CATALYSTS FOR PRODUCING ALCOHOLS AND ETHERS FROM SYNTHESIS GAS

Abstract

Catalysts for the production of an alcohol and/or an ether from synthesis gas, methods of making the catalysts, and uses thereof are described. The catalyst can include catalytic Cu metal particles or oxides thereof and/or Ni metal particles or oxides thereof on an alkali metal or alkaline earth metal silicate support.

Claims

1. A catalyst for the conversion of synthesis gas to an alcohol and/or an ether, the catalyst comprising copper (Cu) particles, nickel (Ni) particles, or oxides thereof, or a combination thereof, impregnated in an alkali metal and/or alkaline earth metal silicate support.

2. The catalyst of claim 1, wherein the support is the alkaline earth metal silicate.

3. The catalyst of claim 1, wherein the support is a magnesia-silicate support.

4. The catalyst of claim 1, wherein the catalyst does not include a phosphorous containing compound, a boron containing compound, a phosphorous and boron containing compound, a noble metal or compound thereof, zinc or a compound thereof, or a combination thereof.

5. The catalyst of claim 1, comprising 0.01 wt. % to 5 wt. % Cu.

6. The catalyst of claim 1, comprising 0.01 wt. % to 15 wt. % Ni, preferably 3.9 to 4.0 wt. %

7. The catalyst of claim 1, wherein the catalyst comprises Cu particles and Ni particles or oxides thereof.

8. The catalyst of any claim 7, wherein the catalyst does not include a NiCu alloy,

9. The catalyst of claim 1, wherein a molar ratio of the alkaline earth metal to silicon oxide, preferably Mg:SiO.sub.2, is 10:90 to 40:60.

10. The catalyst of claim 1, wherein the support has a surface area from 100 to 300 m.sup.3/g.

11. The catalyst of claim 1, wherein the support does not include alumina.

12. The catalyst of claim 1, the method comprising impregnating an alkali metal or alkaline earth metal silicate support with a copper (Cu) precursor material, a nickel (Ni) precursor material or both under conditions sufficient to produce the catalyst.

13. The method of claim 12, wherein the support is obtained by contacting a solution comprising ammonia and an alkali metal precursor material, an alkaline earth metal precursor material, or both with SiO.sub.2 under conditions sufficient to produce an alkali metal or alkaline earth metal silicate.

14. The catalyst of claim 12, wherein the ammonia concentration is 0.1 to 7 molar.

15. A process to produce alcohols and/or ethers, the process comprising contacting a gaseous reactant stream comprising hydrogen H.sub.2 and carbon monoxide (CO) with the catalyst of claim 1 under reaction conditions suitable to produce an alcohol, an ether or both.

16. The process of claim 15, wherein the reaction conditions comprise a temperature of 230 to 280° C. and an alcohol is produced.

17. The process of claim 16, wherein the alcohol is methanol, ethanol, propanol or a mixture thereof.

18. The process of claim 15, wherein the reaction conditions comprise a temperature of 285° C. to 310° C. and an ether is produced.

19. The process of claim 18, wherein the ether is dimethyl ether.

20. The catalyst of claim 15, wherein the reaction conditions comprise a pressure of 4.5 to 5.5 MPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0023] A discovery has been made that provides a solution to problems associated with catalysts used to produce alcohols and/or ethers from synthesis gas. The discovery is premised on using a catalyst that includes a Cu and/or Ni particles, or oxides thereof impregnated in an alkali metal or alkaline earth metal support. Such a catalyst allows for production of ethers in a one-step process, providing an economic advantage over conventional two-step ether production processes.

[0024] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections.

A. Catalysts of the Present Invention

[0025] The catalyst of the present invention can be a Cu and/or Ni metal or oxides thereof supported on an alkali metal or alkaline earth metal silicate support. The Cu or Ni supported catalyst can include at least, equal to or between any two of 0.01, 0.05, 0.1, 0.15, 0.5, 1.0. 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, and 5 wt. % of Cu, and/or at least, equal to or between any two of 0.01, 0.05, 0.1, 0.15, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, and 15 wt. % Ni. The catalyst of the present invention can include up to 20 wt. % of the total amount of total catalytic transition metal, from 0.001 wt. % to 20 wt. %, from 0.01 wt. % to 15 wt. %, or from 1 wt. % to 10 wt. % and all wt. % or at least, equal to, or between any two of 0.001 wt. %, 0.01 wt. %, 0.1 wt. %, 1 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt. %, 15 wt. %, and 20 wt. %, with the balance being support. For example, the catalyst can include 1.90 to 2.0 wt. % Cu, 3.9 to 4.0 wt. % Ni, and 94.0 to 94.1 wt. % alkaline earth metal silicate support (e.g., magnesia silicate support). In another example, the catalyst can include 0.1 to 5.0 wt. % Cu, 0.01 to 15 wt. % Ni, and 80.0 to 99.2 wt. % alkaline earth metal silicate support (e.g., magnesia silicate support). The support material can include alkali metal or alkaline earth metal silicates. Non-limiting examples of alkali metals (Column 1 of the Periodic Table) include lithium, sodium, potassium, rubidium, and cesium. Non-limiting examples of alkaline earth metals (Column 2 of the Periodic Table) include Mg, Ca, Sr, and Ba. In a preferred embodiment, the support material is magnesia silicate. The molar ratio of the alkali metal or alkaline earth metal to silicon oxide, can be at least, equal to, or between any two of 10:90, 15:85, 20:80, 25:75, 30:70, 35:65, and 40:60.

B. Preparation of the Catalysts of the Present Invention

[0026] Methods for producing alcohols or dimethyl ether via a one-step process can include impregnating the alkali metal or alkaline earth metal silicate with a Cu or Ni precursor material.

1. Preparation of Support Material

[0027] The support material can be obtained by mixing silica with an aqueous solution of an alkali metal or alkaline earth metal precursor material (e.g., a magnesium salt) at 15 to 30° C. for 1 to 5 hours, or about 2 hours. Precursor materials can include chlorides, nitrates, sulfates or the like. In a preferred embodiments, MgCl.sub.2 is used. In embodiments of the invention, the aqueous solution may have a metal (e.g., Mg.sup.+2) concentration in a range of 0.5 to 5 M and all ranges and values there between including ranges of 0.5 to 0.8 M, 0.8 to 1.1 M, 1.1 to 1.4 M, 1.4 to 1.7 M, 1.7 to 2.0 M, 2.0 to 2.3 M, 2.3 to 2.6 M, 2.6 to 2.9 M, 2.9 to 3.2 M, 3.2 to 3.5 M, 3.5 to 3.8 M, 3.8 to 4.1 M, 4.1 to 4.4 M, 4.4 to 4.7 M, and 4.7 to 5.0 M. In embodiments of the invention, the aqueous solution may have a silica concentration in a range of 40 to 90 wt. % and all ranges and values there between including ranges of 40 to 45 wt. %, 45 to 50 wt. %, 50 to 55 wt. %, 55 to 60 wt. %, 60 to 65 wt. %, 65 to 70 wt. %, 70 to 75 wt. %, 75 to 80 wt. %, 80 to 85 wt. %, and 85 to 90 wt. %. To this mixture, ammonia solution can be added and the solution agitated at 15 to 30° C. for 1 to 5 hours, or about 2 hours. The ammonia concentration can be at least, equal to, or between any two of 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, and 5 Molar. The resulting alkali metal or alkaline earth metal silicate can be separated using known separation techniques (e.g., filtration, centrifugation, etc.), optionally dried, and then calcined in the presence of an oxidizing source (e.g. air) at 300 to 600° C. and all ranges and values there between including ranges of 300 to 320° C., 320 to 340° C., 340 to 360° C., 360 to 380° C., 380 to 400° C., 400 to 420.sup.v, 420 to 440° C., 440 to 460.sup.v, 460 to 480° C., 480 to 500° C., 500 to 520° C., 520 to 540° C., 540 to 560° C., 560 to 580° C., and 580 to 600° C. A temperature ramp for the calcination may be in a range of 1 to 10 ° C./min.sup.−1 and all ranges and values there between including 2° C./min.sup.−1, 3° C./min.sup.−1, 4° C./min.sup.−1, 5° C./min.sup.−1, 6° C./min.sup.−1, 7° C./min.sup.−1, 8° C./min.sup.−1, and 9° C./min.sup.−1.

2. Preparation of Catalyst of the Present Invention

[0028] The prepared support material can be impregnated at least one of a copper precursor salt and a nickel precursor salt to provide an impregnated catalytic precursor. Non-limiting examples of copper salts can include copper nitrate, copper sulfate, copper chloride, or combinations thereof. Non-limiting examples of nickel salts can include, nickel sulfate, nickel chloride, nickel nitrate, or combinations thereof. The copper and/or nickel concentration can be 0.01 to 1 M and all ranges and values there between including ranges of 0.01 to 0.05 M, 0.05 to 0.10 M, 0.10 to 0.15 M, 0.15 to 0.20 M, 0.20 to 0.25 M, 0.25 to 0.30 M, 0.30 to 0.35 M, 0.35 to 0.40 M, 0.40 to 0.45 M, 0.45 to 0.50 M, 0.50 to 0.55 M, 0.55 to 0.60 M, 0.60 to 0.65 M, 0.65 to 0.70 M, 0.70 to 0.75 M, 0.75 to 0.80 M, 0.80 to 0.85 M, 0.85 to 0.90 M, 0.90 to 0.95 M, and 0.95 to 1 M. The concentration can be sufficient to produce a catalyst having a total of 0.01 wt. % to 20 wt. % of catalytic metal. The resulting support material impregnated with catalytic material can be optionally dried for 1 to 24 hours (e.g., 1, 2, 3, 4, 5, 10, 12, 15, 20, 22, 24 hour or all values there between) at 100 to 125° C., or 110 to 120° C. or any range or value there between. The impregnated catalytic precursor can be calcined at a temperature of 300 to 600° C. and all ranges and values there between including ranges of 300 to 320° C., 320 to 340° C., 340 to 360° C., 360 to 380° C., 380 to 400° C., 400 to 420.sup.v, 420 to 440° C., 440 to 460.sup.v, 460 to 480° C., 480 to 500° C., 500 to 520° C., 520 to 540° C., 540 to 560° C., 560 to 580° C., and 580 to 600° C. A temperature ramp for the calcination may be in a range of 1 to 10° C./min.sup.−1 and all ranges and values there between including 2° C./min.sup.−1, 3° C./min.sup.−1, 4° C./min.sup.−1, 5° C./min.sup.−1, 6° C./min.sup.−1, 7° C./min.sup.−1, 8° C./min.sup.−1, and 9° C./min.sup.−1. A time period for calcination can include 1 to 10 hours or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 hours.

[0029] The catalyst can be pelletized or shaped into a form suitable to be used in a catalytic bed. Binders and/or fillers can be used in the palletization process.

C. Method of Producing an Alcohol or an Ether

[0030] The catalyst of the present invention can be used to produce an alcohol and/or ether from synthesis gas. The amount of alcohol and/or ether can be tuned based on the temperature of the reaction. The method can include obtaining a Cu and/or Ni metal supported catalyst of the present invention as described throughout the specification and examples. The catalyst of the present invention can be contacted with a reactant stream that includes H.sub.2 and CO and optional CO.sub.2 under reaction conditions sufficient to produce dimethyl ether and/or methanol. In a preferred embodiment the reactant stream is synthesis gas. Notably, the dimethyl ether is produced in a single-step process with a selectivity of. According to embodiments of the invention, the synthesis gas has a H.sub.2 to CO volumetric ratio in a range of 1 to 3 and all ranges and values there between including ranges of 1 to 1.2, 1.2 to 1.4, 1.4 to 1.6, 1.6 to 1.8, 1.8 to 2.0, 2.0 to 2.2, 2.2 to 2.4, 2.4 to 2.6, 2.6 to 2.8, and 2.8 to 3.0.

[0031] Any type of reactor can be used. By way of example, a fixed bed reactor that includes the catalyst of the present invention in a fixed catalyst bed can be used. In another example, a fluidized bed reactor that includes catalyst of the present invention in a fluidized catalyst bed. In embodiments of the invention, the reaction conditions can include a reaction temperature in a range of 230 to 310° C. or at least, equal to, or between any two of 230° C., 240° C., 250° C., 260° C., 270° C., 280° C., 285° C., 290° C., 295° C., 300° C., 305° C., and 310° C. In embodiments, when more alcohol is desired, the temperature range can be 230° C. to 280° C., or any value or range there between. In embodiments that favor ether production, the temperature range can be 285 to 310° C.

[0032] In embodiments of the invention, the reaction conditions in block 202 can include a reaction pressure in a range of 4.5 to 7.0 MPa or at least, equal to, or between any two of 4.5, 5, 5.5, 6, 6.5, and 7 MPa. In a preferred instance, a pressure range of 4.5 to 5.5 MPa is used. In embodiments of the invention, the reaction conditions can also include a weight hourly space velocity in a range of 1500 to 2000 hr.sup.−1 and all ranges and values there between including 1500 to 1525 hr.sup.−1, 1525 to 1550 hr.sup.−1, 1550 to 1575 hr.sup.−1, 1575 to 1600 hr.sup.−1, 1600 to 1625 hr.sup.−1, 1625 to 1650 hr.sup.−1, 1650 to 1675 hr.sup.−1, 1675 to 1700 hr.sup.−1, 1700 to 1725 hr.sup.−1, 1725 to 1750 hr.sup.−1, 1750 to 1775 hr.sup.−1, 1775 to 1800 hr.sup.−1, 1800 to 1825 hr.sup.−1, 1825 to 1850 hr.sup.−1, 1850 to 1875 hr.sup.−1, 1875 to 1900 hr.sup.−1, 1900 to 1925 hr.sup.−1, 1925 to 1950 hr.sup.−1, 1950 to 1975 hr.sup.−1, 1975 to 2000 hr.sup.−1.

[0033] The products produced can include an alcohol and/or an ether or mixtures thereof. Non-limiting examples of alcohols include methanol, propanol, iso-propanol, ethanol, butanol or mixtures thereof. In a preferred embodiment, methanol is produced. Non-limiting examples of ether compounds include dimethyl ether, diethyl ether, dipropyl ether or mixtures thereof. Mixed ethers can also be produced. In a preferred embodiment dimethyl ether is produced.

EXAMPLES

[0034] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Materials Used

Example 1

Preparation of Catalyst A-K

[0035] Catalyst A. A magnesium chloride (MgCl.sub.2) solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 h, 5 M ammonia solution (200 ml) was added and the mixture was stirred for 2 h. The mixture was then filtered to collect the solid. The collected solid was then washed with hot water, and dried overnight. The dried solid was then calcined at 400° C. in air at the ramp rate of 5° C.min−1 for 4 hr. Material obtained was impregnated with copper (0.31 g from nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in a furnace at 500° C. with a temperature ramp of 5° C. min−1 for 5 hr to produce catalyst A.

[0036] Catalyst B. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 5 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. The mixture was then filtered, washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst B.

[0037] Catalyst C. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 5 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. The mixture was then filtered, washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) and copper (0.31 g copper nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst C.

[0038] Catalyst D. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 7 M ammonia solution. (200 ml) was added and the mixture was stirred for 2 hr. The mixture was then filtered, washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with copper (0.31 g copper nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst D.

[0039] Catalyst E. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 7 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. The mixture was filtered, washed with hot water, and dried overnight before calcination at 400° C. in air at the ramp rate of 5° C. min−1 for 4 h. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 h) to obtain Catalyst E.

[0040] Catalyst F. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 7 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. After stirring, the mixture was filtered and washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) and copper (0.31 g copper nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 h) to obtain Catalyst F.

[0041] Catalyst G. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 1 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. After stirring, the mixture was filtered and washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with copper (0.31 g copper nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst G.

[0042] Catalyst H. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 1 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. After stirring, the mixture was filtered, washed with hot water, and dried overnight to obtain a solid. The solid was calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst H.

[0043] Catalyst I. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 1 M ammonia solution (200 ml) was added and the mixture was stirred for 2 hr. After stirring, the mixture was filtered, washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) and copper (0.31 g copper nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst I.

[0044] Catalyst J. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 5 M ammonia solution (200 ml) was added and the mixture was stirred for 6 hr. After stirring, the mixture was filtered and washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with copper (0.31 g copper nitrate in 50 ml distilled water) for 4 hr followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst J.

[0045] Catalyst K. A MgCl.sub.2 solution (4.18 g in 100 ml distilled water) was mixed with silica (3 g in 50 ml distilled water). After mixing for 2 hr, 5 M ammonia solution. (200 ml) was added and the mixture was stirred for 6 hr. After stirring, the mixture was filtered, washed with hot water, and dried overnight to obtain a solid. The solid was then calcined at 400° C. in air at the ramp rate of 5° C. min−1 for 4 hr. Material obtained was impregnated with nickel (0.84 g nickel nitrate in 50 ml distilled water) for 4 hr, followed by drying overnight at 120° C. to obtain a catalyst precursor. The catalyst precursor was subsequently calcined in static air in the furnace (500° C./5° C. min−1, 5 hr) to obtain Catalyst K.

Example 2

Catalyst Evaluation

[0046] Each of Catalysts A-K was evaluated for the activity, selectivity, and short term and long term stability. Prior to evaluation, all of the catalysts were subjected to activation procedure under the activation conditions including a temperature of 350° C. with a ramp rate of 3° C. min.sup.−1 for 16 hr by 50:50 H.sub.2/N.sub.2 flow. The weight hourly space velocity during the activation was 3600 h.sup.−1. Catalytic evaluation was carried out in a high throughput fixed bed flow reactor setup, which was housed in a temperature controlled system fitted with regulators to maintain target pressure during the reaction. The products of the reactions were analyzed through online gas chromatography (GC) analysis.

[0047] After activation, each of Catalysts A-K was used for production of dimethyl ether and methanol from synthesis gas (syngas) in the single-step production process, according to embodiments of the invention. Catalyst J includes only Cu and catalyst K included only Ni. The target products including methanol and dimethyl ether and side products including methane and carbon dioxide were analyzed. Both of the products are produced in good selectivities over catalysts A-I, along with side products of carbon dioxide and methane. At pressures less than 7 MPa, the side product formation was reduced. In contrast catalyst J and K had low to zero DME selectivity and produced mostly methane and/or paraffins. Thus, the single catalyst performed both methanol formation and methanol dehydration functions as seen in product distributions where methanol and dimethyl ether are produced side by side. The results are tabulated in Table 1.

[0048] Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein can be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

TABLE-US-00001 TABLE 1 Temperature (° C.) 250/300° C. at 5.0 MPa Catalysts A B C D E F G H I J K Conversion 0.2/2.sup.  0.2/0.7 0/3 0.2/2.4 0.5/11  0.4/23  0/4 0.3/46  0.1/4.5 0/3  5/57 (mol. %) Selectivities (mol. %) Alcohols (total) 55/27 0/8 0/32 32/21 0/4 40/19  0/26 0/2 50/50 0/33 0/2  a) MeOH 55/27 0/8 0/32 32/21 0/3 40/18  0/26 0/1 50/50 0/29  0/0.5 b) EtOH 0/0 0/0 0/0 0/0 0/1 0/1 0/0 .sup. 0/0.5 0/0 0/4  0/1  c) PrOH 0/0 0/0 0/0 0/0 0/0 0/0 0/0 .sup. 0/0.5 0/0 0/0   0/0.5 DME 25/42 48/0  0/20  0/40 0/0 17/5   0/49 0/0 20/31 0/11 0/0  Olefins 0/0 0/0 0/0 0/0 0/0 .sup. 0/0.2 0/0 .sup. 0/0.1 0/0 0/0   0/0.1 Paraffins (C.sub.2+)  6/10 0/0 0/2 19/12 0/7 0/4 0/1  0/10 0/3 0/31 0/10 Methane 14/8  52/78 0/40 18/13 100/73  41/55 0/3 100/70  33/10 0/11 100/78  CO.sub.2  0/10  0/14 0/6  0/15  0/13  0/15  0/20  0/20  0/10 0/14 0/10 Temperature (° C.) 250/300° C. at 7.0 MPa Catalysts A B C D E F G H I J K Conversion 1/3 0.5/1.3 1/4 1/4  1/12 0.4/26  1/5  1/52 1/6 1/4 5/65  (mol. %) Selectivities (mol. %) Alcohols (total) 41/21 0/5 12/30 15/18 0/3 50/21 15/24 7/2 10/47 15/33 2/1.sup.  a) MeOH 41/21 0/5 12/30 15/18 0/3 50/20 15/24 7/1 10/46 15/28 2/0.8 b) EtOH 0/0 0/0 0/0 0/0 0/1 0/1 0/0 .sup. 0/0.8 0/1 0/5 0/0.2 c) PrOH 0/0 0/0 0/0 0/0 0/0 0/0 0/0 .sup. 0/0.1 0/0 0/0 0/0.5 DME 18/37 0/0  8/21  0/38 0/0 25/6  19/50 0/0  9/32 9/9 0/0.sup.  Olefins 0/0 0/0 0/0 0/0 0/0 .sup. 0/0.3 0/0 .sup. 0/0.1 0/0 0/0 0/0.1 Paraffins (C.sub.2+) 10/10 0/0 0/2 10/12 0/7 0/4 0/1  0/10 0/3  0/20 2/10  Methane 20/6  95/75 75/30 75/7  95/83 25/50 60/3  85/77 75/10 70/9  95/75.sup.  CO.sub.2  0/24  0/15  0/20  0/58 0/7  0/22  0/20 0/9 0/8  0/27 0/11