CA1213292A - Process for the manufacture of ethanol from synthesis gas - Google Patents
Process for the manufacture of ethanol from synthesis gasInfo
- Publication number
- CA1213292A CA1213292A CA000338193A CA338193A CA1213292A CA 1213292 A CA1213292 A CA 1213292A CA 000338193 A CA000338193 A CA 000338193A CA 338193 A CA338193 A CA 338193A CA 1213292 A CA1213292 A CA 1213292A
- Authority
- CA
- Canada
- Prior art keywords
- cocatalyst
- catalyst
- rhodium
- weight
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
PROCESS FOR THE MANUFACTURE OF ETHANOL FROM SYNTHESIS GAS
Abstract of the disclosure:
Ethanol is manufactured by reaction of carbon monoxide with hydrogen on a supported rhodium catalyst containing as cocatalyst at least one of the elements zirconium, hafnium, lanthanum, platinum, chromium and mercury.
Abstract of the disclosure:
Ethanol is manufactured by reaction of carbon monoxide with hydrogen on a supported rhodium catalyst containing as cocatalyst at least one of the elements zirconium, hafnium, lanthanum, platinum, chromium and mercury.
Description
3~2
- 2 - HOE 78/F 229 This invention relates to a process for the manufac-lure of ethanol by reaction of carbon monoxide with hydra-gun on a supported rhodium catalyst.
It is known from German Auslegeschriften DE-AS 2,503,233 and 2,628,463 that the gas phase reaction of synthesis gas in the presence of catalysts containing metallic rhodium yield substantially mixtures of oxygen-containing compounds having two carbon atoms in the molecule, such as acetic acid, ethanol and acetaldehyde.
It is further known from DE-AS 2,503,204 that the so-lectivity of ethanol can be increased by the addition of iron salts. The addition of iron salts strongly reduces, however, the activity of the rhodium catalyst. According to Table 1 of DE-AS 2,503,204 the space-time yields with iron containing rhodium catalysts are about 4 times lower than that of an iron-free rhodium catalyst used for Compaq risen. With regard to the economy of a process such a de-crease in the yield with regard to the formation of oxygen-containing C2-compounds is extremely unsatisfactory.
From US-Patent 4,096,164 it is known that the select tivity with respect to the formation of alcohols can be generally increased by adding molybdenum or tungsten to rhodium-containing catalysts. But these two cocatalysts do not lead to a substantially increased formation of ethanol in the first place larger amounts of methanol propanol and buttonhole are formed.
It is, therefore, the aim of the present invention to improve the ethanol selectivity of rhodium catalysts that 29 is to say to reduce the formation of other compounds such I
It is known from German Auslegeschriften DE-AS 2,503,233 and 2,628,463 that the gas phase reaction of synthesis gas in the presence of catalysts containing metallic rhodium yield substantially mixtures of oxygen-containing compounds having two carbon atoms in the molecule, such as acetic acid, ethanol and acetaldehyde.
It is further known from DE-AS 2,503,204 that the so-lectivity of ethanol can be increased by the addition of iron salts. The addition of iron salts strongly reduces, however, the activity of the rhodium catalyst. According to Table 1 of DE-AS 2,503,204 the space-time yields with iron containing rhodium catalysts are about 4 times lower than that of an iron-free rhodium catalyst used for Compaq risen. With regard to the economy of a process such a de-crease in the yield with regard to the formation of oxygen-containing C2-compounds is extremely unsatisfactory.
From US-Patent 4,096,164 it is known that the select tivity with respect to the formation of alcohols can be generally increased by adding molybdenum or tungsten to rhodium-containing catalysts. But these two cocatalysts do not lead to a substantially increased formation of ethanol in the first place larger amounts of methanol propanol and buttonhole are formed.
It is, therefore, the aim of the present invention to improve the ethanol selectivity of rhodium catalysts that 29 is to say to reduce the formation of other compounds such I
- 3 - HOE 78/F 229 as methanol, propanol and buttonhole without diminishing at the same time the space-time-yield of ethanol.
It has now been found that the ethanol selectivity and simultaneously the space-time-yield of ethanol can be sub-staunchly improved by using rhodium catalysts additional-lye containing, applied onto a carrier, at least one of the elements zirconium, hafnium, lanthanum, platinum, cry-mum and mercury.
The present invention thus provides a process for the manufacture ox ethanol by reaction of carbon monoxide with hydrogen in the presence of a supported rhodium catalysts, which comprises using as cocatalyst at least one of the elements zirconium, hafnium, lanthanum, platinum, chromium and mercury.
The finding that the composition of the reaction pro-duct can be shifted by the use of the aforesaid elements in savor of ethanol with simultaneous increase ox the space-time yield is surprising and could not have be foreseen.
Besides ethanol, which is formed with a high select-viny in the process of the invention, smaller amounts of other oxygen containing C2-compounds are formed, such as acetaldehyde and acetic acid and other products which can be wormed from these compounds in a secondary reaction 9 for example by esterification, acetalization or condensation.
Compounds of the latter type are inter alias ethyl acetate and the deathly acutely of acetaldehyde. The proportion of other oxygen-containing compounds having three or more car-bun atoms in the molecule is very low and generally it is ; 29 below 5 mow %, calculated on reacted carbon monoxide. The I
_ 4 = HOE 78/~ 229 total selectivity for oxygen-containing C2-compounds9 in-eluding the products converted into ethyl acetate and act-alluded deathly acutely, is up to 81 %, calculated on the reacted carbon monoxide The remainder of the carbon monk oxide is converted into the aforesaid products having 3 anymore carbon atoms and in addition essentially into methane and other gaseous hydrocarbons and a small proportion of carbon dioxide.
To synthesize the catalyst to be used in the process of the present invention, salts or complex compounds of rhodium can be used, for example chlorides, bromides and iodizes as well as double salts of rhodium with alkali me-tat halides, for example dipotassium-trichlororhodate.
There are also suitable complex compounds containing, be-sides rhodium and halogen, complex-~orming ligands, such as trialkyl-phosphines, triaryl-phosphines, ethylene dip amine, pardon, carbon monoxide, olefins or water. Come pounds of this type are, for example, tristriphenylphos-phine-rhodium~I~chloride9 -bromide or iodide, tristri 2Q phenylphosphine-rhodium-III-chloride, dichloro-bisethyle-ne-diamine-rhodium-I-chloride, trisethylenediamine-rho-dummy chloride, bis-tri-o-tolyl phosphine-rhodium~
chloride, carbollyl-bistriphenylphosphine-rhodium-I-bromide or dlcesiumcarbonyl-pentachlororhodate-III. In addition, compounds of rhodium can be used in which it is bound by ion or complex bonds to a carrier, such as zealots and ion exchangers which have been exchanged with rhodium halides.
29 As cocatalyst in the process ox the invention where is 3~2 used at least one of the elements zirconium, hafnium, fan-thanum, platinum, chromium and mercury applied onto the carrier in the form of their salts or complex compounds.
Zirconium, hafnium, lanthanum, chromium or mercury are pro-S erred and more preferably hafnium, chromium or mercury aroused. The elements can be used in the form of simple in-organic or organic salts for example the chlorides, brow modes, nitrates, formats, acetates, preferably, however, the chlorides. The oxides, hydroxides or carbonates can also be used, provided that they are converted into the aforesaid salts by a treatment with mineral acids or garb-oxylic acids. Especially suitable complex compounds are chloro-complexes of rhodium of the formula Mm/~hCl6 on in which M denotes the element of the cocatalyst, in the case of chromium, for example, the complex Creakily 7-2 H20 ?
which can be obtained by reacting chromium chloride with rhodium chloride at 100C in acetic acid.
Complexes of the aforesaid type can be applied onto the carrier by impregnation. Because of the poor ~olubili-try of some complexes it is often advantageous to impregnate the carrier with a solution of rhodium-III-chloride and one or several chlorides of the elements named as cocatalysts in acetic cold and subsequently to heat the treated carrier to a temperature of 100C, whereupon the complexes form in the pores. Alternatively, the element acting as cocatalyst can be applied to the carrier first or it can be incorpo-rated into a skeleton substance, for example a carrier ma tonal containing a silicate or aluminum oxide, for example 29 silicic acid, al~ninum oxide or aluminum silicate. A fur-then advantageous method consists in binding the cations of the elements acting as cocatalysts by means of ion exchange to a cation exchanger which can also be used as carrier for the rhodium and which is stable under the reaction condo-lions, for example natural or synthetic aluminum silicates known as molecular sieves. Suitable catalysts can also be obtained when the carrier is impregnated in the reverse or-don of succession, i.e. first with a rhodium compound and then with the respective cocatalyst. The catalyst effi-Chinese with an unchanged high selectivity for ethanol canoe further improved by adding other promoters, especially magnesium.
Suitable catalyst carriers are the usual carrier ma-trials having different specific surfaces. Carriers have in a specific surface in the range of from 50 to 1,000 mug are preferred. Suitable materials are, for example 9 Six licic acid, natural or synthetic silicates-of elements of groups It to VIII ox the Periodic Table (that is, for ox ample, the silicates of magnesium, calcium, aluminum, man-I Gaines), furthermore aluminum dioxide, thorium dioxide,zeolites and spinets. Silicic acid and silicates are pro-furred.
For the manufacture of the catalysts the carrier ma-twirl is impregnated with the active components either simultaneously or successively. When rhodium-III-salts are used, a subsequent treatment with a suitable reducing agent such as hydrogen, carbon monoxide or methanol proved advantageous. This reduction can be carried out in a so-29 pirate apparatus or in the reactor itself In general, the .
I
temperatures applied in the reduction are below 300C, pro-drably in the range of from 100 to 275C. In many cases it is expedient to carry out the reduction not with the us-diluted reducing gases but with a gas mixture additionally 5 containing an inert gas, for example nitrogen, carbon dip oxide or a noble gas.
It is likewise possible to produce the carrier material in the presence of the active components, for example by concomitant precipitation of the active components with silicates.
The concentration of rhodium and cocatalyst in the cay talysts can vary within wide limits. In general, a gala-lust contains 0.1 to 20 by weight of rhodium and Q.1 to 25 % by weight of cocatalyst, preferably 1.0 to 10 % by weight of rhodium and 0.1 to 20 % by weight of cocatalyst.
lo carry out the process of thy invention a gas mix-lure wholly or substantially consisting of carbon monoxide and hydrogen and possibly containing other components such as nitrogen, argon, carbon dioxide, or methane is passed over the catalyst. The molar proportion of carbon monoxide to hydrogen can be varied in wide limits Molar proportions ox from 5:1 to 1:5 and especially 3:1 to 1:3 are preferred.
In general, the reaction temperatures are in the range of prom 175C to 375C, preferably 200C to 350C and the no-action pressure ranges from 1 to 300 bar, preferably 20 to 200 bar.
Temperature and pressure should be adjusted to one an-other in such a manner that a high selectivity for the ox-29 gen-containing compounds is ensured while the exothermal formation of methane which is favored by elevated tempera-lures is kept low. Hence, high pressures and low temperate-ryes will be preferred. The conversiorl of carbon monoxide should not exceed 50 g, in general, since a higher conversion may readily lead to the formation ox an increased amount of byproducts consisting not only of methane carbon dioxide and gaseous hydrocarbons but also of liquid hydrocarbons of higher molecular weight and oxygen-containing products.
The process is preferably carried out in the gaseous phase. Conventional fixed bed reactors can be used in which, for a satisfactory dissipation of hefty the gala-lust is used in thin layers. Reactors with moved catalyst bed or fluidized bed reactors can also be used.
Alternatively, the reaction of synthesis gas can be carried out in the presence of a suspension of the solid and finely dispersed catalyst in inert media and/or react lion products.
According to an especially preferred embodiment of the invention, the reaction is carried out in the gaseous phase in an apparatus with gas circulation from which, aft ton separation ox the condensable reaction products, the unrequited gas mixture is recycled into the reactor.
This mode of operation is particularly economic. Due to the fact that the fresh gas is diluted with the recycled residual gas having a lower hydrogen content, higher react lion temperatures can be used so that higher space-time-yields are obtained with an unchanged selectivity. As apt pyrites with gas circulation those with internal or ox-29 vernal gas cycle can be used.
I
.
The following examples illustrate the invention, but they are not intended to limit it thereto E X A M P L E S
_ A) General description of the test The apparatus used consists of a heated reaction tube, having a length of 1 meter and an inner diameter of 16 millimeters and made of corrosion-resistant steel, with coccal fitted housing for a thermometer having an outer diameter of 6 mm, a following condenser a no-sever for the condensate and a compressor for recycling part of the non condensed gas to the reactor (cycle gas).
In each test the reactor is charged with 100 ml of the catalysts defined below. After flushing of the appear-tusk with nitrogen, first a pressure of 100 bar is ad-jutted with a synthesis gas consisting of 49 % by vow fume of CO, 49 % by volume of Ho, 1 % by volume of COY, 1 % by volume of No and minor amounts of other combo-newts and the reactor is heated to 275C. During heat-in and during the course of the test 450 normal liters of synthesis gas having the aforesaid composition are added to the cycle gas over the suction side of the come presser and the mixture is passed over the catalyst.
The gas mixture leaving the reactor is cooled to about ~5C in the condenser cooled with brine and the con-dented fractions are collected in the receiver. Aster the addition of fresh synthesis gas, the non condensed residual gas is returned to the reactor via the compress son. To maintain the pressure and to remove by-products 29 part of the residual gas is branched off as exhaust gas -via a pressure keeping valve. All catalysts defined be-low are tested by this method. In the table are India acted the duration of the tests, the space-time~yields of oxygen-containing C2-compounds per liter of catalyst and hour as well as the selectivities for ethanol, act-~ldehyde and acetic acid (in mow % of CO calculated on reacted CO). Minor amounts of ethyl acetate and act-alluded deathly acutely formed are calculated as acetic acid, ethanol and acetaldehyde.
B) Preparation of the catalyst Each time 40 g of silicic acid having a BET surface of 270 mug a pore volume of 1.27 ml/g and an apparent density of 0.4 kg/l are impregnated with a solution of 5.2 g of RhC13 ' x HO (38.0 % by weight of Rho in 50 ml ox water and dried for 1.5 hours at 80C, for 1.5 hours at 110C and for 1.5 hours at 150C.
This catalyst is used for the comparative Example.
For Examples 1 to 7 the catalyst obtained is further impregnated with an aqueous or alcoholic solution of the hollowing chlorides, each time in 50 ml of solvent, and dried for 2 hours at 80C and then for 2 hours at 150C.
Example no. _ cocatalyst _ amount in g 1 Or Clue 3.4 2 La Clue 4.8 3 Pi Clue 4~9
It has now been found that the ethanol selectivity and simultaneously the space-time-yield of ethanol can be sub-staunchly improved by using rhodium catalysts additional-lye containing, applied onto a carrier, at least one of the elements zirconium, hafnium, lanthanum, platinum, cry-mum and mercury.
The present invention thus provides a process for the manufacture ox ethanol by reaction of carbon monoxide with hydrogen in the presence of a supported rhodium catalysts, which comprises using as cocatalyst at least one of the elements zirconium, hafnium, lanthanum, platinum, chromium and mercury.
The finding that the composition of the reaction pro-duct can be shifted by the use of the aforesaid elements in savor of ethanol with simultaneous increase ox the space-time yield is surprising and could not have be foreseen.
Besides ethanol, which is formed with a high select-viny in the process of the invention, smaller amounts of other oxygen containing C2-compounds are formed, such as acetaldehyde and acetic acid and other products which can be wormed from these compounds in a secondary reaction 9 for example by esterification, acetalization or condensation.
Compounds of the latter type are inter alias ethyl acetate and the deathly acutely of acetaldehyde. The proportion of other oxygen-containing compounds having three or more car-bun atoms in the molecule is very low and generally it is ; 29 below 5 mow %, calculated on reacted carbon monoxide. The I
_ 4 = HOE 78/~ 229 total selectivity for oxygen-containing C2-compounds9 in-eluding the products converted into ethyl acetate and act-alluded deathly acutely, is up to 81 %, calculated on the reacted carbon monoxide The remainder of the carbon monk oxide is converted into the aforesaid products having 3 anymore carbon atoms and in addition essentially into methane and other gaseous hydrocarbons and a small proportion of carbon dioxide.
To synthesize the catalyst to be used in the process of the present invention, salts or complex compounds of rhodium can be used, for example chlorides, bromides and iodizes as well as double salts of rhodium with alkali me-tat halides, for example dipotassium-trichlororhodate.
There are also suitable complex compounds containing, be-sides rhodium and halogen, complex-~orming ligands, such as trialkyl-phosphines, triaryl-phosphines, ethylene dip amine, pardon, carbon monoxide, olefins or water. Come pounds of this type are, for example, tristriphenylphos-phine-rhodium~I~chloride9 -bromide or iodide, tristri 2Q phenylphosphine-rhodium-III-chloride, dichloro-bisethyle-ne-diamine-rhodium-I-chloride, trisethylenediamine-rho-dummy chloride, bis-tri-o-tolyl phosphine-rhodium~
chloride, carbollyl-bistriphenylphosphine-rhodium-I-bromide or dlcesiumcarbonyl-pentachlororhodate-III. In addition, compounds of rhodium can be used in which it is bound by ion or complex bonds to a carrier, such as zealots and ion exchangers which have been exchanged with rhodium halides.
29 As cocatalyst in the process ox the invention where is 3~2 used at least one of the elements zirconium, hafnium, fan-thanum, platinum, chromium and mercury applied onto the carrier in the form of their salts or complex compounds.
Zirconium, hafnium, lanthanum, chromium or mercury are pro-S erred and more preferably hafnium, chromium or mercury aroused. The elements can be used in the form of simple in-organic or organic salts for example the chlorides, brow modes, nitrates, formats, acetates, preferably, however, the chlorides. The oxides, hydroxides or carbonates can also be used, provided that they are converted into the aforesaid salts by a treatment with mineral acids or garb-oxylic acids. Especially suitable complex compounds are chloro-complexes of rhodium of the formula Mm/~hCl6 on in which M denotes the element of the cocatalyst, in the case of chromium, for example, the complex Creakily 7-2 H20 ?
which can be obtained by reacting chromium chloride with rhodium chloride at 100C in acetic acid.
Complexes of the aforesaid type can be applied onto the carrier by impregnation. Because of the poor ~olubili-try of some complexes it is often advantageous to impregnate the carrier with a solution of rhodium-III-chloride and one or several chlorides of the elements named as cocatalysts in acetic cold and subsequently to heat the treated carrier to a temperature of 100C, whereupon the complexes form in the pores. Alternatively, the element acting as cocatalyst can be applied to the carrier first or it can be incorpo-rated into a skeleton substance, for example a carrier ma tonal containing a silicate or aluminum oxide, for example 29 silicic acid, al~ninum oxide or aluminum silicate. A fur-then advantageous method consists in binding the cations of the elements acting as cocatalysts by means of ion exchange to a cation exchanger which can also be used as carrier for the rhodium and which is stable under the reaction condo-lions, for example natural or synthetic aluminum silicates known as molecular sieves. Suitable catalysts can also be obtained when the carrier is impregnated in the reverse or-don of succession, i.e. first with a rhodium compound and then with the respective cocatalyst. The catalyst effi-Chinese with an unchanged high selectivity for ethanol canoe further improved by adding other promoters, especially magnesium.
Suitable catalyst carriers are the usual carrier ma-trials having different specific surfaces. Carriers have in a specific surface in the range of from 50 to 1,000 mug are preferred. Suitable materials are, for example 9 Six licic acid, natural or synthetic silicates-of elements of groups It to VIII ox the Periodic Table (that is, for ox ample, the silicates of magnesium, calcium, aluminum, man-I Gaines), furthermore aluminum dioxide, thorium dioxide,zeolites and spinets. Silicic acid and silicates are pro-furred.
For the manufacture of the catalysts the carrier ma-twirl is impregnated with the active components either simultaneously or successively. When rhodium-III-salts are used, a subsequent treatment with a suitable reducing agent such as hydrogen, carbon monoxide or methanol proved advantageous. This reduction can be carried out in a so-29 pirate apparatus or in the reactor itself In general, the .
I
temperatures applied in the reduction are below 300C, pro-drably in the range of from 100 to 275C. In many cases it is expedient to carry out the reduction not with the us-diluted reducing gases but with a gas mixture additionally 5 containing an inert gas, for example nitrogen, carbon dip oxide or a noble gas.
It is likewise possible to produce the carrier material in the presence of the active components, for example by concomitant precipitation of the active components with silicates.
The concentration of rhodium and cocatalyst in the cay talysts can vary within wide limits. In general, a gala-lust contains 0.1 to 20 by weight of rhodium and Q.1 to 25 % by weight of cocatalyst, preferably 1.0 to 10 % by weight of rhodium and 0.1 to 20 % by weight of cocatalyst.
lo carry out the process of thy invention a gas mix-lure wholly or substantially consisting of carbon monoxide and hydrogen and possibly containing other components such as nitrogen, argon, carbon dioxide, or methane is passed over the catalyst. The molar proportion of carbon monoxide to hydrogen can be varied in wide limits Molar proportions ox from 5:1 to 1:5 and especially 3:1 to 1:3 are preferred.
In general, the reaction temperatures are in the range of prom 175C to 375C, preferably 200C to 350C and the no-action pressure ranges from 1 to 300 bar, preferably 20 to 200 bar.
Temperature and pressure should be adjusted to one an-other in such a manner that a high selectivity for the ox-29 gen-containing compounds is ensured while the exothermal formation of methane which is favored by elevated tempera-lures is kept low. Hence, high pressures and low temperate-ryes will be preferred. The conversiorl of carbon monoxide should not exceed 50 g, in general, since a higher conversion may readily lead to the formation ox an increased amount of byproducts consisting not only of methane carbon dioxide and gaseous hydrocarbons but also of liquid hydrocarbons of higher molecular weight and oxygen-containing products.
The process is preferably carried out in the gaseous phase. Conventional fixed bed reactors can be used in which, for a satisfactory dissipation of hefty the gala-lust is used in thin layers. Reactors with moved catalyst bed or fluidized bed reactors can also be used.
Alternatively, the reaction of synthesis gas can be carried out in the presence of a suspension of the solid and finely dispersed catalyst in inert media and/or react lion products.
According to an especially preferred embodiment of the invention, the reaction is carried out in the gaseous phase in an apparatus with gas circulation from which, aft ton separation ox the condensable reaction products, the unrequited gas mixture is recycled into the reactor.
This mode of operation is particularly economic. Due to the fact that the fresh gas is diluted with the recycled residual gas having a lower hydrogen content, higher react lion temperatures can be used so that higher space-time-yields are obtained with an unchanged selectivity. As apt pyrites with gas circulation those with internal or ox-29 vernal gas cycle can be used.
I
.
The following examples illustrate the invention, but they are not intended to limit it thereto E X A M P L E S
_ A) General description of the test The apparatus used consists of a heated reaction tube, having a length of 1 meter and an inner diameter of 16 millimeters and made of corrosion-resistant steel, with coccal fitted housing for a thermometer having an outer diameter of 6 mm, a following condenser a no-sever for the condensate and a compressor for recycling part of the non condensed gas to the reactor (cycle gas).
In each test the reactor is charged with 100 ml of the catalysts defined below. After flushing of the appear-tusk with nitrogen, first a pressure of 100 bar is ad-jutted with a synthesis gas consisting of 49 % by vow fume of CO, 49 % by volume of Ho, 1 % by volume of COY, 1 % by volume of No and minor amounts of other combo-newts and the reactor is heated to 275C. During heat-in and during the course of the test 450 normal liters of synthesis gas having the aforesaid composition are added to the cycle gas over the suction side of the come presser and the mixture is passed over the catalyst.
The gas mixture leaving the reactor is cooled to about ~5C in the condenser cooled with brine and the con-dented fractions are collected in the receiver. Aster the addition of fresh synthesis gas, the non condensed residual gas is returned to the reactor via the compress son. To maintain the pressure and to remove by-products 29 part of the residual gas is branched off as exhaust gas -via a pressure keeping valve. All catalysts defined be-low are tested by this method. In the table are India acted the duration of the tests, the space-time~yields of oxygen-containing C2-compounds per liter of catalyst and hour as well as the selectivities for ethanol, act-~ldehyde and acetic acid (in mow % of CO calculated on reacted CO). Minor amounts of ethyl acetate and act-alluded deathly acutely formed are calculated as acetic acid, ethanol and acetaldehyde.
B) Preparation of the catalyst Each time 40 g of silicic acid having a BET surface of 270 mug a pore volume of 1.27 ml/g and an apparent density of 0.4 kg/l are impregnated with a solution of 5.2 g of RhC13 ' x HO (38.0 % by weight of Rho in 50 ml ox water and dried for 1.5 hours at 80C, for 1.5 hours at 110C and for 1.5 hours at 150C.
This catalyst is used for the comparative Example.
For Examples 1 to 7 the catalyst obtained is further impregnated with an aqueous or alcoholic solution of the hollowing chlorides, each time in 50 ml of solvent, and dried for 2 hours at 80C and then for 2 hours at 150C.
Example no. _ cocatalyst _ amount in g 1 Or Clue 3.4 2 La Clue 4.8 3 Pi Clue 4~9
4 Or C13 6 H20 5.2 Hi C14 4.7 6 Hug Clue 7.9 29 7 Or Clue + My Clue H20 3.4 -I 3 ~31 I
Next, the catalysts for Example 1 to 7 obtained are heated for 5 hours to 100C in a glass flask with reflex condenser together with 50 ml of acetic acid and then dried for 1.5 hours at 110C, for 3 hours at 150C and finally for 1 hour at 300C under nitrogen.
The catalysts for examples 1 to 7 are then reduced in a flow tube made of glass my passing over 30 Nl/hr of hydrogen. for 3 hours at 225 to 275C under atmosphe-fig pressure.
C) Test results The results obtained are summarized in the follow-in table. The indicated values are average values ox-twined with reaction times of 100 hours each.
-T a b l e Reaction conditions: apparatus with gas circulation, 100 bar, 275C, feed gas 400 Nl/hr with KIWI ratio of 1:1, catalyst volume 0.1 l, duration of test 100 hours (Awoke acetic acid, Ash acetaldehyde, Etch ethanol) Example catalyst space time-yield selectivity (mow % CO) No. in g/l ho C -O Etch QcOH Ash Etch ~C2-0 Comparative Rho 52 31 17~2 6~4 24; 48~0 example 1 Rh/Zr 390 343 I 1 1 ox 70~ 1 76~0 2 Rh/La 380 318 7-0 4~0 67~5 78~5 3 Rapt 350 320 3 2 2.4 75~0 80~6 4 Rh/Cr 390 351 5~4 3~5 68~1 77~0 Rh/Hf 360 311 6~4 2~2 66~4 75~U
6 Rh~Hg 375 340 4~0 2~5 74~5 81~0 7 Rh/Zr/Mg 475 420 4~8 2.8 69~9 77~5 The space~time~yield (STY) is given in gram per liter of catalyst and hour; in the first column the STY of oxygen-containing C2-compounds, I acetic acid, aoetaldehyde and ethanol is given ( ~C2-0) and in the second column the STY ox ethanol alone (Etch) mow % calculated on reacted carbon monoxide
Next, the catalysts for Example 1 to 7 obtained are heated for 5 hours to 100C in a glass flask with reflex condenser together with 50 ml of acetic acid and then dried for 1.5 hours at 110C, for 3 hours at 150C and finally for 1 hour at 300C under nitrogen.
The catalysts for examples 1 to 7 are then reduced in a flow tube made of glass my passing over 30 Nl/hr of hydrogen. for 3 hours at 225 to 275C under atmosphe-fig pressure.
C) Test results The results obtained are summarized in the follow-in table. The indicated values are average values ox-twined with reaction times of 100 hours each.
-T a b l e Reaction conditions: apparatus with gas circulation, 100 bar, 275C, feed gas 400 Nl/hr with KIWI ratio of 1:1, catalyst volume 0.1 l, duration of test 100 hours (Awoke acetic acid, Ash acetaldehyde, Etch ethanol) Example catalyst space time-yield selectivity (mow % CO) No. in g/l ho C -O Etch QcOH Ash Etch ~C2-0 Comparative Rho 52 31 17~2 6~4 24; 48~0 example 1 Rh/Zr 390 343 I 1 1 ox 70~ 1 76~0 2 Rh/La 380 318 7-0 4~0 67~5 78~5 3 Rapt 350 320 3 2 2.4 75~0 80~6 4 Rh/Cr 390 351 5~4 3~5 68~1 77~0 Rh/Hf 360 311 6~4 2~2 66~4 75~U
6 Rh~Hg 375 340 4~0 2~5 74~5 81~0 7 Rh/Zr/Mg 475 420 4~8 2.8 69~9 77~5 The space~time~yield (STY) is given in gram per liter of catalyst and hour; in the first column the STY of oxygen-containing C2-compounds, I acetic acid, aoetaldehyde and ethanol is given ( ~C2-0) and in the second column the STY ox ethanol alone (Etch) mow % calculated on reacted carbon monoxide
Claims (28)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of ethanol in which carbon monoxide is reacted with hydrogen in the presence of a supported rhodium catalyst, and a cocatalyst comprising at least one of the metals hafnium, lanthanum, platinum, chromium and mercury.
2. A process as claimed in claim 1, in which the rhodium catalyst is supported on a member of the group of silicic acid and silicates.
3. A process as claimed in claim 1, in which the catalyst and the cocatalyst are used in the form of a chlorine-containing complex compound of the formula Mm[RhCl6]n in which M denotes the metal of the cocatalyst.
4. A process as claimed in claim 1, claim 2 or claim 3, in which the catalyst also contains magnesium as a promoter.
5. A process as claimed in claim 1, claim 2 or claim 3, in which the catalyst contains 0.1 to 20% by weight of rhodium and 0.1 to 25% by weight of cocatalyst.
6. A process as claimed in claim 1, claim 2 or claim 3, in which the catalyst contains 1.0 to 10% by weight of rhodium and 0.1 to 20% by weight of cocatalyst.
7. A process as claimed in claim 1, claim 2 or claim 3, in which the reaction is carried out at a temperature of from 175 to 375°C. and a pressure of from 1 to 300 bar.
8. A process as claimed in claim 1, claim 2 or claim 3 in which the cocatalyst comprises at least one of the metals hafnium, chromium and mercury.
9. A process as claimed in claim 1, claim 2 or claim 3, in which the metal of the cocatalyst is present in the form of a simple inorganic or organic salt.
10. A process as claimed in claim 1, claim 2 or claim 3, in which the cocatalyst is present in the form of a chloride.
11. A process for the preparation of ethanol in which carbon monoxide is reacted with hydrogen in the presence of a supported rhodium catalyst, and a cocatalyst consisting essentially of lanthanum.
12. A process as claimed in claim 11, in which the rhodium catalyst is supported on a member of the group of silicic acid and silicates.
13. A process as claimed in claim 11, in which the catalyst and the cocatalyst are used in the form of a chlorine-containing complex compound of the formula Mm[RhCl6]n in which M denotes the metal of the cocatalyst.
14. A process as claimed in claim 11, claim 12 or claim 13, in which the catalyst also contains magnesium as a promoter.
15. A process as claimed in claim 11, claim 12 or claim 13, in which the catalyst contains 0.1 to 20% by weight of rhodium and 0.1 to 25% by weight of cocatalyst.
16. A process as claimed in claim 11, claim 12 or claim 13, in which the catalyst contains 1.0 to 10% by weight of rhodium and 0.1 to 20% by weight of cocatalyst.
17. A process as claimed in claim 11, claim 12 or claim 13, in which the reaction is carried out at a temperature of from 175 to 375°C. and a pressure of from 1 to 300 bar.
18. A process as claimed in claim 11, claim 12 or claim 13, in which the metal of the cocatalyst is present in the form of a simple inorganic or organic salt.
19. A process as claimed in claim 11, claim 12 or claim 13, in which the cocatalyst is present in the form of a chloride.
20. A process for the preparation of ethanol in which carbon monoxide is reacted with hydrogen in the presence of a supported rhodium catalyst, and a cocatalyst consisting essentially of at least one of the metals hafnium, lanthanum, platinum, and mercury.
21. A process as claimed in claim 20, in which the rhodium catalyst is supported on a member of the group of silicic acid and silicates.
22. A process as claimed in claim 20, in which the catalyst and the cocatalyst are used in the form of a chlorine-containing complex compound of the formula Mm[RhCl6]n in which M denotes the metal of the cocatalyst.
23. A process as claimed in claim 20, 21 or 22, in which the catalyst also contains magnesium as a promoter.
24. A process as claimed in claim 20, 21 or 22, in which the catalyst contains 0.1 to 20% by weight of rhodium and 0.1 to 25% by weight of cocatalyst.
25. A process as claimed in 20, 21 or 22, in which the catalyst contains 1.0 to 10% by weight of rhodium and 0.1 to 20% by weight of cocatalyst.
26. A process as claimed in claim 20, 21 or 22, in which the reaction is carried out at a temperature of from 175 to 375°C. and a pressure of from 1 to 300 bar.
27. A process as claimed in claim 20, 21 or 22, in which the metal of the cocatalyst is present in the form of a simple inorganic or organic salt.
28. A process as claimed in claim 20, 21 or 22, in which the cocatalyst is present in the form of a chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000338193A CA1213292A (en) | 1978-10-24 | 1979-10-23 | Process for the manufacture of ethanol from synthesis gas |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2846148.5 | 1978-10-24 | ||
| CA000338193A CA1213292A (en) | 1978-10-24 | 1979-10-23 | Process for the manufacture of ethanol from synthesis gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213292A true CA1213292A (en) | 1986-10-28 |
Family
ID=4115406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000338193A Expired CA1213292A (en) | 1978-10-24 | 1979-10-23 | Process for the manufacture of ethanol from synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1213292A (en) |
-
1979
- 1979-10-23 CA CA000338193A patent/CA1213292A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4442228A (en) | Process for the manufacture of ethanol from synthesis gas | |
| EP0269718B1 (en) | Catalytic vapor phase process for producing dihydrocarbyl carbonates | |
| CA1211098A (en) | Conversion of methane to olefins and hydrogen | |
| US4375566A (en) | Process for producing ortho-alkylated phenols from anisoles | |
| US4224236A (en) | Process for the manufacture of oxygen-containing carbon compounds from synthesis gas | |
| CA1168270A (en) | Process for the production of c.sub.1 to c.sub.4 oxygenated hydrocarbons by the catalytic conversion of synthesis gas | |
| US4289710A (en) | Process for producing methanol from synthesis gas with palladium-calcium catalysts | |
| US4398051A (en) | Production of tertiary olefins | |
| EP0030110B1 (en) | Process for the production of an oxygenated hydrocarbon product containing ethanol | |
| KR870000057B1 (en) | Process for preparing oxalic acid diester | |
| US4579976A (en) | Catalytic process for the preparation of trifluoroacetaldehyde | |
| CA1213292A (en) | Process for the manufacture of ethanol from synthesis gas | |
| CA1117140A (en) | Process for the manufacture of oxygen-containing carbon compounds from synthesis gas | |
| US3739020A (en) | Preparation of carboxylic acids | |
| US4579974A (en) | Catalytic process for the preparation of hexafluoroacetone | |
| US2580284A (en) | Production of secondary aromatic amines | |
| CA1147749A (en) | Process for the manufacture of oxygen-containing carbon compounds and olefins from synthesis gas | |
| GB2078745A (en) | Production of alcohols from synthesis gas | |
| US4593147A (en) | Synthesis of neoalkanes | |
| CA1222773A (en) | Process for the manufacture of acetic acid, acetaldehyde and ethanol | |
| CA1248144A (en) | Carbon dioxide enhanced monoalkylene glycol production | |
| CA1220494A (en) | Process for producing ethanol | |
| US4293499A (en) | Process for producing a carboxylate ester using a supported acidic catalyst | |
| EP0004732B1 (en) | Preparation of 2-phenylethanol and 2-phenylethyl acetate | |
| CA1182476A (en) | Process for the manufacture of acetic acid, acetic aldehyde and ethanol from synthesis gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |