Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0053—Details of the reactor
  • B01J19/006—Baffles
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
  • B01J19/246—Stationary reactors without moving elements inside provoking a loop type movement of the reactants internally, i.e. the mixture circulating inside the vessel such that the upward stream is separated physically from the downward stream(s)
• • 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
  • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
• • 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
  • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
  • B01J3/008—Processes carried out under supercritical conditions
• • 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
  • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00761—Details of the reactor
  • B01J2219/00763—Baffles
  • B01J2219/00765—Baffles attached to the reactor wall
  • B01J2219/00777—Baffles attached to the reactor wall horizontal
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/18—Details relating to the spatial orientation of the reactor
  • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/19—Details relating to the geometry of the reactor
  • B01J2219/194—Details relating to the geometry of the reactor round
  • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
  • B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
• • 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
  • Y02P20/10—Process efficiency

Definitions

• the present invention relates to a reactor used in the production of secondary butanol (2-butanol).
• the present invention relates to a reactor and a production method for producing secondary butanol without producing an aqueous catalyst solution outside the reactor in producing secondary butanol by a direct hydration method.
• Secondary butanol is mainly used as a raw material for methyl ethyl ketone (MEK), which is useful as a solvent.
• MEK methyl ethyl ketone
• secondary butanol is obtained by esterifying n-butene with sulfuric acid and hydrolyzing the sulfate with steam.
• sulfuric acid since sulfuric acid is used, processes such as reuse are complicated, and energy consumption is large. Furthermore, there are problems such as equipment corrosion and waste sulfuric acid treatment.
• the present applicant has disclosed a method for obtaining secondary butanol by directly hydrating n-butene using a heteropolyacid aqueous solution as a direct hydration method (see, for example, Patent Document 1). o This method simplifies the process because secondary butanol can be produced without going through the sulfate ester.
• FIG. 4 is a schematic flow diagram showing a conventional method for producing secondary butanol.
• This manufacturing method has three major steps.
• n-butene and water as raw materials, and heteropoly acid aqueous solution as a catalyst are supplied to the reactor 1 ′ and subjected to a hydration reaction to produce secondary butanol (denoted as SBA in the figure). Is synthesized.
• the gas-liquid mixture containing secondary butanol, unreacted raw material and catalyst aqueous solution taken out from the reactor 1 ′ is treated in the catalytic water separation tower 52 to separate it into catalyst water and other components.
• the catalyst The mixture from which water has been separated is purified and separated in separation tower 50, and the desired secondary butanol is recovered.
• the equipment in contact with the aqueous solution is required to have high anticorrosion properties. Specifically, equipment or the like in which a titanium metal layer is formed at the wetted part and an oxide film is further formed is used.
• the mixture containing the catalyst aqueous solution is taken out from the reactor. Therefore, in addition to the reactor 1 ′, the catalyst water separation tower 52, the pump P for circulating the catalyst water, piping, etc. are highly anticorrosive. It was necessary to use this material.
• the equipment with high anti-corrosion properties is more expensive than the normal equipment that has the same strength as stainless steel, which increases equipment costs and manufacturing costs.
• the pressure inside the reactor is high, in order to circulate the heteropolyacid aqueous solution separated in the catalytic water separation tower 52 to the reactor 1 ′, it is necessary to pressurize the aqueous solution with the pump P. It had been.
• Patent Document 1 Japanese Patent Laid-Open No. 60-149536
• the present invention has been made in view of the above-described problems, and an object thereof is to provide a reactor and a production method for producing secondary butanol more efficiently.
• the present inventors further examined the configuration of the reactor, and as a result, by providing a circulation mechanism that can circulate the catalyst water that is a liquid phase inside the reactor and can maintain the gas-liquid interface, The present inventors have found that catalyst water can be produced while confined in the reactor without lowering the production rate of secondary butanol, and the present invention has been completed.
• the following reactor or the method for producing secondary butanol can be provided.
• a secondary butanoic acid that directly hydrates n-butene using an aqueous heteropolyacid solution as a catalyst.
• a reactor for producing secondary butanol characterized in that it has a circulation mechanism for circulating a heteropolyacid aqueous solution inside the reactor.
• n-butene is supplied to a liquid polyheteropolyacid aqueous solution to form secondary butanol, and the supercritical state gas is generated in the reactor. Forming a phase, concentrating the secondary butanol on the n-butene, taking out the secondary butanol and n-butene in the gas phase from the reactor, and then separating the n-butene to separate the secondary butanol.
• FIG. 1 is a schematic cross-sectional view showing an embodiment of a reactor for producing secondary butanol according to the present invention.
• FIG. 2 is a conceptual diagram of the inside of the reactor during the production of secondary butanol
• FIG. 3 is a schematic flow diagram showing a method for producing secondary butanol according to the present invention.
• FIG. 4 is a schematic flow diagram showing a conventional method for producing secondary butanol.
• FIG. 1 is a schematic cross-sectional view of a reactor for producing secondary butanol according to an embodiment of the present invention.
• FIG. 2 is a conceptual diagram of the inside of the reactor during the production of secondary butanol.
• Reactor 1 has a feed port 12 for raw material n-butene at the bottom of a cylindrical body 11. . Further, an upper portion of the main body 11 has an outlet 13 for n-butene gas containing secondary butanol as a product. At the upper part of the supply port 12, a gas dispersion plate 14 is attached so that the liquid phase in the reactor does not leak from the supply port 12, but butene gas passes but liquid does not flow backward.
• a water supply port 15 for supplying water for hydrating n-butene is provided above the gas dispersion plate 14 and in the lower region of the main body 11.
• An inner pipe 20 is attached along the longitudinal center line of the main body 11.
• One end of the inner pipe 20 is on the supply port 12 side, and the other end is in the liquid phase 42 and on the liquid phase and gas phase interface 40 side (see FIG. 2).
• the liquid phase circulates inside and outside the inner pipe 20 due to the difference in specific gravity of the liquid phase caused by the gas component in the liquid phase moving to the gas phase.
• the aqueous solution on the lower side of the reactor 1 has a relatively low specific gravity because it contains a relatively large amount of butene gas and the generated secondary butanol, and therefore moves upward.
• the ratio of the inner pipe inner diameter to the reactor diameter is changed from 0.05 to 0.00 in order to perform an appropriate liquid phase circulation (downflow) and to secure the reaction volume (upflow). 20 is preferable.
• the liquid phase can be circulated appropriately, secondary butanol produced in the liquid phase can be diffused in the liquid phase while the gas-liquid interface is formed. Since the hydration reaction that occurs in the liquid phase is an equilibrium reaction that is considerably biased toward the original system, the hydration reaction can proceed more efficiently by diffusing secondary butanol in the liquid phase.
• a flow rate control valve 22 for controlling the circulation amount of the heteropolyacid aqueous solution is installed inside the inner pipe so that the external force can be controlled by the operation valve 22a. Controlling the circulation speed of the liquid phase with a control valve makes it easy to optimize the hydration reaction. Furthermore, it is preferable to install a flow indicator 24 inside the inner pipe. Good.
• a commonly used butterfly valve, gate valve, globe valve, or the like can be used as the flow control valve.
• two or more regions (tanks) 28 are formed by dividing a portion where the liquid phase circulates by one or more perforated plates 26.
• the porous plate 26 has a function of re-dispersing butene gas, which is a bubble, and improving the contact efficiency with the liquid phase. Further, by installing the perforated plate 26, the same effect as that in which a plurality of tanks are formed in the reactor 1 can be obtained. That is, since it can be close to the plug flow (piston flow), the production efficiency of secondary butanol can be improved.
• five annular porous plates 26 are attached to the outer periphery of the inner pipe 20 so as to cross the main body 11 (the number of tanks is six).
• the number of regions 28 (tanks) is preferably 6 or more, and more preferably 10 to 20.
• the aperture ratio is 0.06-0.10, and the pore diameter is 3 ⁇ 10 mm is preferable.
• a gas-liquid separator 30 (demister) and Z or a washing tray 32 are installed in the vicinity of the outlet 13 of the reactor 1.
• a gas-liquid separator 30 demister
• Z or a washing tray 32 are installed in the vicinity of the outlet 13 of the reactor 1.
• a cleaning water supply port 34 for supplying cleaning water is provided above the cleaning tray 32 of the main body 11.
• FIG. 3 is a schematic flow diagram of the method for producing secondary butanol of the present invention.
• the aqueous heteropolyacid solution is present in the liquid phase in the reactor of the present invention described above, and n-butene is blown into this to produce secondary butanol in the liquid phase.
• the secondary butanol is then concentrated with n-butene and removed from the reactor with gas and separated.
• an aqueous heteropolyacid solution is charged into a reactor in advance.
• the liquid level of the aqueous solution is adjusted to a predetermined position. For example, as shown in FIG. 2, the liquid level is adjusted to a position where the entire inner pipe 20 is immersed in the liquid phase 42 and the heteropolyacid aqueous solution does not leak from the outlet 13.
• heteropolyacid key tungstic acid, phosphotungstic acid, key molybdic acid, linmolybdic acid and the like can be used. Also, a combination of two or more heteroatoms and polyatoms can be used.
• the concentration of the heteropolyacid aqueous solution needs to be adjusted as appropriate depending on the type of heteropolyacid used, but is usually from 0.001 mol Z liter to 0.2 mol Z liter.
• the pH of the aqueous heteropolyacid solution is 2.3 or less.
• n-butene gas (n-butene-1, n-butene-2, or a mixture thereof) is supplied from the supply port 12, and water is supplied from the water supply port 15.
• the n-butene gas becomes bubbles 46 and moves upward in the reactor 1 (directly indicated by white arrows in Fig. 2).
• part of the n-butene dissolves in the catalyst aqueous solution.
• secondary butanol is produced.
• most of the n-butene does not react and passes through the liquid phase 42 to form a gas phase 44 in the upper part of the reactor 1. Therefore, the interface force between the heteropolyacid aqueous solution (liquid phase) 42 and the n-butene (gas phase) 44 is supplied so that the n-butene remains at the predetermined position described above.
• n-butene that forms the gas phase 44 in the reactor 1 is present in a supercritical state.
• the equilibrium conversion rate of hydration to secondary butanol is low.
• the concentration of secondary butanol in the liquid phase 42 is low.
• secondary butanol is distributed at high concentration in the supercritical n-butene, which is the gas phase 44. Therefore, secondary butanol can be efficiently recovered by taking out only the gas phase 44 to the outside of the reactor 1.
• the reaction temperature is set to 140 ° C to 300 ° C, and the reaction pressure is set to 6 MPa or more.
• the reaction temperature is 180 ° C to 230 ° C, and the reaction pressure is 18 MPa to 22 MPa.
• the gas phase 44 is taken out from the outlet 13.
• the liquid phase 42 and the gas phase 44 exist in the reactor 1 while forming the interface 40, only the gas phase 44 can be easily taken out from the reactor 1. That is, the secondary butanol and n-butene that form the gas phase 44 can be selectively extracted while the aqueous catalyst solution is confined in the reactor 1. . Therefore, unlike the flow chart shown in FIG. 4, a catalyst water circulation facility such as the catalyst water separation tower 52 is not required, so that the equipment cost and the manufacturing cost can be reduced.
• the extraction speed of the gas phase 44 is adjusted so that the interface between the catalyst water solution phase 42 and the gas phase 44 is in a predetermined position in consideration of the amount of n-butene supplied, water, and the like.
• the gas phase 44 is mainly a mixture of secondary butanol and n-butene, it is separated from the separation tower.
• No. 149536 can be referred to Japanese Patent Laid-Open No. 4-356434.
• the reactor for producing secondary butanol of the present invention can be used as a production facility for secondary butanol, and can also be used for a production facility for methyl ethyl ketone.
• the method for producing secondary butanol of the present invention is suitable as a method for producing secondary butanol because it can reduce equipment costs and production costs.
• MEK manufacturing efficiency can be improved by incorporating it as part of the MEK manufacturing process.

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• 2006
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