MXPA97005957A - Procedure for the preparation of combusti quality etherdimethylene - Google Patents
Procedure for the preparation of combusti quality etherdimethyleneInfo
- Publication number
- MXPA97005957A MXPA97005957A MXPA/A/1997/005957A MX9705957A MXPA97005957A MX PA97005957 A MXPA97005957 A MX PA97005957A MX 9705957 A MX9705957 A MX 9705957A MX PA97005957 A MXPA97005957 A MX PA97005957A
- Authority
- MX
- Mexico
- Prior art keywords
- methanol
- stream
- product
- water
- dimethyl ether
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 148
- 239000007789 gas Substances 0.000 claims abstract description 65
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 37
- 230000002194 synthesizing Effects 0.000 claims abstract description 37
- 229910001868 water Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004821 distillation Methods 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 238000010926 purge Methods 0.000 claims abstract description 19
- 239000012071 phase Substances 0.000 claims abstract description 17
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 230000003197 catalytic Effects 0.000 claims abstract description 10
- 238000007906 compression Methods 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract 2
- -1 dimethyl dimethyl ether Chemical compound 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000006069 physical mixture Substances 0.000 description 2
- 230000003134 recirculating Effects 0.000 description 2
- 241000252095 Congridae Species 0.000 description 1
- 108060003095 GAS2 Proteins 0.000 description 1
- 240000002552 Prunus padus Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The present invention relates to a process for the preparation of a dimethyl ether product containing up to 20% by mass of methanol and up to 20% by mass of water, which is efficient as a fuel in compression ignition machines starting from a gas of synthesis that contains hydrogen and carbon oxides, the synthesis gas is converted to a mixed gas of dimethyl ether, methanol and water in one or more catalytic reactors in the presence of a catalyst that has activity both in the synthesis of methanol and in the methanol dehydration: the mixed process gas is cooled to obtain a process liquid phase (4) containing the methanol produced, dimethyl ether and water, and a process gas phase (2A) containing unconverted synthesis gas and a part of the dimethyl ether produced, the procedure includes the additional steps of separating the gas phase and the liquid phase, passing the liquid phase to a first distillation unit (column of EDM) and distilling off an upper stream of product (5) containing dimethyl methanol and methanol, and removing a lower stream (6) containing methanol and water, passing the lower stream to a second distillation unit (column of MeOH) and distilling off a stream containing methanol (7), introducing the methanol-containing stream to a purge washing unit, washing the process gas phase coming from the separation step with the methanol in a washing unit purge and remove from the unit a dimethyl methanol washing stream and methanol (B), convert a part of the methanol in the dimethyl ether washing stream and water in a catalytic dehydration reactor (RDM) by contact with a dehydration catalyst; remove and cool from the dehydration reactor a product stream (9) dimethyl dimetyl, water and unconverted methanol, and combine the upper stream of product from the was a distillation unit with the chilled product stream from the dehydration reactor to obtain a combined stream of product (10) dimethyl dimethyl ether
Description
PROCEDURE FOR THE PREPARATION OF DIMETHIC ETHER OF QUALITY OF FUEL
FIELD OF THE INVENTION
This invention is directed to the preparation of dimethyl ether co (EDM). The invention relates in particular to a process for the production of fuel quality EDM or contains small amounts of methanol and water from a synthesis gas comprising H2 / CO / CO2.
BACKGROUND OF THE INVENTION
Currently, EDM is used in the industry for the manufacture of synthetic gasoline. Additional industrial applications include the use of EDM as an aerosol impeller and more recently as an intermediate in the production of acetic acid. The main route in industrial scale EDM production comprises the dehydration of methanol by means of the use of a desorration catalyst in a fixed bed reactor, and rectification of the product to recover an EDM product with high purity, co o it is required by the aerosol industry. Various alternative preparation methods including direct synthesis of EDM from hydrogen and carbon oxides are known from the literature. The preparation of EDM directly from H2 / CO / CO2 synthesis gas in a fixed bed reactor of a combined methane catalyst] and dehydration catalyst is described in DD 291,937, US 5,254,596, EP 154,156, US4,417,000 , US 4,177,167, US 4,375,424, GB 2,093,365, GB 2,097,382, US 4,098,809, EP 409, 0B6, GB?, 099,327, FROM 3,220,547, FROM 3,201155, FROM 3,118,620, FROM 2,757,788, FROM 2,362,944, DK 6031/87 and DK 2169 / 89. The mentioned anronor technique is directed mainly to the preparation and use of catalyst compositions that are active in the preparation of methanol from synthesis gas and dehydration of methanol to EDM by means of the following reaction scheme:
CO2 «- 3H2 ==== CH3OH + H2O (l) 2CH3OH = == OH3-O-CH3 + H2O (2) CO * H20 === CO2 + H2 (3)
The formation of methanol and EDM is limited by chemical equilibrium, with the previous reaction scheme. In this way, the effluent stream of the EDM reactor is a mixed product stream of EDM, ethanol and water together with unreacted synthesis gas. An unreacted synthesis recirculation current is separated from the product stream and recirculated to the reactor. Due to a high partial pressure of EDM in the product stream, part of the produced EDM will be removed along with the recirculation current. To obtain reasonable conversion rates, it is necessary to remove EDM from the recirculation comment before recirculating the current during the direct synthesis of EDM. For this reason, the separation of EDM is usually carried out by means of a gas recirculation wash. DE 4,222,655 discloses an EDM preparation process, wherein EDM is separated from a high pressure separator1 in a recirculation gas stream, washing the gas stream with methanol in a gas wash step. The washed lower stream of the washing unit contains EDM and O2 and is subsequently combined with the product stream of the high pressure liquid separator. The combined stream of product is subsequently washed in a second washing unit with methanol or water for the removal of O 2 from the product stream. The washed stream of product containing EDM and rnetanol in substantially equivalent amounts is finally subjected to a number of rectification steps to provide a high purity EDM product. Recent research has shown that EDM products containing up to 20% by mass of rnetanol and haeta 20% by mass of water are efficient as fuels in machines ignited by understanding (Fle sch T., McCarthy C,
Basu P., Udovich C, Charbonneau? , Slodouske U., Mi elsen S.E., McCandless D., O New Clean Diesel Technology, Int. Congr. »Expos., Detroit, Michigan, February 27 - March 2, 1995). As used in the present, the term "fuel quality EDM" refers to EDM products with the above composition which are useful as fuels in compression ignition gas machines and turbines. By means of the known synthesis processes, the amount of methanol and water contained in the EDM crude product does not meet the EDM specification of fuel quality. Excess methane! in the produced EDM crude product represents a major disadvantage in the preparation of fuel quality EDM by means of known processes. In known processes, methanol has to be supplied from external process sources or the excess methanol has to be removed and recirculated into the process, which reduces the efficiency of the process towards the production of EDM
DESCRIPTION OF THE INVENTION
Therefore, the main objective of this invention is to provide a process for the preparation of fuel quality EDM without the disadvantages of the known procedures for the preparation of EDM. By means of the process of this invention, fuel-grade dimethyl ether is prepared by reacting synthesis gas (thi) containing hydrogen and carbon oxides with a mixed gas of the ether di-ether process, methanol and water in one or more catalytic reactors in presence of a catalyst that has activity both in the synthesis of methanol and in the dehydration of methanol, The mixed process gas is cooled to obtain a liquid phase of process containing methanol, dimethyl ether and water produced and a gas phase of process that contains unconverted synthesis gas and a portion of dimethyl ether produced, said process comprises the additional steps of: Separating the gas phase and the liquid phase, passing the liquid phase to a first distillation unit and distilling off a higher stream of product containing dimethyl ether and methanol, and Remove a lower stream containing methanol and methanol. ua; The lower stream is passed to a second distillation unit and a stream containing rnetanol is distilled off; The stream containing rnetanol is introduced to a purge washing unit; The gaseous phase of procoso is washed with rnetanol in the purge washing unit and a washing stream of dimethyl ether and methanol is removed from the unit; A part of the methanol in the washing stream is converted to dimethyl ether and water in a catalytic dehydration reactor by contact with a dehydration catalyst; A product stream of unconverted dirneric ether, water and methanol is removed from the dehydration reactor and cooled; The upper product content of the first distillation unit is combined with the cooled product stream from the de-ionization reactor to obtain a combined stream of the fuel quality dirnetic ether product. The preparation and conversion of synthesis gas to a process component containing EDM proceeds according to known methods in the direct synthesis of EDM. Suitable catalysts for use in the synthesis gas conversion stage include methane catalysts conventionally employed such as copper, zinc and / or chromium based catalysts and rnetanol dehydration catalysts, which usually comprise alumina or alumina silicates as active compounds. The catalysts can be charged to the EDM reactor as a physical mixture or as a bed in layers with alternating catalyst particles of inert synthesis and methanol dehydration. However, the physical mixtures of the catalysts will result in less selectivity and formation of by-products, mainly higher alcohols and hydrocarbons. In this way, it is preferred to employ a fi xed bed of catalyst compositions comprising combined activity of methanol formation, deviation of water gas and dehydration of rnetanol. Said catalysts can be prepared for example by coprecipitation of the catalytic active materials according to known methods of catalyst preparation, as described in the literature, for example in the aforementioned patent publications, which are incorporated herein by reference. . The operation of the method will be apparent in greater detail from the following description with reference to the drawings in which Figure 1 represents a flow chart of the method according to a specific embodiment of the invention. The flow chart is simplified and several conventional units, such as the heat exchange and cooling units, are not shown. A stream of synthesis gas 1 is reacted in an EDM synthesis circuit (MeOH / EDM reactors), which may comprise a series of adiabatic reactors charged with a combined methanol / EDM catalyst and indirect cooling between the reactors or a reactor cooled down to lower production capacities. Freshly synthesized gas is mixed with a gas recirculation stream 3 separated from a process stream leaving the synthesis circuit.
The synthesis gas is preheated in a feed effluent heat exchanger before its introduction into the first reactor. In the synthesis circuit, the synthesis gas is converted to a mixed gas from the EDM process, methanol and water by means of the first reactions (l) (3). The total reaction is exothermic and the heat of the reaction is removed in intercoolers disposed between the reactors. The mixed process gas of the reactors in the circuit is cooled and separated in a gaseous and liquid process phase stream, 2 and 4, respectively. The gas phase (2A), which contains unconverted synthesis gas, is divided into the recirculation gas stream 3 and the purge gas stream 2. Due to the low condensibility of the EDM in the mixed process gas, the purge gas stream 2 also contains valuable amounts of EDM which are recovered in a purge washing unit by flushing the purge stream with recirculating methanol 7 from a distillation column tle inertol (MeOH column), in one step of final purification of the procedure. The effluent stream 8 of the recovered EDM-containing washing unit is then passed to a dehydration reactor (RDM) with a fixed bed of a conventional methanol dehydration catalyst. By contact with the dehydration catalyst, the methanol in the present effluent is converted to FDM by means of reaction (2) proceeding in the reactor, and a stream of dehydrated product 9 of EDM, methanol and water is removed from the reactor. reactor-. The EDM in the liquid process phase stream 4 is recovered by means of distillation of the stream in an EDM distillation column. A higher product stream of EDM 5 that is removed from the column is combined with stream of dehydrated product 9 to a product stream of EDM of fuel quality 10. The methanol and water separated from the liquid stream of process that it is removed from the EDM distillation column as bottom stream of product 6, subjected to further distillation in methane distillation column]. (MeOH column), from which a separate top-product 7 of the methanol product is circulated to the purge wash unit as described above. The actual composition of the final EDM product stream 10 is adjusted by the process mainly by process parameters used in the FDM synthesis circuit. The results obtained by engineering calculations on a process such as the one described above are summarized in the tables that follow. The comment numbers in the tables correspond to the reference numbers shown in figure 1.
The current number 1 OA in Table 1 and 2 refers to a product stream of EDM obtained by a similar process, except for the methane wash stream! 8 of the purge washing unit that is not subjected to dehydration in the dehydration reactor (RDM). The product stream of EDM 10A is thus obtained by direct combination of the effluent stream 8 with the upper stream of product 5. In the calculation two different synthesis compositions (stream 1) were used resulting in EDM products of high quality. fuel with different content of ethanol and water, as is evident from the tables.
TABLE 1
TABLE 2
As is evident from the results summarized in the tables, the methanol content in the EDM products (stream 10A) obtained by a process without a reactor - ie dehydration is outside the concentration scale, and the products are not Usable in fuel quality EDM products without subsequent rectification.
EXAMPLE This example illustrates the preparation of fuel quality EDM on pilot plant scale by reference to Figure 1.
In a pilot plant comprising a gas feed preheater (not shown), a MeOH / EDM cooled reactor and a subsequent product gas cooler (not shown), a gas / liquid separator and a recirculation compressor (not shown), 6.9 Nm3 / h of a synthesis gas stream are mixed. with 26.5 Nm3 / h of a recirculation gas stream 3. The mixed gas stream is then passed through the reactor and is converted to a pressure of 42 bar and a temperature of 240 ~ 290 ° C in the presence of a catalyst as described earlier. Then, the gas stream that reacted is cooled and separated into a liquid phase (2.8 kg / h) in stream 4, with a composition as shown in Table 3 below, and a gas stream 2A. Current 2A is divided into recirculation current 3 and gas purge stream 2 (0.88 Nrn3 / h). The composition of the previous streams, as analyzed, is summarized in Table 3 below. TABLE 3
c., I recover stream of purge gas 2 by washing with a stream of methanol 7 from the distillation column of ethanol, introducing stream 2 (0.88 Nm3 / h) at a pressure of 40 bar at the bottom of the unit. purge washing and washing the current with anol in stream 7 which is introduced in the upper part of the unit at a speed of 0.87 l < g / h and a temperature of 14 ° C. From the bottom of the purge washing unit, a washed stream 8 is removed at a speed of 1.05 g / h. The analyzed composition of the previous streams is summarized in Table 4 below.
TABLE 4
Then, stream 8 was introduced in a flow of 1.05 kg / h and a pressure of 13 bar in a gas feed preheater (not shown) and preheated to 280 ° C. The preheated stream 8 was passed to the rnetanol dehydration reactor (RDM). In the RDM reactor the methanol contained in the stream was dehydrated by contact with a fixed bed of a dehydration catalyst operated under substantially adiabatic conditions, and a stream of dehydrated product 9 was withdrawn from the reactor with a composition of 17.4. moles% of methanol, 46.2 mole% of EDM and 36.2 mole% of H2O. The product stream 9 was combined with the product top stream 5 of the EDM distillation column (EDM column) into which the EDM contained in the process liquid phase stream was distilled off. The current was recovered 4 (0.67 Nm3 / h) of pure EDM under conventional distillation conditions, and was removed in stream 5 from the EDM distillation column. Stream 5 was combined with stream 9 to 2.43 kg / h of a final product stream 10 consisting of fuel quality EDM with a composition of FDM, ethanol and water as shown in four below :
TABLE 5
As is evident from Table 5, the composition of product stream 10 complies with the FDM specification of fuel quality for use as fuel in compression ignition machines without further processing of the product.
EXAMPLE OF COMPARISON An EDM product was prepared in a pilot plant procedure similar to the previous example, with the exception of the washed methane stream! 8 of the purge washing unit that was not subjected to dehydration treatment. In this procedure, stream 8 was combined directly with stream 5 of the EDM distillation column as shown in Figure 1 with dotted lines, leaving a product stream of EDM 10A with a composition shown in Table 6 to continuation:
TABLE 6
The composition of the EDM product obtained in the comparison example had a methanol concentration outside the perimeter scale to use the product in compression ignition machines.
Claims (2)
1. - A process for the preparation of a dimethyl ether product containing up to 20% by mass of methane! and up to 20% by mass of water, which is efficient as fuel in compression ignition machines from a synthesis gas containing hydrogen and carbon dioxide, the synthesis gas is converted to a mixed gas from the process of dimethyl ether, methanol and water in one plus catalytic reactors in the presence of a catalyst having activity both in methanol synthesis and in methanol dehydration; the mixed process gas is cooled to obtain a liquid process phase (4) containing the produced ethanol, ether dimethyl and water, and a process gas phase (20) containing unconverted synthesis gas and a part of the ether dimethyl produced; the method comprises the additional steps of separating the gas phase and the liquid phase; passing the liquid phase to a first distillation unit (column of EDM) and distilling off an upper stream of product (5) containing dimethyl ether and methanol, and removing a lower stream (6) containing methanol and water; passing the lower stream to a second distillation unit (MeOH column) and distilling off a stream containing methanol (7); introduce the methanol-containing stream to a purge washing unit; washing the process gas phase coming from the separation step with the inert gas in a purge washing unit and removing from the unit a washing stream of dimethyl ether and methanol (8); converting a part of the ethanol into the washing stream in dimethyl ether and water in a catalytic dehydration reactor (RDM) by contact with a dehydration catalyst; removing and cooling from the dehydration reactor a stream of product (9) of dirnetyl ether, water and unconverted methanol; and combining the upper product stream of the first distillation unit with the cooled product stream of the dehydration reactor to obtain a combined stream of product (10) of fuel-grade dimethyl ether.
2. The process according to claim 1, further characterized in that a part of the process gas phase is recirculated to the catalytic reactors. SUMMARY OF THE INVENTION A process for the preparation of dinetilic ether of fuel quality from a synthesis gas containing hydrogen and carbon oxides; the synthesis gas is converted to a mixed process gas of dirnethyl ether, methanol and water in one or more catalytic reactors in the presence of a catalyst having activity both in the synthesis of methanol and in the dehydration of methanol; the mixed process gas is cooled to obtain a liquid process phase containing methanol, dimethyl ether and water produced and a process gas phase containing unconverted synthesis gas and a part of dimethyl ether produced; said method comprises the additional steps of separating the gas phase and the liquid phase; passing the liquid phase to a first distillation unit and distilling off an upper stream of product containing dimethyl ether and methanol, and removing a lower stream containing methanol and water; passing the lower stream to a second distillation unit and distilling off a stream containing methanol; introduce the methanol into a purge washing unit; wash the gaseous process phase with rnetanol in the purge washing unit and remove a washing stream of dimethyl ether and methanol from the unit; converting a part of the methanol in the washing stream to dimethyl ether and water in a catalytic dehydration reactor by contact with a dehydration catalyst; removing a product stream of dimethyl ether, water and unconverted methanol from the dehydration reactor; and combining the upper product stream from the first distillation unit with the product stream from the dehydration reactor to obtain a combined stream of fuel grade dimethyl ether product. EA / lprn * fac * P97 / 762F
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK0120/95 | 1995-02-03 | ||
| DK012095A DK171707B1 (en) | 1995-02-03 | 1995-02-03 | Process for producing fuel grade dimethyl ether |
| PCT/DK1996/000047 WO1996023755A1 (en) | 1995-02-03 | 1996-01-29 | Preparation of fuel grade dimethyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA97005957A true MXPA97005957A (en) | 1998-02-01 |
| MX9705957A MX9705957A (en) | 1998-02-28 |
Family
ID=8089980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9705957A MX9705957A (en) | 1995-02-03 | 1996-01-29 | Preparation of fuel grade dimethyl ether. |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US5908963A (en) |
| EP (1) | EP0871602B1 (en) |
| JP (1) | JP2849475B2 (en) |
| KR (1) | KR100289222B1 (en) |
| CN (1) | CN1085647C (en) |
| AT (1) | ATE193879T1 (en) |
| AU (1) | AU694305B2 (en) |
| BR (1) | BR9607349A (en) |
| CA (1) | CA2211722C (en) |
| DE (1) | DE69608915T2 (en) |
| DK (2) | DK171707B1 (en) |
| ES (1) | ES2148723T3 (en) |
| MX (1) | MX9705957A (en) |
| NO (1) | NO307560B1 (en) |
| NZ (1) | NZ298755A (en) |
| PT (1) | PT871602E (en) |
| RU (1) | RU2144912C1 (en) |
| UA (1) | UA51644C2 (en) |
| WO (1) | WO1996023755A1 (en) |
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| CN1331833C (en) * | 2005-06-23 | 2007-08-15 | 昆山市迪昆精细化工公司 | Process for preparing dimethyl ether |
| US20090264543A1 (en) * | 2005-08-01 | 2009-10-22 | Bp, P.L.C. | Integrated Process for the Co-Production of Methanol and Demethyl Ether From Syngas Containing Nitrogen |
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| US5218003A (en) * | 1988-01-14 | 1993-06-08 | Air Products And Chemicals, Inc. | Liquid phase process for dimethyl ether synthesis |
| DE3817816A1 (en) * | 1988-05-26 | 1989-11-30 | Union Rheinische Braunkohlen | METHOD FOR PRODUCING DIMETHYL ETHER |
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| DE4222655A1 (en) * | 1992-07-10 | 1994-01-13 | Leuna Werke Ag | Direct prepn. of di:methyl ether - from synthesis gas with controllable purity, useful for aerosols or for domestic and industrial heating |
-
1995
- 1995-02-03 DK DK012095A patent/DK171707B1/en not_active IP Right Cessation
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1996
- 1996-01-29 JP JP8523181A patent/JP2849475B2/en not_active Expired - Fee Related
- 1996-01-29 PT PT96900552T patent/PT871602E/en unknown
- 1996-01-29 KR KR1019970705316A patent/KR100289222B1/en not_active IP Right Cessation
- 1996-01-29 NZ NZ298755A patent/NZ298755A/en unknown
- 1996-01-29 BR BR9607349A patent/BR9607349A/en not_active IP Right Cessation
- 1996-01-29 WO PCT/DK1996/000047 patent/WO1996023755A1/en active IP Right Grant
- 1996-01-29 DE DE69608915T patent/DE69608915T2/en not_active Expired - Lifetime
- 1996-01-29 UA UA97094487A patent/UA51644C2/en unknown
- 1996-01-29 RU RU97114880A patent/RU2144912C1/en active
- 1996-01-29 DK DK96900552T patent/DK0871602T3/en active
- 1996-01-29 EP EP96900552A patent/EP0871602B1/en not_active Expired - Lifetime
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- 1996-01-29 CN CN96191760A patent/CN1085647C/en not_active Expired - Lifetime
- 1996-01-29 MX MX9705957A patent/MX9705957A/en unknown
- 1996-01-29 US US08/894,066 patent/US5908963A/en not_active Expired - Lifetime
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- 1996-01-29 AU AU44317/96A patent/AU694305B2/en not_active Expired
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1997
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