AU784978B2 - Process for producing dimethyl ether - Google Patents
Process for producing dimethyl ether Download PDFInfo
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- AU784978B2 AU784978B2 AU97203/01A AU9720301A AU784978B2 AU 784978 B2 AU784978 B2 AU 784978B2 AU 97203/01 A AU97203/01 A AU 97203/01A AU 9720301 A AU9720301 A AU 9720301A AU 784978 B2 AU784978 B2 AU 784978B2
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- methanol
- dimethyl ether
- separated
- water
- producing
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims description 120
- 238000000034 method Methods 0.000 title claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 381
- 239000007789 gas Substances 0.000 claims description 71
- 230000015572 biosynthetic process Effects 0.000 claims description 52
- 238000003786 synthesis reaction Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000004821 distillation Methods 0.000 claims description 30
- 239000004215 Carbon black (E152) Substances 0.000 claims description 24
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 24
- 230000018044 dehydration Effects 0.000 description 21
- 238000006297 dehydration reaction Methods 0.000 description 21
- 238000000926 separation method Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- 239000003345 natural gas Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
AUSTRALIA
Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: Mitsubishi Gas Chemical Company, Inc.
Actual Inventor(s): Kouhei Uchida, Yasushi Hiramatsu, Akira Ishiwada Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attomeys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: PROCESS FOR PRODUCING DIMETHYL ETHER Our Ref: 657831 POF Code: 93170/59182 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): -1eoOBq PROCESS FOR PRODUCING DIMETHYL ETHER BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing dimethyl ether from hydrocarbon and, more particularly, to an improved process for producing the fuel grade dimethyl ether from the standpoint of the environmental protection and the energy saving.
2. Description of Prior Art Dimethyl ether has been used as a solvent in the chemical industry.
Recently, application of dimethyl ether as a novel fuel used for LPG substitution, Diesel engines and fuel cells and a raw material for town gas is attracting attention. As the process for producing the fuel grade dimethyl ether, for example, a process for producing dimethyl ether from a synthesis gas containing hydrogen and carbon oxides using a catalyst having the activity in both of methanol synthesis and methanol dehydration is described in Japanese Patent No. 2849475.
In accordance with the process for producing dimethyl ether described in Japanese Patent No. 2849475, the unreacted synthesis gas and a reaction gas containing methanol, dimethyl ether and water formed by the reaction are obtained from a reactor for producing methanol and dimethyl ether. Since dimethyl ether has a low boiling point, a heat source at a low temperature is required for separation by condensation.
In the methanol synthesis, acidic substances having low boiling points such as methyl formate are formed and circulated in the reaction system. Separation of the acidic substances having low boiling points such as methyl formate from dimethyl ether and water formed by the reaction is difficult. The acidic substances are corrosive. Moreover, treatments for the environmental protection are required when waste water containing these substances is discharged to the outside.
Dimethyl ether for the chemical industry has heretofore been produced by dehydration of purified methanol. In this process, a great amount of energy is required for purification of methanol by distillation.
Moreover, the purification of methanol by distillation requires a huge S.distillation column. Therefore, it is difficult to apply this process to a great scale plant.
~For producing a synthesis gas, steam is required in an amount by mole as much as 1.5 to 3 times the amount by mole of the hydrocarbon used as the raw material. The fuel grade dimethyl ether is produced, in many cases, from inexpensive natural gas. However, water is a valuable material in areas where natural gas is produced.
The discussion of the background to the invention herein is included to explain the context of the invention. This is not to be taken as an admission S".i that any of the material referred to was published, known or part of the common general knowledge in Australia as at the priority date of any of the claims.
The present invention has an object of solving the above problems on the production of the fuel grade dimethyl ether and providing an improved process for producing the fuel grade dimethyl ether from the standpoint of the environmental protection and the energy saving.
SUMMARY OF THE INVENTION As the result of intensive studies by the present inventors on the process for producing dimethyl ether having the above problems, it was found that an improved process for producing dimethyl ether from the standpoint of the environmental protection and the energy saving could be e obtained when dimethyl ether was synthesized by dehydration of crude methanol from which substances having low boiling points were removed in advance and the hydrocarbon used as the raw material was humidified with water formed by the reaction. The present invention has been completed based on the knowledge.
According to a first aspect, the present invention provides a process for producing dimethyl ether which includes the steps of: producing a synthesis gas containing hydrogen, carbon monoxide and carbon dioxide as main components and which is generated by reaction of hydrocarbon with steam or steam and oxygen, synthesizing methanol, wherein methanol is synthesized by reaction of the synthesis gas in the presence of a methanol synthesis catalyst and recovering a 15 formed crude methanol in a liquid state, oo00 distilling methanol, wherein the recovered crude methanol is distilled, dissolved gases and components having lower boiling points are separated at the top of a distillation column and methanol containing water is separated at the bottom of the distillation column, producing dimethyl ether, from the separated methanol containing water, and distilling dimethyl ether, wherein formed dimethyl ether, formed water and unreacted methanol are separated from each other by distillation, •00o wherein at least some of the formed water which is separated in step is utilized 25 for humidifying the hydrocarbon used as a reactant in step According to a second aspect, the present invention provides a process for producing dimethyl ether which includes the steps of: producing a synthesis gas, containing hydrogen, carbon monoxide and carbon dioxide as main components and which is generated by reaction of hydrocarbon with steam or steam and oxygen, synthesizing methanol, wherein methanol is synthesized by reaction of the synthesis gas in the presence of a methanol synthesis catalyst and recovering a formed crude methanol in a liquid state, distilling methanol, wherein the recovered crude methanol is distilled, dissolved gases and components having lower boiling points are separated at the top of a distillation column and methanol having a higher concentration than the concentration of methanol recovered in step is separated at an intermediate stage of the distillation column, producing dimethyl ether, from the separated methanol, and distilling dimethyl ether, wherein formed dimethyl ether, formed water and unreacted methanol are separated from each other by distillation, wherein at least some of the formed water which is separated in step is utilized for humidifying the hydrocarbon used as a reactant in step ~In a preferred form of the process of the invention, the hydrocarbon is •humidified with the formed water separated in step and further humidified with condensed water obtained from the synthesis gas generated in step In another preferred form of the invention, a heat exchange-type humidifier is used for humidifying the hydrocarbon.
ooo* BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a schematic flow diagram of a process used in Example 1 as 2nno 25 an embodiment of the present invention. Figure 2 shows a schematic flow diagram of a process used in Example 2 as another embodiment of the present invention.
In Figures 1 and 2, the numbers have the following meanings: 4: a preheater for natural gas of the raw material; 5: a reactor for hydrogenation; 6: a sulfur adsorption column; 8: a first humidifier; 8a: a heater of a first humidifier; 9: a second humidifier; 14: a preheater for a feed gas to a primary reformer; 16: a primary reformer; 19: a secondary reformer; 21: a heat recovery system; 22: a cooler for a synthesis gas; 23: a gas-liquid separator for a synthesis gas; 26: a compressor for a synthesis gas; 29: a circulator for a reaction gas; 31: a preheater for a feed gas to a methanol synthesis converter; 32: a
S*
methanol synthesis converter; 34: a cooler of an effluent gas from a methanol synthesis converter; 35: a high pressure separator; 38: a low pressure separator; 41: a vent gas scrubber; 45: a crude methanol tank; 49: a crude methanol distillation column; 50: a condenser of a crude methanol distillation column; 54: a methanol evaporator; 56: a reactor for methanol dehydration; 58: a dimethyl ether separation column; 59: a condenser of a dimethyl ether separation column; 62: a methanol separation column; and 63: a condenser of a methanol separation column.
DESCRIPTION OF THE PREFERRED EMBODIMENTS As the hydrocarbon of the raw material in the present invention, natural gas in the gas state containing methane as the main component, LPG in the liquid state, naphtha or gas oil is used.
In step of producing a synthesis gas, hydrocarbon in the gas state or a gas obtained by evaporation of hydrocarbon in the liquid state is reacted with steam or steam and oxygen in a reformer in the presence of a nickel catalyst at 800 to 1,050 0 C and a synthesis gas containing hydrogen, carbon monoxide and carbon dioxide as the main components is produced.
In step of synthesizing methanol, in general, a copper catalyst is used and a crude methanol is produced from the synthesis gas at a pressure of 5 to 20 MPa and a temperature of 200 to 300C.
In step of distilling methanol, the crude methanol from the step of synthesizing methanol is supplied to a distillation column. Organic impurities contained in the crude methanol which are organic compounds having boiling points lower than the boiling point of methanol S(components having lower boiling points) and dissolved gases are separated by distillation and a crude methanol containing organic compounds having boiling points higher than methanol (components having higher boiling points) which is obtained at the bottom of the oooo$ distillation column is supplied to the dehydration step (step of producing dimethyl ether It is preferable that an alkali is added since the crude methanol from the step of synthesizing methanol contains acidic 0000$ substances.
S: Alternatively, a fraction containing methanol as the main •component may be taken out at an intermediate stage of the above distillation column and, at the bottom of the column, mainly water and components having higher boiling points may be taken out. In this manner, methanol having a higher concentration than that of methanol recovered in step is separated at the intermediate stage of the distillation column. The methanol taken out at the intermediate stage of the distillation column is used for the dehydration.
In step of producing dimethyl ether, a conventional dehydration catalyst such as y-alumina catalyst and a silica-alumina catalyst can be used. The pressure of the reaction is 0.5 MPa or higher and preferably 1 to 2 MPa. When the pressure is lower than the above range, condensation of dimethyl ether becomes difficult and a heat source of a low temperature must be used. This causes increases in the plant cost and the energy consumption. The temperature of the dehydration is, in general, 250 to 400 0 C and is decided in accordance with the catalyst used.
In step of distilling dimethyl ether, two distillation columns are used. It is preferable that, in the first distillation column (a dimethyl ether separation column), dimethyl ether as the product is separated at the top of the column and, in the second distillation column (a methanol separation column), the unreacted methanol is separated at the top of the column and water formed by the dehydration is separated at the bottom of the column. In the dimethyl ether separation column, the pressure at the top of the column is adjusted to 1 to 2 MPa so that dimethyl ether as the product can be separated by cooling with the air or with water. In the methanol separation column, the pressure at the bottom of the column is adjusted to about 0.1 to 0.2 MPa so that a heat source such as low pressure steam can be used. The unreacted methanol separated in the methanol separation column is recycled and used in step of producing dimethyl ether.
In the present invention, water formed by the methanol dehydration is used for humidifying the hydrocarbon used as the raw material. The system for the humidification is not limited and various systems such as the spraying type, the scrubber type having a packed column and heat exchange type can be used. It is preferable that a heat exchange-type humidifier in which the humidification is conducted by heating the water formed by the reaction with the synthesis gas or steam is used, so that the entire amount of water formed by the reaction is utilized for the humidification using a heat source of a temperature as low as possible. The water formed by the reaction and separated in step (e) of distilling dimethyl ether contains small amounts of organic impurities and there is the possibility that these impurities adversely affect to the reforming catalyst in step of producing a synthesis gas. Therefore, it .is preferable that the hydrocarbon used as the raw material is humidified with water formed by the methanol dehydration and further humidified with condensed water obtained from the synthesis gas formed in step (a) of producing a synthesis gas so that the hydrocarbon used as the raw material is washed with the condensed water.
In the production of dimethyl ether in accordance with the process of the present invention, separation of dimethyl ether is facilitated by conducting the methanol synthesis and the methanol dehydration 0o$$0 S"separately. Therefore, the condensation and separation by an air cooler or a water cooler is possible to apply and the plant cost and the energy .00o$) consumption can be reduced. When methanol purified by rectification is supplied to the dehydration step as the raw material in accordance with a conventional process, a huge fractionator for methanol is required. In contrast, when dimethyl ether is produced by dehydration of crude methanol, no huge fractionator for methanol is required and the plant cost and the energy consumption can be reduced. Moreover, since the crude methanol is used for the dehydration after components having low boiling points are removed in advance, no adverse effects are exhibited on the methanol dehydration and the dehydration can be conducted with stability for a long time. Since the hydrocarbon used as the raw material is humidified with water formed by the dehydration, the used amount of water, which is a valuable material in areas where natural gas is produced, can be reduced. Moreover, since waste water containing small amounts of organic impurities is not discharged, no treatments for the environmental protection are required for the waste water disposal.
Therefore, the fuel grade dimethyl ether can be produced very advantageously in areas where natural gas is produced in accordance with the process of the present invention.
EXAMPLES
The present invention will be described more specifically with reference to examples in the following. However, the present invention is not limited to the examples.
Example 1 With reference to the flow diagram shown in Figure 1, the application of the process of the present invention to a plant for producing dimethyl ether in the scale of 5,000 ton/day will be described. In Figure 1, hydrocarbon (natural gas) used as the raw material was introduced into a flow route 1 and, via route 2, mixed with a recycled hydrogen for hydrogenation (route The hydrocarbon was preheated to 400 0 C by heat exchange with a gas formed by combustion (route 67) in a preheater heat exchange with a gas formed by combustion (route 67) in a preheater for natural gas of the raw material 4 and desulfurized by hydrogenation in a reactor for hydrogenation 5 and a sulfur adsorption column 6. The natural gas of the raw material which had been desulfurized (route 7) was humidified in a first humidifier 8 with water discharged from a methanol separation column (route 10) and further humidified in a second humidifier 9 with condensed water obtained from a synthesis gas (route The second humidifier 9 was a heat exchange-type humidifier. The humidification in the first humidifier was conducted by heating circulating water by a heater of a first humidifier 8a. As the heat source of the humidifiers, heat recovered by the heat recovery system 21 and recovered from a methanol synthesis converter 32, which will be described olater, was used.
The humidified natural gas (route 12) was mixed with process steam (route 13) in an amount such that the ratio of the amounts by mole oooe• of steam and carbon was adjusted to 1.8. The resultant mixed gas was preliminarily heated in a preheater for a feed gas to a primary reformer 14 at 630C and then introduced into a reaction tube of a primary reformer 16. As the fuel of the primary reformer (route 65), natural gas :and off gas from other synthesis steps (routes 37 and 44) were used and the air for combustion is introduced via route 66.
The effluent gas from the primary reformer (route 17) was further reformed in a secondary reformer 19. The secondary reformer 19 was a partial oxidation reactor using oxygen (route 18) and the temperature at the outlet was 1,000 to 1,050 0 C. The gas discharged from the secondary reformer was introduced into a heat recovery system 21 and the heat was recovered as the heat source for high pressure steam, the humidifiers and the distillation steps. After the gas was cooled to the ordinary temperature in a cooler for a synthesis gas 22, the gas was separated into the synthesis gas (route 24) and condensed water of synthesis gas (route in a gas-liquid separator for a synthesis gas 23.
In the step of synthesizing methanol, the pressure of the synthesis gas (route 24) was raised to about 10 MPa by a compressor for a synthesis gas 26. After the pressurized gas was mixed with an unreacted circulating gas (route 28) from a circulator for a reaction gas 29, the resultant gas was preheated in a preheater for a feed gas to a methanol synthesis converter 31 and methanol was synthesized in a methanol synthesis converter 32. An effluent gas from the methanol synthesis converter (route 33) was cooled to the ordinary temperature by the preheater for a feed gas to a methanol synthesis converter 31 and a cooler of an effluent gas from a methanol synthesis converter 34 and separated into the unreacted gas and a crude methanol (route 36) in a high pressure separator 35. The major portion of the unreacted gas (route 28) was .i recycled and reused as the raw material for the methanol synthesis and a $$$0o small portion of the unreacted gas was purged via route 37 to adjust the i pressure inside the system. A portion of the gas dissolved in the crude methanol (route 36) was removed by a low pressure separator 38 and the crude methanol was introduced into a crude methanol tank 45 via route 39. Since a vent gas of the low pressure separator (route 40) contained some amount of methanol, methanol was recovered by absorption into pure water (route 42) in a vent scrubber 41 and introduced into a crude methanol tank 45 via flow route 43.
lower boiling points in the crude methanol were removed in a crude methanol distillation column 49. Water discharged from the methanol separation column (route 64) was added to the crude methanol via route 47 so that the specific volatility of the impurities having low boiling points is increased and the removal of the impurities having low boiling points are facilitated. Sodium hydroxide (route 48) was added to prevent corrosion since the crude methanol contained acidic components. The gases and the components having low boiling points which were removed from the crude methanol were discharged via route 52 and used as the fuel in the reformer 16.
The crude methanol from which the dissolved gases and the components having lower boiling points had been removed (route 51) was mixed with recycled methanol (route 53), vaporized and superheated at S"300 0 C in a methanol evaporator 54 and introduced into a methanol dehydration reactor 56 and dimethyl ether was synthesized. The content 0o$$o of water in the crude methanol in route 51 is different depending on the process for producing a synthesis gas. When the two-step reforming process shown in the present example was used, the content was about 21% by weight.
The crude dimethyl ether (route 57) from the methanol dehydration $Booo S" 56 was separated in a dimethyl ether separation column 58 and product dimethyl ether (route 60) was obtained. On the other hand, a mixture of methanol and water at the bottom of the column (route 61) was separated in a methanol separation column 62. Methanol at the top of the column (route 53) was recycled and reused as the raw material for the synthesis of dimethyl ether. Water containing small amounts of organic impurities at the bottom of the column (route 64) was reused as the process water of the crude methanol distillation column 49 and the supply water to the humidifier.
Example 2 The step of producing a synthesis gas and the step of methanol synthesis were the same as those in Example 1. A crude methanol was separated into methanol having a smaller concentration of water (route 51) and water containing small amounts of organic impurities (route 51a) in the crude methanol distillation column 49. In accordance with this i process, the methanol having a smaller concentration of water (route 51) was supplied to the methanol dehydration reactor 56. Therefore, the facilities in the following steps could be made compact and the required energy could be reduced. Water containing small amounts of organic impurities (route 51a) was reused as water supplied to the humidifier in combination with water discharged from the methanol separation column 62 (route 64).
Throughout the description and claims of the specification the word .comprise" and variations of the word, such as "comprising" and "comprises", is "not intended to exclude other additives, components, integers or steps.
o. 4
Claims (7)
1. A process for producing dimethyl ether which includes the steps of: producing a synthesis gas containing hydrogen, carbon monoxide and carbon dioxide as main components and which is generated by reaction of hydrocarbon with steam or steam and oxygen, synthesizing methanol, wherein methanol is synthesized by reaction of the synthesis gas in the presence of a methanol synthesis catalyst and recovering a formed crude methanol in a liquid state, distilling methanol, wherein the recovered crude methanol is distilled, dissolved gases and components having lower boiling points are separated at the top of a distillation column and methanol containing water is separated at the bottom of the distillation column, producing dimethyl ether, from the separated methanol containing water, 15 and distilling dimethyl ether, wherein formed dimethyl ether, formed water V and unreacted methanol are separated from each other by distillation, wherein at least some of the formed water which is separated in step is utilized for humidifying the hydrocarbon used as a reactant in step
2. A process for producing dimethyl ether which includes the steps of: producing a synthesis gas, containing hydrogen, carbon monoxide and carbon dioxide as main components and which is generated by reaction of hydrocarbon with steam or steam and oxygen, 25 synthesizing methanol, wherein methanol is synthesized by reaction of the synthesis gas in the presence of a methanol synthesis catalyst and recovering a formed crude methanol in a liquid state, distilling methanol, wherein the recovered crude methanol is distilled, dissolved gases and components having lower boiling points are separated at the top of a distillation column and methanol having a higher concentration than the concentration of methanol recovered in step is separated at an intermediate stage of the distillation column, producing dimethyl ether, from the separated methanol, and distilling dimethyl ether, wherein formed dimethyl ether, formed water and unreacted methanol are separated from each other by distillation, wherein at least some of the formed water which is separated in step is utilized for humidifying the hydrocarbon used as a reactant in step
3. A process according to claim 1 or claim 2, wherein the hydrocarbon is humidified with the formed water separated in step and further humidified with condensed water obtained from the synthesis gas generated in step
4. A process according to any one of the preceding claims, wherein a heat exchange-type humidifier is used for humidifying the hydrocarbon. Dimethyl ether when produced by the process of any one of the preceding claims.
S 15
6. A process according to any one of claims 1 to 5 substantially as hereinbefore described with reference to Figure 1 of the accompanying drawings.
7. A process according to any one of claims 1 to 5 substantially as hereinbefore described with reference to Example 1 or 2. DATED: 14 June 2006 PHILLIPS ORMONDE FITZPATRICK Attorneys for: Mitsubishi Gas Chemical Company, Inc
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-392439 | 2000-12-25 | ||
| JP2000392439A JP4706812B2 (en) | 2000-12-25 | 2000-12-25 | Method for producing dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU9720301A AU9720301A (en) | 2002-06-27 |
| AU784978B2 true AU784978B2 (en) | 2006-08-10 |
Family
ID=18858429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU97203/01A Expired AU784978B2 (en) | 2000-12-25 | 2001-12-12 | Process for producing dimethyl ether |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4706812B2 (en) |
| AU (1) | AU784978B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2464618A4 (en) * | 2009-08-12 | 2015-08-26 | Catalytic Distillation Tech | PROCESS FOR THE PREPARATION OF DIMETHYL ETHER |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4553231B2 (en) * | 2002-11-13 | 2010-09-29 | 日揮株式会社 | Method for producing dimethyl ether |
| JP4905849B2 (en) * | 2006-04-07 | 2012-03-28 | 東京電力株式会社 | Synthesis method of dimethyl ether using microwave |
| US7906559B2 (en) * | 2007-06-21 | 2011-03-15 | University Of Southern California | Conversion of carbon dioxide to methanol and/or dimethyl ether using bi-reforming of methane or natural gas |
| JP5925105B2 (en) | 2012-10-26 | 2016-05-25 | 三菱重工業株式会社 | Saturator and natural gas reforming system having the same |
| CN114605235A (en) * | 2022-04-15 | 2022-06-10 | 南京工业大学 | CO (carbon monoxide)2Method for preparing dimethyl ether by hydrogenation |
| KR102540205B1 (en) * | 2022-11-04 | 2023-06-09 | (주)바이오프랜즈 | Method for converting carbon dioxide of fuel gas to carbon monodioxide, Dimethyl ether production system using flue gas of cement kiln boiler using ths same and Manufacturing method of dimethyl ether using the same |
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| US4665249A (en) * | 1984-12-19 | 1987-05-12 | Mobil Oil Corporation | Method for feeding an MTG conversion reactor |
| WO1996028408A1 (en) * | 1995-03-15 | 1996-09-19 | Starchem Technologies, Inc. | Dimethyl ether production and recovery from methanol |
| US5908963A (en) * | 1995-02-03 | 1999-06-01 | Holdor Topsoe A/S | Preparation of fuel grade dimethyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3171380D1 (en) * | 1980-05-20 | 1985-08-22 | Ici Plc | Methanol production |
| JPS59199648A (en) * | 1983-04-27 | 1984-11-12 | Mitsubishi Chem Ind Ltd | Production of dimethyl ether |
| JPS61257934A (en) * | 1985-05-10 | 1986-11-15 | Mitsubishi Gas Chem Co Inc | Methanol condensation and separation method |
| DE3876790D1 (en) * | 1988-05-04 | 1993-01-28 | Rwe Dea Ag | IMPROVED METHOD FOR PRODUCING PURE DIMETHYL ETHER. |
| US5177114A (en) * | 1990-04-11 | 1993-01-05 | Starchem Inc. | Process for recovering natural gas in the form of a normally liquid carbon containing compound |
| JP3447494B2 (en) * | 1996-12-26 | 2003-09-16 | ジェイエフイーホールディングス株式会社 | Method for producing dimethyl ether |
| JP3523763B2 (en) * | 1996-12-27 | 2004-04-26 | ジェイエフイーホールディングス株式会社 | Reduction activation method and reduction treatment apparatus for dimethyl ether synthesis catalyst |
-
2000
- 2000-12-25 JP JP2000392439A patent/JP4706812B2/en not_active Expired - Lifetime
-
2001
- 2001-12-12 AU AU97203/01A patent/AU784978B2/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665249A (en) * | 1984-12-19 | 1987-05-12 | Mobil Oil Corporation | Method for feeding an MTG conversion reactor |
| US5908963A (en) * | 1995-02-03 | 1999-06-01 | Holdor Topsoe A/S | Preparation of fuel grade dimethyl ether |
| WO1996028408A1 (en) * | 1995-03-15 | 1996-09-19 | Starchem Technologies, Inc. | Dimethyl ether production and recovery from methanol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2464618A4 (en) * | 2009-08-12 | 2015-08-26 | Catalytic Distillation Tech | PROCESS FOR THE PREPARATION OF DIMETHYL ETHER |
| US9481624B2 (en) | 2009-08-12 | 2016-11-01 | Catalytic Distillation Technologies | Process for the production of dimethyl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4706812B2 (en) | 2011-06-22 |
| JP2002193864A (en) | 2002-07-10 |
| AU9720301A (en) | 2002-06-27 |
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