CA1159476A - Process for the production of olefins from synthesis gas, in particular ethylene and propene - Google Patents
Process for the production of olefins from synthesis gas, in particular ethylene and propeneInfo
- Publication number
- CA1159476A CA1159476A CA000370839A CA370839A CA1159476A CA 1159476 A CA1159476 A CA 1159476A CA 000370839 A CA000370839 A CA 000370839A CA 370839 A CA370839 A CA 370839A CA 1159476 A CA1159476 A CA 1159476A
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- Prior art keywords
- catalyst
- dehydration
- olefins
- aliphatic alcohols
- mixture
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT OF THE DISCLOSURE
A process is disclosed for the production of olefins by dehydration of aliphatic alcohols comprising (a) passing a gas containing carbon non-oxide and hydrogen in the range of about 250° to 400°C. and at a pressure in the range from about 80 to 150 bar over a catalyst comprising a major portion by weight of the oxides of copper and zinc in intimate association with each other, a compound of potassium and a promotional amount of a compound selected from the group consisting of chromium, cerium, lanthanum, manganese and thorium, or mixtures thereof and recovering an alcohol mix-ture containing methanol and higher aliphatic alcohols, (b) separating methanol from the alcohol mixture, (c) dehydrating the higher aliphatic alcohols from the alcohol mixture to the respective olefins over a de-hydration catalyst, and recovering an olefin mixture therefrom.
A process is disclosed for the production of olefins by dehydration of aliphatic alcohols comprising (a) passing a gas containing carbon non-oxide and hydrogen in the range of about 250° to 400°C. and at a pressure in the range from about 80 to 150 bar over a catalyst comprising a major portion by weight of the oxides of copper and zinc in intimate association with each other, a compound of potassium and a promotional amount of a compound selected from the group consisting of chromium, cerium, lanthanum, manganese and thorium, or mixtures thereof and recovering an alcohol mix-ture containing methanol and higher aliphatic alcohols, (b) separating methanol from the alcohol mixture, (c) dehydrating the higher aliphatic alcohols from the alcohol mixture to the respective olefins over a de-hydration catalyst, and recovering an olefin mixture therefrom.
Description
11~947'6 This invention relates to a proce!is ~or the production of olefins ~rom synthesls gas, ln particular the production of ethylene and propylene.
Lower aliphatic olefins, particularly ethylene and propene, are today among the most important basic materials of organic chemistry. Both olefins are today produced on an industrial scale exclusively by thermal splitting of saturated hydrocarbons, different raw materials being available in various countries. Thus for example in Western Europe more than 80% of the ethylene is obtained from naphtha, about 10 to 15% by gas oil splitting, and the balance from high-ethane petroleum. The olefin production is entirely dependent on imported petroleum. To alleviate the dependence of the petro-chemical industry on petroleum imports, new methods are being investigated for the production of olefins from synthesis gas and hydrogen.
As is known, ethylene can be produced by hydrogenation of carbon monoxide using cobalt, nickel, or platinum catalysts according to German Patent 1,271,098. However, the profitability of this method is limited by a low yield of ethylene.
Another method of synthesizing olefins is the well-known Fischer-Tropsch synthesis. Because with conventional iron catalysts olefins form only a small portion of the product, iron catalysts have been promoted with V205 and ZnO or MnO and ZnO (DE-OS 25 18 964 published ll November 1976) or only with MnO (DE-OS 25 07 647 published 9 September 1976), to increase the olefin formation. Thus, for example, a manganese-containing iron catalyst produces 8 g ethylene and 28.2 g propene per Nm from a synthesis gas of 54.4 vol.% CO, at 265 C. and a pressure of 10.6 bar and at a space velocity of 310 liters of synthesis gas per hour and liter of catalyst. In addition, 18.8 g butenes, 26.5 g paraffins, 59.8 g liquid products and 198.3 g C02 per ~ ' 1~S'3~7~
Nm3 synthesis gas are formed, with a total CO conversion of 81%. The selectivity of ethylene and propene formation is 11%. Due to the rather low selectivity, this process would be prof:Ltable only if the other - la -li5~3~76 products could be utilized.
The present invention makes available a process for the production of olefins, in particular ethylene and propene, by dehydration of aliphatic alcohols, using coal-based starting materials.
The process according to the invention is characterized in that (a) an alcohol ~ixture containing methanol and higher aliphatic alcohols is producedfrom gases containing carbon monoxide and hydrogen as for example, synthesis gas, using a catalyst which contains copper oxide, zinc oxide and aluminum oxide and potassium oxide and which is promoted with chromium, cerium, lanthanum, manganese, thorium, an alkali metal or a mixture thereof; (b) the methanol is separated from this alcohol mixture; (c) the higher aliphatic alcohols, in particular ethanol and the propanols, are dehydrated to the respective olefins using a dehydration catalyst; and (d) the olefin ~ixture obtained is fractionated if required.
The promoted catalyst used according to the invention in step (a) is the subject of co-pending Canadian application 370,852 filed of even date here-with. This catalyst is obtained by either (a) producing from soluble salts of copper, zinc potassium and optionally alu~inum (main components), by co-precipi-tation with promoter compounds in aIkaline medium, a precipitate which is calcined after removal of the extraneous ions; or (b) impregnating a mixture of the oxides of copper, zinc and optionally aluminum with a solution of potassium and one or more of the promoter compounds and calcining the product obtained. The promoter compounds include compounds of chromium, cerium, lanthanum, manganese, thorium or ~ixtures thereof added at any desired production step.
The starting catalysts used for the producticn of the promoted catalysts preferably contain about 18 - 45 wt.%, preferably about 25 - 40 wt.% copper oxide; about 24 - 50 wt. %, preferably about 30 - 45 wt.% zinc oxide; about 1 1 5~3~l7 ti 5 - 25 wt. % preferably about 10-1 8 wt% aluminum oxide and about 3.~4 wt%
potassiu~ preferably about 1.7 - 2.5 wt% potassium (calculated as K2O), copper and zinc being present in an atomic ratio of about 0.4:1 to 1.9:1.
The promoter compounds are usually present in quantities of about 3 - 18 wt.%
(calculated as oxides). The oxides may be present in various values.
Preferably the promoted catlaysts are produced by either (a) forming a precipitate from a solution of the water-soluble salts, in particular the nitrates, of the main components and the promoter elements in the presence of insoluble potassium compound by addition oE alkali carbonate preferably at abcut 60 to 70C., separating the precipitate and washing and drying it;
or (b) the oxide mixture obtained by thermal decomposition of a copper-zinc-ammLnocarbonate solution in the presence of suspended aluminum oxide is impregnated with salts, preferably the nitrates, of the pr oter elements;
and a soluble salt of potassium and the product obtained according to (a) or (b) is calcined at about 350 to 450C., preferably at about 380 to 400C.
Also, the starting catalysts impregnated with the promoter compounds may be subjected to a re-impregnation with a potassiun compound and to a recalcination, the potassium content (calculated as K2O) being about 0.03 to 3.4 wt.%, preferably about 1.7 to 2.5 wt.%.
Suitable potassium compounds are potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium acetate, potassium chromate or dichro-mate, or mixtures thereof; the recalcination can be carried out at about 350 to 450C., preferably at about 380 to 400C.
To activate the promoted catalysts they are subjected to a reducing after-treatment, which is carried out first with an inert gas as for example, nitrogen containing a small amount of hydrogen. The hydrogen component is then gradually increased, the temperature being simultaneously increased gradually from about 170 to about 350C.,until in the end pure hydrogen is used for the reduction.
The pronoted catalysts of aforementioned Canadian Patent Application 370,852 are used for the synthesis of alcohol mixtures containing methanol 115~476 and higller alcohols, which can be used as fuel or fuel additives for Otto engines .
According to the present invention, such alcohol mixtures serve as a raw materia] base for the production of oleEins. By controlled promotion with chromium, mangallese and thorium, and by the selection of suitahle reaction conditions, the Eormation of the C2 and C3 alcohols can be adjusted.
In step (a) of the process of the invention, a synthesis gas is preferably used containing about 25 to 30 vol.%, preferably about 27 vol.%
CO, O to 15 vol.% N2, 0 to 4 vol.% C02, 0 to 7 vol.% CH4, balance H2, and preferably reacted at about 250 to 400 C., most preferably 350 C., at a pressure of about 80 to 150 bar, most preferably about 100 bar, and at a space velocity of about 500 to 5000, most preferably about 1500 liters of gas per hour and liter of catalyst, in the presence of the promoted catalyst to produce the alcohol mixture.
Preferably the reaction of the synthesis gas in step (a) is carried out in tube reactors swept by cooling medium or in full-space reactors with cold gas coollng, both reactor systems being operated with recycling if desired.
The alcohol mixture obtained in step (a) is fractionated in step (b) using one or more distillation columns, into low-boiling by-products and methanol, on the one hand, and higher alcohols and water, on the other. Besidesthe desired C2 and C3 alcohol fraction, pure methanol is also obtained as well as a mixture of aliphatic C4 to C6 alcohols with only a small proportion of by-products.
According to the invention, the dehydration of the higher aliphatic alcohols in step (c) is carried out over conventional dehydration catalysts, for example A12O3, SiO2, TiO2, AlPO4 or Ca3(PO4)2. Preferably the dehydration is carried out over alkalized aluminum oxide or calcium phosphate in order to suppress secondary reactions, as for example condensations and polymeri~ation 1 of the ole~ins. l`he dehyclration is carried out preferably at atmospheric or reduced pressure of about O.S to 1 bar, preferab~y about 0.75 bar, at a tempera-ture of about 350 to 500 (`., preferahly about 400 to 450 C., and at a space velocity of about 1 to 7, preferably about 2 - 4 liters of alcohol mixture per hour and liter of cat.llyst.
Preferably the alkalization of the dehyclration catalysts is carried out by for example allcalizing aluminum oxide or calcium phospllate by impregna-tion with an aqueous solution of alkali metal hydroxide or alkali metal carbon-ate, preferably a hydroxide as for example, LiOH, KOH or NaOH, preferably LiOH, the alkali metal concentration being about 0.1 to 1.5 wt.~, preferably about 0.3 to 0.8 wt.%.
The selection of suitable reaction conditions (temperature about 400 to 450C. and space velocities of about 2.0 to 2.5 kg alcohol mixture per hour and liter of catalyst) permits reactions up to 91 mol.% and a selectivity of about 98%.
The reaction mixture obtained from step (c) is first cooled in step (d), preferably to a temperature of about 10C.; then prefractionated into liquid and gaseous products, whereupon the gaseous components freed from water are further fractionated by low-temperature distillation and the liquid components by distillation or extractive distillation. By the low-temperature distillation ethylene and propene can be obtained in pure form.
Since product pure methanol and aliphatic C4 to C6 alcohols are also usable (for example as solvents or plasticizers), the profitability of the entire process is thus increased.
Two examples for the preparation of dehydration catalysts that can be used in step (c) of the present process are given as follows:
Preparation of dehydration catalyst I
Aluminum oxide hydrate powder was mixed with 3.6% of its weight of 9~7~
aluminum stearate ~nd compacted to cylindrical pellets of ]ength 4.5 mm and diameter of 4.5 mm by means of a pelletizing machine. Then the tablets were calcined in air for 4 hours at 510C.
lOO g of the calc;ned pellets were immersed at room temperature in an aqueous s~t~tiOI~ of lO g LiOH in 435 ml water for 20 minutes and then dried at 120 C. for 2 hours and calcined at 400C. For 2 hours. The product contained 0.29% Li and had a BET surface of 210 m /g.
Preparation of dehydration catalyst II
Tricalcium phosphate was mixed with 3.6% of its weight of aluminum stearate and compacted to cylindrical pellets of 4.5 mm length and diameter of 4.5 mm by means of a pelletizing machine. Subsequently the pellets were calcined in air for 4 hours at 510C. 100 g of the calcined pellets were immersed at room temperature in an aqueous solution of 10 g LiOH in 166 ml water for 20 minutes and then dried at 120 C. for 2 hours and calcined at 400 C.for 2 hours. The product contained 0.28% Li and had a BET surface of 38.7 m2/g.
The present invention is illustrated by the following examples which are not intended to be limiting to the scope thereof.
Example 1 Promoted catalyst A was prepared as follows:
560 g K2C03 were dissolved in 2 liters of deionized water and heated to 60 - 80C 285.2 g CUtNo3)2.3H2o~ 217.6 g Zn(N03)2, 3 2 2 65.8 g Cr(N03)3.9H20, and 276 g Al(N03)3.9H20 were dissolved in 2 liters deionized water and slowly added into the K2C03 solution with stirring; the temperature was maintained at 60-80C. After mixing with the nitrate solution, the pH was adjusted to 6.8 - 7.0 by addition of a small quantity of aqueous K2C03 solution, whereupon stirring was continued for another 30 minutes.
Then the precipitate was filtered, and the filter cake was washed until nitrate-free by repeated slurrying with 2 liters of deionized water each time 115~3~7~i (ring analysis). I'he waslled filLer cake was ~rie~l for lS hours at 120 C.
and calcined for :l hours at 400C. The calcined ~roduct was mlxed with 2%
of its weight of natural graphite and compacted to cylindrical tablets 3 mm in dinmeter and 3 mm long. Onto 150 g o~ the tabLets thus obtained, a solution of 8.4 g K2C03 dissoLved in 30 ml H20, was sprayed; this was followed by drying at 120C. for 2 hours and calcinin~ at 400C. for 3 hours.
The chemLcal composition and the ~ET surface of catalyst A are given in Table I, Ineo a tubular reactor (diameter 18 mm, length 1000 mm) heated with a liquid medium were charged 30 ml of promoted catalyst A. The catalyst was activated with a gas consisting of 1.2 vol.% H2, balance N2, for 40 hours at 145 to 350 C. The temperature rise was about S C. per hour. After reaching 350C., the catalyst to be tested was treated with pure hydrogen for another 5 hours. Then synthesis gas having a composition of:
CO 29.0 vol.%
C2 1.5 "
CH4 1.4 "
N2 5.0 "
H2 ba]ance was supplied to the reactor and pressure and space velocity adjusted to 100 bar and 2000 liters synthesis gas per hour and liter of catalyst respectively.
The results and the composition of the reaction products are summarized in Tables II and III.
The liquid products obtained by condensation at 10C. were distilled so that a fraction consisting of ethanol and propanols was obtained and subsequently subjected to dehydration. The composition of this fraction is given in Table IV.
The dehydration of the alcohol mixture was carried out at 400 C., a 115'3~L76 pressure of 1 bar slld a s~ace velocity o~ 2.5 kg al,cohol mixture per hour and liter of catalyst, in an electrically heated tubular reactor of diameter 25 ~n and lengtll 500 mm, charged with 50 ml dehydration catalyst I.
After condensation at lO C., the gaseous products were dried and subjected to low-temperature distillation, while the liquid products were subjected to extractive disti]lation. Tlle results of the dehydration and the composition of the individual fractions are given in Table V.
Example 2 Promoted catalyst B was prepared as follows:
600 g K2CO3 were dissolved in 2 liters of deionized water and heated to 60 - 80 C- 285-2 g Cu(NO3)2~3H2O~ 188-2 g Zn(N3)2~ 131-6 g Cr(NO3)3 9H2O~
52.3 g Th(NO3)4.4H2O and 276 g Al(NO3)3.9H2O were dissolved in 2 liters de-ionized water and slowly added into the K2CO3 solution with stirring; the temperature was maintained at 60 - 80 C. After mixing with the nitrate solution, the pH was adjusted to 6.8 - 7.0 by addition of a small quantity of aqueous K2CO3 solution, whereupon stirring was continued for another 30 minutes.
Then the precipitate was filtered, and the filter cake was washed until nitrate-free by repeated slurrying with 2 liters of deionized water each time (ring analysis). The washed filter cake was dried for 15 hours at 120C. and calcined for 3 hours at 400C. The calcined product was mixed with 2% of its weight of natural graphite and compacted to cylindrical tablets 3 mm in diameter and 3 mm long. Onto 150 g of the tablets thus obtained, a solution of 8.4 g K2CO3 dissolved in 30 ml H2O, was sprayed; this was followed by drying at 120 C. for 2 hours and calcining at 400C. for 3 hours.
The chemical composition and the BET surface of catalyst B are given in Table I.
The procedure of Example 1 was repeated except that for the production of a mixture of methanol and hi,gher aliphatic alcohols catalyst B was used.
llt~47~
The results and the coml)osition of the reaction products at the end of step (b) are given in Tables II and III. The composit:ion of the ethanol-propanol fraction obtained by distil]ation is given in Table IV. lhis fraction was dehydrated according to the procedure of Example 1, and the olefin mixture obtained was fractionated.
Example 3 -~romoted catalyst C was prepared as follows:
Into 9000 ml of a copper amminocarbonate solution containing 4.11 g Cu/l~0 ml, 8.8 g NH3/lO0 ml and 7.4 g C02/lO0 ml, were dissolved 355 g ~inc oxide with agitation, adding 177 g A1203. With continued agitation and replacement of evaporated water, the suspension was thermally decomposed by boiling until a sample gave a colorless filtrate. The precipitate was filtered and the resulting filter cake was calcined in a thin layer at 400 C. for 4 hours. The product obtained was mixed with 2~ of its weight of natural graphite and compacted to cylindrical tablets of 3 mm diameter and 3 mm in length.
150 g of the tablets thus obtained were immersed for 20 minutes at room temperature in an aqueous solution of 209.5 g K2Cr207 in 200 ml water and then dried for 2 hours at 120C. and calcined for 3 hours at 400C. The chemical composition and the BET surface area of catalyst C are shown in Table I.
The procedure of Example 1 was repeated with the difference that for the production of a mixture of methanol and higher aliphatic alcohols catalyst C was used. The results and the composition of the reaction products are given in Tables II and III. The composition of the ethanol-propanol fraction obtained by distillation, step (b) is given in Table IV. This fraction was dehydrated according to the procedu~e of Example l, and the olefin mixture obtained was fractionated.
~ 9 _ 1xample 4 -Promoted catalyst D was prepare~ as follows:
In 9000 ml of a copper amminocarhonate solution containing 4.11 g Cu/100 ml, 8.8 g N~i3/100 m]. and 7.4 g C02llO0 ml, were dissolved 355 g zinc oxide with agitation, adding 177 g A12O3. With continued agitation and replacement of evaporated water, the suspension was thermally decomposed by boiling until a sampl.e gave a colorless filtrate. The precipitate was filtered and the resulting filter cake was calcined in a thin layer at 400 C. for 4 hours. The product obtained was admixed with a solution of 190 g Cr(NO3)3.9H20 in 200 ml deioni~ed water and then calcined for 3 hours at 400C. The oxides were then mixed with 2% of their weight of natural graphite and compacted to cylindrical tablets of 3 mm diameter of 3 mm length.
150 g of the product tablets were immersed at room temperature for 20 minutes in an aqueous solution of 96.5 g K2C03 in 200 ml water and then dried for 2 hours at 120C. and calcined for 3 hours at 400C. Table I shows the chemical composition and the BET surface area of catalyst D.
The procedure of Example 1 was repeated with the difference that for the preparation of a mixture of methanol and higher al.iphatic alcohols catalyst D was used. The results and the composition of the reaction products are given in Tables II and III. The composition of the ethanol-propanol fraction obtained by distillation is given in Table IV. The dehydration and fractiona-tion was carried out as in Example 1. The results of the dehydration and the composition of the individual fractions are given in Table V.
Example 5 Tlle dehydration of an ethanol-propanol fraction obtained according to the procedure of Example 1 was carried out at 450 C., at a pressure of 1 bar and a space velocity of 2.0 kg alcohol mixture per hour and liter of catalyst in a reactor according to Example 1 with the use of dehydration ~15~7~
catalyst II. The resu1.ts of the dehydration and the composi.tion of the individual fractions are given in Table V.
Example 6 The clehyclr.3tion of an ethano:L-propanol fraction obtained according to the procedure of Ixample 4 was carri.ed out according to the procedure of Example S. The results of the clehydration and the composition of the individual fractions are given in Table V.
Table I
Composition of promoted copper-, zinc- aluminum- and potassium-containing catalysts (wt.%) Designation Cu/(CuO) ZnO A12O3 K Cr2O3 MnO ThO2 GV* BET surface (m2/g) .
A 27.3 33.8 13.7 3.1 4.5 9.2 - 6.1 (32.0) 31.6 12.8 2.9 4.2 8.6 - 5.7 60.9 B ~ 27.3 29.2 13.7 3.0 9.2 - 9.2 6.1 (32.0) 27.3 12.8 2.8 8.6 - 8.6 5.7 18.3 C 32.9 31.7 15.7 2.9 8.9 - - 7.3 (38.1) 29.3 14.5 2.7 8.2 - - 6.7 43.2 D 34.2 32.9 16.4 3.0 3.3 - - 7.9 (39.4) 30.3 15.1 2.8 3.0 - - 7.3 45.4 * GV = loss on ignition, due mainly to carbon 11~94'76 Table II
C0 conversion (mol.~) and selectivities (%) of the formation of individual reaction products at 350C., 100 bar pressure and at the space velocity of 2000 liters synthesis gas per hour and li~er of catalyst.
Selectivity (%~ of the formation of Catalyst C0 conversion Methanol Higher aliph. C02 By-products (mol.%) alcohols (CH4 + liquid hydrocarbons) A 41.3 42.2 11.8 44.5 1.5 B 39.4 37.8 16.5 40.1 5.6 C 42.1 39.5 18.5 37.8 4.2 D 33.8 45.8 16.2 36.1 1.9 Table III
Yield (g per hr and liter cat. and m3 synthesis gas) of liquid reaction products, methanol and higher aliphatic alcohols Catalyst Liquid re- Methanol Higher aliphatic alcohols Percentage action products of which of ethanol Total C2+C3 C4 C6 2 3 alcohol fraction A 67.3 48.1 13.1 10.32.8 48.5 B 70.7 46.2 16.6 10.56.1 32.2 C 73.7 47.9 21.9 11.610.3 36.1 D 64.4 39.7 19.4 11.28.2 _ 25.6 'l'able IV
Composition of the ethanol-propanol fraction obtalned Synthesis catalyst Alcohol A B C D
Composition of the ethanol-propanol fraction Ethanol 46.6 29.3 34.424.1 n-Propanol 4.7 3.1 3.5 3.5 i-Propanol 44.7 58.037.1 66.3 _4 6 _ 4.6 5.0 6.1 Table V
~esults of the dehydration of ethanol-propanol fraction Dehydration Ethanol- Conversion By-products Composition of the gaseous catalyst propanol (mol.%) (wt.%) products (vol.%) fraction C2H4 C3H6 Higher olefins I 190.5 3.0 53.9 43.7 2.4 I 491.0 4.8 30.5 68.1 1.4 II 189.0 2.0 54.5 44.2 2.3 II 489.8 2.5 30.7 68.0 1.3
Lower aliphatic olefins, particularly ethylene and propene, are today among the most important basic materials of organic chemistry. Both olefins are today produced on an industrial scale exclusively by thermal splitting of saturated hydrocarbons, different raw materials being available in various countries. Thus for example in Western Europe more than 80% of the ethylene is obtained from naphtha, about 10 to 15% by gas oil splitting, and the balance from high-ethane petroleum. The olefin production is entirely dependent on imported petroleum. To alleviate the dependence of the petro-chemical industry on petroleum imports, new methods are being investigated for the production of olefins from synthesis gas and hydrogen.
As is known, ethylene can be produced by hydrogenation of carbon monoxide using cobalt, nickel, or platinum catalysts according to German Patent 1,271,098. However, the profitability of this method is limited by a low yield of ethylene.
Another method of synthesizing olefins is the well-known Fischer-Tropsch synthesis. Because with conventional iron catalysts olefins form only a small portion of the product, iron catalysts have been promoted with V205 and ZnO or MnO and ZnO (DE-OS 25 18 964 published ll November 1976) or only with MnO (DE-OS 25 07 647 published 9 September 1976), to increase the olefin formation. Thus, for example, a manganese-containing iron catalyst produces 8 g ethylene and 28.2 g propene per Nm from a synthesis gas of 54.4 vol.% CO, at 265 C. and a pressure of 10.6 bar and at a space velocity of 310 liters of synthesis gas per hour and liter of catalyst. In addition, 18.8 g butenes, 26.5 g paraffins, 59.8 g liquid products and 198.3 g C02 per ~ ' 1~S'3~7~
Nm3 synthesis gas are formed, with a total CO conversion of 81%. The selectivity of ethylene and propene formation is 11%. Due to the rather low selectivity, this process would be prof:Ltable only if the other - la -li5~3~76 products could be utilized.
The present invention makes available a process for the production of olefins, in particular ethylene and propene, by dehydration of aliphatic alcohols, using coal-based starting materials.
The process according to the invention is characterized in that (a) an alcohol ~ixture containing methanol and higher aliphatic alcohols is producedfrom gases containing carbon monoxide and hydrogen as for example, synthesis gas, using a catalyst which contains copper oxide, zinc oxide and aluminum oxide and potassium oxide and which is promoted with chromium, cerium, lanthanum, manganese, thorium, an alkali metal or a mixture thereof; (b) the methanol is separated from this alcohol mixture; (c) the higher aliphatic alcohols, in particular ethanol and the propanols, are dehydrated to the respective olefins using a dehydration catalyst; and (d) the olefin ~ixture obtained is fractionated if required.
The promoted catalyst used according to the invention in step (a) is the subject of co-pending Canadian application 370,852 filed of even date here-with. This catalyst is obtained by either (a) producing from soluble salts of copper, zinc potassium and optionally alu~inum (main components), by co-precipi-tation with promoter compounds in aIkaline medium, a precipitate which is calcined after removal of the extraneous ions; or (b) impregnating a mixture of the oxides of copper, zinc and optionally aluminum with a solution of potassium and one or more of the promoter compounds and calcining the product obtained. The promoter compounds include compounds of chromium, cerium, lanthanum, manganese, thorium or ~ixtures thereof added at any desired production step.
The starting catalysts used for the producticn of the promoted catalysts preferably contain about 18 - 45 wt.%, preferably about 25 - 40 wt.% copper oxide; about 24 - 50 wt. %, preferably about 30 - 45 wt.% zinc oxide; about 1 1 5~3~l7 ti 5 - 25 wt. % preferably about 10-1 8 wt% aluminum oxide and about 3.~4 wt%
potassiu~ preferably about 1.7 - 2.5 wt% potassium (calculated as K2O), copper and zinc being present in an atomic ratio of about 0.4:1 to 1.9:1.
The promoter compounds are usually present in quantities of about 3 - 18 wt.%
(calculated as oxides). The oxides may be present in various values.
Preferably the promoted catlaysts are produced by either (a) forming a precipitate from a solution of the water-soluble salts, in particular the nitrates, of the main components and the promoter elements in the presence of insoluble potassium compound by addition oE alkali carbonate preferably at abcut 60 to 70C., separating the precipitate and washing and drying it;
or (b) the oxide mixture obtained by thermal decomposition of a copper-zinc-ammLnocarbonate solution in the presence of suspended aluminum oxide is impregnated with salts, preferably the nitrates, of the pr oter elements;
and a soluble salt of potassium and the product obtained according to (a) or (b) is calcined at about 350 to 450C., preferably at about 380 to 400C.
Also, the starting catalysts impregnated with the promoter compounds may be subjected to a re-impregnation with a potassiun compound and to a recalcination, the potassium content (calculated as K2O) being about 0.03 to 3.4 wt.%, preferably about 1.7 to 2.5 wt.%.
Suitable potassium compounds are potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium acetate, potassium chromate or dichro-mate, or mixtures thereof; the recalcination can be carried out at about 350 to 450C., preferably at about 380 to 400C.
To activate the promoted catalysts they are subjected to a reducing after-treatment, which is carried out first with an inert gas as for example, nitrogen containing a small amount of hydrogen. The hydrogen component is then gradually increased, the temperature being simultaneously increased gradually from about 170 to about 350C.,until in the end pure hydrogen is used for the reduction.
The pronoted catalysts of aforementioned Canadian Patent Application 370,852 are used for the synthesis of alcohol mixtures containing methanol 115~476 and higller alcohols, which can be used as fuel or fuel additives for Otto engines .
According to the present invention, such alcohol mixtures serve as a raw materia] base for the production of oleEins. By controlled promotion with chromium, mangallese and thorium, and by the selection of suitahle reaction conditions, the Eormation of the C2 and C3 alcohols can be adjusted.
In step (a) of the process of the invention, a synthesis gas is preferably used containing about 25 to 30 vol.%, preferably about 27 vol.%
CO, O to 15 vol.% N2, 0 to 4 vol.% C02, 0 to 7 vol.% CH4, balance H2, and preferably reacted at about 250 to 400 C., most preferably 350 C., at a pressure of about 80 to 150 bar, most preferably about 100 bar, and at a space velocity of about 500 to 5000, most preferably about 1500 liters of gas per hour and liter of catalyst, in the presence of the promoted catalyst to produce the alcohol mixture.
Preferably the reaction of the synthesis gas in step (a) is carried out in tube reactors swept by cooling medium or in full-space reactors with cold gas coollng, both reactor systems being operated with recycling if desired.
The alcohol mixture obtained in step (a) is fractionated in step (b) using one or more distillation columns, into low-boiling by-products and methanol, on the one hand, and higher alcohols and water, on the other. Besidesthe desired C2 and C3 alcohol fraction, pure methanol is also obtained as well as a mixture of aliphatic C4 to C6 alcohols with only a small proportion of by-products.
According to the invention, the dehydration of the higher aliphatic alcohols in step (c) is carried out over conventional dehydration catalysts, for example A12O3, SiO2, TiO2, AlPO4 or Ca3(PO4)2. Preferably the dehydration is carried out over alkalized aluminum oxide or calcium phosphate in order to suppress secondary reactions, as for example condensations and polymeri~ation 1 of the ole~ins. l`he dehyclration is carried out preferably at atmospheric or reduced pressure of about O.S to 1 bar, preferab~y about 0.75 bar, at a tempera-ture of about 350 to 500 (`., preferahly about 400 to 450 C., and at a space velocity of about 1 to 7, preferably about 2 - 4 liters of alcohol mixture per hour and liter of cat.llyst.
Preferably the alkalization of the dehyclration catalysts is carried out by for example allcalizing aluminum oxide or calcium phospllate by impregna-tion with an aqueous solution of alkali metal hydroxide or alkali metal carbon-ate, preferably a hydroxide as for example, LiOH, KOH or NaOH, preferably LiOH, the alkali metal concentration being about 0.1 to 1.5 wt.~, preferably about 0.3 to 0.8 wt.%.
The selection of suitable reaction conditions (temperature about 400 to 450C. and space velocities of about 2.0 to 2.5 kg alcohol mixture per hour and liter of catalyst) permits reactions up to 91 mol.% and a selectivity of about 98%.
The reaction mixture obtained from step (c) is first cooled in step (d), preferably to a temperature of about 10C.; then prefractionated into liquid and gaseous products, whereupon the gaseous components freed from water are further fractionated by low-temperature distillation and the liquid components by distillation or extractive distillation. By the low-temperature distillation ethylene and propene can be obtained in pure form.
Since product pure methanol and aliphatic C4 to C6 alcohols are also usable (for example as solvents or plasticizers), the profitability of the entire process is thus increased.
Two examples for the preparation of dehydration catalysts that can be used in step (c) of the present process are given as follows:
Preparation of dehydration catalyst I
Aluminum oxide hydrate powder was mixed with 3.6% of its weight of 9~7~
aluminum stearate ~nd compacted to cylindrical pellets of ]ength 4.5 mm and diameter of 4.5 mm by means of a pelletizing machine. Then the tablets were calcined in air for 4 hours at 510C.
lOO g of the calc;ned pellets were immersed at room temperature in an aqueous s~t~tiOI~ of lO g LiOH in 435 ml water for 20 minutes and then dried at 120 C. for 2 hours and calcined at 400C. For 2 hours. The product contained 0.29% Li and had a BET surface of 210 m /g.
Preparation of dehydration catalyst II
Tricalcium phosphate was mixed with 3.6% of its weight of aluminum stearate and compacted to cylindrical pellets of 4.5 mm length and diameter of 4.5 mm by means of a pelletizing machine. Subsequently the pellets were calcined in air for 4 hours at 510C. 100 g of the calcined pellets were immersed at room temperature in an aqueous solution of 10 g LiOH in 166 ml water for 20 minutes and then dried at 120 C. for 2 hours and calcined at 400 C.for 2 hours. The product contained 0.28% Li and had a BET surface of 38.7 m2/g.
The present invention is illustrated by the following examples which are not intended to be limiting to the scope thereof.
Example 1 Promoted catalyst A was prepared as follows:
560 g K2C03 were dissolved in 2 liters of deionized water and heated to 60 - 80C 285.2 g CUtNo3)2.3H2o~ 217.6 g Zn(N03)2, 3 2 2 65.8 g Cr(N03)3.9H20, and 276 g Al(N03)3.9H20 were dissolved in 2 liters deionized water and slowly added into the K2C03 solution with stirring; the temperature was maintained at 60-80C. After mixing with the nitrate solution, the pH was adjusted to 6.8 - 7.0 by addition of a small quantity of aqueous K2C03 solution, whereupon stirring was continued for another 30 minutes.
Then the precipitate was filtered, and the filter cake was washed until nitrate-free by repeated slurrying with 2 liters of deionized water each time 115~3~7~i (ring analysis). I'he waslled filLer cake was ~rie~l for lS hours at 120 C.
and calcined for :l hours at 400C. The calcined ~roduct was mlxed with 2%
of its weight of natural graphite and compacted to cylindrical tablets 3 mm in dinmeter and 3 mm long. Onto 150 g o~ the tabLets thus obtained, a solution of 8.4 g K2C03 dissoLved in 30 ml H20, was sprayed; this was followed by drying at 120C. for 2 hours and calcinin~ at 400C. for 3 hours.
The chemLcal composition and the ~ET surface of catalyst A are given in Table I, Ineo a tubular reactor (diameter 18 mm, length 1000 mm) heated with a liquid medium were charged 30 ml of promoted catalyst A. The catalyst was activated with a gas consisting of 1.2 vol.% H2, balance N2, for 40 hours at 145 to 350 C. The temperature rise was about S C. per hour. After reaching 350C., the catalyst to be tested was treated with pure hydrogen for another 5 hours. Then synthesis gas having a composition of:
CO 29.0 vol.%
C2 1.5 "
CH4 1.4 "
N2 5.0 "
H2 ba]ance was supplied to the reactor and pressure and space velocity adjusted to 100 bar and 2000 liters synthesis gas per hour and liter of catalyst respectively.
The results and the composition of the reaction products are summarized in Tables II and III.
The liquid products obtained by condensation at 10C. were distilled so that a fraction consisting of ethanol and propanols was obtained and subsequently subjected to dehydration. The composition of this fraction is given in Table IV.
The dehydration of the alcohol mixture was carried out at 400 C., a 115'3~L76 pressure of 1 bar slld a s~ace velocity o~ 2.5 kg al,cohol mixture per hour and liter of catalyst, in an electrically heated tubular reactor of diameter 25 ~n and lengtll 500 mm, charged with 50 ml dehydration catalyst I.
After condensation at lO C., the gaseous products were dried and subjected to low-temperature distillation, while the liquid products were subjected to extractive disti]lation. Tlle results of the dehydration and the composition of the individual fractions are given in Table V.
Example 2 Promoted catalyst B was prepared as follows:
600 g K2CO3 were dissolved in 2 liters of deionized water and heated to 60 - 80 C- 285-2 g Cu(NO3)2~3H2O~ 188-2 g Zn(N3)2~ 131-6 g Cr(NO3)3 9H2O~
52.3 g Th(NO3)4.4H2O and 276 g Al(NO3)3.9H2O were dissolved in 2 liters de-ionized water and slowly added into the K2CO3 solution with stirring; the temperature was maintained at 60 - 80 C. After mixing with the nitrate solution, the pH was adjusted to 6.8 - 7.0 by addition of a small quantity of aqueous K2CO3 solution, whereupon stirring was continued for another 30 minutes.
Then the precipitate was filtered, and the filter cake was washed until nitrate-free by repeated slurrying with 2 liters of deionized water each time (ring analysis). The washed filter cake was dried for 15 hours at 120C. and calcined for 3 hours at 400C. The calcined product was mixed with 2% of its weight of natural graphite and compacted to cylindrical tablets 3 mm in diameter and 3 mm long. Onto 150 g of the tablets thus obtained, a solution of 8.4 g K2CO3 dissolved in 30 ml H2O, was sprayed; this was followed by drying at 120 C. for 2 hours and calcining at 400C. for 3 hours.
The chemical composition and the BET surface of catalyst B are given in Table I.
The procedure of Example 1 was repeated except that for the production of a mixture of methanol and hi,gher aliphatic alcohols catalyst B was used.
llt~47~
The results and the coml)osition of the reaction products at the end of step (b) are given in Tables II and III. The composit:ion of the ethanol-propanol fraction obtained by distil]ation is given in Table IV. lhis fraction was dehydrated according to the procedure of Example 1, and the olefin mixture obtained was fractionated.
Example 3 -~romoted catalyst C was prepared as follows:
Into 9000 ml of a copper amminocarbonate solution containing 4.11 g Cu/l~0 ml, 8.8 g NH3/lO0 ml and 7.4 g C02/lO0 ml, were dissolved 355 g ~inc oxide with agitation, adding 177 g A1203. With continued agitation and replacement of evaporated water, the suspension was thermally decomposed by boiling until a sample gave a colorless filtrate. The precipitate was filtered and the resulting filter cake was calcined in a thin layer at 400 C. for 4 hours. The product obtained was mixed with 2~ of its weight of natural graphite and compacted to cylindrical tablets of 3 mm diameter and 3 mm in length.
150 g of the tablets thus obtained were immersed for 20 minutes at room temperature in an aqueous solution of 209.5 g K2Cr207 in 200 ml water and then dried for 2 hours at 120C. and calcined for 3 hours at 400C. The chemical composition and the BET surface area of catalyst C are shown in Table I.
The procedure of Example 1 was repeated with the difference that for the production of a mixture of methanol and higher aliphatic alcohols catalyst C was used. The results and the composition of the reaction products are given in Tables II and III. The composition of the ethanol-propanol fraction obtained by distillation, step (b) is given in Table IV. This fraction was dehydrated according to the procedu~e of Example l, and the olefin mixture obtained was fractionated.
~ 9 _ 1xample 4 -Promoted catalyst D was prepare~ as follows:
In 9000 ml of a copper amminocarhonate solution containing 4.11 g Cu/100 ml, 8.8 g N~i3/100 m]. and 7.4 g C02llO0 ml, were dissolved 355 g zinc oxide with agitation, adding 177 g A12O3. With continued agitation and replacement of evaporated water, the suspension was thermally decomposed by boiling until a sampl.e gave a colorless filtrate. The precipitate was filtered and the resulting filter cake was calcined in a thin layer at 400 C. for 4 hours. The product obtained was admixed with a solution of 190 g Cr(NO3)3.9H20 in 200 ml deioni~ed water and then calcined for 3 hours at 400C. The oxides were then mixed with 2% of their weight of natural graphite and compacted to cylindrical tablets of 3 mm diameter of 3 mm length.
150 g of the product tablets were immersed at room temperature for 20 minutes in an aqueous solution of 96.5 g K2C03 in 200 ml water and then dried for 2 hours at 120C. and calcined for 3 hours at 400C. Table I shows the chemical composition and the BET surface area of catalyst D.
The procedure of Example 1 was repeated with the difference that for the preparation of a mixture of methanol and higher al.iphatic alcohols catalyst D was used. The results and the composition of the reaction products are given in Tables II and III. The composition of the ethanol-propanol fraction obtained by distillation is given in Table IV. The dehydration and fractiona-tion was carried out as in Example 1. The results of the dehydration and the composition of the individual fractions are given in Table V.
Example 5 Tlle dehydration of an ethanol-propanol fraction obtained according to the procedure of Example 1 was carried out at 450 C., at a pressure of 1 bar and a space velocity of 2.0 kg alcohol mixture per hour and liter of catalyst in a reactor according to Example 1 with the use of dehydration ~15~7~
catalyst II. The resu1.ts of the dehydration and the composi.tion of the individual fractions are given in Table V.
Example 6 The clehyclr.3tion of an ethano:L-propanol fraction obtained according to the procedure of Ixample 4 was carri.ed out according to the procedure of Example S. The results of the clehydration and the composition of the individual fractions are given in Table V.
Table I
Composition of promoted copper-, zinc- aluminum- and potassium-containing catalysts (wt.%) Designation Cu/(CuO) ZnO A12O3 K Cr2O3 MnO ThO2 GV* BET surface (m2/g) .
A 27.3 33.8 13.7 3.1 4.5 9.2 - 6.1 (32.0) 31.6 12.8 2.9 4.2 8.6 - 5.7 60.9 B ~ 27.3 29.2 13.7 3.0 9.2 - 9.2 6.1 (32.0) 27.3 12.8 2.8 8.6 - 8.6 5.7 18.3 C 32.9 31.7 15.7 2.9 8.9 - - 7.3 (38.1) 29.3 14.5 2.7 8.2 - - 6.7 43.2 D 34.2 32.9 16.4 3.0 3.3 - - 7.9 (39.4) 30.3 15.1 2.8 3.0 - - 7.3 45.4 * GV = loss on ignition, due mainly to carbon 11~94'76 Table II
C0 conversion (mol.~) and selectivities (%) of the formation of individual reaction products at 350C., 100 bar pressure and at the space velocity of 2000 liters synthesis gas per hour and li~er of catalyst.
Selectivity (%~ of the formation of Catalyst C0 conversion Methanol Higher aliph. C02 By-products (mol.%) alcohols (CH4 + liquid hydrocarbons) A 41.3 42.2 11.8 44.5 1.5 B 39.4 37.8 16.5 40.1 5.6 C 42.1 39.5 18.5 37.8 4.2 D 33.8 45.8 16.2 36.1 1.9 Table III
Yield (g per hr and liter cat. and m3 synthesis gas) of liquid reaction products, methanol and higher aliphatic alcohols Catalyst Liquid re- Methanol Higher aliphatic alcohols Percentage action products of which of ethanol Total C2+C3 C4 C6 2 3 alcohol fraction A 67.3 48.1 13.1 10.32.8 48.5 B 70.7 46.2 16.6 10.56.1 32.2 C 73.7 47.9 21.9 11.610.3 36.1 D 64.4 39.7 19.4 11.28.2 _ 25.6 'l'able IV
Composition of the ethanol-propanol fraction obtalned Synthesis catalyst Alcohol A B C D
Composition of the ethanol-propanol fraction Ethanol 46.6 29.3 34.424.1 n-Propanol 4.7 3.1 3.5 3.5 i-Propanol 44.7 58.037.1 66.3 _4 6 _ 4.6 5.0 6.1 Table V
~esults of the dehydration of ethanol-propanol fraction Dehydration Ethanol- Conversion By-products Composition of the gaseous catalyst propanol (mol.%) (wt.%) products (vol.%) fraction C2H4 C3H6 Higher olefins I 190.5 3.0 53.9 43.7 2.4 I 491.0 4.8 30.5 68.1 1.4 II 189.0 2.0 54.5 44.2 2.3 II 489.8 2.5 30.7 68.0 1.3
Claims (16)
1. A process for the production of olefins by dehydration of aliphatic alcohols comprising:
(a) passing a gas containing carbon monoxide and hydrogen in the range of about 250° to 400°C. and at a pressure in the range from about 80 to 150 bar over a catalyst comprising :
(1) a major portion by weight of the oxides of copper and zinc in intimate association with each other, (a) said oxides of copper and zinc being present in an atomic ratio of between 0.4:1 and 1.9:1;
(2) a minor proportion by weight of a thermal stabilizing metal oxide in intimate association with the oxides of copper and zinc (3) a promotional amount of one or more promoting compounds selected from the group consisting of chromium, cerium, lanthanum, manganese and thorium, in an amount in the range of from 0-10% by weight; and (4) a compound of potassium and a weight concentration of from about 0.03 - 3.4%.
(b) recovering an alcohol mixture containing methanol and higher aliphatic alcohols;
(c) separating methanol from the alcohol mixture;
(d) dehydrating the higher aliphatic alcohols from the alcohol mixture to the respective olefins over a dehydration catalyst, and recovering an olefin mixture therefrom.
(a) passing a gas containing carbon monoxide and hydrogen in the range of about 250° to 400°C. and at a pressure in the range from about 80 to 150 bar over a catalyst comprising :
(1) a major portion by weight of the oxides of copper and zinc in intimate association with each other, (a) said oxides of copper and zinc being present in an atomic ratio of between 0.4:1 and 1.9:1;
(2) a minor proportion by weight of a thermal stabilizing metal oxide in intimate association with the oxides of copper and zinc (3) a promotional amount of one or more promoting compounds selected from the group consisting of chromium, cerium, lanthanum, manganese and thorium, in an amount in the range of from 0-10% by weight; and (4) a compound of potassium and a weight concentration of from about 0.03 - 3.4%.
(b) recovering an alcohol mixture containing methanol and higher aliphatic alcohols;
(c) separating methanol from the alcohol mixture;
(d) dehydrating the higher aliphatic alcohols from the alcohol mixture to the respective olefins over a dehydration catalyst, and recovering an olefin mixture therefrom.
2. The process of claim 1 including the further step (a) fractionating the olefin mixture and recovering the resulting olefin fractions.
3. A process according to claim 1, wherein in part (a) the gas containing carbon monoxide and hydrogen is a synthesis gas containing about 25 to 30 vol.% carbon monoxide, 0 to 15 vol. % nitrogen, 0 to 4 vol.% carbon dioxide, 0-7 vol.% methane and balance hydrogen.
4. A process according to claim 3, wherein the reaction of part (a) is carried out at a space velocity of about 500 to 5000 liters of gas per hour and liter of catalyst.
5. A process as claimed in claim 4, wherein the reaction of step (a) is carried out at a temperature of about 350°C., a pressure of about 100 bar and a space velocity of about 1500 liters of gas per hour per liter of catalyst.
6. A process as claimed in claim 1, wherein the reaction of step (a) is carried out in a tubular reactor swept by a cooling medium or in a full-space reactor with cold gas cooling.
7. A process as claimed in claim 6, wherein recycling is utilized.
8. A process as claimed in claim 1, wherein the alcohol mixture obtained from step (a) is fractionated in step (b) into a first fraction containing low boiling by-products and methanol and a second fraction containing higher alcohols and water.
9. A process as claimed in claim 1, wherein the dehydration of step (d) is carried out over alkalized aluminum oxide or calcium phosphate as catalyst.
10. A process as claimed in claim 9, wherein the dehydration of step (d) is carried out at atmospheric or reduced pressure of about 0.5 to 1 bar, at a temperature of about 350 to 500°C., and at a space velocity of about 1 to 7 liters of alcohol mixture per hour per liter of catalyst.
11. A process as claimed in claim 9 or 10, wherein the aluminum oxide or calcium phosphate catalyst has been alkalized by impregnation with an aqueous solution of an alkali metal hydroxide or alkali metal carbonate, the concentration of the alkali metal in the catalyst being 0.1 to 1.5 wt.%.
12. A process according to claim 1, wherein the olefin mixture obtained from step (d) is cooled to a temperature of about 10°C. and is prefractionated into liquid and gaseous fractions, the gaseous fraction being treated to remove water and further fractionated by low temperature distillation and the liquid fraction is distilled by extractive distillation.
13. A process as claimed in claim 1, wherein in step (d) the higher alcohosl are ethanol and the propanols.
14. A process as claimed in claim 1, wherein the thermal stabilizing metal oxide of the catalyst of step (a), was aluminum oxide.
15. In the process for the production of olefins by dehydration of aliphatic alcohols, as defined in claim 1:
(a) the improvement of increasing the concentration of ethylene in the olefin mixture which comprises:
(b) passing said synthesis gas over the catalyst of claim 1 in which the promoting compounds comprise the oxides of chromium and manganese.
(a) the improvement of increasing the concentration of ethylene in the olefin mixture which comprises:
(b) passing said synthesis gas over the catalyst of claim 1 in which the promoting compounds comprise the oxides of chromium and manganese.
16. In the process for the production of olefins by dehydration of aliphatic alcohols, as defined in claim 1:
(a) the improvement of increasing the concentration of propene in the olefin mixture which comprises:
(b) passing the said synthesis gas mixture over the catalyst of step (a) in which the promoting compounds include the oxides of chromium.
(a) the improvement of increasing the concentration of propene in the olefin mixture which comprises:
(b) passing the said synthesis gas mixture over the catalyst of step (a) in which the promoting compounds include the oxides of chromium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803005550 DE3005550A1 (en) | 1980-02-14 | 1980-02-14 | METHOD FOR PRODUCING OLEFINS |
| DEP3005550.6 | 1980-02-14 |
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| Publication Number | Publication Date |
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| CA1159476A true CA1159476A (en) | 1983-12-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000370839A Expired CA1159476A (en) | 1980-02-14 | 1981-02-13 | Process for the production of olefins from synthesis gas, in particular ethylene and propene |
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| Country | Link |
|---|---|
| US (1) | US4398050A (en) |
| EP (1) | EP0034767B1 (en) |
| JP (1) | JPS56128723A (en) |
| AT (1) | ATE5648T1 (en) |
| AU (1) | AU6730781A (en) |
| CA (1) | CA1159476A (en) |
| DE (2) | DE3005550A1 (en) |
| DK (1) | DK63481A (en) |
| ES (1) | ES8201113A1 (en) |
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|---|---|---|---|---|
| IN155637B (en) * | 1980-04-11 | 1985-02-16 | Imp Chemical Ind Plc Formerly | |
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| US2636057A (en) * | 1949-08-23 | 1953-04-21 | Phillips Petroleum Co | Dehydration of alcohols to olefins |
| DE1142343B (en) * | 1958-01-29 | 1963-01-17 | Pechiney Prod Chimiques Sa | Process for the production of active alumina dehydration catalysts from the crude alumina aliphatic trihydrate obtained in the Bayer process |
| GB917047A (en) * | 1960-10-14 | 1963-01-30 | Castrol Ltd | Aliphatic olefinic compounds |
| GB1205397A (en) * | 1967-05-26 | 1970-09-16 | British Petroleum Co | Production of isoprene |
| DE1930003A1 (en) * | 1969-06-13 | 1970-12-23 | Basf Ag | Process for the production of methanol |
| DE2122952C3 (en) * | 1970-06-09 | 1979-11-08 | Ammonia Casale S.A., Lugano-Massagno (Schweiz) | Cu-Zn-Cr oxide catalyst, process for its preparation and its use |
| AT313863B (en) * | 1970-11-02 | 1974-03-11 | Shell Int Research | Process for the production of methanol |
| JPS4937708B1 (en) * | 1970-12-31 | 1974-10-11 | ||
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| JPS524515A (en) * | 1975-06-30 | 1977-01-13 | Kyoto Ceramic | Ceramic innerrbone implant member having porous contact surface and manufacture thereof |
| US4049741A (en) * | 1975-09-18 | 1977-09-20 | Mobil Oil Corporation | Method for upgrading Fischer-Tropsch synthesis products |
| JPS5426983A (en) * | 1977-08-02 | 1979-02-28 | Mitsubishi Gas Chem Co Inc | Methanol synthesis catalyst |
| JPS5453691A (en) * | 1977-10-06 | 1979-04-27 | Mitsubishi Gas Chem Co Inc | Methanol synthesis catalyst |
| PL120574B1 (en) * | 1978-07-15 | 1982-03-31 | Instytut Ciezkiej Syntezy Organicznej Blachownia | Method of manufacture of copper catalyst |
| US4260841A (en) * | 1979-09-04 | 1981-04-07 | Mobil Oil Corporation | Conversion of oxygenated products of Fischer-Tropsch synthesis |
-
1980
- 1980-02-14 DE DE19803005550 patent/DE3005550A1/en not_active Withdrawn
-
1981
- 1981-02-06 ES ES499212A patent/ES8201113A1/en not_active Expired
- 1981-02-13 DK DK63481A patent/DK63481A/en not_active Application Discontinuation
- 1981-02-13 CA CA000370839A patent/CA1159476A/en not_active Expired
- 1981-02-13 ZA ZA00810982A patent/ZA81982B/en unknown
- 1981-02-13 NO NO810511A patent/NO810511L/en unknown
- 1981-02-13 AT AT81100993T patent/ATE5648T1/en not_active IP Right Cessation
- 1981-02-13 JP JP1912181A patent/JPS56128723A/en active Granted
- 1981-02-13 FI FI810459A patent/FI810459L/en not_active Application Discontinuation
- 1981-02-13 DE DE8181100993T patent/DE3161672D1/en not_active Expired
- 1981-02-13 EP EP81100993A patent/EP0034767B1/en not_active Expired
- 1981-02-13 AU AU67307/81A patent/AU6730781A/en not_active Abandoned
- 1981-02-17 US US06/234,477 patent/US4398050A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0215525B2 (en) | 1990-04-12 |
| ES499212A0 (en) | 1981-12-16 |
| JPS56128723A (en) | 1981-10-08 |
| AU6730781A (en) | 1981-08-20 |
| ES8201113A1 (en) | 1981-12-16 |
| EP0034767B1 (en) | 1983-12-21 |
| DK63481A (en) | 1981-08-15 |
| US4398050A (en) | 1983-08-09 |
| EP0034767A3 (en) | 1981-09-09 |
| ATE5648T1 (en) | 1984-01-15 |
| DE3161672D1 (en) | 1984-01-26 |
| ZA81982B (en) | 1982-02-24 |
| EP0034767A2 (en) | 1981-09-02 |
| NO810511L (en) | 1981-08-17 |
| DE3005550A1 (en) | 1981-08-20 |
| FI810459L (en) | 1981-08-15 |
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