WO2022190962A1 - ブタジエンの製造方法 - Google Patents
ブタジエンの製造方法 Download PDFInfo
- Publication number
- WO2022190962A1 WO2022190962A1 PCT/JP2022/008576 JP2022008576W WO2022190962A1 WO 2022190962 A1 WO2022190962 A1 WO 2022190962A1 JP 2022008576 W JP2022008576 W JP 2022008576W WO 2022190962 A1 WO2022190962 A1 WO 2022190962A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- butadiene
- carbon dioxide
- gas
- electrolytic reduction
- butene
- Prior art date
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 94
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 194
- 239000007789 gas Substances 0.000 claims abstract description 146
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 97
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 97
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000005977 Ethylene Substances 0.000 claims abstract description 64
- 230000009467 reduction Effects 0.000 claims abstract description 57
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000001301 oxygen Substances 0.000 claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 49
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
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- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000000447 dimerizing effect Effects 0.000 claims abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 49
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 7
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- 239000006227 byproduct Substances 0.000 abstract description 10
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- 238000000034 method Methods 0.000 description 20
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- 239000000047 product Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000006471 dimerization reaction Methods 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/24—Catalytic processes with metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B15/025—Measuring, analysing or testing during electrolytic production of electrolyte parameters
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C—CHEMISTRY; METALLURGY
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- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
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- C07C2523/56—Platinum group metals
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- C07C2523/648—Vanadium, niobium or tantalum
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- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/882—Molybdenum and cobalt
Definitions
- the present invention relates to a method for producing butadiene.
- Patent Documents 1 and 2 disclose a method of dimerizing ethylene to produce butene, and then oxidatively dehydrogenating the butene to produce butadiene.
- an object of the present invention is to provide a method for producing butadiene that can reduce carbon dioxide emissions.
- one aspect of the present invention is a method for producing butadiene, comprising an electrolytic reduction step (2) of producing ethylene and oxygen by electrolytic reduction using carbon dioxide and water as raw materials; A butene production step (3) of dimerizing ethylene produced in the electrolytic reduction step to produce butene, oxygen produced in the electrolytic reduction step, butene produced in the butene production step, and air. a mixing step (4) for mixing to prepare a mixed gas; and a butadiene producing step (5) for heating the mixed gas to oxidatively dehydrogenate butene to produce butadiene. The resulting carbon dioxide is used as part of the raw material in the electrolytic reduction step.
- carbon dioxide generated during the production of butadiene by oxidative dehydrogenation can be used to produce ethylene, which is a raw material for butene, and oxygen necessary for oxidative dehydrogenation.
- the emission amount of carbon dioxide, which is a greenhouse gas can be reduced.
- the heat exchange step (6) for cooling the gas composition containing butadiene and carbon dioxide, which flows out from the butadiene production step, and the butadiene cooled and liquefied in the heat exchange step is removed from the gas composition.
- Carbon dioxide may be used as part of the raw material in the electrolytic reduction step.
- carbon dioxide is concentrated and supplied to the electrolytic reduction step. Thereby, the efficiency of electrolytic reduction can be improved.
- the gas composition containing butadiene and carbon dioxide which flows out from the butadiene production step, is heat-exchanged with the gas composition from which carbon dioxide has been separated in the carbon dioxide separation step. should be cooled by
- the gas composition from which carbon dioxide has been separated in the carbon dioxide separation step is heat-exchanged in the heat exchange step with the gas composition containing butadiene and carbon dioxide, which flows out from the butadiene production step, It may be mixed with the mixed gas in the mixing step.
- the gas composition from which carbon dioxide has been separated in the carbon dioxide separation step is heated in the heat exchange step and then supplied to the butadiene production step via the mixing step.
- the energy consumption for heating the reactor of the butadiene production process can be reduced.
- measuring the oxygen concentration and flow rate of the mixed gas in the mixing step It is preferable to control the flow rate of oxygen supplied from the electrolytic reduction process to the mixing process based on the oxygen concentration and flow rate of the mixed gas.
- the oxygen concentration of the mixed gas can be maintained within an appropriate range.
- the efficiency of electrolytic reduction can be improved.
- the above aspect further includes an ethylene production step (101) for producing ethylene using ethane or naphtha as a raw material, and the ethylene obtained in the ethylene production step is used as part of the raw material in the electrolytic reduction step. Good.
- the amount of ethylene supplied can be increased.
- the butene produced as a by-product in the ethylene production step is preferably used in the butadiene production step.
- the supply amount of butene can be increased.
- the butadiene production system 1 according to the embodiment, as shown in FIGS. It has a separation step 7 and a carbon dioxide separation step 8 .
- ethylene and oxygen are produced by electrolytic reduction using carbon dioxide and water as raw materials.
- an electrolytic reduction apparatus using a gas diffusion electrode for the cathode 16 an electrolytic reduction apparatus using a solid polymer membrane for the separator, or the like may be used.
- the electrolytic reduction device 10 used in the electrolytic reduction step 2 may be, for example, a three-chamber type electrolytic reduction device.
- the electrolytic reduction apparatus 10 may include an electrolytic cell 14 having a cathode gas chamber 11, a catholyte chamber 12, and an anolyte chamber 13, which are separated from one another.
- the cathode gas chamber 11 and the catholyte chamber 12 are separated by a cathode 16 as a gas diffusion electrode.
- the catholyte chamber 12 and the anolyte chamber 13 are separated by a partition wall 17 having ion conductivity.
- An anode 18 is arranged in the anolyte compartment 13 . Gaseous carbon dioxide is supplied to the cathode gas chamber 11 .
- Carbon dioxide is supplied from the carbon dioxide separation step 8 as described below.
- the catholyte chamber 12 is supplied with catholyte.
- An anolyte is supplied to the anolyte chamber 13 .
- Anode 18 and cathode 16 are connected to DC power supply 19 .
- Anolyte and catholyte are aqueous solutions in which electrolytes are dissolved.
- the electrolyte includes at least one of potassium, sodium, lithium, or compounds thereof.
- the electrolyte may include, for example, at least one of the group consisting of LiOH, NaOH, KOH, Li2CO3 , Na2CO3 , K2CO3 , LiHCO3 , NaHCO3 , and KHCO3 .
- the cathode 16 is a gas diffusion electrode and has a gas diffusion layer 21 and a microporous layer 22 .
- the gas diffusion layer 21 is permeable to gas containing carbon dioxide, but inhibits the permeation of an aqueous solution containing catholyte.
- the microporous layer 22 is permeable to both gas containing carbon dioxide and aqueous solution containing catholyte.
- the gas diffusion layer 21 and the microporous layer 22 are each formed planar.
- the gas diffusion layer 21 is arranged on the cathode gas chamber 11 side, and the microporous layer 22 is arranged on the catholyte chamber 12 side.
- the gas diffusion layer 21 may be formed by forming a water-repellent film such as polytetrafluoroethylene on the surface of a porous conductive substrate such as carbon paper, carbon felt, or carbon cloth.
- the conductive base material is connected to the negative electrode of the DC power supply 19 and is supplied with electrons.
- the microporous layer 22 is formed on the surface of the gas diffusion layer 21 using carbon black or the like, and carries a catalyst.
- the catalyst may be a known carbon dioxide reduction catalyst, such as a group 11 element such as copper, a group 12 element such as zinc, a group 13 element such as gallium, a group 14 element such as germanium, or any of these At least one metal compound is included.
- Metal compounds include at least one of oxides, sulfides, and phosphides.
- the catalyst is preferably one suitable for reducing carbon dioxide to produce ethylene, e.g. copper or a copper compound with metals of group 11, group 12, group 13 and group 14 elements, and metal compounds thereof are preferably used.
- a binder such as an ion exchange resin may be added to the microporous layer 22 .
- the anode 18 is made of, for example, metal materials such as titanium, nickel, molybdenum, platinum, gold, silver, copper, iron, lead, or metal alloy materials thereof, carbon-based materials such as carbon, or conductive ceramics.
- the shape of the anode 18 may be a flat plate, a flat plate with multiple openings, a mesh, and a porous body.
- the shape of the opening formed in the flat plate may be circular, rhombic, star-shaped, or the like.
- the flat plate may be corrugated or curved, and may have unevenness on the surface.
- the anode 18 carries an oxygen generating catalyst such as platinum or iridium.
- the anode 18 may be provided on the surface of the partition wall 17 on the anolyte chamber 13 side.
- the DC power supply 19 converts electric power obtained from thermal power generation, nuclear power generation, solar power generation, wind power generation, hydraulic power generation, etc. into DC power as necessary and supplies it to the cathode 16 and the anode 18 . From the viewpoint of reducing carbon dioxide emissions, it is preferable to use power obtained from solar power generation, wind power generation, hydraulic power generation, or the like using natural energy (renewable energy) as the DC power supply 19 .
- a DC power supply 19 applies a voltage to the anode 18 so that the cathode 16 has a negative potential.
- the DC power supply 19 preferably obtains the potential of the cathode 16 using a reference electrode and controls the applied voltage so that the potential of the cathode 16 is within a predetermined range.
- the cathode gas chamber 11 has an inlet 24 and an outlet 25 . Carbon dioxide gas is supplied through inlet 24 and discharged through outlet 25 .
- the outlet 25 of the cathode gas chamber 11 is connected to the inlet 24 via a gas circuit 26 .
- the catholyte chamber 12 has an inlet 27 and an outlet 28 .
- the inlet 27 and outlet 28 of the catholyte chamber 12 are connected by a catholyte circuit 29 .
- anolyte compartment 13 has an inlet 31 and an outlet 32 .
- the inlet 31 and outlet 32 of the anolyte chamber 13 are connected by an anolyte circuit 33 .
- Separators 35, 36 are provided in the catholyte circuit 29 and the anolyte circuit 33, respectively. Separators 35, 36 may include gas-liquid separators.
- the catholyte circulation path 29 and the anode fluid circulation path 33 are preferably provided with electrolyte concentration control devices 37 and 38 for adjusting the electrolyte concentrations of the catholyte and the anode fluid within a predetermined range, respectively.
- Electrolyte concentration control devices 37 and 38 include a sensor for detecting the electrolyte concentration of the catholyte and the anolyte, an electrolyte feeder for supplying new catholyte and anolyte having a predetermined concentration, and a circulating catholyte and anolyte. and a drainage device for partially draining.
- the gas circulation path 26 is provided with a gas circulation flow control device 34 for discharging a part of the gas circulating inside.
- a discharge port of the gas circulation flow control device 34 is connected to the first gas passage 39 .
- a gas discharge passage of the separation device 35 is connected to the first gas passage 39 .
- the gas circulation flow rate adjusting device 34 adjusts the flow rate and pressure of the gas circulating through the gas circulation path 26 and the cathode gas chamber 11 by discharging the gas to the first gas passage 39 .
- the gas pressure in the cathode gas chamber 11 is maintained at a predetermined value higher than the liquid pressure in the cathode liquid chamber 12 by the gas circulation flow control device 34 .
- Carbon dioxide in the cathode gas chamber 11 diffuses into the gas diffusion layer 21 of the cathode 16 and is reduced in the microporous layer 22 to obtain the first product.
- the first product contains ethylene as a main product and contains by-products such as methane, hydrogen, carbon monoxide and formic acid. Most of the first product is generated on the cathode gas chamber 11 side of the cathode 16 . A part of the first product is generated on the catholyte chamber 12 side of the cathode 16 .
- the first product in the catholyte chamber 12 is mixed with unreacted carbon dioxide that has flowed into the catholyte chamber 12 .
- the first product in the cathode gas chamber 11 is mixed with unreacted carbon dioxide.
- the first gas passage 39 may be provided with a separation device for separating ethylene out of the first product.
- the separation device may be configured by combining a distillation device, an extraction device, and an adsorption device.
- ethylene, methane, and hydrogen and carbon monoxide as by-products are circulated in the gas circulation path 26 together with unreacted carbon dioxide. It is discharged from the flow control device 34 to the first gas passage 39 .
- the first product containing ethylene, methane, by-product hydrogen and carbon monoxide, and unreacted carbon dioxide produced on the side of the catholyte chamber 12 of the cathode 16 is separated by the separation device 35 and the gas circulation flow rate adjustment. From the device 34 flows into the first gas passage 39 .
- Oxygen is separated from the anolyte by a separator 36 in the anolyte circuit 33 .
- a separator 36 in the anolyte circuit 33 At the anode 18, water and hydroxide ions in the anolyte are oxidized to generate oxygen.
- Oxygen, which is a gas, is separated from the anolyte by the separation device 36 in the anolyte circuit 33 and flows to the second gas passage 40 .
- the catalyst supported on the cathode 16 and the potential of the cathode 16 are preferably set so that the Faraday efficiency for ethylene production at the cathode 16 is 30% or more, preferably 50% or more.
- Faradaic efficiency is defined as the ratio of the current that contributed to the production of each product to the total current that flowed through the electrolytic cell 14 .
- the catalyst supported on the cathode 16 is preferably selected so that the selectivity for ethylene production at the cathode 16 is 30% or more.
- the ethylene produced in the electrolytic reduction step 2 is supplied from the first gas passage 39 to the butene production step 3 through the first line 41 . Also, the oxygen generated in the electrolytic reduction step 2 is supplied to the mixing step 4 from the second gas passage 40 through the second line 42 .
- the butene production step 3 the ethylene produced in the electrolytic reduction step 2 is dimerized to produce butene. 2C2H4 ⁇ C4H8 _ In butene production step 3, butene is produced, the main product being n-butene. As shown in FIG. 2 , the butene production step 3 has a dimerization reactor 44 and a first separation device 45 .
- the dimerization reactor 44 may be, for example, a fixed bed flow reactor filled with an ethylene dimerization catalyst.
- Ethylene dimerization catalysts include nickel, alumina and silica.
- the ethylene dimerization catalyst may be, for example, a silica carrier carrying alumina and nickel, or a silica carrier containing alumina carrying nickel.
- the content of nickel in the ethylene dimerization catalyst is 0.0001 to 1 wt%, preferably 0.0001 to 0.5 wt%, more preferably 0.0001 to 0.05 wt%.
- the carrier preferably has a high specific surface area and a high pore volume.
- the carrier preferably has a specific surface area of 200 to 1200 m 2 /g and a pore volume of 0.4 to 2 cc/g.
- the silica carrier is preferably amorphous silica or mesoporous silica.
- the carrier containing silica and alumina may be Y-type zeolite, X-type zeolite, mordenite, beta-type zeolite, L-type zeolite, MFI-type zeolite.
- the reaction temperature for the dimerization reaction of ethylene is set to 150-400.degree. C., preferably 200-350.degree.
- the reaction temperature is lower than 150°C, the activity of the catalyst is lowered. If the reaction temperature is higher than 400° C., branched olefins will rapidly increase, and nickel agglomeration on the catalyst and coke by-production will easily occur. As a result, the deterioration of the catalyst may be caused.
- the pressure for the dimerization reaction of ethylene is preferably 0.1 to 50 MPa. When the reaction pressure is higher than 50 MPa, by-products are likely to occur. If the reaction pressure is lower than 0.1 MPa, the catalytic activity is lowered.
- the ethylene supply rate (WHSV) per unit weight of catalyst is preferably 0.1 to 50 h -1 , preferably 0.5 to 40 h -1 , more preferably 0.5 to 30 h -1 . If the ethylene feed rate is less than 0.1 h ⁇ 1 , productivity will be low. In addition, the selectivity for dimers and trimers is lowered due to the progress of successive oligomerization reactions. If the ethylene feed rate is greater than 40 h ⁇ 1 , the conversion of ethylene will be low.
- n-butenes including 1-butene, cis-2-butene, and trans-2-butene, as main products.
- Hexenes such as 1-hexene, 2-hexene, and 3-hexene may also be produced as by-products.
- the first separation device 45 separates n-butene from the reaction product obtained by the dimerization of ethylene in the dimerization reactor 44 and unreacted ethylene.
- the first separation device 45 is connected via a third line 47 to the dimerization reactor 44 .
- the first separation device 45 is preferably configured by combining a known distillation device, extraction device, and adsorption device.
- the first separator 45 may also separate unreacted ethylene from the reaction product and return it to the dimerization reactor 44 via return line 48 .
- a hydrocarbon such as hexene separated by the first separation device 45 may be sent to an oxyfuel combustion device 60, which will be described later, and used as fuel.
- the mixing step 4 the oxygen produced in the electrolytic reduction step 2, the butene produced in the butene production step 3, and air are mixed to prepare a mixed gas.
- the mixing process 4 has a gas mixer 51 .
- the gas mixing device 51 is supplied with n-butene from the first separation device 45 of the butene production step 3 via a fourth line 52, is supplied with air via an air line 53, and is supplied with air via a second line 42.
- Oxygen is supplied from the separator 36 of the electrolytic reduction process 2 and recycled gas is supplied from the carbon dioxide separation process 8 via the sixth line 55 .
- the recycled gas mainly contains nitrogen and oxygen.
- Air, oxygen from the electrolytic reduction step 2, and recycled gas are used to adjust the oxygen concentration in the oxidative dehydrogenation reactor 67, which will be described later.
- the mixed gas is prepared so that the molar ratio of oxygen:n-butene is in the range of 1:0.5-3, preferably in the range of 1:0.8-2.
- the air line 53 is provided with a first flow control valve 57 that controls the flow rate of air supplied to the gas mixing device 51 .
- the second line 42 is provided with a second flow control valve 58 for controlling the flow rate of oxygen supplied to the gas mixing device 51 .
- the second flow control valve 58 is connected via a seventh line 59 to an oxygen combustion device 60 such as a boiler that uses oxygen. Thermal energy generated in the oxyfuel burner 60 may be recovered and used to heat the gas exiting the gas mixer 51 . Also, carbon dioxide generated by combustion in the oxygen combustion device 60 may be recovered and used as part of the raw material in the electrolytic reduction step 2 .
- the gas mixer 51 supplies a mixed gas containing ethylene, oxygen, air, and recycle gas to the butadiene production step 5 via the eighth line 61 .
- the exit of the gas mixing device 51 or the eighth line 61 is provided with a first gas flow meter 63 for measuring the flow rate of the mixed gas and an oxygen concentration meter 64 for measuring the oxygen concentration of the mixed gas.
- a pressure pump 65 for pressurizing the mixed gas and a heating furnace 66 for preheating the mixed gas are provided on the eighth line 61 .
- Furnace 66 may be supplied with oxygen from second line 42 or seventh line 59 .
- the mixed gas is heated to oxidatively dehydrogenate butene to produce butadiene.
- the butadiene production step 5 has an oxidative dehydrogenation reactor 67 .
- Oxidative dehydrogenation reactor 67 may be any reactor such as a fixed bed, ebullated bed or moving bed reactor.
- the oxidative dehydrogenation reactor 67 is filled with an oxidative dehydrogenation catalyst.
- the oxidative dehydrogenation catalyst is preferably a composite metal oxide catalyst containing molybdenum and bismuth, an iron oxide catalyst, a vanadium oxide catalyst, or the like.
- the oxidative dehydrogenation catalyst preferably contains iron and cobalt in addition to molybdenum and bismuth.
- the oxidative dehydrogenation catalyst may contain silica in addition to the composite metal oxide.
- the oxidative dehydrogenation reaction is carried out at 300-600°C, preferably 300-500°C, more preferably 320-460°C. Also, the oxidative dehydrogenation reaction is carried out at 0 to 2 MPa, preferably 0 to 0.5 MPa. Also, the feed rate of n-butene per unit weight of catalyst is preferably 0.1 to 10 h -1 , more preferably 0.2 to 5 h -1 . Oxidative dehydrogenation produces butadiene as the main product from n-butene. Complete combustion of n-butene also produces carbon dioxide as a by-product.
- the outlet of the oxidative dehydrogenation reactor 67 is connected to the butadiene separation step 7 via a ninth line 69 .
- a gas composition containing butadiene, carbon dioxide, and unreacted mixed gas flows out from the outlet of the oxidative dehydrogenation reactor 67 .
- the ninth line 69 is provided with a heat exchanger 71 that constitutes the heat exchange step 6 .
- the gas composition passing through ninth line 69 is cooled in heat exchanger 71 .
- the gas composition is supplied to the butadiene separation step 7 via the ninth line 69, and butadiene is separated in the butadiene separation step 7.
- the butadiene separation step 7 has a second separation device 72 .
- the second separation device 72 may, for example, liquefy the butadiene by cooling the gas composition and separate the liquid butadiene from the gas composition by gas-liquid separation.
- the gas composition from which butadiene is separated in the butadiene separation step 7 mainly contains nitrogen, carbon dioxide, and oxygen.
- the gas composition from which butadiene has been separated is supplied to the carbon dioxide separation step 8 via the tenth line 74, and carbon dioxide is separated in the carbon dioxide separation step 8.
- the carbon dioxide separation step 8 includes chemical adsorption methods such as Benfield method and MDEA (methyldiethanolamine) method, physical adsorption methods such as Celexol method and Rectisol method, membrane separation method, PSA method (pressure swing adsorption method), PTSA method. (Pressure temperature fluctuation adsorption method), electrochemical separation method using quinones, or the like may be provided. Carbon dioxide that has been separated from the gas composition and adsorbed on various adsorbents is separated from the adsorbent by a regeneration process and becomes a highly concentrated gaseous state.
- the carbon dioxide separated in the carbon dioxide separation step 8 is supplied from the third separator 75 to the cathode gas chamber 11 in the electrolytic reduction step 2 via the 11th line 76 .
- the carbon dioxide by-produced in the butadiene production step 5 is used as part of the raw material in the electrolytic reduction step 2 .
- a carbon dioxide line 77 for supplying carbon dioxide gas to the eleventh line 76 is connected to the eleventh line 76 .
- a third flow control valve 78 is provided in the carbon dioxide line 77 .
- the eleventh line 76 is provided with a carbon dioxide concentration meter 79 for measuring the concentration of carbon dioxide passing through the eleventh line 76 .
- the eleventh line 76 is provided with a second gas flow meter 80 for measuring the flow rate of carbon dioxide passing through the eleventh line 76 .
- the gas composition from which carbon dioxide has been separated mainly contains nitrogen and oxygen, and is returned to the gas mixing device 51 of the mixing step 4 via the sixth line 55 as recycled gas.
- the sixth line 55 passes through the heat exchanger 71 of the heat exchange step 6 where the recycle gas exchanges heat with the gas composition passing through the ninth line 69 . This increases the temperature of the recycle gas passing through the sixth line 55 and decreases the temperature of the gas composition passing through the ninth line 69 at the outlet of the heat exchanger 71 .
- the control device 85 controls the first flow control valve 57 and the second flow control valve 58 based on signals from the first gas flow meter 63 and the oxygen concentration meter 64 . Based on the signal from the first gas flow meter 63, the controller 85 preferably increases the opening of the first flow control valve 57 as the flow rate of the mixed gas decreases. This increases the amount of air supplied to the gas mixing device 51 and increases the flow rate of the mixed gas. In addition, based on the signal from the oxygen concentration meter 64, the control device 85 adjusts the opening degree of the second flow control valve 58 as the oxygen concentration of the mixed gas becomes lower. It is advisable to increase the flow rate of oxygen flowing to the Thereby, the oxygen concentration of the mixed gas can be maintained within an appropriate range.
- control device 85 preferably controls the potential of the DC power supply 19 based on signals from the carbon dioxide concentration meter 79 and the second gas flow meter 80 . Thereby, the efficiency of electrolytic reduction can be improved.
- controller 85 also controls the third flow control valve 78 based on signals from the carbon dioxide concentration meter 79 and the second gas flow meter 80 to adjust the amount of carbon dioxide supplied to the carbon dioxide separation process 8 .
- the carbon dioxide generated in the butadiene production step 5 is concentrated through the heat exchange step 6, the butadiene separation step 7, and the carbon dioxide separation step 8, and supplied to the electrolytic reduction step 2. Thereby, the efficiency of electrolytic reduction can be improved.
- the gas composition from which carbon dioxide has been separated in the carbon dioxide separation step 8 is heat-exchanged in the heat exchange step 6 with the gas composition containing butadiene and carbon dioxide flowing out of the butadiene production step 5, and then mixed in the mixing step 4. mixed with gas. Thereby, the energy consumption for heating the oxidative dehydrogenation reactor 67 in the butadiene production step 5 can be reduced.
- the gas composition containing butadiene and carbon dioxide that flows out from the butadiene production step 5 can be cooled, and energy efficiency can be improved.
- the butadiene production system 1 may further include an ethylene production step 101 that produces ethylene using ethane or naphtha as a raw material.
- the ethylene production step 101 preferably produces ethylene by ethane cracking using ethane as a raw material or naphtha cracking using naphtha as a raw material.
- a portion of the ethylene produced in the ethylene production step 101 is preferably supplied to the butene production step 3 via the twelfth line 102 and used as part of the raw material in the butene production step 3.
- the butene by-produced in the ethylene production step 101 may be supplied to the mixing step 4 via the thirteenth line 103 and used in the butadiene production step 5.
- the twelfth line 102 may be omitted.
- the carbon dioxide line 77 may be omitted because the amount of ethylene that needs to be produced in the electrolytic reduction step 2 is reduced.
- the cathode 16 is a gas diffusion electrode supporting a copper-zinc composite catalyst, and the anode 18 is A Pt mesh was used.
- a 1 M potassium hydrogen carbonate aqueous solution was flowed into each of the catholyte chamber 12 and the anolyte chamber 13 at 1 mL/min, and a current of 265 mA/cm 2 was applied for 6 hours while carbon dioxide was flowed into the cathode gas chamber 11 at 100 mL/min.
- Analysis of the products in the gas revealed that the cathode 16 produced 37% ethylene, 1% methane, and 25% hydrogen with a faradaic efficiency, and the anode 18 produced a gas with a faradaic efficiency of 99% oxygen.
- /hr of oxygen is supplied, and 50 kg/hr of carbon dioxide is supplied from the butadiene production step 5 to the electrolytic reduction step 2 . That is, 50 kg/hr of carbon dioxide was produced in the butadiene producing step 5, and 12 kg/hr of ethylene and 56 kg/hr of oxygen were produced in the electrolytic reduction step 2 using this carbon dioxide as a raw material. In this case, the selectivity of ethylene in the electrolytic reduction step 2 was set to 80%.
- Butadiene production system 2 Electrolytic reduction process 3: Butene production process 4: Mixing process 5: Butadiene production process 6: Heat exchange process 7: Butadiene separation process 8: Carbon dioxide separation process 10: Electrolytic reduction device 44: Dimerization reaction Device 51 : Gas mixing device 57 : First flow control valve 58 : Second flow control valve 61 : Oxygen combustion device 63 : First gas flow meter 64 : Oxygen concentration meter 67 : Oxidative dehydrogenation reactor 71 : Heat exchanger 72 : Second separation device 75 : Third separation device 79 : Carbon dioxide concentration meter 80 : Second gas flow meter 85 : Control device 101 : Ethylene production step 102 : Twelfth line 103 : Thirteenth line
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Abstract
Description
前記混合ガスの酸素濃度及び流量に基づいて、前記電解還元工程から前記混合工程に供給する酸素の流量を制御するとよい。
2CO2+2H2O→C2H4+3O2
電解還元工程2は、カソード16にガス拡散電極を使用した電解還元装置や、セパレータに固体高分子膜を使用した電解還元装置等を使用するとよい。
2C2H4→C4H8
ブテン生成工程3では、ブテンが生成され、その主生成物はn-ブテンである。図2に示すように、ブテン生成工程3は、二量化反応器44と、第1分離装置45とを有する。
C4H8+1/2O2→C4H6+H2O
2 :電解還元工程
3 :ブテン生成工程
4 :混合工程
5 :ブタジエン生成工程
6 :熱交換工程
7 :ブタジエン分離工程
8 :二酸化炭素分離工程
10 :電解還元装置
44 :二量化反応器
51 :ガス混合装置
57 :第1流量制御弁
58 :第2流量制御弁
61 :酸素燃焼装置
63 :第1ガス流量計
64 :酸素濃度計
67 :酸化脱水素反応器
71 :熱交換器
72 :第2分離装置
75 :第3分離装置
79 :二酸化炭素濃度計
80 :第2ガス流量計
85 :制御装置
101 :エチレン生成工程
102 :第12ライン
103 :第13ライン
Claims (8)
- ブタジエンの製造方法であって、
二酸化炭素と水とを原料として電解還元によってエチレンと酸素とを製造する電解還元工程と、
前記電解還元工程で生成されたエチレンを二量化してブテンを生成するブテン生成工程と、
前記電解還元工程で生成された酸素と、前記ブテン生成工程で生成されたブテンと、空気とを混合し、混合ガスを調製する混合工程と、
前記混合ガスを加熱し、ブテンを酸化脱水素してブタジエンを生成するブタジエン生成工程とを有し、
前記ブタジエン生成工程で副生した二酸化炭素が前記電解還元工程において前記原料の一部として使用されるブタジエンの製造方法。 - 前記ブタジエン生成工程から流出する、ブタジエン及び二酸化炭素を含むガス組成物を冷却する熱交換工程と、
前記熱交換工程において冷却された前記ガス組成物からブタジエンを分離するブタジエン分離工程と、
前記ブタジエン分離工程においてブタジエンが分離された前記ガス組成物から二酸化炭素を分離する二酸化炭素分離工程とを有し、
前記二酸化炭素分離工程において分離された二酸化炭素が前記電解還元工程に前記原料の一部として使用される請求項1に記載のブタジエンの製造方法。 - 前記熱交換工程において、前記ブタジエン生成工程から流出する、ブタジエン及び二酸化炭素を含むガス組成物は、前記二酸化炭素分離工程において二酸化炭素が分離されたガス組成物と熱交換することによって冷却される請求項2に記載のブタジエンの製造方法。
- 前記二酸化炭素分離工程において二酸化炭素が分離されたガス組成物は、前記ブタジエン生成工程から流出する、ブタジエン及び二酸化炭素を含むガス組成物と前記熱交換工程において熱交換した後に、前記混合工程において前記混合ガスに混合される請求項3に記載のブタジエンの製造方法。
- 前記混合工程において前記混合ガスの酸素濃度及び流量を測定し、
前記混合ガスの酸素濃度及び流量に基づいて、前記電解還元工程から前記混合工程に供給する酸素の流量を制御する請求項1~請求項4のいずれか1つの項に記載のブタジエンの製造方法。 - 前記ブタジエン生成工程から前記電解還元工程に供給される二酸化炭素の流量を測定し、二酸化炭素の流量に基づいて、前記電解還元工程における電解還元の電位を制御する請求項1~請求項5のいずれか1つの項に記載のブタジエンの製造方法。
- エタン又はナフサを原料としてエチレンを生成するエチレン生成工程を更に有し、
前記エチレン生成工程で生成されたエチレンが前記ブテン生成工程において前記原料の一部として使用される請求項1~請求項6のいずれか1つの項に記載のブタジエンの製造方法。 - 前記エチレン生成工程で副生したブテンが前記ブタジエン生成工程において使用される請求項7に記載のブタジエンの製造方法。
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JP2015182985A (ja) * | 2014-03-25 | 2015-10-22 | 三菱化学株式会社 | ブタジエンの製造方法 |
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JP2014062094A (ja) | 2012-09-21 | 2014-04-10 | Axens | エチレンを二量化し、得られたブテンを脱水素化することによって1,3−ブタジエンを製造する方法 |
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