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
  • C07C29/132—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 an oxygen containing functional group
  • C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
  • C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0205—Impregnation in several steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/088—Decomposition of a metal salt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/51—Spheres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm

Definitions

• the present invention relates to cobalt and tin catalysts, to processes for making such catalysts, and to processes for reducing alkanoic acids using the catalyst.
• ethanol may be produced by reducing acetic acid in the presence of a catalyst containing cobalt and tin.
• Ethanol for industrial use is conventionally produced from petrochemical feed stocks, such as oil, natural gas, or coal, from feed stock intermediates, such as syngas, or from starchy materials or cellulosic materials, such as corn or sugar cane.
• feed stock intermediates such as syngas
• Conventional methods for producing ethanol from petrochemical feed stocks, as well as from cellulose materials include the acid-catalyzed hydration of ethylene, methanol homologation, direct alcohol synthesis, and Fischer-Tropsch synthesis.
• Instability in petrochemical feed stock prices contributes to fluctuations in the cost of conventionally produced ethanol, making the need for alternative sources of ethanol production all the greater when feed stock prices rise.
• Starchy materials, as well as cellulosic material are converted to ethanol by fermentation. However, fermentation is typically used for consumer production of ethanol, which is suitable for fuels or human consumption. In addition, fermentation of starchy or cellulosic materials competes with food sources and places restraints on the amount of
• US Pat. No. 6,495,730 describes a process for hydrogenating carboxylic acid using a catalyst comprising activated carbon to support active metal species comprising ruthenium and tin.
• US Pat. No. 6,204,417 describes another process for preparing aliphatic alcohols by hydrogenating aliphatic carboxylic acids or anhydrides or esters thereof or lactones in the presence of a catalyst comprising Pt and Re.
• 5,149,680 describes a process for the catalytic hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters in the presence of a catalyst containing a Group VIII metal, such as palladium, a metal capable of alloying with the Group VIII metal, and at least one of the metals rhenium, tungsten or molybdenum.
• a catalyst containing a Group VIII metal such as palladium, a metal capable of alloying with the Group VIII metal, and at least one of the metals rhenium, tungsten or molybdenum.
• US Pat. No. 4,777,303 describes a process for the productions of alcohols by the hydrogenation of carboxylic acids in the presence of a catalyst that comprises a first component which is either molybdenum or tungsten and a second component which is a noble metal of Group VIII on a high surface area graphitized carbon.
• 4,804,791 describes another process for the production of alcohols by the hydrogenation of carboxylic acids in the presence of a catalyst comprising a noble metal of Group VIII and rhenium.
• US Pat. No. 4,517,391 describes preparing ethanol by hydrogenating acetic acid under superatmospheric pressure and at elevated temperatures by a process wherein a predominantly cobalt-containing catalyst.
• the invention is directed to a hydrogenation catalyst for reducing alkanoic acids to alcohols, the catalyst comprising from 3 to 25 wt.% of active metals on a support, wherein the active metals comprise cobalt and tin.
• the active metals are present from 5 to 20 wt.% in a molar ratio from 1.2: 1 to 1 : 1.2.
• the support further comprises a support modifier present fro 0.1 to 50 wt.%.
• the catalyst may comprise less than 2 wt.% of nickel, iron, ruthenium, rhodium, palladium, osmium, iridium or platinum.
• the catalyst is free of copper and/or zinc.
• the invention is directed to a hydrogenation catalyst for reducing alkanoic acids to alcohols, the catalyst comprising cobalt, tin, and a metal selected from the group consisting of nickel, iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum on a support, wherein the metal is present in an amount of less than 2 wt.%.
• the substantially equal molar ratio is from 1.2:1 to 1:1.2.
• the invention is directed to a hydrogenation catalyst for reducing alkanoic acids to alcohols, the catalyst comprising from 3 to 25 wt.% of active metals on a support, wherein the active metals comprise a substantially equal molar ratio of cobalt to tin.
• the invention is directed to a process for formation of ethanol from acetic acid comprising contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with a hydrogenating catalyst comprising from 3 to 25 wt.% of active metals on a support, wherein the active metals comprise cobalt and tin.
• the active metals are present from 5 to 20 wt.% in a molar ratio from 1.2:1 to 1:1.2.
• the support comprises a support modifier present from 0.1 to 50 wt.%.
• the feed stream may be produced by gasifying a oil, coal, natural gas and/or biomass.
• the acetic acid selectivity to ethanol is greater than 60%. Ethanol is separated in one or more columns after the hydrogenation to produce a finished ethanol product.
• the invention is directed to a process for formation of ethanol from acetic acid comprising contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with a hydrogenating catalyst comprising from 3 to 25 wt.% of active metals on a support, wherein the active metals comprise a substantially equal molar ratio of cobalt to tin.
• the invention is directed to a process for formation of ethanol from acetic acid comprising contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with a hydrogenating catalyst comprising cobalt, tin, and a metal selected from the group consisting of nickel, iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum on a support, wherein the metal is present in an amount of less than 2 wt.%.
• the invention is directed to a process for the formation of ethanol from a mixed feed, the steps of the process comprising: contacting a feed stream containing the mixed feed and hydrogen at an elevated temperature with a hydrogenation catalyst comprising from 3 to 25 wt.%, or from 5 to 20 wt.% of a substantially equal molar ratio of cobalt and tin on a support, wherein the mixed feed comprises 5 to 40 wt.% ethyl acetate and 60 to 95 wt.% acetic acid.
• the hydrogenation catalyst comprises no further metals.
• the mixed stream comprises 30 wt.% ethyl acetate and 70 wt.% acetic acid.
• the catalyst may comprise 20 wt.% of a substantially equal molar ratio of cobalt and tin.
• the substantially equal molar ratio of cobalt and tin may be from 1.2:1 to 1:1.2.
• the support material may be present from 25 to 97 wt.% and the support material may be selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica, carbon, alumina, and mixtures thereof.
• the support may further comprise from 0.1 to 50 wt.% of a support modifier.
• the support modifier may be selected from the group consisting of (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group ⁇ metal metasilicates, (vii) Group ⁇ metal oxides, (viii) Group ⁇ metal metasilicates, and mixtures thereof.
• the support modifier may be calcium metasilicate.
• the support modifier may be selected from the group consisting of Ti0 2 , Zr0 2 , Nb 2 0 5 , Ta 2 0 5 , A1 2 0 3 , B 2 0 3 , P 2 0 5 , Sb 2 0 3 , W0 3 , Mo0 3 , Fe 2 0 3 , Cr 2 0 3 , V 2 0 5 , Nb 2 0 5 , Mn0 2 , CuO, Co 2 0 3 , and Bi 2 0 3 .
• the feed stream may be produced by gasifying a carbonaceous material, wherein the
• carbonaceous material may be oil, coal, natural gas or biomass.
• Acetic acid selectivity to ethanol may be greater than 60%.
• the ethanol may then be further separated in one or more columns to produce a finished ethanol product.
• the invention is directed to a hydrogenation catalyst for the formation of ethanol from a mixed stream, the catalyst comprising from 3 to 25 wt.% of a substantially equal molar ratio of cobalt and tin on a support selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica, carbon, alumina, and mixtures thereof, wherein the mixed feed comprises 5 to 40 wt.% acetic acid and from 60 to 95 wt.% ethyl acetate.
• the substantially equal molar ratio of cobalt and tin may be from 1.2:1 to 1:1.2.
• the invention is directed to a hydrogenation catalyst for reducing alkanoic acids to alcohols, the catalyst comprising from 3 to 25 wt.% of active metals and 0.05 to 2 wt.% of a promoter on a support, wherein the active metals comprise cobalt and tin, and wherein the promoter is selected from the group consisting of a first metal and a noble metal.
• the noble metal may be present from 0.1 to 0.7 wt.% and the active metals may be present from 5 to 20 wt.%.
• the active metals may be present in a substantially equal molar ratio.
• the catalyst further comprises a support and a support modifier.
• the present invention is directed to a hydrogenation catalyst for reducing alkanoic acids to alcohols, the catalyst comprising from 3 to 25 wt.% of active metals and 0.05 to 2 wt.% a first metal on a support, wherein the active metals comprise cobalt and tin, and wherein the first metal is selected from the group consisting of barium, potassium, cesium, and combinations thereof.
• the support may comprise a support modifier. When the first metal is cesium, cesium is impregnated onto the support prior to the impregnation of the active metals. When the first metal is potassium, potassium is impregnated onto the support after the impregnation of the active metals.
• the present invention is directed to a hydrogenation catalyst for reducing alkanoic acids to alcohols, the catalyst comprising from 3 to 25 wt.% of active metals and 0.05 to 2 wt.% a noble metal on a support, wherein the active metals comprise cobalt and tin, and wherein the noble metal is selected from the group consisting of rhodium, ruthenium, palladium, gold, iridium, and combinations thereof.
• the present invention is directed to a process for formation of ethanol from acetic acid comprising: contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with a hydrogenating catalyst comprising from 3 to 25 wt.% of active metals and 0.05 to 2 wt.% of a promoter on a support, wherein the active metals comprise cobalt and tin, and wherein the promoter is selected from the group consisting of a first metal and a noble metal.
• the first metal may be barium, potassium, cesium or combinations thereof and the noble metal may be rhodium or gold, present from 0.1 to 0.7 wt.%.
• the first metal may be present from 0.05 to 0.5 wt.%.
• the catalyst further comprises a support and a support modifier. Selectivity of acetic acid to ethanol is greater than 60%. The ethanol may then be further separated in one or more columns to produce a finished ethanol product.
• the present invention is directed to a process for formation of ethanol from acetic acid comprising: contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with a hydrogenating catalyst comprising from 3 to 25 wt.% of active metals and 0.05 to 2 wt.% of a first metal on a support, wherein the active metals comprise cobalt and tin, and wherein the first metal is selected from the group consisting of barium, potassium, cesium, and combinations thereof.
• the support further comprises a support modifier. When the first metal is cesium, cesium is impregnated onto the support prior to the impregnation of the active metals. When the first metal is potassium, potassium is impregnated onto the support after the impregnation of the active metals.
• the invention is directed to a process for formation of ethanol from acetic acid comprising: contacting a feed stream containing acetic acid and hydrogen at an elevated temperature with a hydrogenating catalyst comprising from 3 to 25 wt.% of active metals and 0.05 to 2 wt.% a noble metal on a support, wherein the active metals comprise cobalt and tin, and wherein the noble metal is selected from the group consisting of rhodium, ruthenium, palladium, gold, iridium, and combinations thereof.
• this invention relates to a catalyst for reducing alkanoic acids and/or esters thereof, and preferably for reducing acetic acid and/or ethyl acetate.
• the catalyst comprises active metals on a support.
• the active metals comprise cobalt and tin.
• the presence of tin in the catalyst may promote the activity of the catalyst to convert acetic acid, increase selectivity to ethanol, and stabilize the catalyst over a longer period of use.
• Tin which demonstrates poor hydrogenation abilities when used alone, surprisingly and unexpectedly may increase the performance of catalyst comprising cobalt.
• the combination of cobalt and tin surprisingly and advantageously produces a low selectivity for methane.
• the bimetallic combination of cobalt and tin is advantageous in producing ethanol from acetic acid.
• the total metal loading is from 3 to 25 wt.%, and more preferably from 5 to 20 wt.% or 10 to 20 wt.%. In some embodiments, the total metal loading is 20 wt.%. In some embodiments, cobalt may be present in an amount of at least 1.5 wt%, e.g., at least 3 wt.%. When the metal loading is lower, the acetic acid conversion may be reduced. Cobalt and/or tin may be present on the catalyst as an oxide. In one embodiment the molar ratio of cobalt and tin may be from 1.9:1 to 1:1.9, e.g. from 1.5:1 to 1:1.5, or from 1.4:1 to 1:1.4. In a more preferred embodiment there may be a substantially equal molar ratio of cobalt and tin on a support, that is, in a molar ratio from 1.2:1 to 1:1.2 and more preferably a molar ratio of 1:1.
• additional active metals there may be additional active metals that may be used in combination with cobalt/tin catalyst.
• additional active metals include nickel, iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
• the additional active metal is platinum.
• the additional active metal is preferably present in an amount less than the total metal loading of cobalt and tin. In one embodiment, the metal loading of the active metal is less than 2 wt.%, e.g., less than 1.75 wt.% or less than 1.5 wt.%.
• the metal loading of the active metal is from 0.4 wt.% to 1 wt.%, e.g., from 0.4 wt.% to 0.7 wt.% or from 0.4 wt.% to 0.6 wt.%.
• the cobalt/tin catalyst does not contain any copper or zinc.
• the combination of cobalt and tin may be promoted by a first metal or a noble metal.
• the promoter metal may be present from 0.05 to 2 wt.%, e.g., from 0.1 to 1.5 wt.% or from 0.2 to 0.4 wt.%.
• the first metal may be selected from the group consisting of barium, potassium, cesium, and combinations thereof.
• the first metal may be present from 0.05 to 2 wt.%, e.g., from 0.05 to 0.5 wt.% or from 0.1 to 0.4 wt.% .
• the noble metal may be selected from the group consisting of rhodium, ruthenium, palladium, gold, iridium, and combinations thereof.
• the noble metal may be selected from the group consisting of rhodium and gold.
• the noble metal may be present from 0.05 to 2 wt.%, e.g., from 0.1 to 0.7 wt.% or from 0.1 to 0.4 wt.%.
• the catalyst comprises cobalt and tin as active metals, and is free of any further metals.
• the catalyst may be free of metals including iron, copper, palladium, rhenium, rhodium, and ruthenium.
• the catalysts of the present invention may be on any suitable support.
• the support may be an inorganic oxide.
• the support may be selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica, carbon, alumina, titania, zirconia, graphite, zeolites, and mixtures thereof.
• the support may be selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica, carbon, alumina, and mixtures thereof.
• the support comprises silica.
• the support is present in an amount from 25 wt.% to 97 wt.%, e.g., from 30 wt. to 95 wt.% or from 35 wt. to 80 wt.%.
• the surface area of silicaceous support e.g., silica
• the silicaceous support preferably has a surface area of from 50 to 600 m 2 /g, e.g., from 100 to 500 m 2 /g or from 100 to 300 m 2 /g.
• High surface area silica refers to silica having a surface area of at least about 250 m 2 /g.
• surface area refers to BET nitrogen surface area, meaning the surface area as determined by ASTM D6556-04, the entirety of which is incorporated herein by reference.
• the silicaceous support also preferably has an average pore diameter of from 5 to 100 nm, e.g., from 5 to 30 nm, from 5 to 25 nm or from about 5 to 10 nm, as determined by mercury intrusion porosimetry, and an average pore volume of from 0.5 to 2.0 cm 3 /g, e.g., from 0.7 to 1.5 cm 3 /g or from about 0.8 to 1.3 cm 3 /g, as determined by mercury intrusion porosimetry.
• the morphology of the support, and hence of the resulting catalyst composition may vary widely.
• the morphology of the support and/or of the catalyst composition may be pellets, extrudates, spheres, spray dried microspheres, rings, pentarings, trilobes, quadrilobes, multi-lobal shapes, or flakes although cylindrical pellets are preferred.
• the silicaceous support has a morphology that allows for a packing density of from 0.1 to 1.0 g cm 3 , e.g., from 0.2 to 0.9 g/cm 3 or from 0.3 to 0.8 g/cm 3 .
• the silica support preferably has an average particle size, e.g., meaning the diameter for spherical particles or equivalent spherical diameter for non-spherical particles, of from 0.01 to 1.0 cm, e.g., from 0.1 to 0.7 cm or from 0.2 to 0.5 cm. Since the one or more active metal(s) that are disposed on or within the support are generally very small in size, those active metals should not substantially impact the size of the overall catalyst particles. Thus, the above particle sizes generally apply to both the size of the support as well as to the final catalyst particles.
• a preferred silica support is SS61138 High Surface Area (HS A) Silica Catalyst Carrier from Saint-Gobain NorPro.
• the Saint-Gobain NorPro SS61138 silica contains approximately 95 wt.% high surface area silica; a surface area of about 250 m 2 /g; a median pore diameter of about 12 nm; an average pore volume of about 1.0 cm 3 /g as measured by mercury intrusion
• a preferred silica alumina support is KA-160 (Slid Chemie) silica spheres having a nominal diameter of about 5 mm, a density of about 0.562 g/ml, in absorptivity of about 0.583 g H 2 0/g support, a surface area of about 160 to 175 m 2 /g, and a pore volume of about 0.68 ml/g. Support modifiers
• the support may also comprise a support modifier.
• the total weight of the support modifiers are present in an amount from 0.1 wt.% to 50 wt.%, e.g., from 0.2 wt.% to 25 wt.%, from 0.5 wt.% to 15 wt.%, or from 1 wt.% to 8 wt.%, based on the total weight of the catalyst.
• Support modifiers may adjust the acidity of the support.
• the acid sites e.g. Br0nsted acid sites
• the acidity of the support may be adjusted by reducing the number or reducing the availability of Br0nsted acid sites on the support.
• the support may also be adjusted by having the support modifier change the pKa of the support. Unless the context indicates otherwise, the acidity of a surface or the number of acid sites thereupon may be determined by the technique described in F. Delannay, Ed., "Characterization of Heterogeneous Catalysts"; Chapter ⁇ : Measurement of Acidity of Surfaces, p.
• the support modifier may be an acidic modifier that increases the acidity of the catalyst.
• Suitable acidic support modifiers may be selected from the group consisting of: oxides of Group IVB metals, oxides of Group VB metals, oxides of Group VHB metals, oxides of Group VIIB metals, oxides of Group VIII metals, aluminum oxides, and mixtures thereof.
• Acidic support modifiers include those selected from the group consisting of Ti0 2 , Zr0 2 , Nb 2 0 5 , Ta 2 0 5 , A1 2 0 3 , B 2 0 3 , P 2 0 5 , and Sb 2 0 3 .
• Preferred acidic support modifiers include those selected from the group consisting of Ti0 2 , Zr0 2 , Nb 2 0 5 , Ta 2 0 5 , and A1 2 0 3 .
• the acidic modifier may also include those selected from the group consisting of W0 3 , Mo0 3 , Fe 2 0 3 , Cr 2 0 3 , V 2 0 5 , Nb 2 0 5 , Mn0 2 , CuO, Co 2 0 3 , and Bi 2 0 3 .
• the support modifier may be a basic modifier that has a low volatility or no volatility.
• Such basic modifiers may be selected from the group consisting of: (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group ⁇ metal metasilicates, (vii) Group IID3 metal oxides, (viii) Group HIB metal metasilicates, and mixtures thereof.
• the support modifier is selected from the group consisting of oxides and metasilicates of any of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, as well as mixtures of any of the foregoing. More preferably, the basic support modifier is a calcium silicate, and even more preferably calcium metasilicate (CaSi0 3 ). The calcium metasilicate may be crystalline or amorphous.
• the catalyst comprises from 0.25 to 1.25 wt.% platinum and 0.25 to 3 wt.% tin. These preferred active metals are on a silica support.
• the silica support also comprises a support modifier such as CaSi0 3 .
• there may be a basic modifier and an acidic modifier. W0 3 and CaSi0 3 may both be used on a silica or silica-alumina support material.
• the present invention also relates to processes for making the catalyst.
• One or more support modifiers may also be added to the support by mixing or through
• Powdered materials of the modified supports or a precursor thereto may pelletized, crushed and sieved and added to the support.
• a solvent such as water, glacial acetic acid, a strong acid such as hydrochloric acid, nitric acid, or sulfuric acid, or an organic solvent, may be preferred.
• the resulting mixture may be stirred and added to additional support using, for example, incipient wetness techniques in which the precursor to the support modifier is added to a support having the same pore volume as the volume of the solution. Capillary action then draws the precursor to the support modifier into the pores in the support.
• the support containing precursor to the support modifier can then be formed by drying to drive off water and any volatile components within the support solution and depositing the tin on the support. Drying may occur, for example, at a temperature of from 50°C to 300°C, e.g., from 100°C to 200°C or about 120°C, optionally for a period of from 1 to 24 hours, e.g., from 3 to 15 hours or from 6 to 12 hours.
• the modified supports may be shaped into particles having the desired size distribution, e.g., to form particles having an average particle size in the range of from 0.2 to 0.4 cm.
• the supports may be extruded, pelletized, tabletized, pressed, crushed or sieved to the desired size distribution. Any of the known methods to shape the support into desired size distribution can be employed.
• cobalt and tin are impregnated onto the support.
• a precursor of the active metals preferably is used in the metal impregnation step, such as a water soluble compound or water dispersible compound/complex that includes the first metal of interest.
• a solvent such as water, glacial acetic acid or an organic solvent, may be preferred.
• the second active metal precursor also preferably is impregnated into the support from a second metal precursor.
• Impregnation occurs by adding, optionally drop wise, either or both the first metal precursor and/or the second metal precursor and/or additional metal precursors, preferably in suspension or solution, to the dry support.
• the resulting mixture may then be heated, e.g., optionally under vacuum, in order to remove the solvent. Additional drying and calcining may then be performed, optionally with ramped heating to form the final catalyst composition.
• the metal(s) of the metal precursor(s) preferably decompose into their elemental (or oxide) form.
• the completion of removal of the liquid carrier may not take place until the catalyst is placed into use and calcined, e.g., subjected to the high temperatures encountered during operation.
• the calcination step or at least during the initial phase of use of the catalyst, such compounds are converted into a catalytically active form of the metal or a catalytically active oxide thereof.
• Impregnation of the active metal onto the support may occur simultaneously (co- impregnation) or sequentially.
• simultaneous impregnation the active metal precursors are mixed together and added to the support together, followed by drying and calcination to form the final catalyst composition.
• a dispersion agent, surfactant, or solubilizing agent e.g., ammonium oxalate, to facilitate the dispersing or solubilizing of the first and second metal precursors in the event the two precursors are incompatible with the desired solvent, e.g., water.
• Suitable metal precursors include, for example, metal halides, amine solubilized metal hydroxides, metal nitrates or metal oxalates.
• suitable compounds for tin precursors and cobalt precursors include potassium stannate, sodium stannate, stannic chloride, stannous chloride, stannous nitrate, stannous oxalate, and cobalt nitrate hexahydrate.
• Suitable compounds for the first metal and noble metal precursors include, but are not limited to, ruthenium(ni) nitrosyl nitrate, palladium(II) nitrate, gold ( ⁇ ) nitrate, rhodium(HI) nitrate dehydrate, cesium nitrate, potassium nitrate, and barium nitrate.
• ruthenium(ni) nitrosyl nitrate palladium(II) nitrate, gold ( ⁇ ) nitrate, rhodium(HI) nitrate dehydrate, cesium nitrate, potassium nitrate, and barium nitrate.
• aqueous solutions of soluble compounds are preferred.
• a particularly preferred precursor to tin is stannous oxalate, SnQifyC xI ⁇ O.
• a particularly preferred precursor to cobalt is cobalt nitrate hexahydrate, Co(N0 3 ) 2 -6H 2 0.
• Calcining of the solution with the support and active metal may occur, for example, at a temperature of from 250°C to 800°C, e.g., from 300°C to 700°C or from 350°C to 500°C, optionally for a period of from 1 to 12 hours, e.g., from 2 to 10 hours, from 4 to 8 hours or about 6 hours.
• the tin precursor is first added to the support, followed by the cobalt metal precursor.
• the reverse order of addition is also possible.
• each impregnation step preferably is followed by drying and calcination.
• nitrogenous amine and/or nitrate based precursors it is generally preferable to use nitrogenous amine and/or nitrate based precursors.
• the promoter metal or promoter metal precursor may be added using sequential impregnation, starting with the addition of the promoter metal followed by a second impregnation step involving co-impregnation of cobalt and tin.
• exemplary precursors for promoter metals include metal halides, amine solubilized metal hydroxides, metal nitrates or metal oxalates.
• the promoter is barium.
• the support for barium promoted cobalt- tin catalyst preferably comprises a support modifier.
• the support modifier is a basic modifier selected from the group consisting of: (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group ⁇ metal oxides, (vi) Group IIB metal metasilicates, (vii) Group ⁇ metal oxides, (viii) Group MB metal metasilicates, and mixtures thereof.
• calcium metasilicate is the basic support modifier for barium promoted cobalt-tin catalyst. Using a support modifier with barium may increase the acetic acid conversion and/or ethanol selectivity.
• the cesium promoter may be impregnated on the support before the active metals.
• the order of impregnation may improve the alkanoic acid conversion and/or alcohol selectivity of the cesium promoted cobalt-tin catalyst.
• the potassium promoter may be impregnated on the support after the active metals.
• the order of impregnation may improve the alkanoic acid conversion and/or alcohol selectivity of the potassium promoted cobalt-tin catalyst.
• catalysts of the present invention is the stability or activity of the catalyst for producing ethanol. Accordingly, it can be appreciated that the catalysts of the present invention are fully capable of being used in commercial scale industrial applications for hydrogenation of acetic acid, particularly in the production of ethanol. In particular, it is possible to achieve such a degree of stability such that catalyst activity will have a rate of productivity decline that is less than 6% per 100 hours of catalyst usage, e.g., less than 3% per 100 hours or less than 1.5% per 100 hours. Preferably, the rate of productivity decline is determined once the catalyst has achieved steady-state conditions.
• a feedstock comprises acetic acid.
• the feedstock is a mixed feedstock and may comprise acetic acid and ethyl acetate, in addition to hydrogen.
• the feedstock may comprise from 5 to 40 wt.% ethyl acetate and 60 to 95 wt.% acetic acid, e.g., from 5 to 30 wt.% ethyl acetate and 70 to 95 wt.% acetic acid.
• the feedstock comprises 30 wt.% ethyl acetate and 70 wt.% acetic acid.
• the hydrogenation reaction may be represented as follows:
• the raw materials, acetic acid, ethyl acetate and hydrogen, fed to the primary reactor used in connection with the process of this invention may be derived from any suitable source including natural gas, petroleum, coal, biomass, and so forth.
• acetic acid may be produced via methanol carbonylation, acetaldehyde oxidation, ethane oxidation, oxidative fermentation, and anaerobic fermentation. Methanol carbonylation processes suitable for production of acetic acid are described in U.S. Pat. Nos. 7,208,624; 7,115,772; 7,005,541;
• some or all of the raw materials for the above-described acetic acid hydrogenation process may be derived partially or entirely from syngas.
• the acetic acid may be formed from methanol and carbon monoxide, both of which may be derived from syngas.
• the syngas may be formed by partial oxidation reforming or steam reforming, and the carbon monoxide may be separated from syngas.
• hydrogen that is used in the step of hydrogenating the acetic acid to form the crude ethanol product may be separated from syngas.
• the syngas may be derived from variety of carbon sources.
• the carbon source for example, may be selected from the group consisting of natural gas, oil, petroleum, coal, biomass, and combinations thereof.
• Syngas or hydrogen may also be obtained from bio-derived methane gas, such as bio-derived methane gas produced by landfills or agricultural waste.
• the acetic acid used in the hydrogenation step may be formed from the fermentation of biomass.
• the fermentation process preferably utilizes an acetogenic process or a homoacetogenic microorganism to ferment sugars to acetic acid producing little, if any, carbon dioxide as a by-product.
• the carbon efficiency for the fermentation process preferably is greater than 70%, greater than 80% or greater than 90% as compared to conventional yeast processing, which typically has a carbon efficiency of about 67%.
• the microorganism employed in the fermentation process is of a genus selected from the group consisting of Clostridium, Lactobacillus, Moorella, Thermoanaerobacter,
• Propionibacterium, Propionispera, Anaerobiospirillum, and Bacteriodes and in particular, species selected from the group consisting of Clostridium formicoaceticum, Clostridium butyricum, Moorella thermoacetica, Thermoanaerobacter kivui, Lactobacillus delbrukii, Propionibacterium acidipropionici, Propionispera arboris, Anaerobiospirillum
• succinicproducens Bacteriodes amylophilus and Bacteriodes ruminicola.
• all or a portion of the unfermented residue from the biomass e.g., lignans, may be gasified to form hydrogen that may be used in the hydrogenation step of the present invention.
• Exemplary fermentation processes for forming acetic acid are disclosed in U.S. Pat. Nos.
• biomass examples include, but are not limited to, agricultural wastes, forest products, grasses, and other cellulosic material, timber harvesting residues, softwood chips, hardwood chips, tree branches, tree stumps, leaves, bark, sawdust, off-spec paper pulp, corn, corn stover, wheat straw, rice straw, sugarcane bagasse, switchgrass, miscanthus, animal manure, municipal garbage, municipal sewage, commercial waste, grape pumice, almond shells, pecan shells, coconut shells, coffee grounds, grass pellets, hay pellets, wood pellets, cardboard, paper, plastic, and cloth. See, e.g., U.S. Pat. No. 7,884,253, the entirety of which is incorporated herein by reference.
• Black liquor a thick, dark liquid that is a byproduct of the Kraft process for transforming wood into pulp, which is then dried to make paper.
• Black liquor is an aqueous solution of lignin residues, hemicellulose, and inorganic chemicals.
• U.S. Pat. No. RE 35,377 also incorporated herein by reference, provides a method for the production of methanol by conversion of carbonaceous materials such as oil, coal, natural gas and biomass materials.
• the process includes hydrogasification of solid and/or liquid
• the acetic acid fed to the hydrogenation reactor may also comprise other carboxylic acids and anhydrides, as well as aldehyde and/or ketones, such as acetaldehyde and acetone.
• a suitable acetic acid feed stream comprises one or more of the compounds selected from the group consisting of acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and mixtures thereof. These other compounds may also be hydrogenated in the processes of the present invention.
• carboxylic acids such as propanoic acid or its anhydride, may be beneficial in producing propanol. Water may also be present in the acetic acid feed.
• acetic acid in vapor form may be taken directly as crude product from the flash vessel of a methanol carbonylation unit of the class described in U.S. Pat. No. 6,657,078, the entirety of which is incorporated herein by reference.
• the crude vapor product may be fed directly to the hydrogenation reactor without the need for condensing the acetic acid and light ends or removing water, saving overall processing costs.
• the acetic acid may be vaporized at the reaction temperature, following which the vaporized acetic acid may be fed along with hydrogen in an undiluted state or diluted with a relatively inert carrier gas, such as nitrogen, argon, helium, carbon dioxide and the like.
• a relatively inert carrier gas such as nitrogen, argon, helium, carbon dioxide and the like.
• the temperature should be controlled in the system such that it does not fall below the dew point of acetic acid.
• the acetic acid may be vaporized at the boiling point of acetic acid at the particular pressure, and then the vaporized acetic acid may be further heated to the reactor inlet temperature.
• the acetic acid is mixed with other gases before vaporizing, followed by heating the mixed vapors up to the reactor inlet temperature.
• the acetic acid is transferred to the vapor state by passing hydrogen and/or recycle gas through the acetic acid at a temperature at or below 125°C, followed by heating of the combined gaseous stream to the
• the reactor in some embodiments, may include a variety of configurations using a fixed bed reactor or a fluidized bed reactor.
• an "adiabatic" reactor can be used; that is, there is little or no need for internal plumbing through the reaction zone to add or remove heat.
• a radial flow reactor or reactors may be employed as the reactor, or a series of reactors may be employed with or without heat exchange, quenching, or introduction of additional feed material.
• a shell and tube reactor provided with a heat transfer medium may be used.
• the reaction zone may be housed in a single vessel or in a series of vessels with heat exchangers therebetween.
• the catalyst is employed in a fixed bed reactor, e.g., in the shape of a pipe or tube, where the reactants, typically in the vapor form, are passed over or through the catalyst.
• a fixed bed reactor e.g., in the shape of a pipe or tube
• Other reactors such as fluid or ebullient bed reactors, can be employed.
• the hydrogenation catalysts may be used in conjunction with an inert material to regulate the pressure drop of the reactant stream through the catalyst bed and the contact time of the reactant compounds with the catalyst particles.
• the hydrogenation in the reactor may be carried out in either the liquid phase or vapor phase.
• the reaction is carried out in the vapor phase under the following conditions.
• the reaction temperature may range from 125°C to 350°C, e.g., from 200°C to 325°C, from 225°C to 300°C, or from 250 D C to 300°C.
• the pressure may range from 10 kPa to 3000 kPa, e.g., from 50 kPa to 2300 kPa, from 100 kPa to 2100 kPa, or from 200 kPa to 2100 kPa.
• the reactants may be fed to the reactor at a gas hourly space velocity (GHSV) of greater than 500 hr " ', e.g., greater than 1000 hr “1 , greater than 2500 hr “1 or even greater than 5000 hr “1 .
• GHSV gas hourly space velocity
• the GHSV may range from 50 hr “1 to 50,000 hr “1 , e.g., from 500 hr "1 to 30,000 hr “1 , from 1000 hr "1 to 10,000 hr "1 , or from 1000 hr “1 to 6500 hr "1 .
• the hydrogenation optionally is carried out at a pressure just sufficient to overcome the pressure drop across the catalytic bed at the GHSV selected, although there is no bar to the use of higher pressures, it being understood that considerable pressure drop through the reactor bed may be experienced at high space velocities, e.g., 5000 hr "1 or 6,500 hr "1 .
• the reaction consumes two moles of hydrogen per mole of acetic acid to produce one mole of ethanol
• the actual molar ratio of hydrogen to acetic acid in the feed stream may vary from about 100: 1 to 1:100, e.g., from 50:1 to 1:50, from 20:1 to 1:2, or from 18:1 to 8:1.
• the molar ratio of hydrogen to acetic acid is greater than 2:1, e.g., greater than 4: 1 or greater than 8:1.
• the reactor may use an excess of hydrogen, while the secondary hydrogenation reactor may use a sufficient amount of hydrogen as necessary to hydrogenate the impurities. In one aspect, a portion of the excess hydrogen from the reactor is directed to the secondary reactor for hydrogenation.
• the secondary reactor could be operated at a higher pressure than the hydrogenation reactor and a high pressure gas stream comprising hydrogen may be separated from the secondary reactor liquid product in an adiabatic pressure reduction vessel, and the gas stream could be directed to the hydrogenation reactor system.
• Contact or residence time can also vary widely, depending upon such variables as amount of acetic acid, catalyst, reactor, temperature, and pressure. Typical contact times range from a fraction of a second to more than several hours when a catalyst system other than a fixed bed is used, with preferred contact times, at least for vapor phase reactions, of from 0.1 to 100 seconds, e.g., from 0.3 to 80 seconds or from 0.4 to 30 seconds.
• the hydrogenation of acetic acid may achieve favorable conversion of acetic acid and favorable selectivity and productivity to ethanol.
• conversion refers to the amount of acetic acid in the feed that is converted to a compound other than acetic acid, respectively. Conversion is expressed as a percentage based on acetic acid or ethyl acetate in the feed.
• the conversion of acetic acid or ethyl acetate may be at least 10%, e.g., at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%.
• the conversion of ethyl acetate acid preferably is greater than 0%, meaning that more ethyl acetate is consumed than produced.
• ethyl acetate may be produced. Without consuming any ethyl acetate from the mixed vapor phase reactants, the conversion of ethyl acetate would be negative. However, for purposes of the present invention, enough of the ethyl acetate is consumed to at least offset the produced ethyl acetate.
• conversion of ethyl acetate may be at least 0%, e.g., at least 5%, at least 10%, at least 20%, or at least 35%.
• catalysts that have high conversions are desirable, especially acetic acid conversions that are at least 80% or at least 90%, in some embodiments a low acetic acid or ethyl acetate conversion may be acceptable at high selectivity for ethanol. It is, of course, well understood that in many cases, it is possible to compensate for low acetic acid conversion by appropriate recycle streams or use of larger reactors, but it is more difficult to compensate for poor selectivity.
• Selectivity is expressed as a mole percent based on converted acetic acid and/or ethyl acetate. It should be understood that each compound converted from acetic acid and or ethyl acetate has an independent selectivity and that selectivity is independent from conversion. For example, if 60 mole % of the converted acetic acid is converted to ethanol, we refer to the ethanol selectivity as 60%.
• the catalyst have a selectivity to ethanol is at least 50%, e.g., at least 60%, or at least 70%.
• the selectivity to ethanol may be high and is at least 75%, e.g., at least 80% or at least 85%.
• Preferred embodiments of the hydrogenation process also have low selectivity to undesirable products, such as methane, ethane, and carbon dioxide.
• the selectivity to these undesirable products preferably is less than 4%, e.g., less than 2% or less than 1%. More preferably, these undesirable products are present in undetectable amounts.
• Formation of alkanes may be low, and ideally less than 2%, less than 1%, or less than 0.5% of the acetic acid passed over the catalyst is converted to alkanes, which have little value other than as fuel.
• the catalyst has a total selectivity based on the combined conversion of acetic acid and ethyl acetate to ethanol. The total selectivity may be at least 60%, e.g., at least 70%, at least 80%, at least 85% or at least 88%.
• productivity refers to the grams of a specified product, e.g., ethanol, formed during the hydrogenation based on the kilograms of catalyst used per hour.
• the productivity preferably is from 100 to 3,000 grams of ethanol per kilogram of catalyst per hour, e.g., from 400 to 2,500 grams of ethanol per kilogram of catalyst per hour or from 600 to 2,000 grams of ethanol per kilogram of catalyst per hour.
• the crude ethanol product produced by the reactor, before any subsequent processing, such as purification and separation, will typically comprise unreacted acetic acid, ethanol and water.
• Exemplary compositional ranges for the crude ethanol product are provided in Table 1.
• the "others” identified in Table 1 may include, for example, esters, ethers, aldehydes, ketones, alkanes, and carbon dioxide.
• the crude ethanol product may comprise acetic acid in an amount less than 20 wt.%, e.g., of less than 15 wt.%, less than 10 wt.% or less than 5 wt.%.
• the acetic acid concentration of Table 1 may range from 0.1 wt.% to 20 wt.%, e.g., 0.2 wt.% to 15 wt.%, from 0.5 wt.% to 10 wt.% or from 1 wt.% to 5 wt.%.
• the conversion of acetic acid is preferably greater than 75%, e.g., greater than 85% or greater than 90%.
• the selectivity to ethanol may also be preferably high, and is greater than 75%, e.g., greater than 85% or greater than 90%.
• An ethanol product may be recovered from the crude ethanol product produced by the reactor using the catalyst of the present invention may be recovered using several different techniques.
• the ethanol product may be an industrial grade ethanol comprising from 75 to 96 wt.% ethanol, e.g., from 80 to 96 wt.% or from 85 to 96 wt.% ethanol, based on the total weight of the ethanol product.
• the ethanol product when further water separation is used, preferably contains ethanol in an amount that is greater than 97 wt.%, e.g., greater than 98 wt.% or greater than 99.5 wt.%.
• the ethanol product in this aspect preferably comprises less than 3 wt.% water, e.g., less than 2 wt.% or less than 0.5 wt.%.
• the finished ethanol composition produced by the embodiments of the present invention may be used in a variety of applications including fuels, solvents, chemical feedstocks, pharmaceutical products, cleansers, sanitizers, hydrogen transport or consumption.
• the finished ethanol composition may be blended with gasoline for motor vehicles such as automobiles, boats and small piston engine aircraft.
• the finished ethanol composition may be used as a solvent for toiletry and cosmetic preparations, detergents, disinfectants, coatings, inks, and pharmaceuticals.
• the finished ethanol composition may also be used as a processing solvent in manufacturing processes for medicinal products, food preparations, dyes, photochemicals and latex processing.
• the finished ethanol composition may also be used as a chemical feedstock to make other chemicals such as vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ethers, ethylamines, ethyl benzene, aldehydes, butadiene, and higher alcohols, especially butanol.
• the finished ethanol composition may be esterified with acetic acid.
• the finished ethanol composition may be dehydrated to produce ethylene.
• Any known dehydration catalyst such as zeolite catalysts or phosphotungstic acid catalysts, can be employed to dehydrate ethanol, such as those described in copending U.S. Pub. Nos.
• a zeolite catalyst for example, may be employed as the dehydration catalyst.
• the zeolite has a pore diameter of at least about 0.6 nm, and preferred zeolites include dehydration catalysts selected from the group consisting of mordenites, ZSM-5, a zeolite X and a zeolite Y.
• Zeolite X is described, for example, in U.S. Pat. No.
• Silica (1.0 g) of uniform particle size distribution was dried at 120°C in an oven under nitrogen atmosphere overnight and then cooled to room temperature to form the support material.
• a preferred silica support material is SS61138 High Surface Area (HSA) Silica Catalyst Carrier from Saint-Gobain NorPro.
• a stock solution of 0.5 g sa it/mL of Co(N0 3 ) 2 ⁇ 6H 2 0 (Alfa Aesar) in 8M nitric acid was prepared.
• a stock solution of 0.25 gsait/mL of Sn in 8M nitric acid was prepared with SnC 4 H (VxH 2 0 (Alfa Aesar).
• Silica-alumina (1.0 g) of uniform particle size distribution was dried at 120°C in an oven under nitrogen atmosphere overnight and then cooled to room temperature.
• the support contained 13.4 wt.% A1 2 0 3 . 457.6 ⁇ -, of the stock cobalt solution from Example A, 564.3 ⁇ L ⁇ of the stock tin solution from Example A and 518.1 of water was prepared and this mixture was impregnated on 1 g of the silica-alumina support. The impregnation was repeated so that the total active metal loading of cobalt and tin was 20 wt.%. The drying and calcining of Example A was repeated for this catalyst material.
• Example A Silica (1.0 g) of Example A was used. A stock solution of 0.5 g sa it/niL of Co(N0 3 ) 2 ⁇ 6H 2 0 (Alfa Aesar) in 8M nitric acid was prepared. 193.05 ⁇ ⁇ of the stock cobalt solution and 66.55 ⁇ , of nitric acid was prepared and 1200 ⁇ . of this mixture was impregnated on 1 g of the support. The impregnation of cobalt was repeated so that the total metal loading was 20 wt.%. The drying and calcining of Example A was repeated for this catalyst material.
• Silica-alumina (1.0 g) of uniform particle size distribution was dried at 120°C in an oven under nitrogen atmosphere overnight and then cooled to room temperature.
• a stock solution of 0.5 g sa i t /mL of Co(N0 3 ) 2 ⁇ 6H 2 0 (Alfa Aesar) in 8M nitric acid was prepared.
• 193.05LL of the stock cobalt solution and 66.55 ⁇ - of nitric acid was prepared and 1200 ⁇ iL of this mixture was impregnated on 1 g of the silica-alumina support.
• the impregnation of cobalt was repeated so that the total metal loading was 20 wt.%.
• the drying and calcining of Example A was repeated for this catalyst material.
• Example F Comparative
• Example G The catalyst of Example B was repeated, except the tin was replaced with copper and the nitric acid was replaced with water.
• Example G Example G
• Example H Comparative
• Example A Silica (1.0 g) of Example A was used. A stock solution of 0.5 g sa it/mL of Co(N0 3 ) 2 ⁇ 6H 2 0 (Alfa Aesar) in 8M nitric acid was prepared. A stock solution of 0.25 gsai/mL of Sn in 8M nitric acid was prepared with SnQHUCvxHbO (Alfa Aesar). 193.05 ⁇ . of the stock cobalt solution, 1060.4 ⁇ . of the stock tin solution and 66.55 ⁇ of nitric acid was prepared and 1200 of this mixture was impregnated on 1 g of the support.
• Example I Comparative
• Example G The modified support containing calcium metasilicate of Example G was used.
• a stock solution of 0.5 gsait/mL of Co(N0 3 ) 2 ⁇ 6H 2 0 (Alfa Aesar) in 8M nitric acid was prepared.
• a stock solution of 0.25 g sa it/mL of Sn in 8M nitric acid was prepared with SnC 4 H 4 0 6 -xH 2 0 (Alfa Aesar). 193.05 ⁇ . of the stock cobalt solution, 1060.4 ⁇ . of the stock tin solution and 66.55 ⁇ - of nitric acid was prepared and 1200 ⁇ . of this mixture was impregnated on 1 g of the modified support.
• the impregnation of the active metals was repeated so that the total active metal loading was 20 wt.%, with 75 mol.% Co and 25 mol.% Sn.
• the drying and calcining of Example A was repeated for this
• the modified support containing calcium metasilicate of Example G was used.
• a stock solution of 0.5 gsait/mL of Co(N0 3 ) 2 ⁇ 6H 2 0 (Alfa Aesar) in 8M nitric acid was prepared.
• a stock solution of 0.25 g sa it/mL of Sn in 8M nitric acid was prepared with SnC 4 H 4 0 6 -xH 2 0 (Alfa Aesar).
• 193.05 ⁇ , of the stock cobalt solution, 1060.4 ⁇ , of the stock tin solution and 66.55 ⁇ . of nitric acid was prepared and 1200 ⁇ . of this mixture was impregnated on 1 g of the modified support.
• the impregnation of the active metals was repeated so that the total active metal loading was 20 wt.%, with 25 mol.% Co and 75 mol.% Sn.
• the drying and calcining of Example A was repeated for this
• the analysis of the products was carried out by online GC.
• the front channel was equipped with an FID and a CP-Sil 5 (20 m) + WaxFFap (5 m) column and was used to quantify: Acetaldehyde, Ethanol, Acetone, Methyl acetate, Vinyl acetate, Ethyl acetate, Acetic acid, Ethylene glycol diacetate, Ethylene glycol, Ethylidene diacetate, and Paraldehyde.
• the middle channel was equipped with a TCD and Porabond Q column and was used to quantify: C0 2 , Ethylene, and Ethane.
• the back channel was equipped with a TCD and Porabond Q column and was used to quantify: Helium, Hydrogen, Nitrogen, Methane, and Carbon monoxide.
• GHSV GHSV
• Examples A and B showed an increase performance in terms of conversion and selectivity over the comparative catalysts that did not contain tin in Comparative Examples C through F.
• the 50-50 molar ratio in Example G demonstrated improved performance over other molar ratios in Comparative Examples H through J.
• Example L The catalyst of Example A was used. Pt(N0 3 ) 2 (Sigma Aldrich) was added to the support prior to drying and calcining. There were different amounts of platinum used; 0 wt. , 0.2 wt.%, 0.4 wt.%, and 0.6 wt.%.
• Pt(N0 3 ) 2 Sigma Aldrich
• Example G The catalyst of Example G was used. Pt(N0 3 ) 2 (Sigma Aldrich) was added to the support prior to drying and calcining. There were different amounts of platinum used; 0 wt.%, 0.2 wt.%, 0.4 wt.%, and 0.6 wt.%. The catalysts of Examples A to J were tested.
• Nitrate precursors of noble metals are impregnated on the catalysts of Example A.
• the metal loading level of the noble metals was 0.4 wt.%.
• acetic acid feed liquid was evaporated and charged to the reactor along with hydrogen and helium as a carrier gas with an average combined gas hourly space velocity (GHSV) of about 2430 hr "1 at a temperature of about 250°C and pressure of 2500 kPa.
• GHSV gas hourly space velocity
• a portion of the vapor effluent was passed through a gas chromatograph for analysis of the contents of the effluents.
• Nitrate precursors of first metal promoters are impregnated on the catalysts of Examples A (Si0 2 ) and L (Si0 2 -CaSi0 3 ) before the impregnation of the active metals, e.g., cobalt and tin.
• the metal loading level of the first metal promoters was 0.2 wt. .
• Nitrate precursors of first metal promoters are impregnated on the catalysts of Examples A (Si0 2 ) and L (Si0 2 -CaSi0 3 ) after the impregnation of the active metals, e.g., cobalt and tin. Barium was not test in this example.
• the metal loading level of the first metal promoters was 0.2 wt.%.
• the impregnated catalyst was dried at 50°C in air with a ramp rate of l°C/minute, followed by a ramp rate of 2°C/minute up to 120°C.
• the catalyst was kept at 120°C for 2 hours and then calcined at 450°C for four hours with a 2°C/minute heating rate in air.
• the impregnated catalyst was dried at 50°C in air with a ramp rate of l°C/minute, followed by a ramp rate of 2°C/minute up to 120°C.
• the catalyst was kept at 120°C for 2 hours and then calcined at 450°C for four hours with a 2°C/minute heating rate in air.
• Nitrate precursors of first metal promoters are impregnated on the catalysts of Example M (Si0 2 -CaSi0 3 ) before the impregnation of the active metals, e.g., cobalt and tin.
• the metal loading level of the first metal promoters was 0.2 wt.%.
• the catalyst was 50 mol.% cobalt and 50 mol.% tin on silica, prepared in accordance with the procedure of Example A.
• a feed liquid was comprised essentially of 70 wt.% acetic acid and 30 wt.% ethyl acetate.
• the feed liquid was evaporated and charged to the reactor along with hydrogen and helium as a carrier gas with an average combined gas hourly space velocity (GHSV) of about - 2430 hr "1 at a temperature of about 250°C and pressure of 2500 kPa.
• GHSV gas hourly space velocity
• a portion of the vapor effluent was passed through a gas chromatograph for analysis of the contents of the effluents.
• the selectivity of ethyl acetate to ethanol was from 4.1% to 10.8%.
• the catalyst utilized was 100 mol.% cobalt on silica-calcium metasilicate (10 wt.%) support prepared in accordance with the procedure of Example M.
• Example 2 The procedure as set forth in Example 1 is substantially repeated. A portion of the vapor effluent is passed through a gas chromatograph for analysis of the contents of the effluents. The selectivity of ethyl acetate to ethanol was from 0.6% to 7.1%.
• the catalyst utilized was 100 mol.% cobalt on silica-calcium metasilicate support prepared in accordance with the procedure of Example N.
• Example 1 The procedure as set forth in Example 1 is substantially repeated. A portion of the vapor effluent is passed through a gas chromatograph for analysis of the contents of the effluents. The selectivity of ethyl acetate to ethanol was from 0.6% to 7.1%.

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