US20200165176A1 - Single-reactor conversion of ethanol to 1-/2-butenes - Google Patents
Single-reactor conversion of ethanol to 1-/2-butenes Download PDFInfo
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- US20200165176A1 US20200165176A1 US15/994,531 US201815994531A US2020165176A1 US 20200165176 A1 US20200165176 A1 US 20200165176A1 US 201815994531 A US201815994531 A US 201815994531A US 2020165176 A1 US2020165176 A1 US 2020165176A1
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- United States
- Prior art keywords
- ethanol
- feed
- butenes
- conversion
- sio2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 title description 23
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 19
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 32
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 7
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 45
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 25
- 239000000377 silicon dioxide Substances 0.000 description 23
- 150000001336 alkenes Chemical class 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 229910052681 coesite Inorganic materials 0.000 description 17
- 229910052906 cristobalite Inorganic materials 0.000 description 17
- 235000012239 silicon dioxide Nutrition 0.000 description 17
- 229910052682 stishovite Inorganic materials 0.000 description 17
- 229910052905 tridymite Inorganic materials 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 238000006384 oligomerization reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- -1 silica metal oxide Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229960004132 diethyl ether Drugs 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Images
Classifications
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- 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
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/043—Noble metals
-
- B01J35/1019—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/48—Silver or gold
- C07C2523/50—Silver
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
- C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
Definitions
- the present disclosure provides examples of simplified processes for producing desired chemicals such as butenes from feedstocks containing ethanol.
- this is performed in a single step, wherein a feed containing ethanol in a gas phase is passed over an acidic metal oxide catalyst having a transition metal dispersion of at least 5% on a metal oxide support.
- the acidic metal oxide catalyst comprises a Group 11 metal.
- this Group 11 metal is selected from the group consisting of copper (Cu), silver (Ag), and gold (Au).
- this metal oxide catalyst comprises a silica metal oxide having a surface area of at least 200 m ⁇ circumflex over ( ) ⁇ 2/g.
- the silica metal oxide support comprises a silica metal oxide selected from the group consisting of a high purity silica gel, mesoporous silica and fumed silica.
- the silica metal oxide is a high purity SBA16.
- high purity SBA15, or Davisil grade 646 may be used.
- hydrogen may be added to the mixture, and ethanol content of the mixture may vary from 10 to 100 percent of the feed. In those non neat applications the ethanol feed may contain water.
- a process for producing butene from an ethanol containing feed stream in a single step wherein a feed containing ethanol in a gas phase is passed over a Ag/ZrO2/SiO2 catalyst having a transition metal dispersion of at least 30% on a silica metal oxide support to produce butene.
- the catalyst was 1% Ag/4% ZrO2SiO2-SBA-16, the temperature was 325° C., the pressure was 1 atm, and a the flow rate was 0.23 hr-1. This process was effective with various mixtures containing various constituent proportions of ethanol and water.
- FIG. 1 shows ethanol conversion as a function of time in a first embodiment of the invention.
- FIG. 2 shows ethanol conversion as a function of time in a second embodiment of the invention.
- the present disclosure includes a series of examples for a converting ethanol in a gas feed into a preselected commodity chemical.
- this is performed by the single step conversion of ethanol (either aqueous or neat) to 1- and 2-butenes, which can be oligomerized into a variety of materials including gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants.
- This provides a significant advantage over the prior art inasmuch as production of 1- and 2-butene from ethanol is typically performed by first dehydrating ethanol into ethylene and then dimerizing ethylene into 1- and 2-butene in a second step.
- methods for producing 1- and 2-butene mixtures directly from ethanol in some cases included in a water and ethanol mixture) have been developed that remove this step and make the use of ethanol as a fuel base more practical and economical.
- the process uses specially tailored polyfunctional catalysts having a metal component with relatively weak hydrogenation ability (e.g., Ag) and mildly acidic support materials (e.g., ZrO2 supported on SiO2). These catalysts allow for carbon to oxygen and carbon to carbon coupling take place without saturation of the material with hydrogen. This is believed to be obtained by taking advantage of the various oxidation states of a metal (such as silver) and the Lewis Acid site (i.e., acidity) nature of the catalysts. Under certain process conditions, as shown in the attached tables and figures, direct formation of butenes from an ethanol stream in a gaseous phase, without the need for additional process steps as required by the prior art embodiments.
- a metal component with relatively weak hydrogenation ability e.g., Ag
- mildly acidic support materials e.g., ZrO2 supported on SiO2
- FIGS. 1 and 2 Examples of such instantiations are provided in FIGS. 1 and 2 wherein the time on stream in hours and the conversion percentages are shown for particular embodiments where in a 24.3% ethanol feed in a N2 or N2 and H2 mixture is shown passing over a 4Ag/4ZrO2/SiO2 (Davisil 646) catalyst ( FIG. 1 ) or a 2Ir/4ZrO2/SiO2 catalyst under the following conditions. Temperature 325 degrees C., Pressure 1 atm, WHSV 0.23/hr. As these figures show conversion percentages are relatively high (>75 percent) over a designated period of time. While these exemplary samples are provided it is to be distinctly understood that the invention are not limited to these examples but may be variously alternatively embodied as necessary.
- the product from the ethanol conversion contains primarily butenes and ethylene olefins mixed with H 2 which can be oligmerized for the formation of fuels.
- Table 5 shows the results of this testing under the following conditions. Zeolite beta catalyst, temperature 260 degrees C.; pressure 200 psig; WHSV 0.42-46 hr-1. Time on stream extended up to 50 hours
- the quantity of C8 olefins produced is about 10% higher in the presence of H2 and ethylene and is likely due to ethylene oligomerization to C8+ product occurring in the meantime as butenes oligomerization.
- oligomerization of 1-butene is feasible in the presence of H 2 and/or ethylene co-feed.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
- This disclosure was made with Government support under Contract DE-AC0576RL01830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
- Petroleum depletion and environmental issues caused by the chemical and petrochemical industries have led to a renewal of interest for using biomass as a carbon source for biofuels production. Various research organizations including program offices within the United States Department of Energy have sought, and continue to seek, transformative and revolutionary sustainable bioenergy technologies. Ethanol conversion to biofuels is one of these attractive bioenergy technologies. Ethanol can be commercially produced at large scale from renewable biomass or waste sources, and continuing advancements in production efficiency and feedstock diversification are envisioned to lead to excess ethanol at competitive prices. The broad availability and cost effective supply of ethanol as a feed stock would enable the production of a wide range of fuels and commodity chemicals.
- While ethanol supplies are predicted to rise, a reduction in supplies of other commodity chemicals is also expected. A variety of approaches have been taken attempting to identify simple and cost effective processes for generating desired fuels and commodity chemicals in newer, greener and more cost efficient ways. While a variety of processes have been shown to have some efficacy continued development is needed to find methods that can simply and cost effectively produce the desired result and do so in a sufficiently cost effective manner so as to be adopted in industrial and commercial applications. The present disclosure describes significant advances in this regard.
- The following description provides examples and information surrounding successful demonstration of a proof of concept for single step conversion of (aqueous) ethanol into butenes, such as 1-butene. As will be explained below in further detail, oligomerization of mixed 1- and 2-butenes, produced by the single step methods described hereafter allow for the creation of various hydrocarbon fuel configurations both in the presence of and/or absence of hydrogen and/or ethylene.
- By directly producing a C4-rich olefin mixture (that can then be selectively oligomerized into gasoline, jet and/or diesel fuels) from an ethanol containing steam various advantages are presented including, but not limited to, significant cost reduction in capital expenses and operational expenses as this simplified process allows for a closer term transformation of a feedstock to a useable product. In some embodiments the conversion of ethanol to butenes can be conducted one single reactor. In one arrangement, the present process was demonstrated using an aqueous ethanol feedstock indicating that typical ethanol/water separations may not always be necessary. This coupled with a reduction of stages in additional chemical processing and allows for various simplified operation units, which can present a significant step forward in reducing costs and complexities and moving renewable transportation fuels forward toward a practical reality.
- Additional advantages and novel features of the present disclosure will be set forth as follows and will be readily apparent from the descriptions and demonstrations set forth herein. Accordingly, the following descriptions of the present disclosure should be seen as illustrative of the disclosure and not as limiting in any way.
- The present disclosure provides examples of simplified processes for producing desired chemicals such as butenes from feedstocks containing ethanol. In one set of embodiments this is performed in a single step, wherein a feed containing ethanol in a gas phase is passed over an acidic metal oxide catalyst having a transition metal dispersion of at least 5% on a metal oxide support. In some applications the acidic metal oxide catalyst comprises a Group 11 metal. In some instances this Group 11 metal is selected from the group consisting of copper (Cu), silver (Ag), and gold (Au). In one set of embodiments this metal oxide catalyst comprises a silica metal oxide having a surface area of at least 200 m{circumflex over ( )}2/g. The silica metal oxide support comprises a silica metal oxide selected from the group consisting of a high purity silica gel, mesoporous silica and fumed silica. In some instances the silica metal oxide is a high purity SBA16. In other instances high purity SBA15, or Davisil grade 646 may be used. Under some processing conditions hydrogen may be added to the mixture, and ethanol content of the mixture may vary from 10 to 100 percent of the feed. In those non neat applications the ethanol feed may contain water.
- In one specific instance a process for producing butene from an ethanol containing feed stream in a single step is described wherein a feed containing ethanol in a gas phase is passed over a Ag/ZrO2/SiO2 catalyst having a transition metal dispersion of at least 30% on a silica metal oxide support to produce butene. In this particular instance the catalyst was 1% Ag/4% ZrO2SiO2-SBA-16, the temperature was 325° C., the pressure was 1 atm, and a the flow rate was 0.23 hr-1. This process was effective with various mixtures containing various constituent proportions of ethanol and water.
- The purpose of the foregoing abstract is to enable the United States Patent and Trademark Office and the public generally, especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the disclosure of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the disclosure in any way.
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FIG. 1 shows ethanol conversion as a function of time in a first embodiment of the invention. -
FIG. 2 shows ethanol conversion as a function of time in a second embodiment of the invention. - The following description includes examples of exemplary modes of implementation. It will be clear from this description of the disclosure that the invention is not limited to these illustrated embodiments but that the disclosure also includes a variety of modifications and embodiments thereto. Therefore, the present description should be seen as illustrative and not limiting. While the disclosure is susceptible of various modifications and alternative constructions, it should be understood, that there is no intention to limit the disclosure to the specific form disclosed, but, on the contrary, the disclosure is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the disclosure as defined in the claims.
- The present disclosure includes a series of examples for a converting ethanol in a gas feed into a preselected commodity chemical. In one embodiment this is performed by the single step conversion of ethanol (either aqueous or neat) to 1- and 2-butenes, which can be oligomerized into a variety of materials including gasoline, jet, and diesel fuels and/or into valuable fuel additives and lubricants. This provides a significant advantage over the prior art inasmuch as production of 1- and 2-butene from ethanol is typically performed by first dehydrating ethanol into ethylene and then dimerizing ethylene into 1- and 2-butene in a second step. However as described hereafter, methods for producing 1- and 2-butene mixtures directly from ethanol (in some cases included in a water and ethanol mixture) have been developed that remove this step and make the use of ethanol as a fuel base more practical and economical.
- The process uses specially tailored polyfunctional catalysts having a metal component with relatively weak hydrogenation ability (e.g., Ag) and mildly acidic support materials (e.g., ZrO2 supported on SiO2). These catalysts allow for carbon to oxygen and carbon to carbon coupling take place without saturation of the material with hydrogen. This is believed to be obtained by taking advantage of the various oxidation states of a metal (such as silver) and the Lewis Acid site (i.e., acidity) nature of the catalysts. Under certain process conditions, as shown in the attached tables and figures, direct formation of butenes from an ethanol stream in a gaseous phase, without the need for additional process steps as required by the prior art embodiments.
- Examples of such instantiations are provided in
FIGS. 1 and 2 wherein the time on stream in hours and the conversion percentages are shown for particular embodiments where in a 24.3% ethanol feed in a N2 or N2 and H2 mixture is shown passing over a 4Ag/4ZrO2/SiO2 (Davisil 646) catalyst (FIG. 1 ) or a 2Ir/4ZrO2/SiO2 catalyst under the following conditions. Temperature 325 degrees C., Pressure 1 atm, WHSV 0.23/hr. As these figures show conversion percentages are relatively high (>75 percent) over a designated period of time. While these exemplary samples are provided it is to be distinctly understood that the invention are not limited to these examples but may be variously alternatively embodied as necessary. - In one application a 24% ethanol feed in a gaseous state was passed over a 4Ag/4ZrO2/SiO2/SBA16 catalyst under the following conditions: temperature 325° C., pressure=7 bar (100 psig), flow rate (space velocity) WHSV=0.23 hr-1. An incremental addition of H2 to the feed gas from 0% to 100% (carrier gas content) was varied and produced the results shown in Table 1. Various other modifications to the processing conditions effectuated the variations described and set forth in subsequent tables that follow thereafter.
-
TABLE 1 Effect of Hydrogen on process results H2 % 0% H2 18.5% H2 45% H2 100% H2 Carbon Balance 91.0 89.0 96.3 97.5 Conversion % 99 98 95.9 85.2 C2= 8.6 6.2 9.6 25.8 C3= 0.0 2.0 2.5 3.2 C4= 15.8 35.3 41.7 51.1 C5= 0.9 1.8 1.5 0.7 BD 63.7 6.6 1.2 0.4 butadiene C2-C6 0.5 1.3 2.0 2.8 alkanes Acetaldehyde 2.9 0.7 0.8 2.3 HAC Other 3.8 7.5 10.2 5.3 Oxygenates (e.g. C1-C4 alcohols, Ethyl acetate, acetic acid, 2-butanone, acetone) Crotonaldehyde 0.7 0 0 0 Diethylether 3.1 4.1 4.0 8.4 C4- C8 olefins 0 10.0 11.9 0 Liquid Cyclic 0 24.5 14.6 0 Hydrocarbon Liquids Olefins w/o 25.3 55.3 67.2 80.8 Butadiene Total Gas and Liquid Olefins w/o 25.3 45.3 55.3 80.8 Butadiene Total in gas - As the data in this table shows, as the percentage of hydrogen increases the percentage of the ethanol converted decreases from 99 to 85% accompanied by an increase of the 1- and 2-butene combined selectivity from ˜16 to 51%. Meanwhile the ethylene selectivity increased from ˜8.6 to 26% while the butadiene selectivity decreased from 63.7% to 0%. Generally speaking, 1- and 2-butene is formed at the expense of 1,3-butadiene when H2 content is added to the feed. Table 2 shows the effect of altering the flow rate (space velocity) on catalytic performance for the conversion of ethanol to butenes over this same catalytic composition.
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TABLE 2 Effect of flow rate (space velocity) variation on catalytic performance Run ID 227 243 272 237 253 231 233 235 Pressure 100 100 100 100 100 100 100 100 (Psig) WHSV 0.10 0.23 0.7 1.4 2.0 3.6 7.3 14.6 (hr-1) Conversion 87.6 87.1 75.3 67.5 65.7 65.5 34.9 11.7 (%) Carbon Balance 85 104 104 112 95.5 91 103 104 Selectivity butadiene 0.0 3.8 4.2 19.5 0.6 0 0 0 % C2= 7.1 16.7 2.9 13.1 10.6 9.0 11.1 15.0 C3= 1.0 2.7 1.2 1.5 1.7 1.2 0.9 0.8 C4= 47.3 40.7 46.3 24.3 51.1 51.9 27.9 13.0 C5= 0.2 0.6 1.0 0.3 0.2 0.5 0.3 0.0 Diethylether 10.2 8.6 3.3 6.8 6.2 6.5 6.5 7.7 Acetaldehyde 0.6 1.4 3.1 3.7 7.2 8.1 18.6 26.5 C2-C5 14.6 1.6 0.8 1.0 2.5 1.7 1.0 0.9 Alkanes C4+ 6.9 0 0 0 0 0 0 0 Alkanes Liquids Butyraldeheyde 0 1.9 2.1 15.5 16.2 17 26.1 31.4 C4-C8 olefins 4.2 11.0 16.1 0 0 0 0 0 liquids butanol 0 0.1 1.2 0.2 1.7 1.7 1.8 1.2 Others (e.g.cyclic 15.0 10.9 17.8 14.1 2.0 2.4 6.8 3.5 hydrocarbons and oxygenates (e.g. C1-C4 alcohols, ethyl acetate, acetic acid, 2-butanone, acetone) Total olefins 59.8 71.7 67.5 39.2 63.6 62.6 40.2 28.8 - Table 3 shows the effect of pressure on catalytic performance for the conversion of ethanol to butenes on a 4Ag/4ZrO2/SiO2/SBA16 catalyst under the following conditions: temperature 325° C., pressure =7 bar (100 psig), 24% ethanol in hydrogen gas, time on stream (TOS) 5 hours.
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TABLE 3 Run ID MO236 MO237 MO216 Pressure (Psig) atm 100 200 WHSV (hr-1) 1.4 1.4 1.4 Conversion % 53.4 67.5 82.5 Carbon Balance 110 112 106 Selectivity butadiene 43.8 19.5 0 % C2= 22.2 13.1 7.1 C3= 1.2 1.5 0 C4= 8.2 24.3 28.2 diethylether 11.3 6.8 8.2 acetaldehyde 8.1 3.7 2.7 butyraldehyde 2.1 15.5 3.8 BuOH 0.6 0.2 2.3 C2-C5 0.2 1.0 9.0 alkanes C4- C8 olefins 0 0 16.0 in liquid Others 2.3 14.4 20.6 (e.g. cyclic hydrocarbons and oxygenates (C1-C4 alcohols, ethyl acetate, acetic acid, 2- butanone, acetone) C6- C7 0 0 2.1 alkanes Total olefins 31.6 38.9 51.3 - Table 4 shows the effect of water content in the ethanol feed stream on the conversion of ethanol to butenes when passed over a 4Ag/4ZrO2/SiO2/SBA16 catalyst under the following conditions: temperature 325° C., pressure=7 bar (100 psig), 11% ethanol in gas, flow rate (space velocity) WHSV=0.23 hr-1.
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TABLE 4 Feed Composition Pure 95% EtOH 35% EtOH EtOH in H2O in H2O Pressure (Psig) 100 100 100 WHSV (hr-1) 0.23 0.23 0.23 Conversion % 93.9 93.9 76.4 Carbon Balance 120 112 103 Selectivity butadiene 0 0 0 % C2= 25.7 19.4 8.8 C3= 2.0 1.6 2.1 C4= 57.7 56.9 54.8 diethylether 6.0 6.1 2.8 acetaldehyde 0.4 0.3 6.5 butyraldehyde 0.1 0.1 2.3 BuOH 0 0 2.6 C2-C5 6.1 12.9 2.1 alkanes C4- C8 olefins 0 0 0 in liquid Acetic Acid 0.7 0.5 11.8 Others (cyclic 1.3 2.2 6.2 hydrocarbons and oxygenates (C1-C4 alcohols, ethyl acetate, acetic acid, 2-butanone, acetone) Total olefins 85.4 77.9 65.7 - In addition to these results we also demonstrated that catalytic stability is enhanced when H2 is added to N2 as the carrier gas for the process. (See
FIGS. 1 and 2 ) Hence the addition of H2 (to the ethanol feed) not only alters the product distribution favoring a butene product slate but it also significantly suppresses coking allowing for enhanced catalytic stability. While H2 addition to the feed may add cost to the overall process, hydrogen is usually needed anyhow for fuels production as the final olefin product after oligomerization needs to be hydrotreated. Thus, the added hydrogen can be used in the latter hydrotreatment step and unconverted hydrogen can be recycled to the front end of the process. - Higher contact times favor the formation of 1- and 2-butenes. Decreasing the space velocity from 14.6 to 0.23 hr-1 while operating under H2 gas leads to an increase of the conversion from ˜11 to 85% and an increase of both 1- and 2-butenes and ethylene selectivity from ˜13 to 51% and ˜15 to 26%, respectively. In addition the fractions transition to acetaldehyde and butyraldehyde decrease while the effect on butadiene selectivity remains negligible. This suggests that the mechanism for butene formation involves the conversion of acetaldehyde to crotyl alcohol, isomerization of crotyl alcohol to butyraldehyde, and butenes formation from butyraldehyde deoxygenation. The effect of operating pressure was also investigated and it was found that higher pressure favors the formation of butenes at the expense of butadiene (see Table 3).
- For example, increasing the pressure from atmospheric to 14 bar while operating under H2 gas leads to an increase of the conversion from 52 to 83% and an increase of the C4+ olefins selectivity from 8.1 to 44% while the selectivity toward butadiene and ethylene decreases from 43 to 0% and 22 to 7%, respectively. Addition of water to the feed also leads to a decrease of the conversion, from 94.0%, with 100% ethanol as a feedstock, and to 76%, with 35% ethanol in H2O as a feedstock (see Table 4). The butenes selectivity is only slightly affected by the presence of water since it decreases from 58% to 55%. However, this demonstrates that diluted feeds of ethanol can be used as feedstock and separation of water and ethanol is not required prior to conversion. In addition alteration and modification of a variety of other factors including H2 concentration, H2O concentration, space velocity and pressure were demonstrated to have significant effect on conversion, selectivity, and stability. H2-addition to the feed favors the formation of 1- and 2-butene at the expense of butadiene.
- The product from the ethanol conversion contains primarily butenes and ethylene olefins mixed with H2 which can be oligmerized for the formation of fuels. In a series of experiments intended to demonstrate the feasibility of producing fuels from the olefin precursors obtained from the single step process we co-feed ethylene and/or H2 with butene mixtures over zeolite catalysts and obtained favorable results. Table 5 shows the results of this testing under the following conditions. Zeolite beta catalyst, temperature 260 degrees C.; pressure 200 psig; WHSV 0.42-46 hr-1. Time on stream extended up to 50 hours
-
TABLE 5 Olefin Liquid Products (mg/min/gram catalyst) Feed C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 1-butene 2.2 0.0 0.6 8.7 50.0 10.3 3.3 4.0 43.4 3.9 0.7 5.2 H2 + 1- 3.0 0.4 2.3 6.6 36.2 12.9 8.7 7.6 28.0 2.4 1.5 0.5 butene C2= + 1- 3.8 1.3 4.1 11.2 55.8 16.5 9.0 10.3 37.2 4.6 4.2 0.0 butene H2 + C2= 3.8 1.4 4.6 12. 53.9 14.1 7.8 15.2 38.5 4.7 1.8 0.0 + 1butene - These results show that oligomerization of butenes in the presence of H2 was feasible. Adding H2 to the feed leads to about 20% lower C8+ olefins production. Adding ethylene to the feed was also demonstrated to lead to higher paraffins/olefins ratio due to hydrogenation activity but does not affect the production of C8+ olefins since the same quantity of product was obtained w and w/o ethylene addition to the feed. The ratio paraffins/olefins is equal to about 0.4 in the presence of H2+ ethylene as opposed to <0.5 without H2+ ethylene indicating a significant hydrogenation activity. The quantity of C8 olefins produced is about 10% higher in the presence of H2 and ethylene and is likely due to ethylene oligomerization to C8+ product occurring in the meantime as butenes oligomerization. Thus, we demonstrate that oligomerization of 1-butene is feasible in the presence of H2 and/or ethylene co-feed.
- The product distribution for 2-butene oligomerization to be very similar to that of 1-butene. Thus, a feed containing mixtures and 1- and 2-butene arising from the single step process would produce a similar product distribution when passed through this oligmerization step. This process provides a promising way for developing a bio-derived jet/diesel fuel from ethanol upon oligomerization followed by hydrogenation as demonstrated by this disclosure.
- In another set of experiments various catalyst configurations were tested to determine the effect of various catalyst compositions and performance parameters on obtaining the desired outcomes. The following Table 6 presents the data from this testing. This data demonstrates that monitoring the quantity and quality of metals in the catalyst composition is important in maintaining desired performance. Experimental results have shown that when Ag percentages rise above that 16 percent that saturation of the hydrocarbon increases and increased yields of C2-C5 alkanes begin to take place. We believe that this is due to the ability of Ag to become partially oxidized which may be a factor in hydrogenation suppression. Similarly, adding other metals with stronger hydrogenation capability such as Ir, Pd, or Pt will render a significant number of parrafins. These metals that are stronger for hydrogenation will also push toward the formation of alkanes rather than the desired alkenes. This was demonstrated even 0.4% Ir was added to the 4Ag/4Zr/SiO2 system.”
-
TABLE 6 Operating Conditions Pressure 1000 psig, Temp 325 C., 24% EtOH in H2 Selectivity (%) WHSV Conv C C2-C5 Total Catalyst (hr-1) (%) bal B C2= C3= C4= C5= D A Alkanes BA BL MEK Others* olefins 4%Ag/1%ZrO 1.4 49.7 95.2 0 5.1 0.0 54.2 0.2 4.0 4.1 1.9 4.1 8.0 5.1 13.3 59.5 2/SiO2 4%Ag/2%ZrO 1.4 61.5 95.8 7.8 4.5 0.0 56.6 1.2 6.5 2.8 0.6 2.8 3.5 4.7 5.2 62.4 2/SiO2 4%Ag/4%ZrO 1.4 67.5 112 19.5 13.1 1.5 24.3 0.3 6.8 15.5 1.0 15.5 0.2 12.2 1.9 39.2 2/SiO2 1Ag/4%ZrO2/ 0.5 57.7 107 39.8 5.9 2.2 28.5 0.2 8.7 0 0.4 0 0.7 7.2 3.4 36.8 SiO2 1Ag/4%ZrO2/ 1.4 33.8 107 46.6 5.2 1.5 15.2 0.4 8.5 0 0.4 0 1.3 12.2 3.6 22.3 SiO2 2Ag/4%ZrO2/ 1.4 52.6 105 27.2 3.5 1.5 38.1 0.9 7.1 2.8 0.5 2.8 2.4 6.0 3.5 44.0 SiO2 4%Ag/4%ZrO 1.4 67.5 112 19.5 13.1 1.5 24.3 0.3 6.8 15.5 1.0 15.5 0.2 12.2 1.9 39.2 2/SiO2 8%Ag/4%ZrO 1.4 65.2 100.6 9.4 5.6 1.7 59.8 1.1 7.0 3.1 0.7 3.1 1.5 3.8 2.0 68.2 2/SiO2 0.4Ir4Ag/4ZrO 0.23 89.1 80.8 0 0.1 1.2 8.7 2.9 5.1 1.5 55.3 0 0.9 24.3 12.9 2/SBA16 4Ag4ZrO2/ 0.23 87.1 103 3.8 16.7 2.7 40.7 0.6 8.6 1.4 1.6 1.9 0.1 10.9 71.7 SBA16 16Ag4ZrO2/ 1.4 66.3 91 0 8.8 1.7 57.8 1.2 6.0 3.9 3.1 3.3 3.4 3.8 7.0 69.5 SiO2 B- Butadiene, D- Diethylether, A-acetylaldehyde, C2-C5 Alkanes, BA, Butyrlaldehyde, BL- butanol, Others: CO2, MeOh, PrOh, PenOH, EA, Acetic Acid, pentanone, phenol/cresol for MO277 - While various preferred embodiments of the disclosure are shown and described, it is to be distinctly understood that this disclosure is not limited thereto but may be variously embodied to practice within the scope of the following claims. From the foregoing description, it will be apparent that various changes may be made without departing from the spirit and scope of the disclosure as defined by the following claims.
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