CA1243044A - Process for the preparation of mixed alcohols - Google Patents
Process for the preparation of mixed alcoholsInfo
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- CA1243044A CA1243044A CA000539853A CA539853A CA1243044A CA 1243044 A CA1243044 A CA 1243044A CA 000539853 A CA000539853 A CA 000539853A CA 539853 A CA539853 A CA 539853A CA 1243044 A CA1243044 A CA 1243044A
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Abstract
ABSTRACT
A process for producing a mixed alcohol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by:
calcining a mixture of (A) a copper or zinc compound, (B) a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II -VII of the Periodic Table;
impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound;
calcining the resulting mixture; and reducing the thus-calcined product.
The selectivity of the mixed alcohol is high in the process of the present invention. This is one of the advantages of the present invention. Furthermore the proportion of alcohols other than methanol in the mixed alcohol is relatively high, and thus the mixed alcohol is suitable for use as an alcohol component to be com-pounded to gasoline.
A process for producing a mixed alcohol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by:
calcining a mixture of (A) a copper or zinc compound, (B) a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II -VII of the Periodic Table;
impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound;
calcining the resulting mixture; and reducing the thus-calcined product.
The selectivity of the mixed alcohol is high in the process of the present invention. This is one of the advantages of the present invention. Furthermore the proportion of alcohols other than methanol in the mixed alcohol is relatively high, and thus the mixed alcohol is suitable for use as an alcohol component to be com-pounded to gasoline.
Description
12 ~3 PROCESS FOR THE PRODUCTION OF MIXED
ALCOHOLS
This ls a divisional of Canadian patent application 442,014 filed November 25, 1983.
BACKGROUND OF THE INVENTION
.
In view of a xise in pric0 of gasoline fox cars due to the aggravation o oil situation an attempt to pro--duce inexpensive car fuel by adding mixed alcohols to gasoline have been made in recent years. The reason why mixed alcohols are used as an alcohol component to be added to gasoline is that if methanol alone is added to gasoline, it combines together with water in gasoline to form a water/~nethanol mixture, resulting in the formation sf two layers5 i.e., a gasolinelayer and a water/met~anol mixed layer, in a storage tank.
Various methods of producing such mix~d'alcohols lS have been proposed Japanese Patent Application Laid-Open No. ~727/1981, for example, discloses a process for produc-ing mixed alcohols from synthesis gas by the use of a rhodium-base catalyst. This process, however is not preferred in that large amounts of by-products such as acetic acid and aldehyde result. In addItion, as catalysts for use in the production of mixed alcohols from synthesis gas, a ruthenium-base catalyst (Japanese ~aten~ Application Laid-Open No. 82327/1982~, alkali metal-modified ones of a Zinc-chromium catalyst and a copper~zinc catalyst (Japanese Patent Application Laid-Open No. 10689/198~), and a copper-cobalt catalyst (Japanese Patent Application Laid-Open No. 85530/1980) are known. Methods utilizing these catalysts, however, should be performed under elevated pressures. This will need expensive equipment and cause many side reactions. Hence the cannot be said to be advantageous for practical use.
~2 ~3~ Lo SUMMERY OF THE INVENTION
-The present invention is intended to overcome the above-described problems of conventional metnods, and an object of the invention is to provide a process for produc-ing mixed alcohols from synthesis gas with efficiency under relatively low pressures.
One embodiment of the present invention relates to a process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting synthesis gas with a catalyst, wherein the catalyst is a solid sub-stance prepared by:
calcining a mixture of (Al) a copper compound (Bl) a nickel compound, and (C') a compound of at least one metal selected from the metals belonging to Groups II, III and IV and the fourth period of Groups V, VI and VII
of the Periodic Table;
impregnating the above-calcined product with (D) an alkali metal compound ancl/or an alkaline earth metal compound;
calcining the resull:ing mixture; and reducing the thus-calcined product J
The other embodiment of the present invention relates to a process for producing a mixed alcohol compris.ing methanol and higher alcohols than methanol by contacting synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by:
; .
calcining a mixture of (A2) a zi.nc compound, (B2) a ¦ compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II, ITI and 1243~
1 IV and the fourth period of Groups VD VI and VII of the Periodic Table;
impregnating the above-calcined product with (Do an alkali metal compound and/or an alkaline earth metal compound, calcining the resulting mixture, and reducing the thus-calcined product DETAILED DESCRIPTION OF THE INVENTION
-A method of preparing the catalysl: of the invention will hereinafter be explained in detail. In the prepara-tion of the catalyst,Compounds (A), (B` and O are first mixed and calcined~
As Compound (A), Compound (Al) or Compound ~A2) can be used.
As Compound (Al) used herein, any suitable compound containing copper can be listed. usually water-soluble compounds are preferred. Suitable examples of copper com-pounds include copper nitrate, copper s,ulfate r and copper chloride.
As Compound (A2) used herein, any suitable compound containins zinc can be listed Usually water~soluble compounds are preferred. Suitable examples of zinc com-pounds include zinc nitrate, zinc sulfate, and zinc chloride.
As Compound (B), Compound (Bl) or Compound (B2) can be used.
lZ~ V
1 Compound (Bl) used herein, any suitable compound con-taining nickel can be listed. Particularly preferred are water-soluble compounds. Suitable examples of nickel compounds include nickel nitrate nickel sulfate, and nickel chlorideO
Compound (B2) is a compound containing at least one of iron, cobalt and nickel. Particularly preferred are water soluble compounds. Suitable examples are the nitrates, sulfates, and chlorides of the metals.
Compound (Al) can be used in combination with Compound (Bl). Similar by, Compound (A2) can be used in combination with Compound (B2).
Compound (C) is a compound Qf at least one metal selected from the metals belonging to Groups II, III and IV, and the fourth period of Groups V, VI and VII of the Periodic Table. Typical examples of the metals belonging to Groups II, III and IV of the Periodic Table are magnesium, calcium, zinc, boron, aluminum, gallium, lanthanum, silicon, germanium, titanium, tin, and zirconium Suitable examples of the metals belonging to the fourth period of Groups Vr VI and VII of the Periodic Table are vanadium, chromium, and manganese. As Compound (C), various compounds of the metals as described above, such as the nitrates, sulfates, chlorides, and oxides thereof, can be used. Particularly preferred are water-soluble compounds.
As Compound (C), salt of titanium is one of the preferable compounds. Especially sulfate of it is preferable. Other salts such as titanium tetrachloride are undesirable here. When dissolved into water, titanium tetrachloride, for instance, is difficult to treat since it fumes and is hydrolyzed not to be dispersed homogeneously ~.2~
1 Moreover, other salts are insoluble in water.
Titanium sulfate is a favourable salt for dispersing of titanium into catalyst as is descried above, but sulfate radicals tend to remain in catalyst When sulfur portion is 0.5% by weight or more catalytic activity is scarcely observedO
accordingly, when titanium sulfate is employed for producing catalyst, it is inevitable to remove sulfate radicals to make sulfur portion less than 0~5% by weight after precipitate results.
After earnest researches in removal of sulfate radicals, we have found that following two processes are desirable One of the processes is to repeat washing with aqueous solution of sodium chloride after the precipitate results, and to exchange sulfate radicals with chlorine :ions to reduce sulfate radicals, and thus make sulfur portion less than 0.5~ by weight. Thereupon, the con-entration of the aqueous solution of sodium chloride is desired to be 0.1 mole per liter - 5 mole per liter.
Another process is to adjust pH at co-precipitating by addition of sodium carbonate. There, once co-precip-itation is made at pH 9.0 or more, after that the washing with plain water can reduce the sulfate radicals to make 1 25 the sulfur portion less than 0.5~ by weight. When pH is less than 9.0, activity does not arise sufficiently.
., In the preparation of the catalyst of the invention, Compounds (A), (B) and (C) are first mixed and calcined.
3~
l Compounds (A), (B) and (C) can be mixed by techniques such as a co-pr~cipitation met~od~ a kneadiny method t and a dipping method In accordance with the co-pxecipita-tion method, fvr example, they are added to water to form aqueous solutions or suspensions, which are then mixed and co-precipitated by adjusting the pH through addition of a co precipitating agent such as sodium carbonate sodium hydroxide and potassium hydroxide at room temper-ature or at elevated temperatures. Then, the resulting precipitate it aged, if necessary r and washed with water, dried and calcined at a temperature of from 200 to 500C.
The above-calcinated product is then impregnated with Compound (D), i.e., an alkali metal compound and/or an alkaline earth metal compound. Compound (D) is prefer-ably water-soluble. Suitable examples include sodium carbonate and magnesium acetate. In the impregnation of the calcined product, Compound (D) is used as an aqueous solution; tha1: is, the calcined product is impregnated with an aqueous solution of Compound ED). After the process of impregnation the resulting mixture should ye calcined again. This calcination is usually performed at a temperat1lre of from lO0 to 500C~
Although the composition of toe thus-calcined pro-duct varies with the amounts of Compounds (A), (B), (C) and (D) being added, it is necessary for the molar ratio of (A) to (B) to O to (D) (calculated as oxide) to be controlled so that 0.05 < (A) <0.7, O.Ol c 0.7, O.Ol<(C) < 0.7, and 0.005 < (D) <0.3.
The calcined product is then reduced. This reduc-tion is suficient to be performed at a temperature of from 20b to 400C by the use of a reducing atmosphere, for example, in the presence of hydrogen or carbon monoxide.
3~
1 The thus-prepared solid substance is used as the catalyst of the invention.
Although Compounds (A), (B), O and (D) can be mixed -and calcined simultaneously, Compound ED) of alkali ox alkaline earth metal compound is disperc~ed only insuffi-ciently and unevenly in the final product by such a procedure. Hence this procedure fails to produce the desired catalyst.
In the process of the invention, the solid substance as prepared above is used as a catalyst, and synthesis gas, i.e., a mixed gas of hydrogen and carbon monoxide, is contacted with the catalyst to produce a mixed alcoholn The composition of the synthesis gas to be used as a feed in the process o the invention is no ¢ritical.
In general, however, it is preferred to use synthesis gas in which the molar rat:io of hydrogen to carbon monoxide is within the range of from 1:3 to 3^1.
Other reaction condil:ions for the process of the invention are not criticaL and can be determined appropri-ately. The reaction temperature is usually from 200 to 550C and preferably from 240 to 450C; the reaction pres-sure may be relatively lo, in general, ranges between 20 and 200 kilograms per squire centimeter (by gauge) and preferably between 40 and 100 kilograms per square centi-meter (by gauge); and the gas hourly space velocity (GHSV) is from 500 to 100,000 per hour and preferably from 1,000 to 50,000 per hour.
The process of the invention as described above produces mixed alcohols comprising methanol and higher alcohols than methanol, such as ethanol, propanol, and butanol, and other compounds such as aldehydes end esters.
The selectivity of the mixed alcohol is high in the process of the invention. This is one of the advantages of the 36..~
1 present invention. Another advantage is that the costs of equipment and operation, or example, can be greatly reduced, since the reaction pressure in the process of the invention is sufficient to be relatively low. Further-more the proportion of alcohols other than methanol in the mixed alcohol as produced by the process of the invention is relatively high, and thus the mixed alcohol is suitable for use as an alcohol component to be compounded to gasoline.
The present invention is described in greater detail with xeference to the following examples.
I- An aqueous solution (Aqueous Solution I) ~2.5 liters) containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate and 59.5 grams of zinc nitrate (6 hydrate) was prepared and heated to 60C. Separately 2.5 liters of an aqueous solution (Aqueous Solution II) containing 81.3 grams of sodium carbonate (anhydrous) was prepared and heated to 60C.
These aqueous solutions were mixed rapidly and, after completion of precipitation, aged. Then the result-ing mixture was filtered, and the pricipitate thus ob-tained was washed sufficiently with water, dried at 120C
for about 12 hours and then calcined at ~50C for 2 hours The thus-calcined product was impregnated with an aqueous solution (Aqueous Solution III) containing 6.8 grams of sodium carbonate (anhydrous) and dried at;120C
for about 12 hours. Then graphite was added, and the resulting mixture was pelletized and pulverized to produce 16-32 mesh grains. The thus-prepared catalyst ~3~
1 precursor had a composition of Cu:Ni:Zn~Na=0~36:0.18^
0O36:0O10 (molar ratio)O
Then 1 milliliter of the catalyst precursor was packed in a reaction tube of stainless steel While passing a 1:9 (molar ratio) mixture of carbon monoxide and nitrogen as a reduciny gas through the reaction tube at a gas hourly space velocity IGHSV) of 4,000 per hour, the catalyst precursor was gradually heated and reduced at 240C for 5-20 hours to produce a catalyst.
A synthesis gas (carbon monoxide:hydrogen=1:2 (molar ratio)) was introduced int:o the reaction tube at a gas hourly space velocity (GH',V) of 4,000 per hour. The pressure was gradually increased to 50 kilograms per square centimeter (by gauche). Then the tempçrature was increased to a reaction temperature at which the conver-sion of carbon monoxide (excluding the one converted into carbon dioxide) reached about 20%. The reaction products were passed through a tube maintained at 200C, without being condensed at: the outlet of the reaction tube, and introduced into a gas chromatography instrument where they were analyzed. The column filler as used in this gas chromatography analysis was a mixture of activ-ated carbon, Porapak-Q*(produced by Water Co.) and Porapak-R*(produced by Water Co.). The results are shown in Table 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate ~3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 75~0 grams of aluminum nitrate (9 hydrate) was used as * Trade Mark ~2~3~
1 Aqueous Solution I and 2.5 liters of an aqueous solution containing 90.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a com-position of Cu:Ni~Al:Na=0O36:0 a 18:0~36O0.10 (molar ratio).
The catalyst pxecursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared ca~alyst~ the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
~:XAMPLE 3 A catalyst precursor was prepared in the same manner clS in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and '15.0 grams of aluminum nitrate (9 hydrate) was used as l~queous Solution I, 2.5 liters~of an aqueous solution containing 90.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and an aqueous solution containing :L3.7 grams of magnesium acetate (4 hydrate) as Aqueous ';olution III for the process of impregnation. This catalyst precursor had a composition of Cu:Ni:Al:Mg=
0.3600.18:0O36:0.10 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48~3 grams of copper nitrate (3 hydrate), 29~1 grams of nickel nitrate (6 hydrate), and 79.9 grams of gallium nitrate (8 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solu~
tion containing 91.6 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition ox Cu:N~:Ga:Na=0.36:0.1~:0.36:Q.10 (molar ratio)O
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prep-ared catalyst, the production of mixed alcohol from syn-thesis gas was performed in the same manner as in Example 1. The results are shown in Table 1 .:
A catalyst precursor was prepared in toe same manner as in Example 1 except that 2.5 liters of an aqueous solu-tion containing 48.3 grams of copper nitrate (3 hydrate) and 29.1 grams of nickel nitrate (6 hydrate was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 61.7 grams of water glass (SiO2 content: 28.6%
by weight) and 37.2 grams of sodium carbonate ~anhydrou~) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Si:Na=0.3~:0.18~0.36:0.10 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst,the production of mixed alcohol from ~Z43~
1 synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 64.4 grams of zirconium oxychloride (8 hydrate) was used as Agueous Solution I, and 2.5 liters of an aqueous solution containing 63~7 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a compositi.on of Cu:Ni:Zr:Na=0 36:0~18:0.36 0.10 molar ratio).
The catalyst precuror~was reduced in the same manner as in Example 1 to form a catalyst. Using the thus--prepared catalyst, the production of mixed alcohol from synthesis gas was perfornled in the same manner as in - Example 1. The results are shown in Table 1.
ExAMæLE 7 An aqueous solution (2.5 liters) containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 161.1 grams of titanium sulfate (Ti(So4)2 content: 29.8% by weight) was prepared and heated to 60C. Separately 2.5 liters of an aqueous solution containing 128.0 grams of sodium carbonate (anhydrous) was prepared and heated to 60C: These aqueous solutions were mixed rapidly and, after comple-tion of precipitation, aged. The resulting mixture was filtered, and the precipitat- thus obtained was treated 1 with an aqueous solution of sodium chloride (concentra-tion: 0.5 mole per liter) and further washed sufficiently with waterO
Thereafter the same procedure as in Example 1 was performed to form a catalyst precursor. This catalyst precursor had a composit,ion of Cu:NiOTi:Na=0.36^0.18:0.36:
0.10 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table lr A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 8000 grams of chromium nitrate was used as Aqueous Solu-tion I, and 2.5 liters of an aqueous solution containing 90.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Cr:Na=0.38:0.19:0.31:0.12 (molar ratio The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. UsinCJ the thus-prepared catalyst, the production of mixed alcoho,l from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
~4~
1 EXAMPLE g A catalyst precurssr was prepared in the same manner as in Example 1 except that 2.5 liters a àn aqueous solution containing 4803 grams of copper nitrate (3 S hydrate), ~9.1 grams of nickel nitrate (6 hydrate), and 86.6 grams of lanthanvm nitrate (6 hydrate) was used as' Aqueous Solution I, and 2u5 liters of an agueous solution containing 74.2 grams of sodium carbonate ~anhydrou~ as Aqueous Solution II. This catalyst precursor had a com-position of Cu:Ni:La:Na=0.36:0.18:0.36:0.10 (molar ratio .
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using -the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1.
The results are shown in Tale 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters ox an aqueous solu-tion containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate t6 hydrate), and 86.6 grams of lanthanum nitrate (6 hydrate) was used as Aqueous Solution I, 2.5 liters of an aqueous solution containing 74.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and an aqueous solution containing 13.7 grams of magnesium acetate (4 hydrate) as A~ueQus Solution III
for the process of impregnation. This catalyst precursor had a composition of Cu:Ni:La:Mg=0.36:0.18:0.36:0.10 (molar ratio). ;
The catalyst precursor was reduced in the same manner as in Example 1 to form catalyst. Using the thus-1 prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2~5 liters of an aqueous solu-tion containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 25~6 grams of magnesium nitrate (6 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solution contain-ing 50.3 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Mg:Na=0.43:0.22:0.22:0.13 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst" the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
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,_ ox us o o I:
,~
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_ :~: o o o o Jo x C) 00 O O
~¢ 'ox x P. ' o o a x g co a co 1` oo o 1` n o o O m m , o o Y ,~ o O CO us X Us _ X ox D C
l _1 l O-- .
_I ~rl O O Us 00 i D O Us N 1` l .,1 0 O
u -- r` us O .~ h aJ g , o s:: X t Us o ' l I) o c: ¦ = O En X
X do ¦ NO N 'I .--1 I N_I N N N C E I-- O C
O I O ,--1 0 ,~ I l C o U ~1 o $
_I o l o _I or) o ') l 0 ¢ ~1 IJ h I-- P 3 D3C c a) . .~
X Z ,, 1 EXP~lPLE 12 An aqueous solution (Aqueous Solution I) (1.5 liters) containing 24.2 grams of copper nitrate (3 hydrate 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate (Ti(So4)2 content 29 8% by weight) was prepared and heated to 60Co Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66~ 3 grams of sodium carbonate (anhydrous) was prepared and heated to 60C. These aqueous solutions~were mixed rapidly and, after completion of precipitation, aged.
The resulting mixture was filtered, and the thus-obtained precipitate was treated with an aqueous sodium chloride solution (concentration: 0.5 mole per liter) and wished sufficiently with water.
... .
The precipitate was dried at 120C for about L2 hours and then calcined at 450C for 2 hours.
The thus-calcined product was impregnated with 38 milliliters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: l.O mole per liter), and dried at 120C for about 12 hours Then graphite was added, and the resulting mixture was pelletized and pul-verized to form 16-32 mesh grains. The thus-prepaced catalyst precursor had a composition of Cu:Ni:Ti:Na=
1:1:1:0.38 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to foxm a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 2~
~LZ'~3t~
A catalyst precursor was prepared in the same manner as in Example 12 except that 1.5 liters of an aqueous solution containing 1601 grams of copper nitrate (3 hydrate 29.1 grams of nickel nitrate (6 hydrate), and 106.7 qrams of titanium sulfate (the same as used in Example 12) was used as Aqueous Solution I, and 1.5 liters of an aqueous solution containing 79.5 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Ti:Na=
ALCOHOLS
This ls a divisional of Canadian patent application 442,014 filed November 25, 1983.
BACKGROUND OF THE INVENTION
.
In view of a xise in pric0 of gasoline fox cars due to the aggravation o oil situation an attempt to pro--duce inexpensive car fuel by adding mixed alcohols to gasoline have been made in recent years. The reason why mixed alcohols are used as an alcohol component to be added to gasoline is that if methanol alone is added to gasoline, it combines together with water in gasoline to form a water/~nethanol mixture, resulting in the formation sf two layers5 i.e., a gasolinelayer and a water/met~anol mixed layer, in a storage tank.
Various methods of producing such mix~d'alcohols lS have been proposed Japanese Patent Application Laid-Open No. ~727/1981, for example, discloses a process for produc-ing mixed alcohols from synthesis gas by the use of a rhodium-base catalyst. This process, however is not preferred in that large amounts of by-products such as acetic acid and aldehyde result. In addItion, as catalysts for use in the production of mixed alcohols from synthesis gas, a ruthenium-base catalyst (Japanese ~aten~ Application Laid-Open No. 82327/1982~, alkali metal-modified ones of a Zinc-chromium catalyst and a copper~zinc catalyst (Japanese Patent Application Laid-Open No. 10689/198~), and a copper-cobalt catalyst (Japanese Patent Application Laid-Open No. 85530/1980) are known. Methods utilizing these catalysts, however, should be performed under elevated pressures. This will need expensive equipment and cause many side reactions. Hence the cannot be said to be advantageous for practical use.
~2 ~3~ Lo SUMMERY OF THE INVENTION
-The present invention is intended to overcome the above-described problems of conventional metnods, and an object of the invention is to provide a process for produc-ing mixed alcohols from synthesis gas with efficiency under relatively low pressures.
One embodiment of the present invention relates to a process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting synthesis gas with a catalyst, wherein the catalyst is a solid sub-stance prepared by:
calcining a mixture of (Al) a copper compound (Bl) a nickel compound, and (C') a compound of at least one metal selected from the metals belonging to Groups II, III and IV and the fourth period of Groups V, VI and VII
of the Periodic Table;
impregnating the above-calcined product with (D) an alkali metal compound ancl/or an alkaline earth metal compound;
calcining the resull:ing mixture; and reducing the thus-calcined product J
The other embodiment of the present invention relates to a process for producing a mixed alcohol compris.ing methanol and higher alcohols than methanol by contacting synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by:
; .
calcining a mixture of (A2) a zi.nc compound, (B2) a ¦ compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II, ITI and 1243~
1 IV and the fourth period of Groups VD VI and VII of the Periodic Table;
impregnating the above-calcined product with (Do an alkali metal compound and/or an alkaline earth metal compound, calcining the resulting mixture, and reducing the thus-calcined product DETAILED DESCRIPTION OF THE INVENTION
-A method of preparing the catalysl: of the invention will hereinafter be explained in detail. In the prepara-tion of the catalyst,Compounds (A), (B` and O are first mixed and calcined~
As Compound (A), Compound (Al) or Compound ~A2) can be used.
As Compound (Al) used herein, any suitable compound containing copper can be listed. usually water-soluble compounds are preferred. Suitable examples of copper com-pounds include copper nitrate, copper s,ulfate r and copper chloride.
As Compound (A2) used herein, any suitable compound containins zinc can be listed Usually water~soluble compounds are preferred. Suitable examples of zinc com-pounds include zinc nitrate, zinc sulfate, and zinc chloride.
As Compound (B), Compound (Bl) or Compound (B2) can be used.
lZ~ V
1 Compound (Bl) used herein, any suitable compound con-taining nickel can be listed. Particularly preferred are water-soluble compounds. Suitable examples of nickel compounds include nickel nitrate nickel sulfate, and nickel chlorideO
Compound (B2) is a compound containing at least one of iron, cobalt and nickel. Particularly preferred are water soluble compounds. Suitable examples are the nitrates, sulfates, and chlorides of the metals.
Compound (Al) can be used in combination with Compound (Bl). Similar by, Compound (A2) can be used in combination with Compound (B2).
Compound (C) is a compound Qf at least one metal selected from the metals belonging to Groups II, III and IV, and the fourth period of Groups V, VI and VII of the Periodic Table. Typical examples of the metals belonging to Groups II, III and IV of the Periodic Table are magnesium, calcium, zinc, boron, aluminum, gallium, lanthanum, silicon, germanium, titanium, tin, and zirconium Suitable examples of the metals belonging to the fourth period of Groups Vr VI and VII of the Periodic Table are vanadium, chromium, and manganese. As Compound (C), various compounds of the metals as described above, such as the nitrates, sulfates, chlorides, and oxides thereof, can be used. Particularly preferred are water-soluble compounds.
As Compound (C), salt of titanium is one of the preferable compounds. Especially sulfate of it is preferable. Other salts such as titanium tetrachloride are undesirable here. When dissolved into water, titanium tetrachloride, for instance, is difficult to treat since it fumes and is hydrolyzed not to be dispersed homogeneously ~.2~
1 Moreover, other salts are insoluble in water.
Titanium sulfate is a favourable salt for dispersing of titanium into catalyst as is descried above, but sulfate radicals tend to remain in catalyst When sulfur portion is 0.5% by weight or more catalytic activity is scarcely observedO
accordingly, when titanium sulfate is employed for producing catalyst, it is inevitable to remove sulfate radicals to make sulfur portion less than 0~5% by weight after precipitate results.
After earnest researches in removal of sulfate radicals, we have found that following two processes are desirable One of the processes is to repeat washing with aqueous solution of sodium chloride after the precipitate results, and to exchange sulfate radicals with chlorine :ions to reduce sulfate radicals, and thus make sulfur portion less than 0.5~ by weight. Thereupon, the con-entration of the aqueous solution of sodium chloride is desired to be 0.1 mole per liter - 5 mole per liter.
Another process is to adjust pH at co-precipitating by addition of sodium carbonate. There, once co-precip-itation is made at pH 9.0 or more, after that the washing with plain water can reduce the sulfate radicals to make 1 25 the sulfur portion less than 0.5~ by weight. When pH is less than 9.0, activity does not arise sufficiently.
., In the preparation of the catalyst of the invention, Compounds (A), (B) and (C) are first mixed and calcined.
3~
l Compounds (A), (B) and (C) can be mixed by techniques such as a co-pr~cipitation met~od~ a kneadiny method t and a dipping method In accordance with the co-pxecipita-tion method, fvr example, they are added to water to form aqueous solutions or suspensions, which are then mixed and co-precipitated by adjusting the pH through addition of a co precipitating agent such as sodium carbonate sodium hydroxide and potassium hydroxide at room temper-ature or at elevated temperatures. Then, the resulting precipitate it aged, if necessary r and washed with water, dried and calcined at a temperature of from 200 to 500C.
The above-calcinated product is then impregnated with Compound (D), i.e., an alkali metal compound and/or an alkaline earth metal compound. Compound (D) is prefer-ably water-soluble. Suitable examples include sodium carbonate and magnesium acetate. In the impregnation of the calcined product, Compound (D) is used as an aqueous solution; tha1: is, the calcined product is impregnated with an aqueous solution of Compound ED). After the process of impregnation the resulting mixture should ye calcined again. This calcination is usually performed at a temperat1lre of from lO0 to 500C~
Although the composition of toe thus-calcined pro-duct varies with the amounts of Compounds (A), (B), (C) and (D) being added, it is necessary for the molar ratio of (A) to (B) to O to (D) (calculated as oxide) to be controlled so that 0.05 < (A) <0.7, O.Ol c 0.7, O.Ol<(C) < 0.7, and 0.005 < (D) <0.3.
The calcined product is then reduced. This reduc-tion is suficient to be performed at a temperature of from 20b to 400C by the use of a reducing atmosphere, for example, in the presence of hydrogen or carbon monoxide.
3~
1 The thus-prepared solid substance is used as the catalyst of the invention.
Although Compounds (A), (B), O and (D) can be mixed -and calcined simultaneously, Compound ED) of alkali ox alkaline earth metal compound is disperc~ed only insuffi-ciently and unevenly in the final product by such a procedure. Hence this procedure fails to produce the desired catalyst.
In the process of the invention, the solid substance as prepared above is used as a catalyst, and synthesis gas, i.e., a mixed gas of hydrogen and carbon monoxide, is contacted with the catalyst to produce a mixed alcoholn The composition of the synthesis gas to be used as a feed in the process o the invention is no ¢ritical.
In general, however, it is preferred to use synthesis gas in which the molar rat:io of hydrogen to carbon monoxide is within the range of from 1:3 to 3^1.
Other reaction condil:ions for the process of the invention are not criticaL and can be determined appropri-ately. The reaction temperature is usually from 200 to 550C and preferably from 240 to 450C; the reaction pres-sure may be relatively lo, in general, ranges between 20 and 200 kilograms per squire centimeter (by gauge) and preferably between 40 and 100 kilograms per square centi-meter (by gauge); and the gas hourly space velocity (GHSV) is from 500 to 100,000 per hour and preferably from 1,000 to 50,000 per hour.
The process of the invention as described above produces mixed alcohols comprising methanol and higher alcohols than methanol, such as ethanol, propanol, and butanol, and other compounds such as aldehydes end esters.
The selectivity of the mixed alcohol is high in the process of the invention. This is one of the advantages of the 36..~
1 present invention. Another advantage is that the costs of equipment and operation, or example, can be greatly reduced, since the reaction pressure in the process of the invention is sufficient to be relatively low. Further-more the proportion of alcohols other than methanol in the mixed alcohol as produced by the process of the invention is relatively high, and thus the mixed alcohol is suitable for use as an alcohol component to be compounded to gasoline.
The present invention is described in greater detail with xeference to the following examples.
I- An aqueous solution (Aqueous Solution I) ~2.5 liters) containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate and 59.5 grams of zinc nitrate (6 hydrate) was prepared and heated to 60C. Separately 2.5 liters of an aqueous solution (Aqueous Solution II) containing 81.3 grams of sodium carbonate (anhydrous) was prepared and heated to 60C.
These aqueous solutions were mixed rapidly and, after completion of precipitation, aged. Then the result-ing mixture was filtered, and the pricipitate thus ob-tained was washed sufficiently with water, dried at 120C
for about 12 hours and then calcined at ~50C for 2 hours The thus-calcined product was impregnated with an aqueous solution (Aqueous Solution III) containing 6.8 grams of sodium carbonate (anhydrous) and dried at;120C
for about 12 hours. Then graphite was added, and the resulting mixture was pelletized and pulverized to produce 16-32 mesh grains. The thus-prepared catalyst ~3~
1 precursor had a composition of Cu:Ni:Zn~Na=0~36:0.18^
0O36:0O10 (molar ratio)O
Then 1 milliliter of the catalyst precursor was packed in a reaction tube of stainless steel While passing a 1:9 (molar ratio) mixture of carbon monoxide and nitrogen as a reduciny gas through the reaction tube at a gas hourly space velocity IGHSV) of 4,000 per hour, the catalyst precursor was gradually heated and reduced at 240C for 5-20 hours to produce a catalyst.
A synthesis gas (carbon monoxide:hydrogen=1:2 (molar ratio)) was introduced int:o the reaction tube at a gas hourly space velocity (GH',V) of 4,000 per hour. The pressure was gradually increased to 50 kilograms per square centimeter (by gauche). Then the tempçrature was increased to a reaction temperature at which the conver-sion of carbon monoxide (excluding the one converted into carbon dioxide) reached about 20%. The reaction products were passed through a tube maintained at 200C, without being condensed at: the outlet of the reaction tube, and introduced into a gas chromatography instrument where they were analyzed. The column filler as used in this gas chromatography analysis was a mixture of activ-ated carbon, Porapak-Q*(produced by Water Co.) and Porapak-R*(produced by Water Co.). The results are shown in Table 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate ~3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 75~0 grams of aluminum nitrate (9 hydrate) was used as * Trade Mark ~2~3~
1 Aqueous Solution I and 2.5 liters of an aqueous solution containing 90.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a com-position of Cu:Ni~Al:Na=0O36:0 a 18:0~36O0.10 (molar ratio).
The catalyst pxecursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared ca~alyst~ the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
~:XAMPLE 3 A catalyst precursor was prepared in the same manner clS in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and '15.0 grams of aluminum nitrate (9 hydrate) was used as l~queous Solution I, 2.5 liters~of an aqueous solution containing 90.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and an aqueous solution containing :L3.7 grams of magnesium acetate (4 hydrate) as Aqueous ';olution III for the process of impregnation. This catalyst precursor had a composition of Cu:Ni:Al:Mg=
0.3600.18:0O36:0.10 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48~3 grams of copper nitrate (3 hydrate), 29~1 grams of nickel nitrate (6 hydrate), and 79.9 grams of gallium nitrate (8 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solu~
tion containing 91.6 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition ox Cu:N~:Ga:Na=0.36:0.1~:0.36:Q.10 (molar ratio)O
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prep-ared catalyst, the production of mixed alcohol from syn-thesis gas was performed in the same manner as in Example 1. The results are shown in Table 1 .:
A catalyst precursor was prepared in toe same manner as in Example 1 except that 2.5 liters of an aqueous solu-tion containing 48.3 grams of copper nitrate (3 hydrate) and 29.1 grams of nickel nitrate (6 hydrate was used as Aqueous Solution I, and 2.5 liters of an aqueous solution containing 61.7 grams of water glass (SiO2 content: 28.6%
by weight) and 37.2 grams of sodium carbonate ~anhydrou~) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Si:Na=0.3~:0.18~0.36:0.10 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst,the production of mixed alcohol from ~Z43~
1 synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1 A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 64.4 grams of zirconium oxychloride (8 hydrate) was used as Agueous Solution I, and 2.5 liters of an aqueous solution containing 63~7 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a compositi.on of Cu:Ni:Zr:Na=0 36:0~18:0.36 0.10 molar ratio).
The catalyst precuror~was reduced in the same manner as in Example 1 to form a catalyst. Using the thus--prepared catalyst, the production of mixed alcohol from synthesis gas was perfornled in the same manner as in - Example 1. The results are shown in Table 1.
ExAMæLE 7 An aqueous solution (2.5 liters) containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 161.1 grams of titanium sulfate (Ti(So4)2 content: 29.8% by weight) was prepared and heated to 60C. Separately 2.5 liters of an aqueous solution containing 128.0 grams of sodium carbonate (anhydrous) was prepared and heated to 60C: These aqueous solutions were mixed rapidly and, after comple-tion of precipitation, aged. The resulting mixture was filtered, and the precipitat- thus obtained was treated 1 with an aqueous solution of sodium chloride (concentra-tion: 0.5 mole per liter) and further washed sufficiently with waterO
Thereafter the same procedure as in Example 1 was performed to form a catalyst precursor. This catalyst precursor had a composit,ion of Cu:NiOTi:Na=0.36^0.18:0.36:
0.10 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table lr A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters of an aqueous solution containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 8000 grams of chromium nitrate was used as Aqueous Solu-tion I, and 2.5 liters of an aqueous solution containing 90.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Cr:Na=0.38:0.19:0.31:0.12 (molar ratio The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. UsinCJ the thus-prepared catalyst, the production of mixed alcoho,l from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
~4~
1 EXAMPLE g A catalyst precurssr was prepared in the same manner as in Example 1 except that 2.5 liters a àn aqueous solution containing 4803 grams of copper nitrate (3 S hydrate), ~9.1 grams of nickel nitrate (6 hydrate), and 86.6 grams of lanthanvm nitrate (6 hydrate) was used as' Aqueous Solution I, and 2u5 liters of an agueous solution containing 74.2 grams of sodium carbonate ~anhydrou~ as Aqueous Solution II. This catalyst precursor had a com-position of Cu:Ni:La:Na=0.36:0.18:0.36:0.10 (molar ratio .
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using -the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1.
The results are shown in Tale 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2.5 liters ox an aqueous solu-tion containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate t6 hydrate), and 86.6 grams of lanthanum nitrate (6 hydrate) was used as Aqueous Solution I, 2.5 liters of an aqueous solution containing 74.2 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and an aqueous solution containing 13.7 grams of magnesium acetate (4 hydrate) as A~ueQus Solution III
for the process of impregnation. This catalyst precursor had a composition of Cu:Ni:La:Mg=0.36:0.18:0.36:0.10 (molar ratio). ;
The catalyst precursor was reduced in the same manner as in Example 1 to form catalyst. Using the thus-1 prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
A catalyst precursor was prepared in the same manner as in Example 1 except that 2~5 liters of an aqueous solu-tion containing 48.3 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 25~6 grams of magnesium nitrate (6 hydrate) was used as Aqueous Solution I, and 2.5 liters of an aqueous solution contain-ing 50.3 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Mg:Na=0.43:0.22:0.22:0.13 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst" the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 1.
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X Z ,, 1 EXP~lPLE 12 An aqueous solution (Aqueous Solution I) (1.5 liters) containing 24.2 grams of copper nitrate (3 hydrate 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate (Ti(So4)2 content 29 8% by weight) was prepared and heated to 60Co Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66~ 3 grams of sodium carbonate (anhydrous) was prepared and heated to 60C. These aqueous solutions~were mixed rapidly and, after completion of precipitation, aged.
The resulting mixture was filtered, and the thus-obtained precipitate was treated with an aqueous sodium chloride solution (concentration: 0.5 mole per liter) and wished sufficiently with water.
... .
The precipitate was dried at 120C for about L2 hours and then calcined at 450C for 2 hours.
The thus-calcined product was impregnated with 38 milliliters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: l.O mole per liter), and dried at 120C for about 12 hours Then graphite was added, and the resulting mixture was pelletized and pul-verized to form 16-32 mesh grains. The thus-prepaced catalyst precursor had a composition of Cu:Ni:Ti:Na=
1:1:1:0.38 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 1 to foxm a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1. The results are shown in Table 2~
~LZ'~3t~
A catalyst precursor was prepared in the same manner as in Example 12 except that 1.5 liters of an aqueous solution containing 1601 grams of copper nitrate (3 hydrate 29.1 grams of nickel nitrate (6 hydrate), and 106.7 qrams of titanium sulfate (the same as used in Example 12) was used as Aqueous Solution I, and 1.5 liters of an aqueous solution containing 79.5 grams of sodium carbonate (anhydrous) as Aqueous Solution II. This catalyst precursor had a composition of Cu:Ni:Ti:Na=
2:3:4 1.15 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
_ . , .
A catalyst: precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous solu-tion containing 24.1 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 28.7 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate ~anhydrous~ as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=1:1:1:0.38 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the 9~Z~3c~
1 thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
ExAMæLE 15 A catalyst precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous solu-tion containing 14.5 grams of copper nitrate (3 hydrate), 8.7 grams of nickel nitrate (6 hydrate), and 60.3 grams of manganese nitrate (6 hydrate) was used as aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole për liter as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=2:1:7:1.28 (molar ratio).
The cata:lyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Usin~.the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
-A catalyst precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous 801u-tion containing 50.7 grams of copper nitrate (3 hydrate), 8.7 grams of nickel nitrate (6 hydrate), and 17.2 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium 1 carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III~ This catal.yst precursor had a composition of Cu:Ni Mn:Na=7:1:2:1O28 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 12 to form a catalystO Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
.
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us o s ,~ l l Us ED O us
The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
_ . , .
A catalyst: precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous solu-tion containing 24.1 grams of copper nitrate (3 hydrate), 29.1 grams of nickel nitrate (6 hydrate), and 28.7 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate ~anhydrous~ as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=1:1:1:0.38 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Using the 9~Z~3c~
1 thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
ExAMæLE 15 A catalyst precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous solu-tion containing 14.5 grams of copper nitrate (3 hydrate), 8.7 grams of nickel nitrate (6 hydrate), and 60.3 grams of manganese nitrate (6 hydrate) was used as aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium carbonate (concentration: 1.0 mole për liter as Aqueous Solution III. This catalyst precursor had a composition of Cu:Ni:Mn:Na=2:1:7:1.28 (molar ratio).
The cata:lyst precursor was reduced in the same manner as in Example 12 to form a catalyst. Usin~.the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
-A catalyst precursor was prepared in the same manner as in Example 1 except that 1.5 liters of an aqueous 801u-tion containing 50.7 grams of copper nitrate (3 hydrate), 8.7 grams of nickel nitrate (6 hydrate), and 17.2 grams of manganese nitrate (6 hydrate) was used as Aqueous Solution I, 1.5 liters of an aqueous solution containing 39.8 grams of sodium carbonate (anhydrous) as Aqueous Solution II, and 38 milliliters of a solution of sodium 1 carbonate (concentration: 1.0 mole per liter) as Aqueous Solution III~ This catal.yst precursor had a composition of Cu:Ni Mn:Na=7:1:2:1O28 (molar ratio).
The catalyst precursor was reduced in the same manner as in Example 12 to form a catalystO Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 12. The results are shown in Table 2.
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An aqueous solution (2.5 liters) containing 59.5 grams of zinc nitrate (6 hydrate), 29.1 grams of cobalt nitrate (6 hydrate, and 25. 6 grams of m~n~ium nitrate was prepared and heated to 60C. Separately 2.5 li~cr5 of an aqueous solution containing 88.3 grams of sodium carbonate (anhydrous) as a co-precipitating agent was prepared and heated to 60C. These aqueous solutions were mixed rapidly and, after completion ox precipita~
tion, aged. Then the resulting mixture was filtered, and the precipitate thus obtained was washed sufficiently with water.
The thus-obtained co-precipitate was dried at 120C
for about 12 hours and then calcined at 450C for 2 hours.
, .
The thus-calcined product was impregnated with an aqueous solution containing 3.4 grams of sodium carbonate ~anhydrous) and then dried at 120C for about 12 hours.
Then graphite was added, and the resulting mixture was pelletized and pulverized to form 16-32 mesh grains.
This catalyst precursor had a composition of Zn:Co:Mg:Na=
0.43:0.22:0.22:0.13 solar ratio.
Then 1 milliliter of the catalyst precursor was packed in a reaction tube of stainless steel. While passing a 1:9 (molar ratio) mixture of carbon monoxide and nitrogen as a reducing gas through the reaction tube at a gas hourly space velocity (GHSV) of 4,Q00 per hour the catalyst precursor was gradually heated and reduced at 240C for 12 hours to produce a catalyst.
A synthesis gas (carbon monoxide:hydrogen=l:2 (molar ratio)) was introduced into the reaction tube at .
1 a gas hourly space velocity (GHSV) of 4,000 per hour.
The pressure was increased to 50 kilograms per sguare centimeter (by gauge). Then the temperature was increased to a reaction temperature at which the conversion of carbon monoxide (excluding the one converted into carbon dioxide) reached about 20%.
The reaction products were introduced, without being condensed at the outlet of the reaction tube, through a tube maintained at 200C into a gas chromatography instru ment where they were analyzed. The column filler as used in this gas chromatography analysis was a mixture of ac-tivated carbon, Porapak-Q (produced by Water Co.), and Porapak-N (produced by Water Co.). The results are shown in Table 3.
..~ .. , i EXAMæLE 18 .
The procedure of Example 17 was repeated wherein l:he preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) ~0.2 grams (co-precipitating agent) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor:
Zn:Co:Al:Na=0.36:0.18: b . 36 o . lo (molar ratio) Thè results are shown in Table 3.
( -The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 90.2 grams (for co-precipitation) magnesium acetate (4 hydrate 13.7 grams Composition of catalyst precursor:
Zn:Co:Al:Mg=0.36:0.18:0036:0.10 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
Zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams gallium nitrate (8 hydrate) 79.9 grams sodium carbonate (anhydrous) 89.2 grams (for co-precipitation) sodium carbonate ~anhydrous) 3.4 grams (for impregnation Composition of catalyst precursor:
Zn:Co:Ga:Na-0.36:0.18:0.36:0.10 molar ratio);
The results are shown in Table 3.
3 Lo The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds-zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams water glass (SiO2 content: 61.7 grams 28.6% by weight) sodium carbonate (anhydrous) 35.3 grams (for ~o-precipitation) sodium carbonate (anhydrous)' 3.4 grams (for impregnation) Composition of catalyst precursor:
Zn:Co:Si:Na=0.36:0.18:0.36:0.10'''(molar ratio) .
The results are shown in Table'3.
.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 trams cobalt nitrate (6 hydrate) 29.1 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 63.8 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor:
Zn:Co:Zr:K=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
Y
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate3 59.5 grams cobalt nitrate (6 hydrate)29.1 grams chromium nitrate ~9 hydrate) 80.0 grams sodium carbonate (anhydrous) 92.5 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precurso r:
Zn:Co:Cr:Na=0.36:0.18:0.36:0.10 (molar iatio) The results are shown in Table 3.
The procedure of Example 17 was cepeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 5g.5 grams cobalt nitrate (6 hydrate)29.1 yrams lanthanum nitrate ~6 hydrate) 86.6 grams sodium carbonate (anhydrous) 74.2 grams (for co-pxecipitation) magnesium acetate (4 hydrate) 13.7 grams Composition of catalyst precursor:
Zn:Co:La:Mg=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
3~
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the . following compounds:
zinc nitrate (6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 81~3 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor:
Zn:Ni:Al:Na=0.36:0.18:0.36:0..10 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the cata.lyst was performed using the following compounds:
zinc nitrate.(6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 70.~ grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams.
(for impregnation) Composition of cakalyst precursor: ;
Zn:Ni:Zr:Na=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
~43~
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate)59.5 grams nickel nitrate (6 hydrate) 29.1 grams Aqueous titanium sulfate161.1 grams solution (Ti(So4)2 content:
29.8~ by weight) sodium carbonate (anhydrous) 133.0 grams (for co-precipitation) .
(After co-precipitation followed by filtration, the resulting co-precipitate was washed with water and further with an aqueous solution of NaCl (0.5 mole per liter) to remove S042-).
sodium carbonate (anhydrous) 4.2 grams for impregnation) Composition of cata]yst precursor:
Zn:Ni:Ti:Na=0.34:0.17:0.34:0.15 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams iron nitrate (9 hydrate) 40.4 grams aluminum nitrate (9 hydrate) 75.0 grams - 2~ -1 sodium carbonate (anhydrous) 93.4 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impxegnation) Composition of catalyst precursor:
Zn:Fe:Al:Na=0.36rO.18:0.36~0.10 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams iron nitrate (9 hydrate) 40.4 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 89.3 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor:
Zn:Fe:Zr:Na-0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
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One and half liters o an aqueous solution l~queous Solution I) containing 24c2 grams of copper nitrate ~3 hydrate 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate solution (Ti~SO412 content 30% by weight) was prepared and heated to 60C. Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 90~C. These aqueous solutions I
and II were mixed rapidly and maintained at 85C for about 2 hours with stirring vigorously to be precipitated The pH of the above described solution was 9.2. Then the solution containing the precipitate was filtered, and the thus obtained precipitate was washed with water in 200 fold amount of the precipitate. i The precipitate was dried at 120C for about 10 hours and then was calcined at 450C for 2 hours. The thus calcined product was cooled to a room temperature, - and then the product was impregnated with l9.r 2 milli-liters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter) in the water bath heated at 90C and evaporated to dryness.
The thus-obtained product was dried at 120C for about 5 hours. Then graphite of 2~ by weight based on the product was added thereto, and the resulting mixture way pel-letized (catalyst precursor). Sulfur content in the thus prepared catalyst precursor is 0.2% by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a cd'alyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centi-meter (by gauge).
~J Lo 3 - 3~
1 The results are shown in Table 4.
A catalyst precursor was prepared in the same manner as in Example 30 except that 1.5 .liters of an aqueous solution containing 199.0 grams of sodium carbonate (anhydrous) was used as Aqueous Solution II and the pH
of the above described soluti.on was 9.9. Sulfur content in the thus-prepared catalyst precursor was 0.1~ by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centi-.
meter (by gauge).
The results are shown in Table 4.
One and half liters of an aqueous solution aqueous Solution I) containing 24.2 grams ox copper n.itrate ~3 hydrate), 29.1 grams of nickel nitrate t6`hydrate), and 80 grams of titanium sulfate solution (Ti(So4)2 content:
30% by weight) was prepared and heated to 60C.
Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 90C. These aqueous solutions I and II were mixed rapidly and main-tained at 85~C or about 2 hours with stirring vigourously 3~ t 1 to be precipitated. The pH of the above described solution was 9.3. Then the solution containing the precipitate was filtered, and thus obtained precipitate was washed with water in 200 fold amount of the precipitate.
The precipitate was sufficiently suspended in 2 liters of an aqueous solution ~80C) of sodium chro~ide concentration: 0.5 mole per liter), and was separated by filtration. Then the precipitate was washed again with water in 200 fold amount of the precipitate.
The precipitate was dried at 120C for about 10 hours and then calcined at 450C for 2 hours. The thus-calcined product was cooled to a room temperature, and then the product was impregnated with 19.2 milliliters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter) in the water bath heated at 90C and evaporated to dryness.
The thus-obtained product was dried at 120C for about 'i hours. Then graphite of 2% by weight based on the product was added thereto, and the resulting mixture was pelletized (catalyst precursor). Sulfur content in the thus-prepared catalyst precursor is 0.2% by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilogxams per square centi-meter (by gauge).
The results are shown in Table 4.
:~43~
o 3~ _ A catalyst precursor was prepared in the same manner as in Example 32 except that 1.5 liters of an aqueous solution containing 15300 grams of sodium carbonate (anhydrous) was used as Aqueous Solution II and the pH of the above solution was 8Ø Sulfur content in the thus-prepared catalyst precursor was 0.5~ by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthes:is gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square genii meter (by gauge).
;l 15 The results are shown in Table 4.
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An aqueous solution (2.5 liters) containing 59.5 grams of zinc nitrate (6 hydrate), 29.1 grams of cobalt nitrate (6 hydrate, and 25. 6 grams of m~n~ium nitrate was prepared and heated to 60C. Separately 2.5 li~cr5 of an aqueous solution containing 88.3 grams of sodium carbonate (anhydrous) as a co-precipitating agent was prepared and heated to 60C. These aqueous solutions were mixed rapidly and, after completion ox precipita~
tion, aged. Then the resulting mixture was filtered, and the precipitate thus obtained was washed sufficiently with water.
The thus-obtained co-precipitate was dried at 120C
for about 12 hours and then calcined at 450C for 2 hours.
, .
The thus-calcined product was impregnated with an aqueous solution containing 3.4 grams of sodium carbonate ~anhydrous) and then dried at 120C for about 12 hours.
Then graphite was added, and the resulting mixture was pelletized and pulverized to form 16-32 mesh grains.
This catalyst precursor had a composition of Zn:Co:Mg:Na=
0.43:0.22:0.22:0.13 solar ratio.
Then 1 milliliter of the catalyst precursor was packed in a reaction tube of stainless steel. While passing a 1:9 (molar ratio) mixture of carbon monoxide and nitrogen as a reducing gas through the reaction tube at a gas hourly space velocity (GHSV) of 4,Q00 per hour the catalyst precursor was gradually heated and reduced at 240C for 12 hours to produce a catalyst.
A synthesis gas (carbon monoxide:hydrogen=l:2 (molar ratio)) was introduced into the reaction tube at .
1 a gas hourly space velocity (GHSV) of 4,000 per hour.
The pressure was increased to 50 kilograms per sguare centimeter (by gauge). Then the temperature was increased to a reaction temperature at which the conversion of carbon monoxide (excluding the one converted into carbon dioxide) reached about 20%.
The reaction products were introduced, without being condensed at the outlet of the reaction tube, through a tube maintained at 200C into a gas chromatography instru ment where they were analyzed. The column filler as used in this gas chromatography analysis was a mixture of ac-tivated carbon, Porapak-Q (produced by Water Co.), and Porapak-N (produced by Water Co.). The results are shown in Table 3.
..~ .. , i EXAMæLE 18 .
The procedure of Example 17 was repeated wherein l:he preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) ~0.2 grams (co-precipitating agent) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor:
Zn:Co:Al:Na=0.36:0.18: b . 36 o . lo (molar ratio) Thè results are shown in Table 3.
( -The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 90.2 grams (for co-precipitation) magnesium acetate (4 hydrate 13.7 grams Composition of catalyst precursor:
Zn:Co:Al:Mg=0.36:0.18:0036:0.10 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
Zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams gallium nitrate (8 hydrate) 79.9 grams sodium carbonate (anhydrous) 89.2 grams (for co-precipitation) sodium carbonate ~anhydrous) 3.4 grams (for impregnation Composition of catalyst precursor:
Zn:Co:Ga:Na-0.36:0.18:0.36:0.10 molar ratio);
The results are shown in Table 3.
3 Lo The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds-zinc nitrate (6 hydrate) 59.5 grams cobalt nitrate (6 hydrate) 29.1 grams water glass (SiO2 content: 61.7 grams 28.6% by weight) sodium carbonate (anhydrous) 35.3 grams (for ~o-precipitation) sodium carbonate (anhydrous)' 3.4 grams (for impregnation) Composition of catalyst precursor:
Zn:Co:Si:Na=0.36:0.18:0.36:0.10'''(molar ratio) .
The results are shown in Table'3.
.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 trams cobalt nitrate (6 hydrate) 29.1 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 63.8 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor:
Zn:Co:Zr:K=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
Y
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate3 59.5 grams cobalt nitrate (6 hydrate)29.1 grams chromium nitrate ~9 hydrate) 80.0 grams sodium carbonate (anhydrous) 92.5 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precurso r:
Zn:Co:Cr:Na=0.36:0.18:0.36:0.10 (molar iatio) The results are shown in Table 3.
The procedure of Example 17 was cepeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 5g.5 grams cobalt nitrate (6 hydrate)29.1 yrams lanthanum nitrate ~6 hydrate) 86.6 grams sodium carbonate (anhydrous) 74.2 grams (for co-pxecipitation) magnesium acetate (4 hydrate) 13.7 grams Composition of catalyst precursor:
Zn:Co:La:Mg=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
3~
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the . following compounds:
zinc nitrate (6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams aluminum nitrate (9 hydrate) 75.0 grams sodium carbonate (anhydrous) 81~3 grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams (for impregnation) Composition of catalyst precursor:
Zn:Ni:Al:Na=0.36:0.18:0.36:0..10 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the cata.lyst was performed using the following compounds:
zinc nitrate.(6 hydrate) 59.5 grams nickel nitrate (6 hydrate) 29.1 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 70.~ grams (for co-precipitation) potassium carbonate (anhydrous) 4.2 grams.
(for impregnation) Composition of cakalyst precursor: ;
Zn:Ni:Zr:Na=0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
~43~
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate)59.5 grams nickel nitrate (6 hydrate) 29.1 grams Aqueous titanium sulfate161.1 grams solution (Ti(So4)2 content:
29.8~ by weight) sodium carbonate (anhydrous) 133.0 grams (for co-precipitation) .
(After co-precipitation followed by filtration, the resulting co-precipitate was washed with water and further with an aqueous solution of NaCl (0.5 mole per liter) to remove S042-).
sodium carbonate (anhydrous) 4.2 grams for impregnation) Composition of cata]yst precursor:
Zn:Ni:Ti:Na=0.34:0.17:0.34:0.15 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams iron nitrate (9 hydrate) 40.4 grams aluminum nitrate (9 hydrate) 75.0 grams - 2~ -1 sodium carbonate (anhydrous) 93.4 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impxegnation) Composition of catalyst precursor:
Zn:Fe:Al:Na=0.36rO.18:0.36~0.10 (molar ratio) The results are shown in Table 3.
The procedure of Example 17 was repeated wherein the preparation of the catalyst was performed using the following compounds:
zinc nitrate (6 hydrate) 59.5 grams iron nitrate (9 hydrate) 40.4 grams zirconium oxychloride (8 hydrate) 64.4 grams sodium carbonate (anhydrous) 89.3 grams (for co-precipitation) sodium carbonate (anhydrous) 3.4 grams (for impregnation) Composition of catalyst precursor:
Zn:Fe:Zr:Na-0.36:0.18:0.36:0.10 (molar ratio) The results are shown in Table 3.
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rl o I: ~o~ o o a O ? so a rQ
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P. 5 O it O oO oO 00 0 0 0 g Go C C
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~L2':~3~
One and half liters o an aqueous solution l~queous Solution I) containing 24c2 grams of copper nitrate ~3 hydrate 29.1 grams of nickel nitrate (6 hydrate), and 80 grams of titanium sulfate solution (Ti~SO412 content 30% by weight) was prepared and heated to 60C. Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 90~C. These aqueous solutions I
and II were mixed rapidly and maintained at 85C for about 2 hours with stirring vigorously to be precipitated The pH of the above described solution was 9.2. Then the solution containing the precipitate was filtered, and the thus obtained precipitate was washed with water in 200 fold amount of the precipitate. i The precipitate was dried at 120C for about 10 hours and then was calcined at 450C for 2 hours. The thus calcined product was cooled to a room temperature, - and then the product was impregnated with l9.r 2 milli-liters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter) in the water bath heated at 90C and evaporated to dryness.
The thus-obtained product was dried at 120C for about 5 hours. Then graphite of 2~ by weight based on the product was added thereto, and the resulting mixture way pel-letized (catalyst precursor). Sulfur content in the thus prepared catalyst precursor is 0.2% by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a cd'alyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centi-meter (by gauge).
~J Lo 3 - 3~
1 The results are shown in Table 4.
A catalyst precursor was prepared in the same manner as in Example 30 except that 1.5 .liters of an aqueous solution containing 199.0 grams of sodium carbonate (anhydrous) was used as Aqueous Solution II and the pH
of the above described soluti.on was 9.9. Sulfur content in the thus-prepared catalyst precursor was 0.1~ by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square centi-.
meter (by gauge).
The results are shown in Table 4.
One and half liters of an aqueous solution aqueous Solution I) containing 24.2 grams ox copper n.itrate ~3 hydrate), 29.1 grams of nickel nitrate t6`hydrate), and 80 grams of titanium sulfate solution (Ti(So4)2 content:
30% by weight) was prepared and heated to 60C.
Separately 1.5 liters of an aqueous solution (Aqueous Solution II) containing 66.3 grams of sodium carbonate (anhydrous) was prepared and heated to 90C. These aqueous solutions I and II were mixed rapidly and main-tained at 85~C or about 2 hours with stirring vigourously 3~ t 1 to be precipitated. The pH of the above described solution was 9.3. Then the solution containing the precipitate was filtered, and thus obtained precipitate was washed with water in 200 fold amount of the precipitate.
The precipitate was sufficiently suspended in 2 liters of an aqueous solution ~80C) of sodium chro~ide concentration: 0.5 mole per liter), and was separated by filtration. Then the precipitate was washed again with water in 200 fold amount of the precipitate.
The precipitate was dried at 120C for about 10 hours and then calcined at 450C for 2 hours. The thus-calcined product was cooled to a room temperature, and then the product was impregnated with 19.2 milliliters of an aqueous solution (Aqueous Solution III) of sodium carbonate (concentration: 1.0 mole per liter) in the water bath heated at 90C and evaporated to dryness.
The thus-obtained product was dried at 120C for about 'i hours. Then graphite of 2% by weight based on the product was added thereto, and the resulting mixture was pelletized (catalyst precursor). Sulfur content in the thus-prepared catalyst precursor is 0.2% by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthesis gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilogxams per square centi-meter (by gauge).
The results are shown in Table 4.
:~43~
o 3~ _ A catalyst precursor was prepared in the same manner as in Example 32 except that 1.5 liters of an aqueous solution containing 15300 grams of sodium carbonate (anhydrous) was used as Aqueous Solution II and the pH of the above solution was 8Ø Sulfur content in the thus-prepared catalyst precursor was 0.5~ by weight.
The catalyst precursor was reduced in the same manner as in Example 1 to form a catalyst. Using the thus-prepared catalyst, the production of mixed alcohol from synthes:is gas was performed in the same manner as in Example 1 except that the reaction pressure was gradually increased to 61 kilograms per square genii meter (by gauge).
;l 15 The results are shown in Table 4.
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Claims (11)
1. A process for producing a mixed alcohol comprising methanol and higher alcohols than methanol by contacting a synthesis gas with a catalyst, wherein the catalyst is a solid substance prepared by:
calcining a mixture of (A2) a zinc compound, (B2)-a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II, III and IV
and the fourth period of Groups V, VI and VII of the Periodic Table, impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound;
wherein the molar ratio of (A2) to (B2) to (C) to (D), calculated as the oxide, is controlled so that 0.05 < (A2) < 0.7 0.01 < (B2) < 0.7 0.01 < (C) < 0.7 and 0.005 < (D) < 0.3;
calcining the resulting mixture; and reducing the thus-calcined product.
calcining a mixture of (A2) a zinc compound, (B2)-a compound of at least one metal selected from iron, cobalt, and nickel, and (C) a compound of at least one metal selected from the metals belonging to Groups II, III and IV
and the fourth period of Groups V, VI and VII of the Periodic Table, impregnating the above-calcined product with (D) an alkali metal compound and/or an alkaline earth metal compound;
wherein the molar ratio of (A2) to (B2) to (C) to (D), calculated as the oxide, is controlled so that 0.05 < (A2) < 0.7 0.01 < (B2) < 0.7 0.01 < (C) < 0.7 and 0.005 < (D) < 0.3;
calcining the resulting mixture; and reducing the thus-calcined product.
2. The process for the production of mixed alcohols as claimed in Claim 1, wherein the Compound (C) is a compound of at least one metal selected from the groups consisting of magnesium, aluminum, gallium, lanthanum, silicon, titanium, zirconium, chromium and manganese.
3. The process for the production of mixed alcohols as claimed in Claim 1, wherein the Compound (D) is a compound of at least one metal selected from the groups consisting of sodium, magnesium and potassium.
4. In a process for producing a mixed alcohol compris-ing methanol and higher alcohols than methanol comprising contacting a synthesis gas with a catalyst whereby methanol and higher alcohols are formed and recovered, the improvement comprising using as said catalyst, a solid catalyst prepared by:
calcining a mixture consisting essentially of (A) from 5 to 70% by weight, calculated as oxide, of a zinc compound, (B) from 1 to 50% of a nickel compound, and (C) from 1 to 70% of an aluminum compound or of a zirconium compound to form a calcined product;
impregnating said calcined product with (D) from 0.1 to 15% of an alkali metal compound;
calcining said calcined product impregnated with said alkali metal compound to form an alkali metal-containing calcined product; and reducing said alkali metal-containing calcined product to form said catalyst.
calcining a mixture consisting essentially of (A) from 5 to 70% by weight, calculated as oxide, of a zinc compound, (B) from 1 to 50% of a nickel compound, and (C) from 1 to 70% of an aluminum compound or of a zirconium compound to form a calcined product;
impregnating said calcined product with (D) from 0.1 to 15% of an alkali metal compound;
calcining said calcined product impregnated with said alkali metal compound to form an alkali metal-containing calcined product; and reducing said alkali metal-containing calcined product to form said catalyst.
5. The process for the production of mixed alcohols as claimed in Claim 4, wherein said component (C) is an aluminum compound.
6. The process for the production of mixed alcohols as claimed in Claim 4, wherein said component (C) is a zirconium compound.
7. The process for the production of mixed alcohols as claimed in Claim 4, wherein the Compound (D) is a compound of at least one metal selected from the group consisting of sodium and potassium.
8. The process for the production of mixed alcohols as.
claimed in Claim 4, wherein the Compound (C) is aluminum compound and the Compound (D) is sodium compound.
claimed in Claim 4, wherein the Compound (C) is aluminum compound and the Compound (D) is sodium compound.
9. The process for the production of mixed alcohols as claimed in Claim 4, wherein the Compound (C) is zirconium compound and the Compound (D) is potassium compound.
10. The process for the production of mixed alcohols as claimed in Claim 4, wherein the Compound (C) is aluminum compound and the Compound (D) is potassium compound.
11. The process for the production of mixed alcohols as claimed in Claim 4, wherein the Compound (C) is zirconium compound and the Compound (D) is sodium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000539853A CA1243044A (en) | 1982-12-29 | 1987-06-16 | Process for the preparation of mixed alcohols |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP229834/1982 | 1982-12-29 | ||
| JP57229834A JPS59122432A (en) | 1982-12-29 | 1982-12-29 | Production of mixed alcohol |
| CA000442014A CA1243042A (en) | 1982-11-29 | 1983-11-25 | Process for the production of mixed alcohols |
| CA000539853A CA1243044A (en) | 1982-12-29 | 1987-06-16 | Process for the preparation of mixed alcohols |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000442014A Division CA1243042A (en) | 1982-11-29 | 1983-11-25 | Process for the production of mixed alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1243044A true CA1243044A (en) | 1988-10-11 |
Family
ID=25670223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000539853A Expired CA1243044A (en) | 1982-12-29 | 1987-06-16 | Process for the preparation of mixed alcohols |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1243044A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113145132A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院上海高等研究院 | Ruthenium-based catalyst and preparation method and application thereof |
-
1987
- 1987-06-16 CA CA000539853A patent/CA1243044A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113145132A (en) * | 2021-04-26 | 2021-07-23 | 中国科学院上海高等研究院 | Ruthenium-based catalyst and preparation method and application thereof |
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