# Patent

## Title
Preparation of bead-form expandable styrene polymers

## Abstract

A catalyst and method for preparing a mixture of lower aliphatic alcohols is provided. The method includes reacting a mixture of carbon monoxide and hydrogen under suitable conditions of temperature and pressure in the presence of a catalyst composition. The catalyst composition comprises rhodium, cobalt, molybdenum and a combination of potassium and rubidium.

## Background
1. Field of the Invention

This invention relates to a catalyst and method for preparing lower aliphatic alcohols. More particularly, this invention relates to the production of a mixture of lower aliphatic alcohols characterized by containing, in addition to methanol, a substantial proportion of alcohols having from 2 to 6 carbon atoms.

2. Description of Background Art

Lower aliphatic alcohols have been proposed as fuel extenders or as replacements for gasoline for fueling internal combustion engines. Certain mixtures of lower aliphatic alcohols have the EPA approval for use and are currently being marketed in the United States. The lower aliphatic alcohols can be produced from domestically available non-petroleum sources. Therefore, their use in fuels would serve to lessen the dependence of the nation on imported petroleum and petroleum products.

Hydrogen and carbon monoxide, or a synthesis gas mixture of hydrogen and carbon monoxide, can be reacted to form lower aliphatic alcohols. The synthesis gas feed stream can be produced from non-petroleum sources, such as coal, biomass or other hydrocarbonaceous materials. The synthesis gas mixture itself is produced in a partial oxidation reaction of the hydrocarbonaceous material in commercially available processes, such as coal gasification.

Numerous catalysts and catalytic methods have been studied in attempts to provide a viable method for the production of aliphatic alcohols from synthesis gas or from a mixture of hydrogen and carbon monoxide. Heretofore, the emphasis has been primarily directed to the production of methanol. In contrast, the present process is directed to a method for producing an alcohol mixture containing, in addition to methanol, a substantial amount of aliphatic alcohols having 2 or more (preferably between 2 to 6) carbon atoms.

One of the shortcomings associated with the known methods of making alcohols from synthesis gas is the substantial amount of hydrocarbons that are coproduced. The hydrocarbons so produced represent a major loss in carbon utilization. Surprisingly, under selected reaction conditions, the catalyst and method of the present invention result in the production of a significant fraction of aliphatic alcohols having from 2 to 6 carbon atoms, without the substantial coproduction of undesirable hydrocarbons.

U.S. Pat. No. 4,096,164 discloses a process for reacting hydrogen and carbon monoxide in the presence of a solid catalyst comprising rhodium with molybdenum or tungsten to produce two carbon atom oxygenated hydrocarbons in which ethanol is the major component. This disclosure is incorporated herein by reference.

U.S. Pat. No. 4,380,589 discloses a Fischer-Tropsch process for producing hydrocarbons with improved selectivity to C.sub.2 -C.sub.4 olefins by contacting hydrogen and carbon monoxide in the presence of a catalyst. The catalyst disclosed comprises molybdenum, a promoter comprising an alkali or alkaline earth metal and a binder comprising an iron-containing calcium aluminate cement.

U.S. Pat. No. 4,607,055 discloses a process for producing lower aliphatic alcohols from a mixture of carbon monoxide and hydrogen in the presence of a catalyst comprising molydbdenum; a metal from the group consisting of cobalt, iron and nickel; and silver. The catalyst is modified by the addition of a promoter from the class consisting of potassium, cesium and rubidium. This disclosure is incorporated herein by reference.

U.S. Pat. No. 4,661,525 discloses a process for producing lower aliphatic alcohols from a mixture of carbon monoxide and hydrogen in the presence of a catalyst comprising molybdenum and a metal selected from the group consisting of cobalt, iron and nickel which has been promoted by an alkali metal selected from the group consisting of potassium, cesium and rubidium. This disclosure is incorporated herein by reference.

EPA No. 119609 discloses a process for producing alcohols from synthesis gas using a catalyst containing molybdenum with tungsten, rhenium and an alkali metal. This disclosure is incorporated herein by reference. E.P. No. 79132 discloses a similar process in which the catalyst contains rhenium, molybdenum and potassium.

Co-assigned application Serial No. 939,392 filed on Dec. 12, 1986 is directed to a process for producing lower aliphatic alcohols from a mixture of carbon monoxide and hydrogen in the presence of a catalyst comprising rhodium, molybdenum and an alkali metal. This disclosure is incorporated herein by reference.

Previous catalytic methods have been notably effective for converting carbon monoxide and hydrogen feedstocks into hydrocarbons or methanol, but none have been particularly selective for providing, in addition to methanol, a substantial yield of a lower aliphatic alcohol mixture at a moderate reaction temperature and reaction pressure.

It has now been discovered that a mixture of carbon monoxide and hydrogen can be reacted to form a mixture of lower aliphatic alcohols containing a substantial amount of lower aliphatic alcohols having from 2 to 6 carbon atoms. This reaction is conducted by contacting a feed mixture containing carbon monoxide and hydrogen, such as synthesis gas, with a novel catalyst composition which exhibits good selectivity for the production of lower aliphatic alcohols under suitable conditions of temperature and pressure. The catalyst composition comprises a mixture of rhodium, cobalt, molybdenum and a combination of potassium and rubidium; especially preferred is a combination of potassium and rubidium in equal atomic ratio. Surprisingly, the prescribed catalyst exhibits a high selectivity for the desired alcohols at a relatively low reaction temperature and pressure.

The lower aliphatic alcohols produced in accordance with the method of the present invention are useful as, among other things, a blending component in hydrocarbon motor fuels.

FIG. 1 is a contour plot illustrating the alcohol selectivity for the catalyst composition of the present invention.

In accordance with this invention, a mixture of carbon monoxide and hydrogen as, for example, a synthesis gas mixture of same, is reacted in the presence of a catalyst composition comprising rhodium, cobalt, and molybdenum which has been modified by the addition of a promoter which includes a combination of potassium and rubidium. The preferred combination of potassium and rubidium includes a potassium to rubidium atomic ratio of from about 0.7-1.0 to about 1.0-1.3, respectively. In a most preferred embodiment, the potassium and rubidium are employed in an equal atomic ratio. As indicated in FIG. 1, when potassium and rubidium are employed in an equal atomic ratio, the present catalyst exhibits the highest degree of selectivity, i.e. 87%, towards alcohols.

The catalyst composition can be prepared in a number of ways known in the art. In general, the use of a catalyst support or carrier comprising a relatively refractory, porous, adsorptive and high surface area material is preferred. Conventional carriers or supports, such as alumina, silica, titania, magnesia, silica-alumina and boron phosphates, are suitable support materials for preparing the catalyst of the present invention. Other conventional carriers or supports are to be considered within the scope of this invention. The disclosure in U.S. Pat. No. 4,098,683 is illustrative and is incorporated herein by reference.

A preferred method for preparing the catalyst composition is to impregnate the carrier with the metal components in the form of a soluble salt. The metal components may be impregnated simultaneously or sequentially. The impregnated carrier is dried and then calcined according to known procedures.

The catalyst composition comprises from about 0.1 to about 3 weight percent rhodium, from about 0.1 to about 3 weiqht percent of cobalt, from about 1 to about 12 weight percent molybdenum and from about 1 to about 20 weight percent of the potassium and rubidium combination. Preferably, all of the components are well dispersed on a carrier or support, the most preferred being gamma-alumina. A preferred catalyst composition comprises from about 0.5 to about 2 weight percent rhodium, from about 0.2 to about 1.4 weight percent cobalt, from about 1 to about 6 weight percent molybdenum and an equal atomic mixture of potassium and rubidium where the total number of moles of alkali atoms is from about 0.01 to about 0.1 moles of atoms per 100 g of catalyst.

In another embodiment, the catalyst composition of the present invention further includes from about 1 part per million to about 100 parts per million of chlorine which, surprisingly, promotes the production of C.sub.2 -C.sub.6 alcohols relative to the production of hydrocarbons, thereby improving the carbon efficiency of the present method.

The carbon monoxide and hydrogen, or a mixture of same, employed to form the lower aliphatic alcohols in this method can be provided from any available source. One particularly useful source is synthesis gas which, for instance, is produced in the gasification of hydrocarbonaceous materials, such as oil, coals and biomass. An effective gasification process is described in U.S. Pat. No. 3,544,291 where a hydrocarbonaceous fuel is partially oxidized with a free oxygen-containing gas in a gas generator. In general, the mole ratio of hydrogen to carbon monoxide employed in this process should range from about 0.5 to about 5 moles of hydrogen per mole of carbon monoxide, with the preferred ratio being from about 0.5 to about 2 moles of hydrogen per mole of carbon monoxide.

The reaction conditions for effecting the conversion of the carbon monoxide-hydrogen feed into lower aliphatic alcohols employing the catalyst of the present invention include a reaction temperature ranging from about 240.degree. C. to about 400.degree. C. with the preferred temperature ranging from about 260.degree. C. to about 310.degree. C.

Effective hydrogenation of carbon monoxide is accomplished at elevated pressures. An effective pressure range for this process is from about 500 to about 3500 psig. A preferred pressure range is from about 750 to about 1500 psig.

The space Velocity employed to effect the conversion of carbon monoxide and hydrogen over the present catalyst to produce the aliphatic alcohols is a significant feature of this method. In general, the space velocity, that is the volume of gas passed through a given volume of catalyst per hour expressed as GHSV (hr.sup.-1), must be at least about 1000. A preferred range is from about 5000 to about 20,000. A highly effective method is realized when the space velocity employed ranges from about 5,000 to about 15,000.

The present invention is more fully described in Examples I-XVIII. In each example, approximately 30 cc of catalyst was diluted with 10 cc of alpha-alumina and packed into a 1/2" I.D. type 316 stainless steel reactor tube. The catalyst was first reduced in flowing hydrogen for 4 hours at 400.degree. C., 1500 psig and 10,000 hr.sup.-1 GHSV. The catalyst was then cooled to reaction temperature and subjected to a mixture of hydrogen and carbon monoxide in the ratio of 2:1, respectively. Reaction pressure was 1500 psig and the GHSV was 10,000 hr .sup.-. The gases emerging from the exit of the reactor were sent through a condenser which liquefied the alcohol and water products. The resulting liquids and non-condensable gases were analyzed by gas chromatography.

Catalytic performance of the catalyst compositions produced in accordance with Examples I-XVIII was evaluated in accordance with the following definitions: ##EQU1## 2. Productivity for Alcohols (P): ##EQU2## 3. Higher Alcohol Ratio (R): ##EQU3## 4. TR=Reaction Temperature

A catalyst was prepared by first impregnating gamma-alumina (Norton SA637) with a 0.06 M solution of ammonium heptamolybdate (Aesai) until the point of incipient wetness. The catalyst precursor was calcined in flowing air (2 SCFH) at 500.degree. C. for 3 hours. The precursor was then coimpregnated with cobalt nitrate (0.17 M) and rhodium nitrate (0.14 M) until the point of incipient wetness. The precursor was dried overnight at 120.degree. C. Cesium carbonate was added to the catalyst to obtain a catalyst composition including the following components (weight percent): 3.38% Mo, 1.14% Rh, 0.7% Co, and 9.21% Cs.

A catalyst was prepared according to Example I except that the concentration of the ammonium heptamolybdate solution was 0.14 M. The composition of the catalyst was weight percent): 6.33% Mo, 1.06% RH, 0.66% Co and 8.99% Cs.

A catalyst was prepared according to Example I except that the concentration of the ammonium heptamolybdate solution was 0.30 M. The composition of the catalyst was (weight percent): 12.1% Mo, 0.93% Rh, 0.68% CO and 9.87% Cs.

The results of the evaluation of the catalysts prepared in Examples I-III are shown in Table I. It is evident that the selectivity is strongly influenced by the concentration of molybdenum and that high selectivity is obtained for molybdenum concentrations in the range of about 3 to about 6%.

A catalyst was prepared according to Example I except that the concentration of the cobalt nitrate was 0.29 M. The composition of the catalyst was (weight percent): 3.30% Mo, 1.10% Rh, 1.20% Co and 9.40% Cs.

A catalyst was prepared according to Example I except that the concentration of ammonia heptamolybdate solution was 0.14 M and the concentrate of cobalt nitrate was 0.05 M. The composition of the catalyst was (weight percent): 6.20% Mo, 0.99% Rh, 0.2% Co and 9.40% Cs.

A catalyst was prepared according to Example V except that the concentration of the cobalt nitrate was 0.29 M. The composition of the catalyst was (weight percent): 6.30% Mo, 1.10% Rh, 1.10% Co and 8.76% Cs.

The catalyst of Examples IV, V and VI were evaluated as described above. The results are compared to those of Examples I and II in Table II. It is evident from these results that cobalt increases the ratio of higher alcohols to methanol and cobalt is most effective in the range of 0.2-1.1 weight percent.

A catalyst was prepared according to Example VI except iron nitrate was used instead of cobalt nitrate at the same concentration. The composition of the catalyst was (weight percent): 5.70% Mo, 1.10% Rh, 1.20% Fe and 7.70% Cs.

A catalyst was prepared according to Example VI except that nickel nitrate was used instead of cobalt nitrate at the same concentration. The composition of the catalyst was (weight percent): 5.80% Mo, 1.00% Rh, 1.10% Ni and 9.80% Cs.

The catalysts of Examples VII and VIII were evaluated as described above. The results are compared in Table III to those obtained with Example VI. These results indicate that cobalt is the preferred element.

A catalyst precursor containing molybdenum, rhodium and cobalt was prepared according to Example I. The precursor was divided into ten equal amounts (Examples IX-XVIII); each was impregnated with potassium carbonate, rubidium carbonate and/or cesium carbonate according to Table IV. In these catalysts the number of moles of alkali atoms was about 0.08 moles of atoms per 100 g of catalyst.

The catalysts of Examples IX-XVIII were evaluated as described above and the results are shown in Table IV and FIG. 1 It is evident that for very selective catalysts, a mixture of potassium and rubidium in which the atomic ratio is in the range of 0.71-1.3/1 is preferred. ______________________________________ Example Mo (weight Percent) Tr      S    P    R ______________________________________ I      3.4             282     82   0.4  0.26 II     6.3             286     75   0.4  0.39 III    12.1            288     58   0.2  0.83 ______________________________________ ______________________________________ Example   Mo     Co       Tr   S     P   R ______________________________________ I         3.4    0.7      282  82    0.4 0.26 IV        3.3    1.2      282  79    0.3 0.32 V         6.2    0.2      284  75    0.3 0.40 II        6.3    0.7      286  75    0.4 0.39 VI        6.3    1.1      283  74    0.3 0.50 ______________________________________ ______________________________________ Example  Group VIII   Tr     S     P   R ______________________________________ VII      Fe           285    51    0.1 0.78 VI       Co           283    74    0.3 0.49 VIII     Ni           285    62    0.4 0.88 ______________________________________ ______________________________________ Example K       Rb      Cs    Tr    S    P    R ______________________________________ IX     1       0       0     290   85   0.6  0.22 X      0       1       0     290   81   0.5  0.28 XI     0       0       1     290   78   0.4  0.33 XII    1/2     1/2     0     290   88   0.5  0.20 XIII   1/2     0       1/2   290   85   0.4  0.24 XIV    0       1/2     1/2   290   81   0.4  0.30 XV     1/3     1/3     1/3   290   83   0.4  0.27 XVI    2/3     1/6     1/6   290   87   0.4  0.22 XVII   1/6     2/3     1/6   290   84   0.3  0.29 XVIII  1/6     1/6     2/3   290   77   0.4  0.32 ______________________________________

## Claims

1. A method for preparing lower aliphatic alcohols which comprises reacting carbon monoxide and hydrogen in the presence of a catalyst composition which includes rhodium, cobalt, molybdenum and a combination of potassium and rubidium, said potassium and rubidium being present in said catalyst composition at an atomic ratio of from between about 0.7-1.0 to about 1.0-1.3, respectively.

2. The method of claim 1 wherein said catalyst composition further includes a support for supporting said rhodium, cobalt, molybdenum and combination of potassium and rubidium.

3. The method of claim 2 wherein said support is selected from the group consisting of alumina, silica, titania, magnesia, silica-alumina and boron phosphates.

4. The method of claim 3 wherein said support is gamma-alumina.

5. The method of claim 1 wherein said reaction takes place at a temperature of about 240.degree. C. to about 400.degree. C.

6. The method of claim 5 wherein said reaction takes place at a temperature of about 260.degree. C. to about 310.degree. C.

7. The method of claim 1 wherein said reaction takes place at a pressure of about 500 to about 3500 psig.

8. The method of claim 7 wherein said reaction takes place at a pressure of about 750 to about 1500 psig.

9. The method of claim 1 wherein said reaction takes place at a gas hourly space velocity of at least about 1000 hr.sup.-1.

10. The method of claim 9 wherein said reaction takes place at a gas hourly space velocity of between about 5000 hr.sup.-1 to about 20,000 hr.sup.-1.

11. The method of claim 1 wherein said catalyst composition includes from about 0.1 to about 3 weight percent of rhodium; from about 0.1 to about 3 weight percent of cobalt; from about 1 to about 12 weight percent of molybdenum; and from about 1 to about 20 weight percent of said combination of potassium and rubidium.

12. The method of claim 11 wherein said catalyst composition includes from about 0.5 to about 2 weight percent of rhodium; from about 0.2 to about 1.4 weight percent of cobalt; and from about 1 to about 6 weight percent of molybdenum.

13. The method of claim 12 wherein said rubidium and potassium are present in said catalyst composition at an equal atomic ratio and wherein the total number of moles of rubidium and potassium is from about 0.01 to about 0.1 per 100 g of catalyst.

14. The method of claim 1 wherein said catalyst composition further comprises from about 1 part per million to about 100 parts per million of chlorine.

15. The method of claim 1 wherein the source of said carbon monoxide and hydrogen is synthesis gas.

16. The method of claim 1 wherein the mole ratio of hydrogen to carbon monoxide is from about 0.5 to about 5 moles of hydrogen per mole o carbon monoxide.

17. A method for preparing lower aliphatic alcohols which comprises reacting carbon monoxide and hydrogen in the presence of a catalyst composition at a temperature of about 240.degree. C. to about 400.degree. C., at a pressure of about 500 to about 3500 psig. and at a gas hourly space velocity of at least about 1000 hr.sup.-1, said catalyst composition including from about 0.1 to about 3 weight percent of rhodium, from about 0.1 to about 3 weight percent of cobalt, from about 1 to about 20 weight percent of a combination of potassium and rubidium, said potassium and rubidium being present in said catalyst composition at an atomic ratio of from between about 0.7-1.0 to about 1.0-1.3, respectively.

18. The method of claim 17 wherein said catalyst composition includes from about 0.5 to about 2 weight percent of rhodium; from about 0.2 to about 1.4 weight percent of colbalt; and from about 1 to about 6 weight percent of molybedenum, wherein said rubidium and potassium are present in said catalyst composition at an equal atomic ratio and wherein the total number of moles of potassium and rubidium is from about 0.01 to about 0.1 per 100 g of catalyst.

19. The method of claim 17 wherein said catalyst composition further comprises from about 1 part per million to about 100 part per million of chlorine.