CA1299199C - Preparation of alcohols from synthesis gas - Google Patents
Preparation of alcohols from synthesis gasInfo
- Publication number
- CA1299199C CA1299199C CA000567803A CA567803A CA1299199C CA 1299199 C CA1299199 C CA 1299199C CA 000567803 A CA000567803 A CA 000567803A CA 567803 A CA567803 A CA 567803A CA 1299199 C CA1299199 C CA 1299199C
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- accordance
- catalyst
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- catalyst composition
- catalyst zone
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
Abstract of the Disclosure A process for converting synthesis gas (CO + H2) to aliphatic alcohols containing at least 2 carbon atoms comprises the steps of passing the synthesis gas first through a catalyst zone comprising (a) Co metal and/or Co oxide and (b) MgO and/or ZnO (preferably MgO), and then through a catalyst zone comprising (c) Cu metal and/or Cu oxide and (d) ZnO.
Description
~2~ g PREPARATION O~ ALCOHOLS
EROM SYNTHESIS GAS
~ackground This invention relates to the use of a new, effective catalyst system in a process for preparing alcohols Erom a mixture of carbon monoxide and hydrogen (synthesis gas). In anothex aspect, this invention relates to a process for producing higher aliphatic alcohols (C
alcohols) from synthesis gas.
The catalytic production of saturated alcohols from mixtures of carbon monoxide and hydrogen is a well known technology. The primary objective of most of these processes is to produce methanol. Nore recently, however, higher alcohols having two or more carbon atoms per molecule have become increasingly valuable as fuels or as additives -to gasoline. Thus there is a need for developing new, improved catalyst systems and employing them in processes for conver~ing synthesis gas to alcohol products containing substantial amounts of C2-~ alcohols.
Su~mar~ of the Invention It is an object of this invention to produce aliphatic alcohols from a mixture of carbon monoxide and hydrogen (frequently referred to as synthesis gas) employing a ne~, effective catalyst syste!n. It is a further object o~ this invention to catalytically convert carbon monoxide and hydrogen to linear and/or branched aliphatic alcohols, at a high selectivity to C2t alcohols. Other objects and advantages will become apparent from the detailed description and the appended claims.
In accordance with this invention, a process for con~erting synthesis gas to alcohols comprises the steps of ' ~ - .
- .~
~L2~9~
(A) passing a gas mixture comprising (preferably consisting essentially of) carbon monoxide and free hydrogen through a first catalyst zone comprising (preferably consisting essentially of) (a) cobalt metal or at least one compound of cobalt (preferably cobalt oxide) or a mixture of cobalt metal and at least one compound of cobalt, and (b) magnesium oxide (preferred) or zinc oxide or a mixture of magnesium oxide and zinc oxide; and (B) passing the effluent from the first catalyst zone in step (A) through a second catalys-t zone comprising (preferably consis-ting essentially of) (c) copper metal or at least one oxide of copper or a mixture of copper metal and a-t least one oxide of copper, and (d) zinc oxide;
wherein the contacting conditions in catalyst zones (~) and (B) are such as to obtain a product comprising a-t least one aliphatic alcohol (linear and/or branched) having at least 2 (preferably 2-8) carbon atoms per molecule.
In a preferred embodiment, the catalyst composition in the second catalyst zone further comprises (e) an inorganic refractory oxide support material (more preferably alumina). In a particularly preferred embodiment, the catalyst composition in the second catalyst zone consists essentially of components (c), (d) and (e).
Detailed Description of the Invention First Catalyst Zone The catalyst composition in the first catalyst zone (hereinafter referred to as first catalyst composi-tion) can contain any suitable relative amounts of components (a) and (b), as defined a`bove.
The weight percentage of (a) in the first catalyst composition is generally about 5-80 weight-%, preferably about 10-50 weight-%; and the weight percentage of (b) in the first catal~st composition is generally about 5-80 weight-%, preferably about 10-50 weight-%. Preferably, the first catalyst composition comprises ~more preferably consists essentially of) (a) Co and/or CoO and (b) MgO.
Other ingredients and additives besides components (a) and (b) can also be present in the first catalyst composition, as long as their presence does not deleteriously affect the cooperative function of the two essential components (a) and (b). Such optional additives can be alumina, silica, aluminum phosphate, titania, zirconia, clays, zeolites, ~29~99 3230~CA
alkali metal oxides or hydroxides and -the like. These additives, if present, may comprise up to 30 weight-% of the entire first catalyst composition. Presently, however, the presence of these optional additives in the first catalyst composition is not preferred.
The first catalyst composition can be prepared in any suitable manner. In one preferred embodiment, the first catalyst composition is prepared by a process comprising the steps of coprecipitating at least one of carbonates, hydroxides and hydrated oxides (more preferably carbonates) of Co and of Mg (or, less preferably, Zn or mixtures of Mg and Zn in lieu of Mg alone) from aqueous solution containing dissolved compounds of Co and of Mg (or Zn or mixtures of ng and Zn); then heating the formed coprecipitate (preferably after washing of the coprecipitate with water) at a first temperature so as to a-t least partially dry the coprecipitate (more preEerably to reduce the water content to below 20 weight-% of the coprecipitate); and thereafter heating (i.e., calcining) the at least partially dried coprecipitate obtained in the previolls step at a second temperature, which is higher than said first temperature, under such conditions as to substantially convert said at least partially dried coprecipitate obtained in the previous step to oxides of Co and of Mg (or, less preferably, Zn or mixtures of Mg and Zn).
The coprecipitating step can be carried out by adding an aqueous solution of a base (such as NaOH) or of a soluble alkali metal carbonate or bicarbonate or ammonium carbonate or bicarbona-te to an aqueous solution containing soluble compounds of Co and of Mg (or ~n or mix-tures of Mg and Zn) under suitable pH conditions (preferably a-t a pH
of about 6-9). Any compounds of cobalt, magnesium and/or ~inc that are substantially soluble in water can be employed, such as halides~
nitrates, sulfates, bisulfates, carboxylates and the like. At present, the preferred compounds of Co and Mg are Co(NO3)2 and Mg(NO3)2, more preferably their hydrates (with about 6 moles of H20 per mole of nitrate). Any suitable concentration of the above-described compounds in each of the aqueous solutions can be employed so as to give the desired weight ratio or atomic ratio of Co to ~g and/o~ ~n. Preferred concentrations are described in Example I.
Preferably, the formed coprecipitate is separated from the aqueous phase, e.g., by filtration, centrifugation or any other suitable separation technique. Also pre~erably~ the coprecipitate is washed with ~2gl9~99 32304C~
water and, optionally, thereafter with a water-soluble alcoho] or ~qith acetone.
The drying step can be carried under any suitable conditions, at atmospheric or vacuum conditions, preferably a-t a temperature of about 20-150C. The subsequent calcining step can be carriecl out at any suitable conditions in an inert or, preferably, oxidizing atmosphere (e.g., in air). Generally the calcinlng temperature is in the range of from about 150 to about 600C (preferably about 300 to 450C). The time of calcination is preferably in the range of from about 1 hour to about 20 hours.
Other, presently less preferred methods for preparing the first catalyst composition comprise impregnating support materia:l. comprising MgO or ZnO or both (preferably ~IgO alone) with a dissolved cobalt compound, drying the impregnated material (at drying conditions described above) and then calcining the dried material (at calcining cond:itions described above). Or a solution of a cobalt compound can ~e sprayed onto the support material defined above (preferably consisting essentially o-E
MgO), followed by drying and calcining.
The finished first catalyst composition generally has a surface area (determined by BET/N2 method; ASTM D3037) in the range of from about 10 to about 300 m2/g, more preferably from about 20 to about 150 m2/g.
The material can, if desired, be ground and sieved so as to obtain a desired particle size range (preferably 10-80 mesh). The material can also be pelletized or compacted into various shapes (e.g., spherical, cylindrical, trilobal and the like). The first catalyst composition can be heated in the presence of a reducing gas, preferably in a free hydrogen containing gas at about 150-500C, preferably for about 1-20 hours, under such conditions as to at least par-tially reduce cobalt oxide to metallic cobalt. Preferably this reducing step is carried out before the catalyst composition is used in the conversion of synthesis gas to alcohols.
Second ~atalyst ~one The catalyst composition emp:Loyed in the second catalyst zone (hereinafter referred to a second catalys-t composition) comprises a mixture of (c) oxide of copper and/or copper metal and (d) zinc oxide.
The second catalys-t composition can be prepared by any suitable preparation technique. Preferably mixed oxides of Cu and Zn are prepared by coprecipitation of either the hydroxides of copper and zinc and/or the ~2~ 3230~C~
hydrated ox:ides of copper and zinc and/or the carbonates of copper snd zinc, e.g., by addition of a base such as MaOII or a soluble carbona-te such as Na2CO3, to an aqueous solu-tion of copper and zinc salts such as nitrates, halides or sulfates of copper and zinc; a-t least partially drying of the formed coprecipita-te; and then calcining (preferably :Ln air) the coprecipitate under such condi-tions as to at least partially conver-t lt to the oxides of copper and zinc. Drying and calcining conditions in Ihe prepnration of -the second ca-talys-t composition ar0 substant:ially the same as described Eor -the f:irst ca-talyst composition.
It is within the scope of this i.nvention (yet presently less preferred) to impregnate zinc oxide with a copper compound (e.g. J copper nitrate) and then calcine the thus impregnated material under such conditions as to convert the copper compound to CuO.
In a preferred embodiment, an inorgan:i.c refractory ox:ide mater:lal, such as alumina, silica, a]uminosil:Lcate (e.g., clay), t:ltall:i.a, æirconia, chromLa, magnesia, alumina phosphate, z:lrcot~ n phospllate, mixtures of the above an~l the like, preEerably alum:lna, :ls also present :ln sn:id socond c~talyst composltion. More preEerably thc second cataly~at composi-tion is prepared by either coprecipltation of hydroxides and/or hydrated oxides and/or carbonates of copper, zinc and aluminum and subsequen-t calcination under such conditions as to form the oxides of copper, zinc and aluminum; or by coprecipita-tion of hydroxides and/or carbonates of copper and zinc from an aqueous solution containing dispersed alumina, and subsequent calcina-tion; or by the method 25 described in U.S. Patent 3,790,505. CuO-ZnO containing ca-talyst compositions are commercially available from United Catalysts, Inc., Louisville, Kentucky and from BASF Wyandot-te Corporation, Parsippany, New Jersey.
In a preferred embodiment, a CuO-ZnO containing ca-talys-t composition used in the second catalyst zone is pretreated by heating with a reducing gas (e.g, H2, CO), preferably a free hydrogen containing gas, so as to partially reduce CuO -to Cu2O and/or Cu metal, before -the ca-talyst composition is employed in the process of this invent:ion. More preferably, said heating is carried out with a free hydrogen containing 35 gas, more preferably a ll2/N2 mixture at about 200-500C for about 1-20 hours.
' /~ ''`
~29~g~ 32304CA
Preferably the weight ratio of ~u (present as me-tal and/or oxide) to Zn (present as oxide) in the second catalyst composition ranges from about 1:20 to abou-t 20:1, more preferably from about 1:3 to abou~
3:1. If alumina (Al203) or another, less preferred inert refractory material (as defined above) is also present in said catalyst composition, the weight percentage of said inert material (preferably alumina) in the entire second catalyst composition can range from about 1 to about 90 weight-%, preferably from about 10 to about 70 weight-%. Generally the surface area (determined by the BET/N2 method, AST~ D3037) o-f the second catalyst composition ranges from about 10 m2/g to abou-t 300 m2/g, preferably from about 20 m2/g to about 200 m2Jg.
Alcohol Synthesis Any reactant mixture comprising chiefly carbon monoxide and free hydrogen gas (synthesis gas) can be employed in the alcohol synthesis process of this invention. Generally, operable reactants will contain about 5 to about 65 volume percent hydrogeu, about 35 to about 95 volume percent carbon monoxide, about 0 to about 30 vol~e percent carbon dioxide, and about 0 to about 10 volume percent nitrogen. Preferred reactants will have a H2:C0 volume ratio in the range of from about 1 2 to about 4:1, more preferably from about 1:1 to about 3:1. Reaction mixtures suitable for the process of this invention include commercially available synthesis gas. The reactant components, chiefly ~I2 and C0, generally are in admixture when they are introduced into the reaction zone, where the contact with the catalyst compositions occurs.
However, it is possible (yet less preferred) to introduce a carbon monoxide containing gas and a free hydrogen containing gas separately into a suitable reactor and to mix the two feed streams, e.g., by static mixing means located in the reactor, so as to provide a mixture of hydrogen gas and carbon monoxide at the site of contact with the first catalyst compositions ~described above).
Any suitable weight ratio of the first ca-talyst composition to the second catalyst composition can be employed. Generally this weight ratio is in -the range of from about 0.2:1 to about 20:1, preferably in -the range of from about 0.5:1 to about 10:1. More preferably the weight ratio of the first catalyst composition to the second catalyst composition is higher than 1:1, and most preferably is in the range of from about 1.1:1 to about 8:1.
~2~9~
Any suitable reactor or train of reactors -that affords contac-t of the feed (reactant mi~ture) with the ca~alyst compositions contained in the first and second catalyst zones can be employed. Preferably, the catalyst compositions are confined in a stacked fixed bed in a hea-ted reactor (generally tubular), and the reactan-t mixture passes through a layer of the first ca-talyst composition and then through a layer of the second catalyst composition at desired reaction conditions (either upflow or downflow). In another embodiment, the first catalyst composition is placed in a first reactor, and the second catalyst composition is placed in a second reactor in series. *he process of this invention can be carried out as a batch process or, preferably, as a continuous process.
Typical contac-ting conditions to be employed in the synthesis reactions of the invention are well known. The :Eollowing are merely suggested parameters from which the skilled artisan can extrapolate.
Reaction conditions in both catalyst zones generally comprise a reaction temperature in the range of from abont 200C to about 400C, with about 250-350C preferred; and a reaction pressure in the range of Erom about 300 to about 3000 psig, with about 500-1500 psig preferred. Other reac-tion variables such as flow rate of the gas feed mixture and catalys-t volume may be selected in accordance with the particular reactants and reaction vessel involved. Generally, the gas hourly space velocity (GHSV) of the gas feed mixture is in the range of from about 500 to about 10,000 vol/vol/hour (volume of gas mixture per volume of catalyst composition per hour) at S.T.P. condi-tions (0C, 1 atm).
The principal liquid products derived by the reaction of the instant process are straight chain and branched aliphatic alcohols.
Generally, the chemical species produced ~ill be saturated (aliphatic) alcohols containing from about 1 to about 10 carbon atoms. Non-limiting examples of formed aliphatic alcohols are methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-2-butanol, n- and isohexanols, n- and isoheptanols, n- and isooctanols, n- and isodecanols and the like, and mixtures thereof.
~igher aliphatic alcohols having 2-8 carbon atoms per molecule are the prefPrred products of the instant process. The presen-tly more preferred alcohols are those having 2-6 carbon atoms per molecule. It is desirable that the selectivity of C~t alcohols be maintained at ~ z ~ 32~0~C~
acceptably high levels. If one operates within -the teachings of this invention, selectivities to alcohols containing -two carbons or more per molecule will generally be above 20 percent, and be preferably about 30 percent to 60 percent.
The formed liquid product (mainly me-thanol and C2-C8 aliphatic alcohols) can be condensed and then separa-ted into two or ~ore fractions con-taining different alcohols. The separation can be carried out by any conventional technique such as fractionated distillation. Generally, a methanol fraction, an ethanol fraction, a C3-C5 alcohol fraction (useful as additive to gasoline) and a higher alcohol fraction (C5-C8) are obtained, and can be recovered as separate product streams. Gaseous reaction effluents, mainly unreacted hydrogen and carbon monoxide, can be utilized as fuel or can be recycled to the reactant(s) described above.
The following examples are presented in further illustration of the invention and are not to be considered as unduly limiting scope oE
this invention.
~xample I
This example illustrates the preparation of the catalysts used in the first and second catalyst zones.
Catalyst A (CoQ/MgO) was prepared by dissolving 207.3 grams of Co(NO3)2 6H2O and 212.2 grams of Mg(NO3)2-6H2O in 650 cc of distilled water, heating this first solution (pH=3) to about 50C, then dropwise adding the first solution to a second solution comprising 166.3 grams of Na2CO3 in 500 cc of distilled water having a temperature of about 60C
and a pH of 1~. The final mixture of the two solutions, which had a pX
of 7.5, was filtered, and the filter cake of carbonates and/or oxides of Co and Mg was washed by slurring it in 900 cc of distillea wa-ter at 60C.
The slurry was ~iltered, and the filter cake was washed again five more times, as described above. The washed filter cake was dried under an IR
heat lamp in a nitrogen atmosphere and then calcined for 12 hours at a temperature ranging from 220C to 350C. Calcined Catalyst A was crushed and sieved. A 16/40 mesh fraction was recovered, which contained about 33 weight-% Co, about 16 weight-% Mg and about 3 weight-% Na, and had a BETjN2 surface a~ea of about 85 m~/g.
Catalyst B (CoO~ZnO) was prepared substantially in accordance with the procedure for Catalyst A, except that ~n(NO3~3 6H2O was used in ~L2991g9~ 3230l~C~
lieu of Mg(N03)2 6H20. Catalyst B contairled 32 weight-% Co, 25 weight-/~
Zn and 0.4 weight-% Na, and had a BET/N2 surface area of 6~ m2/g.
Catalyst C (CuO/ZnO/Al2~3), prepared substan~ially in accordance with the procedure of Example I of U.S. Patent No. 3,790,505, S was supplied by United Catalysts, Inc., ~ouisville, KY. The material was crushed and sieved so as to obtain a 16/40 mesh fraction. Catalyst C
contained about 35 weight-% Cu, about 35 weigh-t-% 2n, about 4 weight-% ~l (thus about 8 weight-% Al203) and about 4 weight-% graphi-te. The BET/N2 surface area of Catalyst C was of about 40 m2/g.
~
This example illustrates the use of Catalysts A, B and C in the conversion of C0 + H2 (synthesis gas) to alcohols. All test runs were carried out using one and two catalyst layers, respectively, containing 5 cc of one of the catalyst composi-tions of Example I and 25 cc of 3 mm glass beads, placed in a 1" pipe stainless steel reactor, mounted vertically in a furnace equipped with temperature control. Synthesis gas feed passed in a downflow manner through the reactor. The product stream exited the reactor via a cold trap cooled to 0C. The cold trap could be isolated and removed from the system for weighing, so as to determine -the quantity of liquid that it contained. The liquid was weighed and sampled for analysis by gas liquid chromatography.
Table I summarized pertinent information of runs made with catalysts A and C, at comparable process conditions ~temperature:
285-320C; pressure: about 900 psig; gas hourly space -veloci-ty: about 25 2600 volume of feed/volume of catalyst/hour; H2/C0 volume ratio:about 1:1).
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p!; p~ ~ ~ 00 ~ ~n o ~ u ~ ~ ~ I
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Test results in Table I show:
(a) Run 1 using a stacked bed with Catalyst A in the first catalyst layer (first catalyst zone) and Catalys-t C in ~he second (i.e., subsequent) catalyst layer (second catalyst zone), wherein the amount of A was greater than the amount o-f C, yielded more of the desirable C2-C6 alcohol fraction than any of the other runs7 including Run 4 with only Catalyst A and Run 5 with only Catalyst C. The above result is quite unexpected.
(b) Nei-ther Run 1 nor Run 2 yielded undesirable aldehyde by-products. This result is quite unexpected because Run 4 with only Catalyst A yielded considerable amounts of aldehydes.
(c) Invention Run 1 using a greater weight ratio of A to C
than invention ~un 2 yielded more C2-C6 alcohols and is thus considered the preferred mode of this invention.
(d) Control Run 3 using Catalyst C in the :Eirst cataLyst layer and Catalyst A in the second catalyst layer yielded considerably less C2-C6 alcohols and considerably more undesirable gases, aldehydes, esters and water than invention Runs 1 and 2 using Catalyst A in the first catalyst zone and Catalyst C in the second catalyst zone. The results of Run 3 makes the beneficial results of Runs 1 and 2 (higher C2-C6 alcohol yield; no aldehyde formation) even more unexpected and surprising.
The effect of the reaction temperature was investigated for the invention process using a stacked bed of Catalyst A in the first catalyst layer (catalyst zone) and Catalyst C in the second catalyst layer. Test results are summarized in Table II.
- .
~29!9~39 Table II
Run (Invention) (Invention) (Invention) First Catalyst layer A A
5 Second Catalyst layer C C C
Wt. Ratio of A : C 2.7:1 2.7:1 2.7:1 Temperature (C~ 285 300 320 Yield of Organic Products ~mg/g Catalyst/Hour) 1~4 226 536 10 Selectivity (Wt.-%):
to Gaseous l~ydrocarbons 33 33 42 to Methanol 17 15 10 to C2-C6 Alcoho:Ls 40 38 34 to C7+ ~lcohols 3 4 to Aldehydes O O
to Esters 1 2 5 to Liquid Hydrocarbons 6 7 7 Yield of Water (mg/g Catalyst/Hour) 35 29 40 Test results in Table II indicate that at the above test conditions a higher reaction tempera-ture resulted in enhanced overall product yield but in somewhat lower C2-C6 alcohol yield and slightly higher yield of ester by-products. At the present reac-tion conditions, a temperature of about 300-310C is an optimal reaction temperature range (in terms of total product yield, yield of C2-C6 alcohols and yield of undesirable by-products). It is expected that the optimal temperature will be higher when flow rates of syngas are used that are higher than those in these test runs. .
~
In this example the preformance of Catalyst A in a syngas reaction is compared with that of Catalyst B. The experimental s-tep was substantially the same as described in the first paragraph of ~xample II.
Reaction conditions were: reaction temperature of 250C, reaction ~L2~ 3230~CA
pressure of 900 psig, gas hourly space velocity of about 2000 volume/volume catalyst/hour, and H2/CO volume ratio of about 2:1. Test results are summarized in Table III.
Table III
Run 8 Catalyst A-7 B
Yield of Organic Products (mg/g Catalyst/Hour) 212 88 Selectivity (Wt.-%) to Gaseous Hydrocarbons 30 33 to Methanol 5 3 to C2-C7 Alcohols 28 18 to Aldehydes 20 25 to Liquid Hydrocarbons 17 21 ~ield of Water (mg/g Catalyst/Flow) 178 38 Data in Table III show that Catalyst B (CoO/ZnO) is an active catalyst for the conversion of syngas to higher alcohols, but is not as active and selective to alcohols as Catalyst A. Based on these resul-ts, it is concluded that a CoO/ZnO catalyst composition can be used in the irst catalyst zone of the process of this inven-tio~, but the CoO/MgO
catalyst composition is more preferred than the CoO/ZnO catalyst composition.
Reasonable variations, modifica-tions and adaptations for various usages and conditions can be made within the scope of the disclosure and ~he appended claims, without departing from the scope of this invention.
EROM SYNTHESIS GAS
~ackground This invention relates to the use of a new, effective catalyst system in a process for preparing alcohols Erom a mixture of carbon monoxide and hydrogen (synthesis gas). In anothex aspect, this invention relates to a process for producing higher aliphatic alcohols (C
alcohols) from synthesis gas.
The catalytic production of saturated alcohols from mixtures of carbon monoxide and hydrogen is a well known technology. The primary objective of most of these processes is to produce methanol. Nore recently, however, higher alcohols having two or more carbon atoms per molecule have become increasingly valuable as fuels or as additives -to gasoline. Thus there is a need for developing new, improved catalyst systems and employing them in processes for conver~ing synthesis gas to alcohol products containing substantial amounts of C2-~ alcohols.
Su~mar~ of the Invention It is an object of this invention to produce aliphatic alcohols from a mixture of carbon monoxide and hydrogen (frequently referred to as synthesis gas) employing a ne~, effective catalyst syste!n. It is a further object o~ this invention to catalytically convert carbon monoxide and hydrogen to linear and/or branched aliphatic alcohols, at a high selectivity to C2t alcohols. Other objects and advantages will become apparent from the detailed description and the appended claims.
In accordance with this invention, a process for con~erting synthesis gas to alcohols comprises the steps of ' ~ - .
- .~
~L2~9~
(A) passing a gas mixture comprising (preferably consisting essentially of) carbon monoxide and free hydrogen through a first catalyst zone comprising (preferably consisting essentially of) (a) cobalt metal or at least one compound of cobalt (preferably cobalt oxide) or a mixture of cobalt metal and at least one compound of cobalt, and (b) magnesium oxide (preferred) or zinc oxide or a mixture of magnesium oxide and zinc oxide; and (B) passing the effluent from the first catalyst zone in step (A) through a second catalys-t zone comprising (preferably consis-ting essentially of) (c) copper metal or at least one oxide of copper or a mixture of copper metal and a-t least one oxide of copper, and (d) zinc oxide;
wherein the contacting conditions in catalyst zones (~) and (B) are such as to obtain a product comprising a-t least one aliphatic alcohol (linear and/or branched) having at least 2 (preferably 2-8) carbon atoms per molecule.
In a preferred embodiment, the catalyst composition in the second catalyst zone further comprises (e) an inorganic refractory oxide support material (more preferably alumina). In a particularly preferred embodiment, the catalyst composition in the second catalyst zone consists essentially of components (c), (d) and (e).
Detailed Description of the Invention First Catalyst Zone The catalyst composition in the first catalyst zone (hereinafter referred to as first catalyst composi-tion) can contain any suitable relative amounts of components (a) and (b), as defined a`bove.
The weight percentage of (a) in the first catalyst composition is generally about 5-80 weight-%, preferably about 10-50 weight-%; and the weight percentage of (b) in the first catal~st composition is generally about 5-80 weight-%, preferably about 10-50 weight-%. Preferably, the first catalyst composition comprises ~more preferably consists essentially of) (a) Co and/or CoO and (b) MgO.
Other ingredients and additives besides components (a) and (b) can also be present in the first catalyst composition, as long as their presence does not deleteriously affect the cooperative function of the two essential components (a) and (b). Such optional additives can be alumina, silica, aluminum phosphate, titania, zirconia, clays, zeolites, ~29~99 3230~CA
alkali metal oxides or hydroxides and -the like. These additives, if present, may comprise up to 30 weight-% of the entire first catalyst composition. Presently, however, the presence of these optional additives in the first catalyst composition is not preferred.
The first catalyst composition can be prepared in any suitable manner. In one preferred embodiment, the first catalyst composition is prepared by a process comprising the steps of coprecipitating at least one of carbonates, hydroxides and hydrated oxides (more preferably carbonates) of Co and of Mg (or, less preferably, Zn or mixtures of Mg and Zn in lieu of Mg alone) from aqueous solution containing dissolved compounds of Co and of Mg (or Zn or mixtures of ng and Zn); then heating the formed coprecipitate (preferably after washing of the coprecipitate with water) at a first temperature so as to a-t least partially dry the coprecipitate (more preEerably to reduce the water content to below 20 weight-% of the coprecipitate); and thereafter heating (i.e., calcining) the at least partially dried coprecipitate obtained in the previolls step at a second temperature, which is higher than said first temperature, under such conditions as to substantially convert said at least partially dried coprecipitate obtained in the previous step to oxides of Co and of Mg (or, less preferably, Zn or mixtures of Mg and Zn).
The coprecipitating step can be carried out by adding an aqueous solution of a base (such as NaOH) or of a soluble alkali metal carbonate or bicarbonate or ammonium carbonate or bicarbona-te to an aqueous solution containing soluble compounds of Co and of Mg (or ~n or mix-tures of Mg and Zn) under suitable pH conditions (preferably a-t a pH
of about 6-9). Any compounds of cobalt, magnesium and/or ~inc that are substantially soluble in water can be employed, such as halides~
nitrates, sulfates, bisulfates, carboxylates and the like. At present, the preferred compounds of Co and Mg are Co(NO3)2 and Mg(NO3)2, more preferably their hydrates (with about 6 moles of H20 per mole of nitrate). Any suitable concentration of the above-described compounds in each of the aqueous solutions can be employed so as to give the desired weight ratio or atomic ratio of Co to ~g and/o~ ~n. Preferred concentrations are described in Example I.
Preferably, the formed coprecipitate is separated from the aqueous phase, e.g., by filtration, centrifugation or any other suitable separation technique. Also pre~erably~ the coprecipitate is washed with ~2gl9~99 32304C~
water and, optionally, thereafter with a water-soluble alcoho] or ~qith acetone.
The drying step can be carried under any suitable conditions, at atmospheric or vacuum conditions, preferably a-t a temperature of about 20-150C. The subsequent calcining step can be carriecl out at any suitable conditions in an inert or, preferably, oxidizing atmosphere (e.g., in air). Generally the calcinlng temperature is in the range of from about 150 to about 600C (preferably about 300 to 450C). The time of calcination is preferably in the range of from about 1 hour to about 20 hours.
Other, presently less preferred methods for preparing the first catalyst composition comprise impregnating support materia:l. comprising MgO or ZnO or both (preferably ~IgO alone) with a dissolved cobalt compound, drying the impregnated material (at drying conditions described above) and then calcining the dried material (at calcining cond:itions described above). Or a solution of a cobalt compound can ~e sprayed onto the support material defined above (preferably consisting essentially o-E
MgO), followed by drying and calcining.
The finished first catalyst composition generally has a surface area (determined by BET/N2 method; ASTM D3037) in the range of from about 10 to about 300 m2/g, more preferably from about 20 to about 150 m2/g.
The material can, if desired, be ground and sieved so as to obtain a desired particle size range (preferably 10-80 mesh). The material can also be pelletized or compacted into various shapes (e.g., spherical, cylindrical, trilobal and the like). The first catalyst composition can be heated in the presence of a reducing gas, preferably in a free hydrogen containing gas at about 150-500C, preferably for about 1-20 hours, under such conditions as to at least par-tially reduce cobalt oxide to metallic cobalt. Preferably this reducing step is carried out before the catalyst composition is used in the conversion of synthesis gas to alcohols.
Second ~atalyst ~one The catalyst composition emp:Loyed in the second catalyst zone (hereinafter referred to a second catalys-t composition) comprises a mixture of (c) oxide of copper and/or copper metal and (d) zinc oxide.
The second catalys-t composition can be prepared by any suitable preparation technique. Preferably mixed oxides of Cu and Zn are prepared by coprecipitation of either the hydroxides of copper and zinc and/or the ~2~ 3230~C~
hydrated ox:ides of copper and zinc and/or the carbonates of copper snd zinc, e.g., by addition of a base such as MaOII or a soluble carbona-te such as Na2CO3, to an aqueous solu-tion of copper and zinc salts such as nitrates, halides or sulfates of copper and zinc; a-t least partially drying of the formed coprecipita-te; and then calcining (preferably :Ln air) the coprecipitate under such condi-tions as to at least partially conver-t lt to the oxides of copper and zinc. Drying and calcining conditions in Ihe prepnration of -the second ca-talys-t composition ar0 substant:ially the same as described Eor -the f:irst ca-talyst composition.
It is within the scope of this i.nvention (yet presently less preferred) to impregnate zinc oxide with a copper compound (e.g. J copper nitrate) and then calcine the thus impregnated material under such conditions as to convert the copper compound to CuO.
In a preferred embodiment, an inorgan:i.c refractory ox:ide mater:lal, such as alumina, silica, a]uminosil:Lcate (e.g., clay), t:ltall:i.a, æirconia, chromLa, magnesia, alumina phosphate, z:lrcot~ n phospllate, mixtures of the above an~l the like, preEerably alum:lna, :ls also present :ln sn:id socond c~talyst composltion. More preEerably thc second cataly~at composi-tion is prepared by either coprecipltation of hydroxides and/or hydrated oxides and/or carbonates of copper, zinc and aluminum and subsequen-t calcination under such conditions as to form the oxides of copper, zinc and aluminum; or by coprecipita-tion of hydroxides and/or carbonates of copper and zinc from an aqueous solution containing dispersed alumina, and subsequent calcina-tion; or by the method 25 described in U.S. Patent 3,790,505. CuO-ZnO containing ca-talyst compositions are commercially available from United Catalysts, Inc., Louisville, Kentucky and from BASF Wyandot-te Corporation, Parsippany, New Jersey.
In a preferred embodiment, a CuO-ZnO containing ca-talys-t composition used in the second catalyst zone is pretreated by heating with a reducing gas (e.g, H2, CO), preferably a free hydrogen containing gas, so as to partially reduce CuO -to Cu2O and/or Cu metal, before -the ca-talyst composition is employed in the process of this invent:ion. More preferably, said heating is carried out with a free hydrogen containing 35 gas, more preferably a ll2/N2 mixture at about 200-500C for about 1-20 hours.
' /~ ''`
~29~g~ 32304CA
Preferably the weight ratio of ~u (present as me-tal and/or oxide) to Zn (present as oxide) in the second catalyst composition ranges from about 1:20 to abou-t 20:1, more preferably from about 1:3 to abou~
3:1. If alumina (Al203) or another, less preferred inert refractory material (as defined above) is also present in said catalyst composition, the weight percentage of said inert material (preferably alumina) in the entire second catalyst composition can range from about 1 to about 90 weight-%, preferably from about 10 to about 70 weight-%. Generally the surface area (determined by the BET/N2 method, AST~ D3037) o-f the second catalyst composition ranges from about 10 m2/g to abou-t 300 m2/g, preferably from about 20 m2/g to about 200 m2Jg.
Alcohol Synthesis Any reactant mixture comprising chiefly carbon monoxide and free hydrogen gas (synthesis gas) can be employed in the alcohol synthesis process of this invention. Generally, operable reactants will contain about 5 to about 65 volume percent hydrogeu, about 35 to about 95 volume percent carbon monoxide, about 0 to about 30 vol~e percent carbon dioxide, and about 0 to about 10 volume percent nitrogen. Preferred reactants will have a H2:C0 volume ratio in the range of from about 1 2 to about 4:1, more preferably from about 1:1 to about 3:1. Reaction mixtures suitable for the process of this invention include commercially available synthesis gas. The reactant components, chiefly ~I2 and C0, generally are in admixture when they are introduced into the reaction zone, where the contact with the catalyst compositions occurs.
However, it is possible (yet less preferred) to introduce a carbon monoxide containing gas and a free hydrogen containing gas separately into a suitable reactor and to mix the two feed streams, e.g., by static mixing means located in the reactor, so as to provide a mixture of hydrogen gas and carbon monoxide at the site of contact with the first catalyst compositions ~described above).
Any suitable weight ratio of the first ca-talyst composition to the second catalyst composition can be employed. Generally this weight ratio is in -the range of from about 0.2:1 to about 20:1, preferably in -the range of from about 0.5:1 to about 10:1. More preferably the weight ratio of the first catalyst composition to the second catalyst composition is higher than 1:1, and most preferably is in the range of from about 1.1:1 to about 8:1.
~2~9~
Any suitable reactor or train of reactors -that affords contac-t of the feed (reactant mi~ture) with the ca~alyst compositions contained in the first and second catalyst zones can be employed. Preferably, the catalyst compositions are confined in a stacked fixed bed in a hea-ted reactor (generally tubular), and the reactan-t mixture passes through a layer of the first ca-talyst composition and then through a layer of the second catalyst composition at desired reaction conditions (either upflow or downflow). In another embodiment, the first catalyst composition is placed in a first reactor, and the second catalyst composition is placed in a second reactor in series. *he process of this invention can be carried out as a batch process or, preferably, as a continuous process.
Typical contac-ting conditions to be employed in the synthesis reactions of the invention are well known. The :Eollowing are merely suggested parameters from which the skilled artisan can extrapolate.
Reaction conditions in both catalyst zones generally comprise a reaction temperature in the range of from abont 200C to about 400C, with about 250-350C preferred; and a reaction pressure in the range of Erom about 300 to about 3000 psig, with about 500-1500 psig preferred. Other reac-tion variables such as flow rate of the gas feed mixture and catalys-t volume may be selected in accordance with the particular reactants and reaction vessel involved. Generally, the gas hourly space velocity (GHSV) of the gas feed mixture is in the range of from about 500 to about 10,000 vol/vol/hour (volume of gas mixture per volume of catalyst composition per hour) at S.T.P. condi-tions (0C, 1 atm).
The principal liquid products derived by the reaction of the instant process are straight chain and branched aliphatic alcohols.
Generally, the chemical species produced ~ill be saturated (aliphatic) alcohols containing from about 1 to about 10 carbon atoms. Non-limiting examples of formed aliphatic alcohols are methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, n-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-2-butanol, n- and isohexanols, n- and isoheptanols, n- and isooctanols, n- and isodecanols and the like, and mixtures thereof.
~igher aliphatic alcohols having 2-8 carbon atoms per molecule are the prefPrred products of the instant process. The presen-tly more preferred alcohols are those having 2-6 carbon atoms per molecule. It is desirable that the selectivity of C~t alcohols be maintained at ~ z ~ 32~0~C~
acceptably high levels. If one operates within -the teachings of this invention, selectivities to alcohols containing -two carbons or more per molecule will generally be above 20 percent, and be preferably about 30 percent to 60 percent.
The formed liquid product (mainly me-thanol and C2-C8 aliphatic alcohols) can be condensed and then separa-ted into two or ~ore fractions con-taining different alcohols. The separation can be carried out by any conventional technique such as fractionated distillation. Generally, a methanol fraction, an ethanol fraction, a C3-C5 alcohol fraction (useful as additive to gasoline) and a higher alcohol fraction (C5-C8) are obtained, and can be recovered as separate product streams. Gaseous reaction effluents, mainly unreacted hydrogen and carbon monoxide, can be utilized as fuel or can be recycled to the reactant(s) described above.
The following examples are presented in further illustration of the invention and are not to be considered as unduly limiting scope oE
this invention.
~xample I
This example illustrates the preparation of the catalysts used in the first and second catalyst zones.
Catalyst A (CoQ/MgO) was prepared by dissolving 207.3 grams of Co(NO3)2 6H2O and 212.2 grams of Mg(NO3)2-6H2O in 650 cc of distilled water, heating this first solution (pH=3) to about 50C, then dropwise adding the first solution to a second solution comprising 166.3 grams of Na2CO3 in 500 cc of distilled water having a temperature of about 60C
and a pH of 1~. The final mixture of the two solutions, which had a pX
of 7.5, was filtered, and the filter cake of carbonates and/or oxides of Co and Mg was washed by slurring it in 900 cc of distillea wa-ter at 60C.
The slurry was ~iltered, and the filter cake was washed again five more times, as described above. The washed filter cake was dried under an IR
heat lamp in a nitrogen atmosphere and then calcined for 12 hours at a temperature ranging from 220C to 350C. Calcined Catalyst A was crushed and sieved. A 16/40 mesh fraction was recovered, which contained about 33 weight-% Co, about 16 weight-% Mg and about 3 weight-% Na, and had a BETjN2 surface a~ea of about 85 m~/g.
Catalyst B (CoO~ZnO) was prepared substantially in accordance with the procedure for Catalyst A, except that ~n(NO3~3 6H2O was used in ~L2991g9~ 3230l~C~
lieu of Mg(N03)2 6H20. Catalyst B contairled 32 weight-% Co, 25 weight-/~
Zn and 0.4 weight-% Na, and had a BET/N2 surface area of 6~ m2/g.
Catalyst C (CuO/ZnO/Al2~3), prepared substan~ially in accordance with the procedure of Example I of U.S. Patent No. 3,790,505, S was supplied by United Catalysts, Inc., ~ouisville, KY. The material was crushed and sieved so as to obtain a 16/40 mesh fraction. Catalyst C
contained about 35 weight-% Cu, about 35 weigh-t-% 2n, about 4 weight-% ~l (thus about 8 weight-% Al203) and about 4 weight-% graphi-te. The BET/N2 surface area of Catalyst C was of about 40 m2/g.
~
This example illustrates the use of Catalysts A, B and C in the conversion of C0 + H2 (synthesis gas) to alcohols. All test runs were carried out using one and two catalyst layers, respectively, containing 5 cc of one of the catalyst composi-tions of Example I and 25 cc of 3 mm glass beads, placed in a 1" pipe stainless steel reactor, mounted vertically in a furnace equipped with temperature control. Synthesis gas feed passed in a downflow manner through the reactor. The product stream exited the reactor via a cold trap cooled to 0C. The cold trap could be isolated and removed from the system for weighing, so as to determine -the quantity of liquid that it contained. The liquid was weighed and sampled for analysis by gas liquid chromatography.
Table I summarized pertinent information of runs made with catalysts A and C, at comparable process conditions ~temperature:
285-320C; pressure: about 900 psig; gas hourly space -veloci-ty: about 25 2600 volume of feed/volume of catalyst/hour; H2/C0 volume ratio:about 1:1).
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Test results in Table I show:
(a) Run 1 using a stacked bed with Catalyst A in the first catalyst layer (first catalyst zone) and Catalys-t C in ~he second (i.e., subsequent) catalyst layer (second catalyst zone), wherein the amount of A was greater than the amount o-f C, yielded more of the desirable C2-C6 alcohol fraction than any of the other runs7 including Run 4 with only Catalyst A and Run 5 with only Catalyst C. The above result is quite unexpected.
(b) Nei-ther Run 1 nor Run 2 yielded undesirable aldehyde by-products. This result is quite unexpected because Run 4 with only Catalyst A yielded considerable amounts of aldehydes.
(c) Invention Run 1 using a greater weight ratio of A to C
than invention ~un 2 yielded more C2-C6 alcohols and is thus considered the preferred mode of this invention.
(d) Control Run 3 using Catalyst C in the :Eirst cataLyst layer and Catalyst A in the second catalyst layer yielded considerably less C2-C6 alcohols and considerably more undesirable gases, aldehydes, esters and water than invention Runs 1 and 2 using Catalyst A in the first catalyst zone and Catalyst C in the second catalyst zone. The results of Run 3 makes the beneficial results of Runs 1 and 2 (higher C2-C6 alcohol yield; no aldehyde formation) even more unexpected and surprising.
The effect of the reaction temperature was investigated for the invention process using a stacked bed of Catalyst A in the first catalyst layer (catalyst zone) and Catalyst C in the second catalyst layer. Test results are summarized in Table II.
- .
~29!9~39 Table II
Run (Invention) (Invention) (Invention) First Catalyst layer A A
5 Second Catalyst layer C C C
Wt. Ratio of A : C 2.7:1 2.7:1 2.7:1 Temperature (C~ 285 300 320 Yield of Organic Products ~mg/g Catalyst/Hour) 1~4 226 536 10 Selectivity (Wt.-%):
to Gaseous l~ydrocarbons 33 33 42 to Methanol 17 15 10 to C2-C6 Alcoho:Ls 40 38 34 to C7+ ~lcohols 3 4 to Aldehydes O O
to Esters 1 2 5 to Liquid Hydrocarbons 6 7 7 Yield of Water (mg/g Catalyst/Hour) 35 29 40 Test results in Table II indicate that at the above test conditions a higher reaction tempera-ture resulted in enhanced overall product yield but in somewhat lower C2-C6 alcohol yield and slightly higher yield of ester by-products. At the present reac-tion conditions, a temperature of about 300-310C is an optimal reaction temperature range (in terms of total product yield, yield of C2-C6 alcohols and yield of undesirable by-products). It is expected that the optimal temperature will be higher when flow rates of syngas are used that are higher than those in these test runs. .
~
In this example the preformance of Catalyst A in a syngas reaction is compared with that of Catalyst B. The experimental s-tep was substantially the same as described in the first paragraph of ~xample II.
Reaction conditions were: reaction temperature of 250C, reaction ~L2~ 3230~CA
pressure of 900 psig, gas hourly space velocity of about 2000 volume/volume catalyst/hour, and H2/CO volume ratio of about 2:1. Test results are summarized in Table III.
Table III
Run 8 Catalyst A-7 B
Yield of Organic Products (mg/g Catalyst/Hour) 212 88 Selectivity (Wt.-%) to Gaseous Hydrocarbons 30 33 to Methanol 5 3 to C2-C7 Alcohols 28 18 to Aldehydes 20 25 to Liquid Hydrocarbons 17 21 ~ield of Water (mg/g Catalyst/Flow) 178 38 Data in Table III show that Catalyst B (CoO/ZnO) is an active catalyst for the conversion of syngas to higher alcohols, but is not as active and selective to alcohols as Catalyst A. Based on these resul-ts, it is concluded that a CoO/ZnO catalyst composition can be used in the irst catalyst zone of the process of this inven-tio~, but the CoO/MgO
catalyst composition is more preferred than the CoO/ZnO catalyst composition.
Reasonable variations, modifica-tions and adaptations for various usages and conditions can be made within the scope of the disclosure and ~he appended claims, without departing from the scope of this invention.
Claims (26)
1. A process for converting synthesis gas to alcohols comprising the steps of (A) passing a gas mixture comprising carbon monoxide and free hydrogen through a first catalyst zone comprising (a) cobalt metal or at least one compound of cobalt or a mixture thereof and (b) magnesium oxide or zinc oxide or a mixture thereof; and (B) passing the effluent from the first catalyst zone in step (A) through a second catalyst zone comprising (c) copper metal or at least one oxide of copper or a mixture thereof and (d) zinc oxide;
wherein the contacting conditions in steps (A) and (B) are such as to obtain a product comprising at least one aliphatic alcohol having at least 2 carbon atoms per molecule.
wherein the contacting conditions in steps (A) and (B) are such as to obtain a product comprising at least one aliphatic alcohol having at least 2 carbon atoms per molecule.
2. A process in accordance with claim 1 wherein catalyst component (b) in said first catalyst zone is MgO.
3. A process in accordance with claim l wherein the weight percentage of component (a) of the catalyst composition in said first catalyst zone is in the range of from about 5 to about 80, and the weight percentage of component (b) of the catalyst composition in said first catalyst zone is in the range of from about S to about 80.
4. A process in accordance with claim 3 wherein said weight percentage of component (a) is in the range of from about 10 to about 50, and said weight percentage of component (b) is in the range of from about 10 to about 50.
5. A process in accordance with claim 1 wherein the weight ratio of Cu to Zn in the catalyst composition in said second catalyst zone is in the range of from about 1:20 to about 20:1.
6. A process in accordance with claim 5 wherein said weight ratio of Cu to Zn is in the range of from about 1:3 to about 3:1.
7. A process in accordance with claim 1 wherein the catalyst composition in said second catalyst zone further comprises (e) an inorganic refractory oxide material.
8. A process in accordance with claim 7 wherein said inorganic refractory oxide material is alumina.
9. A process in accordance with claim 7 wherein the weight percentage of said inorganic refractory oxide material in the catalyst composition in said second catalyst zone is in the range of from about 1 to about 90 weight-%.
10. A process in accordance with claim 7 wherein said inorganic refractory oxide material is alumina and the weight percentage of alumina in the catalyst composition in said second catalyst zone is in the range of from about 10 to about 70.
11. A process in accordance with claim 1 wherein the weight ratio of the catalyst composition in said first catalyst zone to the catalyst composition in said second catalyst zone is in the range of from about 0.2:1 to about 20:1.
12. A process in accordance with claim 11 wherein said weight ratio of the two catalyst compositions in the range of from about 0.5:1 to about 10:1.
13. A process in accordance with claim 11 wherein said weight ratio of the two catalyst compositions is in the range of from about 1.1:1 to about 8:1.
14. A process in accordance with claim 1 wherein the BET/N2 surface area of the catalyst composition in said first catalyst zone is in the range of from about 20 to about 150 m2/g, and the BET/N2 surface area of the catalyst composition in said second catalyst zone is in the range of from about 20 to about 200 m2/g.
15. A process in accordance with claim 1 wherein the catalyst composition in said first catalyst zone has been prepared by a process comprising the steps of (i) coprecipitating at least one of carbonates, hydroxides and hydrated oxides of Co and Mg; (ii) heating the coprecipitate formed in step (i) under such conditions as to at least partially dry said coprecipitate; and (iii) calcining the at least partially dried coprecipitate obtained in step (ii) under such conditions as to obtain oxides of Co and Mg.
16. A process in accordance with claim 15 wherein the preparation process additionally comprises the step of (iv) heating the calcined material obtained in step (iii) with a reducing gas under such conditions as to at least partially reduce cobalt oxide to cobalt metal.
17. A process in accordance with claim 1 wherein the catalyst composition in said second catalyst zone has been prepared by a process comprising the steps of (I) coprecipitating at least one of carbonates, hydroxides and hydrated oxides of Cu and Zn; (II) drying the coprecipitate formed in step (I) under such conditions as to at least partially dry the coprecipitate formed in step (I); and (III) calcining the at least partially dried coprecipitate obtained in step (II) under such conditions as to obtain oxides of Cu and Zn.
18. A process in accordance with claim 17 wherein the preparation process additionally comprises the step of (IV) heating the calcined material obtained in step (III) with a reducing gas under such conditions as to at least partially reduce CuO to at least one of Cu2O
and Cu metal.
and Cu metal.
19. A process in accordance with claim 17 wherein the coprecipitate formed in step (I) additionally comprises at least one of carbonates, hydroxides and hydrated oxides of alumina; and the calcined material obtained in step (III) additionally comprises alumina.
20. A process in accordance with claim 1 wherein said gas mixture used in step (A) comprises about 5 to about 65 volume percent hydrogen and about 35 to about 95 volume percent carbon monoxide.
21. A process in accordance with claim l wherein the volume ratio of H2 : CO in said gas mixture is in the range of from about 1:2 to about 4:1.
22. A process in accordance with claim 21 wherein said contacting conditions in steps (A) and (B) comprise a reaction temperature in the range of from about 200 to about 400°C and a reaction pressure in the range of from about 300 to about 3000 psig.
23. A process in accordance with claim 22 wherein said reaction temperature is about 250-350°C and said reaction pressure is about 500-1500 psig.
24. A process in accordance with claim 22 wherein said contacting conditions further comprise a gas hourly space velocity of said gas mixture in the range of from about 500 to about 10,000 volume gas mixture / volume catalyst composition / hour.
25. A process in accordance with claim 1 wherein said product comprises aliphatic alcohols containing 2-8 carbon atoms per molecule.
26. A process in accordance with claim 1 further comprising the step of (C) separating the product which contains a plurality of alcohols into at least two liquid fractions comprising different alcohols.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69,149 | 1987-07-02 | ||
| US07/069,149 US4751248A (en) | 1987-07-02 | 1987-07-02 | Preparation of alcohols from synthesis gas |
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| Publication Number | Publication Date |
|---|---|
| CA1299199C true CA1299199C (en) | 1992-04-21 |
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|---|---|---|---|
| CA000567803A Expired - Lifetime CA1299199C (en) | 1987-07-02 | 1988-05-26 | Preparation of alcohols from synthesis gas |
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| Country | Link |
|---|---|
| US (1) | US4751248A (en) |
| EP (1) | EP0297458A3 (en) |
| JP (1) | JPS6426526A (en) |
| AU (1) | AU587362B2 (en) |
| CA (1) | CA1299199C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5096688A (en) * | 1989-06-13 | 1992-03-17 | Amoco Corporation | Catalytic process for producing higher alcohols from synthesis gas |
| US5109027A (en) * | 1989-06-13 | 1992-04-28 | Amoco Corporation | Catalytic process for producing olefins or higher alcohols from synthesis gas |
| US5169869A (en) * | 1990-01-16 | 1992-12-08 | Amoco Corporation | Process for producing higher alcohols or n-paraffins from synthesis gas |
| BR0111558A (en) * | 2000-06-12 | 2003-07-01 | Sasol Tech Pty Ltd | Processes for preparing a cobalt-based catalyst precursor and for preparing a cobalt-based fischer-tropsch catalyst |
| US6664207B2 (en) * | 2001-09-26 | 2003-12-16 | Conocophillips Company | Catalyst for converting carbon dioxide to oxygenates and processes therefor and therewith |
| EP1358934A1 (en) * | 2002-04-25 | 2003-11-05 | Engelhard Corporation | Fischer-Tropsch catalyst |
| US20040247498A1 (en) * | 2003-06-04 | 2004-12-09 | Jonathan Phillips | Catalytic reactor system |
| US7288689B2 (en) | 2003-11-19 | 2007-10-30 | Exxonmobil Chemical Patents Inc. | Methanol and fuel alcohol production for an oxygenate to olefin reaction system |
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| US2626275A (en) * | 1947-02-18 | 1953-01-20 | Hydrocarbon Research Inc | Process for catalytic conversion of carbon monoxide and hydrogen to hydrocarbons, oxygenated hydrocarbons, and the like |
| US2750430A (en) * | 1950-02-03 | 1956-06-12 | Ruhrchemie Ag | Production of synthetic aliphatic alcohols |
| US3598527A (en) * | 1968-10-11 | 1971-08-10 | Pullman Inc | Ammonia and methanol production |
| US3790505A (en) * | 1971-05-04 | 1974-02-05 | Catalysts & Chem Inc | Low temperature methanol synthesis catalyst |
| CA1041553A (en) * | 1973-07-30 | 1978-10-31 | John P. Longwell | Methanol and synthetic natural gas concurrent production |
| DE2705673A1 (en) * | 1976-02-13 | 1977-08-18 | Davy Powergas Ltd | Catalytic syntheses with high yields - suitable for mfg. ammonia, methane, methanol, or the conversion of carbon monoxide |
| FR2444654A1 (en) * | 1978-12-19 | 1980-07-18 | Inst Francais Du Petrole | PROCESS FOR THE MANUFACTURE OF ALCOHOLS AND MORE PARTICULARLY PRIMARY, SATURATED AND LINEAR ALCOHOLS FROM SYNTHESIS GAS |
| FR2453125B1 (en) * | 1979-04-05 | 1985-06-07 | Inst Francais Du Petrole | PRODUCTION OF ALCOHOLS FROM SYNTHESIS GAS |
| DE3005550A1 (en) * | 1980-02-14 | 1981-08-20 | Süd-Chemie AG, 8000 München | METHOD FOR PRODUCING OLEFINS |
| NL8001342A (en) * | 1980-03-06 | 1980-07-31 | Shell Int Research | METHOD FOR PERFORMING CATALYTIC CONVERSIONS |
| IT1140947B (en) * | 1980-05-16 | 1986-10-10 | Snam Progetti | PROCESS FOR THE PRODUCTION OF A MIXTURE OF METHANOL AND HIGHER ALCOHOL "FUEL DEGREE" |
| DE3065830D1 (en) * | 1980-08-28 | 1984-01-12 | Theodore Oscar Wentworth | Process for the synthesis of methanol from hydrogen and the oxides of carbon using catalysts |
| US4396539A (en) * | 1981-08-14 | 1983-08-02 | Sapienza Richard S | Hydrocarbon synthesis catalyst and method of preparation |
| US4348487A (en) * | 1981-11-02 | 1982-09-07 | Exxon Research And Engineering Co. | Production of methanol via catalytic coal gasification |
| JPS59122432A (en) * | 1982-12-29 | 1984-07-14 | Res Assoc Petroleum Alternat Dev<Rapad> | Production of mixed alcohol |
| AU565013B2 (en) * | 1982-11-29 | 1987-09-03 | Research Association For Petroleum Alternatives Development | Production of mixed alcohols |
| DE3403492A1 (en) * | 1984-02-02 | 1985-08-08 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PRODUCING A MIXTURE OF METHANOL AND HIGHER ALCOHOLS |
| DE3403491A1 (en) * | 1984-02-02 | 1985-08-14 | Süd-Chemie AG, 8000 München | CATALYST FOR THE SYNTHESIS OF METHANOL AND ALCOHOL MIXTURES CONTAINING HIGHER ALCOHOLS |
| FR2564091B1 (en) * | 1984-05-10 | 1986-10-03 | Inst Francais Du Petrole | PROCESS FOR THE SYNTHESIS OF A MIXTURE OF PRIMARY ALCOHOLS FROM SYNTHESIS GAS IN THE PRESENCE OF A CATALYST CONTAINING COPPER, COBALT, ZINC AND ALUMINUM |
| FR2581988B1 (en) * | 1985-05-17 | 1987-07-24 | Inst Francais Du Petrole | PROCESS FOR IMPLEMENTING A CATALYST FOR SYNTHESIS OF SATURATED PRIMARY ALIPHATIC ALCOHOLS |
-
1987
- 1987-07-02 US US07/069,149 patent/US4751248A/en not_active Expired - Fee Related
-
1988
- 1988-05-26 CA CA000567803A patent/CA1299199C/en not_active Expired - Lifetime
- 1988-06-03 AU AU17356/88A patent/AU587362B2/en not_active Ceased
- 1988-06-23 JP JP63153700A patent/JPS6426526A/en active Granted
- 1988-06-24 EP EP19880110122 patent/EP0297458A3/en not_active Ceased
- 1988-06-29 NO NO882910A patent/NO171675C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU1735688A (en) | 1989-01-05 |
| AU587362B2 (en) | 1989-08-10 |
| JPH0515696B2 (en) | 1993-03-02 |
| JPS6426526A (en) | 1989-01-27 |
| NO882910D0 (en) | 1988-06-29 |
| US4751248A (en) | 1988-06-14 |
| EP0297458A2 (en) | 1989-01-04 |
| EP0297458A3 (en) | 1991-04-17 |
| NO171675C (en) | 1993-04-21 |
| NO171675B (en) | 1993-01-11 |
| NO882910L (en) | 1989-01-03 |
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