EP2493611A2 - Procédés pour fabriquer de l'éthanol ou de l'acétate d'éthyle à partir d'acide acétique en utilisant des catalyseurs bimétalliques - Google Patents

Procédés pour fabriquer de l'éthanol ou de l'acétate d'éthyle à partir d'acide acétique en utilisant des catalyseurs bimétalliques

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Publication number
EP2493611A2
EP2493611A2 EP10703747A EP10703747A EP2493611A2 EP 2493611 A2 EP2493611 A2 EP 2493611A2 EP 10703747 A EP10703747 A EP 10703747A EP 10703747 A EP10703747 A EP 10703747A EP 2493611 A2 EP2493611 A2 EP 2493611A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
support
acetic acid
hydrogenation
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10703747A
Other languages
German (de)
English (en)
Inventor
Victor J. Johnston
Laiyuan Chen
Barbara F. Kimmich
Josefina T. Chapman
James H. Zink
Heiko Weiner
John L. Potts
Radmila Jevtic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese International Corp
Original Assignee
Celanese International Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/588,727 external-priority patent/US8309772B2/en
Application filed by Celanese International Corp filed Critical Celanese International Corp
Publication of EP2493611A2 publication Critical patent/EP2493611A2/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
    • 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
    • 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
    • B01J37/0207—Pretreatment of the support
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates generally to processes for hydrogenating acetic acid to form ethanol and/or ethyl acetate depending on the molar ratio of the metals in the bimetallic catalyst.
  • Vapor-phase acetic acid hydrogenation was studied further over a family of supported Pt-Fe catalysts in Rachmady, W.; Vannice, M. A. J Catal. (2002) Vol. 209, pg. 87-98) and Rachmady, W.; Vannice, M. A. J Catal. (2000) Vol. 192, pg. 322-334).
  • United States Patent No. 5,149,680 to Kitson et al. describes a process for the catalytic hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters utilizing Group VIII metal alloy catalysts.
  • United States Patent No. 4,777,303 to Kitson et al. describes a process for the productions of alcohols by the hydrogenation of carboxylic acids.
  • United States Patent No. 4,804,791 to Kitson et al. describes another process for the production of alcohols by the hydrogenation of carboxylic acids. See also USP 5,061,671; USP 4, 990,655; USP 4,985,572; and USP 4,826,795.
  • Bimetallic ruthenium-tin/silica catalysts have been prepared by reaction of tetrabutyl tin with ruthenium dioxide supported on silica.
  • Hindermann et al. (Hindermann et al, J. Chem. Res., Synopses (1980), (11), 373), disclosing catalytic reduction of acetic acid on iron and on alkali-promoted iron.
  • the present invention relates to processes for selectively making ethanol, ethyl acetate, or mixtures of ethanol and ethyl acetate, from the hydrogenation of acetic acid. It has now been discovered that the relative amounts of ethanol and ethyl acetate formed in the hydrogenation of acetic acid may be advantageously controlled based on the molar ratio of metals used in the hydrogenation catalyst.
  • the catalyst comprises platinum and tin and is selective for making ethanol.
  • the invention is to a process for producing ethanol, comprising hydrogenating acetic acid in the presence of a catalyst comprising a platinum, tin and at least one support, wherein the molar ratio of platinum to tin is from 0.4:0.6 to 0.6:0.4.
  • the catalyst comprises rhenium and palladium and is selective for making ethanol.
  • the invention is to a process comprising hydrogenating acetic acid in the presence of a catalyst comprising a rhenium, palladium and at least one support, wherein the molar ratio of rhenium to palladium is from 0.7:0.3 to 0.85:0.15.
  • the catalyst preferably further comprises at least one support modifier is 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 IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof.
  • at least one support modifier is 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 IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof.
  • the at least one support modifier optionally is selected from the group consisting of oxides and metasilicates of sodium, potassium, magnesium, calcium, scandium, yttrium, and zinc, and may be present in an amount of 0.1 wt.% to 50 wt.%, based on the total weight of the catalyst.
  • the hydrogenation preferably is performed in a vapor phase at a temperature of from 125°C to 350°C, a pressure of 10 KPa to 3000 KPa, and a hydrogen to acetic acid mole ratio of greater than 4:1.
  • the catalyst comprises platinum and tin and is selective for making ethyl acetate.
  • the invention is to a process for producing acetate, comprising hydrogenating acetic acid in the presence of a catalyst comprising a platinum, tin and at least one support, wherein the molar ratio of platinum to tin is less than 0.4:0.6 or greater than 0.6:0.4.
  • the catalyst comprises rhenium and palladium and is selective for making ethyl acetate.
  • the invention is to a process for producing acetate, comprising hydrogenating acetic acid in the presence of a catalyst comprising a rhenium, palladium and at least one support, wherein the molar ratio of rhenium to palladium is less than 0.7:0.3 or greater than 0.85:0.15.
  • the catalyst optionally further comprises at least one support modifier selected from the group consisting of oxides of Group IVB metals, oxides of Group VB metals, oxides of Group VIB metals, iron oxides, aluminum oxides, and mixtures thereof, e.g., at least one support modifier is selected from the group consisting of W0 3 , Mo0 3 , Fe 2 0 3 , Ti0 2 , Zr0 2 , Nt ⁇ Os, Ta 2 Os, and AI2O3.
  • the at least one support modifier for example, may be present in an amount of 0.1 wt.% to 50 wt.%, based on the total weight of the catalyst.
  • the hydrogenation preferably is performed in a vapor phase at a temperature of from 125°C to 350°C, a pressure of 10 KPa to 3000 KPa, and a hydrogen to acetic acid mole ratio of greater than 4:1.
  • the support optionally is present in an amount of 25 wt.% to 99 wt.%, based on the total weight of the catalyst, and preferably has a surface area of from 50 m /g to 600 m /g.
  • the support for example, may be selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof.
  • the support optionally contains less than 1 wt% of aluminum, based on the total weight of the catalyst.
  • the catalysts also preferably have a productivity that decreases less than 6% per 100 hours of catalyst usage.
  • At least 10% of the acetic acid preferably is converted during hydrogenation, and preferably the hydrogenation has a selectivity to ethanol or ethyl acetate, as desired, of at least 50%, or at least 60%, and a selectivity to methane, ethane, and carbon dioxide and mixtures thereof of less than 4%.
  • FIG. 1 A is a graph of the selectivity to ethanol and ethyl acetate using a Si0 2 -Pt m Sn 1-m catalyst according to one embodiment of the invention
  • FIG. IB is a graph of the productivity to ethanol and ethyl acetate of the catalyst of FIG. 1A;
  • FIG. 1C is a graph of the convention of the acetic acid of the catalyst of FIG. 1 A;
  • FIG. 2A is a graph of the selectivity to ethanol and ethyl acetate using a Si0 2 -Re n Pd 1-n catalyst according to one embodiment of the invention
  • FIG. 2B is a graph of the productivity to ethanol and ethyl acetate of the catalyst of FIG. 2A;
  • FIG. 2C is a graph of the convention of the acetic acid of the catalyst of FIG. 2 A.
  • the present invention relates to processes for producing ethanol and/or ethyl acetate by hydrogenating acetic acid in the presence of a bimetallic catalyst. It has now been discovered that the relative amounts of ethanol and ethyl acetate formed in the hydrogenation of acetic acid may be advantageously controlled based on the molar ratio of metals used in the hydrogenation catalyst.
  • the bimetallic catalyst comprises platinum and tin. In another embodiment, the bimetallic catalyst comprises rhenium and palladium.
  • the Pt/Sn molar ratio preferably is from 0.4:0.6 to 0.6:0.4, e.g., from 0.45:0.55 to 0.55:0.45 or about 1 :1.
  • the Re/Pd molar ratio preferably is from 0.6:0.4 to 0.85:0.15, e.g., from 0.7:0.3 to 0.85:0.15, or a molar ratio of about 0.75:0.25.
  • the Pt Sn molar ratio preferably is less than 0.4:0.6 or greater than 0.6:0.4. More preferably, for this embodiment, the Pt/Sn molar ratio is from 0.65:0.35 to 0.95:0.05, e.g., from 0.7:0.3 to 0.95:0.05. In another embodiment, the Pt Sn molar ratio is from 0.05:0.95 to 0.35:0.65.
  • the Re/Pd molar ratio preferably is less than 0.7:0.3 or greater than 0.85:0.15. More preferably, for this embodiment, the Pt/Sn molar ratio is from 0.05:0.95 to 0.7:0.3, e.g., from 0.1 :0.9 to 0.6:0.4. In another embodiment, the Pt/Sn molar ratio is from 0.85:0.15 to 0.95:0.05.
  • ethyl acetate may also be formed, and conversely, for processes that use catalysts favoring ethyl acetate formation, ethanol may also be formed.
  • a catalyst favors ethanol or ethyl acetate formation when the selectivity to one product is greater than the other.
  • selectivities to ethanol or ethyl acetate that are greater than 50%, e.g., greater than 75% or greater than 80%, may be achieved.
  • conversion refers to the amount of acetic acid in the feed that is convert to a compound other than acetic acid. Conversion is expressed as a mole percentage based on acetic acid in the feed. The conversion of acetic acid
  • the conversion 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%.
  • catalysts that have high conversions are desirable, such as at least 80% or at least 90%, a low conversion may be acceptable at high selectivity to the desired product, e.g., either ethanol or ethyl acetate. It is, of course, well understood that in many cases it is possible to compensate for poor conversion by incorporating recycle streams or using larger reactors, while it is typically more difficult to compensate for poor selectivity.
  • Selectivity is expressed as a mole percent based on converted acetic acid. It should be understood that each compound converted from acetic acid has an independent selectivity and that selectivity is independent of conversion. For example, if 50 mole % of the converted acetic acid is converted to ethanol, we refer to the ethanol selectivity as 50%.
  • Selectivity to ethanol (EtOH) is calculated from gas chromatography (GC) data using the following equation:
  • Total mmol C refers to total mmols of carbon from all of the products analyzed by gas chromatograph.
  • selectivity to ethyl acetate may be similarly calculated by substituting mmol EtOAc (GC) for mmol EtOH (GC) in the above equation.
  • the selectivity to ethoxylates of the catalyst preferably is at least 60%, e.g., at least 70%, or at least 80%.
  • ethoxylates refers specifically to the compounds ethanol and ethyl acetate.
  • the selectivity to ethanol preferably is at least 60%, e.g., at least 75% or at least 80%.
  • the selectivity to ethyl acetate preferably is at least 50%, e.g., at least 75% or at least 80%. It is also generally desirable to 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%.
  • alkanes are low. For example, in some embodiments, less than 2%, less 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 first metal e.g., platinum or palladium
  • the first metal optionally is present in the catalyst in an amount from 0.1 to 10 wt.%, e.g. from 0.1 to 5 wt.%, or from 0.1 to 3 wt.%.
  • the second metal e.g., tin or rhenium, preferably is present in an amount from 0.1 and 20 wt.%, e.g., from 0.1 to 10 wt.%, or from 0.1 to 5 wt.%.
  • the two or more metals may be alloyed with one another or may comprise a non- alloyed solid solution or mixture. Unless otherwise indicated, all catalyst metal loadings expressed herein are provided in weight percent, based on the total weight of the catalyst including all metals, support and support modifier, if present.
  • the catalyst further comprises a third metal, which preferably is selected from the group consisting of cobalt, palladium, ruthenium, copper, zinc, platinum, tin,
  • the third metal is selected from cobalt, palladium, and ruthenium.
  • the total weight of the third metal preferably is from 0.05 and 4 wt.%, e.g., from 0.1 to 3 wt.%, or from 0.1 to 2 wt.%.
  • the metals of the catalysts of the present invention may be dispersed throughout the support, coated on the outer surface of the support (egg shell) or decorated on the surface of the support.
  • the catalysts of the present invention further comprise a support that optionally includes a support modifier.
  • a support material should be selected such that the catalyst system is suitably active, selective and robust under the process conditions employed for the formation of the desired product, e.g., ethanol and/or ethyl acetate.
  • Suitable support materials may include, for example, stable metal oxide-based supports or ceramic-based supports as well as molecular sieves, such as zeolites.
  • suitable support materials include without limitation, iron oxide, silica, alumina, silica/aluminas, titania, zirconia, magnesium oxide, a Group IIA silicate such as calcium metasilicate, carbon, graphite, high surface area graphitized carbon, activated carbons, and mixtures thereof.
  • a Group IIA silicate such as calcium metasilicate, carbon, graphite, high surface area graphitized carbon, activated carbons, and mixtures thereof.
  • Preferred supports include silica, silica/alumina, a Group IIA silicate such as calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof. It has now been discovered that increasing acidity of the support tends to increase selectivity to ethyl acetate over ethanol, and vice versa. Thus, in the case where silica is used as the support, it may be beneficial, particularly if ethanol is the desired product, to ensure that the amount of aluminum, which is a common acidic contaminant for silica, is low, preferably under 1 wt.%, e.g., under 0.5 wt.% or under 0.3 wt.%, based on the total weight of the modified support.
  • a Group IIA silicate such as calcium metasilicate
  • pyrogenic silica high purity silica and mixtures thereof.
  • pyrogenic silica may be preferred as it commonly is available in purities exceeding 99.7 wt.%.
  • High purity silica refers to silica in which acidic contaminants such as aluminum are present, if at all, at levels of less than 0.3 wt.%, e.g., less than 0.2 wt.% or less than 0.1 wt.%.
  • the aluminum content of such silica may be less than 10 wt.%, e.g., less than 5 wt.% or less than 3 wt.%, based on the total weight of the silica including any contaminants contained therein.
  • the support comprises a basic support modifier in the range of from 2 wt.% to 10 wt.%, larger amount of acidic impurities, such as aluminum, can be tolerated so long as they are substantially counterbalanced by an appropriate amount of a support modifier.
  • the surface area of the support material preferably is at least about 50 m /g, e.g., at least about 100 m /g, at least about 150 m /g, at least about 200 m 2 /g or at least about 250 m 2 /g.
  • the silicaceous support material 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 /g. For purposes of the present
  • 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 support material e.g., silicaceous support material
  • the support material 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 material may vary widely.
  • the morphology of the support material 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 support material e.g., silicaceous support material
  • the support material preferably has an average particle size, 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 0.5 cm or from 0.2 to 0.4 cm. Since the metals that are disposed on or within the modified support are generally very small in size, they should not substantially impact the size of the overall catalyst particles. Thus, the above particle sizes generally apply to both the size of the modified supports as well as to the final catalyst particles.
  • a preferred silica support material is SS61138 High Surface Area (HSA) 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 porosimetry and a packing density of about 0.352 g/cm 3 (22 lb/ft 3 ).
  • a preferred silica/alumina support material is KA-160 (Sud 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.
  • the total weight of the support preferably is from 75 wt.% to 99.9 wt.%, e.g., from 78 wt.% to 97 wt.%, or from 80 wt.% to 95 wt.%.
  • the support further comprises a support modifier, which, for example, may adjust the acidity of the support material.
  • the acidity of the support material may be adjusted, for example, by incorporating one or more of a basic support modifier, an acidic support modifier or a redox support modifier.
  • the acid sites, e.g., Bransted acid sites, on the support material may be adjusted by the support modifier to favor selectivity to ethanol or ethyl acetate, as desired, during the hydrogenation of acetic acid.
  • the acidity of the support material may be adjusted to favor formation of ethanol, for example, by reducing the number or reducing the availability of Bronsted acid sites on the support material.
  • the support material may also be adjusted by having the support modifier change the pKa of the support material. 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
  • the support comprises a basic support modifier having a low volatility or that is non- volatile.
  • Low volatility modifiers have a rate of loss that is low enough such that the acidity of the support modifier is not reversed during the life of the catalyst.
  • Such basic modifiers may be selected from the group consisting of: (i) alkaline earth oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB 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, and mixtures of any of the foregoing.
  • the support modifier is a calcium silicate, more preferably calcium metasilicate (CaSi0 3 ). If the support modifier comprises calcium metasilicate, it is preferred that at least a portion of the calcium metasilicate is in crystalline form.
  • the support modifier comprises a basic support modifier 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.
  • the catalyst includes a modified support comprising a support material and calcium metasilicate as support modifier in an amount effective to balance Bransted acid sites resulting, for example, from residual alumina in the silica.
  • the calcium metasilicate may be present in an amount from 1 wt.% to 10 wt.%, based on the total weight of the catalyst, in order to ensure that the support is essentially neutral or basic in character.
  • the support modifier e.g., calcium metasilicate
  • the support material e.g., silicaceous support material
  • the support material comprises a silicaceous support material that includes at least about 80 wt.%, e.g., at least about 85 wt.% or at least about 90 wt.%, high surface area silica in order to counteract this effect of including a support modifier.
  • the support comprises an acidic or redox support modifier.
  • support modifiers include, for example, those selected from the group consisting of oxides of Group IVB metals, oxides of Group VB metals, oxides of Group VIB metals, iron oxides, aluminum oxides, and mixtures thereof.
  • Preferred redox support modifiers include those selected from the group consisting of W0 3 , Mo0 3 , Fe 2 0 3 , and Cr 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 support modifier preferably has a low volatility or is non- volatile. Low volatility modifiers have a rate of loss that is low enough such that the acidity of the support modifier is not reversed during the life of the catalyst.
  • Catalysts of the present invention are particulate catalysts in the sense that, rather than being impregnated in a wash coat onto a monolithic carrier similar to automotive catalysts and diesel soot trap devices, the catalysts of the invention preferably are formed into particles, sometimes also referred to as beads or pellets, having any of a variety of shapes and the catalytic metals are provided to the reaction zone by placing a large number of these shaped catalysts in the reactor.
  • Commonly encountered shapes include extrudates of arbitrary cross- section taking the form of a generalized cylinder in the sense that the generators defining the surface of the extrudate are parallel lines.
  • any convenient particle shape including pellets, extrudates, spheres, spray dried microspheres, rings, pentarings, trilobes, quadrilobes and multi-lobal shapes may be used, although cylindrical pellets are preferred.
  • the shapes are chosen empirically based upon perceived ability to contact the vapor phase with the catalytic agents effectively.
  • catalysts of the present invention is the stability or activity of the catalyst for producing ethanol and/or ethyl acetate. 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 and/or ethyl acetate. In particular, it is possible to achieve such a degree of stability such that catalyst activity will have 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.
  • the catalyst activity may extend or stabilize, the productivity and selectivity of the catalyst for prolonged periods extending into over one week, over two weeks, and even months, of commercially viable operation in the presence of acetic acid vapor at temperatures of 125°C to 350°C at space velocities of greater than 2500 hr "1 .
  • the catalyst compositions of the invention preferably are formed through metal impregnation of the support or modified support, although other processes such as chemical vapor deposition may also be employed.
  • a precursor to the support modifier such as an acetate or a nitrate, may be used.
  • the support modifier e.g., CaSi0 3
  • the support material e.g., Si0 2 .
  • an aqueous suspension of the support modifier may be formed by adding the solid support modifier to deionized water, followed by the addition of colloidal support material thereto.
  • the resulting mixture may be stirred and added to additional support material using, for example, incipient wetness techniques in which the support modifier is added to a support material having the same pore volume as the volume of the support modifier solution. Capillary action then draws the support modifier into the pores in the support material.
  • the modified support can then be formed by drying and calcining to drive off water and any volatile components within the support modifier solution and depositing the support modifier on the support material. 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 materials into desired size distribution can be employed. Calcining of the shaped modified support may occur, for example, at a temperature of from 250°C to 800°C, e.g., from 300 to 700°C or about 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 metals are impregnated onto the support or modified support.
  • a precursor of the first metal 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 organic solvent, may be preferred.
  • the second metal also preferably is impregnated into the support or modified support from a second metal precursor. If desired, a third metal or third metal precursor may also be impregnated into the support or modified support.
  • 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 or modified 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 first and second metals (and optional additional metals) into the support or modified support may occur simultaneously (co-impregnation) or sequentially.
  • simultaneous impregnation the first and second metal precursors (and optionally additional metal precursors) are mixed together and added to the support or modified 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.
  • the first metal precursor is first added to the support or modified support followed by drying and calcining, and the resulting material is then impregnated with the second metal precursor followed by an additional drying and calcining step to form the final catalyst composition.
  • Additional metal precursors e.g., a third metal precursor
  • a third metal precursor may be added either with the first and/or second metal precursor or an a separate third impregnation step, followed by drying and calcination.
  • combinations of sequential and simultaneous impregnation may be employed if desired.
  • Suitable metal precursors include, for example, metal halides, amine solubilized metal hydroxides, metal nitrates or metal oxalates.
  • suitable compounds for platinum precursors and palladium precursors include chloroplatinic acid, ammonium chloroplatinate, amine solubilized platinum hydroxide, platinum nitrate, platinum tetra ammonium nitrate, platinum chloride, platinum oxalate, palladium nitrate, palladium tetra ammonium nitrate, palladium chloride, palladium oxalate, sodium palladium chloride, and sodium platinum chloride.
  • a particularly preferred precursor to platinum is platinum ammonium nitrate, Pt(NH 3 ) (N0 4 ) 2 .
  • Pt(NH 3 ) (N0 4 ) 2 platinum ammonium nitrate
  • aqueous solutions are preferred.
  • the first metal precursor and the second metal precursor are not metal halides and are substantially free of metal halides.
  • non-(metal halide) precursors are believed to increase selectivity to ethanol.
  • the "promoter" metal or metal precursor is first added to the support, e.g., modified support, followed by the "main" or “primary” metal or metal precursor.
  • the reverse order of addition is also possible.
  • Exemplary precursors for promoter metals include metal halides, amine solubilized metal hydroxides, metal nitrates or metal oxalates.
  • each impregnation step preferably is followed by drying and calcination.
  • a sequential impregnation may be used, starting with the addition of the promoter metal followed by a second impregnation step involving co-impregnation of the two principal metals, e.g., Pt and Sn.
  • PtSn CaSi0 3 on Si0 2 may be prepared by first impregnating CaSi0 3 onto the Si0 2 , followed by co-impregnation with Pt(NH 3 ) 4 (N0 4 ) 2 and Sn(AcO) 2 . Again, each impregnation step may be followed by drying and calcination steps. In most cases, the impregnation may be carried out using metal nitrate solutions. However, various other soluble salts, which upon calcination release metal ions, can also be used. Examples of other suitable metal salts for impregnation include, metal acids, such as perrhenic acid solution, metal oxalates, and the like. In those cases where substantially pure ethanol is to be produced, it is generally preferable to avoid the use of halogenated precursors for the platinum group metals, using the nitrogenous amine and/or nitrate based precursors instead.
  • the process of hydrogenating acetic acid to form ethanol and/or ethyl acetate according to one embodiment of the invention may be conducted in a variety of configurations using a fixed bed reactor or a fluidized bed reactor as one of skill in the art will readily appreciate.
  • 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 shell and tube reactor provided with a heat transfer medium can be used.
  • the reaction zone may be housed in a single vessel or in a series of vessels with heat exchangers therebetween. It is considered significant that acetic acid reduction processes using the catalysts of the present invention may be carried out in adiabatic reactors as this reactor configuration is typically far less capital intensive than tube and shell configurations.
  • the catalyst is employed in a fixed bed reactor, e.g., in the shape of an elongated 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 an elongated pipe or tube where the reactants, typically in the vapor form, are passed over or through the catalyst.
  • Other reactors such as fluid or ebullient bed reactors, can be employed, if desired.
  • 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 reaction 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 the range from of 125°C to 350°C, e.g., from 200°C to 325°C, from 225°C to about 300°C, or from 250°C to about 300°C.
  • the pressure may range from 10 KPa to 3000 KPa (about 0.1 to 30 atmospheres), e.g., from 50 KPa to 2300 KPa, or from 100 KPa to 1500 KPa.
  • the reactants may be fed to the reactor at a gas hourly space velocities (GHSV) of greater than 500 hr "1 , e.g., greater than 1000 hr “1 , greater than 2500 hr 1 and even greater than 5000 hr "1 .
  • GHSV gas hourly space velocities
  • 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 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 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 12:1 to 1:1. Most preferably, the molar ratio of hydrogen to acetic acid is greater than 4:1, e.g., greater than 5:1 or greater than 10:1.
  • 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, from 0.1 to 100 seconds, e.g., from 0.3 to 80 seconds or from 0.4 to 30 seconds.
  • the acetic acid may be vaporized at the reaction temperature, and then the vaporized acetic acid can be fed along with hydrogen in 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.
  • Productivity refers to the grams of a specified product, e.g., ethanol or ethyl acetate, formed during the hydrogenation based on the kilogram of catalyst used per hour.
  • a productivity of at least 200 grams of ethanol per kilogram catalyst per hour e.g., at least 400 grams of ethanol or least 600 grams of ethanol, is preferred.
  • the productivity preferably is from 200 to 3,000 grams of ethanol per kilogram catalyst per hour, e.g., from 400 to 2,500 or from 600 to 2,000.
  • a productivity of at least 200 grams of ethyl acetate per kilogram catalyst per hour e.g., at least 400 grams of ethyl acetate or least 600 grams of ethyl acetate, is preferred.
  • the productivity preferably is from 200 to 3,000 grams of ethyl acetate per kilogram catalyst per hour, e.g., from 400 to 2,500 or from 600 to 2,000.
  • the raw materials 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. It is well known to produce acetic acid through methanol carbonylation, acetaldehyde oxidation, ethylene oxidation, oxidative fermentation, and anaerobic fermentation. As petroleum and natural gas prices fluctuate becoming either more or less expensive, methods for producing acetic acid and intermediates such as methanol and carbon monoxide from alternate carbon sources have drawn increasing interest. In particular, when petroleum is relatively expensive compared to natural gas, it may become advantageous to produce acetic acid from synthesis gas (“syn gas”) that is derived from any available carbon source.
  • Syn gas synthesis gas
  • United States Patent No. RE 35,377 to Steinberg et al 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
  • 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 United States Patent No. 6,657,078 to Scates et al., the entirety of which is incorporated herein by reference.
  • the crude vapor product may be fed directly to the ethanol synthesis reaction zones of the present invention without the need for condensing the acetic acid and light ends or removing water, saving overall processing costs.
  • Ethanol obtained from hydrogenation processes of the present invention, may be used in its own right as a fuel or subsequently converted to ethylene which is an important commodity feedstock as it can be converted to polyethylene, vinyl acetate and/or ethyl acetate or any of a wide variety of other chemical products.
  • ethylene can also be converted to numerous polymer and monomer products. The dehydration of ethanol to ethylene is shown below.
  • dehydration catalysts can be employed in to dehydrate ethanol, such as those described in copending applications U.S. Application No. 12/221,137 and U.S.
  • a zeolite catalyst for example, may be employed as the dehydration catalyst. While any zeolite having a pore diameter of at least about 0.6 nm can be used, 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. 2,882,244 and zeolite Y in U.S. Pat. No. 3,130,007, the entireties of which are hereby incorporated by reference.
  • Ethanol may also be used as a fuel, in pharmaceutical products, cleansers, sanitizers, hydrogenation transport or consumption. Ethanol may also be used as a source material for making ethyl acetate, aldehydes, and higher alcohols, especially butanol.
  • any ester, such as ethyl acetate, formed during the process of making ethanol according to the present invention may be further reacted with an acid catalyst to form additional ethanol as well as acetic acid, which may be recycled to the hydrogenation process.
  • Ethyl acetate obtained by the present invention may be used in its own right, polymerized, or converted to ethylene through a cracking process.
  • the cracking of ethyl acetate to ethylene is shown below.
  • the cracking may be a catalyzed reaction utilizing a cracking catalyst.
  • Suitable cracking catalysts include sulfonic acid resins such as perfluorosulfonic acid resins disclosed in United States Patent No. 4,399,305, noted above, the disclosure of which is incorporated herein by reference. Zeolites are also suitable as cracking catalysts as noted in United States Patent No. 4,620,050, the disclosure of which is also incorporated herein by reference.
  • the catalyst supports were dried at 120°C overnight under circulating air prior to use. All commercial supports (i.e., Si0 2 , Zr0 2 ) were used as a 14/30 mesh, or in its original shape (1/16 inch or 1/8 inch pellets) unless mentioned otherwise. Powdered materials (i.e., CaSi0 3 ) were pelletized, crushed and sieved after the metals had been added. The individual catalyst preparations are described in detail below.
  • the catalysts were prepared by first adding Sn(OAc) 2 (tin acetate, Sn(OAc) 2 from Aldrich ) (0.1421 g, 0.60 mmol) to a vial containing 6.75 ml of 1 :1 diluted glacial acetic acid (Fisher). The mixture was stirred for 15 min at room temperature, and then, 0.2323 g (0.60 mmol) of solid Pt(NH 3 ) 4 (N0 3 ) 2 (Aldrich) were added.
  • Example 1 the weight percentage of the catalyst is 2.3 wt.% platinum and 1.4 wt.% tin.
  • the weight percent in Example 3 is 1.1 wt.% platinum and 2.1 wt.% tin and Example 4 is 3.4 wt.% platinum and 0.7 wt.% tin.
  • Example 2 which contains no platinum, contains 2.7 wt% of tin and Example 5, which contains no tin, contains 4.5 wt% of platinum.
  • the material was prepared by first adding CaSi0 3 (Aldrich) to the Si0 2 catalyst support, followed by the addition of Pt/Sn as described previously. First, an aqueous suspension of CaSi0 3 ( ⁇ 200 mesh) was prepared by adding 0.52 g of the solid to 13 ml of deionized H 2 0, followed by the addition of 1.0 ml of colloidal Si0 2 (15 wt% solution,
  • FIGS. 1A-1C also illustrate the performance of the catalyst from Examples 1-5 and FIGS. 2A-2C illustrate the performance of the catalyst from Examples 7-11.
  • 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
  • Molsieve 5 A column and was used to quantify: Helium; Hydrogen; Nitrogen; Methane; and Carbon monoxide.

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Abstract

La présente invention concerne un procédé pour la formation sélective d'éthanol et/ou d'acétate d'éthyle à partir d'acide acétique par hydrogénation d'acide acétique en présence d'un catalyseur Pt/Sn ou d'un catalyseur Re/Pd. Le catalyseur peut comprendre en outre un modifieur de support pour améliorer la sélectivité pour le produit souhaité.
EP10703747A 2009-10-26 2010-02-02 Procédés pour fabriquer de l'éthanol ou de l'acétate d'éthyle à partir d'acide acétique en utilisant des catalyseurs bimétalliques Withdrawn EP2493611A2 (fr)

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US12/588,727 US8309772B2 (en) 2008-07-31 2009-10-26 Tunable catalyst gas phase hydrogenation of carboxylic acids
PCT/US2010/022954 WO2011056248A2 (fr) 2009-10-26 2010-02-02 Procédés pour fabriquer de l'éthanol ou de l'acétate d'éthyle à partir d'acide acétique en utilisant des catalyseurs bimétalliques

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US8211821B2 (en) * 2010-02-01 2012-07-03 Celanese International Corporation Processes for making tin-containing catalysts
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CN111298780A (zh) * 2018-12-12 2020-06-19 国家能源投资集团有限责任公司 复合粘结剂和载体及其制备方法和应用以及乙酸加氢制乙醇催化剂及其应用

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US4399305A (en) 1982-10-18 1983-08-16 Union Carbide Corporation Production of ethylene by the pyrolysis of ethyl acetate
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