WO2012074841A2 - Copper chromite hydrogenation catalysts for production of fatty alcohols - Google Patents
Copper chromite hydrogenation catalysts for production of fatty alcohols Download PDFInfo
- Publication number
- WO2012074841A2 WO2012074841A2 PCT/US2011/061867 US2011061867W WO2012074841A2 WO 2012074841 A2 WO2012074841 A2 WO 2012074841A2 US 2011061867 W US2011061867 W US 2011061867W WO 2012074841 A2 WO2012074841 A2 WO 2012074841A2
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- WIPO (PCT)
- Prior art keywords
- catalyst
- range
- copper chromite
- alkali metal
- alkaline earth
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 150000002191 fatty alcohols Chemical class 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 32
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 32
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 26
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 239000004927 clay Substances 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000005749 Copper compound Substances 0.000 claims description 5
- 150000001845 chromium compounds Chemical class 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000006187 pill Substances 0.000 description 4
- -1 sodium Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B01J35/613—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/66—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/04—Mixing
-
- 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
Definitions
- This invention relates to catalysts that are particularly useful as hydrogenation catalysts, and more particularly, catalysts that are useful for hydrogenating carboxylic esters to form fatty alcohols, The invention also relates to a method of preparing these catalysts and to the use of the catalysts in hydrogenation reactions.
- reaction 220°C and above are higher than those used for the fixed-bed, liquid-phase process.
- the main reasons such temperatures are used are to keep the feed in gaseous phase and to avoid condensation.
- endothermic reactions (reactions 2 through 4) are accelerated giving by-products such as hydrocarbons, carbonyl compounds and ethers.
- Reaction (2) shows dehydration of the fatty alcohol to an olefin followed by hydrogenation to a hydrocarbon.
- reaction (3) shows dehydration of the fatty alcohol to an ether.
- reaction (4) shows dehydrogenation of the fatty alcohol to a carbonyl compound.
- the catalysts comprise a copper chromite, a mixture of a copper compound and a chromium compound; an alkali metal or alkaline earth metal component; and an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the inorganic matrix component are processed together to form the catalyst.
- Such catalysts have an increased selectivity for fatty alcohol as compared to a copper chromite catalyst having no alkali metal or alkaline earth metal component as used in hydrogenation reactions.
- One embodiment provides a catalyst formed from a blend consisting essentially of copper chromite; an alkali metal or alkaline earth metal component; and at least one an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the at least one inorganic matrix component are processed together to form the catalyst.
- a method of making a catalyst for hydrogenation comprises: mixing a copper chromite powder, a combination of a copper compound and a chromium compound, or both with an inorganic matrix component to form a dry mixture; adding a solution containing an alkali metal or alkaline earth metal component to the dry mixture to form a blend; and forming the catalyst.
- a method for making fatty alcohols comprises: providing a feedstock comprising a methyl ester; contacting the feedstock with one of the catalysts of the present invention; and yielding fatty alcohols.
- FIG. 1 is a graph showing % methyl-ester conversion versus time for a catalyst of the present invention and a comparison catalyst.
- the catalysts are for vapor-phase hydrogenation of methyl esters to fatty alcohols under fixed-bed conditions, where conditions are typically in a temperature range of 200 to 250°C and a pressure range of 30 to 50 bar. Methods of making and using the same are also provided.
- These catalysts comprise a copper chromite, an alkali metal or alkaline earth metal component, and an inorganic matrix component, which are processed together to form the catalyst.
- a copper chromite means that copper chromite is present, which can be provided neat as the compound itself, or as a mixture of a copper compound and a chromium compound, or both. When provided as a mixture, without intended to be bound by theory, it is thought that the mixture forms copper chromite in situ.
- the alkali metal component can comprise sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), or combinations thereof.
- Alkaline earth metals can comprise magnesium (Mg), calcium (Ca), barium (Ba),
- these catalysts contain a significant amount of mesoporosity.
- Reference to "mesoporosity” means those pores having a pore diameter in the range of 20 to 700 Angstroms (A).
- the catalyst has a mesopore volume of 0.20 cc/g or more and an overall pore volume of 0.25 cc/g or more.
- the mesopore volume is in the range of 0.20 to 0.50 cc/g, or 0.25 to 0.40 cc/g, or even 0.29 to 0.33 cc/g and an overall pore volume in the range of 0.25 to 0.60 cc/g, or 0.30 to 0.50, or even 0.35 to 0.40 cc/g, That is, the pore volume of pores having a diameter in the range of 20 to 700 A is about 80% of the total pore volume, or more generally, in the range of about 80 to 85% of the total pore volume.
- the catalyst has a surface area in the range of 30 to 80 m 2 /g , or even 45 to 70 m /g.
- Catalysts will generally not contain ingredients that will affect selectivity or acidity.
- the catalysts will not contain nickel, which could affect selectivity.
- up to trace amounts of zeolites may be suitable, but not amounts that would appreciably increase acidity.
- the catalytic material is free of such materials if their presence is in an amount that does not materially affect the physical, chemical and catalytic characteristics of the compositions when compared to those which are completely free of such materials.
- such materials will be present in trace amounts, but in amounts not greater than about 0.5% by weight, more preferably not greater than 0.1% weight.
- catalysts for hydrogenation comprising: a copper chromite; an alkali metal or alkaline earth metal component; and an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the inorganic matrix component are processed together to form the catalyst.
- Such catalysts have an increased selectivity for fatty alcohol as compared to a copper chromite catalyst having no alkali metal or alkaline earth component as used in hydrogenation reactions.
- the catalyst is prepared from a blend of: an amount of the copper chromite in the range of 60 to 90 % by weight of the blend; an amount of the alkali metal or alkaline earth metal component in the range of 0.5 to 3.0 % by weight of the blend; and an amount of the inorganic matrix component in the range of 10 to 40 % by weight of the blend.
- a detailed embodiment provides a blend of 70-80 weight % copper chromite, 1.5-2.0 weight % alkali metal or alkaline earth metal component, and 20-30 weight % inorganic matrix.
- the catalyst is prepared from a blend of copper chromite, sodium hydroxide, silica sol, and, optionally, clay.
- a detailed embodiment provides that the catalyst is effective to convert 95% or more of methyl laurate to fatty alcohol under fixed-bed conditions at 220°C, 40 bar, and an LHSV of 2.5 hr. -1 after 200 hours, or 400 hours, or 600 hours, or 800 hours, or even 950 hours.
- Another aspect provides catalysts for hydrogenation formed from a blend consisting essentially of a copper chromite; an alkali metal or alkaline earth metal component; and at least one an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the at least one inorganic matrix component are processed together to form the catalyst.
- the blend can consist essentially of copper chromite, sodium hydroxide, silica sol, and, optionally, clay.
- a further aspect is directed to a method of making a catalyst for hydrogenation comprising: mixing a copper chromite powder, a combination of a copper compound and a chromium compound, or both with an inorganic matrix component to form a dry mixture; adding a solution containing an alkali metal component to the dry mixture to form a blend; and forming the catalyst.
- a method for making fatty alcohols comprising: providing a feedstock comprising a methyl ester; contacting the feedstock with one of the catalysts of the present invention; and yielding fatty alcohols,
- inorganic matrix component means a material suitable for binding components together to form a catalyst in a shape.
- the inorganic matrix component is ex tradable and used to form extruded catalysts.
- the inorganic matrix component, or binder material may be alumina, silica, zinc oxide, zirconium oxide, clay such as Bentonite or Attapulgite, zeolites or molecular sieves, silicates such as calcium silicate, etc., and mixtures thereof.
- the silica source is silica sol. Suitable clays include Attagel-30.
- a preferred way to process the blend of all of the ingredients is to extrude it through a shaping orifice to form an extruded catalyst body, or extrudate.
- Other catalyst bodies can be shaped into spheres or any other convenient formation.
- a series of copper chromite catalysts having varying levels of the alkali metal sodium were prepared as follows. Copper chromite powder was dry mixed with Attagel- 30 clay in a mixer. Silica sol and a sodium-containing soluble salt, sodium hydroxide, were added to the dry mix. A solution containing copper nitrate was added to these ingredients with continuous mixing to form a wet-pill mix. The wet-pill mix was extruded using an extruder.
- the catalysts had the following properties:
- the copper chromite catalysts of Example 1 were tested for activity and C-12 hydrocarbon selectivity under conditions of pressure 30 bar, temperature 220 °C, LHSV 2.5 hr 1, hydrogen/feed ratio 250: 1, feed of methyl ester (having a saponification value (SAP) of about 260 mg KOH/g).
- SAP value saponification value
- a copper chromite catalyst having no sodium was prepared as follows.
- Copper chromite powder was dry mixed with Attagel-30 clay in a mixer. Silica sol was added to the dry mix. A solution containing copper nitrate was added to these ingredients with continuous mixing to form a wet-pill mix. The wet-pill mix was extruded using an extruder,
- FIG. 1 shows the superior conversion of the extruded alkali component-containing catalyst as compared to the comparison catalyst.
Abstract
Provided are hydrogenation catalysts for processing esters into fatty alcohols. More particularly, the catalysts are for vapor-phase hydrogenation of methyl esters to fatty alcohols under fixed-bed conditions, where conditions are typically in a temperature range of 200 to 250°C and a pressure range of 30 to 50 bar. Methods of making and using the same are also provided. These catalysts comprise a copper chromite, an alkali metal or alkaline earth metal component, and an inorganic matrix component, which are processed together to form the catalyst. The alkali metal component can comprise sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), or combinations thereof. The alkaline earth metal can comprise magnesium (Mg), calcium (Ca), barium (Ba), or combinations thereof.
Description
COPPER CHROMITE HYDROGENATION CATALYSTS FOR PRODUCTION OF FATTY
ALCOHOLS
TECHNICAL FIELD
[0001] This invention relates to catalysts that are particularly useful as hydrogenation catalysts, and more particularly, catalysts that are useful for hydrogenating carboxylic esters to form fatty alcohols, The invention also relates to a method of preparing these catalysts and to the use of the catalysts in hydrogenation reactions.
BACKGROUND
[0002] Hydrogenation is a chemical reaction that involves the addition of hydrogen
(な) and is used in large scale industrial processes or smaller scale laboratory procedures. Copper is a known catalyst for hydrogenation reactions, and, the form that copper is provided in can impact activity and selectivity of such a catalyst. U.S. Patent No. 5,124,295 (Nebesh), for example, is directed to copper chromite catalysts. Methyl esters having carbon chains on the order of C12 to CJS, as an example, can be hydrogenated to the corresponding saturated fatty alcohols according to hydrogenolysis reaction (1).
[0003] In fixed-bed, vapor-phase fatty alcohol processes, the operating temperatures
(220°C and above) are higher than those used for the fixed-bed, liquid-phase process. The main reasons such temperatures are used are to keep the feed in gaseous phase and to avoid condensation. At these temperatures, however, endothermic reactions (reactions 2 through 4) are accelerated giving by-products such as hydrocarbons, carbonyl compounds and ethers. Reaction (2) shows dehydration of the fatty alcohol to an olefin followed by hydrogenation to a hydrocarbon. Reaction (3) shows dehydration of the fatty alcohol to an ether. Reaction (4) shows dehydrogenation of the fatty alcohol to a carbonyl compound.
[0004] There is a continuing need to provide catalysts that maximize alcohol production while eliminating by-product formation. It is also desirable to provide hydrogenation catalysts, methods for their manufacture and methods of use, which exhibit higher catalytic activity than existing catalysts.
SUMMARY
[0005] Provided are catalysts for hydrogenation, and methods of making and using the same. The catalysts comprise a copper chromite, a mixture of a copper compound and a chromium compound; an alkali metal or alkaline earth metal component; and an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the inorganic matrix component are processed together to form the catalyst. Such catalysts have an increased selectivity for fatty alcohol as compared to a copper chromite catalyst having no alkali metal or alkaline earth metal component as used in hydrogenation reactions. One embodiment provides a catalyst formed from a blend consisting essentially of copper chromite; an alkali metal or alkaline earth metal component; and at least one an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the at least one inorganic matrix component are processed together to form the catalyst.
[0006] A method of making a catalyst for hydrogenation comprises: mixing a copper chromite powder, a combination of a copper compound and a chromium compound, or both with an inorganic matrix component to form a dry mixture; adding a solution containing an alkali metal or alkaline earth metal component to the dry mixture to form a blend; and forming the catalyst.
[0007] A method for making fatty alcohols comprises: providing a feedstock comprising a methyl ester; contacting the feedstock with one of the catalysts of the present invention; and yielding fatty alcohols.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 is a graph showing % methyl-ester conversion versus time for a catalyst of the present invention and a comparison catalyst.
DETAILED DESCRIPTION
[0009] Provided are hydrogenation catalysts for processing esters into fatty alcohols.
More particularly, the catalysts are for vapor-phase hydrogenation of methyl esters to fatty alcohols under fixed-bed conditions, where conditions are typically in a temperature range of 200 to 250°C and a pressure range of 30 to 50 bar. Methods of making and using the same are also provided. These catalysts comprise a copper chromite, an alkali metal or alkaline earth metal component, and an inorganic matrix component, which are processed together to form the catalyst. Reference to "a copper chromite" means that copper chromite is present, which can be provided neat as the compound itself, or as a mixture of a copper compound and a chromium compound, or both. When provided as a mixture, without intended to be bound by theory, it is thought that the mixture forms copper chromite in situ. The alkali metal component can comprise sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), or combinations thereof. Alkaline earth metals can comprise magnesium (Mg), calcium (Ca), barium (Ba), or combinations thereof
[0010] It has been found that acidity from a feed and/or a catalyst surface can catalyze the undesirable side-reactions (2), (3), and (4) under vapor-phase, fixed-bed hydrogenation conditions. Without intending to be bound by theory, it is thought that the presence of the alkali metal component reduces acid sites on the catalyst surface, thereby, discouraging the undesirable side-reactions (2), (3), and (4) under conditions. Thus, the presence of an alkali metal, such as sodium, or of an alkaline earth metal, such as calcium, permits a higher selectivity for fatty alcohol as compared to catalysts without the alkali metal or alkaline earth metal. These catalysts are also beneficial for long life in vapor phase, fixed bed operations, where selectivity for fatty alcohol remains high even with periodic increases of temperature as the catalyst ages.
[0011] In a preferred embodiment, these catalysts contain a significant amount of mesoporosity. Reference to "mesoporosity" means those pores having a pore diameter in the range of 20 to 700 Angstroms (A). In one or more embodiments, the catalyst has a mesopore volume of 0.20 cc/g or more and an overall pore volume of 0.25 cc/g or more. In specific
embodiments, the mesopore volume is in the range of 0.20 to 0.50 cc/g, or 0.25 to 0.40 cc/g, or even 0.29 to 0.33 cc/g and an overall pore volume in the range of 0.25 to 0.60 cc/g, or 0.30 to 0.50, or even 0.35 to 0.40 cc/g, That is, the pore volume of pores having a diameter in the range of 20 to 700 A is about 80% of the total pore volume, or more generally, in the range of about 80 to 85% of the total pore volume. Other embodiments provide that the catalyst has a surface area in the range of 30 to 80 m2 /g , or even 45 to 70 m /g.
[0012] All references to pore diameters and pore volumes in the specification and claims of this application are based upon measurements utilizing mercury porosimetry, A typical method is described by R. Anderson, Experimental Methods in Catalytic Research, Academic Press, New York, 1968. The pore volumes are determined utilizing the catalysts in their oxide forms. That is, the pore diameters and pore volumes reported herein are obtained for the catalyst after calcination, but prior to any reduction of the oxide. Those skilled in the art often refer to the catalyst containing the metal oxides as the "oxide" or "oxide precursor" form of the catalyst.
[0013] Catalysts will generally not contain ingredients that will affect selectivity or acidity. For example, the catalysts will not contain nickel, which could affect selectivity. Up to trace amounts of zeolites may be suitable, but not amounts that would appreciably increase acidity. As used herein the catalytic material is free of such materials if their presence is in an amount that does not materially affect the physical, chemical and catalytic characteristics of the compositions when compared to those which are completely free of such materials. Preferably, if present, such materials will be present in trace amounts, but in amounts not greater than about 0.5% by weight, more preferably not greater than 0.1% weight.
[0014] In a first aspect, provided are catalysts for hydrogenation comprising: a copper chromite; an alkali metal or alkaline earth metal component; and an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the inorganic matrix component are processed together to form the catalyst. Such catalysts have an increased selectivity for fatty alcohol as compared to a copper chromite catalyst having no alkali metal or alkaline earth component as used in hydrogenation reactions.
[0015] In one embodiment, the catalyst is prepared from a blend of: an amount of the copper chromite in the range of 60 to 90 % by weight of the blend; an amount of the alkali metal or alkaline earth metal component in the range of 0.5 to 3.0 % by weight of the blend; and an amount of the inorganic matrix component in the range of 10 to 40 % by weight of the
blend. A detailed embodiment provides a blend of 70-80 weight % copper chromite, 1.5-2.0 weight % alkali metal or alkaline earth metal component, and 20-30 weight % inorganic matrix. Another detailed embodiment provided that the catalyst is prepared from a blend of copper chromite, sodium hydroxide, silica sol, and, optionally, clay.
(0016] A detailed embodiment provides that the catalyst is effective to convert 95% or more of methyl laurate to fatty alcohol under fixed-bed conditions at 220°C, 40 bar, and an LHSV of 2.5 hr.-1 after 200 hours, or 400 hours, or 600 hours, or 800 hours, or even 950 hours.
[0017] Another aspect provides catalysts for hydrogenation formed from a blend consisting essentially of a copper chromite; an alkali metal or alkaline earth metal component; and at least one an inorganic matrix component; wherein the copper chromite, the alkali metal or alkaline earth metal component, and the at least one inorganic matrix component are processed together to form the catalyst. The blend can consist essentially of copper chromite, sodium hydroxide, silica sol, and, optionally, clay.
[0018] A further aspect is directed to a method of making a catalyst for hydrogenation comprising: mixing a copper chromite powder, a combination of a copper compound and a chromium compound, or both with an inorganic matrix component to form a dry mixture; adding a solution containing an alkali metal component to the dry mixture to form a blend; and forming the catalyst.
[0019] In yet another aspect, provided is a method for making fatty alcohols comprising: providing a feedstock comprising a methyl ester; contacting the feedstock with one of the catalysts of the present invention; and yielding fatty alcohols,
[0020] Reference to "inorganic matrix component" means a material suitable for binding components together to form a catalyst in a shape. Generally, the inorganic matrix component is ex tradable and used to form extruded catalysts. Thus, the inorganic matrix component, or binder material, may be alumina, silica, zinc oxide, zirconium oxide, clay such as Bentonite or Attapulgite, zeolites or molecular sieves, silicates such as calcium silicate, etc., and mixtures thereof. In a preferred embodiment, the silica source is silica sol. Suitable clays include Attagel-30.
[0021] A preferred way to process the blend of all of the ingredients is to extrude it through a shaping orifice to form an extruded catalyst body, or extrudate. Other catalyst bodies can be shaped into spheres or any other convenient formation.
[0022] Before describing several exemplary embodiments of the invention, it is to be understood that the invention is not limited to the details of construction or process steps set forth in the description. The invention is capable of other embodiments and of being practiced or being carried out in various ways.
EXAMPLES EXAMPLE 1
[0023] A series of copper chromite catalysts having varying levels of the alkali metal sodium were prepared as follows. Copper chromite powder was dry mixed with Attagel- 30 clay in a mixer. Silica sol and a sodium-containing soluble salt, sodium hydroxide, were added to the dry mix. A solution containing copper nitrate was added to these ingredients with continuous mixing to form a wet-pill mix. The wet-pill mix was extruded using an extruder. The catalysts had the following properties:
EXAMPLE 2
TESTING
[0024] The copper chromite catalysts of Example 1 were tested for activity and C-12 hydrocarbon selectivity under conditions of pressure 30 bar, temperature 220 °C, LHSV 2.5 hr 1, hydrogen/feed ratio 250: 1, feed of methyl ester (having a saponification value (SAP) of about 260 mg KOH/g). The catalyst yielded the following activities (as measured by SAP value) and selectivities.
[0025] The data of Table 2 show that selectivity for the C-12 hydrocarbon, which is the by-product according to reaction (2) above, generally decreases as the sodium content increases. The SAP value is lowest for a sodium level of 2.0%, which indicates the highest conversion of the feed.
EXAMPLE 3
COMPARATIVE
[0026] A copper chromite catalyst having no sodium was prepared as follows.
Copper chromite powder was dry mixed with Attagel-30 clay in a mixer. Silica sol was added to the dry mix. A solution containing copper nitrate was added to these ingredients with continuous mixing to form a wet-pill mix. The wet-pill mix was extruded using an extruder,
EXAMPLE 4
TESTING
[0027] A copper chromite catalyst according to Example 1, having a Na20 level of
1.5 % by weight, was tested for methyl ester conversion under conditions of pressure 40 bar, temperature 220°C, hydrogen/feed 250:1 , feed of fatty methyl ester. Testing occurred at LHSV 2.5 hi--1 until just before 1000 hours, when the LHSV was increased to 1 hr-1. A comparison CuZn tabletted catalyst having no alkali metal component was tested under the same conditions until just before 200 hours, FIG. 1 shows the superior conversion of the extruded alkali component-containing catalyst as compared to the comparison catalyst.
[0028] Reference throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments" or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases such as "in one or more embodiments," "in certain embodiments," "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.
[0029] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention include modifications and variations that are within the scope of the appended claims and their equivalents.
Claims
1. A catalyst for hydrogenation comprising:
a copper chromite;
an alkali metal or alkaline earth metal component; and
an inorganic matrix component;
wherein the copper chromite, the alkali metal or alkaline earth metal component, and the inorganic matrix component are processed together to form the catalyst.
2. The catalyst of claim 1 that is prepared from a blend of:
an amount of the copper chromite in the range of 60 to 90 % by weight of the blend;
an amount of the alkali metal component in the range of 0.5 to 3.0 % by weight of the blend; and
an amount of the inorganic matrix component in the range of 10 to 40 % by weight of the blend.
3. The catalyst of claim 1, wherein the alkali metal component comprises sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), or combinations thereof or the alkaline earth metal comprises magnesium (Mg), calcium (Ca), barium (Ba), or combinations thereof.
4. The catalyst of claim 1 that is prepared from a blend of copper chromite, sodium hydroxide, silica sol, and, optionally, clay.
5. The catalyst of claim 1 having a mesopore volume in the range of 0.20 to 0.50 cc/g and an overall pore volume in the range of 0.25 to 0.60 cc/g.
6. The catalyst of claim 1 having a surface area in the range of 45 to 70 m /g.
7. A catalyst for hydrogenation formed from a blend consisting essentially of a copper chromite; an alkali metal or alkaline earth metal component; and at least one an inorganic matrix component; wlierein the copper chromite, the alkali metal or alkaline earth metal component, and the at least one inorganic matrix component are processed together to form the catalyst.
8. A method of making a catalyst for hydrogenation comprising: mixing a copper chromite powder, a combination of a copper compound and a chromium compound, or both with an inorganic matrix component to form a dry mixture;
adding a solution containing an alkali metal or alkaline earth metal component to the dry mixture to form a blend; and
forming the catalyst.
9. The method of claim 8, wherein the blend comprises:
an amount of the copper chromite in the range of 60 to 90 % by weight;
an amount of the alkali metal or alkaline earth metal component in the range of 0.5 to 3.0 % by weight; and
an amount of the inorganic matrix component in the range of 10 to 40 % by weight.
10. The method of claim 8, wherein the alkali metal component comprises sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), or combinations thereof or the alkaline earth metal comprises magnesium (Mg), calcium (Ca), barium (Ba), or combinations thereof.
11. The method of claim 8, wherein the blend comprises copper chromite, sodium hydroxide, silica sol, and, optionally, clay.
12. A method for making fatty alcohols comprising:
providing a feedstock comprising a methyl ester;
contacting the feedstock with the catalyst of claim 1; and
yielding fatty alcohols.
13. The method of claim 12, wherein the catalyst has a mesopore volume in the range of 0.20 to 0.50 cc/g and an overall pore volume in the range of 0.25 to 0.60 cc/g.
14. The method of claim 12, wherein the catalyst has a surface area in the range of 45 to 70 m2/g.
15. The method of claim 12, wherein the catalyst is effective to convert 99.5% or more of methyl laurate to fatty alcohol under fixed-bed conditions at 220°C, 30 bar, and an LHSV of 2 hr -1 after 200 hours.
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US41806310P | 2010-11-30 | 2010-11-30 | |
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Cited By (2)
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US20120136179A1 (en) * | 2010-11-30 | 2012-05-31 | Basf Corporation | Copper Chromite Hydrogenation Catalysts For Production Of Fatty Alcohols |
EP3750866A1 (en) * | 2019-06-12 | 2020-12-16 | Evonik Operations GmbH | Method for manufacturing alcohol made of hydrocarbons |
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US20160038917A1 (en) * | 2014-08-11 | 2016-02-11 | Basf Corporation | Hydrogenation catalysts |
BR112017020321B1 (en) * | 2015-03-26 | 2021-01-26 | Basf Corporation | catalyst, method for making a catalyst, and, process |
FR3065175A1 (en) * | 2017-04-14 | 2018-10-19 | IFP Energies Nouvelles | PROCESS FOR PROCESSING ALCOHOLS WITH SOLID COPPER CATALYSTS AND AN ELEMENT SELECTED AMONG NA, CA, BA AND K |
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US20120136179A1 (en) | 2012-05-31 |
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