WO2023276407A1 - アルコールの製造方法 - Google Patents

アルコールの製造方法 Download PDF

Info

Publication number
WO2023276407A1
WO2023276407A1 PCT/JP2022/017423 JP2022017423W WO2023276407A1 WO 2023276407 A1 WO2023276407 A1 WO 2023276407A1 JP 2022017423 W JP2022017423 W JP 2022017423W WO 2023276407 A1 WO2023276407 A1 WO 2023276407A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
reactor
acid
reaction
heteropolyacid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/017423
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
玄 井上
季弘 木村
雅史 小谷野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP2023531463A priority Critical patent/JPWO2023276407A1/ja
Priority to CN202280045433.1A priority patent/CN117561230A/zh
Priority to US18/571,837 priority patent/US20240360058A1/en
Priority to GB2318688.5A priority patent/GB2621960A/en
Publication of WO2023276407A1 publication Critical patent/WO2023276407A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/065—Feeding reactive fluids
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • C07C31/08—Ethanol
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00327—Controlling the temperature by direct heat exchange
    • B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
    • B01J2208/00353—Non-cryogenic fluids
    • B01J2208/00362—Liquid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing alcohol through a hydration reaction of olefins using a heteropolyacid catalyst.
  • the present invention is particularly suitable for producing ethanol from ethylene.
  • Industrial ethanol is an important industrial chemical product that is widely used as an intermediate for organic solvents, raw materials for organic synthesis, disinfectants and chemicals.
  • Industrial ethanol can be produced by adding liquid acids such as sulfuric acid, sulfonic acid, zeolite catalysts, metal oxide catalysts such as tungsten, niobium, tantalum, or heteropolyacids such as phosphotungstic acid, silicotungstic acid, or phosphoric acid to silica carriers, diatomaceous earth. It is known to be obtained by a hydration reaction of ethylene in the presence of a solid catalyst supported on a carrier or the like.
  • Metal oxide catalysts are known as catalysts for ethylene hydration reactions that do not cause phosphoric acid to flow out, and include zeolite catalysts (Patent Document 1), metal oxide catalysts containing titanium oxide and tungsten oxide as essential components ( Patent Document 2), a metal oxide catalyst containing tungsten and niobium as essential components (Patent Document 3), and the like are known.
  • Patent Document 1 metal oxide catalysts containing titanium oxide and tungsten oxide as essential components
  • Patent Document 3 a metal oxide catalyst containing tungsten and niobium as essential components
  • ethylene hydration reactions using these metal oxide catalysts are less active and less selective than those using phosphoric acid catalysts.
  • a solid acid catalyst in which a heteropolyacid is supported on a carrier is known.
  • a supported catalyst for ethanol production by a hydration reaction of ethylene with improved performance a catalyst in which a heteropolyacid is supported on fumed silica of a combustion method is disclosed (Patent Document 4).
  • Patent Document 5 As a method for improving the performance of heteropolyacid-supported catalysts, use of catalysts in which a heteropolyacid is supported on a clay carrier treated with thermal acid has been proposed (Patent Document 5).
  • a silica carrier with specified pore volume, specific surface area, and pore diameter is disclosed as a supported catalyst carrier suitable for the hydration reaction of olefins.
  • a catalyst for ethanol production is also exemplified (Patent Document 6).
  • the hydration reaction of olefins is an exothermic reaction, and if the heat of reaction cannot be sufficiently removed, zones of particularly high temperature, so-called hot spots, occur within the catalyst layer. If the catalyst is used for a long period of time in the presence of large hot spots, the raw material olefin and its by-products accumulate on the surface of the catalyst at temperature peaks, which is thought to adversely affect the stable use of the catalyst. However, until now, it has not been clarified how the temperature peak affects the long-term use of the olefin hydration reaction using heteropolyacid catalysts.
  • An object of the present invention is to provide a method that enables the stable use of a catalyst over a long period of time in the production of alcohol through the hydration reaction of olefins using a heteropolyacid catalyst.
  • the present inventors have found that the temperature difference in the catalyst layer has a significant effect on catalyst deterioration, especially coking, in the production of alcohol through the hydration reaction of olefins using a heteropolyacid catalyst. . Therefore, in the olefin hydration reaction using a heteropolyacid catalyst, it was confirmed that the catalyst can be stably used for a long period of time by keeping the temperature difference in the catalyst layer below a certain value, and the present invention was completed.
  • the present invention relates to the following [1] to [9].
  • [1] Using a solid acid catalyst in which a heteropolyacid or a salt thereof is supported on a carrier, a raw material gas containing water and an olefin having 2 to 5 carbon atoms is fed into a reactor equipped with a catalyst layer filled with the solid acid catalyst.
  • a method for producing alcohol by continuously supplying and hydrating in the gas phase to obtain alcohol,
  • a method for producing alcohol, wherein the hydration reaction is carried out with a temperature difference in the catalyst layer of 6° C. or less.
  • [2] The method for producing alcohol according to [1], wherein the reactor is a multitubular reactor.
  • [3] The method for producing alcohol according to [2], wherein the solid acid catalyst is packed in the tube of the multitubular reactor.
  • [4] The method for producing alcohol according to [3], wherein the tube of the multitubular reactor has an inner diameter of 40 mm or less.
  • [5] The method for producing alcohol according to any one of [1] to [4], wherein the reactor uses liquid-phase water as a coolant.
  • [6] The method for producing alcohol according to any one of [1] to [5], wherein the raw material gas has a superficial linear velocity in the reactor of 0.1 to 1.0 m/s.
  • [7] The method for producing alcohol according to any one of [1] to [6], wherein the conversion rate of the olefin having 2 to 5 carbon atoms is 2 to 6%.
  • coking of the heteropolyacid catalyst is suppressed in the production of alcohol through the hydration reaction of olefins using a heteropolyacid catalyst, and the catalyst can be used stably over a long period of time.
  • the solid acid catalyst of one embodiment is a heteropolyacid or a salt thereof (collectively referred to as a "heteropolyacid catalyst") supported on a carrier, and a catalyst containing a heteropolyacid or a salt thereof as a main active component of the catalyst. is.
  • heteropolyacid is an acid composed of a central element and peripheral elements to which oxygen is bonded.
  • the central element is usually silicon or phosphorus, but can be selected from any one of the many elements of Groups 1-17 of the Periodic Table of the Elements.
  • Examples of the central element constituting the heteropolyacid include cupric ions; divalent ions of beryllium, zinc, cobalt, or nickel; trivalent ions of boron, aluminum, gallium, iron, cerium, arsenic, antimony, Ions of phosphorus, bismuth, chromium, or rhodium; ions of tetravalent silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese, nickel, platinum, thorium, hafnium, cerium, and other rare earth ions pentavalent phosphorus, arsenic, vanadium, antimony ions; hexavalent tellurium ions; and heptavalent iodine ions, but are not limited thereto.
  • peripheral elements include tungsten, molybdenum, vanadium, niobium, and tantalum, but are not limited to these.
  • heteropolyacids are known as “polyoxoanions”, “polyoxometal salts", or “metal oxide clusters”.
  • Some structures of well-known anions are named after researchers in the field, e.g., Keggin-type structures, Wells-Dawson type structures, and Anderson-Evans-Perloff type structures are known.
  • Keggin-type structures e.g., Keggin-type structures
  • Wells-Dawson type structures e.g., and Anderson-Evans-Perloff type structures are known.
  • Heteropolyacids are usually of high molecular weight, eg, having a molecular weight in the range of 700-8500, and include not only their monomers but also dimer complexes.
  • the heteropolyacid salt is not particularly limited as long as it is a metal salt or onium salt in which some or all of the hydrogen atoms of the above heteropolyacid are substituted.
  • Examples include, but are not limited to, metal salts of lithium, sodium, potassium, cesium, magnesium, barium, copper, gold, and gallium, and onium salts such as ammonium salts.
  • Heteropolyacids have a relatively high solubility in water or other polar solvents such as oxygenated solvents, especially when the heteropolyacid is in the form of the free acid or some salt.
  • the solubility of heteropolyacids can be controlled by choosing appropriate counterions.
  • heteropolyacids that can be used as catalysts include, but are not limited to: Silicotungstic acid H 4 [SiW 12 O 40 ].xH 2 O Phosphotungstic acid H 3 [PW 12 O 40 ].xH 2 O Phosphomolybdic acid H 3 [PMo 12 O 40 ].xH 2 O Silicomolybdic acid H4[ SiMo12O40 ] .xH2O Sivanadotungstic acid H 4+n [SiV n W 12-n O 40 ].xH 2 O Phosphorvanadotungstic acid H 3+n [PV n W 12-n O 40 ].xH 2 O Phosphovanadomolybdate H 3+n [PV n Mo 12-n O 40 ].xH 2 O Sivanadomolybdate H 4+n [SiV n Mo 12-n O 40 ].xH 2 O Silicomolybdotungstic acid H 4 [SiMo n W 12-n O 40 ].xH 2 O Sil
  • the heteropolyacid is preferably silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, silicomolybdic acid, silicobanadotungstic acid, phosphovanadotungstic acid, or phosphovanadomolybdic acid, and silicotungstic acid, phosphotungstic acid, silicobanadotungstic acid More preferred are acids or phosphovanadotungstic acid.
  • a method for synthesizing such a heteropolyacid is not particularly limited, and any method may be used.
  • a heteropolyacid can be obtained by heating an acidic aqueous solution (about pH 1 to pH 2) containing a salt of molybdic acid or tungstic acid and a heteroatom simple oxygen acid or a salt thereof.
  • the heteropolyacid compound can be isolated, for example, by crystallization and separation as a metal salt from the produced heteropolyacid aqueous solution.
  • heteropolyacids A specific example of the production of heteropolyacids can be found in 1413 of "New Experimental Chemistry Course 8 Synthesis of Inorganic Compounds (III)" (edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., August 20, 1984, 3rd edition). page, but is not limited to this.
  • the structure of the synthesized heteropolyacid can be confirmed by X-ray diffraction, UV, or IR measurement as well as chemical analysis.
  • heteropolyacid salts include lithium salts, sodium salts, potassium salts, cesium salts, magnesium salts, barium salts, copper salts, gold salts, gallium salts, and ammonium salts of the above preferred heteropolyacids.
  • heteropolyacid salts include lithium silicotungstic acid, sodium silicotungstic acid, cesium silicotungstic acid, copper silicotungstic acid, gold silicotungstic acid, and gallium silicotungstic acid.
  • heteropolyacid salts include lithium silicotungstic acid, sodium silicotungstic acid, cesium silicotungstic acid, copper silicotungstic acid, gold silicotungstic acid, gallium silicotungstic acid; Lithium salt of acid, sodium salt of phosphotungstic acid, cesium salt of phosphotungstic acid, copper salt of phosphotungstic acid, gold salt of phosphotungstic acid, gallium salt of phosphotungstic acid; Sodium salt of tungstic acid, cesium salt of siliconvanadotungstic acid, copper salt of siliconvanadotungstic acid, gold salt of siliconvanadotungstic acid, gallium salt of siliconvanadotungstic acid; lithium salt of phosphovanadotungstic acid, phosphovanadotungstic acid , the cesium salt of phosphovanadotungstic acid, the copper salt of phosphovanadotungstic acid, the gold salt of phosphovanadotungstic acid, or the gallium salt of phosphovanadotungstic acid.
  • lithium silicotungstic acid As the heteropolyacid salt, lithium silicotungstic acid, cesium silicotungstic acid, lithium phosphotungstic acid, or cesium phosphotungstic acid is particularly suitable.
  • the heteropolyacid catalyst can be used as it is, it is preferably supported on a carrier.
  • the carrier is preferably at least one selected from the group consisting of silica, diatomaceous earth, titania, activated carbon, alumina, and silica-alumina, more preferably silica.
  • the shape of the carrier is not particularly limited.
  • spherical, columnar, hollow columnar, plate, elliptical, sheet, and honeycomb shapes can be mentioned. It is preferably spherical, cylindrical, hollow cylindrical or ellipsoidal, more preferably spherical or cylindrical, which facilitates filling the reactor and supporting the catalytically active components.
  • the size of the carrier is not particularly limited, but it affects the handling of the solid acid catalyst on which the catalytically active component is supported during production or when the catalyst is filled, the differential pressure after filling the reactor, and the reaction performance of the catalytic reaction. Therefore, it is desirable to have a size that takes these into account.
  • the thickness is preferably 1 to 20 mm, more preferably 2 to 10 mm.
  • the crushing strength of the carrier is preferably 5 N or more, and 10 N or more. is more preferred.
  • the crushing strength is a value when a load is applied to the carrier using a KHT-40N digital hardness tester manufactured by Fujiwara Seisakusho Co., Ltd. and the carrier breaks.
  • the specific surface area of the carrier is not limited, but the higher the specific surface area, the higher the activity of the catalyst. preferable.
  • the method for supporting the heteropolyacid or its salt on the carrier there is no particular limitation on the method for supporting the heteropolyacid or its salt on the carrier.
  • a solution or suspension obtained by dissolving or suspending a heteropolyacid or a salt thereof in a solvent is absorbed into a carrier, and the solvent is evaporated.
  • the amount of the heteropolyacid or its salt supported on the carrier can be adjusted, for example, by dissolving the heteropolyacid or its salt in distilled water corresponding to the water absorption amount of the carrier and impregnating the carrier with the solution.
  • the amount of the heteropolyacid or its salt supported on the carrier is determined by immersing the carrier in a solution of an excess amount of the heteropolyacid or its salt while moving it moderately, and then filtering the excess heteropolyacid or its salt. It can also be adjusted by removing the salt.
  • the volume of the solution or suspension varies depending on the carrier used, the supporting method, etc.
  • a solid acid catalyst supported on a carrier can be obtained by placing the carrier impregnated with a heteropolyacid or a salt thereof in a heating oven for several hours to evaporate the solvent.
  • the drying method is not particularly limited, and various methods such as a stationary method and a belt conveyor method can be used.
  • the amount of the heteropolyacid or its salt supported on the carrier can be accurately measured by chemical analysis such as ICP and XRF.
  • the amount of the heteropolyacid or its salt supported on the carrier is preferably 10 to 300 parts by mass, preferably 20 to 200 parts by mass, based on 100 parts by mass of the carrier. more preferred.
  • the alcohol is obtained by using a solid acid catalyst in which a heteropolyacid or a salt thereof is supported on a carrier, and a raw material gas containing water and an olefin having 2 to 5 carbon atoms is provided with a catalyst layer filled with a solid acid catalyst. It can be obtained by continuously supplying it to a reactor and causing a hydration reaction in the gas phase.
  • R 1 to R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and the total number of carbon atoms of R 1 to R 4 is 0 to 3.
  • the olefins having 2 to 5 carbon atoms that can be used are not particularly limited.
  • Examples of olefins having 2 to 5 carbon atoms include ethylene, propylene, n-butene, isobutene, pentene, or mixtures of two or more thereof. Among them, ethylene is more preferable.
  • a preferred format is the fixed bed format from the viewpoint of high reaction efficiency and requiring the least energy for separation from the catalyst.
  • a solid acid catalyst of one embodiment is packed in a fixed-bed reactor to form a catalyst layer.
  • a multi-tubular reactor with good heat removal efficiency is preferable as a fixed bed reactor.
  • a reactor with poor heat removal efficiency is not preferable because the temperature difference in the catalyst layer increases.
  • a shell-and-tube reactor is equipped with a plurality of tubes as reaction tubes, and the solid acid catalyst can be filled in these tubes to form a catalyst layer.
  • the inner diameter of the tubes of the multitubular reactor is preferably 40 mm or less. Moreover, from the viewpoint of uniformly circulating the raw material gas in each tube, it is preferable that the inner diameter and length of each tube are uniform.
  • the number of tubes depends on the size of the reactor and can range from a few to thousands.
  • a reactor other than a multitubular reactor is used as the fixed bed reactor
  • a plurality of small adiabatic reactors and heat exchangers are alternately combined in series to reduce the temperature difference in the catalyst layer. can be made smaller.
  • liquid water used as the coolant used to remove heat from the reactor.
  • the heat of vaporization of the coolant can efficiently remove heat from the process fluid in the reactor.
  • the superficial linear velocity of the source gas flowing through the reactor is preferably 0.1 to 1.0 m/s. If it is 0.1 m/s or more, the overall heat transfer coefficient does not decrease too much, and heat removal efficiency is maintained. If it is 1.0 m/s or less, the pressure loss in the reactor does not become too large, and the collapse of the catalyst or the load increase of the circulating gas compressor hardly occurs.
  • the gas space velocity in the reactor is not particularly limited, it is preferably 500 to 15000/hr, more preferably 1000 to 4000/hr from the viewpoint of energy and reaction efficiency. If the gas space velocity is 500/hr or more, the amount of catalyst used can be effectively reduced, and if it is 15000/hr or less, the amount of gas circulation can be reduced. If so, the production of alcohol can be carried out more efficiently.
  • reaction pressure in the olefin hydration reaction using a heteropolyacid catalyst there is no limit to the reaction pressure in the olefin hydration reaction using a heteropolyacid catalyst. Since the hydration reaction of olefins is a reaction that reduces the number of molecules, it is generally advantageous to carry it out at high pressure.
  • a preferable reaction pressure is 0.5 to 7.0 MPaG, more preferably 1.5 to 4.0 MPaG. "G" means gauge pressure. If the reaction pressure is 0.5 MPaG or more, a sufficient reaction rate can be obtained. Installation is no longer required, and further energy costs can be further reduced.
  • the reaction temperature for the olefin hydration reaction using a heteropolyacid catalyst is not particularly limited, and can be carried out at a wide range of temperatures.
  • a preferable reaction temperature is 100 to 550°C, more preferably 150 to 350°C, considering the thermal stability of the heteropolyacid or its salt and the temperature at which water, one of the raw materials, does not condense.
  • the temperature difference between the position showing the highest temperature and the position showing the lowest temperature in the catalyst layer is 6°C or less, more preferably 5°C or less.
  • the temperature difference within the catalyst layer referred to herein is the difference between the maximum and minimum temperatures across the entire catalyst layer, including both vertical and horizontal directions.
  • the reason why the temperature difference in the catalyst layer is important is the difference in temperature dependence between the main reaction, which is the olefin hydration reaction, and the side reaction.
  • the reaction rate of hydration reaction rises moderately as the temperature rises, but the reaction rate of side reactions such as olefin polymerization and aldehyde formation exponentially rises as the temperature rises.
  • the conversion of olefin hydration reactions is often correlated with the average temperature across the catalyst bed, and the by-product selectivity is often correlated with the peak temperature at any location within the catalyst bed. If the temperature difference in the catalyst layer is 6° C. or less, the main reaction, which is the olefin hydration reaction, can proceed while suppressing the progress of side reactions such as the polymerization of olefins and the formation of aldehydes.
  • the hydration reaction of olefins using a heteropolyacid catalyst is an equilibrium reaction, and the maximum conversion rate of olefins is the equilibrium conversion rate.
  • the equilibrium conversion rate in the production of ethanol by hydration of ethylene is calculated to be 7.5% at a temperature of 200°C and a pressure of 2.0 MPaG. Therefore, in the process of alcohol production by hydration of olefins, the maximum conversion is determined by the equilibrium conversion.
  • the olefin conversion rate in the olefin hydration reaction is preferably 2 to 6%.
  • a conversion rate of 2% or more is economically advantageous because the amount of unreacted ethylene circulated can be reduced.
  • the conversion rate is 6% or less, the difference from the equilibrium conversion rate can be made to the extent necessary to maintain the reaction rate, and severe conditions such as high pressure are not essential. Therefore, it is advantageous from the economic and facility aspects.
  • the loss of olefin can be reduced by recycling unreacted olefin to the reactor.
  • the olefins may be isolated from the process fluid leaving the reactor and recycled, or may be recycled together with other inert components.
  • Technical grade olefins often contain very small amounts of paraffins. Therefore, for example, when using ethane-containing ethylene and recycling unreacted ethylene to the reactor, a portion of the recovered reaction gas (ethylene gas) is used to prevent condensation and accumulation of ethane. It is desirable to discharge (purge) out of the system.
  • the product alcohols may undergo further dehydration reactions, and ether compounds may be produced as by-products.
  • ether compounds may be produced as by-products.
  • diethyl ether is produced as a by-product. This diethyl ether is considered to be produced by a dehydration reaction from two molecules of ethanol, and when ethanol is produced by a hydration reaction of ethylene, it significantly reduces the yield of the reaction.
  • diethyl ether is converted to ethanol, and ethanol can be produced from ethylene with extremely high efficiency.
  • the method of recycling the by-produced ether compound to the reactor is not particularly limited. There is a method of recycling to the reactor as a component.
  • the alcohol produced is dissolved in a large amount of water that has not been converted as a reaction raw material, and is sent to the separation and purification process along with other by-products.
  • the separation and purification process alcohol, water, and other by-products are separated, and the alcohol whose purity reaches a certain level or higher through purification becomes the product.
  • the water obtained at the same time may be disposed of as waste water, but from the perspective of environmental impact and load, it is desirable to recycle it within the process and use it again as a reaction raw material.
  • silica carrier Fumed silica: Aerosil (trademark) 300 (Nippon Aerosil Co., Ltd.) 40 parts by mass Silica gel: CARiACT G6 (Fuji Silysia Chemical Co., Ltd.) 60 parts by mass Colloidal silica: Snowtex O (Nissan Chemical Co., Ltd.)
  • a kneader water and methyl cellulose as an additive: Metolose (registered trademark) SM-4000 (Shin-Etsu Chemical Co., Ltd.) and Celander (registered trademark) YB-132A as a resin binder ( Yuken Kogyo Co., Ltd.) was put into a kneader and further kneaded to prepare a kneaded product.
  • the kneaded material was put into an extruder equipped with a die having a circular hole of 3 mm ⁇ at the tip.
  • the kneaded product was extruded from an extruder, and the extruded intermediate product was cut with a cutter to a size of 3 mm to obtain a cylindrical pre-fired compact.
  • the obtained pre-fired compact was formed into a spherical shape using Marumerizer (registered trademark) and pre-dried at 70° C. for 24 hours or more.
  • a sintering treatment was performed at 820° C. in an air atmosphere and cooled to obtain a silica carrier.
  • the water absorption of the obtained silica carrier was measured by the following method. (1) About 5 g of the carrier was weighed (W1 (g)) with a balance and placed in a 100 mL beaker. (2) About 15 mL of pure water (ion-exchanged water) was added to the beaker so as to completely cover the carrier. (3) Leave for 30 minutes. (4) The carrier and pure water were poured over the wire mesh, the pure water was drained off by the wire mesh, and the carrier was taken out. (5) Water adhering to the surface of the carrier was removed by lightly pressing with a paper towel until the surface became dull.
  • the total mass of the carrier obtained in (5) and pure water was measured (W2 (g)).
  • the aqueous solution of silicotungstic acid is transferred to a 200 mL volumetric flask, then 100 mL of the weighed silica carrier is added to the 200 mL volumetric flask, and the volumetric flask is stirred so that the aqueous solution of silicotungstic acid spreads over the entire carrier.
  • the contents were mixed to support the silicotungstic acid on the silica carrier.
  • the silica carrier supporting silicotungstic acid was transferred to a magnetic dish, air-dried for 1 hour, and then dried for 5 hours in a hot-air dryer adjusted to 150°C. After drying, it was transferred into a desiccator and cooled to room temperature to obtain a heteropolyacid catalyst (solid acid catalyst).
  • reaction liquid After the reaction started, hot water was circulated on the shell side of the double-tube reactor to remove the heat of reaction.
  • the reaction gas after passing through the reactor was cooled, and the condensed reaction liquid, the reaction gas passed through the scrubber after removing the condensate (reaction liquid), and the washing water of the scrubber were each sampled for a certain period of time.
  • the sampled reaction solution, reaction gas, and washing water were analyzed using a gas chromatography analyzer and a Karl Fischer analyzer by the method described below, and the reaction results were calculated.
  • thermometer protection tube (outer diameter 8 mm, inner diameter 6 mm) is placed in the center of the reaction tube, and a 10-point thermocouple (interval between points: 0.7 m) is inserted into the protection tube to measure the vertical temperature inside the catalyst layer.
  • the catalyst layer center temperature was measured at six locations in the direction and used as the catalyst layer horizontal center temperature.
  • the hot water circulated through the shell portion of the double tube reaction tube for cooling was supplied from the lower end of the outside of the double tube and was withdrawn from the upper end, and the supply temperature and the extraction temperature of the hot water were the same. It was assumed that the outer wall temperature of the reaction tube is the same as the temperature of the hot water, and that the temperature distribution in the horizontal direction of the reaction tube changes linearly assuming conductive heat transfer.
  • the temperature difference in the catalyst layer was the difference between the maximum horizontal center temperature of the catalyst layer and the outer wall temperature of the reaction tube.
  • the integrated temperature on the horizontal surface (disc) of the reaction tube at a certain height (temperature measurement point) in the vertical direction in the catalyst layer is the volume of the cone (the radius of the bottom of the cone R: 1/2 of the inner diameter of the reaction tube, the height of the cone h: the temperature difference between the horizontal center temperature in the catalyst layer and the outer wall temperature of the reaction tube), and the temperature difference a from the outer wall temperature of the reaction tube at a radial position r from the center of the reaction tube where the volume is 1/2 of the conical volume; The sum with the temperature of the outer wall of the reaction tube was taken as the average temperature of the catalyst layer at that height.
  • the average temperature of the entire catalyst layer was the arithmetic mean of the average temperatures of the catalyst layer at six height positions in the six vertical directions in the catalyst layer measured above.
  • Ethylene conversion rate and acetaldehyde selectivity were determined by the following equations.
  • Ethylene conversion rate (mol%) (number of moles of ethylene reacted/number of moles of ethylene supplied) x 100
  • Acetaldehyde selectivity (mol%) (number of moles of acetaldehyde produced/number of moles of ethylene supplied) x 100
  • Example 1 3.1 L of heteropolyacid catalyst (solid acid catalyst) was packed in a vertically installed double-tube reactor (made of SUS316, inner diameter 34 mm, length 6.7 m). At this time, the height of the catalyst layer was 3.6 m. After replacing the inside of the reactor with nitrogen gas, the pressure was increased to 2.4 MPaG. Next, the reactor was heated to 180° C., and when the temperature was stabilized, the GHSV (gas hourly space velocity) was 3000/hr, the superficial linear velocity was 0.2 m/s, and the molar ratio of water to ethylene was 0.3. The amount of water and ethylene vaporized by the evaporator, and the amount of diethyl ether that balances before and after the reactor, were fed into the reactor from above to carry out the hydration reaction of ethylene.
  • GHSV gas hourly space velocity
  • reaction liquid, cleaning liquid, and reaction gas from which the reaction liquid had been removed were sampled.
  • the obtained reaction liquid, cleaning liquid, and reaction gas were each analyzed by the above methods, and the reaction performance of the catalyst was calculated from the mass, gas flow rate, and analysis results.
  • Example 1 A reaction was carried out in the same manner as in Example 1, except that 5.9 L of the heteropolyacid catalyst (solid acid catalyst) was filled in a double-tube reactor (made of SUS316, inner diameter 47 mm, length 6.7 m). The height of the catalyst layer was 3.6 m, the same as in Example 1, and the temperature difference within the catalyst layer was 7.7° C. (196.0° C.-188.5° C.). Table 1 shows the temperature measurement results. In addition, the reaction results were calculated in the same manner as in Example 1, and the transition of the reaction results over a period of one year (change over time in selectivity of acetaldehyde, a typical by-product) was predicted. Results are shown in Table 1 and FIG.
  • Example 1 ⁇ Prediction of reaction performance for one year>
  • a low acetaldehyde selectivity can be maintained throughout the year, and alcohol can be stably produced over a long period of time.
  • the rate of increase in the acetaldehyde selectivity is large, exceeding 1% of the acetaldehyde selectivity, which is a criterion for stably using the catalyst.
  • the present invention is industrially useful in that the catalyst can be stably used for a long period of time and is economically advantageous in the production of alcohol by the hydration reaction of olefins using a heteropolyacid catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/JP2022/017423 2021-06-30 2022-04-08 アルコールの製造方法 Ceased WO2023276407A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2023531463A JPWO2023276407A1 (https=) 2021-06-30 2022-04-08
CN202280045433.1A CN117561230A (zh) 2021-06-30 2022-04-08 醇的制备方法
US18/571,837 US20240360058A1 (en) 2021-06-30 2022-04-08 Method for producing alcohols
GB2318688.5A GB2621960A (en) 2021-06-30 2022-04-08 Method for producing alcohols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021109235 2021-06-30
JP2021-109235 2021-06-30

Publications (1)

Publication Number Publication Date
WO2023276407A1 true WO2023276407A1 (ja) 2023-01-05

Family

ID=84692685

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/017423 Ceased WO2023276407A1 (ja) 2021-06-30 2022-04-08 アルコールの製造方法

Country Status (5)

Country Link
US (1) US20240360058A1 (https=)
JP (1) JPWO2023276407A1 (https=)
CN (1) CN117561230A (https=)
GB (1) GB2621960A (https=)
WO (1) WO2023276407A1 (https=)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08192047A (ja) * 1994-09-26 1996-07-30 Bp Chem Internatl Ltd オレフィンの水和方法と触媒
JP2003206244A (ja) * 2002-01-11 2003-07-22 Mitsubishi Chemicals Corp 気相接触酸化方法
WO2006035951A1 (ja) * 2004-09-27 2006-04-06 Sumitomo Chemical Company, Limited 接触気相反応用多管式反応装置
JP2020070266A (ja) * 2018-11-01 2020-05-07 昭和電工株式会社 アルコールの製造方法及びアルコール製造用触媒

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08192047A (ja) * 1994-09-26 1996-07-30 Bp Chem Internatl Ltd オレフィンの水和方法と触媒
JP2003206244A (ja) * 2002-01-11 2003-07-22 Mitsubishi Chemicals Corp 気相接触酸化方法
WO2006035951A1 (ja) * 2004-09-27 2006-04-06 Sumitomo Chemical Company, Limited 接触気相反応用多管式反応装置
JP2020070266A (ja) * 2018-11-01 2020-05-07 昭和電工株式会社 アルコールの製造方法及びアルコール製造用触媒

Also Published As

Publication number Publication date
US20240360058A1 (en) 2024-10-31
JPWO2023276407A1 (https=) 2023-01-05
CN117561230A (zh) 2024-02-13
GB2621960A (en) 2024-02-28
GB202318688D0 (en) 2024-01-24

Similar Documents

Publication Publication Date Title
US9145342B2 (en) Processes for production of isobutene and tertiary butanol
JP5512543B2 (ja) グリセリンからアクロレインを製造する方法
US7655818B2 (en) Process for dehydrating glycerol to acrolein
RU2415121C2 (ru) Способ получения этилена
RU2419596C2 (ru) Способ получения олефинов
JP2008545004A (ja) オレフィンリサイクルでの反応性蒸留
JP2009500383A (ja) 混合アルコールの脱水のための反応性蒸留
Bhadra et al. Solventless triarylmethane synthesis via hydroxyalkylation of anisole with benzaldehyde by modified heteropoly acid on mesocellular foam silica (MCF)
JPH01279854A (ja) メチル―ｔ―ブチルエーテルの一段階合成方法
RU2415832C2 (ru) Способ получения пропилена
JP2021079317A (ja) アルコール製造用触媒及びその製造方法、並びにアルコールの製造方法
WO2023276407A1 (ja) アルコールの製造方法
US20220227691A1 (en) Method for producing alcohol
WO2023276406A1 (ja) アルコールの製造方法
JP2020070266A (ja) アルコールの製造方法及びアルコール製造用触媒
US20220251009A1 (en) Method for producing alcohol
US6696598B2 (en) Process for producing lower aliphatic carboxylic acid ester
JP4332951B2 (ja) 低級オレフィンと低級脂肪族カルボン酸との混合ガスの製造方法、及び該混合ガスを用いた低級脂肪族エステルの製造方法
JP7685138B2 (ja) 酢酸エチルの製造方法
JP2002079089A (ja) 低級脂肪族カルボン酸エステル製造用触媒、該触媒の製造方法、及び該触媒を用いた低級脂肪族カルボン酸エステルの製造方法
JP3998973B2 (ja) 低級脂肪酸エステル製造用触媒、及び低級脂肪酸エステルの製造法
US6818790B1 (en) Process for producing mixed gas of lower olefin and lower aliphatic carboxylic acid, and process for producing lower aliphatic ester using the mixed gas
EP1218331B1 (en) Process for producing mixed gas of lower olefin and lower aliphatic carboxylic acid, and process for producing lower aliphatic ester using the mixed gas
JP2002079090A (ja) 低級脂肪族カルボン酸エステル製造用触媒、該触媒の製造方法、及び該触媒を用いた低級脂肪族カルボン酸エステルの製造方法
JP2004018404A (ja) 低級脂肪族カルボン酸エステルの製造方法及び該製造方法で製造された低級脂肪族カルボン酸エステル

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22832568

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023531463

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 202318688

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20220408

WWE Wipo information: entry into national phase

Ref document number: 2318688.5

Country of ref document: GB

WWE Wipo information: entry into national phase

Ref document number: 202280045433.1

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 2318688.5

Country of ref document: GB

122 Ep: pct application non-entry in european phase

Ref document number: 22832568

Country of ref document: EP

Kind code of ref document: A1