CA1175798A - Method for the production of methyl formate and methanol - Google Patents
Method for the production of methyl formate and methanolInfo
- Publication number
- CA1175798A CA1175798A CA000406634A CA406634A CA1175798A CA 1175798 A CA1175798 A CA 1175798A CA 000406634 A CA000406634 A CA 000406634A CA 406634 A CA406634 A CA 406634A CA 1175798 A CA1175798 A CA 1175798A
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- Prior art keywords
- methanol
- methyl formate
- metal alcoholate
- catalyst
- reaction
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Abstract A method in the production of methyl formate and methanol from a syngas comprising carbon monoxide and hydrogen in one reaction step, the reaction being carried out catalytically in a liquid phase mainly consisting of methanol, simultaneously with continuous removal of methyl formate and methanol from the reaction as a gas.
Description
- 1~757~3 The pxesent invention relates to a process for the production of methyl format~ and methanol from carbon monoxide and hydrogen - so called syngas.
The production of methyl formate and methanol is carxied out in one step and is catalyzed by a system of catalysts ccmprising an aIkali or alkaline earth metal alcoholate and a heterogeneous Cu, Cr catalyst. The reaction occurs in a liquid phase.
Methanol and methyl formate æ e formed by a chemical reaction of carbon monoxide and hydrogen according to the following 10 total reactions:
I. CO 2 > CH30H
c æbon monoxide hydrogen methanol II. 2 C0 2H2 HCOOCH3 carbon hydrogen methyl fo~mate monoxide It is previously known to provide methyl formate from methanol and caxbon monoxide in the presence of an alkali or alkaline eæ th metal alcoholate (cf. DE-AS 1 147 214, Norw. Specification 135 749), and it is, furthermore, known that methanol can be produced by hydrogenolysis of methyl formate. DE-PS 902 375, thus, indicates a method, wherein methyl formate and hydrogen are reacted in a catalytic gas phase reaction to form methanol.
It is furtherm~re, known to manufacture methyl formate and methanol in a catalytic gas phase reaction at elevated tenpera-tures, althou~h this has not been utilized for industrial production on a l~rye scale.
Also, it has been suggested to carry out the reactions I and II in one and the same step ~cf. DE-PS 809 803), where the formation of methanol is indicated. m is method has not been 7S~
utilized industrially so far, since the catalyst systems stated have low productivity and are rapidly deactivated. Industrial production of methanol to day is carried out by a catalytic gas phase reaction of carbon monoxide and hydrogen with the aid of a hetero-geneous metal catalyst. The reaction takes place at a pressure of approx. 100 atm. and a temperature of approx.
250C. The gas phase reaction h-as the disadvantage that relatively large amounts of gas must be recompressed and recirculated to the reactor, the conversion in each pas-sage through the reactor is relatively low. This disad-vantage is strongly enhanced by the fact that the cost of energy is rapidly increasing.
In accordance with one aspect of the invention there is provided a method for the production of methanol and methyl formate by reacting gases containing carbon monoxide and hydrogen in the presence of a catalyst system comprising a metal alcoholate and a copper-chromium oxide in a reactiOn zone, characterized in that methanol and methyl formate are co-produced in one reaction step in a liquid phase, and removed in a gaseous phase from the reaction zone.
In accordance with another aspect of the invention there is provided a Cu-Cr oxide catalyst, characterized in that it is obtained by thermal decom-position of Cu(OH)(NH4)CrO4 in an inert atmosphere at a temperature below 320C.
In accordance with yet another aspect of the inven ion there is provided the method of producing the Cu-Cr oxide catalyst.
In accordance with still another aspect of the invention there is provided a catalyst system com-prising the Cu-Cr oxide catalyst and a metal alcoholate~
~, L757~8 2a In connection with the present invention it was surprisingly found that the product methyl formate together with methanol are advantageously removed from the reaction zone as a gas simultaneously with their formation by the chemical reaction in the liquid phase.
This fact indicates that methanol is not formed via methyl formate as an intermediate product as conven-tionally assumed, but rather by a reaction which is in-dependent o~ the methyl formate concentration, even though the mechanism of such reaction is not known.
The principle of driving-off produced meth-anol/methyl formate from the reactor brings several advantages, technically speaking, which are so important that they will make the process technically/economically competitive.
The chemical reactions taking place at the formation of methyl formate and methanol involve the liberation of considerable ~uantities of heat. Since the process i.a. requires defined temperatures in the reactor, heat must be removed from the zone of reaction.
The reaction occurring in a liquid phase, this can be done in a simple and efficient manner as comp æ ed to a gas phase reactor. As the product, furthermore, :i .
~7~7~
is driven off from the liquid phase and removed from the reactor together with non-reacted carbon monoxide and hydrogen, the reaction heat will gradually be compensated by loss of heat due to the evaporation of reaction products. As regards heat economy, this is very advantageous, since the quantities of energy that would otherwise be necessary in the reactor for cooling, can thus be reduced. m e evaporati~n of the product also in an advan-tageous manner renders it possible to achieve an indirect heat control of the process by varying the amount of driven off pro-duct, since the temperature of the reactor can be adjusted in this manner~
By removing the product as a gas, process technical advantages associated with the catalyst, its activity and lifetime and its handling in the process are also achieved. The catalyst, which is present as suspended ~aterial and dissolved salt (alcoholate) in the reaction medium, will not be removed, but on the contrary remains in the reactor when the product is driven off. This means the elimination of any necessary separation to remove catalyst - from product in case the product had been removed from the reactor in the liquid phase~ The catalyst can, thus, be h2ndled via a separate process flow for any desire1 supply of fresh or regen-eration of used catalyst.
In connection with the present invention it was also surprisingly found that there is a connection between the lifetime of the catalyst and the utilization of the principle of driving off the products ~rcm the reaction ~edium. The principle of driving off methyl formate from the reaction medium can, thus, suitably be utilized to minimize the concentration of methyl formate in order to increase the lifetime of the catalyst.
The reaction accord~ng to the invention occurs in a liquid reac-tion phase in the presence of an aIkali or alkaline earth alco-holate, preferably an alcoholate formed frcn methanol, and a heterogeneous catalyst cc~prising a Cu-Cr oxide compound suspended in the liquid reaction mixture. me pressure -,i ~7S~
and the temperature of the reaction may be varied within wide limits. Preferably, pressures from 10 to 100 bar are used. The temperature is chosen to achieve a practical rate for the reaction.
Preferably, the reaction is carried out at a temperature in the range of 50& to 240C.
It is known to produce "copper c~romite" catalysts by calcination of a chemical ccmpound with an approximate ccmposition Cu(OH) (N~I4)CrO4 in the presence of air at a temperature of apprcxImately 350 C and subsequent reduction of the product with hydrogen.
Copper chromlte catalysts of said kind may be utilized in the process, but according to the present invention it proved espec-ially suitable to utilize specific Cu-Cr oxide catalysts, which are produced when the above mentioned calcination process in air instead is carried out in an inert atmosphere, e.g. argon, helium, nitrogen or similar inert gases, and is subsequently reduced with hydrogen according to known methods. It is not known in detail what chemical changes occur to the catalyst during thermal decom~
position in an inert atmosphere as ccmpared to the known method of calcination. The thermal decomposition of Cu(OH) (NH4)CrO4 in an inert atmosphere can be carried out at a temperature in the range of 250-500C, most suitably in the range of ~70-320C.
In addition to the above mentioned Cu-Cr oxide component, the cat-alyst system can naturally also comprise other components or carriers conventionally utilized in connection with heterogeneous hydrogenation catalysts, as for instance ~nO, A12O3, Fe203, MnO, M30, CaO, BaO, SiO2, activated carbon and the like.
The reaction occurs in a technical reactor that is known for solid~liquid phase~gas systems. Preferably a kind of reactor is chosen that is characterized by good mIxture of gas/liquid/
solids. In the reaction methyl formate as well as methanol are formed, and the ratio between said co~ponents in the product can be varie~ within wide limits by changing the process conditions and the composition of the catalyst.
l7$79B
Methanol naturally functions a5 a solvent for the reaction. Other organic solYents, as for instance higher alcohols, ether, satur-ated hydrocarbons and aromatics could also be utilized. A syngas free of water, sulphur and CO2, and wherein the molar ratio of car~on monoxide and hydrogen can be varied, is used in the present method~
On account of the conversion rate as well as the selectivity regard~ng the conversion to the desired products it is critical that the reaction takes place in an approximately anhydrous reaction medium.
Methyl formate and methanol are recovered as top and bottom pro-ducts respectively in a separation column. Part of the produced amount of methanol is suitably returned to the reactor. The produced-methanol has an especially high degree of purity (appro-ximately ar~ydrousJ and is, thus, especially well suited for this object.
The present invention represents an advantageous and very flexible process alternative for coproduction of methyl formate and methanol. The product composition may vary from pure methyl for-mate to pure methanol, and it is possible to control productionaccording to the actual state of the market at any time. The prospects of the market of methanol as well as methyl formate æ e very promising, as will be known. me characteristics of methanol are studied with a view to future utilization of methanol as an energy carrier. me expected and considerable increase in production ~ecause of this will involve the need of additional plants with larger throughput. Thus, there should be a de~and as well as good chances of adapting novel and impro~ed process technology for methanol production in an industrial scale.
~ethyl formate seems to become an essential intern~iate in Cl~based chemistry, since it is reasonably priced for utili-zation as a raw material for a series of essential petro-` 1~7~7~8 chemical products.
The invention is further explained by reference to theaccompanying drawings in which:
Figures 1 to 9 illustrate graphically the results achieved in Examples 1 to 9 in two different reactor systems;
Figure 10 illustrates ~raphically the formation of methanol and methyl formate as a function of maximum decomposition temperature; and Figure 11 illustrates schematically a system for pro-duction of methyl formate and methanol.
With further reference to Figure 11 there is shown a system comprising a reactor I and a distillation unit II.
Carbon monoxide and hydrogen are reacted in reactor I, in the presence of a catalyst in accordance with the invention, to produce methanol and methyl formate.
The methyl formate and methanol are delivered from reactor I to unit II where they are separated. Methyl formate is removed from the top of unit II and methanol is removed from the bottom of unit II~ A part of the methanol is recycled to the reactor I. ~
The methanol produced has an especially high degree of purity (approximately anhydrous).
The following examples will further illuminate the object of the present invention.
Exam~les 1 - 9 The reaction of carbon monoxide and hydrogen was studied in two essentially different reactor systems.
It is common to both systems that the reaction occurs in one step in the presence of a catalyst system consisting ~L~7~7~3 6a of an alkali or alkaline earth metal alcoholate and a Cu-catalyst. For both systems a micro reactor with a volume of 120 ml was used.
In one reactor system formed methyl formate and meth-anol are removed from the reactor by bubbling an excess of carbon monoxide and hydrogen through the reactor. In this case the products are removed as gases. The amount of gas is adjusted to keep a constant liquid level. In this case the catalyst remains in the reactor. The re-sults are shown by graph I in the Figures 1-9.
In the other reactor system formed methyl formate and methanol are removed from the reactor in the liquid phase, so that dissolved and suspended catalyst is carried with the product flow from the reactor. Hetero-geneous catalyst is recovered in a hydrocyclone and is pumped back to the reactor. Methanol and methyl for-mate are flashed by the product flow in a separation zone and recovered homogeneous catalyst is recircu-lated to the reactor. The results are shown in graph II of Figures 1~9.
The activity of the catalyst system as a function of time is shown for various compositions of pressure, temperature and catalyst. As a heterogeneous catalyst a commercially available catalyst from Girdler-S~dchemie Katalysator GmbH, Munich, labelled "G 89"
with the nominal composition: 39% Cu, 32% Cr, and
The production of methyl formate and methanol is carxied out in one step and is catalyzed by a system of catalysts ccmprising an aIkali or alkaline earth metal alcoholate and a heterogeneous Cu, Cr catalyst. The reaction occurs in a liquid phase.
Methanol and methyl formate æ e formed by a chemical reaction of carbon monoxide and hydrogen according to the following 10 total reactions:
I. CO 2 > CH30H
c æbon monoxide hydrogen methanol II. 2 C0 2H2 HCOOCH3 carbon hydrogen methyl fo~mate monoxide It is previously known to provide methyl formate from methanol and caxbon monoxide in the presence of an alkali or alkaline eæ th metal alcoholate (cf. DE-AS 1 147 214, Norw. Specification 135 749), and it is, furthermore, known that methanol can be produced by hydrogenolysis of methyl formate. DE-PS 902 375, thus, indicates a method, wherein methyl formate and hydrogen are reacted in a catalytic gas phase reaction to form methanol.
It is furtherm~re, known to manufacture methyl formate and methanol in a catalytic gas phase reaction at elevated tenpera-tures, althou~h this has not been utilized for industrial production on a l~rye scale.
Also, it has been suggested to carry out the reactions I and II in one and the same step ~cf. DE-PS 809 803), where the formation of methanol is indicated. m is method has not been 7S~
utilized industrially so far, since the catalyst systems stated have low productivity and are rapidly deactivated. Industrial production of methanol to day is carried out by a catalytic gas phase reaction of carbon monoxide and hydrogen with the aid of a hetero-geneous metal catalyst. The reaction takes place at a pressure of approx. 100 atm. and a temperature of approx.
250C. The gas phase reaction h-as the disadvantage that relatively large amounts of gas must be recompressed and recirculated to the reactor, the conversion in each pas-sage through the reactor is relatively low. This disad-vantage is strongly enhanced by the fact that the cost of energy is rapidly increasing.
In accordance with one aspect of the invention there is provided a method for the production of methanol and methyl formate by reacting gases containing carbon monoxide and hydrogen in the presence of a catalyst system comprising a metal alcoholate and a copper-chromium oxide in a reactiOn zone, characterized in that methanol and methyl formate are co-produced in one reaction step in a liquid phase, and removed in a gaseous phase from the reaction zone.
In accordance with another aspect of the invention there is provided a Cu-Cr oxide catalyst, characterized in that it is obtained by thermal decom-position of Cu(OH)(NH4)CrO4 in an inert atmosphere at a temperature below 320C.
In accordance with yet another aspect of the inven ion there is provided the method of producing the Cu-Cr oxide catalyst.
In accordance with still another aspect of the invention there is provided a catalyst system com-prising the Cu-Cr oxide catalyst and a metal alcoholate~
~, L757~8 2a In connection with the present invention it was surprisingly found that the product methyl formate together with methanol are advantageously removed from the reaction zone as a gas simultaneously with their formation by the chemical reaction in the liquid phase.
This fact indicates that methanol is not formed via methyl formate as an intermediate product as conven-tionally assumed, but rather by a reaction which is in-dependent o~ the methyl formate concentration, even though the mechanism of such reaction is not known.
The principle of driving-off produced meth-anol/methyl formate from the reactor brings several advantages, technically speaking, which are so important that they will make the process technically/economically competitive.
The chemical reactions taking place at the formation of methyl formate and methanol involve the liberation of considerable ~uantities of heat. Since the process i.a. requires defined temperatures in the reactor, heat must be removed from the zone of reaction.
The reaction occurring in a liquid phase, this can be done in a simple and efficient manner as comp æ ed to a gas phase reactor. As the product, furthermore, :i .
~7~7~
is driven off from the liquid phase and removed from the reactor together with non-reacted carbon monoxide and hydrogen, the reaction heat will gradually be compensated by loss of heat due to the evaporation of reaction products. As regards heat economy, this is very advantageous, since the quantities of energy that would otherwise be necessary in the reactor for cooling, can thus be reduced. m e evaporati~n of the product also in an advan-tageous manner renders it possible to achieve an indirect heat control of the process by varying the amount of driven off pro-duct, since the temperature of the reactor can be adjusted in this manner~
By removing the product as a gas, process technical advantages associated with the catalyst, its activity and lifetime and its handling in the process are also achieved. The catalyst, which is present as suspended ~aterial and dissolved salt (alcoholate) in the reaction medium, will not be removed, but on the contrary remains in the reactor when the product is driven off. This means the elimination of any necessary separation to remove catalyst - from product in case the product had been removed from the reactor in the liquid phase~ The catalyst can, thus, be h2ndled via a separate process flow for any desire1 supply of fresh or regen-eration of used catalyst.
In connection with the present invention it was also surprisingly found that there is a connection between the lifetime of the catalyst and the utilization of the principle of driving off the products ~rcm the reaction ~edium. The principle of driving off methyl formate from the reaction medium can, thus, suitably be utilized to minimize the concentration of methyl formate in order to increase the lifetime of the catalyst.
The reaction accord~ng to the invention occurs in a liquid reac-tion phase in the presence of an aIkali or alkaline earth alco-holate, preferably an alcoholate formed frcn methanol, and a heterogeneous catalyst cc~prising a Cu-Cr oxide compound suspended in the liquid reaction mixture. me pressure -,i ~7S~
and the temperature of the reaction may be varied within wide limits. Preferably, pressures from 10 to 100 bar are used. The temperature is chosen to achieve a practical rate for the reaction.
Preferably, the reaction is carried out at a temperature in the range of 50& to 240C.
It is known to produce "copper c~romite" catalysts by calcination of a chemical ccmpound with an approximate ccmposition Cu(OH) (N~I4)CrO4 in the presence of air at a temperature of apprcxImately 350 C and subsequent reduction of the product with hydrogen.
Copper chromlte catalysts of said kind may be utilized in the process, but according to the present invention it proved espec-ially suitable to utilize specific Cu-Cr oxide catalysts, which are produced when the above mentioned calcination process in air instead is carried out in an inert atmosphere, e.g. argon, helium, nitrogen or similar inert gases, and is subsequently reduced with hydrogen according to known methods. It is not known in detail what chemical changes occur to the catalyst during thermal decom~
position in an inert atmosphere as ccmpared to the known method of calcination. The thermal decomposition of Cu(OH) (NH4)CrO4 in an inert atmosphere can be carried out at a temperature in the range of 250-500C, most suitably in the range of ~70-320C.
In addition to the above mentioned Cu-Cr oxide component, the cat-alyst system can naturally also comprise other components or carriers conventionally utilized in connection with heterogeneous hydrogenation catalysts, as for instance ~nO, A12O3, Fe203, MnO, M30, CaO, BaO, SiO2, activated carbon and the like.
The reaction occurs in a technical reactor that is known for solid~liquid phase~gas systems. Preferably a kind of reactor is chosen that is characterized by good mIxture of gas/liquid/
solids. In the reaction methyl formate as well as methanol are formed, and the ratio between said co~ponents in the product can be varie~ within wide limits by changing the process conditions and the composition of the catalyst.
l7$79B
Methanol naturally functions a5 a solvent for the reaction. Other organic solYents, as for instance higher alcohols, ether, satur-ated hydrocarbons and aromatics could also be utilized. A syngas free of water, sulphur and CO2, and wherein the molar ratio of car~on monoxide and hydrogen can be varied, is used in the present method~
On account of the conversion rate as well as the selectivity regard~ng the conversion to the desired products it is critical that the reaction takes place in an approximately anhydrous reaction medium.
Methyl formate and methanol are recovered as top and bottom pro-ducts respectively in a separation column. Part of the produced amount of methanol is suitably returned to the reactor. The produced-methanol has an especially high degree of purity (appro-ximately ar~ydrousJ and is, thus, especially well suited for this object.
The present invention represents an advantageous and very flexible process alternative for coproduction of methyl formate and methanol. The product composition may vary from pure methyl for-mate to pure methanol, and it is possible to control productionaccording to the actual state of the market at any time. The prospects of the market of methanol as well as methyl formate æ e very promising, as will be known. me characteristics of methanol are studied with a view to future utilization of methanol as an energy carrier. me expected and considerable increase in production ~ecause of this will involve the need of additional plants with larger throughput. Thus, there should be a de~and as well as good chances of adapting novel and impro~ed process technology for methanol production in an industrial scale.
~ethyl formate seems to become an essential intern~iate in Cl~based chemistry, since it is reasonably priced for utili-zation as a raw material for a series of essential petro-` 1~7~7~8 chemical products.
The invention is further explained by reference to theaccompanying drawings in which:
Figures 1 to 9 illustrate graphically the results achieved in Examples 1 to 9 in two different reactor systems;
Figure 10 illustrates ~raphically the formation of methanol and methyl formate as a function of maximum decomposition temperature; and Figure 11 illustrates schematically a system for pro-duction of methyl formate and methanol.
With further reference to Figure 11 there is shown a system comprising a reactor I and a distillation unit II.
Carbon monoxide and hydrogen are reacted in reactor I, in the presence of a catalyst in accordance with the invention, to produce methanol and methyl formate.
The methyl formate and methanol are delivered from reactor I to unit II where they are separated. Methyl formate is removed from the top of unit II and methanol is removed from the bottom of unit II~ A part of the methanol is recycled to the reactor I. ~
The methanol produced has an especially high degree of purity (approximately anhydrous).
The following examples will further illuminate the object of the present invention.
Exam~les 1 - 9 The reaction of carbon monoxide and hydrogen was studied in two essentially different reactor systems.
It is common to both systems that the reaction occurs in one step in the presence of a catalyst system consisting ~L~7~7~3 6a of an alkali or alkaline earth metal alcoholate and a Cu-catalyst. For both systems a micro reactor with a volume of 120 ml was used.
In one reactor system formed methyl formate and meth-anol are removed from the reactor by bubbling an excess of carbon monoxide and hydrogen through the reactor. In this case the products are removed as gases. The amount of gas is adjusted to keep a constant liquid level. In this case the catalyst remains in the reactor. The re-sults are shown by graph I in the Figures 1-9.
In the other reactor system formed methyl formate and methanol are removed from the reactor in the liquid phase, so that dissolved and suspended catalyst is carried with the product flow from the reactor. Hetero-geneous catalyst is recovered in a hydrocyclone and is pumped back to the reactor. Methanol and methyl for-mate are flashed by the product flow in a separation zone and recovered homogeneous catalyst is recircu-lated to the reactor. The results are shown in graph II of Figures 1~9.
The activity of the catalyst system as a function of time is shown for various compositions of pressure, temperature and catalyst. As a heterogeneous catalyst a commercially available catalyst from Girdler-S~dchemie Katalysator GmbH, Munich, labelled "G 89"
with the nominal composition: 39% Cu, 32% Cr, and
2.5% Mn was used in all tests. The activity is given as kg produced methanol per kg catalyst ~alcoholate~
per time - ~1757~8 unit, and the results are shown in the attached diagrammes. m e results clearly show that the catalyst activity declines slower when the reacti~n products are removed in the gas phase and not the liquid phase, Example 10 Small portions of Cu (OH) NH4CrO (approx. 2 g) were thermally decomposed in an inert atmosphere (He). The sample was kept at maxImum decomposition temperature as stated in Figure 10 for one hour. Simultaneously 120 nl~min of helium were passed through the decomposition zone. 0,75 g oE the decomposed product in 12 g methanol were then prereduced with hydrogen in a micro autoclave having a volume of 30 ml and provided with magnetic stirring and temperature control at 185C and 100 bar hydrogen. After 16 hours the mixture was cooled to 20C and the catalyst was separated from the methanol by centrifugation. The catalyst rem~ined in the autoclave whereas the methanol was removed. The autoclave was then supplied with 10 g dried methanol containing 1 mole % Na methylate as catalyst 1~ The conversion of carbon monoxide and hydrogen was then carried out at 130C and 75 bar for 2.5 hours.
After the test reaction mixture was cooled to 20C and analysed by gas~liquid chromatography (glc). The formation of methanol and methyl formate (indicated as % of weight increase) as a function of maximum decomposition temperature is shcwn by graph I in Figure 10. The selectivity of the reaction of CO and H2 to methanol/methyl formate was more than 95% in all these tests.
~r comparison Cu(OH)NH4CrO was calcinated in air according to the known methods and tested as a catalyst for the reaction of carbon monoxide and hydrogen according to the same method as stated above. me results are shown by graph II in Figure 10, The results show tha~ a catalyst that is more active in an substantial degree is provided by thermal deccmposition of CU(OH)NH4 ~n an inert atmosphere, as compared to the activity achie~ed by known processes of calcination.
~7S7~8 The following process conditions and results were employed in Examples 1 to 10 as illustrated in Figures 1 to 10 .
Pro~uction of methanol and methyl formate from CO/H2 = 1/2 Catl : Ba(/Me)2, 0.5 mole% in MeOH
Cat2 : "~39", 3.0g Pressure: 75 bar Temp: 130C
Selectivity as regards MeCH: 94.1%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Ba(OMe)2, 0.5 mole% in MeOH
Cat2 : "~39", 3.0g Pressure: 68 bar Temp: 150C
Selectivity as regards MeOH: 99%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Na(OMe), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g : Pressure: 75 bar Temp: 130C
Selectivity as regards MeOH: 87.9%
'Yd~ .
~7~i7~8 g EXA~PLE 4 -Production of methanol and methyl formate from CO/H2 = lJ2 Catl : Na(OMe), 5.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 75 bar Temp: 130C
Selectivity as regards MeOH: 94.1%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : ~a(OMe), 10.0 mole% in MeOH
Cat2 : "G89", 1.2g Pressure: 75 bar Temp: 130C
Selectivity as regards MeOH: 70.2%
EXAMPLE _ Production of mathanol and methyl formate from CO/H2 = 1/2 Catl : ~a(OMe), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 80 bar - Temp: 90C
Selectivity as regards MeOH: 50.5%
Production of methanol and methyl formate from CO/~ = 1/2 Catl : ~a(OMe), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 67 bar Temp: 150C
Selectivity as regards MeOH: 89.2%
, ~17~798 Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Na(OMe), 1.0 mole% in MeOH
Cat2 : "G89i', 3.0g Pressure: 58 bar Temp: 170C
Selectivity as regards MeOH: 92.6%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Na(OEt), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 75 bar Tempo 130C
Selectivity as regards MeOH: 90.4%
Production of methanol and methyl formate from CO/H2 as a function of maximum decomposition temperature for Cu(OH/NH4CrO4)~
~A~
per time - ~1757~8 unit, and the results are shown in the attached diagrammes. m e results clearly show that the catalyst activity declines slower when the reacti~n products are removed in the gas phase and not the liquid phase, Example 10 Small portions of Cu (OH) NH4CrO (approx. 2 g) were thermally decomposed in an inert atmosphere (He). The sample was kept at maxImum decomposition temperature as stated in Figure 10 for one hour. Simultaneously 120 nl~min of helium were passed through the decomposition zone. 0,75 g oE the decomposed product in 12 g methanol were then prereduced with hydrogen in a micro autoclave having a volume of 30 ml and provided with magnetic stirring and temperature control at 185C and 100 bar hydrogen. After 16 hours the mixture was cooled to 20C and the catalyst was separated from the methanol by centrifugation. The catalyst rem~ined in the autoclave whereas the methanol was removed. The autoclave was then supplied with 10 g dried methanol containing 1 mole % Na methylate as catalyst 1~ The conversion of carbon monoxide and hydrogen was then carried out at 130C and 75 bar for 2.5 hours.
After the test reaction mixture was cooled to 20C and analysed by gas~liquid chromatography (glc). The formation of methanol and methyl formate (indicated as % of weight increase) as a function of maximum decomposition temperature is shcwn by graph I in Figure 10. The selectivity of the reaction of CO and H2 to methanol/methyl formate was more than 95% in all these tests.
~r comparison Cu(OH)NH4CrO was calcinated in air according to the known methods and tested as a catalyst for the reaction of carbon monoxide and hydrogen according to the same method as stated above. me results are shown by graph II in Figure 10, The results show tha~ a catalyst that is more active in an substantial degree is provided by thermal deccmposition of CU(OH)NH4 ~n an inert atmosphere, as compared to the activity achie~ed by known processes of calcination.
~7S7~8 The following process conditions and results were employed in Examples 1 to 10 as illustrated in Figures 1 to 10 .
Pro~uction of methanol and methyl formate from CO/H2 = 1/2 Catl : Ba(/Me)2, 0.5 mole% in MeOH
Cat2 : "~39", 3.0g Pressure: 75 bar Temp: 130C
Selectivity as regards MeCH: 94.1%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Ba(OMe)2, 0.5 mole% in MeOH
Cat2 : "~39", 3.0g Pressure: 68 bar Temp: 150C
Selectivity as regards MeOH: 99%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Na(OMe), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g : Pressure: 75 bar Temp: 130C
Selectivity as regards MeOH: 87.9%
'Yd~ .
~7~i7~8 g EXA~PLE 4 -Production of methanol and methyl formate from CO/H2 = lJ2 Catl : Na(OMe), 5.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 75 bar Temp: 130C
Selectivity as regards MeOH: 94.1%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : ~a(OMe), 10.0 mole% in MeOH
Cat2 : "G89", 1.2g Pressure: 75 bar Temp: 130C
Selectivity as regards MeOH: 70.2%
EXAMPLE _ Production of mathanol and methyl formate from CO/H2 = 1/2 Catl : ~a(OMe), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 80 bar - Temp: 90C
Selectivity as regards MeOH: 50.5%
Production of methanol and methyl formate from CO/~ = 1/2 Catl : ~a(OMe), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 67 bar Temp: 150C
Selectivity as regards MeOH: 89.2%
, ~17~798 Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Na(OMe), 1.0 mole% in MeOH
Cat2 : "G89i', 3.0g Pressure: 58 bar Temp: 170C
Selectivity as regards MeOH: 92.6%
Production of methanol and methyl formate from CO/H2 = 1/2 Catl : Na(OEt), 1.0 mole% in MeOH
Cat2 : "G89", 3.0g Pressure: 75 bar Tempo 130C
Selectivity as regards MeOH: 90.4%
Production of methanol and methyl formate from CO/H2 as a function of maximum decomposition temperature for Cu(OH/NH4CrO4)~
~A~
Claims (22)
1. A method for the production of methanol and methyl formate by reacting gases containing carbon monoxide and hydrogen in the presence of a catalyst system comprising a metal alcoholate and a copper-chromium oxide in a reaction zone, characterized in that methanol and methyl formate are co-produced in one reaction step in a liquid phase, and removed in a gaseous phase from the reaction zone.
2. A method according to claim 1, characterized in that said methanol and methyl formate are separated by fractional distillation, whereafter at least part of the methanol is recirculated to the reaction zone.
3. A method according to claim 2, wherein all of the methanol is recirculated to the reaction zone.
4. A method according to claim 2, wherein a part of the methanol is recirculated to the reaction zone.
5. A method according to claim 1, characterized in that said metal alcoholate is barium methoxide.
6. A method according to claim 2, 3 or 4, characterized in that said metal alcoholate is barium methoxide.
7. A method according to claim 1, characterized in that in addition to methanol and methyl formate an organic inert solvent is present in said liquid phase.
8. A method according to claim 2, 3 or 4, characterized in that in addition to methanol and methyl formate an organic inert solvent is present in said liquid phase.
9, A method according to claim 1, characterized in that said copper-chromium oxide is prepared by thermal decomposition of Cu(OH)(NH4)CrO4 in an inert atmosphere.
10. A method according to claim 2, 3 or 4, characterized in that said copper-chromium oxide is prepared by thermal decomposition of Cu(OH)(NH4)CrO4 in an inert atmosphere.
11. A method according to claim l, 2 or 5, characterized in that the reacting is effected at a temperature below 240°C and at a pressure below 100 bar.
12. A method according to claim 7 or 9, characterized in that the reacting is effected at a temperature below 240°C and at a pressure below 100 bar.
13. A method according to claim 1, 2 or 3, wherein said metal alcoholate is an alkali metal or alkaline earth metal alcoholate.
14. A method according to claim 5, 7 or 9, wherein said metal alcoholate is an alkali metal or alkaline earth metal alcoholate.
15. A Cu-Cr oxide catalyst, characterized in that it is obtained by thermal decomposition of Cu(OH)(NH4)CrO4 in an inert atmosphere at a temperature below 320°C.
16. A Cu-Cr oxide catalyst, characterized in that it is obtained by thermal decomposition of Cu(OH)(NH4)CrO4 in an inert atmosphere at a temperature in the range of 270-320°C, followed by reduction with hydrogen.
17. A method of producing a Cu-Cr oxide catalyst comprising thermally decomposing Cu(OH)(NH4)CrO4 in an inert atmosphere at a temperature below 320°C.
18. A method of producing a Cu-Cr oxide catalyst, comprising: thermally decompositing Cu(OH)(NH4)CrO4 in an inert atmosphere at a temperature in the range of 270-320°C., followed by reduction with hydrogen.
19. A catalyst system comprising a Cu-Cr oxide as defined in claim 15, and a metal alcoholate.
20. A catalyst system according to claim 19, wherein said metal alcoholate is an alkali or alkaline earth metal alcoholate.
21. A catalyst system comprising a Cu-Cr oxide as defined in claim 16, and a metal alcoholate.
22. A catalyst system according to claim 21, wherein said metal alcoholate is an alkali or alkaline earth metal alcoholate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO812279A NO152045C (en) | 1981-07-03 | 1981-07-03 | PROCEDURE FOR THE PREPARATION OF METHYL FORMINATE AND METHANOL FOR THE REACTION OF CARBON MONOXIDE AND HYDROGEN |
| NO81.2279 | 1981-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175798A true CA1175798A (en) | 1984-10-09 |
Family
ID=19886150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000406634A Expired CA1175798A (en) | 1981-07-03 | 1982-07-05 | Method for the production of methyl formate and methanol |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1175798A (en) |
| NO (1) | NO152045C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5032618A (en) * | 1988-12-23 | 1991-07-16 | Snamprogetti S.P.A. | Process for producing methanol form synthesis gas, in the liquid phase |
| US5221652A (en) * | 1991-03-26 | 1993-06-22 | The University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis |
| US5385949A (en) * | 1991-03-26 | 1995-01-31 | University Of Pittsburgh | Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters |
| CN1061027C (en) * | 1998-02-20 | 2001-01-24 | 中国科学院山西煤炭化学研究所 | System for reaction and separation integration for synthesis of methanol by two step process at low temperature |
| CN1074305C (en) * | 1997-09-02 | 2001-11-07 | 中国科学院成都有机化学研究所 | Composite catalyst for low temperature combined production of methanol and methyl formate and process therefor |
| DE19781891B4 (en) * | 1996-07-18 | 2006-06-29 | Stepan Co., Northfield | Improved process for the conversion of fatty acid amides into -amines |
-
1981
- 1981-07-03 NO NO812279A patent/NO152045C/en unknown
-
1982
- 1982-07-05 CA CA000406634A patent/CA1175798A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5032618A (en) * | 1988-12-23 | 1991-07-16 | Snamprogetti S.P.A. | Process for producing methanol form synthesis gas, in the liquid phase |
| US5221652A (en) * | 1991-03-26 | 1993-06-22 | The University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis |
| US5384335A (en) * | 1991-03-26 | 1995-01-24 | University Of Pittsburgh | Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite |
| US5385949A (en) * | 1991-03-26 | 1995-01-31 | University Of Pittsburgh | Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters |
| DE19781891B4 (en) * | 1996-07-18 | 2006-06-29 | Stepan Co., Northfield | Improved process for the conversion of fatty acid amides into -amines |
| CN1074305C (en) * | 1997-09-02 | 2001-11-07 | 中国科学院成都有机化学研究所 | Composite catalyst for low temperature combined production of methanol and methyl formate and process therefor |
| CN1061027C (en) * | 1998-02-20 | 2001-01-24 | 中国科学院山西煤炭化学研究所 | System for reaction and separation integration for synthesis of methanol by two step process at low temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| NO152045B (en) | 1985-04-15 |
| NO152045C (en) | 1985-07-24 |
| NO812279L (en) | 1983-01-04 |
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