WO2017170915A1 - エチレンオキシドの製造方法 - Google Patents
エチレンオキシドの製造方法 Download PDFInfo
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- WO2017170915A1 WO2017170915A1 PCT/JP2017/013372 JP2017013372W WO2017170915A1 WO 2017170915 A1 WO2017170915 A1 WO 2017170915A1 JP 2017013372 W JP2017013372 W JP 2017013372W WO 2017170915 A1 WO2017170915 A1 WO 2017170915A1
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- heat exchanger
- ethylene oxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
- F28D15/02—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/082—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys
- F28F21/083—Heat exchange elements made from metals or metal alloys from steel or ferrous alloys from stainless steel
Definitions
- the present invention relates to a method for producing ethylene oxide.
- Ethylene oxide is produced today by catalytic vapor phase oxidation of ethylene with a molecular oxygen-containing gas in the presence of a silver catalyst.
- the purification method in the ethylene oxide production process is generally as follows (see Japanese Patent Application Laid-Open No. 62-103072).
- reaction process ethylene and molecular oxygen-containing gas are subjected to catalytic gas phase oxidation on a silver catalyst to obtain a reaction product gas containing ethylene oxide (reaction process).
- reaction product gas is guided to an ethylene oxide absorption tower and brought into contact with an absorption liquid mainly composed of water to recover ethylene oxide as an aqueous solution (absorption process).
- absorption liquid mainly composed of water
- the recovered aqueous ethylene oxide solution is sent to an ethylene oxide purification system, and high purity ethylene oxide is obtained through several stages.
- This ethylene oxide purification system usually comprises a stripping step, a rectification step, a dehydration step, a light fraction separation step, a heavy fraction separation step, and the like.
- an object of the present invention is to provide a means capable of suppressing corrosion in the heat exchanger inner tube and enabling continuous production for a long period in the ethylene oxide production process.
- the present inventors have conducted intensive research in order to solve the above problems.
- the present inventors also indicate that corrosion occurs in the inner tube of the heat exchanger because the source gas contains a chlorine compound and the gas to be cooled that is cooled by the heat exchanger contains a chlorine compound and water. confirmed.
- the present inventors have surprisingly found that the gas linear velocity is 7 m / s or more when the gas to be cooled containing water and a chlorine compound is cooled by passing through the inner tube side of the heat exchanger.
- the inventors have found that the above problems can be solved, and have completed the present invention.
- one embodiment of the present invention relates to a method for producing ethylene oxide.
- the production method includes supplying a raw material gas containing ethylene, molecular oxygen and a chlorine compound to an ethylene oxidation reactor, and in the ethylene oxidation reactor, in the presence of a silver catalyst, ethylene and molecular oxygen in the raw material gas Gas phase oxidation to produce a gas containing ethylene oxide, water and a chlorine compound, and cooling a cooled gas containing water and a chlorine compound with a heat exchanger.
- the said manufacturing method has the characteristics in the point which cools the to-be-cooled gas containing water and a chlorine compound in the heat exchanger at the gas linear velocity of the heat exchanger inner pipe side of 7 m / s or more.
- FIG. 2 corresponds to a diffusion process described later. It is a block diagram which shows the structural example of the rectification process until the diffused ethylene oxide is finally refine
- X to Y indicating a range means “X or more and Y or less”.
- One embodiment of the present invention is to supply a raw material gas containing ethylene, molecular oxygen, and a chlorine compound to an ethylene oxidation reactor.
- ethylene oxidation reactor in the presence of a silver catalyst, ethylene and molecular gas in the raw material gas Production of ethylene oxide comprising catalytic gas phase oxidation with oxygen to produce a gas containing ethylene oxide, water and a chlorine compound, and cooling a cooled gas containing water and the chlorine compound with a heat exchanger
- the method is a manufacturing method in which, in the heat exchanger, a gas to be cooled containing water and a chlorine compound is cooled at a gas linear velocity on the heat exchanger inner tube side of 7 m / s or more.
- the manufacturing method according to this embodiment in the ethylene oxide manufacturing process, corrosion of the heat exchanger inner pipe is suppressed, and continuous production for a long period of time is enabled.
- the process for producing ethylene oxide according to the present invention makes it possible to significantly reduce the exchange frequency of the heat exchanger, so that it is possible to improve the production efficiency. sell.
- the raw material gas essentially contains ethylene, molecular oxygen and chlorine compound. Moreover, 1 type, or 2 or more types, such as nitrogen, helium, argon, a carbon dioxide, water vapor
- the raw material gas composition is not particularly limited.
- ethylene is 0.5 to 40% by mass, preferably 10 to 30% by mass, and oxygen (for example, molecular oxygen gas) 5 to 15% by mass based on the mass of the raw material gas.
- carbon dioxide gas 0.5 to 30% by mass, preferably 8 to 13% by mass, the balance being water vapor, an inert gas such as nitrogen, argon or lower hydrocarbons, and the raw material gas Examples thereof include a mixed gas composed of 0.01 to 1000 ppm by volume of chlorine compound on a volume basis.
- the chlorine compound functions as a reaction regulator and exists in a gas at least in the reactor.
- the chlorine compound is preferably an organic chlorine compound, such as vinyl chloride, methyl chloride, t-butyl chloride, dichloromethane, dichloroethylene, trichloroethylene, chloroform, chlorinated biphenyl, monochlorobenzene, dichloropropane, dichloropropene, chlorobutane, dichlorobutane.
- chlorinated alkanes having 1 to 6 carbon atoms such as chlorobutene, chlorinated alkenes having 1 to 6 carbon atoms, and chlorinated benzenes. These can be used alone or in combination of two or more. .
- chlorinated ethylene it is preferable to use chlorinated ethylene.
- concentration of these chlorine compounds in the source gas is preferably 0.01 to 1000 ppm by volume, more preferably 0.1 to 100 ppm by volume, particularly preferably 0.5 to 50 ppm by volume, based on the volume of the source gas. is there.
- a heat exchanger in order to cool a gas containing water and a chlorine compound.
- the installation position of the heat exchanger for cooling the cooled gas containing water and chlorine compound is not particularly limited, and may be provided at any position in the ethylene oxide production process.
- a heat exchanger having a gas linear velocity of 7 m / s or more on the inner tube side of the heat exchanger is in a system for producing ethylene oxide by an ethylene oxidation reaction described later (in this specification, simply referred to as “reaction system”).
- One or more heat exchangers arranged, or optionally a carbon dioxide recovery system starting with the introduction of gas into the carbon dioxide absorption tower described below (herein simply referred to as “carbon dioxide gas”
- One or more heat exchangers, also referred to as “system” preferably in one or more heat exchangers arranged in the reaction system, and in the carbon dioxide system
- One or more heat exchangers are preferably arranged, more preferably all heat exchangers present in the production system for cooling the cooled gas containing water and chlorine compounds. .
- the heat exchanger for cooling the cooled gas containing water and chlorine compound is not particularly limited in terms of the specific structure, and heat exchange between the cooled gas containing water and chlorine compound and the endothermic medium is possible. Any device can be used. Thus, a known heat exchanger can be used as the heat exchanger. Among these, it is preferable to use a multi-tube heat exchanger.
- a multi-tube heat exchanger has a structure in which a tube bundle in which a large number of thin and thin heat transfer tubes (hereinafter also referred to as inner tubes) are bundled together is arranged inside a cylindrical body. Heat exchange is performed between a heat medium that is a fluid that contacts the inside and outside and a heat absorption medium.
- a baffle plate is provided to make the flow of the trunk side fluid flow most effectively with respect to the inner pipe, to improve heat transfer efficiency and to hold the inner pipe.
- the heat exchanger either a vertical heat exchanger or a horizontal heat exchanger may be used. From the viewpoint of preventing corrosion, a vertical heat exchanger that is less likely to generate stagnant in the inner pipe is preferable, but in a system that is more susceptible to corrosion, from the viewpoint of more effectively utilizing the corrosion preventing effect of the present invention.
- the horizontal heat exchanger can be preferably used.
- the material forming the inner tube of the heat exchanger is not particularly limited, but is preferably made of stainless steel.
- the inner tube made of stainless steel it is possible to reduce the occurrence of corrosion that occurs at the contact portion between the inner tube and the gas and cracks called stress corrosion cracking.
- the kind of stainless steel forming the inner tube of the heat exchanger is not particularly limited, and known stainless steels such as martensitic stainless steel, ferritic stainless steel, austenitic stainless steel and precipitation hardening stainless steel can be used. Among these, those which have been conventionally considered to sometimes cause corrosion during long-term production due to the corrosion-preventing effect during long-term production according to the present invention can be preferably used. That is, as a heat exchanger according to an embodiment of the present invention, from the viewpoint of more effectively utilizing the corrosion prevention effect of the present invention, it is relatively inexpensive and is a general stainless steel heat exchange used for industrial use. Those having an inner tube can also be preferably used. Of course, a heat exchanger having a stainless steel heat exchanger inner tube having a special composition to enhance corrosion prevention can be used.
- the chromium (Cr) content (mass%) and the molybdenum (Mo) content (mass%) with respect to the total mass of the stainless steel ) Preferably satisfies the following formula 1.
- the value of the above formula 1 represents the corrosion susceptibility of stainless steel, and the smaller the value, the easier the corrosion occurs. Therefore, satisfying the above formula 1 is preferable from the viewpoint that a heat exchanger having a stainless steel heat exchanger inner tube that is more likely to be corroded more effectively utilizes the corrosion prevention effect of the present invention. Means. From the same viewpoint, as the stainless steel forming the heat exchanger inner pipe, the value of the following formula 1 is more preferably 20 or less, and further preferably 18 or less. In addition, a lower limit is a preferable value as stainless steel for industrial use.
- stainless steel satisfying the above formula 1 examples include martensitic stainless steels SUS403, SUS410, SUS410J1, SUS410F2, SUS416, SUS420J1, SUS420J2, SUS420F, SUS420F2, SUS431, SUS440A, SUS440B, SUS440C, and SUS440F.
- SUS430, SUS430F, SUS304, SUS304L, SUS304N1, SUS304N2, SUS304LN, SUS304J3, SUS316, SUS316L, SUS316N, and SUS316Ti are preferable from the viewpoint of compatibility with mass productivity and mechanical properties.
- SUS316 and SUS316L are preferable, and SUS430 is more preferable. Note that these are notations based on JIS (Japanese Industrial Standards).
- the endothermic medium a medium having a boiling point lower than that of the gas to be cooled and containing water and a chlorine compound as a heat medium supplied to the heat exchanger, and having a boiling point higher than normal temperature and a large heat capacity is preferably used.
- the endothermic medium of the heat exchanger is not particularly limited, but the endothermic medium is preferably a gas containing ethylene, molecular oxygen and a chlorine compound.
- the reaction product gas in the reaction system is preferably a gas containing ethylene, molecular oxygen and a chlorine compound in addition to ethylene oxide and water.
- the supply gas in the carbon dioxide gas system which will be described later, can contain water and a chlorine compound, so that the present invention can be applied not only to the heat exchanger of the reaction system but also to the heat exchanger of the carbon dioxide gas system. This is because the present invention can be better utilized.
- the supply gas in the carbon dioxide gas system can be a gas that can be reused as a raw material gas containing ethylene, molecular oxygen, and a chlorine compound.
- the supply gas in the carbon dioxide gas system is preferably a gas containing water and a chlorine compound
- the unabsorbed gas in the carbon dioxide gas system is a gas containing ethylene, molecular oxygen and a chlorine compound. It is more preferable.
- the present invention can be applied not only to the heat exchanger of the reaction system but also to the heat exchanger of the carbon dioxide gas system, so that the present invention can be utilized better. Moreover, it is because the reuse rate of source gas can improve more and more efficient production can be performed.
- the raw material gas in the reaction system described later and the reaction product gas generated from the raw material gas, or the supply gas and the unabsorbed gas in the carbon dioxide gas system described later exchange heat, and various kinds of processes in the process This is because the heat energy generated by the reaction can be recovered and utilized more effectively.
- a heat exchanger in a heat exchanger, it is essential to cool a gas to be cooled containing water and a chlorine compound at a gas linear velocity on the inner side of the heat exchanger of 7 m / s or more.
- Chlorine compounds in the state do not corrode stainless steel. From this, the present inventors, the occurrence of corrosion of the heat exchanger inner pipe, in a long-term production, the chlorine compound is decomposed to change to a compound that can destroy the passive film such as hydrochloric acid, And it thinks that it is one cause that such a compound adheres partially to an inner pipe, and stays in a heat exchanger inner pipe.
- corrosion of stainless steel occurs on the heat exchanger inner tube side, which is the side to be cooled in the heat exchanger, details are unknown, but when the gas temperature decreases in the heat exchanger, It is considered that the component condensing on the exchanger inner tube side promotes decomposition or retention of the chlorine compound.
- the cause of corrosion is set to a certain value or higher.
- Something that suppresses the retention of compounds that cause the decomposition of chlorine compounds, the retention of chlorine compounds, or the cause of corrosion, such as the removal of the chlorine compounds that can change to the compounds that become or the components that promote the retention of chlorine compounds It is presumed that an effect will be produced.
- the gas linear velocity on the heat exchanger inner tube side is preferably 7 m / s or more and 30 m / s or less. This is because the upper limit of the gas linear velocity on the heat exchanger inner pipe side is not particularly limited, but it is necessary to set the speed at which the heat exchanger inner pipe is not damaged. Further, although it varies depending on the type and configuration of the heat exchanger, it is preferable that the value is equal to or less than the value of the gas linear velocity on the general heat exchanger inner tube side.
- the gas linear velocity on the heat exchanger inner tube side is more preferably 7 m / s or more and 25 m / s or less, further preferably 8 m / s or more and 20 m / s or less, and 9 m / s. It is particularly preferably 15 m / s or less.
- the gas linear velocity on the heat exchanger inner tube side can be controlled by the number of revolutions of the booster blower for the source gas.
- the heat exchanger for cooling the cooled gas containing water and chlorine compound has a temperature at the inlet of the heat exchanger inner pipe equal to or higher than the dew point of water, and the cooled gas containing water and chlorine compound is converted into the heat exchanger. It is preferable that the cooling is performed so that the temperature at the outlet of the inner tube is equal to or lower than the dew point of water.
- Drain refers to the liquid water that condenses and adheres to the inner tube of the heat exchanger as a result of the latent heat moving from the water vapor to the heat absorbing medium of the heat exchanger.
- the reason why the effect of the present invention appears more prominently in the heat exchanger in which drain is generated is that the chlorine compound is dissolved in the drain, so that the retention of the chlorine compound on the inner side of the heat exchanger is more likely to occur. This is probably because the decomposition of the chlorine compound is further promoted.
- the present invention suppresses corrosion by cooling the to-be-cooled gas containing water and chlorine compounds in the heat exchanger at a gas line speed on the inner side of the heat exchanger of 7 m / s or higher, regardless of the amount of drain generated. can do. Therefore, it is more preferable to use the present invention in a heat exchanger under conditions where the amount of drain generation is large from the viewpoint of more effectively utilizing the corrosion prevention effect of the present invention.
- steam which becomes the origin of drain may be the water which arises by the side reaction at the time of the water contained in raw material gas and ethylene oxide production
- the temperature at the heat exchanger inlet of the gas to be cooled containing water and a chlorine compound is preferably not less than the dew point of water, and more preferably not less than 100 ° C.
- the temperature of the cooled gas containing water and a chlorine compound at the inlet of the heat exchanger is preferably 300 ° C. or lower, and more preferably 250 ° C. or lower.
- the temperature at the outlet of the heat exchanger of the gas to be cooled containing water and a chlorine compound is preferably 15 ° C. or higher.
- the temperature of the cooled gas containing water and the chlorine compound at the outlet of the heat exchanger is preferably not more than the dew point of water, more preferably less than the dew point of water, and further preferably not more than 60 ° C. It is preferably 20 ° C. or less.
- the corrosion of the heat exchanger inner tube can be confirmed by visual test, fiberscope test and eddy current flaw detection. Details of the method for evaluating corrosion of the heat exchanger inner tube using these are described in the Examples.
- FIG. 1 is a block diagram showing a configuration example of an ethylene oxide production process for carrying out an ethylene oxide production method according to an embodiment of the present invention.
- the manufacturing process of ethylene oxide shown in FIG. 1 is roughly composed of three systems: a reaction system, a carbon dioxide gas system, and a purification system.
- reaction product gas containing ethylene oxide used in the present invention is produced in a step of catalytic vapor phase oxidation of ethylene with a molecular oxygen-containing gas in the presence of a silver catalyst (hereinafter also referred to as “ethylene oxidation reaction step”). Anything that has been done.
- the molecular oxygen-containing gas is a gas containing molecular oxygen, and examples thereof include air, pure oxygen, a mixture of pure oxygen and an inert gas, and an oxygen-enriched gas.
- the technology of this catalytic gas phase oxidation reaction itself is widely known, and conventionally known knowledge can be appropriately referred to in the practice of the present invention.
- the specific form of the reaction product gas is not particularly limited, but 0.5 to 5% by mass of ethylene oxide, 0.3 to 1.2% by mass of product water based on the mass of the reaction product gas, It is preferable to contain 0.01 to 1000 ppm by volume of chlorine compound based on the volume of the reaction product gas.
- the reaction product gas includes 0.5 to 5% by mass of ethylene oxide based on the mass of the reaction product gas, 0.01 to 1000 ppm by volume of chlorine compound based on the volume of the reaction product gas, unreacted oxygen, In addition to gases such as unreacted ethylene, generated water, carbon dioxide (carbon dioxide), nitrogen, argon, methane, ethane, etc., those containing trace amounts of organic acids such as formaldehyde, aldehydes of acetaldehyde, acetic acid, etc. .
- a raw material gas containing ethylene, molecular oxygen, and a chlorine compound is heated by passing through a heat exchanger 112 through a conduit 118 after being pressurized by a booster blower 110, and through a conduit 101.
- the ethylene oxidation reactor 111 is supplied.
- the ethylene oxidation reactor 111 is usually a multi-tube reactor equipped with a number of reaction tubes filled with a silver catalyst.
- the reaction product gas generated in the ethylene oxidation reaction step is cooled by passing through the heat exchanger 112 through the conduit 102 and then supplied to an ethylene oxide absorption tower (hereinafter also simply referred to as “absorption tower”) 113 through the conduit 103.
- an ethylene oxide absorption tower hereinafter also simply referred to as “absorption tower”
- the reaction product gas is supplied from the bottom of the absorption tower 113.
- an absorption liquid mainly composed of water is supplied from the top of the absorption tower 113.
- the temperature of the reaction product gas supplied to the absorption tower 113 is preferably about 15 to 80 ° C.
- the composition of the absorbing solution is not particularly limited, and propylene carbonate as disclosed in JP-A-8-127573 may be used as the absorbing solution in addition to those mainly composed of water. Moreover, an additive may be added to the absorbent as necessary.
- the additive that can be added to the absorbing liquid examples include an antifoaming agent and a pH adjusting agent.
- the antifoaming agent any antifoaming agent can be used as long as it is inactive with respect to ethylene oxide and by-product ethylene glycol and has an antifoaming effect of the absorbing solution.
- a water-soluble silicone emulsion is effective because it is excellent in dispersibility in an absorbing solution, dilution stability, and thermal stability.
- the pH of the absorbing solution is preferably 5 to 12, more preferably 6 to 11.
- the absorption tower 113 a tray tower type or packed tower type absorption tower can be usually used.
- the operating condition of the absorption tower 113 is that the ethylene oxide concentration in the reaction product gas is preferably 0.5 to 5% by mass, more preferably 1.0 to 4% by mass, based on the mass of the reaction product gas.
- the operating pressure of the column 113 is preferably 0.2 to 4.0 MPa gauge, more preferably 1.0 to 3.0 MPa gauge.
- the absorption operation is more advantageous at higher pressures, but the possible values can be determined according to the operating pressure of the oxidation reactor.
- the molar flow rate ratio (L / V) of the absorbing liquid to the reaction product gas is usually preferably from 0.30 to 2.00.
- the space linear velocity (GHSV [NTP]) in the standard state of the reaction product gas is usually preferably 400 to 4000 h ⁇ 1 .
- a gas containing chlorine-based compound, ethylene, oxygen, carbon dioxide, inert gas (nitrogen, argon, methane, ethane), aldehyde, acidic substance, or the like that has not been absorbed in the absorption tower 113 is supplied from the top of the absorption tower 113. It is discharged through the conduit 109.
- the exhaust gas is increased in pressure by the booster blower 110, heated by passing through the heat exchanger 112 through the conduit 118, and circulated to the ethylene oxidation reactor 111 through the conduit 101.
- the details of the ethylene oxidation reaction step are as described above.
- the ethylene oxidation reaction step is usually performed under pressure (preferably a pressure of about 1.0 to 3.0 MPa gauge) in an oxidation reactor equipped with a number of reaction tubes filled with a silver catalyst. Is called. For this reason, before the exhaust gas from the top of the absorption tower 113 is circulated to the ethylene oxidation reaction step, it is necessary to increase the pressure using a pressure increasing means such as the pressure increasing blower 110.
- the drain generated in the heat exchanger 112 is taken out from the bottom of the heat exchanger 112 and supplied to the conduit 202 (FIG. 2) through the conduit 104 to join with the bottom liquid (absorbed liquid) of the absorption tower 113. , And supplied to the heat exchanger 203 through the conduit 202.
- the gas pressure at that time is a constant pressure, preferably 0.2 to 4.0 MPa.
- the gas temperature is adjusted to a certain level, preferably about 80 to 120 ° C.
- a carbon dioxide gas diffusion tower 116 is installed at the subsequent stage of the carbon dioxide gas absorption tower 115, and an alkaline absorbing liquid is supplied to the upper part of the carbon dioxide gas absorption tower 115 from the bottom of the carbon dioxide gas diffusion tower 116.
- the drain generated in the heat exchanger 114 is taken out from the bottom of the heat exchanger 114 and discharged out of the system through the conduit 108.
- the carbon dioxide concentrated absorbent that has absorbed the carbon dioxide gas in the carbon dioxide absorption tower 115 is withdrawn from the bottom of the carbon dioxide absorption tower, and then a constant pressure, preferably a pressure of about 0.01 to 0.5 MPa gauge. , Preferably about 80 to 120 ° C., and supplied to the upper part of the carbon dioxide gas diffusion tower 116 equipped with a reboiler (not shown) at the bottom of the tower.
- the absorbing liquid causes a pressure flush due to the pressure difference between the carbon dioxide gas absorption tower 115 and the carbon dioxide gas diffusion tower 116.
- the carbon dioxide gas preferably 10 to 30% by volume
- most of the inert gas in the absorption liquid are separated from the absorption liquid and discharged from the top of the carbon dioxide gas diffusion tower 116.
- the remaining carbon dioxide absorption liquid from which a part of the carbon dioxide gas has been separated by the pressure flash described above enters a gas-liquid contact portion (not shown) provided below the liquid supply portion, and from a reboiler (not shown).
- the generated vapor and gas-liquid contact part (not shown) Carbon dioxide gas generated from the following part is counter-contacted with the main gas, and part of the carbon dioxide gas in the absorption liquid and most of other inert gases Is separated from the absorbent.
- High purity carbon dioxide gas is obtained from the inside of the column 116. That is, the inert gas in the carbon dioxide absorption liquid at the gas-liquid contact portion (not shown) causes countercurrent gas-liquid contact with the carbon dioxide gas containing a very small amount of inert gas rising from the lower part and water vapor. This causes the inert gas concentration to be very low. Therefore, a high-purity carbon dioxide gas can be obtained by taking out the gas after the emission.
- FIG. 2 is a block diagram showing a configuration example of a process for carrying out an ethylene oxide production process according to an embodiment of the present invention.
- the tower bottom liquid (absorbing liquid) of the absorption tower 113 is supplied to the ethylene oxide stripping tower (hereinafter also simply referred to as “stripping tower”) 201, it is usually preheated to a temperature suitable for stripping in the stripping tower 201. Is done. Specifically, as shown in FIG. 2, the bottom liquid (absorbed liquid) of the absorption tower 113 is supplied to the heat exchanger 203 through a conduit 202. In this heat exchanger 203, heat exchange is performed with the bottom liquid of the diffusion tower 201, and if necessary, the heat is heated by the heater 204, and the bottom liquid (absorption liquid) of the absorption tower 113 is obtained. Is heated to a constant temperature, preferably about 70 to 110 ° C.
- the tower bottom liquid (absorbed liquid) of the absorption tower 113 heated by heat exchange with the tower bottom liquid of the stripping tower 201 is supplied to the gas-liquid separation tank 206 through the conduit 205.
- a light component gas of an inert gas partially containing ethylene oxide and water is separated and discharged through a conduit 207.
- the remaining absorption liquid flushed with the light component gas is supplied to the upper portion of the stripping tower 201 through the conduit 208.
- the residence time of the absorbing liquid can be shortened by taking into consideration that the disposition distance is as short as possible for the site where ethylene oxide coexists with water, particularly under high temperature conditions such as the conduit 208. As a result, it can contribute to prevention of by-production of ethylene glycol.
- a heating medium such as water vapor is supplied to the heater 209, and the diffusion tower 201 is heated using the heating medium heated in the heater 209, or the diffusion tower 201 is used.
- the stripping tower 201 is heated by supplying steam directly to the bottom of the tower.
- ethylene oxide usually 99% by mass or more is preferable contained in the absorption liquid supplied from the upper part of the stripping tower 201 is stripped, and the top of the stripping tower 201 is dissipated. Is discharged through a conduit 210.
- the operating condition of the stripping tower 201 is preferably an operating pressure (top pressure) of 3 to 60 kPa gauge, more preferably 3 to 30 kPa gauge.
- the lower the tower top pressure the lower the temperature in the tower.
- ethylene oxide is a substance that is relatively easy to ignite, from the viewpoint of preventing oxygen from leaking into the system, operation at or below atmospheric pressure is not normally performed, and is slightly higher than atmospheric pressure as described above. Operated with pressure.
- the tower top temperature is preferably 82 to 93 ° C
- the tower bottom temperature is preferably 101 to 115 ° C.
- the remaining absorption liquid after the ethylene oxide is diffused is extracted as the bottom liquid of the diffusion tower 201 and supplied to the upper portion of the absorption tower 113 as the absorption liquid in the absorption tower 113 for circulation use. Can be done.
- fresh water or the above-described additives may be supplied to the absorption tower 113 through a separately provided conduit.
- the bottom liquid of the stripping tower 201 does not substantially contain ethylene oxide.
- the concentration of ethylene oxide contained in the tower bottom liquid is preferably 10 ppm by mass or less, more preferably 0.5 ppm by mass or less.
- This column bottom liquid contains ethylene glycol by-produced in the absorption liquid between the ethylene oxidation reaction step and the ethylene oxide diffusion step, and a part thereof is extracted through the conduit 211 and the conduit 212.
- the extracted liquid is subjected to a combustion treatment or supplied to an ethylene glycol concentration step for concentrating and recovering the contained ethylene glycol.
- the ethylene glycol contained in the extracted liquid is disclosed in Japanese Patent Publication No. 45-9926, Japanese Patent Publication No. 4-28247, etc. as it is or after the ethylene glycol concentration step. In addition to chemical treatment, it may be recovered as a fiber grade product by performing physical treatment in some cases.
- the bottom liquid of the stripping tower 201 also contains low-boiling impurities such as formaldehyde, and high-boiling impurities such as acetaldehyde and acetic acid, so that by extracting a part thereof from the system as described above, There is also an advantage that accumulation of these impurities in the absorption liquid circulated through the absorption tower 113 can be prevented.
- Dispersed matter containing ethylene oxide diffused from the top of the stripping tower 201 is sent to the stripping tower condenser 215 through which the cooling water passes through the conduit 213 and the conduit 214 through the conduit 210, and the condensate passes through the conduit 216. Reflux to the top of the column, and the uncondensed vapor is supplied to the dehydration column 301 (FIG. 3) through the conduit 217.
- the vapor containing ethylene oxide supplied to the dehydration tower 301 comes into contact with the liquid refluxed through the conduit 302 to become a vapor with a higher ethylene oxide concentration, and the liquid with a low ethylene oxide concentration withdrawn from the bottom of the tower passes through the conduit to the stripping tower condenser. 215 (FIG. 2).
- Vapor containing ethylene oxide discharged from the top of the dehydrating tower 301 is sent through a conduit 303 to a dehydrating tower condenser 306 through which cooling water passes through a conduit 304 and a conduit 305, and a part of the condensate is passed through a conduit 302.
- the uncondensed vapor (ethylene oxide-containing uncondensed gas) of the dehydrating tower condenser 306 is returned to an ethylene oxide reabsorbing tower (hereinafter also simply referred to as “reabsorbing tower”) 119 shown in FIG. Supplied.
- the remainder of the condensate in the dehydration tower condenser 306 is supplied to the light fraction separation tower 309 through the conduit 308. Heating is performed by a heater 310 of the light fraction separation tower 309 using a heating medium such as steam through a conduit 311, and ethylene oxide vapor containing light components from the top of the light fraction separation tower 309 passes through a conduit 312 through a conduit 313 and a conduit 314. To the light fraction separator condenser 315 through which the cooling water passes, and the condensate is refluxed to the top of the light fraction separator tower 309 through the conduit 316, and uncondensed vapor (uncondensed gas containing ethylene oxide) of the light fraction separator condenser 315. ) Is fed through conduit 317 to reabsorption tower 119 shown in FIG. 1 to recover ethylene oxide.
- the bottom liquid of the light fraction separation column 309 is fed to an ethylene oxide rectification column (hereinafter also simply referred to as “rectification column”) 319 through a conduit 318.
- Steam at a constant pressure, preferably about 0.05 to 0.10 MPa gauge, is supplied to the heater 320 of the rectifying column 319, and preferably the bottom temperature of the rectifying column 319 is 35 to 80 ° C.
- Rectification is performed at a tower bottom pressure of 0.10 to 0.80 MPa gauze, and an ethylene oxide vapor having a tower top temperature of 35 to 75 ° C.
- a tower top pressure of 0.10 to 0.80 MPa gauge from the top of the rectifying tower 319 Is sent to a rectification column condenser 323 through which cooling water passes through conduits 321 and 322 to liquefy ethylene oxide, a part being supplied as a reflux liquid to the top of the rectification column 319 through a conduit 324 and the remainder being a conduit 325. And extracted as product ethylene oxide (product EO).
- product EO product ethylene oxide
- the uncondensed vapor (ethylene oxide-containing uncondensed gas) of the rectifying column condenser 323 is supplied to the reabsorption tower 119 shown in FIG. 1 through the conduit 326 to recover ethylene oxide.
- the bottom liquid of the rectifying column 319 is withdrawn through a conduit 327 as necessary for separating heavy components of high-boiling impurities such as acetaldehyde, water, and acetic acid.
- uncondensed steam discharged from the purification system in the embodiment shown in FIG. 3, uncondensed steam derived from the dehydration tower condenser 306, the light fraction separation tower condenser 315, and the rectification tower condenser 323). Contains ethylene oxide. For this reason, these uncondensed vapor
- the reabsorption tower 119 similarly to the absorption tower 113 described above, ethylene oxide is reabsorbed by countercurrent contact with the absorption liquid.
- the composition and pH of the absorption liquid used for the reabsorption of ethylene oxide in the reabsorption tower 119, the form of the reabsorption tower (plate tower form or packed tower form), and the like are the same as those described above for the absorption tower 113. Therefore, detailed description is omitted here.
- the operating pressure of the reabsorption tower 119 is preferably 100 to 150 kPa gauge.
- the bottom liquid of the reabsorption tower 119 is circulated through the conduit 120 to the purification system (specifically, in the present embodiment, the stripping tower 201) in the same manner as the bottom liquid of the absorption tower 113 described above. More specifically, it is circulated to the conduit 202 shown in FIG. 2 and preheated before being introduced into the stripping tower 201.
- uncondensed gas that has not been absorbed in the reabsorption tower 119 is discharged from the top of the reabsorption tower 119 through the conduit 121.
- uncondensed gas discharged through conduit 121 is circulated to absorption tower 113 via conduit 123 and conduit 103 after the pressure has been increased by gas compressor 122.
- the uncondensed gas discharged from the top of the reabsorption tower 119 contains a large amount of carbon dioxide gas (usually about 5 to 60% by volume), the uncondensed gas is circulated to the absorption tower 113. Then, the amount of carbon dioxide in the gas supplied from the absorption tower 113 to the carbon dioxide absorption tower 115 increases.
- the amount of carbon dioxide gas processed in the carbon dioxide gas absorption tower 115 and the carbon dioxide gas diffusion tower 116 increases, and it becomes necessary to increase the amount of steam supplied to the reboiler (not shown) of the carbon dioxide gas diffusion tower 116, or carbon dioxide gas. It may be necessary to increase the amount of the absorption promoter. Therefore, the uncondensed gas discharged from the top of the reabsorption tower 119 through the conduit 121 may be supplied to the carbon dioxide absorption tower 115 after the pressure is increased by the gas compressor 122.
- the flow rate of the gas supplied to the carbon dioxide absorption tower 115 is only slightly increased, but as described above, the uncondensed gas discharged from the top of the ethylene oxide reabsorption tower is A large amount of carbon dioxide gas (usually about 5 to 60% by volume) is contained. Therefore, when the ethylene oxide-containing uncondensed gas discharged from the top of the reabsorption tower 119 is supplied to the carbon dioxide absorption tower 115, the concentration of carbon dioxide in the gas supplied to the carbon dioxide absorption tower 115 slightly increases. Become. As described above, according to the present embodiment, various advantageous industrially advantageous effects can be achieved by introducing a gas containing a higher concentration of carbon dioxide into the carbon dioxide gas system.
- the suction pressure of the gas compressor 122 for increasing the pressure of the uncondensed gas discharged from the top of the reabsorption tower 119 through the conduit 121 is slightly pressurized. Specifically, it is preferably 3 to 5 kPa gauge.
- the uncondensed gas discharged from the top of the reabsorption tower 119 contains ethylene as a reaction raw material, but as described above, the unabsorbed gas discharged from the top of the carbon dioxide absorption tower 115. Is heated by passing through the heat exchanger 112 via the conduit 109 and the conduit 118, and is circulated to the ethylene oxidation reactor 111. Since ethylene is hardly absorbed in the carbon dioxide absorption tower 115, as described above. Even if such a configuration is adopted, there is no possibility of loss of ethylene as a reaction raw material.
- Ethylene oxide was produced by the ethylene oxide production process shown in FIGS.
- a manufacturing apparatus for performing the manufacturing process of FIGS. 1 to 3 a pilot plant similar to this plant is used except that the pipe diameter (tube cross-sectional area) of the heat exchanger is different. The operation was performed with the same gas composition and operating conditions to produce ethylene oxide.
- the source gas in the conduit 101 contains 27% by mass of ethylene and 11% by mass of molecular oxygen gas on the basis of the mass of the source gas, and further contains chlorinated ethylene as a reaction regulator, It added so that it might become a density
- the material of the inner tube is stainless steel SUS430: Cr content 16 to 18% by mass, Mo content 0% by mass). A vertical heat exchanger was used.
- the number of revolutions of the source gas booster 110 was adjusted so that the gas linear velocity on the inner tube side of the heat exchanger 112 and the heat exchanger 114 was 10.4 m / s.
- the gas linear velocity on the inner tube side of the heat exchanger 112 is calculated by calculation from the flow meter installed in the conduit 101, the ratio of the main reaction and the side reaction in the reactor 111, the ethylene conversion rate, and the temperature of the conduit 102.
- the gas linear velocity on the inner tube side of the heat exchanger 114 is as follows: the flow meter installed in the conduit 105, the ratio of the main reaction and side reaction in the reactor 111, the ethylene conversion rate, the outlet temperature of the carbon dioxide absorption tower 115, Calculation was performed from the outlet pressure and the rate at which carbon dioxide gas was absorbed.
- the dew point of water at the gas composition and pressure of the conduit 102 was 67 ° C.
- the dew point of water at the gas composition and pressure of the conduit 106 was 104 ° C.
- each component amount of carbon dioxide gas, ethylene oxide (EO) and water, and the remaining gas which is a gas other than these at each position in the process is “mass%”.
- Table 1 shows the operating conditions.
- the remaining gas contained ethylene, molecular oxygen and a chlorine compound, and was inactive at the measurement position of each component amount in the process.
- the amount of each component is the value of carbon dioxide, ethylene oxide (EO) and the balance gas rounded off to the nearest two decimal places. Moreover, the numerical value of water was a value obtained by rounding off three decimal places. And MPa gauge was described as MPaG. The same applies to Tables 2 and 3 below.
- Example 2 In Example 1, ethylene oxide was produced in the same manner as in Example 1 except that the outlet temperature of the heat exchanger was higher and the operating conditions were changed to those shown in Table 2.
- Example 3 In Example 1, ethylene oxide was produced in the same manner as in Example 1 except that the outlet temperature of the heat exchanger was made lower and the operating conditions were changed to the conditions shown in Table 3.
- Example 1 In Example 1, the same procedure as in Example 1 was performed, except that the rotational speed of the source gas pressure booster 110 was adjusted so that the gas linear velocity on the inner tube side of the heat exchanger 112 and the heat exchanger 114 was 5 m / s. Ethylene oxide was produced. Here, even when the gas linear velocity was changed, there was no change in the gas composition and drain amount (the amount of water in the conduit 104 and the conduit 108), and the gas composition and operating conditions were the same as in Table 1.
- Example 2 In Example 2, the same procedure as in Example 2 was performed except that the rotational speed of the source gas pressure booster 110 was adjusted so that the gas linear velocity on the inner tube side of the heat exchanger 112 and the heat exchanger 114 was 5 m / s. Ethylene oxide was produced. Here, even when the gas linear velocity was changed, there was no change in the gas composition and the drain amount, and the gas composition and operating conditions were the same as in Table 2.
- Example 3 In Example 3, the same procedure as in Example 3 was performed except that the rotational speed of the source gas booster 110 was adjusted so that the gas linear velocity on the inner tube side of the heat exchanger 112 and the heat exchanger 114 was 5 m / s. Ethylene oxide was produced. Here, even when the gas linear velocity was changed, there was no change in the gas composition and drain amount, and the gas composition and operating conditions were the same as in Table 3.
- the gas in the conduit 105 contains 25% by mass of ethylene on a mass basis, 8% by mass of molecular oxygen, and 6 ppm by volume of chlorine compound on a volume basis. It was.
- the gas in the conduit 102 contained 6 ppm by volume of chlorine compound on a volume basis
- the gas in the conduit 106 contained 5 ppm by volume of chlorine compound on a volume basis.
- Eddy current flaw detection is a type of electromagnetic induction test.
- a time-varying magnetic field is applied to a DUT by an alternating current coil, the eddy current generated in the DUT becomes a defect or shape in the DUT.
- This is an inspection for evaluating the presence / absence of a defect in a test object, a change in shape and dimension, a composition, and the like using changes in dimensions and electrical conductivity. More specifically, in the eddy current flaw inspection, a probe in which two inspection coils are incorporated is scanned on the object to be tested, and a change in eddy current generated in the defective portion is captured.
- the two coils form a four-sided bridge, and are inspections for checking the presence / absence of a defect in the device under test and a change in the thickness of the pair under test by taking out a change in impedance of the test coil due to a change in eddy current.
- the eddy current inspection is a non-destructive inspection of the material, and is suitable for confirming the change with time of the member during the manufacturing process at regular intervals.
- each of the heat exchanger 112 and the inner tube of the heat exchanger 114 used for the production of each ethylene oxide under the conditions of Examples 1 to 3 and Comparative Examples 1 to 3 was inspected by eddy current inspection.
- the thickness change of the heat exchanger inner pipe (ratio (%) of the reduced thickness (thickening thickness) to the initial thickness) was evaluated.
- flaw detector Nippon Denki Sokki Co., Ltd. ND-382D
- recorder A & D RA2300
- self-comparison method 38 kHz
- standard comparison method 38 kHz Measurements were made.
- Table 4 shows the evaluation results after 1 year from the start of ethylene oxide production
- Table 5 shows the evaluation results after 2 years from the start of ethylene oxide production.
- the manufacturing process of ethylene oxide according to the present invention can significantly reduce the replacement frequency of the heat exchanger, which is extremely advantageous from an industrial point of view that the production efficiency can be improved.
- the effect is played.
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Abstract
Description
まず、図1を参照しつつ、エチレンの酸化反応によってエチレンオキシドを製造する系(単に「反応系」とも称する)について説明する。図1は、本発明の一実施形態に係るエチレンオキシドの製造方法を実施するエチレンオキシドの製造プロセスの構成例を示すブロック図である。図1に示すエチレンオキシドの製造プロセスは、大きく分けて反応系、炭酸ガス系、および精製系の3つの系から構成されている。
好ましい実施形態においては、図1に示すように、吸収塔113の塔頂部から排出されるガスの少なくとも一部を、昇圧ブロワ110等の昇圧手段により昇圧し、導管105を通じて熱交換器114を通過することで加熱し、導管117を通じて炭酸ガス吸収塔115へ供給する。以下、図1を参照しつつ、炭酸ガス吸収塔115へのガスの導入に始まる炭酸ガス回収系(単に「炭酸ガス系」とも称する)について説明する。
吸収塔113においてエチレンオキシドを吸収した吸収液は、当該吸収塔113の塔底液として、エチレンオキシド精製系(以下、単に「精製系」とも称する)へと送られる。精製系の具体的な形態について特に制限はなく、従来公知の知見が適宜参照されうる。一例として、精製系は通常、放散工程、精留工程、脱水工程、軽質分分離工程、重質分分離工程などからなっている。以下、図2および図3を参照しつつ、これらのうちのいくつかの工程からなる精製系について説明する。図2は、本発明の一実施形態に係るエチレンオキシドの製造プロセスを実施するためのプロセスの構成例を示すブロック図である。
[実施例1]
図1~図3に示すエチレンオキシドの製造プロセスによりエチレンオキシドを製造した。本実験において、図1~図3の製造プロセスを行うための製造装置としては、熱交換器の管径(管断面積)が異なる以外は本プラントと同様のパイロットプラントを用いて、本プラントと同様のガス組成および運転条件で運転を行い、エチレンオキシドを製造した。
実施例1において、熱交換器の出口温度をより高温とし、運転条件を表2の条件へと変更した以外は実施例1と同様にして、エチレンオキシドを製造した。
実施例1において、熱交換器の出口温度をより低温とし、運転条件を表3の条件へと変更した以外は実施例1と同様にして、エチレンオキシドを製造した。
実施例1において、熱交換器112および熱交換器114の内管側のガス線速を5m/sとなるよう原料ガスの昇圧ブロワ110の回転数を調整した以外は実施例1と同様にして、エチレンオキシドを製造した。ここで、ガス線速を変化させた際も、ガス組成およびドレン量(導管104および導管108の水の量)の変化はなく、ガス組成および運転条件は表1と同様であった。
実施例2において、熱交換器112および熱交換器114の内管側のガス線速を5m/sとなるよう原料ガスの昇圧ブロワ110の回転数を調整した以外は実施例2と同様にして、エチレンオキシドを製造した。ここで、ガス線速を変化させた際も、ガス組成およびドレン量の変化はなく、ガス組成および運転条件は表2と同様であった。
実施例3において、熱交換器112および熱交換器114の内管側のガス線速を5m/sとなるよう原料ガスの昇圧ブロワ110の回転数を調整した以外は実施例3と同様にして、エチレンオキシドを製造した。ここで、ガス線速を変化させた際も、ガス組成およびドレン量の変化はなく、ガス組成および運転条件は表3と同様であった。
特記しない限り、熱交換器内管の腐食評価の操作は室温(20~25℃)/相対湿度40~50%RHの条件で行う。
実施例1~3および比較例1~3の条件における各エチレンオキシドの製造に用いた熱交換器112および熱交換器114の内管を、それぞれ目視で確認し、腐食の有無および形状変化を確認した。評価基準は下記のものを採用した。
×:腐食あり
(ファイバースコープ試験)
実施例1~3および比較例1~3の条件における各エチレンオキシドの製造に用いた熱交換器112および熱交換器114の内管内に、ファイバースコープカメラ(オリンパス株式会社製 IPLEX(登録商標) MX R シリーズ)を挿入し、映像を目視で確認することで、内管の腐食の有無および形状変化を確認した。評価基準は下記のものを採用した。
×:腐食あり
(渦流探傷検査)
渦流探傷検査は、電磁誘導試験の一種であり、交流を流したコイルにより時間的に変化する磁場を被試験体に加えたとき、被試験体に生じる渦電流が被試験体中の欠陥、形状、寸法および電気伝導率などに変化することを使用して、被試験体の欠陥の有無、形状および寸法の変化、ならびに組成などを評価する検査である。より具体的には、渦流探傷検査は、検査用のコイルが2つ組み込まれたプローブを被試験体上で走査させ、欠陥部分において生じた渦電流の変化をとらえる。ここで、2つのコイルは四辺ブリッジになっており、渦電流の変化による検査コイルのインピーダンス変化を取り出すことで、被試験体の欠陥有無および被試験対の厚み変化を確認する検査である。なお、渦流探傷検査は、材料の非破壊検査であるため、製造プロセス中の部材の経時変化を一定期間毎に確認することに適する。
110 昇圧ブロワ
111 エチレン酸化反応器
112 熱交換器
113 エチレンオキシド吸収塔
114 熱交換器
115 炭酸ガス吸収塔
116 炭酸ガス放散塔
119 エチレンオキシド再吸収塔
122 ガス圧縮機
201 エチレンオキシド放散塔
202、205、207、208、210、211、212、213、214、216、217 導管
203 熱交換器
204 加熱器
206 気液分離タンク
209 放散塔加熱器
215 放散塔凝縮器
301 脱水塔
302、303、304、305、307、308、311、312、313、314、316、317、318、321、322、324、325、326、327 導管
306 脱水塔凝縮器
309 軽質分分離塔
310 軽質分分離塔加熱器
315 軽質分分離塔凝縮器
319 エチレンオキシド精留塔
320 精留塔加熱器
323 精留塔凝縮器。
Claims (6)
- エチレン、分子状酸素および塩素化合物を含む原料ガスをエチレン酸化反応器に供給すること、
前記エチレン酸化反応器において、銀触媒の存在下で、前記原料ガス中における前記エチレンと前記分子状酸素とを接触気相酸化して、エチレンオキシド、水および塩素化合物を含むガスを生成すること、ならびに、
前記水および前記塩素化合物を含む被冷却ガスを熱交換器で冷却すること、
を含むエチレンオキシドの製造方法であって、
前記熱交換器において、前記被冷却ガスを、7m/s以上の熱交換器内管側のガス線速で冷却する、製造方法。 - 前記熱交換器は、熱交換器内管入口での温度が水の露点以上であり、前記被冷却ガスを、熱交換器内管出口での温度が水の露点以下となるように冷却する、請求項1に記載の製造方法。
- 前記原料ガスにおける前記塩素化合物の濃度は、前記原料ガスの容積基準で、0.01容量ppm以上1000容量ppm以下である、請求項1または2に記載の製造方法。
- 前記熱交換器において、前記被冷却ガスを冷却するための吸熱媒体がエチレン、分子状酸素および塩素化合物を含むガスである、請求項1~3のいずれか1項に記載の製造方法。
- 前記熱交換器が多管式熱交換器である、請求項1~5のいずれか1項に記載の製造方法。
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MYPI2018703525A MY184208A (en) | 2016-03-30 | 2017-03-30 | Ethylene oxide production method |
SG11201808380XA SG11201808380XA (en) | 2016-03-30 | 2017-03-30 | Method for producing ethylene oxide |
US16/088,748 US10858328B2 (en) | 2016-03-30 | 2017-03-30 | Method for producing ethylene oxide |
EP17775449.6A EP3438100B1 (en) | 2016-03-30 | 2017-03-30 | Method for producing ethylene oxide |
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Title |
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JAPAN SOCIETY FOR CHEMICAL ENGINEERING: "Chapter 9: Echiren'okishido - echirengurikōnore [Ethylene oxide - Ethylene glycol]", KAGAKU PROCESS -KISO KARA GIJUTSU KAIHATSU MADE, 1998, pages 121 - 128, XP009515921, ISBN: 4-8079-0473-6 * |
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MY184208A (en) | 2021-03-26 |
SG11201808380XA (en) | 2018-10-30 |
EP3438100B1 (en) | 2020-11-18 |
EP3438100A4 (en) | 2019-12-04 |
US20190077778A1 (en) | 2019-03-14 |
JP2017178864A (ja) | 2017-10-05 |
JP6723049B2 (ja) | 2020-07-15 |
US10858328B2 (en) | 2020-12-08 |
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