CA1182797A - Dimethylether production process - Google Patents
Dimethylether production processInfo
- Publication number
- CA1182797A CA1182797A CA000404189A CA404189A CA1182797A CA 1182797 A CA1182797 A CA 1182797A CA 000404189 A CA000404189 A CA 000404189A CA 404189 A CA404189 A CA 404189A CA 1182797 A CA1182797 A CA 1182797A
- Authority
- CA
- Canada
- Prior art keywords
- case
- atoms
- total metallic
- metallic atoms
- dimethylether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT
A process for producing dimethylether from CO, H2 and possibly CO2, characterised in that the dimethylether is formed in the presence of a catalytic composition constituted overall by:
a) crystalline silica in which some silicon atoms in the crystal lattice have been replaced by aluminium, and which corresponds to the general formula:
lSi (0.0012-0.0050)Al Oy where y varies between 2.0018 and 2.0075 b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxides and/or salts.
The Al can also be present together with the Cr.
A process for producing dimethylether from CO, H2 and possibly CO2, characterised in that the dimethylether is formed in the presence of a catalytic composition constituted overall by:
a) crystalline silica in which some silicon atoms in the crystal lattice have been replaced by aluminium, and which corresponds to the general formula:
lSi (0.0012-0.0050)Al Oy where y varies between 2.0018 and 2.0075 b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxides and/or salts.
The Al can also be present together with the Cr.
Description
?t~
CAS~ 13'J2 Thi.s ;n~eIl~ion rel~tes to ~I di.methy].ether production proccss.
Dimethyle~ller~ known hereinafter as Dl~, i:, generally prepared in t~o stages~ by synthesising methanol from CO
5 and II2 and possibly CO2, and then dehydrating the met}lanol thus obtained to give DI~IE.
Sorde processes are however known in which the DII~ synthesis is carried out in a single stage9 by coupl:ing a methanol .synthesis catalyst to a dehydxati.on catalyst9 wh.ich is grenerally alumina.
In the known processes, the methanol synthesis cata].yst :is a composition constituted by Cu, Zn, Cr or Cu, Zn, A]., ~Ihe.reas the dehydration catalyst is generally alumina.
One embodiment descxibed in German ratent Application 2757778 (US Patent 4177167) comp.rises a D~IE synthesis c.atalyst constituted by metal oxi.des and/or ~etal salts l~h.ich have becn st<3bi.1ised by treatIllent with a silicon compound~
the stabilisation consisting o~ makin~ the material obtained after the treatment capable of resisting thermal and mechanical .forces and the action of steam at high temperatureO
The metal oxides and/or metal salts used according to the ~foresaid patent application are generally Al, Cr, La, I~, Cu or Zn oxides and/or salts or their mix-tures~ The problem presented by the catalysts of the known art9 and thus by the catalyst of the aforesai~ German Patent Application, is related to the fact that the dehydrating agent used exhihits its activity to any significant extent only at relati~-ely .~
7~
high temper~tures ~t which copper~baeed methanol Gynthesis catalyste a~le to operate at low temperature and 1DW pressure Dre unstable, giving rise to sintering phenomena and thus to lnss Df activity with time.
~he optimum temperature for the dehydration in accordance with the afore~aid patents is of the order of 280-300 C, whereas copper-based catalysts have a long life only if used at temperature of between 200 and 260 C~
It has now been surprisingly found possible to operate ~t a much lower average temperature while at the same time o~tain_ ing fcirly high DME conversion yields by using a catalyst formed by intimately mixing together powdered crystalli~e siliceous material substituted with aluminium, and powdereZ
oxides or salts of Cu, Zn and Cr (or Al).
The process according to the present invention consists of feeding C0 and H2, and possibly C02, to a reaction zone filled with a catalyst constituted by a mixture of the following substances:
a) crystalline silica in which some silicon atoms in the silica crystsl lattice have been replaced by aluminium, and which satisfiee the follo~ing general formula:
lSi (0.0012 0.0050)A1 Oy where y varies between 2J0018 and 200075 b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxideS and/or salts; where Al can also be pre.sent together with Cr.
The crystallinc silica u~ed in th~ invention and its preparation are de~cribed in ~lgian Patent NoO
877, ~68 to which reference should be made.
40 to 70% of all the metallic atoms present in the aforesaid catalytic composition (a-~b) as defined above, that is computing only metallic atoms, are silicon atoms.
The percentage of copper atoms in the total (a~b) varies from 15 to 30%, the zinc from 8 to 15~, the chromium from 0 to 10% (the value 0 being obtained when aluminium is present), and the aluminium from 0.1 to 10%.
The DME production process according to the invention is carried out at a temperature of between 150 and 250C and at a pressure between 4000 and 15000 KPa.
The invention will be more apparent from the non-limiting examples given hereinafter.
A catalyst was prepared based on Cu, Zn, Al and silice modifiPd with aluminium according to the following procedure.
676 g of Cu(No3~2.3H20, 327 g of Zn(NO3)2-6H2O and 57 g of sodium aluminate were dissolved in 10 1 of water. The solution was heated to 85C,and a 10~ solution of NaOH in water was added under stirring until the pH reached 7.5.
The precipitate was allowed to settle during cooling, the liquid was decanted and the precipitate washed repeatedly with water until the sodium and nitrates disappeared, using decantation and finally filtration.
The precipitate was dried in an oven at 120C in air~
The material was ground to granules not larger than 20 mesh ASTM, and was mixed with 325 g of silica modified with aluminium prepared as described in ~xample 5 of Belgian Patent ~ --., -- 3 a7 _ 4 _ No. 877,168.
The powder was compreOsed ;into pelletG havin¢ D diametcr of 4 mm and a len~th o 6 mm, The Cu, Zn, Al and Si were present in the cataly~t in the ~tomic ratios of 28~ 7:54.
100 cm3 of catalyst were placed in a tubular reactor of diameter 2.54 cm.
A shesth of ~uter diameter 8 millimetres to ~ouse a thermo-couple wa located axially at the centre of the reactor.
The temperature Wa& ~radually increased while feeding a mixture of H2 and N2 to the reactor in order to reduce the catalyst under controlled conditions.
When the temperature had reached 220 C and catalyst redustion was complete, the pressure was reduced to 7000 KPa, and the mixture of H2 and N2 was ~adually replaced by a 1:1 mixture of Co and H2 at a GHSV of 21~ h The catalyst tempersture was stabilised at 200 C (example 1) and 230C (ex~mple 2).
The water, methanol and part of the dimethylether produced in the reaction were condensed in a condenser located do-mstream of the reactor.
The condensed water, methanol and DME were withdrawn ~nder pressure and analy6ed by gas chromatography.
The gas leaving the reactor was fed to a sample valve of a gas chromato6raph and analysed, and then fed to ~n integrating flowmeter in order to measure the gas quantity.
Table 1 shows the results obtained under the aforesaid conditions. By_product~ present in a quantity of less than 1% have not been considered~
_, _ GHSV R T P ~olar Selectivity of the h H2/C0 C XPa conver~ion CO converted into %~Iv~ C~OH C~2 EY~'~LE 1 2100 1200 7000 22 61.8 4.1 34~1 E ~IPL~ 2 2100 1230 7000 69 63.4 3.0 3~6 E~.PLES 3 - 4 . _ A c~talyst was pr0pared as 6pecifisd based on Cu, Zn~ Cr, Si and Al, the components being present in the atomic ratios o~
CAS~ 13'J2 Thi.s ;n~eIl~ion rel~tes to ~I di.methy].ether production proccss.
Dimethyle~ller~ known hereinafter as Dl~, i:, generally prepared in t~o stages~ by synthesising methanol from CO
5 and II2 and possibly CO2, and then dehydrating the met}lanol thus obtained to give DI~IE.
Sorde processes are however known in which the DII~ synthesis is carried out in a single stage9 by coupl:ing a methanol .synthesis catalyst to a dehydxati.on catalyst9 wh.ich is grenerally alumina.
In the known processes, the methanol synthesis cata].yst :is a composition constituted by Cu, Zn, Cr or Cu, Zn, A]., ~Ihe.reas the dehydration catalyst is generally alumina.
One embodiment descxibed in German ratent Application 2757778 (US Patent 4177167) comp.rises a D~IE synthesis c.atalyst constituted by metal oxi.des and/or ~etal salts l~h.ich have becn st<3bi.1ised by treatIllent with a silicon compound~
the stabilisation consisting o~ makin~ the material obtained after the treatment capable of resisting thermal and mechanical .forces and the action of steam at high temperatureO
The metal oxides and/or metal salts used according to the ~foresaid patent application are generally Al, Cr, La, I~, Cu or Zn oxides and/or salts or their mix-tures~ The problem presented by the catalysts of the known art9 and thus by the catalyst of the aforesai~ German Patent Application, is related to the fact that the dehydrating agent used exhihits its activity to any significant extent only at relati~-ely .~
7~
high temper~tures ~t which copper~baeed methanol Gynthesis catalyste a~le to operate at low temperature and 1DW pressure Dre unstable, giving rise to sintering phenomena and thus to lnss Df activity with time.
~he optimum temperature for the dehydration in accordance with the afore~aid patents is of the order of 280-300 C, whereas copper-based catalysts have a long life only if used at temperature of between 200 and 260 C~
It has now been surprisingly found possible to operate ~t a much lower average temperature while at the same time o~tain_ ing fcirly high DME conversion yields by using a catalyst formed by intimately mixing together powdered crystalli~e siliceous material substituted with aluminium, and powdereZ
oxides or salts of Cu, Zn and Cr (or Al).
The process according to the present invention consists of feeding C0 and H2, and possibly C02, to a reaction zone filled with a catalyst constituted by a mixture of the following substances:
a) crystalline silica in which some silicon atoms in the silica crystsl lattice have been replaced by aluminium, and which satisfiee the follo~ing general formula:
lSi (0.0012 0.0050)A1 Oy where y varies between 2J0018 and 200075 b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxideS and/or salts; where Al can also be pre.sent together with Cr.
The crystallinc silica u~ed in th~ invention and its preparation are de~cribed in ~lgian Patent NoO
877, ~68 to which reference should be made.
40 to 70% of all the metallic atoms present in the aforesaid catalytic composition (a-~b) as defined above, that is computing only metallic atoms, are silicon atoms.
The percentage of copper atoms in the total (a~b) varies from 15 to 30%, the zinc from 8 to 15~, the chromium from 0 to 10% (the value 0 being obtained when aluminium is present), and the aluminium from 0.1 to 10%.
The DME production process according to the invention is carried out at a temperature of between 150 and 250C and at a pressure between 4000 and 15000 KPa.
The invention will be more apparent from the non-limiting examples given hereinafter.
A catalyst was prepared based on Cu, Zn, Al and silice modifiPd with aluminium according to the following procedure.
676 g of Cu(No3~2.3H20, 327 g of Zn(NO3)2-6H2O and 57 g of sodium aluminate were dissolved in 10 1 of water. The solution was heated to 85C,and a 10~ solution of NaOH in water was added under stirring until the pH reached 7.5.
The precipitate was allowed to settle during cooling, the liquid was decanted and the precipitate washed repeatedly with water until the sodium and nitrates disappeared, using decantation and finally filtration.
The precipitate was dried in an oven at 120C in air~
The material was ground to granules not larger than 20 mesh ASTM, and was mixed with 325 g of silica modified with aluminium prepared as described in ~xample 5 of Belgian Patent ~ --., -- 3 a7 _ 4 _ No. 877,168.
The powder was compreOsed ;into pelletG havin¢ D diametcr of 4 mm and a len~th o 6 mm, The Cu, Zn, Al and Si were present in the cataly~t in the ~tomic ratios of 28~ 7:54.
100 cm3 of catalyst were placed in a tubular reactor of diameter 2.54 cm.
A shesth of ~uter diameter 8 millimetres to ~ouse a thermo-couple wa located axially at the centre of the reactor.
The temperature Wa& ~radually increased while feeding a mixture of H2 and N2 to the reactor in order to reduce the catalyst under controlled conditions.
When the temperature had reached 220 C and catalyst redustion was complete, the pressure was reduced to 7000 KPa, and the mixture of H2 and N2 was ~adually replaced by a 1:1 mixture of Co and H2 at a GHSV of 21~ h The catalyst tempersture was stabilised at 200 C (example 1) and 230C (ex~mple 2).
The water, methanol and part of the dimethylether produced in the reaction were condensed in a condenser located do-mstream of the reactor.
The condensed water, methanol and DME were withdrawn ~nder pressure and analy6ed by gas chromatography.
The gas leaving the reactor was fed to a sample valve of a gas chromato6raph and analysed, and then fed to ~n integrating flowmeter in order to measure the gas quantity.
Table 1 shows the results obtained under the aforesaid conditions. By_product~ present in a quantity of less than 1% have not been considered~
_, _ GHSV R T P ~olar Selectivity of the h H2/C0 C XPa conver~ion CO converted into %~Iv~ C~OH C~2 EY~'~LE 1 2100 1200 7000 22 61.8 4.1 34~1 E ~IPL~ 2 2100 1230 7000 69 63.4 3.0 3~6 E~.PLES 3 - 4 . _ A c~talyst was pr0pared as 6pecifisd based on Cu, Zn~ Cr, Si and Al, the components being present in the atomic ratios o~
2~:12:8:60:0.2.
1600 g of Cu(N03)2~3H20, 1182 g of Zn(N03)2-6HzO and 1060 g of 15 Cr(N03)3.9~20 were dissolved in 20 1 of distilled water. The solution was heatea to 9~ C, and 20 litres of an aqueous solution of 1300 g of NaOH were then added under stirring.
The precipit~te was cooled, washed with water by decanting, filtered and washed repeatedly with water. The precipitate was dried in sn oven at 120 C. The material was ground to granules less than 20 mesh ASTM, then mixed with 1192 g of silica modified with aluminium (example 5 of Belgian Patent No. 877,168.
Pellets were formed having a diameter of 4 mm and length 6 mm.
25 100 cm3 of catalyst were examined under the same condition6 as in examples 1 - 2, the results being given in table 2~
GHSV ~ T P Molar Selectivity o~ the h-l ~2/C0 C KP~ conver~ion C0 convertod into o/O DME CI~30II C 2 5 _ _ _ _ ~
EXR~'LE 3 2100 1 200 7000 12 62.6 3.8 33.6 ~XAMPL~ 4 2100 1 230 7000 45 64~7 1.8 33.5 EXAMPLES 5 _ 6 (comparative) 10 The c~talyst of example 1 of USA Patent 4,177,1~7, in whi.ch the atomic Cu:Zn:Cr:Al ratios were 20:12:8:60, was ex~mined under the same conaitions as in e~amples 1 and 20 The results are given in table 3q . 'l'ABLE 3 - - ~
G~ISV R T P Molar Selectivity of the h ~I2/c C KPa conversion C0 converted into C~30~I co2 ~XAIvlPLE 5 2100 1 200 7000 11 11.9 54.0 34.1 20 EXA~LE 6 Z100 1 230 7000 42 18~5 1~7~0 35~
These comp3rison examples show that at lo~ operating temper-stures, the catalyst based on stabilised aluminium does not exhibit su~ficient dehydl~ating activity, so that the D~ is present only in small quantities.
1600 g of Cu(N03)2~3H20, 1182 g of Zn(N03)2-6HzO and 1060 g of 15 Cr(N03)3.9~20 were dissolved in 20 1 of distilled water. The solution was heatea to 9~ C, and 20 litres of an aqueous solution of 1300 g of NaOH were then added under stirring.
The precipit~te was cooled, washed with water by decanting, filtered and washed repeatedly with water. The precipitate was dried in sn oven at 120 C. The material was ground to granules less than 20 mesh ASTM, then mixed with 1192 g of silica modified with aluminium (example 5 of Belgian Patent No. 877,168.
Pellets were formed having a diameter of 4 mm and length 6 mm.
25 100 cm3 of catalyst were examined under the same condition6 as in examples 1 - 2, the results being given in table 2~
GHSV ~ T P Molar Selectivity o~ the h-l ~2/C0 C KP~ conver~ion C0 convertod into o/O DME CI~30II C 2 5 _ _ _ _ ~
EXR~'LE 3 2100 1 200 7000 12 62.6 3.8 33.6 ~XAMPL~ 4 2100 1 230 7000 45 64~7 1.8 33.5 EXAMPLES 5 _ 6 (comparative) 10 The c~talyst of example 1 of USA Patent 4,177,1~7, in whi.ch the atomic Cu:Zn:Cr:Al ratios were 20:12:8:60, was ex~mined under the same conaitions as in e~amples 1 and 20 The results are given in table 3q . 'l'ABLE 3 - - ~
G~ISV R T P Molar Selectivity of the h ~I2/c C KPa conversion C0 converted into C~30~I co2 ~XAIvlPLE 5 2100 1 200 7000 11 11.9 54.0 34.1 20 EXA~LE 6 Z100 1 230 7000 42 18~5 1~7~0 35~
These comp3rison examples show that at lo~ operating temper-stures, the catalyst based on stabilised aluminium does not exhibit su~ficient dehydl~ating activity, so that the D~ is present only in small quantities.
Claims (4)
1. A process for producing dimethylether from CO, H2 and possibly CO2, characterised in that the dimethylether is formed in the presence of a composition constituted by:
a) crystalline silica in which some silicon atoms of the crystal lattice have been replaced by aluminium, and which satisfies the general formula:
lSi (0.0012-0.0050)Al Oy where y varies between 2.0018 and 2.0075:
b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxides and/or salts, in which Al can also be present together with Cr.
a) crystalline silica in which some silicon atoms of the crystal lattice have been replaced by aluminium, and which satisfies the general formula:
lSi (0.0012-0.0050)Al Oy where y varies between 2.0018 and 2.0075:
b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxides and/or salts, in which Al can also be present together with Cr.
2. A process as claimed in claim 1, wherein the percentage of atoms of the various elements of the overall composition is as follows:
40 to 70% of the total metallic atoms in the case of Si 15 to 30% of the total metallic atoms in the case of Cu 8 to 15% of the total metallic atoms in the case of Zn 0 to 10% of the total metallic atoms in the case of Cr 0.1 to 10% of the total metallic atoms in the case of Al,
40 to 70% of the total metallic atoms in the case of Si 15 to 30% of the total metallic atoms in the case of Cu 8 to 15% of the total metallic atoms in the case of Zn 0 to 10% of the total metallic atoms in the case of Cr 0.1 to 10% of the total metallic atoms in the case of Al,
3. A catalytic composition constituted by:
a) crystalline silica in which some silicon atoms of the crystal lattice have been replaced by aluminium, and which satisfies the general formula:
lSi (0.0012-0.0050)Al Oy where y varies between 2.0018 and 2.0075:
b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxides and/or salts, in which Al can also be present together with Cr.
a) crystalline silica in which some silicon atoms of the crystal lattice have been replaced by aluminium, and which satisfies the general formula:
lSi (0.0012-0.0050)Al Oy where y varies between 2.0018 and 2.0075:
b) a mixture of Cu, Zn, Cr or Cu, Zn, Al oxides and/or salts, in which Al can also be present together with Cr.
4. A catalytic composition as claimed in claim 3, wherein the percentage of atoms of the various elements of the overall composition is as follows:
40 to 70% of the total metallic atoms in the case of Si 15 to 30% of the total metallic atoms in the case of Cu 8 to 15% of the total metallic atoms in the case of Zn 0 to 10% of the total metallic atoms in the case of Cr 0.1 to 10% of the total metallic atoms in the case of Al.
40 to 70% of the total metallic atoms in the case of Si 15 to 30% of the total metallic atoms in the case of Cu 8 to 15% of the total metallic atoms in the case of Zn 0 to 10% of the total metallic atoms in the case of Cr 0.1 to 10% of the total metallic atoms in the case of Al.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22081/81A IT1137176B (en) | 1981-06-02 | 1981-06-02 | PROCESS FOR THE PRODUCTION OF DIMETHYLETER |
| IT22081A/81 | 1981-06-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1182797A true CA1182797A (en) | 1985-02-19 |
Family
ID=11191199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000404189A Expired CA1182797A (en) | 1981-06-02 | 1982-06-01 | Dimethylether production process |
Country Status (30)
| Country | Link |
|---|---|
| JP (1) | JPS57204229A (en) |
| KR (1) | KR830010034A (en) |
| AR (1) | AR230829A1 (en) |
| AU (1) | AU553865B2 (en) |
| BE (1) | BE893373A (en) |
| BR (1) | BR8202979A (en) |
| CA (1) | CA1182797A (en) |
| CH (1) | CH649519A5 (en) |
| CU (1) | CU21425A3 (en) |
| DD (1) | DD208973A5 (en) |
| DE (1) | DE3220547C2 (en) |
| DK (1) | DK239982A (en) |
| ES (1) | ES8305297A1 (en) |
| FI (1) | FI821958L (en) |
| FR (1) | FR2506756A1 (en) |
| GB (1) | GB2099327B (en) |
| GR (1) | GR76005B (en) |
| IN (1) | IN155752B (en) |
| IT (1) | IT1137176B (en) |
| LU (1) | LU84166A1 (en) |
| MX (1) | MX158200A (en) |
| NL (1) | NL8202206A (en) |
| NO (1) | NO155488C (en) |
| NZ (1) | NZ200599A (en) |
| PH (1) | PH17161A (en) |
| PL (1) | PL236730A1 (en) |
| SE (1) | SE8203409L (en) |
| SU (1) | SU1329614A3 (en) |
| YU (1) | YU111382A (en) |
| ZA (1) | ZA823801B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4590176A (en) * | 1984-06-05 | 1986-05-20 | Shell Oil Company | Catalyst for dimethyl ether synthesis and a process for its preparation |
| IT1207499B (en) * | 1985-07-26 | 1989-05-25 | Montedipe Spa | PROCEDURE FOR THE OXIDATION OF FLUORINATED OLEFINS AND CATALYST SUITABLE FOR THE PURPOSE. |
| ES2053820T3 (en) * | 1988-01-14 | 1994-08-01 | Air Prod & Chem | A PROCEDURE FOR DIRECT SYNTHESIS OF DIMETHYL ETHER USING A LIQUID PHASE REACTOR SYSTEM. |
| EP0340324B1 (en) * | 1988-05-04 | 1992-12-16 | RWE-DEA Aktiengesellschaft für Mineraloel und Chemie | Process for the preparation of pure dimethyl ether |
| CA2020929A1 (en) * | 1989-07-18 | 1991-01-19 | Thomas H. L. Hsiung | One-step liquid phase process for dimethyl ether synthesis |
| WO1993010069A1 (en) * | 1991-11-11 | 1993-05-27 | Nkk Corporation | Process for producing dimethyl ether |
| US5344365A (en) * | 1993-09-14 | 1994-09-06 | Sematech, Inc. | Integrated building and conveying structure for manufacturing under ultraclean conditions |
| DK173614B1 (en) | 1999-02-02 | 2001-04-30 | Topsoe Haldor As | Process for preparing methanol / dimethyl ether mixture from synthesis gas |
| KR100812099B1 (en) | 2006-11-28 | 2008-03-12 | 한국가스공사 | Method of preparing catalyst for making dimethylether from syngas with carbon dioxide |
| 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 |
| EP2072491A1 (en) | 2007-12-17 | 2009-06-24 | BP p.l.c. | Process for the conversion of alcohol(s) into alcohol(s) with increased carbon-chain |
| EP2072486A1 (en) | 2007-12-17 | 2009-06-24 | BP p.l.c. | Process for the conversion of hydrocarbons to ethanol |
| EP2072492A1 (en) | 2007-12-17 | 2009-06-24 | BP p.l.c. | Process for the conversion of hydrocarbons to ethanol |
| EP2357037A1 (en) * | 2010-02-17 | 2011-08-17 | LANXESS Deutschland GmbH | Method for producing mechanically stable shaped catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1177167A (en) * | 1914-06-30 | 1916-03-28 | Levis Miller Booth | Apparatus for purifying liquids. |
| IT972655B (en) * | 1972-12-20 | 1974-05-31 | Snam Progetti | PROCEDURE FOR THE PRODUCTION OF DIMETHYL ETHER |
| DK155176C (en) * | 1978-06-22 | 1989-07-17 | Snam Progetti | PROCEDURE FOR THE PREPARATION OF ALUMINUM OXIDE MODIFIED SILICON Dioxide |
| US4341069A (en) * | 1980-04-02 | 1982-07-27 | Mobil Oil Corporation | Method for generating power upon demand |
-
1981
- 1981-06-02 IT IT22081/81A patent/IT1137176B/en active
-
1982
- 1982-05-13 GR GR68145A patent/GR76005B/el unknown
- 1982-05-13 NZ NZ200599A patent/NZ200599A/en unknown
- 1982-05-20 BR BR8202979A patent/BR8202979A/en unknown
- 1982-05-24 GB GB8215101A patent/GB2099327B/en not_active Expired
- 1982-05-24 KR KR1019820002280A patent/KR830010034A/en unknown
- 1982-05-25 LU LU84166A patent/LU84166A1/en unknown
- 1982-05-26 YU YU01113/82A patent/YU111382A/en unknown
- 1982-05-27 DK DK239982A patent/DK239982A/en not_active Application Discontinuation
- 1982-05-27 CH CH3277/82A patent/CH649519A5/en not_active IP Right Cessation
- 1982-05-27 PH PH27354A patent/PH17161A/en unknown
- 1982-05-28 ZA ZA823801A patent/ZA823801B/en unknown
- 1982-05-28 FR FR8209332A patent/FR2506756A1/en active Pending
- 1982-05-28 NL NL8202206A patent/NL8202206A/en not_active Application Discontinuation
- 1982-05-31 MX MX192936A patent/MX158200A/en unknown
- 1982-05-31 JP JP57091501A patent/JPS57204229A/en active Pending
- 1982-06-01 CU CU8235638A patent/CU21425A3/en unknown
- 1982-06-01 NO NO821816A patent/NO155488C/en unknown
- 1982-06-01 CA CA000404189A patent/CA1182797A/en not_active Expired
- 1982-06-01 DE DE3220547A patent/DE3220547C2/en not_active Expired
- 1982-06-01 SU SU823449249A patent/SU1329614A3/en active
- 1982-06-01 BE BE0/208237A patent/BE893373A/en not_active IP Right Cessation
- 1982-06-02 FI FI821958A patent/FI821958L/en not_active Application Discontinuation
- 1982-06-02 SE SE8203409A patent/SE8203409L/en not_active Application Discontinuation
- 1982-06-02 ES ES513916A patent/ES8305297A1/en not_active Expired
- 1982-06-02 AR AR289587A patent/AR230829A1/en active
- 1982-06-02 AU AU84414/82A patent/AU553865B2/en not_active Ceased
- 1982-06-02 DD DD82240389A patent/DD208973A5/en unknown
- 1982-06-02 PL PL23673082A patent/PL236730A1/en unknown
- 1982-06-02 IN IN632/CAL/82A patent/IN155752B/en unknown
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