AU603070B2 - Process for the purification of dimethylether - Google Patents
Process for the purification of dimethylether Download PDFInfo
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- AU603070B2 AU603070B2 AU65506/86A AU6550686A AU603070B2 AU 603070 B2 AU603070 B2 AU 603070B2 AU 65506/86 A AU65506/86 A AU 65506/86A AU 6550686 A AU6550686 A AU 6550686A AU 603070 B2 AU603070 B2 AU 603070B2
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- Prior art keywords
- dimethylether
- methanol
- impurities
- column
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Pure dimethyl ether is prepared by catalytic dehydration of methanol over a gamma -Al2O3 catalyst which preferably contains small amounts of SiO2 and purification of the dehydration product by addition thereof to a distillation column to obtain pure dimethyl ether on certain plates of this column and taking off the pure dimethyl ether and impurities above certain plates of the same column.
Description
r, 7 I1 COPUMONWEALTH OF AUSTrJ\JLIA Form Ruation PATENTS AC~2, 1952 CONMPLETE SPEC IF ICATION.
(ORIGINAL)
FOR OFFICE USE 0307 Short Title: Int. Cl.
Application Nurber- Lodged- Z T506/ Complete Specification-Lod 1 ged% Accepted: Lavpsed Published: 'Priority: TI is, IPIr]ip r h Scrc for 'Related Art: TO BE COMPLETED BY APPLIC.2f Nam~e of Applicant; Union Rheinisohe Braunkohlen Kraftstoff AG.
Address of Applicant; Postfach 1663, D-5o47 Wesseling, Germany Actual Inventor; Address for Service: Horst DOPNHAGEN, I-artmut HATTDER Ewald NEISENBURG ARTHUR S. CAVE CO., Patent and Trade Mark Attorneys, 1 Al1fred Street, Sydney, New South Wales, Australia, 2000.
Complete Specification for the invention entitled: Process for the purification of Dimethylether The followiingT statement is a full description of this invention, including the best method of performing it known to mez- ASC-4 9Q Process for the purification of dimethylether Background of the invention 1. Field of the invention The instant invention relates to a process for the purification of dimethylether, which contains impurities, by feeding a mixture which contains the dimethylether at specific trays to a distillation column and withdrawal of the dimethylether and of impurities at specific trays of the same column.
2. Description of the prior art i Before the development of low pressure processes for the production of methanol, dimethylether was obtained as a side-product of high pressure methanol processes, usually in a quantity of 2 to 3 weight-% based on the total quantity of products withdrawn from the methdnol synthesis Sreactor. Dimethylether was separated from raw methanol together with other impurities as first runnings in the distillation unit for the production of pure methanol.
After introduction of low pressure methanol processes, which form only negligible quantities of dimethylether, specific processes for the synthesis of dimethylether by catalytic dehydration of methanol were developed.
lae UK 372 Numerous catalysts and processes are disclosed in the patent literature.
According to DE-PS 680 328 aliphatic ethers are obtained by heating alcohols in the presence of ZnCl 2 Other suitable catalysts for the production of ethers from alcohols are according to British Patent Publications No. 332 756, No. 350 010 and No. 403 402, U.S. Pat. No. 1,873,537 and French Patent Publication No. 701 335 ferric chloride, copper sulfate, stannic chloride, manganese chloride, aluminum chloride and sulfate, chromium sulfate, alums, thorium derivates, aluminum oxide, titanium oxide, barium oxide, silica gel or aluminum phosphate.
S The synthesis of dimethylether directly from synthesis gas CO H 2 has also been described (DE-PS 23 62 944, DE-PS 27 57 788 and DE-PS 32 20 547).
The technically most important catalysts have proven to be according to DE-PS 28 18 831, DE-OS 32 01 155, European Patent Application No. 0 099 676 and European Patent Application No. 0 124 078 in particular aluminum oxide and aluminum silicate catalysts with and without doping.
The raw dimethylether thus obtained contains reaction 0 water, unconverted methanol as well as small quantities of impurities like for example methylformate, hydrocarbons, amines and sulfides.
In these production plants raw dimethylether is worked up in two concecutive distillation columns, in the first of which, dimethylether is distilled off under pressure and in the second of which unconverted methanol 2 -7 UK 372 is separated and recycled.
Thus in European Patent Application No. 0 124 078 a process is disclosed, according to which in a fist pressurized column, dimethylether is separated as a side-stream, whereas in a second column, which is operated at a lower pressure, the impurities with boiling points between methanol and dimethylether are withdrawn as a head product. Unconverted methanol is separated also in the second column as a side-product.
Although this process leads to dimethylether of high purity, it has the considerable economic disadvantage, that not only the first but also the seco.,, -olumn have to be provided with a high number of trays, resulting in high capital expenditure and in particular in high operating costs. Furthermore there is a;-isqu that impurities with boiling points between dimethylether and methanol remain at least in small quantities in the first column resulting in contamination of j |dimethylether.
Since dimethylether is of increasing importance as a propellant in aerosol sprays, very high demands are made on the purity of dimethylether for certain applications. In particular for cosmetic, human and houschold applications dimethylether must be free of irritating substances. Furthermore dimethylether must be odorless for these applications. Thus the problem existed, to make available on the one hand a more economical production process for dimethylether compared to the state of the art and on the other hand to produce dimethylether in high purity and practically quantitatively based on feed methanol.
3 ^j^ 3. Smay fteineto I pllOI)illl-- ~bCi 3. Summary of the invention The problem outlined above has been solved by the applicant in a non-obvious, surprising manner by the inventive process for the production of dimethylether of high purity by distillation of dimethylether which contains impurities and/or distillation of mixtures which contain dimethylether, methanol and impurities, characterized in that the dimethylether-mixture which contains the impurities is fed to a distillation column below the twentyfifth tray (from the top of the column) at one or several trays, that pure dimethylether is withdrawn above the fifteenth tray, preferably above the tenth tray (from the top of the column) and that the impurities are withdrawn at a tray, which is at least five trays above the (highest) tray which is used as feed tray for the feed mixture containing dimethylether and impurities, and below the lowest tray from which dimethylether is withdrawn.
4. Description of the preferred embodiments Raw methanol from a high pressure methanol production unit as well as dimethylether which is catalytically produced from methanol, contain, as outlined already above, numerous 0 impurities, some of which have strong odors.
In high pressure methanol production units raw methanol is 0* 0* obtained, which usually contains 2 to 3, however may contain up to 5 weight-% of dimethylether.
In dimethylether synthesis from raw or pure methanol, usually mixtures which contain 20 to 80 weight-% of dimethylether based on methanol feed are obtained at the synthesis reactor exit, depending on operating conditions. In addition the raw dimethylether contains impurities mentioned above, reaction Swater and unconverted methanol.
S0230g 4 UK 372 The boiling points of the impurities for example of dimethylamine (6,9 0 dimethylsulfide (37,3°C), methylmercaptane (5,8 0 formic acid (100,75 0
C),
formic acid methylester (31,5 0 formaldehyde 21°C), formaldehyde dimethylacetale (45,5 0 C) or acetic acid methylester (56,95°C) as well as their solubilities and vapor pressures in the product mixture, are very different from each other. Since the subjectively noticed intensities of odors of the individual impurities are also very different, the solution of the problem of producing very pure dimethvlether in nearly quantitative yield by a process which is more economical with regard S to the state of the art, is very difficult.
a S Applicant therefore has found as a result of numerous tests during several years in laboratory, pilot plant A and technical unit, that the problem identified above can be solved by the inventive purification process in a particularly economical way. It is obvious for the artisan that according to the instan. invention the second column has only to be a distillation column with a small number of trays, since only methanol with a boiling point of 64,7°C has to be separated from water.
According to the instant invention, distillation columns of the state of the art can be used, the size of which depending on the capacity of the unit.
The trays used can be trays in accordance with the state of the art, like for example valve trays, sieve trays, bubble trays and others.
In principle also filling and packing material can be used as rectification devices like for example ceramics, glass materials, wire packing and others, whereby the inventive location of the feed introduction and the I 7.i 4t locations for withdrawal of dimethylether and impurities can be calculated in accordance with the tray-locations disclosed in the instant invention.
In Figure 1 as an example a unit for production and purification of dimethylether is represented.
In Figure 2 as an example a distillation column for the production of pure dimethylether is represented.
In Figure 3 as an example this column is equipped with a side-stripper.
see"
S
5 *.00.
fee 0 tii The investigations of the applicant have led to the result that 1* in order to solve the problem outlined above, namely the production of highly pure dimethylether in nearly quantitative yield based on methanol feed, in a particularly economical way, introduction of the feed into the column has to take place Ro* *.g below the twentyfifth (25th) tray (from the top of the column) at one or several trays. In case the feed is introduced at a tray closer to the top of the column, the purity of dimethylether desired, is not obtained, in particular with regard to absence of odor.
Furthermore pure dimethylether has to be withdrawn according to the invention above the fifteenth (15th) tray, preferably above the tenth (10th) tray (from the top of the column). This can be for example the sixth (6th) tray, but also the first (1st) to fifth (5th) or sixth (6th) to fifteenth (15th) tray.
Alternatively condensate at the head of the column can be withdrawn. Also several trays can be used.
0230g I- 6 -0.
n
I
9 S 9
I'
9i I r i ^^fi The investigations of the applicant have shown furthermore that components with boiling points between those of methanol and dimethylether can be withdrawn from the same column at one or several trays located at least 5 trays above the (highest) feed tray, where feed containing contaminated dimethylether an'/or a mixture containing dimethylether, methanol and impurities is introduced into the column, and below the lowest tray from which dimethylether is withdrawn.
If a feed is introduced, which for example contains 1 weight-% of dimethylether, methanol and other components with boiling points between those of methanol and dimethylether and optionally water and other oxygen containing hydrocarbons like for example alcohols with a number of C-atoms 1, the column is operated with a reflux ratio of 1 1 to 1 25, depending on the portion of dimethylether. Thus in case of, for example, a dimethylether portion of 1 weight-%, the reflux ratio can be 1 i. reflux ratio of, for example, 1 1 means that the quantity of dimethylether withdrawn is equal to 1 part, whereas the quantity of vapor for condensation at the head of the column is 1 1 parts.
In case of a dimethylether content of, for example, 3 4 weight-% a reflux ratio of 1 5 8 is preferred. These quantities of dimethylether correspond to the quantities present in raw methanol of high pressure methanol production units. Dimethylether can only be obtained in a very pure state in nearly quantitative yield if the inventive feed tray(s) and S trays for withdrawal of dimethylether and impurities are used.
0230g 7- UK 372 In case of for example a dimethylether content of to 80 weight-% and in the presence of methanol and other components with boiling points between those of methanol and dimethylether and optionally of water and other oxygen containing hydrocarbons like for example alcohols with a number of C-atoms 1, the reflux ratio according to the instant invention is 1 0,4 to 1 5, preferably of 1 1 to 1 depending on the dimethylether content.
In case of for example a mixture, which contains weight-% of dimethylether,15 weight-% of methanol and additionally water and impurities, a reflux ratio of 1 1,5 to 1 2,5 can be used.
These feeds are typical mixtures obtained by the S catalytic conversion of methanol to dimethylether with Al203- respectively Al 2 0 3 /SiO 2 -cata ysts at the exit of the syntheses reactor.
SCa If the dimethylether portions are between 5 to weight-% or higher than 80 weight-%, the inventive .s reflux ratios are to be chosen on the basis of the ratios disclosed.
The distillation column for the purification of dimethyl- Sether is operated in general at a pressure of 5 10 bar, whereby in case of a synthesis reactor preceeding the column, the pressure of the column is preferably P adapted to the pressure of the synthesis reactor.
Pressures outside of this range can also be used according to the invention.
Throughput is, as usual, determind by capacity of the column, heat applied and reflux ratio.
8ii---~~ei g6 6 64 00 U "6 66 6 6 a UK 372 In order to obtain pure dimethylether in nearly quantitative yield, in particular in case of low portions of dimethylether in the feed, the gas mixture withdrawn at the head of the column, which contains in general
CO
2
N
2 hydrocarbons and small quantities of dimethylether, can be washed according to the invention.
Suitable washing liquids are for example methanol and/or bottoms of the dimethylether distillation column.
The washing liquid which contains dimethylether can be recycled to the distillation column or to the dimethylether synthesis reactor. Washing can be carried out in direct current or countercurrently. The latter procedure is prefered.
Furthermore the impurities withdrawn from the column can additionally be stripped in a side-stripper, whereby dimethylether separated by stripping is recycled to the column. By this procedure, dimethylether withdrawn with the impurities can practically quantitatively recycled to the column.
Examples and figures The following examples have been carried out in continuous operation.
Example 1 4000 kg/h of a mixture consisting of 2400 kg of dimethylether, 580 kg of methanol, 910 kg of water and 110 kg of impurities are fed at the 49th tray (from the top of the column) to a distillation column containing 65 valve trays.
9 L UK 372 The column is operated at 8,5 bar. The reflux ratio is 1 1,9.
At the head of the column 30 m 3 of a gas mixture are withdrawn, which essentially contain CO 2 N2' hydrocarbons and a small quantity of dimethylether.
At the sixth (6th) tray of the column (from the top of the column) 2385 kg/h of pure dimethylether are withdrawn with a methanol content of 10 ppm.
At the 44th tray (from the top of the column) 90 kg/h of impurities are withdrawn. 10 kg/h of higher boiling impurities (than methanol), 580 kg/h of methanol and 910 kg/h of water are withdrawn from the bottom of the column and fed to a second column, where methanol is separated from water by distillation.
Example 2 Example 1 is repeated, however the impurities withdrawn are fed to a side-stripper.
2395 kg/h of pure dimethylether and 80 kg/h of impurities at the exit of the side-stripper are obtained.
Example 3 61000 kg/h of a mixture consisting of 55000 kg methanol, 2000 kg of dimethylether, 3500 kg of water and 500 kg of impurities are fed to a distillation column containing 100 valve trays.
The reflux ratio is 1 7.
The mixture is fed to the column at the 35th tray (from the top of the column).
10 aulsM~n-.XCr UK 372 At the ninth (9th) tray (from the top of the column) 1996 kg/h of dimethylether are withdrawn.
At the 30th tray (from the top of the column) 302 kg/h of impurities are withdrawn at the exit of the stripper.
55000 kg/h of methanol, 3500 kg/h of water and 200 kg/h of impurities, which consist essentially of higher alcohols, are withdrawn fromt the bottom of the column.
The pressure in the column is between 6 and 8 bar.
Overhead gas is washed countercurrently with methanol.
The washing methanol containing small quantities of dimethylether is fed to the column.
Example 4 °i 4000 kg/h of a mixture consisting of 800 kg of dimethylether, 2825 kg of methanol, 300 kg of water and 75 kg of impurities, boiling between methanol and dimethylether, are fed at the 48th tray (from the top of the column) to a column containing 70 bubble trays. The reflux ratio is 1 At the fourth (4th) tray (from the top of the column) 796 kg/h of dimethylether are withdrawn.
At the fortieth (40th) tray (from the top of the column) 77 kg/h of impurities are withdrawn.
From the bottom of the column 2825 kg/h of methanol and 300 kg/h of water are withdrawn.
11 I II i~ I II UK 372 Example 2000 kg/h of a mixture containing 1750 kg of dimethylether, 100 kg of methanol, 100 kg of water and 50 kg of impurities are fed to the 38th tray of a distillation column (from the top of the column) which contains 45 bubble trays.
The reflux ratio is 1 1.
1745 kg/h of dimethylether are withdrawn at the third (3rd) tray of the column (from the top of the column) and 48 kg/h of impurities are withdrawn at the thirtythird S (33rd) tray of the column (from the top of the column).
100 kg/h of water, 100 kg of methanol and 5 kg/h of impurities which have higher boiling points than methanol, are withdrawn from the bottom of the column.
9 In Figurel the distillation column for the purification of dimethylether is represented by Very pure dimethylether is withdrawn at Head gas passes through (11) to condenser Reflux passes through (12) 0* 0.
to column Waste gas passes through (15) to scrubbing unit where the gas is washed with methanol (16).
In principle also other washing liquids can be used, like for example raw methanol or bottoms of column whereby in the latter case the washing liquid containing dimethylether is recycled to column Small quantities of dimethylether combined with methanol pass through (17) to the syntheses reactor for dimethylether Waste gas leaves the unit through (23).
The main quantity of methanol feed is pumped by pump (4) through heat exchanger and vaporizer to Synthesis product (19) passes through to 12 p.- UK 372 At (20) impurities with boiling points between those of methanol and dimethylether are withdrawn and pass through (22) for example to an incineration.
Bottoms of which essentially contain water and methanol pass to methanol distillation column is operated in general at atmospheric pressure.
In principle, pressures can also be applied which are somewhat higher or lower than the pressure in In general however the pressure in is below that of Methanol is withdrawn through (10) and recycled to the synthesis reactor. Waste water is withdrawn through If required, impurities with boiling points higher than methanol can be withdrawn through (21).
In Figure2 represents the distillation column S* for the production of pure dimethylether. Feed is introduced through Pure dimethylether is withdrawn through Impurities are withdrawn through Head product passes through to condenser Reflux passes through to column Waste gas leaves the unit at represents the reboiler cycle. At bottoms are withdrawn.
In Figure3 the impurities pass through to stripper which is equipped with reboiler cycle Dimethylether which is separated by stripping, passes through to column Feed is added at Pure dimethylether is withdrawn at Head gas passes through (11) to condenser Reflux passes through to column At (12) the impurities which are stripped of dimethylether are withdrawn.
13 UK 372 According to the instant inventions highly pure dimethylether is produced in almost quantitative yield based on methanol feed. Dimethylether thus obtained is free of odor, contains less than 10 ppm of methanol, and a maximum of 0,1 weight-% of hydrocarbons. Its purity is at least 99,9 weight-% of dimethylether.
Dimethylether obtained by the instant invention is excellently suited for any application in any aerosol spray as a propellant.
Compared to the state of the art only one column with high rectification efficiency is needed according to the instant invention. The second column serves in contrast to the state of the art only for the separation of methanol from water. Thus a relatively t low rectification efficiency is needed.
S
:o In addition the inventive process permits the separation of impurities with boiling points higher than methanol in the second column. As a result waste water from
S
the bottom of the second column contains only small amounts of impurities and can relatively easily be purified by waste water treatment.
S
p> 14
Claims (9)
1. A process for the purification of dimethylether by d 'tillation of dimethylether which contains impurities and/or mixtures which contain dimethylether, methanol and impurities, characterized in that the feed mixture which contains dimethylether and impurities is fed into the distillation column below the twentyfifth tray (from the top of the column) at one or several trays, that pure dimethylether is withdrawn above the fifteenth tray (from the top of the column) and that a distillation product, which contains impurities with lower boiling points than that of methanol, is withdrawn at a tray, which is located at least five trays above the (highest) feed tray 0 for the introduction of dimethylether containing feed, and below the lowest tray from which dimethylether is withdrawn.
2. Process according to claim 1, characterized in that the pure dimethylether is withdrawn above the tenth tray (from the top of the column).
3. Process according to claim 1, characterized in that in S the case of feed, which contains 1 5 weight-% of S dimethylether and predominantly methanol and additionally impurities with boiling points between those of methanol and dimethylether and optionally water and other oxygen containing hydrocarbons, the distillation column for the production of pure dimethylether is operated at a reflux ratio of 1 1 to 1
4. Process according to claim 1, characterized in that in the case of feed which contains 20 80 weight-% of dimethylether, and methanol and impurities with boiling p oints between those of methanol and dimethylether and 0230g wra i I lii ii Ii (1 UI- t: 0* optionally water and other oxygen containing hydrocarbons, the distillation column for the production of pure dimethylether is operated at a reflux ratio of 1 0,4 to 1 Process according to claim 4, characterized in that the distillation column for the production of pure dimethylether is operated at a reflux ratio of 1:1 to 1:2.5. 6 Process according to any one of claims 1 to 3, characterized in that the light components, which are withdrawn at the head of the column and which contain in general C0 2 N 2 light hydrocarbons and small quantities of dimethylether, are scrubbed by direct current or countercurrently with methanol.
7. Process according to any one of claims 1 to 4, characterized in that the impurities, which are withdrawn at a tray below the tray where pure dimethylether is withdrawn, are treated in a side-stripper and that dimethylether thus separated, is recycled to the distillation column.
8. Dimethylether purified in accordance with the process of any one of the preceding claims.
9. A process for the purification of dimethylether by distillation of dimethylether which contains impurities and/or mixtures which contain dimethylether, methanol and impurities, substantially as herein defined, with reference to any one of the Examples.
10. A process for the purification of dimethylether by Vi. pt \1 K 6 s d 16 distillation of dimethylether which contains impurities and/or mixtures which contain dimethylether, methanol and impurities substantially as herein defined, with reference to any of the drawings.
11. Purified dimethylether, whenever purified by the process defined in any one of the preceding claims. DATED this 2nd day of January, 1990. ii II I [1 UNION RHEINISCHE BRAUNKOHLEN KRAFTSTOFF AG By Its Patent Attorneys ARTHUR S. CAVE CO. 9*e* soo 0 o 00 0230g 17
Priority Applications (21)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU65506/86A AU603070B2 (en) | 1986-11-18 | 1986-11-18 | Process for the purification of dimethylether |
| IN1014/DEL/86A IN168048B (en) | 1986-11-18 | 1986-11-20 | |
| BR8606293A BR8606293A (en) | 1986-11-18 | 1986-12-19 | PROCESS FOR PURIFICATION OF DIMETHYL ETER |
| ES198787116477T ES2003076T3 (en) | 1986-11-18 | 1987-11-07 | PROCEDURE FOR OBTAINING PURE DIMETILETER. |
| EP87116477A EP0270852B1 (en) | 1986-11-18 | 1987-11-07 | Process for the preparation of pure dimethyl ether |
| DE8787116477T DE3775902D1 (en) | 1986-11-18 | 1987-11-07 | METHOD FOR PRODUCING PURE DIMETHYL ETHER. |
| AT87116477T ATE71354T1 (en) | 1986-11-18 | 1987-11-07 | PROCESS FOR PRODUCTION OF PURE DIMETHYL ETHER. |
| EP91105495A EP0455004A1 (en) | 1986-11-18 | 1987-11-07 | Process for the preparation of dimethyl ether |
| HU875073A HUT45956A (en) | 1986-11-18 | 1987-11-16 | Process for producing pure dimethyl-ether |
| DD87309082A DD270901A1 (en) | 1986-11-18 | 1987-11-16 | METHOD FOR THE CONTINUOUS PREPARATION OF DIMETHYL ETHER |
| FI875046A FI875046A7 (en) | 1986-11-18 | 1987-11-16 | Method for the preparation of pure dimethyl ether. |
| CA000551972A CA1322767C (en) | 1986-11-18 | 1987-11-17 | Process for the production of pure dimethylether |
| SU874203754A SU1602392A3 (en) | 1986-11-18 | 1987-11-17 | Method of continuous production of dimethyl ester |
| DK603187A DK603187A (en) | 1986-11-18 | 1987-11-17 | PROCEDURE FOR CONTINUOUS PREPARATION OF PURE DIMETHYLETHER |
| PL26885687A PL268856A1 (en) | 1986-11-18 | 1987-11-17 | Method for manufacturing pure dimethyl ether |
| NO874787A NO165914C (en) | 1986-11-18 | 1987-11-17 | PROCEDURE FOR THE PREPARATION OF PURE DIMETYLETS. |
| YU02080/87A YU208087A (en) | 1986-11-18 | 1987-11-17 | Process for preparing pure dimethylether |
| JP62289645A JPS63208546A (en) | 1986-11-18 | 1987-11-18 | Production method of pure dimethyl ether |
| NZ222597A NZ222597A (en) | 1986-11-18 | 1987-11-18 | Process for the production of pure dimethyl ether |
| CN88101729.9A CN1036199A (en) | 1986-11-18 | 1988-03-28 | Produce the method for pure Dimethyl ether |
| GR88300102T GR880300102T1 (en) | 1986-11-18 | 1989-06-22 | Process for the preparation of pure dimethyl ether |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU65506/86A AU603070B2 (en) | 1986-11-18 | 1986-11-18 | Process for the purification of dimethylether |
| DE19863642845 DE3642845A1 (en) | 1986-12-16 | 1986-12-16 | Process for the preparation of dimethyl ether and catalyst used for this purpose |
| BR8606293A BR8606293A (en) | 1986-11-18 | 1986-12-19 | PROCESS FOR PURIFICATION OF DIMETHYL ETER |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6550686A AU6550686A (en) | 1988-05-19 |
| AU603070B2 true AU603070B2 (en) | 1990-11-08 |
Family
ID=27155597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU65506/86A Ceased AU603070B2 (en) | 1986-11-18 | 1986-11-18 | Process for the purification of dimethylether |
Country Status (20)
| Country | Link |
|---|---|
| EP (2) | EP0455004A1 (en) |
| JP (1) | JPS63208546A (en) |
| CN (1) | CN1036199A (en) |
| AT (1) | ATE71354T1 (en) |
| AU (1) | AU603070B2 (en) |
| BR (1) | BR8606293A (en) |
| CA (1) | CA1322767C (en) |
| DD (1) | DD270901A1 (en) |
| DE (1) | DE3775902D1 (en) |
| DK (1) | DK603187A (en) |
| ES (1) | ES2003076T3 (en) |
| FI (1) | FI875046A7 (en) |
| GR (1) | GR880300102T1 (en) |
| HU (1) | HUT45956A (en) |
| IN (1) | IN168048B (en) |
| NO (1) | NO165914C (en) |
| NZ (1) | NZ222597A (en) |
| PL (1) | PL268856A1 (en) |
| SU (1) | SU1602392A3 (en) |
| YU (1) | YU208087A (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3876790D1 (en) * | 1988-05-04 | 1993-01-28 | Rwe Dea Ag | IMPROVED METHOD FOR PRODUCING PURE DIMETHYL ETHER. |
| JP2819600B2 (en) * | 1989-04-10 | 1998-10-30 | 三菱瓦斯化学株式会社 | Method for producing dimethyl ether |
| DE4132993A1 (en) * | 1991-10-04 | 1993-04-08 | Rwe Dea Ag | METHOD FOR PRODUCING DIMETHYL ETHER |
| DE19943219A1 (en) * | 1999-09-09 | 2001-03-15 | Axiva Gmbh | Process for the preparation of dimethyl ether |
| JP4938941B2 (en) * | 2001-08-30 | 2012-05-23 | 関西電力株式会社 | Synthesis method of dimethyl ether |
| US6924399B2 (en) | 2001-12-28 | 2005-08-02 | Mitsubishi Heavy Industries, Ltd. | Method of manufacturing dimethyl ether |
| KR100501922B1 (en) * | 2003-02-19 | 2005-07-18 | 에스케이 주식회사 | Process for preparing dimethyl ether from methanol |
| US7138557B2 (en) * | 2003-04-22 | 2006-11-21 | Uop Llc | Selective dimethylether recovery and recycle in a methanol-to-olefin process |
| UA68183C2 (en) * | 2003-11-07 | 2005-06-15 | Khimtekhnolohiia State Res And | Method for separation of dimethyl ether |
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| RU2282613C2 (en) * | 2004-08-10 | 2006-08-27 | Открытое акционерное общество Научно-исследовательский институт "Ярсинтез" (ОАО НИИ "Ярсинтез") | High-purity dimethyl ether production process |
| CN1304369C (en) * | 2004-10-12 | 2007-03-14 | 山东新华万博化工有限公司 | Technique for preparing dimehtyl sulfate |
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| CN101058534B (en) * | 2006-04-18 | 2011-01-12 | 杭州林达化工技术工程有限公司 | Device and method for preparing dimethyl ether from methanol |
| RU2315031C1 (en) * | 2006-06-19 | 2008-01-20 | Юрий Куртович Вайль | Methanol processing method |
| KR100812099B1 (en) | 2006-11-28 | 2008-03-12 | 한국가스공사 | Mixed catalyst for the production of dimethyl ether, preparation method thereof and preparation method for the dimethyl ether using the same |
| FR2909666B1 (en) | 2006-12-08 | 2009-03-06 | Centre Nat Rech Scient | DEHYDRATION OF METHANOL TO DIMETHYL ETHER EMPLOYING CATALYSTS BASED ON ZEOLITHE SUPPORTED ON SILICON CARBIDE |
| CN100513374C (en) * | 2007-03-07 | 2009-07-15 | 中国科学院大连化学物理研究所 | Method for preparing dimethyl ether by dehydration of methanol |
| CN101270034B (en) * | 2008-05-12 | 2010-06-02 | 钱进华 | Technique for preparing dimethyl ether |
| DE102008058931B4 (en) * | 2008-11-25 | 2010-12-30 | Lurgi Gmbh | Process and apparatus for producing dimethyl ether from methanol |
| CN101412665B (en) * | 2008-11-27 | 2011-01-12 | 何东 | Apparatus for coproduction of refined methanol and dimethyl ether or production of each of refined methanol and dimethyl ether from coarse methyl alcohol |
| CN101550066B (en) * | 2008-12-26 | 2013-06-05 | 新奥新能(北京)科技有限公司 | Production method of aerosol grade dimethyl ether |
| CN101941891B (en) * | 2009-07-06 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing dimethyl ether by dehydrating methanol |
| US8378150B2 (en) * | 2009-08-12 | 2013-02-19 | Catalytic Distillation Technologies | Process for the production of dimethyl ether |
| DE102012018341A1 (en) | 2012-09-15 | 2014-05-15 | Thyssenkrupp Uhde Gmbh | Process for the preparation of dimethyl ether and apparatus suitable therefor |
| CN103012076A (en) * | 2012-12-24 | 2013-04-03 | 新奥科技发展有限公司 | Method and device of rectifying dimethyl ether and recovering dimethyl ether from non-condensable gas |
| CN103435454B (en) * | 2013-09-16 | 2015-04-29 | 凯瑞化工股份有限公司 | Method for preparing dimethyl ether through methanol dehydration |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1231724A (en) * | 1982-07-01 | 1988-01-19 | E. I. Du Pont De Nemours And Company | Catalytic preparation of dimethyl ether |
| JPS59199648A (en) * | 1983-04-27 | 1984-11-12 | Mitsubishi Chem Ind Ltd | Production of dimethyl ether |
-
1986
- 1986-11-18 AU AU65506/86A patent/AU603070B2/en not_active Ceased
- 1986-11-20 IN IN1014/DEL/86A patent/IN168048B/en unknown
- 1986-12-19 BR BR8606293A patent/BR8606293A/en unknown
-
1987
- 1987-11-07 ES ES198787116477T patent/ES2003076T3/en not_active Expired - Lifetime
- 1987-11-07 AT AT87116477T patent/ATE71354T1/en not_active IP Right Cessation
- 1987-11-07 EP EP91105495A patent/EP0455004A1/en not_active Withdrawn
- 1987-11-07 EP EP87116477A patent/EP0270852B1/en not_active Expired - Lifetime
- 1987-11-07 DE DE8787116477T patent/DE3775902D1/en not_active Expired - Lifetime
- 1987-11-16 HU HU875073A patent/HUT45956A/en unknown
- 1987-11-16 FI FI875046A patent/FI875046A7/en not_active Application Discontinuation
- 1987-11-16 DD DD87309082A patent/DD270901A1/en not_active IP Right Cessation
- 1987-11-17 CA CA000551972A patent/CA1322767C/en not_active Expired - Fee Related
- 1987-11-17 NO NO874787A patent/NO165914C/en not_active IP Right Cessation
- 1987-11-17 SU SU874203754A patent/SU1602392A3/en active
- 1987-11-17 YU YU02080/87A patent/YU208087A/en unknown
- 1987-11-17 DK DK603187A patent/DK603187A/en not_active Application Discontinuation
- 1987-11-17 PL PL26885687A patent/PL268856A1/en unknown
- 1987-11-18 JP JP62289645A patent/JPS63208546A/en active Pending
- 1987-11-18 NZ NZ222597A patent/NZ222597A/en unknown
-
1988
- 1988-03-28 CN CN88101729.9A patent/CN1036199A/en active Pending
-
1989
- 1989-06-22 GR GR88300102T patent/GR880300102T1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA1322767C (en) | 1993-10-05 |
| JPS63208546A (en) | 1988-08-30 |
| FI875046L (en) | 1988-05-19 |
| ES2003076A4 (en) | 1988-10-16 |
| IN168048B (en) | 1991-01-26 |
| ATE71354T1 (en) | 1992-01-15 |
| NO165914B (en) | 1991-01-21 |
| BR8606293A (en) | 1988-07-05 |
| SU1602392A3 (en) | 1990-10-23 |
| NO874787L (en) | 1988-05-19 |
| NO874787D0 (en) | 1987-11-17 |
| EP0270852A3 (en) | 1988-12-28 |
| NO165914C (en) | 1991-05-02 |
| DK603187D0 (en) | 1987-11-17 |
| EP0270852A2 (en) | 1988-06-15 |
| DD270901A1 (en) | 1989-08-16 |
| HUT45956A (en) | 1988-09-28 |
| CN1036199A (en) | 1989-10-11 |
| YU208087A (en) | 1988-10-31 |
| FI875046A7 (en) | 1988-05-19 |
| GR880300102T1 (en) | 1989-06-22 |
| AU6550686A (en) | 1988-05-19 |
| FI875046A0 (en) | 1987-11-16 |
| EP0455004A1 (en) | 1991-11-06 |
| PL268856A1 (en) | 1988-10-13 |
| NZ222597A (en) | 1990-09-26 |
| DK603187A (en) | 1988-05-19 |
| DE3775902D1 (en) | 1992-02-20 |
| EP0270852B1 (en) | 1992-01-08 |
| ES2003076T3 (en) | 1992-07-01 |
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Legal Events
| Date | Code | Title | Description |
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| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |