WO2018128402A1 - Procédé de production de méthyl-tert-butyléther - Google Patents

Procédé de production de méthyl-tert-butyléther Download PDF

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Publication number
WO2018128402A1
WO2018128402A1 PCT/KR2018/000155 KR2018000155W WO2018128402A1 WO 2018128402 A1 WO2018128402 A1 WO 2018128402A1 KR 2018000155 W KR2018000155 W KR 2018000155W WO 2018128402 A1 WO2018128402 A1 WO 2018128402A1
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Prior art keywords
reaction
butyl ether
methyl tert
fresh feed
reactor
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PCT/KR2018/000155
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English (en)
Korean (ko)
Inventor
이성호
이상범
신준호
정인용
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180000673A external-priority patent/KR102086563B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18736760.2A priority Critical patent/EP3395792B2/fr
Priority to JP2018559978A priority patent/JP6740536B2/ja
Priority to CN201880001171.2A priority patent/CN108834410B/zh
Priority to US16/073,294 priority patent/US10626072B2/en
Publication of WO2018128402A1 publication Critical patent/WO2018128402A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • 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
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • 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
    • B01J8/04—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 the fluid passing successively through two or more beds
    • B01J8/0403—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 the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
    • B01J8/0423—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 the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds
    • B01J8/0442—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 the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more otherwise shaped beds the beds being placed in separate reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00038—Processes in parallel
    • 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
    • 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 methyl tert-butyl ether production method, and more particularly, by reducing the amount of unreacted isobutene and the amount of impurities contained in the reactor, methyl 3 which can reduce the amount of thermal energy in the reaction distillation column It relates to a process for preparing a tert-butyl ether.
  • Methyl tertary-butyl ether is a compound produced by reacting isobutene type olefin with methanol. It contains oxygen atoms in the molecule to reduce the occurrence of nitrogen oxides and carbon monoxide. Used in gasoline mixing, the octane number is very high, about 118, which is also a useful ingredient to improve octane number of gasoline.
  • Such methyl tert-butyl ether can be prepared by reacting methanol with isobutene in the presence of an acid catalyst. Since such a reaction is an equilibrium reaction, there is a limit to the reaction in a general reactor. Therefore, by installing a distillation column at the rear of the reactor to produce the MTBE product in a way to overcome the equilibrium reaction.
  • Patent Document Korean Patent No. 10-0853947
  • the present invention by reducing the amount of unreacted isobutene and the amount of impurities contained in the reactor, the production of methyl tert-butyl ether which can reduce the amount of thermal energy in the reaction distillation column It is an object to provide a method.
  • the present invention is a reaction step of producing methyl tert-butyl ether by reacting methanol and isobutene under an acid catalyst; And purifying the reaction product obtained from the reaction step by introducing it into a reaction distillation column including a packing stage including an acid catalyst.
  • the reaction step includes one reactor or two or more reactors connected in parallel.
  • a first reaction part including a second reaction part including one or more reactors connected in series with the first reaction part; And a portion of the reaction product discharged from the first reaction part to the first reaction part, when the total volume of the reactor included in the first reaction part is 30 m 3 or less, a flow rate ratio between the recycle and the fresh feed (recycle / fresh feed) is greater than 0.9 to less than 1.7, the total volume of the reactor included in the first reaction unit is more than 30m 3 to less than 60m 3 , the recycle / fresh feed flow rate (recycle / fresh feed) is When the amount is greater than 2.2 to less than 4.8 and the total volume of the reactor included in the first reaction unit is greater than 60 m 3 , the recycle / fresh feed ratio of recycle / fresh feed is greater than 3.1 to less than 9.8 Provided is a process for preparing tert-butyl ether.
  • FIG. 1 is a configuration diagram schematically showing a process operation in which two reactors according to one embodiment of the present invention are connected in series with a first reactor connected in parallel and a second reactor including one reactor; to be.
  • FIG. 2 is a configuration diagram schematically showing a process operation in which three reactors according to one embodiment of the present invention are connected in series with a first reaction unit connected in parallel and a second reaction unit including one reactor in series; to be.
  • FIG. 3 is a configuration diagram schematically illustrating a process operation in which a first reaction unit including a reactor and a second reaction unit including a reactor according to one embodiment of the present invention are connected in series. .
  • the inventors further installed reactors in parallel and changed the flow rate at which the reactor effluent was recycled, so that when the residence time inside the reactor and the composition of the reactor inlet were adjusted to a certain range, the conversion rate of isobutene was increased. It was confirmed that a section in which the amount of impurities is reduced occurs, thereby completing the present invention.
  • Method for producing methyl tert-butyl ether of the present invention for example, a reaction step of producing methyl tert-butyl ether by reacting methanol and isobutene under an acid catalyst; And purifying the reaction product obtained from the reaction step by introducing it into a reaction distillation column including a packing stage including an acid catalyst.
  • the reaction step includes one reactor or two or more reactors connected in parallel.
  • a first reaction part including a second reaction part including one or more reactors connected in series with the first reaction part; And a portion of the reaction product discharged from the first reaction part to the first reaction part, when the total volume of the reactor included in the first reaction part is 30 m 3 or less, a flow rate ratio between the recycle and the fresh feed (recycle / fresh feed) is greater than 0.9 to less than 1.7, the total volume of the reactor included in the first reaction unit is more than 30m 3 to less than 60m 3 , the recycle / fresh feed flow rate (recycle / fresh feed) is When more than 2.2 to less than 4.8, the total volume of the reactor included in the first reaction unit is more than 60m 3 , characterized in that the recycle / fresh feed flow rate (recycle / fresh feed) is more than 3.1 to less than 9.8.
  • the equilibrium reaction step is performed as follows.
  • the isobutene for example, a C 4 -hydrocarbon mixture containing isobutene may be used.
  • the C4-hydrocarbon mixture may include n-butane, isobutane, butene-1, butene-2, butadiene and the like in addition to isobutene.
  • C4 hydrocarbon fractions obtainable by pyrolysis, steam cracking, catalytic cracking, etc. of petroleum can be effectively used.
  • the methanol may be, for example, a commercially available product, but preferably has a moisture content of less than 1% by weight.
  • the methanol may be, for example, methanol having a purity of 99.9% or more, and may be introduced into the reactor through a separate pipe.
  • the acid catalyst may be used without particular limitation in the case of a method which can be used in the art.
  • the reactor may include, for example, 200 to 1200 kg, or 300 to 1000 kg, preferably 300 to 800 kg, of acid catalyst per unit volume (m 3 ) of the reactor, and the conversion rate of isobutene is increased within this range, Since the amount of impurities is reduced, it is possible to obtain an effect of reducing the reflux amount of the reaction distillation column, and as a result, there is an effect of reducing the amount of thermal energy used in the reaction distillation column.
  • each reactor included in the first reaction unit and the second reaction unit may be filled with the same amount of acid catalyst per unit volume (m 3 ), in which case the effect of reducing the amount of thermal energy used in the reaction distillation column There is.
  • an acid ion exchange resin it is preferable to use an acid ion exchange resin because the acid catalyst has high selectivity for isobutene oligomer formation and a small amount of byproduct is produced.
  • the acid ion exchange resin may be an acid ion exchange resin that can generally be used in the reaction to produce methyl tert-butyl ether (MTBE), and for example sulfonation of a copolymer of a phenol / aldehyde condensate or an aromatic vinyl compound It may be a resin produced by.
  • the aromatic vinyl compound for preparing the oligomer may be at least one selected from the group consisting of styrene, vinyltoluene, vinylnaphthalene, vinylethylbenzene, methylstyrene, vinylchlorobenzene, vinylxylene and divinylbenzene.
  • the acid ion exchange resins can be prepared, for example, in the form of gels, macropores or sponges, and the properties of these resins, in particular the specific surface area, porosity, stability, swelling or shrinkage and exchange capacity can be controlled by the production process.
  • the fresh feed of the present disclosure may mean a pure feed stream comprising a C 4 -hydrocarbon mixture containing isobutene, for example as a feed initially fed to the first reaction section without being recycled.
  • the fresh feed introduced into the first reaction part may include, for example, a C 4 -hydrocarbon mixture containing 20 to 60 wt%, or 30 to 60 wt%, preferably 40 to 55 wt% of isobutene, Within this range, the conversion of isobutene is increased, and there is an effect of producing high purity methyl tert-butyl ether.
  • the C4-hydrocarbon mixture is, for example, propane, propene, isobutane, isobutene, 1-butene, 1,3butadiene, 1,2 butadiene, n-butane, tert-2-butene, cis-2-butene, C5 Mixtures of hydrocarbons may be included.
  • Recycling of the present disclosure may refer to a stream in which a part of a stream between the first reaction part and the second reaction part is recycled to the first reaction part as a stream discharged after passing through the first reaction part at least once.
  • the recycling may mean, for example, a recycled stream comprising a C4-hydrocarbon mixture containing isobutene and methanol and methyl tert-butylether.
  • Recycling introduced into the first reaction unit includes, for example, 1 to 20% by weight, or 3 to 10% by weight, or 2 to 5% by weight, 1 to 20% by weight, or 1 to 11% by weight of methanol. %, Preferably 2 to 5% by weight, and methyl tert-butylether may be included in 20 to 60% by weight, or 24 to 50% by weight, preferably 45 to 50% by weight, within this range There is an effect that the conversion of isobutene is increased and the amount of impurities is reduced.
  • the first reaction unit may include, for example, one reactor or two or more reactors connected in parallel.
  • the first reaction unit may include, for example, one reactor or two or three reactors connected in parallel.
  • the ratio of recycle / fresh feed to the first reaction unit may vary depending on the total volume of the reactor included in the first reaction unit.
  • the recycle / fresh feed flow rate (recycle / fresh feed) is more than 0.9 to less than 1.7, and included in the first reaction unit
  • the recycle / fresh feed flow rate (recycle / fresh feed) is greater than 2.2 to less than 4.8
  • the total volume of the reactor included in the first reaction unit is 60m 3
  • the recycle / fresh feed flow rate (recycle / fresh feed) may be more than 3.1 to less than 9.8, within this range isobutene conversion is increased, the amount of impurities is reduced, the reflux of the reaction distillation column A reduced effect can be obtained, and as a result, there is an effect of reducing the amount of thermal energy used in the reaction distillation column.
  • the recycle / fresh feed flow rate (recycle / fresh feed) is 1.0 to 1.6, or 1.1 to It may be 1.5, preferably 1.3 to 1.5, there is an effect of reducing the amount of thermal energy used in the reaction distillation column within this range.
  • the recycle / fresh feed flow ratio (recycle / fresh feed) is 2.4 to 6.2 Or 2.5 to 5.0, preferably 2.6 to 3.1, and there is an effect of reducing the amount of thermal energy used in the reaction distillation column within this range.
  • the recycle / fresh feed flow rate ratio (recycle / fresh feed) It may be 2.5 to 6.5, or 3.1 to 6.5, preferably 4.8 to 6.2, there is an effect of reducing the amount of thermal energy used in the reaction distillation column within this range.
  • the flow rate ratio of the recycle and the fresh feed may be 2.5 to 6.5, or 3.1 to 6.5, preferably 4.8 to 6.2, there is an effect of reducing the amount of thermal energy used in the reaction distillation column within this range.
  • the recycle / fresh feed ratio is 1.1 to 9.8, preferably 1.1 to 6.5, more preferably 1.2 to 6.2 days. It can be, within this range has the effect of reducing the amount of thermal energy used in the reaction distillation column.
  • the one reactor may have a volume of 10 to 120m 3 , or 20 to 105m 3 preferably 25 to 105m 3 .
  • the recycle / fresh feed flow rate (recycle / fresh feed) is greater than 2.2 to less than 9.8, or 2.3 to 6.5, preferably 2.4 to 6.2 It may be, by reducing the amount of unreacted isobutene and the amount of impurities contained in the reactor within this range, there is an effect that can reduce the amount of thermal energy used in the reaction distillation column.
  • the volume per reactor may be 10 to 80m 3 , or 20 to 70m 3 , preferably 25 to 70m 3 .
  • the recycle / fresh feed flow rate (recycle / fresh feed) is greater than 3.1 to less than 9.8, or 2.5 to 6.5, preferably 3.1 to 6.5, more preferably 4.8 to 6.2, the conversion rate of isobutene within this range is increased, the amount of impurities can be reduced, it is possible to obtain the effect of reducing the reflux of the reaction distillation column, and consequently in the reaction distillation column There is an effect of reducing the amount of thermal energy used.
  • the one reactor may have a volume of 10 to 40m 3 or 20 to 35m 3 , preferably 25 to 35m 3 .
  • the second reaction unit may include one or more reactors connected in series with the first reaction unit.
  • the second reaction unit 1 reactor; Or two or more reactors connected in series or in parallel.
  • the second reaction unit may include, for example, one reactor or two to five reactors connected in series, and preferably includes one reactor in consideration of process efficiency.
  • the molar ratio of methanol and isobutene may be, for example, 3: 1 to 1: 3 or 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5.
  • the isobutene conversion can be increased while sufficiently lowering the reaction temperature, and the cost of separating side reactants and methanol is reduced, which is economical.
  • the fresh feed flow rate introduced into the first reaction part may be, for example, 10 to 60 ton / hr, or 15 to 55 ton / hr, preferably 20 to 50 ton / hr.
  • the total volume of the reactor included in the first reaction unit may be, for example, 10 to 150 m 3 , or 15 to 130 m 3 , preferably 20 to 125 m 3 , to increase the conversion of isobutene within this range, and to improve impurities. By reducing the amount of, there is an effect that can reduce the thermal energy consumption of the reaction distillation column.
  • the reactor volume may be 10 to 120 m 3 , or 20 to 105 m 3 , preferably 25 to 105 m 3 , and the conversion rate of isobutene is increased within this range. As a result, the amount of impurities is reduced, thereby reducing the amount of reflux in the reaction distillation column.
  • the volume per reactor may be 10 to 80 m 3 , or 20 to 70 m 3 , preferably 25 to 70 m 3 , and isopart within this range.
  • the conversion of ten is increased, the amount of impurities is reduced, and the amount of reflux in the reaction distillation column is reduced.
  • the volume per reactor may be 10 to 40 m 3 or 20 to 35 m 3 , preferably 25 to 35 m 3 , and isopart within this range.
  • the conversion of ten is increased, the amount of impurities is reduced, and the amount of reflux in the reaction distillation column is reduced.
  • the reactor may be used without particular limitation, in the case of a reactor that can be commonly used in the art, for example, may be a fixed bed reactor.
  • the temperature of the stream introduced into the first reaction unit may be, for example, 20 to 80 ° C. or 30 to 70 ° C., preferably 35 to 60 ° C., and has an effect of increasing the conversion rate of isobutene within this range. .
  • the temperature of the stream introduced into the second reaction unit may be, for example, 20 to 80 °C or 30 to 70 °C, preferably 35 to 60 °C, the effect of increasing the conversion rate of isobutene within this range. There is.
  • the first reaction unit and the second reaction unit may further include a flow control valve in the raw material input pipe of each reactor.
  • the flow control valve may be used without particular limitation in the case of a flow control valve that can be used in the art in general.
  • the conversion rate of isobutene in the first reaction unit may be, for example, 40 to 99%, or 45 to 98%, preferably 50 to 95%, in which case the effect of reducing the thermal energy consumption of the reaction distillation column is have.
  • the conversion rate of isobutene in the second reaction unit may be, for example, 50 to 99%, or 55 to 98%, preferably 60 to 95%, in which case the effect of reducing the thermal energy consumption of the reaction distillation column is have.
  • the conversion rate of the isobutene may be calculated by, for example, the following equation by using a gas chromatography (Gas Chromatography) apparatus.
  • the reaction temperature of the reaction step may be, for example, 20 to 80 °C, or 35 to 75 °C, preferably 35 to 70 °C, the reaction pressure is 0.5 to 15kgf / cm 2 -g, 2 to 14kgf / cm 2- g, preferably 5 to 13 kgf / cm 2 -g, there is an effect that can increase the conversion rate of isobutene within the above range.
  • the reaction temperature in the first reaction unit may be 20 to 80 °C or 30 to 70 °C, preferably 35 to 65 °C, excellent reaction rate within this range, the equilibrium reaction advantageous to the product There is an effect going on.
  • the reaction temperature in the second reaction unit may be 20 to 80 °C, or 30 to 70 °C, preferably 35 to 60 °C, more preferably 42 to 47 °C,
  • reaction rate is excellent, and there is an effect that an equilibrium reaction favorable to the product proceeds.
  • the reaction pressure in the first reaction unit is, for example, 0.5 to 15 kgf / cm 2 -g, 2 to 14 kgf / cm 2 -g, preferably 4 to 13 kgf / cm 2 -g, more preferably 4 It may be from 8kgf / cm 2 -g, there is an effect that can increase the conversion rate of isobutene within the above range.
  • the reaction pressure in the second reaction unit is, for example, 0.5 to 15 kgf / cm 2 -g, 2 to 14 kgf / cm 2 -g, preferably 5 to 13 kgf / cm 2 -g, more preferably 5 It may be from 8kgf / cm 2 -g, there is an effect that can increase the conversion rate of isobutene within the above range.
  • the acid catalyst packed in the reaction distillation column may be, for example, an acidic cationic resin.
  • the acidic cationic resin is usually an acidic cationic resin that can be used in the art is not particularly limited and may be used.
  • the acidic cation resin may contain sulfonic acid groups, and may include those obtained by sulfonation after polymerization or copolymerization of an aromatic vinyl compound.
  • the aromatic vinyl compound may be, for example, one or two or more selected from the group consisting of styrene, vinyl toluene, vinyl naphthalene, vinyl ethylbenzene, methyl styrene, vinyl chlorobenzene, and vinyl xylene.
  • polymerization or copolymerization may further include a crosslinking agent such as divinylbenzene, divinyl toluene or divinyl phenyl ether.
  • a crosslinking agent such as divinylbenzene, divinyl toluene or divinyl phenyl ether.
  • the acidic cationic resin may be prepared, for example, in the presence or absence of a solvent or a dispersant, and the polymerization initiator may be, for example, an inorganic or organic peroxide, persulfate, or the like.
  • the acidic cation resin may be the same resin as the acid ion exchange resin used in the reaction unit.
  • the reaction product obtained from the reaction step is preferably added in a direction closer to the reboiler than the filling stage of the reaction distillation column. This can prevent poisoning of the catalyst by metal ions, which may be present in the stream introduced into the reaction distillation column, and prevent overheating that can occur in the lower region of the reaction distillation column, thereby reducing catalyst damage.
  • the reboiler may be a heat exchanger generally used in the art and may be, for example, a vertical circulation heat exchanger type.
  • the reaction distillation column may comprise, for example, 1 to 40, or 5 to 25, preferably 5 to 20, packing stages, within which the methyl tert-butyl ether of the bottom stream of the reaction distillation column is present. There is an effect to increase the concentration of.
  • reaction distillation column may further include an additional packing stage in order to further lower the concentration of isobutene in the top stream of the reaction distillation column.
  • the reaction distillation column may add additional methanol to the bottom of the packing (packing) or the reaction distillation column. This has the effect of further increasing the concentration of methyl tert-butyl ether in the bottom of the reaction distillation column.
  • the average temperature of the packing end region may be 55 °C to 70 °C, particularly preferably 58 °C to 67 °C.
  • the reflux ratio of the reaction distillation column of the purification step may be, for example, 0.5 to 1.3, or 0.6 to 1.2, preferably 0.7 to 0.95, within the range of 98% by weight or more of methyl tert-butyl ether in the lower stream. It is possible to obtain an isobutene concentration of less than 200 ppm in the top stream, which has the effect of reducing the amount of thermal energy used.
  • Reflux ratio of the present description means the ratio of the reflux flow rate to the outflow flow rate flowing out of the reaction distillation column.
  • the present invention can significantly reduce the steam used to lower the reflux ratio, it is possible to reduce the amount of thermal energy used in the reaction distillation column.
  • the inlet temperature of the reaction product in the reaction distillation column is 40 to 90 °C for example, the pressure may be 0.5 to 10gf / cm 2 -g.
  • the inlet temperature of the reaction distillation column is preferably 60 to 75 ° C., and has an effect of reducing the amount of thermal energy used in the reaction distillation tower by increasing the conversion rate of isobutene within the above range and reducing impurities.
  • pressure of the reactive distillation column can be for example, from 4 to 10kgf / cm 2 -g, preferably 4 to 6kgf / cm 2 -g, increase the conversion rate of isobutene in the range, by reducing the impurity It is effective to reduce the amount of thermal energy used in the reaction distillation column.
  • the stream discharged to the top of the reaction distillation column is, for example, is less than 1% by weight , or less than 0.8% by weight, preferably less than 0.6% by weight, within this range, the reflux of the reaction distillation column is reduced, It is effective to reduce the amount of thermal energy used in the reaction distillation column.
  • the stream exiting the bottom of the reaction distillation column may include, for example, 50 to 99.9 wt% or more, or 90 to 99.9 wt%, preferably 98 to 99.9 wt% of methyl tert-butyl ether.
  • methyl tert-butyl ether obtained in the bottoms stream contains only a very small amount of methyl secondary-butyl ether (MSBE) and thus may be suitable for the preparation of high purity isobutene by relysis.
  • MSBE methyl secondary-butyl ether
  • the amount of thermal energy used in the reaction distillation column of the purification step may be less than 0.99 or 0.80 to 0.95, or 0.88 to 0.94 in the reference process.
  • the thermal energy usage is determined based on the thermal energy usage of the reaction distillation tower in the reference process operating conditions (see Example 5) described as an example, it can be calculated by the following equation (2).
  • the thermal energy usage may be measured by a method generally used in the art, and may be confirmed by, for example, a flow rate, a temperature, and a pressure of steam introduced into a reboiler of a reaction distillation tower.
  • the manufacturing apparatus used in the methyl tert-butyl ether production method in the present invention is not limited to this, it is preferable to use the apparatus shown in Figures 1 to 3 below.
  • the production apparatus for carrying out the methyl tert-butyl ether production method the raw material supply pipe for introducing a first stream containing isobutene and methanol into the first reaction unit ( 1), a first reaction unit including two reactors connected in parallel, a second reaction unit including one reactor connected in series with the first reaction unit, and a part of the reaction product discharged from the first reaction unit It may include a recycle pipe (2) for recycling to the first reaction unit, and a reaction distillation column connected to the second reaction unit.
  • the production apparatus for carrying out the methyl tert-butyl ether production method the raw material supply pipe for introducing a first stream containing isobutene and methanol into the first reaction unit (1), a first reaction part including three reactors connected in parallel, a second reaction part including one reactor connected in series with the first reaction part, and a part of the reaction product discharged from the first reaction part It may include a recycle pipe (2) for recycling to the first reaction unit, and a reaction distillation column connected to the second reaction unit.
  • a manufacturing apparatus for carrying out the methyl tert-butyl ether production method includes a raw material supply for introducing a first stream containing isobutene and methanol into a first reaction unit.
  • the pipe 1 a first reaction unit including one reactor, a second reaction unit including one reactor connected in series with the first reaction unit, and a part of the reaction product discharged from the first reaction unit It may include a recirculation pipe (2) for recycling to one reaction unit, and a reaction distillation column connected to the second reaction unit.
  • the front end of the first reaction unit may further include a mixing device for mixing the components contained in the first stream before entering the reactor.
  • a pre-heater may be installed at the front end of the first reaction unit, and a cooler may be installed at the rear end.
  • each component of the first stream may include a separate pipeline for introducing each of the components into the first reaction section, or the components included in the first stream may be separately branched from one pipeline directly connected to the reactor. It may include a plurality of individual pipelines to be injected.
  • a first stream including isobutene and methanol introduced through the raw material supply pipe 1 and a part of the reaction product discharged from the first reaction part introduced through the recycle pipe 2 are included.
  • a third stream combined with a second stream is added to the first reaction unit, and a recycle / fresh feed rate of recycle and fresh feed may vary depending on the total volume of the reactor included in the first reaction unit. have.
  • the recycle / fresh feed flow rate (recycle / fresh feed) is more than 0.9 to less than 1.7, and included in the first reaction unit
  • the recycle / fresh feed flow rate (recycle / fresh feed) is greater than 2.2 to less than 4.8
  • the total volume of the reactor included in the first reaction unit is 60m 3
  • the recycle / fresh feed ratio may be greater than 3.1 to less than 9.8, in which case the conversion of isobutene is increased and the amount of impurities is reduced, thereby reducing the reflux of the reaction distillation column. The effect can be obtained, and as a result, there is an effect of reducing the amount of thermal energy used in the reaction distillation column.
  • the conversion rate of isobutene in the reaction product discharged from the second reaction unit is preferably 90 to 96%.
  • reaction product discharged from the second reaction unit is introduced into the reaction distillation column through a pipeline, the stream containing less than 200ppm of isobutene may be discharged from the upper portion of the reaction distillation column, methyl at the bottom of the reaction distillation column A stream containing from 50 to 99.9% by weight, preferably at least 98% by weight, of tert-butyl ether can be withdrawn.
  • each reactor has a volume of 30 m 3 in the first reaction part, and two reactors filled with a catalyst at 600 kg per unit volume (m 3 ) of the reactor are connected in parallel (the total volume of the reactor is 60 m 3 ).
  • Fresh feed component is isobutane, isobutene, 1-butene, 1,3 butadiene, n-butane, tert-2-butene, cis-2 butene, 1,2 butadiene, C5 carbon compound, 41.7 ton / hr, and the recycle component includes the fresh feed component and methyl tert-butyl ether.
  • methanol having a purity of 99.9% or more was introduced into the reactor through a separate pipe so that the molar ratio of methanol and isobutene (methanol: isobutene) was 1: 1.03.
  • the recycle / fresh feed ratio of recycle and fresh feed is 2.6, and under the reaction conditions in which the first reaction part has an input temperature of 37 ° C, a temperature of 37-65 ° C and a pressure of 4.7-5.0 kgf / cm 2 -g in the reactor.
  • the reaction was carried out, and the second reaction part was subjected to the reaction under the condition that the input temperature was 42 ° C, the temperature in the reactor was 42-47 ° C, and the pressure was 6.3-6.7 kgf / cm 2 -g.
  • Example 1 Except that the recycle / fresh feed flow rate (recycle / fresh feed) of 3.1 in Example 1 was carried out in the same manner as in Example 1.
  • one reactor having a reactor volume of 30 m 3 was used in the first reaction part (the total volume of the reactor was 30 m 3 ), except that the recycle / fresh feed ratio was 1.4. And the same method as in Example 1.
  • Example 1 the same procedure as in Example 1 was performed except that the recycle / fresh feed ratio was 2.2.
  • Example 1 the same procedure as in Example 1 was performed except that the recycle / fresh feed ratio was 4.8.
  • Example 3 the same procedure as in Example 3 was performed except that the recycle / fresh feed ratio was 3.1.
  • Example 3 the same procedure as in Example 3 was performed except that the recycle / fresh feed ratio was 9.8.
  • Example 5 the same procedure as in Example 5 was performed except that the flow rate ratio between the recycle and the fresh feed was 0.9.
  • Example 5 the same procedure as in Example 5 was performed except that the flow rate ratio between the recycle and the fresh feed was 1.7.
  • the conversion of isobutene in Examples 1 to 5 and Comparative Examples 1 to 6 was about 99.7%, the isobutene content was 200 ppm or less in the upper part of the reaction distillation column, and the MTBE content was 98.8 weight in the lower part of the reaction distillation column. It was over%.
  • the total volume of the reactor included in the first reaction unit is 60m 3
  • the thermal energy consumption was significantly reduced compared to Comparative Example 1 and Comparative Example 2
  • the flow rate (recycle / fresh feed) of the recycle and fresh feed is 2.2 or 4.8.
  • Example 5 in which the recycle / fresh feed ratio was 1.4, the heat energy consumption was higher than that of Comparative Examples 5 and 6, in which the recycle / fresh feed ratio was 0.9 or 1.7. It was confirmed that the decrease significantly.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production de méthyl-tert-butyléther, le procédé consistant à : faire réagir, dans une étape de réaction du méthanol et de l'isobutène en présence d'un catalyseur acide pour produire du méthyl-tert-butyléther; et introduire un produit de réaction obtenu dans l'étape de réaction dans une colonne de distillation de réaction comprenant un lit de garnissage qui contient un catalyseur acide, ce qui permet de purifier le produit de réaction, la quantité d'isobutène n'ayant pas réagi et la quantité d'impuretés contenues dans le réacteur étant réduites en faisant varier le rapport du courant de la charge de l'aliment recyclé/frais en fonction du volume du réacteur, et ainsi la quantité d'énergie thermique utilisée dans la colonne de distillation de réaction peut être réduite.
PCT/KR2018/000155 2017-01-06 2018-01-04 Procédé de production de méthyl-tert-butyléther Ceased WO2018128402A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18736760.2A EP3395792B2 (fr) 2017-01-06 2018-01-04 Procédé de production de méthyl-tert-butyléther
JP2018559978A JP6740536B2 (ja) 2017-01-06 2018-01-04 メチル第三級ブチルエーテルの製造方法
CN201880001171.2A CN108834410B (zh) 2017-01-06 2018-01-04 甲基叔丁基醚的制备方法
US16/073,294 US10626072B2 (en) 2017-01-06 2018-01-04 Method of preparing methyl tert-butyl ether

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20170002605 2017-01-06
KR10-2017-0002605 2017-01-06
KR1020180000673A KR102086563B1 (ko) 2017-01-06 2018-01-03 메틸 3급-부틸 에테르 제조방법
KR10-2018-0000673 2018-01-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024042265A1 (fr) * 2022-08-26 2024-02-29 Neste Oyj Procédé et système de production d'éther

Citations (5)

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Publication number Priority date Publication date Assignee Title
KR830002476B1 (ko) * 1980-03-11 1983-10-26 닛뽕 세끼유 가부시끼 가이샤 메틸 t-부틸 에테르의 제조방법
EP0071238B1 (fr) * 1981-07-27 1986-09-10 Phillips Petroleum Company Procédé pour la préparation de méthyl tertiobutyl éther
JPH06199722A (ja) * 1992-11-19 1994-07-19 Texaco Chem Co メチル−ｔｅｒｔ−ブチルエーテルの製造・回収方法
JPH09110769A (ja) * 1995-08-18 1997-04-28 Texaco Dev Corp メチルｔｅｒｔ−ブチルエーテルの製造における原料供給流を得る方法
US5789627A (en) * 1997-02-20 1998-08-04 Huntsman Specialty Chemicals Corp. Method for the purification of tertiary butyl alcohol and to its use in the manufacture of MTBE

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR830002476B1 (ko) * 1980-03-11 1983-10-26 닛뽕 세끼유 가부시끼 가이샤 메틸 t-부틸 에테르의 제조방법
EP0071238B1 (fr) * 1981-07-27 1986-09-10 Phillips Petroleum Company Procédé pour la préparation de méthyl tertiobutyl éther
JPH06199722A (ja) * 1992-11-19 1994-07-19 Texaco Chem Co メチル−ｔｅｒｔ−ブチルエーテルの製造・回収方法
JPH09110769A (ja) * 1995-08-18 1997-04-28 Texaco Dev Corp メチルｔｅｒｔ−ブチルエーテルの製造における原料供給流を得る方法
US5789627A (en) * 1997-02-20 1998-08-04 Huntsman Specialty Chemicals Corp. Method for the purification of tertiary butyl alcohol and to its use in the manufacture of MTBE

Non-Patent Citations (1)

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Title
See also references of EP3395792A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024042265A1 (fr) * 2022-08-26 2024-02-29 Neste Oyj Procédé et système de production d'éther

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