2023190038A1 publication Critical patent/WO2023190038A1/ja
Priority to US18/898,518 priority patent/US20250019327A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins

Definitions

  • the present invention relates to a method for producing tertiary butyl alcohol (hereinafter also referred to as TBA).
  • Tertiary butyl alcohol is used as a raw material for the production of methyl methacrylate by gas phase catalytic oxidation.
  • a method for producing tertiary butyl alcohol a method is known in which isobutylene (2-methylpropene) and water are subjected to a hydration reaction using a catalyst. In this reaction, since the mutual solubility of raw materials isobutylene and water is low, the reaction generally occurs in a heterogeneous liquid phase in which isobutylene and water are phase separated.
  • Patent Document 1 and Patent Document 2 disclose a method in which isobutylene and water are brought into contact with each other on the surface of strongly acidic cation exchange resin catalyst particles using a predetermined method. The method is described.
  • Patent Document 1 and Patent Document 2 have a low reaction rate, and a large reactor is required to ensure production volume, which increases equipment costs. Therefore, from an industrial perspective, a method that can realize a higher reaction rate is desired.
  • Patent Document 3 describes a method of reacting in a homogeneous liquid phase using an aqueous solution of aliphatic carboxylic acid having 1 to 6 carbon atoms.
  • this method requires a step of separating the carboxylic acid ester of tertiary butyl alcohol from the reaction solution in order to obtain tertiary butyl alcohol, which increases equipment costs.
  • Patent Document 4 describes a method in which the reaction is carried out in a homogeneous liquid phase and includes a tertiary butyl alcohol separation step in the middle.
  • an aqueous tertiary butyl alcohol solution is added to the reactor to form a homogeneous liquid phase, so the conversion rate is limited by equilibrium.
  • Japanese Unexamined Patent Publication No. 54-030104 Japanese Unexamined Patent Publication No. 54-30105 Special Publication No. 60-051451 Japanese Unexamined Patent Publication No. 60-233024
  • the present invention has been made to solve the above problems, and its purpose is to provide a method for producing tertiary butyl alcohol with a high isobutylene conversion rate while reducing equipment costs and manufacturing costs. .
  • the present inventors have conducted extensive studies to solve the above problems. As a result, surprisingly, even in a reaction in a heterogeneous liquid phase separated into an isobutylene phase and an aqueous phase, the linear velocity of the raw material liquid and the volume of the aqueous phase in the fluid during the hydration reaction can be kept within a specific range. It was discovered that a sufficient reaction rate could be obtained, and the present invention was completed. That is, the present invention includes the following.
  • a method for producing tertiary butyl alcohol comprising: (i) supplying a raw material liquid containing isobutylene and water to a reactor having a cation exchange resin; (ii) producing a reaction product containing tertiary butyl alcohol by a hydration reaction of isobutylene in the reactor;
  • a method for producing tertiary butyl alcohol wherein the volume (Vw) of the aqueous phase in the fluid A is 4 to 12% by volume with respect to the total volume of the fluid (fluid A) in the reactor.
  • [2] The method for producing tertiary butyl alcohol according to [1], wherein in the step (ii), the average linear velocity of the raw material liquid on a sky column basis is 5 to 29 m/hr.
  • [3] The method for producing tertiary butyl alcohol according to [1] or [2], wherein in the step (ii), the average linear velocity of the raw material liquid on a sky column basis is 7 to 13 m/hr. .
  • [4] The method for producing tertiary butyl alcohol according to any one of [1] to [3], wherein in the step (ii), the Vw is 5 to 10% by volume.
  • [5] The method for producing tertiary butyl alcohol according to any one of [1] to [4], wherein in the step (ii), the outlet temperature of the reactor is 75° C. or lower.
  • a numerical range expressed using " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower limit and upper limit, and "A to B” means A This means that it is greater than or equal to B and less than or equal to B.
  • the method for producing tertiary butyl alcohol according to the present embodiment includes the following steps (i) and (ii).
  • (i) A step of supplying a raw material solution containing isobutylene and water to a reactor having a cation exchange resin.
  • (ii) In the reactor, a reaction product containing tertiary butyl alcohol is produced by a hydration reaction of isobutylene.
  • the average linear velocity of the raw material liquid on the empty column basis calculated by the following formula (I) is 5 m/hr. That's all.
  • Average linear velocity of raw material liquid (m/hr) Volumetric flow rate of raw material liquid (m 3 /hr) / Cross-sectional area of reactor (m 2 ) (I) Further, the volume (Vw) of the aqueous phase in the fluid A is 4 to 12% by volume with respect to the total volume of the fluid (fluid A) in the reactor.
  • the method for producing tertiary butyl alcohol according to the present embodiment further includes the following step (iii).
  • step (iii) Step of separating unreacted isobutylene from the reaction product containing tertiary butyl alcohol produced in step (ii) to produce tertiary butyl alcohol.
  • step (i) a raw material liquid containing isobutylene and water is supplied to a reactor having a cation exchange resin.
  • any form such as a stirred tank type reactor, fixed bed type reactor, or column type reactor can be used.
  • the reaction mode may be a batch type, a semi-batch type, or a continuous flow type.
  • the reactors may be provided in series or in parallel, preferably a plurality of reactors are provided in series as shown in Figure 1, and 2 to 5 reactors are provided in series. is more preferable.
  • the effects of the present invention can be obtained as long as the average linear velocity of the raw material liquid and the Vw satisfy specified conditions in at least one reactor.
  • the term "reactor" in this specification means the reactor to which the raw material liquid is first supplied, unless otherwise specified.
  • the cation exchange resin a strongly acidic cation exchange resin is preferable. Examples include Revachit (trade name) manufactured by Bayer and Amberlyst (trade name) manufactured by DuPont.
  • the position of the cation exchange resin in the reactor, the proportion of the cation exchange resin in the reactor, etc. are not particularly limited, and commonly used forms can be applied.
  • the reactor shown in FIG. 1 supplies raw materials, isobutylene and water, from an isobutylene supply port 1 and a water supply port 2, respectively, and transfers the raw materials to a first reactor 5 using a pump 3.
  • the raw material is cooled to a predetermined temperature by the raw material cooler 4.
  • the reactant in the first reactor 5 is transferred to the second reactor 7, and a portion thereof is supplied again as a raw material.
  • the reactant in the first reactor 5 is cooled to a predetermined temperature by the raw material cooler 6.
  • the reactants in the second reactor 7 are cooled by a raw material cooler 8 and transferred to a third reactor 9.
  • the reactant in the third reactor 9 is transferred to the TBA separation column 10.
  • unreacted isobutylene in the reactant in the third reactor 9 is cooled by a condenser 11 and discharged from an unreacted isobutylene outlet 13 . Further, the TBA in the reactant in the third reactor 9 is heated by the reboiler 12 and discharged from the TBA outlet 14, and a part of it is returned to the first reactor 5 from the TBA circulation line 15 as a raw material. Supplied.
  • the raw material liquid contains isobutylene and water.
  • the concentration of isobutylene in the raw material liquid is preferably 4 to 35 mol%.
  • the reaction rate of the hydration reaction is improved in step (ii) described below.
  • the isobutylene concentration is 35 mol % or less, isobutylene can be obtained at a low cost, so manufacturing costs can be suppressed.
  • the lower limit of the isobutylene concentration is more preferably 8 mol% or more, and the upper limit is more preferably 18 mol% or less.
  • Water is not particularly limited, but deionized water, distilled water, etc. are preferred, and deionized water is more preferred. Impurities in water can deactivate the catalyst and adversely affect product quality, so it is preferable to remove them as much as possible.
  • the raw material liquid may contain tertiary butyl alcohol.
  • the amount of tertiary butyl alcohol supplied per unit time to the reactor in step (i) is Mi (mol/hr)
  • the amount of tertiary butyl alcohol produced per unit time in step (iii) described below is Mi (mol/hr).
  • the amount of butyl alcohol is Miii (mol/hr)
  • it is preferable that Mi/Miiii is 1 to 7. This improves the isobutylene conversion rate in the step (ii) described later, so that the manufacturing cost can be suppressed in the step (iii) described later.
  • the upper limit of Mi/Miii is more preferably 5 or less, even more preferably 4.5 or less, and particularly preferably 4 or less.
  • the tertiary butyl alcohol contained in the raw material liquid may include recycled TBA using tertiary butyl alcohol produced in step (iii) described below.
  • Mi/Miii can be adjusted, for example, by changing the feed rate of the raw material liquid supplied to the reactor or the tertiary butyl alcohol concentration of the raw material liquid.
  • the raw material liquid may also contain hydrocarbons and the like in addition to the above.
  • the hydrocarbon is one or more types selected from hydrocarbons having 4 carbon atoms, such as butenes other than isobutylene (1-butene and/or 2-butene) and butanes (n-butane, isobutane, etc.). It is preferable.
  • Such isobutylene-containing hydrocarbons are by-products obtained when ethylene is obtained by thermally cracking naphtha in the presence of steam, by-products obtained during catalytic cracking of heavy oil, or from these by-products. It can be obtained by removing butadiene.
  • step (ii) described below so that the average linear velocity based on the empty column calculated by the formula (I) is 5 m/hr or more. This improves the reaction rate of the hydration reaction when Vw is within the specified range in step (ii).
  • the reason for this is thought to be as follows.
  • step (ii) described below when Vw is within a specified range, a portion of the aqueous phase is dispersed in the isobutylene phase to form water droplets. At this time, if the raw material liquid is supplied at a specified rate, the diameter of the water droplets will decrease and the number of water droplets will increase.
  • the lower limit of the average linear velocity of the raw material liquid is preferably 7 m/hr or more, more preferably 8 m/hr or more.
  • the upper limit is preferably 29 m/hr, more preferably 15 m/hr, even more preferably 14 m/hr, particularly preferably 13 m/hr, and most preferably 12 m/hr. preferable.
  • step (ii) a reaction product containing tertiary butyl alcohol is produced by a hydration reaction of isobutylene in the reactor.
  • step (ii) the average linear velocity of the raw material liquid based on the empty column calculated by the following formula (I) is 5 m/hr or more.
  • Average linear velocity of raw material liquid (m/hr) Volumetric flow rate of raw material liquid (m 3 /hr) / Cross-sectional area of reactor (m 2 ) (I)
  • the volumetric flow rate of the raw material liquid is the volumetric flow rate of the raw material liquid supplied to the reactor in the step (i).
  • the cross-sectional area of the reactor is the cross-sectional area using an interpolated portion in the reactor.
  • the cross-sectional area of the reactor is not uniform, the cross-sectional area of the part of the reactor with the largest cross-sectional area is taken as the cross-sectional area.
  • the average linear velocity of the raw material liquid based on the sky column can be adjusted, for example, by changing the volumetric flow rate of the raw material liquid supplied to the reactor in step (i).
  • the volume (Vw) of the aqueous phase in the fluid A is 4 to 12% by volume with respect to the total volume of the fluid (fluid A) in the reactor.
  • the aqueous phase herein means a phase containing 90 mol% or more of water.
  • the fact that fluid A has an aqueous phase means that the reaction takes place in a heterogeneous liquid phase separated into an aqueous phase and an isobutylene phase within the reactor.
  • Vw is within the specified range, the reaction rate of the isobutylene hydration reaction is improved.
  • Vw can be adjusted, for example, by adjusting the concentration of tertiary butyl alcohol contained in the raw material liquid.
  • Vw can be set to 4 to 12% by volume.
  • Vw can be set to 5 to 10% by volume.
  • Vw is 4 to 12 volume %. Based on the composition of hydrocarbons, water, and TBA in the raw material liquid containing tertiary butyl alcohol, if the composition of fluid A is within the range shown by the shaded area in Figure 2, it is determined that Vw is 4 to 12% by volume. can. Similarly, if the composition of fluid A is within the range shown by the shaded area in FIG. 3, it can be determined that Vw is 5 to 10% by volume. Further, Vw can also be determined by the following method.
  • the outlet temperature of the reactor during the hydration reaction is preferably 75°C or lower. Thereby, the amount of by-products produced in the hydration reaction can be suppressed. This is thought to be because by setting the reaction temperature to 75° C. or lower, the relative reaction rate of side reactions such as the dimerization reaction of isobutylene to the hydration reaction rate of isobutylene can be kept small. More preferably, the lower limit of the reactor outlet temperature is 40°C or higher, and the upper limit is 65°C or lower.
  • the pressure inside the reactor during the hydration reaction is preferably 0.2 to 2.0 MPa (G). However, (G) indicates gauge pressure. This sufficiently liquefies the raw material isobutylene.
  • the lower limit of the pressure in the reactor is more preferably 0.4 MPa (G), and the upper limit is more preferably 1.6 MPa (G).
  • an inert gas that does not participate in the hydration reaction may be introduced into the reactor. Examples of the inert gas include nitrogen, argon, and the like.
  • step (iii) In step (iii), unreacted isobutylene is separated from the reaction product containing tertiary butyl alcohol produced in step (ii) to produce tertiary butyl alcohol.
  • a separation device such as a distillation device, an extraction device, a membrane separation device, etc. can be used to separate unreacted isobutylene, and it is preferable to use a distillation device.
  • the distillation apparatus it is preferable to use a distillation column or a flash drum.
  • the distillation column a plate column or a packed column is used, and a plate column is preferable.
  • the temperature and pressure are generally such that unreacted isobutylene is vaporized and tertiary butyl alcohol is liquefied.
  • the tower top temperature is preferably 20 to 70°C, and the tower bottom temperature is preferably 100 to 160°C. Further, the tower top pressure is preferably 0.25 to 0.9 MPa (G). As described above, tertiary butyl alcohol can be produced at a high isobutylene conversion rate while reducing equipment costs and manufacturing costs.
  • Average linear velocity of raw material liquid volumetric flow rate of raw material liquid (m 3 /hr) / Cross-sectional area of reactor (m 2 ) (I) Note that the cross-sectional area of the reactor was the cross-sectional area excluding the interpolated material in the reactor.
  • Vw Vw was determined by the following procedure. Using Aspen Plus manufactured by Aspen Technology, from the composition, temperature and pressure of fluid A, the density D (mol/m 3 ) of fluid A, the density Dw (mol/m 3 ) of the aqueous phase of fluid A, and the isobutylene of fluid A The density Do (mol/m 3 ) of the phase was calculated. Note that the outlet temperature and pressure of the first reactor 5 were used as the temperature and pressure of the fluid A.
  • the amount of steam heated by the reboiler was determined by measuring the amount of steam supplied to the reboiler 12 with a flow meter.
  • Example 1 Using the reaction apparatus shown in FIG. 1, DuPont's Amberlyst 15 was filled as a cation exchange resin. Note that fixed bed reactors are used as the first reactor 5, the second reactor 7, and the third reactor 9, and the amount of cation exchange resin charged is 100 parts in the first reactor 5 and 100 parts in the second reactor 7. and 50 parts in the third reactor 9. A raw material liquid having an isobutylene concentration of 12.0 mol%, a water concentration of 33.6 mol%, and a TBA concentration of 29.8 mol% is supplied so that the average linear velocity in the first reactor 5 becomes the value shown in Table 1. did. Note that the raw material liquid contained recycled TBA, and Mi/Miii was 4.15.
  • Isobutylene is hydrated under the following conditions: the reactor inlet temperature of the first reactor 5 is adjusted to 52.2°C, the reactor outlet temperature is 65.0°C, the pressure is 0.876 MPa (G), and the average residence time is 0.634 hours. The reaction was carried out. Next, 30.3% by mass of the reaction product obtained in the first reactor 5 was supplied to the second reactor 7. In the second reactor 7, isobutylene is hydrated under the following conditions: the reactor inlet temperature is adjusted to 50.0°C, the reactor outlet temperature is 53.8°C, the pressure is 0.804 MPa (G), and the average residence time is 1.05 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9.
  • the reactor inlet temperature was adjusted to 53.1°C
  • the reactor outlet temperature was 56.3°C
  • the pressure was 0.800 MPa (G)
  • the average residence time was 1.04 hours to hydrate isobutylene.
  • the reaction was carried out.
  • the Vw in the first reactor 5 and the total isobutylene conversion in all reactors are shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 61.1 mol%. .
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • Example 2 The reactor, cation exchange resin, and its filling amount were the same as in Example 1.
  • a raw material liquid having an isobutylene concentration of 11.7 mol%, a water concentration of 31.4 mol%, and a TBA concentration of 30.0 mol% is supplied so that the average linear velocity in the first reactor 5 becomes the value shown in Table 1. did.
  • Isobutylene is hydrated under the following conditions: the reactor inlet temperature of the first reactor 5 is adjusted to 52.7°C, the reactor outlet temperature is 64.9°C, the pressure is 0.875 MPa (G), and the average residence time is 0.618 hours. The reaction was carried out.
  • the second reactor 7 was used for hydration of isobutylene under the following conditions: the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 53.3°C, the pressure was 0.805 MPa (G), and the average residence time was 1.04 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 52.9°C, the reactor outlet temperature was 55.5°C, the pressure was 0.800 MPa (G), and the average residence time was 1.03 hours to hydrate isobutylene. The reaction was carried out.
  • the Vw in the first reactor 5 and the total isobutylene conversion in all reactors are shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 63.9 mol%.
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • Example 3 The reactor, cation exchange resin, and its filling amount were the same as in Example 1.
  • a raw material liquid having an isobutylene concentration of 16.8 mol%, a water concentration of 31.2 mol%, and a TBA concentration of 18.8 mol% is supplied so that the average linear velocity in the first reactor 5 becomes the value shown in Table 1. did. Note that the raw material liquid did not contain recycled TBA, and Mi/Miii was 2.22.
  • Isobutylene is hydrated under the following conditions: the reactor inlet temperature of the first reactor 5 is adjusted to 49.2°C, the reactor outlet temperature is 65.0°C, the pressure is 0.860 MPa (G), and the average residence time is 0.642 hours. The reaction was carried out.
  • the second reactor 7 was used for hydration of isobutylene under the following conditions: the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 58.8°C, the pressure was 0.797 MPa (G), and the average residence time was 1.18 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 54.0°C, the pressure was 0.800 MPa (G), and the average residence time was 1.18 hours to hydrate isobutylene. The reaction was carried out.
  • the Vw in the first reactor 5 and the total isobutylene conversion in all reactors are shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 64.6 mol%.
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • Example 4 The reactor, cation exchange resin, and its filling amount were the same as in Example 1.
  • a raw material liquid having an isobutylene concentration of 16.0 mol%, a water concentration of 32.4 mol%, and a TBA concentration of 22.7 mol% is supplied so that the average linear velocity in the first reactor 5 becomes the value shown in Table 1. did. Note that the raw material liquid contained recycled TBA, and Mi/Miii was 3.50.
  • Isobutylene is hydrated under the following conditions: the reactor inlet temperature of the first reactor 5 is adjusted to 54.6°C, the reactor outlet temperature is 64.9°C, the pressure is 0.903 MPa (G), and the average residence time is 0.482 hours. The reaction was carried out.
  • the second reactor 7 was used for hydration of isobutylene under the following conditions: the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 61.2°C, the pressure was 0.807 MPa (G), and the average residence time was 1.05 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 53.0°C, the reactor outlet temperature was 58.3°C, the pressure was 0.800 MPa (G), and the average residence time was 1.04 hours to hydrate isobutylene. The reaction was carried out.
  • the Vw in the first reactor 5 and the total isobutylene conversion in all reactors are shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 63.5 mol%.
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • Example 5 The reactor, cation exchange resin, and its filling amount were the same as in Example 1.
  • a raw material liquid having an isobutylene concentration of 14.6 mol%, a water concentration of 28.0 mol%, and a TBA concentration of 20.6 mol% is supplied so that the average linear velocity in the first reactor 5 becomes the value shown in Table 1. did. Note that the raw material liquid did not contain recycled TBA, and Mi/Miii was 4.71.
  • Isobutylene is hydrated under the following conditions: the reactor inlet temperature of the first reactor 5 is adjusted to 58.6°C, the reactor outlet temperature is 65.0°C, the pressure is 1.06 MPa (G), and the average residence time is 0.425 hours. The reaction was carried out.
  • the second reactor 7 was used for hydration of isobutylene under the following conditions: the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 62.0°C, the pressure was 0.870 MPa (G), and the average residence time was 1.52 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 52.0°C, the reactor outlet temperature was 56.2°C, the pressure was 0.841 MPa (G), and the average residence time was 1.52 hours to hydrate isobutylene. The reaction was carried out.
  • the Vw in the first reactor 5 and the total isobutylene conversion in all reactors are shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 62.6 mol%. .
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • the second reactor 7 was used for hydration of isobutylene under the following conditions: the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 54.1°C, the pressure was 0.812 MPa (G), and the average residence time was 0.999 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 53.2°C, the pressure was 0.800 MPa (G), and the average residence time was 0.999 hours to hydrate isobutylene. The reaction was carried out.
  • fluid A was a homogeneous phase and did not have an isobutylene phase and an aqueous phase.
  • the total isobutylene conversion in all reactors is shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 62.5 mol%. .
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • the second reactor 7 hydrates isobutylene under the following conditions: the reactor inlet temperature is adjusted to 50.0°C, the reactor outlet temperature is 53.4°C, the pressure is 0.815 MPa (G), and the average residence time is 0.978 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 53.1°C, the pressure was 0.800 MPa (G), and the average residence time was 0.978 hours to hydrate isobutylene. The reaction was carried out.
  • fluid A was a homogeneous phase and did not have an isobutylene phase and an aqueous phase.
  • the total isobutylene conversion in all reactors is shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 61.9 mol%. .
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • a raw material liquid having an isobutylene concentration of 13.7 mol%, a water concentration of 34.1 mol%, and a TBA concentration of 29.4 mol% is supplied so that the average linear velocity in the first reactor 5 becomes the value shown in Table 1. did. Note that the raw material liquid contained recycled TBA, and Mi/Miii was 3.79.
  • Isobutylene is hydrated under the following conditions: the reactor inlet temperature of the first reactor 5 is adjusted to 51.1°C, the reactor outlet temperature is 65.1°C, the pressure is 0.902 MPa (G), and the average residence time is 0.610 hours. The reaction was carried out. Next, 35.0% by mass of the reaction product obtained in the first reactor 5 was supplied to the second reactor 7.
  • the second reactor 7 was used for hydration of isobutylene under the following conditions: the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 54.0°C, the pressure was 0.828 MPa (G), and the average residence time was 0.873 hours. The reaction was carried out. Then, the entire amount of the reaction product obtained in the second reactor 7 was supplied to the third reactor 9. In the third reactor 9, the reactor inlet temperature was adjusted to 50.0°C, the reactor outlet temperature was 53.3°C, the pressure was 0.800 MPa (G), and the average residence time was 0.873 hours to hydrate isobutylene. The reaction was carried out.
  • the Vw in the first reactor 5 and the total isobutylene conversion in all reactors are shown in Table 1.
  • the reaction product containing TBA obtained from the third reactor 9 was supplied to the TBA separation column 10, and unreacted isobutylene was separated by distillation to obtain a TBA aqueous solution with a TBA concentration of 61.4 mol%. .
  • Table 1 shows the amount of reboiler heating steam required to produce 1000 parts of the TBA aqueous solution.
  • Examples 1 to 5 in which the average linear velocity and Vw of the raw material liquid met the specified conditions, were able to produce TBA with a higher isobutylene conversion than the comparative example. Furthermore, the amount of reboiler heating steam in the TBA separation tower was smaller than that of the comparative example, indicating that manufacturing costs could be suppressed. Furthermore, unlike the conventional method, there is no need for the step of separating carboxylic acid ester of TBA, so equipment costs can be reduced.
  • tertiary butyl alcohol can be obtained at a high conversion rate while reducing equipment costs and manufacturing costs.
  • Isobutylene supply port 2 Water supply port 3: Pump 4: Raw material cooler 5: First reactor 6: Raw material cooler 7: Second reactor 8: Raw material cooler 9: Third reactor 10: TBA separation Column 11: Condenser 12: Reboiler 13: Unreacted isobutylene outlet 14: TBA outlet 15: TBA circulation line

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5430104A (en) * 1977-08-08 1979-03-06 Nippon Oil Co Ltd Continuous production of tertiary butyl alcohol
JPS5585529A (en) * 1978-12-22 1980-06-27 Nippon Oil Co Ltd Separation and recovery of isobutene
JPS60233024A (ja) * 1984-05-02 1985-11-19 Mitsui Toatsu Chem Inc 第３級ブチルアルコ−ルの製造方法
WO2006064874A1 (ja) * 2004-12-17 2006-06-22 Mitsubishi Rayon Co., Ltd. 第三級ブチルアルコールの製造法
CN101423454A (zh) * 2007-11-01 2009-05-06 中国石油天然气股份有限公司 一种由含异丁烯的碳四烃反应萃取制叔丁醇的方法
JP2012219042A (ja) * 2011-04-06 2012-11-12 Mitsubishi Rayon Co Ltd 不均一液相反応方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5430105A (en) 1977-08-10 1979-03-06 Nippon Oil Co Ltd Continuous production of tertiary butyl alcohol
JPS6051451A (ja) 1983-08-26 1985-03-22 Sankyo Seiki Mfg Co Ltd リニアステツピングモ−タ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5430104A (en) * 1977-08-08 1979-03-06 Nippon Oil Co Ltd Continuous production of tertiary butyl alcohol
JPS5585529A (en) * 1978-12-22 1980-06-27 Nippon Oil Co Ltd Separation and recovery of isobutene
JPS60233024A (ja) * 1984-05-02 1985-11-19 Mitsui Toatsu Chem Inc 第３級ブチルアルコ−ルの製造方法
WO2006064874A1 (ja) * 2004-12-17 2006-06-22 Mitsubishi Rayon Co., Ltd. 第三級ブチルアルコールの製造法
CN101423454A (zh) * 2007-11-01 2009-05-06 中国石油天然气股份有限公司 一种由含异丁烯的碳四烃反应萃取制叔丁醇的方法
JP2012219042A (ja) * 2011-04-06 2012-11-12 Mitsubishi Rayon Co Ltd 不均一液相反応方法

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