US20140336418A1 - Production of Fuel from Chemicals Derived from Biomass - Google Patents
Production of Fuel from Chemicals Derived from Biomass Download PDFInfo
- Publication number
- US20140336418A1 US20140336418A1 US14/322,037 US201414322037A US2014336418A1 US 20140336418 A1 US20140336418 A1 US 20140336418A1 US 201414322037 A US201414322037 A US 201414322037A US 2014336418 A1 US2014336418 A1 US 2014336418A1
- Authority
- US
- United States
- Prior art keywords
- alkali metal
- pentanoate
- anolyte
- levulinate
- reaction
- 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.)
- Abandoned
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 92
- -1 carbon sugars Chemical class 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 51
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 33
- 235000000346 sugar Nutrition 0.000 claims abstract description 31
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 23
- 229940070710 valerate Drugs 0.000 claims abstract description 21
- 229940058352 levulinate Drugs 0.000 claims abstract description 20
- 150000002402 hexoses Chemical class 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 230000000911 decarboxylating effect Effects 0.000 claims abstract 2
- 239000012528 membrane Substances 0.000 claims description 27
- 238000006114 decarboxylation reaction Methods 0.000 claims description 24
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 18
- 150000001720 carbohydrates Chemical class 0.000 claims description 17
- 235000014633 carbohydrates Nutrition 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 6
- FJNCXZZQNBKEJT-UHFFFAOYSA-N 8beta-hydroxymarrubiin Natural products O1C(=O)C2(C)CCCC3(C)C2C1CC(C)(O)C3(O)CCC=1C=COC=1 FJNCXZZQNBKEJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003254 gasoline additive Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 24
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 49
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 44
- 150000003254 radicals Chemical class 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000002585 base Substances 0.000 description 28
- 229940040102 levulinic acid Drugs 0.000 description 28
- 239000000463 material Substances 0.000 description 22
- LHYPLJGBYPAQAK-UHFFFAOYSA-M sodium;pentanoate Chemical compound [Na+].CCCCC([O-])=O LHYPLJGBYPAQAK-UHFFFAOYSA-M 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 15
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 15
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052708 sodium Inorganic materials 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- 229940058349 sodium levulinate Drugs 0.000 description 12
- RDKYCKDVIYTSAJ-UHFFFAOYSA-M sodium;4-oxopentanoate Chemical compound [Na+].CC(=O)CCC([O-])=O RDKYCKDVIYTSAJ-UHFFFAOYSA-M 0.000 description 12
- 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 description 11
- 238000007127 saponification reaction Methods 0.000 description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000006612 Kolbe reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 10
- 230000008901 benefit Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 150000001447 alkali salts Chemical class 0.000 description 9
- 150000007942 carboxylates Chemical class 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003502 gasoline Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical class [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000007348 radical reaction Methods 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 5
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229940005605 valeric acid Drugs 0.000 description 5
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical class CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 4
- CBCFXXRAKZUAFN-UHFFFAOYSA-N C.C#CC#CC.O.O=O.[HH].[HH].[HH] Chemical compound C.C#CC#CC.O.O=O.[HH].[HH].[HH] CBCFXXRAKZUAFN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000002816 fuel additive Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- UPMPZNAIGBBQEM-UHFFFAOYSA-N C.C.O.O=CO Chemical compound C.C.O.O=CO UPMPZNAIGBBQEM-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 0 *C(CCCCON)=O Chemical compound *C(CCCCON)=O 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical class CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- HSRGLCOQGBJYLK-UHFFFAOYSA-N CCCCCCCC.[CH2]CCC.[CH2]CCC Chemical compound CCCCCCCC.[CH2]CCC.[CH2]CCC HSRGLCOQGBJYLK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 229910000833 kovar Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NLQMSBJFLQPLIJ-UHFFFAOYSA-N (3-methyloxetan-3-yl)methanol Chemical compound OCC1(C)COC1 NLQMSBJFLQPLIJ-UHFFFAOYSA-N 0.000 description 1
- 125000005523 4-oxopentanoic acid group Chemical group 0.000 description 1
- VVGSZQLXWIWAJD-UHFFFAOYSA-N CC(=O)CCCCC(C)=O.[CH2]CC(C)=O.[CH2]CC(C)=O Chemical compound CC(=O)CCCCC(C)=O.[CH2]CC(C)=O.[CH2]CC(C)=O VVGSZQLXWIWAJD-UHFFFAOYSA-N 0.000 description 1
- WGZRGXJXHZLOTA-UHFFFAOYSA-N CC(CC[NH+]([O-])O)=O Chemical compound CC(CC[NH+]([O-])O)=O WGZRGXJXHZLOTA-UHFFFAOYSA-N 0.000 description 1
- WEXZIBXGPWTCRO-UHFFFAOYSA-N CCOCC.CCOCC.[CH2]COCC.[CH2]COCC.[HH].[H].[H] Chemical compound CCOCC.CCOCC.[CH2]COCC.[CH2]COCC.[HH].[H].[H] WEXZIBXGPWTCRO-UHFFFAOYSA-N 0.000 description 1
- ZACHURHWFOKFDD-UHFFFAOYSA-J CCOCCC(=O)O.CCOCCC(=O)O[Na].O.O.O=CO.O=CO[Na].O[Na].O[Na] Chemical compound CCOCCC(=O)O.CCOCCC(=O)O[Na].O.O.O=CO.O=CO[Na].O[Na].O[Na] ZACHURHWFOKFDD-UHFFFAOYSA-J 0.000 description 1
- XZGIFCKVTZUMSY-UHFFFAOYSA-M CCOCCC(=O)O[Na].O=C=O.[CH2]COCC.[Na+] Chemical compound CCOCCC(=O)O[Na].O=C=O.[CH2]COCC.[Na+] XZGIFCKVTZUMSY-UHFFFAOYSA-M 0.000 description 1
- FOCVMTUNBVZOHO-UHFFFAOYSA-N CCOCCCCCOC.[CH2]COCC.[CH2]COCC Chemical compound CCOCCCCCOC.[CH2]COCC.[CH2]COCC FOCVMTUNBVZOHO-UHFFFAOYSA-N 0.000 description 1
- WMRVCBPZPPGVBN-UHFFFAOYSA-N COCCCCCCCCOC.OCCCCCCCCO Chemical compound COCCCCCCCCOC.OCCCCCCCCO WMRVCBPZPPGVBN-UHFFFAOYSA-N 0.000 description 1
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- XBCWSAYOKAIWKT-UHFFFAOYSA-M O=C=O.O=CO[Na].[H].[Na+] Chemical compound O=C=O.O=CO[Na].[H].[Na+] XBCWSAYOKAIWKT-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XBJREXNIVZHIPF-UHFFFAOYSA-N [HH].[H].[H] Chemical compound [HH].[H].[H] XBJREXNIVZHIPF-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007073 chemical hydrolysis Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- NZGDDIUIXYFYFO-UHFFFAOYSA-N octane-2,7-dione Chemical compound CC(=O)CCCCC(C)=O NZGDDIUIXYFYFO-UHFFFAOYSA-N 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- Hydrocarbon fuels are currently used throughout the world.
- One specific example of a hydrocarbon fuel is gasoline (which includes octane).
- Another common hydrocarbon fuel is diesel fuel, which is used in diesel engines. Accordingly, there is a need for methods for producing hydrocarbons that may be used as fuels.
- Biomass is a renewable feedstock.
- Biomass may comprise lipids (such as fats or oils) that are available from plant, algal, or animal origin. These fats or oils may include fatty acids. Obviously, given its abundance in nature, it is desirable to find a way to use this biomass as a starting material to form a useable product, such as a hydrocarbon fuel.
- Disclosed herein is a method for the manufacture of hydrocarbon fuels from biomass.
- This method relates to the conversion of the biomass based starting materials such as carbohydrates and sugars, to carboxylic acids or alkali metal salts of carboxylic acids (and other carboxylic acid derivatives such as esters) that may be used to form hydrocarbon fuels.
- Also disclosed are methods for turning biomass into lactones that may also be converted into hydrocarbon fuels.
- the biomass can be of plant, algal, or animal origin.
- the biomass is converted to sugars (mainly hexoses that include one or more rings).
- sugars mainly hexoses that include one or more rings.
- These hexose sugars will generally have 6 carbon atoms which in turn are chemically converted to carboxylic acids.
- examples of these types of sugar materials include glucose, etc.
- a sugar monomer which has the formula C 6 H 12 O 6 , may be reacted as follows to form levulinic acid, water and formic acid:
- C 5 H 8 O 3 is the empirical formula of levulinic acid.
- this acid has the following chemical structure:
- these two acids may be saponified by reaction with a base (such as NaOH, NaOCH 3 , or any other base) to form the corresponding alkali metal salt (e.g., alkali metal salts of formate and levulinate):
- a base such as NaOH, NaOCH 3 , or any other base
- sugars are directly converted to alkali salts of carboxylic acids.
- alkali salts of carboxylic acids are then dissolved in a solvent and optionally with a second alkali carboxylate to yield a reacting mixture.
- the mixture is then converted to hydrocarbon fuel by electrolytic (anodic) decarboxylation and subsequent carbon-carbon coupling.
- the electrolysis cell deployed for this reaction utilizes a selective alkali transport solid electrolyte membrane technology.
- the product formed by this carbon-carbon coupling may be a hydrocarbon fuel material—e.g., a hydrocarbon that may be used as a fuel, a fuel additive, etc.
- FIG. 1 is a flow diagram showing the overall process by which biomass may be converted into hydrocarbon fuels
- FIG. 2A is a flow diagram showing the conversion of sugar moieties into levulinic acid and formic acid;
- FIG. 2B is a flow diagram showing the conversion of levulinic acid and formic acid to sodium formate and sodium levulinate;
- FIG. 3 is a schematic view of an embodiment of an electrolytic cell for conversion of sodium levulinate to a hydrocarbon fuel compound
- FIG. 4 is a schematic view of an embodiment of an electrolytic cell for conversion of sodium valerate to a hydrocarbon fuel compound
- FIG. 5 is a flow diagram showing the conversion of levulinic acid into sodium valerate
- FIG. 6A is a flow diagram showing the conversion of ⁇ -valerolactone into HO(CH 2 ) 4 COONa;
- FIG. 6B is a flow diagram showing the conversion of ⁇ -valerolactone into H 3 CO(CH 2 ) 4 COONa;
- FIG. 7 is a schematic view of yet an embodiment of an electrolytic cell for conversion of HO(CH 2 ) 4 COONa or H 3 CO(CH 2 ) 4 COONa into a diol or diether product that may be used as a fuel additive;
- FIG. 8 is a flow diagram showing an exemplary method of the present embodiments.
- FIG. 9 is another flow diagram showing another exemplary method of the present embodiments.
- FIG. 10 shows a graph of current density and voltage for an example decarboxylation process
- FIG. 11 shows a gas chromatogram of a decarboxylation process that was performed.
- FIG. 1 a flow diagram which shows the method 10 in which biomass 14 may be converted into a hydrocarbon according to the process outlined herein.
- a quantity of biomass 14 is obtained.
- the biomass 14 may then be converted into a carbohydrate 18 .
- This carbohydrate 18 may be a starch material, a cellulose material, a polysaccharide material, etc.
- This process for converting the biomass 14 into the carbohydrate 18 is known.
- the carbohydrate 18 may be converted into a hexose sugar material 22 (such as glucose, etc.).
- the conversion of the carbohydrate material 18 into a hexose sugar material 22 may occur via chemical hydrolysis or enzymatic hydrolysis.
- Such processes are known and are described, for example, in the following article:
- this material 22 may undergo a catalytic dehydration 24 (or other process) to convert the sugar moieties into levulinic acid 32 .
- a catalytic dehydration 24 or other process to convert the sugar moieties into levulinic acid 32 .
- the process for converting a hexose sugar into levulinic acid is described, for example, in the following article:
- the levulinic acid 32 may undergo a saponification reaction 38 to produce an alkali salt of a carboxylic acid 44 .
- this alkali salt of a carboxylic acid may be the alkali metal salt of levulinic acid (e.g., an alkali metal levulinate).
- the saponification reaction 38 uses a base (such as an alkali metal methoxide or an alkali metal hydroxide).
- the levulinic acid 32 may undergo a catalytic reduction process 46 to gamma-valerolactone 50 ( ⁇ -valerolactone).
- This gamma-valerolactone 50 (a cyclic ester) is produced by catalytic hydrogenation:
- this ⁇ -valerolactone 50 may undergo a catalytic hydrogenation reaction 54 to produce valeric acid 62 :
- This valeric acid 62 can undergo the saponfication reaction 38 to form the alkali salt of a carboxylic acid 44 .
- the alkali salt of a carboxylic acid would be the alkali metal valerate.
- the ⁇ -valerolactone 50 may undergo a base hydrolysis process 66 to form the alkali salt of a carboxylic acid 44 .
- This hydrolysis reaction of the cyclic ester ( ⁇ -valerolactone) uses a base (alkali methoxide or alkali hydroxide) to form an ether or an alcohol. This reaction is shown below using sodium as the alkali cation:
- the reaction of the alkali salt of a carboxylic acid 44 will now be described.
- the alkali salt of a carboxylic acid 44 may be used in an electrochemical cell.
- the electrochemical cell produces a decarboxylation reaction 70 using a sodium conductive membrane.
- This electrochemical reaction 70 produces a quantity of carbon dioxide 80 as well as a quantity of base 84 .
- This base 84 may be sodium hydroxide, sodium methoxide, sodium methylate, etc. (In turn, this quantity of base 84 may be reused in the saponification reaction 38 , as shown by arrow 88 .)
- the electrochemical reaction 70 also produces a hydrocarbon 90 .
- This hydrocarbon may be a hydrocarbon fuel or other similar chemical that may be used as a fuel additive. (This process will be described in greater detail herein).
- this process may involve converting a hexose sugar 118 (such as glucose, etc.) into levulinic acid.
- This process is a dehydration reaction as water 140 is produced.
- the dehydration of a sugar 118 which is performed by treatment with acid, ultimately forms levulinic acid 120 and formic acid 130 .
- the saponification reaction involves reacting levulinic acid 120 and/or the formic acid 130 with a base 160 .
- the base 160 is NaOH.
- other bases may be used (such as sodium methoxide, sodium ethoxide, KOH, potassium methoxide, etc.)
- This saponification reaction produces water 140 , sodium formate 170 and sodium levulinate 180 .
- sodium instead of sodium, another alkali metal may be used as the corresponding cation.
- R is the remaining section of levulinic or valeric acids.
- the alkali metal salt of the acid (such as, for example R—COONa (or the carboxylate with additional ether or alcohol functional group)) may be separated and used to prepare an anolyte for an electrochemical cell.
- This anolyte may further include a solvent and optionally a second sodium carboxylate.
- the anolyte may then be fed into an electrolytic cell that uses a sodium ion conductive ceramic membrane that divides the cell into two compartments: an anolyte compartment and a catholyte compartment.
- the electrolytic cell may be of standard parallel plate cell where flat plate electrodes and membranes are used or of tubular type cell where tubular electrodes and membranes are used.
- An electrochemically active first anode e.g. smooth platinum, stainless steel, metal alloy anodes e.g.
- Kolbe reaction This reaction involves an oxidation (decarboxylation) step. Specifically, in the standard Kolbe reaction, anodic decarboxylation/oxidative coupling of carboxylic acids occurs. This reaction is a free radical reaction and is shown below:
- This Kolbe reaction is typically conducted in non-aqueous methanolic solutions, with partially neutralized acid (in the form of alkali salt) used with a parallel plate type electrochemical cell.
- the anolyte used in the cell may have a high density.
- the Kolbe reaction has been known and used. In fact, the following article summarizes and explains the Kolbe reaction:
- the Kolbe reaction is a free radical reaction in which two “R radicals” (R.) are formed and are subsequently combined together to form a carbon-carbon bond.
- the present embodiments relate to a modified “Kolbe” reaction. Specifically, the present embodiments involve decarboxylation to form an “R radical” (R.) These radical species may couple together to form hydrocarbon products.
- sodium levulinate may be decarboxylated at the anode of a cell to produce a radical.
- This reaction may be represented as follows:
- the formate may also react as follows:
- the H radicals and the other radicals may react together to form a variety of species, including hydrocarbons.
- the above decarboxylation reactions are typically conducted in non-aqueous solutions at high current densities.
- the carboxylate is sodium levulinate (CH 3 CO(CH 2 ) 2 COONa)
- the product obtained is CH 3 CO(CH 2 ) 4 COCH 3 . More specifically, this radical reaction occurs as follows:
- This dimer product is very similar to octane and could be used as an additive to gasoline.
- the carboxylate is sodium valerate (CH 3 (CH 2 ) 3 COONa)
- the product is octane, CH 3 (CH 2 ) 6 CH 3 , the primary component gasoline.
- the cell 200 includes a catholyte compartment 204 and an anolyte compartment 208 .
- the catholyte compartment 204 and the anolyte compartment 208 may be separated by a membrane 212 .
- Other embodiments may be designed in which there is only a single compartment that houses both the anode and the cathode.
- each cell 200 may be a standard parallel plate cell, where flat plate electrodes and/or flat plate membranes are used. In other embodiments, the cell 200 may be a tubular type cell, where tubular electrodes and/or tubular membranes are used.
- An electrochemically active anode 218 is housed, at least partially or wholly, within the anolyte compartment 208 . More than one anode 218 may also be used.
- the anode 218 may comprise, for example, a smooth platinum electrode, a stainless steel electrode, or a carbon based electrode.
- Examples of a typical carbon based electrode include boron doped diamond, glassy carbon, synthetic carbon, Dimensionally Stable Anodes (DSA) and relatives, and/or lead dioxide.
- Other electrodes may comprise metals and/or alloys of metals, including S.S, Kovar, Inconel/monel.
- Other electrodes may comprise RuO 2 —TiO 2 /Ti, PtO x —PtO 2 /Ti, IrO x , CO 3 O 4 , MnO 2 , Ta 2 O 5 and other valve metal oxides.
- the cathode compartment 204 includes at least one cathode 214 .
- the cathode 214 is partially or wholly housed within the cathode compartment 204 .
- the material used to construct the cathode 214 may be the same as the material used to construct the anode 218 .
- Other embodiments may be designed in which a different material is used to construct the anode 218 and the cathode 214 .
- the anolyte compartment 208 is designed to house a quantity of anolyte 228 .
- the catholyte compartment 204 is designed to house a quantity of catholyte 224 .
- the anolyte 228 and the catholyte 224 are both liquids, although solid particles and/or gaseous particles may also be included in either the anolyte 228 , the catholyte 224 , and/or both the anolyte 228 and the catholyte 224 .
- the anode compartment 208 and the cathode compartment 204 are separated by an alkali metal ion conductive membrane 212 .
- the membrane utilizes a selective alkali metal transport membrane.
- the membrane is a sodium ion conductive membrane 212 .
- the sodium ion conductive solid electrolyte membrane 212 selectively transfers sodium ions (Na + ) from the anolyte compartment 208 to the catholyte compartment 204 under the influence of an electrical potential, while preventing the anolyte 228 and the catholyte 224 from mixing.
- solid electrolyte membranes include those based on NaSICON structure, sodium conducting glasses, beta alumina and solid polymeric sodium ion conductors.
- NaSICON typically has a relatively high ionic conductivity at room temperature.
- the alkali metal is lithium, then a particularly well suited material that may be used to construct an embodiment of the membrane is LiSICON.
- the alkali metal is potassium, then a particularly well suited material that may be used to construct an embodiment of the membrane is KSICON.
- the saponification reaction shown in FIG. 2B (and/or other reactions) are designed to produce a quantity of an alkali metal salt of levulinic acid 180 (e.g., sodium levulinate).
- This alkali metal salt of a levulinic acid 180 may be separated and/or purified, as needed Likewise, as desired, if the alkali metal salt of levulinic acid 180 comprises a mixture of fatty acid salts, these compounds may be separated. Alternatively, the alkali metal salt of levulinic acid 180 may not be separated and may comprise a mixture of different salts.
- the anolyte compartment 208 may include one or more inlets 240 through which the anolyte 228 may be added. Alternatively, the components that make up the anolyte 228 may be separately added to the anolyte compartment 208 via the inlets 240 and allowed to mix in the cell.
- the anolyte includes a quantity of the alkali metal salt of levulinic acid 180 . In the specific embodiment shown, sodium is the alkali metal, so that alkali metal salt of levulinic acid 180 is a sodium salt 180 a.
- the anolyte 228 also includes a first solvent 160 , which as noted above, may be an alcohol, such as methyl alcohol 160 a. Of course, other types of solvents may also be used.
- the catholyte compartment 204 may include one or more inlets 242 through which the catholyte 224 may be added.
- the catholyte 224 includes a second solvent 160 b.
- the second solvent 160 b may be an alcohol or water (or a mixture of alcohol and water). As shown in FIG. 3 , the alcohol is methyl alcohol.
- the solvent 160 b in the catholyte 224 may not necessarily be the same as the first solvent 160 a in the anolyte 228 . In some embodiments, the solvents 160 a, 160 b may be the same. The reason for this is that the membrane 212 isolates the compartments 208 , 204 from each other.
- the solvents 160 a, 160 b may be each separately selected for the reactions in each particular compartment (and/or to adjust the solubility of the chemicals in each particular compartment).
- the designer of the cell 200 may tailor the solvents 160 a, 160 b for the reaction occurring in the specific compartment, without having to worry about the solvents mixing and/or the reactions occurring in the other compartment.
- This is a significant advantage in designing the cell 200 .
- a typical Kolbe reaction only allows for one solvent used in both the anolyte and the catholyte. Accordingly, the use of two separate solvents may be advantageous.
- either the first solvent 160 a, the second solvent 160 b, and/or the first and second solvents 160 a, 160 b may comprise a mixture of solvents.
- the catholyte 224 may also include a base 150 .
- the base 150 may be NaOH or sodium methoxide, or a mixture of these chemicals.
- the base 150 may be the same base 150 as used in the saponification reaction of FIG. 2B .
- the base may be a different base than that which was used in the saponification reaction.
- This reaction uses sodium ions from the solvent and the solvent to form hydrogen gas 270 as well as an additional quantity of base 150 .
- the reduction reaction(s) may be written as follows:
- the hydrogen gas 270 and/or the base 150 may be extracted through outlets 244 .
- the hydrogen gas 270 may be gathered for further processing for use in other reactions, and/or disposed of or sold.
- the production of the base 150 is a significant advantage because the base 150 that was consumed in the saponification reaction of FIG. 1 is generated in this portion of the cell 200 .
- the base formed in the cell may be collected and re-used in future saponification reactions (or other chemical processes). As the base may be re-used, the hassle and/or the fees associated with disposing of the base are avoided.
- the reactions that occur at the anode 218 may involve decarboxylation. These reactions may involve an advanced Kolbe reaction (which is a free radical reaction) to form a quantity of a product 271 and carbon dioxide 272 .
- the solvent 160 / 160 a may also be recovered and recycled, if desired, back to the inlet 240 for future use.
- the carbon dioxide 272 may be vented off (via one or more outlets 248 ). This is a safe, naturally-occurring chemical that may be collected, disposed of, or re-used.
- the advanced Kolbe reaction may comprise a free radical reaction. As such, the reaction produces (as an intermediate) a radical designated as CH 3 —C(O)—CH 2 CH 2 . Radical species are highly reactive. Accordingly, when two of these radicals react together, the following product is formed:
- this octanedione makes up the product 271 .
- the octanedione may be the predominant product.
- These products may be formed based upon the presence of H radicals, (which are formed from the decarboxylation of formate and/or from hydrogen gas). These H radicals can react with these species (either in a radical reaction or in a hydrogen extraction reaction):
- H radicals H radicals
- these H radicals may react to form hydrogen gas, MEK or other products.
- Those skilled in the art will appreciate that such embodiments that produce H radicals may also be used in conjunction with the present embodiments. However, for purposes of brevity, the description of these methods for forming H radicals will not be repeated.
- FIG. 3 is designed in which there are two compartments to the cell. However, those skilled in the art will appreciate that embodiments may be constructed in which there is a single chamber (compartment) in the cell.
- the octanedione that is produced in the cell of FIG. 3 may be used as a fuel additive (such as, for example, an additive to gasoline) and/or as a hydrocarbon fuel.
- a fuel additive such as, for example, an additive to gasoline
- a hydrocarbon fuel such as, for example, gasoline
- the biomass has been converted, using the cell of FIG. 3 , into a hydrocarbon fuel.
- FIG. 4 shows an embodiment of a cell 300 that is similar to the cell 200 of FIG. 3 .
- the anolyte comprises sodium valerate instead of sodium levulinate.
- This sodium valerate may be formed from the biomass.
- the hexose sugar may be converted into levulinic acid and formic acid:
- the levulinic acid may be reacted to form ⁇ -valerolactone:
- this ⁇ -valerolactone may further be reacted with hydrogen to form valeric acid (C 5 H 10 O 2 ), as shown by FIG. 5A .
- this valeric acid may be reacted with a base (such as NaOH, NaOCH 3 , etc.) to form sodium valerate (or another alkali metal valerate).
- a base such as NaOH, NaOCH 3 , etc.
- valerate 180 e.g., sodium valerate 180 a
- the valerate 180 will decarboxylate in the cell 300 of FIG. 4 to form the CH 3 —CH 2 —CH 2 CH 2 . radical. These two radicals may couple together within the cell to form octane.
- Octane is a valuable hydrocarbon as it is used in gasoline and other fuels. This octane product is shown as product 371 in FIG. 4 . Accordingly, by using these embodiments, octane may be formed.
- FIGS. 6A and 6B the hydrolysis reaction of ⁇ -valerolactone is shown.
- the ⁇ -valerolactone may be reacted with a base.
- FIG. 6A shows the reaction of ⁇ -valerolactone with NaOH
- FIG. 6B shows the reaction of ⁇ -valerolactone with NaOCH 3 .
- Those skilled in the art will appreciate that other bases may also be used in a similar manner.
- the reaction of ⁇ -valerolactone with NaOH produces HO(CH 2 ) 4 COONa.
- FIG. 6B the reaction of ⁇ -valerolactone with NaOCH 3 produces CH 3 O(CH 2 ) 4 COONa.
- the species HO(CH 2 ) 4 COONa and/or CH 3 O(CH 2 ) 4 COONa may be used in a cell 400 similar to the embodiments discussed herein.
- the species HO(CH 2 ) 4 COONa and/or CH 3 O(CH 2 ) 4 COONa may be formed using the reactions of FIGS. 6A-6B .
- the HO(CH 2 ) 4 COONa and/or CH 3 O(CH 2 ) 4 COONa may be added as shown by number 180 / 180 a.
- element 180 a represents a sodium salt of the particular anions whereas element 180 represents a more generic “alkali metal salt” of the anions.
- these species decarboxylate and form the following radicals: HO(CH 2 ) 4 . and H 3 CO(CH 2 ) 4 .
- radicals may couple as follows:
- diol or diether products are shown as product 471 in FIG. 7 .
- Such diol or diether products may be used as additives to gasoline or other fuels.
- the cells 200 , 300 and 400 may have specific advantages. For example, there may be specific advantages associated with using sodium salt of carboxylic acid in the cells 200 , 300 and 400 , instead of carboxylic acid itself . These advantages include:
- the sodium ion conductive solid electrolyte membrane selectively transfers sodium ions (Na + ) from the anolyte compartment to the first catholyte compartment under the influence of an electrical potential while preventing anolyte and catholyte mixing.
- sodium ions Na +
- solid electrolyte membranes include those based on NaSICON structure, sodium conducting glasses, beta alumina and solid polymeric sodium ion conductors.
- FIGS. 1-7 collectively, an additional embodiment will be described. Specifically, the present embodiments have been designed to result in a R (R radical) to R (R radical) coupling, thereby producing compounds that suitable for use in fuels.
- R R radical
- R R radical
- R radical R radical
- a second alkali metal carboxylate could be used in conjunction with the compounds described herein and used as part of the anolyte solution.
- This second carboxylate species may have between 1 to 7 carbon atoms.
- the use of this second carboyxlate may have some advantages such as:
- the method 800 comprises obtaining 804 quantity of biomass. As noted above, this biomass may be from plant, animal, algal, or other sources. This biomass may then be converted 808 into a carbohydrate. The carbohydrate may be converted 812 into a hexose sugar.
- the hexose sugar may then be reacted to form an alkali metal levulinate, an alkali metal valerate, an alkali metal 5-hydroxy pentanoate (HO(CH 2 ) 4 COONa), or an alkali metal 5-alkoxy pentanoate (RO(CH 2 ) 4 COONa, where “R” is an alkyl group such as methyl, ethyl, butyl, propyl, isopropyl, or any desired alkyl group).
- R is an alkyl group such as methyl, ethyl, butyl, propyl, isopropyl, or any desired alkyl group.
- alkali metal levulinate alkali metal valerate, alkali metal 5-hydroxy pentanoate (HO(CH 2 ) 4 COONa), or alkali metal 5-alkoxy pentanoate may be purchased or otherwise obtained.
- this alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate, or alkali metal 5-alkoxy pentanoate may be added 820 to an anolyte. Once prepared, the anolyte may be placed in the electrolytic cell. The alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate, or alkali metal 5-alkoxy pentanoate may then be decarboxylated 824 in the electrolytic cell.
- This decarboxylation operates to convert the alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate, or alkali metal 5-alkoxy pentanoate into radicals that may react to form a hydrocarbon fuel product.
- the radicals may react (couple) to form 2,7-octadione (which may be a gasoline additive).
- the radicals may react (couple) to form octane.
- the radicals may react (couple) to form 1,8-dialkoxy octane.
- the radicals may react (couple) to form 1,8-hydroxy octane.
- the method 900 may be used to form hydrocarbon fuel compound.
- the method involves obtaining 904 a quantity of a six carbon sugar. Once obtained, the six carbon sugar is reacted 908 into an alkali metal levulinate, an alkali metal valerate, an alkali metal 5-hydroxy pentanoate, or an alkali metal 5-alkoxy pentanoate.
- the anolyte will then be prepared 912 .
- the anolyte comprises a quantity of the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate.
- the anolyte may be placed 920 in an electrolytic cell, such as those described herein.
- the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate is decarboxylated 924 .
- This decarboxylation may involve electrolysis.
- Such decarboxylation forms one or more radicals that react to form a hydrocarbon fuel product such as, for example, octane, octadione, 1,8-hydroxy octane, and/or 1,8-dialkoxy octane.
- Tests were run in order to test the decarboxylation of products.
- an electrochemical cell was prepared. This cell consisted of a two compartment electrochemical cell with minimal membrane-anode gap. The minimal gap is necessary for creating optimum mass transfer conditions in the anolyte compartment.
- a smooth platinum anode was used where decarboxylation occurs.
- a 1′′ (one inch) diameter and 1 mm thick NaSICON ceramic membrane was used between the anode and cathode compartment.
- the NaSICON membrane was obtained from the Ceramatec company of Salt Lake City, Utah.
- a nickel cathode was used in the cathode compartment.
- the test set up consisted of 1 liter glass flasks sealed with 3 holed rubber stoppers as anolyte and catholyte reservoirs. Each reservoir was placed on a hot plate and thermocouples were placed in each of the reservoirs. About 300 mL of anolyte (18.6% (wt/wt) sodium levulinate in methanol) and catholyte (15 wt. % aqueous NaOH) were used. The temperature was controlled by a temperature controller to maintain the temperature of feed solutions to the anolyte, and catholyte at 45° C. Pumps were used to circulate the anolyte and catholyte solutions.
- Electrochemical decarboxylation was conducted at a current density of ⁇ 50 mA per cm 2 of membrane area for 7 hours. The cell was operated until 20% (wt/wt) of the starting available sodium content was removed. The voltage profile for this constant current test data is shown in FIG. 10 . The voltage stayed constant during the sodium removal and decarboxylation process.
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Abstract
Hydrocarbons may be formed from six carbon sugars. This process involves obtaining a quantity of a hexose sugar. The hexose sugar may be derived from biomass. The hexose sugar is reacted to form an alkali metal levulinate, an alkali metal valerate, an alkali metal 5-hydroxy pentanoate, or an alkali metal 5-alkoxy pentanoate. An anolyte is then prepared for use in a electrolytic cell. The anolyte contains the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate. The anolyte is then decarboxylated. This decarboxylating operates to decarboxylate the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate to form radicals, wherein the radicals react to form a hydrocarbon fuel compound.
Description
- This application is a divisional of, and claim priority to, U.S. application Ser. No. 13/357,463 (the “'463 Application”) filed Jan. 24, 2012 and titled “Production of Fuel from Chemicals Derived from Biomass.” The '463 Application claims the benefit of U.S. Provisional Patent Application Ser. No. 61/577,496 filed Dec. 19, 2011, entitled “Decarboxylation of Levulinic Acid to Make Solvent.” The '463 Application also claims the benefit of U.S. Provisional Patent Application Ser. No. 61/436,088 filed Jan. 25, 2011, entitled “Production of Fuel from Chemicals Derived from Biomass.” Both of these provisional applications are expressly incorporated herein by reference.
- Hydrocarbon fuels are currently used throughout the world. One specific example of a hydrocarbon fuel is gasoline (which includes octane). Another common hydrocarbon fuel is diesel fuel, which is used in diesel engines. Accordingly, there is a need for methods for producing hydrocarbons that may be used as fuels.
- Biomass is a renewable feedstock. Biomass may comprise lipids (such as fats or oils) that are available from plant, algal, or animal origin. These fats or oils may include fatty acids. Obviously, given its abundance in nature, it is desirable to find a way to use this biomass as a starting material to form a useable product, such as a hydrocarbon fuel.
- Current methods to convert biomass to a hydrocarbon fuel involve the process known as “hydroreacting” in which hydrogen gas is added to the biomass (in the presence of a catalyst) to convert the biomass to hydrocarbons. Unfortunately, hydroreacting is generally expensive because hydrogen gas is an expensive reactant. Also, a catalyst is involved in this process, and such catalysts are often intolerant with Ca, Cl, V, N, As, Hg, Si, P, Cr or other materials that may be found in the biomass. Other impurities include soluble vitamins, steroids, terpenes, alkaloids, etc. Another process to convert biomass to hydrocarbons is decarboxylation, wherein the carboxylic acid functionality of a fatty acid is “decarboxylated,” thereby leaving a hydrocarbon. (In some situations, this decarboxylation step may be preceded by a fermentation step and/or a hydrolysis step, depending upon the starting material.) Employing the decarboxylation process to produce the hydrocarbon is generally expensive.
- Accordingly, there is a need for a new process by which biomass may be converted into a hydrocarbon. Such a process is disclosed herein.
- Disclosed herein is a method for the manufacture of hydrocarbon fuels from biomass. This method relates to the conversion of the biomass based starting materials such as carbohydrates and sugars, to carboxylic acids or alkali metal salts of carboxylic acids (and other carboxylic acid derivatives such as esters) that may be used to form hydrocarbon fuels. Also disclosed are methods for turning biomass into lactones that may also be converted into hydrocarbon fuels. The biomass can be of plant, algal, or animal origin.
- In the present method, the biomass is converted to sugars (mainly hexoses that include one or more rings). These hexose sugars will generally have 6 carbon atoms which in turn are chemically converted to carboxylic acids. Examples of these types of sugar materials include glucose, etc. Specifically, a sugar monomer, which has the formula C6H12O6, may be reacted as follows to form levulinic acid, water and formic acid:
- C5H8O3 is the empirical formula of levulinic acid. However, this acid has the following chemical structure:
-
CH3—C(O)—CH2CH2COOH - Once these two acids (levulinic acid and formic acid) are obtained, these two acids may be saponified by reaction with a base (such as NaOH, NaOCH3, or any other base) to form the corresponding alkali metal salt (e.g., alkali metal salts of formate and levulinate):
- Alternatively, the sugars are directly converted to alkali salts of carboxylic acids.
- These alkali salts of carboxylic acids are then dissolved in a solvent and optionally with a second alkali carboxylate to yield a reacting mixture. The mixture is then converted to hydrocarbon fuel by electrolytic (anodic) decarboxylation and subsequent carbon-carbon coupling. The electrolysis cell deployed for this reaction utilizes a selective alkali transport solid electrolyte membrane technology. The product formed by this carbon-carbon coupling may be a hydrocarbon fuel material—e.g., a hydrocarbon that may be used as a fuel, a fuel additive, etc.
- In order that the manner in which the above-recited and other features and advantages of the invention are obtained will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
-
FIG. 1 is a flow diagram showing the overall process by which biomass may be converted into hydrocarbon fuels; -
FIG. 2A is a flow diagram showing the conversion of sugar moieties into levulinic acid and formic acid; -
FIG. 2B is a flow diagram showing the conversion of levulinic acid and formic acid to sodium formate and sodium levulinate; -
FIG. 3 is a schematic view of an embodiment of an electrolytic cell for conversion of sodium levulinate to a hydrocarbon fuel compound; -
FIG. 4 is a schematic view of an embodiment of an electrolytic cell for conversion of sodium valerate to a hydrocarbon fuel compound; -
FIG. 5 is a flow diagram showing the conversion of levulinic acid into sodium valerate; -
FIG. 6A is a flow diagram showing the conversion of γ-valerolactone into HO(CH2)4COONa; -
FIG. 6B is a flow diagram showing the conversion of γ-valerolactone into H3CO(CH2)4COONa; -
FIG. 7 is a schematic view of yet an embodiment of an electrolytic cell for conversion of HO(CH2)4COONa or H3CO(CH2)4COONa into a diol or diether product that may be used as a fuel additive; -
FIG. 8 is a flow diagram showing an exemplary method of the present embodiments; -
FIG. 9 is another flow diagram showing another exemplary method of the present embodiments; -
FIG. 10 shows a graph of current density and voltage for an example decarboxylation process; and -
FIG. 11 shows a gas chromatogram of a decarboxylation process that was performed. - The presently preferred embodiments of the present invention will be best understood by reference to the drawings, wherein like parts are designated by like numerals throughout. It will be readily understood that the components of the present invention, as generally described and illustrated in the figures herein, could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of the present embodiments, as represented in the Figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of presently preferred embodiments of the invention.
- Referring now to
FIG. 1 , a flow diagram which shows themethod 10 in whichbiomass 14 may be converted into a hydrocarbon according to the process outlined herein. For example, a quantity ofbiomass 14 is obtained. Thebiomass 14 may then be converted into acarbohydrate 18. Thiscarbohydrate 18 may be a starch material, a cellulose material, a polysaccharide material, etc. This process for converting thebiomass 14 into thecarbohydrate 18 is known. After acarbohydrate 18 has been obtained, thecarbohydrate 18 may be converted into a hexose sugar material 22 (such as glucose, etc.). The conversion of thecarbohydrate material 18 into ahexose sugar material 22 may occur via chemical hydrolysis or enzymatic hydrolysis. Such processes are known and are described, for example, in the following article: -
- Fan et. al., “Cellulose Hydrolysis,” Biotechnology Monographs, Vol. 3, Springer NY, 1987.
- After obtaining the
hexose sugar material 22, thismaterial 22 may undergo a catalytic dehydration 24 (or other process) to convert the sugar moieties intolevulinic acid 32. The process for converting a hexose sugar into levulinic acid is described, for example, in the following article: -
- Bozell J., Connecting Biomass and Petroleum Processing with a Chemical Bridge, Science, Vol. 239, pp 522-523, (2010).
This process is a dehydration reaction as water is produced. Formic acid may also be produced during this reaction. The ratio oflevulinic acid 32 to formic acid that is produced in this reaction may be approximately a 3:1 weight ratio. (Water is also formed during this process.) This transformation has been known for decades. Accordingly, those skilled in the art are familiar with the processes needed to create levulinic acid. Further information regarding the production of levulinic acid is found in the following article: - Bond, Jesse Q., et al., Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels, Science 327, 1110-1114 (2010).
- Bozell J., Connecting Biomass and Petroleum Processing with a Chemical Bridge, Science, Vol. 239, pp 522-523, (2010).
- The reaction of the hexose sugar to levulinic acid (CH3CO(CH2)2COOH) is summarized as follows:
- As shown by
arrow 36, thelevulinic acid 32 may undergo asaponification reaction 38 to produce an alkali salt of acarboxylic acid 44. More specifically, this alkali salt of a carboxylic acid may be the alkali metal salt of levulinic acid (e.g., an alkali metal levulinate). Thesaponification reaction 38 uses a base (such as an alkali metal methoxide or an alkali metal hydroxide). - Additionally or alternatively, the levulinic acid 32 may undergo a catalytic reduction process 46 to gamma-valerolactone 50 (γ-valerolactone). This gamma-valerolactone 50 (a cyclic ester) is produced by catalytic hydrogenation:
- In turn, this γ-valerolactone 50 may undergo a catalytic hydrogenation reaction 54 to produce valeric acid 62:
- This
valeric acid 62 can undergo thesaponfication reaction 38 to form the alkali salt of acarboxylic acid 44. (In this case, the alkali salt of a carboxylic acid would be the alkali metal valerate.) Alternatively, the γ-valerolactone 50 may undergo abase hydrolysis process 66 to form the alkali salt of acarboxylic acid 44. This hydrolysis reaction of the cyclic ester (γ-valerolactone) uses a base (alkali methoxide or alkali hydroxide) to form an ether or an alcohol. This reaction is shown below using sodium as the alkali cation: -
C5H8O2+CH3ONa→CH3O—C4H8—COONa -
C5H8O2+NaOH→HO—C4H8—COONa - The reaction of the alkali salt of a
carboxylic acid 44 will now be described. The alkali salt of acarboxylic acid 44 may be used in an electrochemical cell. As will be described in detail herein, the electrochemical cell produces adecarboxylation reaction 70 using a sodium conductive membrane. (An alcohol orwater material 76 is used in this electrochemical reaction.) Thiselectrochemical reaction 70 produces a quantity ofcarbon dioxide 80 as well as a quantity ofbase 84. This base 84 may be sodium hydroxide, sodium methoxide, sodium methylate, etc. (In turn, this quantity ofbase 84 may be reused in thesaponification reaction 38, as shown byarrow 88.) Theelectrochemical reaction 70 also produces ahydrocarbon 90. This hydrocarbon may be a hydrocarbon fuel or other similar chemical that may be used as a fuel additive. (This process will be described in greater detail herein). - Referring now to
FIG. 2A , the process for converting sugar moieties into levulinic acid is described. Specifically, this process may involve converting a hexose sugar 118 (such as glucose, etc.) into levulinic acid. This process is a dehydration reaction aswater 140 is produced. The dehydration of asugar 118, which is performed by treatment with acid, ultimately formslevulinic acid 120 andformic acid 130. - Referring now to
FIG. 2B , the saponification reaction of levulinic acid is described. (Those skilled in the art will appreciate that a similar saponification reaction may occur using valeric acid.) The saponification reaction involves reactinglevulinic acid 120 and/or theformic acid 130 with abase 160. InFIG. 2B , thebase 160 is NaOH. However, other bases may be used (such as sodium methoxide, sodium ethoxide, KOH, potassium methoxide, etc.) This saponification reaction produceswater 140,sodium formate 170 andsodium levulinate 180. Of course, instead of sodium, another alkali metal may be used as the corresponding cation. These saponfication reactions can be summarized as follows (with sodium as the alkali metal cation): -
R—COOH+CH3ONa→R COONa+CH3OH -
R—COOH+NaOH→R—COONa+H2O - Where, R is the remaining section of levulinic or valeric acids.
- The chemical reactions that occur in the electrochemical cell will now be described. Specifically, the alkali metal salt of the acid (such as, for example R—COONa (or the carboxylate with additional ether or alcohol functional group)) may be separated and used to prepare an anolyte for an electrochemical cell. This anolyte may further include a solvent and optionally a second sodium carboxylate.
- The anolyte may then be fed into an electrolytic cell that uses a sodium ion conductive ceramic membrane that divides the cell into two compartments: an anolyte compartment and a catholyte compartment. The electrolytic cell may be of standard parallel plate cell where flat plate electrodes and membranes are used or of tubular type cell where tubular electrodes and membranes are used. An electrochemically active first anode (e.g. smooth platinum, stainless steel, metal alloy anodes e.g. Kovar, carbon based electrodes such as boron doped diamond, glassy carbon, synthetic carbon, Dimensionally Stable Anodes (DSA), lead dioxide) that allow the desired reaction to take place) is housed in the first anolyte compartment where oxidation (decarboxylation) reaction and subsequent free radical carbon-carbon coupling takes place.
- At the anode of the electrochemical cell, various reactions may occur. One type of these reactions is referred to as the “Kolbe reaction.” This reaction involves an oxidation (decarboxylation) step. Specifically, in the standard Kolbe reaction, anodic decarboxylation/oxidative coupling of carboxylic acids occurs. This reaction is a free radical reaction and is shown below:
- This Kolbe reaction is typically conducted in non-aqueous methanolic solutions, with partially neutralized acid (in the form of alkali salt) used with a parallel plate type electrochemical cell. The anolyte used in the cell may have a high density. The Kolbe reaction has been known and used. In fact, the following article summarizes and explains the Kolbe reaction:
-
- Hans-Jurgen Schafer, Recent Contributions of Kolbe electrolysis to organic synthesis, Topics in Current Chemistry, Vol. 153, Issue: Electrochemistry IV, 1990, pp. 91-151.
- As can be seen from the Kolbe reaction, the “R” groups of two fatty acid molecules are coupled together, thereby resulting in a hydrocarbon product. The Kolbe reaction is a free radical reaction in which two “R radicals” (R.) are formed and are subsequently combined together to form a carbon-carbon bond.
- The present embodiments relate to a modified “Kolbe” reaction. Specifically, the present embodiments involve decarboxylation to form an “R radical” (R.) These radical species may couple together to form hydrocarbon products.
- As noted above, sodium levulinate may be decarboxylated at the anode of a cell to produce a radical. This reaction may be represented as follows:
- If formate is present in the anolyte, the formate may also react as follows:
- Thus, when a solution containing formate and levulinate are decarboxylated together, the H radicals and the other radicals may react together to form a variety of species, including hydrocarbons. The above decarboxylation reactions are typically conducted in non-aqueous solutions at high current densities. When the carboxylate is sodium levulinate (CH3CO(CH2)2COONa), the product obtained is CH3CO(CH2)4COCH3. More specifically, this radical reaction occurs as follows:
- This dimer product is very similar to octane and could be used as an additive to gasoline.
- When the carboxylate is sodium valerate (CH3(CH2)3COONa), the product is octane, CH3(CH2)6CH3, the primary component gasoline.
- In a similar manner, when the carboxylate is CH3O—C4H8—COONa (e.g., a CH3ONa hydrolysis product of γ-valerolactone), the product obtained is CH3O(CH2)8OCH3. When the carboxylate is HO—C4H8—COONa (e.g., a NaOH hydrolysis product of γ-valerolactone), the product obtained is HO(CH2)8OH. These products could be used as additives to gasoline.
- Referring now to
FIG. 3 , anelectrochemical cell 200 is shown to which a voltage may be applied. The advanced Kolbe reaction discussed above occurs within theelectrochemical cell 200. Thecell 200 includes acatholyte compartment 204 and ananolyte compartment 208. Thecatholyte compartment 204 and theanolyte compartment 208 may be separated by amembrane 212. Other embodiments may be designed in which there is only a single compartment that houses both the anode and the cathode. - The particulars of each
cell 200 will depend upon the specific embodiment. For example, thecell 200 may be a standard parallel plate cell, where flat plate electrodes and/or flat plate membranes are used. In other embodiments, thecell 200 may be a tubular type cell, where tubular electrodes and/or tubular membranes are used. An electrochemicallyactive anode 218 is housed, at least partially or wholly, within theanolyte compartment 208. More than oneanode 218 may also be used. Theanode 218 may comprise, for example, a smooth platinum electrode, a stainless steel electrode, or a carbon based electrode. Examples of a typical carbon based electrode include boron doped diamond, glassy carbon, synthetic carbon, Dimensionally Stable Anodes (DSA) and relatives, and/or lead dioxide. Other electrodes may comprise metals and/or alloys of metals, including S.S, Kovar, Inconel/monel. Other electrodes may comprise RuO2—TiO2/Ti, PtOx—PtO2/Ti, IrOx, CO3O4, MnO2, Ta2O5 and other valve metal oxides. In addition, other materials may be used to construct the electrode such as SnO2, Bi2Ru2O7 (BRO), BiSn2O7, noble metals such as platinum, titanium, palladium, and platinum clad titanium, carbon materials such as glassy carbon, BDD, or Hard carbons. Additional embodiments may have RuO2—TiO2, hard vitrems carbon, and/or PbO2. Again, the foregoing serve only as examples of the type of electrodes that may be employed. Thecathode compartment 204 includes at least onecathode 214. Thecathode 214 is partially or wholly housed within thecathode compartment 204. The material used to construct thecathode 214 may be the same as the material used to construct theanode 218. Other embodiments may be designed in which a different material is used to construct theanode 218 and thecathode 214. - The
anolyte compartment 208 is designed to house a quantity ofanolyte 228. Thecatholyte compartment 204 is designed to house a quantity ofcatholyte 224. In the embodiment ofFIG. 3 , theanolyte 228 and thecatholyte 224 are both liquids, although solid particles and/or gaseous particles may also be included in either theanolyte 228, thecatholyte 224, and/or both theanolyte 228 and thecatholyte 224. - The
anode compartment 208 and thecathode compartment 204 are separated by an alkali metal ionconductive membrane 212. The membrane utilizes a selective alkali metal transport membrane. For example, in the case of sodium, the membrane is a sodium ionconductive membrane 212. The sodium ion conductivesolid electrolyte membrane 212 selectively transfers sodium ions (Na+) from theanolyte compartment 208 to thecatholyte compartment 204 under the influence of an electrical potential, while preventing theanolyte 228 and the catholyte 224 from mixing. Examples of such solid electrolyte membranes include those based on NaSICON structure, sodium conducting glasses, beta alumina and solid polymeric sodium ion conductors. Such materials are commercially available. NaSICON typically has a relatively high ionic conductivity at room temperature. Alternatively, if the alkali metal is lithium, then a particularly well suited material that may be used to construct an embodiment of the membrane is LiSICON. Alternatively, if the alkali metal is potassium, then a particularly well suited material that may be used to construct an embodiment of the membrane is KSICON. - As noted above, the saponification reaction shown in
FIG. 2B (and/or other reactions) are designed to produce a quantity of an alkali metal salt of levulinic acid 180 (e.g., sodium levulinate). This alkali metal salt of alevulinic acid 180 may be separated and/or purified, as needed Likewise, as desired, if the alkali metal salt oflevulinic acid 180 comprises a mixture of fatty acid salts, these compounds may be separated. Alternatively, the alkali metal salt oflevulinic acid 180 may not be separated and may comprise a mixture of different salts. - The
anolyte compartment 208 may include one ormore inlets 240 through which theanolyte 228 may be added. Alternatively, the components that make up theanolyte 228 may be separately added to theanolyte compartment 208 via theinlets 240 and allowed to mix in the cell. The anolyte includes a quantity of the alkali metal salt oflevulinic acid 180. In the specific embodiment shown, sodium is the alkali metal, so that alkali metal salt oflevulinic acid 180 is asodium salt 180 a. Theanolyte 228 also includes a first solvent 160, which as noted above, may be an alcohol, such asmethyl alcohol 160 a. Of course, other types of solvents may also be used. - The
catholyte compartment 204 may include one ormore inlets 242 through which thecatholyte 224 may be added. Thecatholyte 224 includes a second solvent 160 b. The second solvent 160 b may be an alcohol or water (or a mixture of alcohol and water). As shown inFIG. 3 , the alcohol is methyl alcohol. Significantly, the solvent 160 b in thecatholyte 224 may not necessarily be the same as the first solvent 160 a in theanolyte 228. In some embodiments, thesolvents membrane 212 isolates thecompartments solvents cell 200 may tailor thesolvents cell 200. A typical Kolbe reaction only allows for one solvent used in both the anolyte and the catholyte. Accordingly, the use of two separate solvents may be advantageous. In other embodiments, either the first solvent 160 a, the second solvent 160 b, and/or the first andsecond solvents - The
catholyte 224 may also include abase 150. In the embodiment ofFIG. 1 , thebase 150 may be NaOH or sodium methoxide, or a mixture of these chemicals. The base 150 may be thesame base 150 as used in the saponification reaction ofFIG. 2B . Alternatively, the base may be a different base than that which was used in the saponification reaction. - The reactions that occur at the
anode 218 andcathode 214 will now be described. As with all electrochemical cells, such reactions may occur when a voltage is applied to thecell 200 via (source 201). - At the
cathode 214, a reduction reaction takes place. This reaction uses sodium ions from the solvent and the solvent to formhydrogen gas 270 as well as an additional quantity ofbase 150. Using sodium as the alkali metal, the reduction reaction(s) may be written as follows: -
2Na++2H2O+2e−→2NaOH+H2 -
2Na++2CH3OH+2e−→2NaOCH3 +H2 - The
hydrogen gas 270 and/or the base 150 may be extracted throughoutlets 244. Thehydrogen gas 270 may be gathered for further processing for use in other reactions, and/or disposed of or sold. The production of thebase 150 is a significant advantage because the base 150 that was consumed in the saponification reaction ofFIG. 1 is generated in this portion of thecell 200. Thus, the base formed in the cell may be collected and re-used in future saponification reactions (or other chemical processes). As the base may be re-used, the hassle and/or the fees associated with disposing of the base are avoided. - The reactions that occur at the
anode 218 may involve decarboxylation. These reactions may involve an advanced Kolbe reaction (which is a free radical reaction) to form a quantity of aproduct 271 andcarbon dioxide 272. The solvent 160/160 a may also be recovered and recycled, if desired, back to theinlet 240 for future use. - Using the chemicals of
FIGS. 2A and 2B as an example, the oxidation reactions may be written as follows: - The
carbon dioxide 272 may be vented off (via one or more outlets 248). This is a safe, naturally-occurring chemical that may be collected, disposed of, or re-used. -
- As shown in
FIG. 2 , this octanedione makes up the product 271. If the sodium levulinate is purified, then the octanedione may be the predominant product. However, in other embodiments, there may be other products formed in addition to the octanedione. These products may be formed based upon the presence of H radicals, (which are formed from the decarboxylation of formate and/or from hydrogen gas). These H radicals can react with these species (either in a radical reaction or in a hydrogen extraction reaction): - Accordingly, this reaction produces MEK (methyl ethyl ketone), which may be a portion of the product. Additionally, if H radicals (H.) are present in the system, such as from decarboxylation of formate or a hydrogen extraction process, these radicals can react together to form hydrogen gas:
- It should be noted that U.S. Provisional Patent Application Ser. No. 61/577,496 includes a variety of different embodiments which disclose various ways to create H. (H radicals) within the reaction cell. (These methods to create H radicals involve photolysis, the use of a Pd catalyst, etc.) As described in this patent application, these H radicals may react to form hydrogen gas, MEK or other products. Those skilled in the art will appreciate that such embodiments that produce H radicals may also be used in conjunction with the present embodiments. However, for purposes of brevity, the description of these methods for forming H radicals will not be repeated.
- It should be noted that the embodiments of
FIG. 3 are designed in which there are two compartments to the cell. However, those skilled in the art will appreciate that embodiments may be constructed in which there is a single chamber (compartment) in the cell. - It should be noted that the octanedione that is produced in the cell of
FIG. 3 may be used as a fuel additive (such as, for example, an additive to gasoline) and/or as a hydrocarbon fuel. Thus, as shown in the present disclosure, the biomass has been converted, using the cell ofFIG. 3 , into a hydrocarbon fuel. - The above-recited embodiments have been shown using sodium levulinate in the anolyte compartment. However, as noted above, embodiments may also be formed using different starting materials other than sodium levulinate. For example,
FIG. 4 shows an embodiment of a cell 300 that is similar to the cell 200 ofFIG. 3 . However, in the embodiment ofFIG. 4 , the anolyte comprises sodium valerate instead of sodium levulinate. (The cell 300 is similar to the cell 200 in other aspects, and as such, for purposes of brevity, a repeat description of the features of the cell 300 that similar to that which was described above is omitted.) This sodium valerate may be formed from the biomass. Specifically, as noted above, the hexose sugar may be converted into levulinic acid and formic acid: - As noted above, the levulinic acid may be reacted to form γ-valerolactone:
- In turn, this γ-valerolactone may further be reacted with hydrogen to form valeric acid (C5H10O2), as shown by
FIG. 5A . - In turn, this valeric acid may be reacted with a base (such as NaOH, NaOCH3, etc.) to form sodium valerate (or another alkali metal valerate). These reactions are shown in
FIG. 5B . - This valerate may then be reacted in the cell of
FIG. 4 to form octane. More specifically, the valerate 180 (e.g.,sodium valerate 180 a) will decarboxylate in thecell 300 ofFIG. 4 to form the CH3—CH2—CH2CH2. radical. These two radicals may couple together within the cell to form octane. - Octane is a valuable hydrocarbon as it is used in gasoline and other fuels. This octane product is shown as
product 371 inFIG. 4 . Accordingly, by using these embodiments, octane may be formed. - Referring now to
FIGS. 6A and 6B , the hydrolysis reaction of γ-valerolactone is shown. Specifically, the γ-valerolactone may be reacted with a base. Specifically,FIG. 6A shows the reaction of γ-valerolactone with NaOH whereasFIG. 6B shows the reaction of γ-valerolactone with NaOCH3. Those skilled in the art will appreciate that other bases may also be used in a similar manner. As shown inFIG. 6A , the reaction of γ-valerolactone with NaOH produces HO(CH2)4COONa. Similarly, as shown inFIG. 6B , the reaction of γ-valerolactone with NaOCH3 produces CH3O(CH2)4COONa. - As shown in
FIG. 7 , the species HO(CH2)4COONa and/or CH3O(CH2)4COONa may be used in acell 400 similar to the embodiments discussed herein. (The species HO(CH2)4COONa and/or CH3O(CH2)4COONa may be formed using the reactions ofFIGS. 6A-6B .) The HO(CH2)4COONa and/or CH3O(CH2)4COONa may be added as shown bynumber 180/180 a. (More specifically,element 180 a represents a sodium salt of the particular anions whereaselement 180 represents a more generic “alkali metal salt” of the anions.) In turn, these species decarboxylate and form the following radicals: HO(CH2)4. and H3CO(CH2)4 . These radicals may couple as follows: - These diol or diether products are shown as
product 471 inFIG. 7 . Such diol or diether products may be used as additives to gasoline or other fuels. - It should be noted that the
cells cells -
- R—COONa is more polar than R—COOH and so more probable to decarboxylate at lower voltages;
- The electrolyte conductivity may be higher for sodium salts of fatty acids than fatty acids themselves; and/or
- The anolyte and catholyte can be completely different allowing favorable reactions to take place at either electrode.
- Additionally, in the
cells - Referring now to
FIGS. 1-7 collectively, an additional embodiment will be described. Specifically, the present embodiments have been designed to result in a R (R radical) to R (R radical) coupling, thereby producing compounds that suitable for use in fuels. Those skilled in the art will appreciate that a second alkali metal carboxylate could be used in conjunction with the compounds described herein and used as part of the anolyte solution. This second carboxylate species may have between 1 to 7 carbon atoms. The use of this second carboyxlate may have some advantages such as: -
- The second carboxylate can act as a suitable supporting electrolyte providing high electrolyte conductivity;
- The second carboxylate will itself decarboxylate and produces alkyl radicals by the following reaction:
-
- The second alkyl radical can then be reacted with radicals formed from first sodium carboxylate (from sodium levulinate or sodium valerate or the base hydrolysis products of γ-valerolactone) to form hydrocarbons with additional CH3— (or other alkyl) functional groups:
-
- The R—R′ product can be a hydrocarbon that has number of carbon atoms in the range of diesel fuel or diesel fuel additive.
- Referring now to
FIG. 8 , a flow diagram is shown of amethod 800 for producing a hydrocarbon fuel compound. Themethod 800 comprises obtaining 804 quantity of biomass. As noted above, this biomass may be from plant, animal, algal, or other sources. This biomass may then be converted 808 into a carbohydrate. The carbohydrate may be converted 812 into a hexose sugar. As described herein, the hexose sugar may then be reacted to form an alkali metal levulinate, an alkali metal valerate, an alkali metal 5-hydroxy pentanoate (HO(CH2)4COONa), or an alkali metal 5-alkoxy pentanoate (RO(CH2)4COONa, where “R” is an alkyl group such as methyl, ethyl, butyl, propyl, isopropyl, or any desired alkyl group). The methods for forming these compounds are described above. Alternatively, the alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate (HO(CH2)4COONa), or alkali metal 5-alkoxy pentanoate may be purchased or otherwise obtained. - As noted herein, this alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate, or alkali metal 5-alkoxy pentanoate may be added 820 to an anolyte. Once prepared, the anolyte may be placed in the electrolytic cell. The alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate, or alkali metal 5-alkoxy pentanoate may then be decarboxylated 824 in the electrolytic cell. This decarboxylation operates to convert the alkali metal levulinate, alkali metal valerate, alkali metal 5-hydroxy pentanoate, or alkali metal 5-alkoxy pentanoate into radicals that may react to form a hydrocarbon fuel product. For example, if the material is an alkali metal levulinate, the radicals may react (couple) to
form 2,7-octadione (which may be a gasoline additive). If the material is an alkali metal valerate, the radicals may react (couple) to form octane. If the material is alkali metal 5-alkoxy pentanoate, the radicals may react (couple) to form 1,8-dialkoxy octane. If the material is an alkali metal 5-hydroxy pentanoate the radicals may react (couple) to form 1,8-hydroxy octane. - Referring now to
FIG. 9 , anotherexemplary method 900 according to the present embodiments is illustrated. Themethod 900 may be used to form hydrocarbon fuel compound. The method involves obtaining 904 a quantity of a six carbon sugar. Once obtained, the six carbon sugar is reacted 908 into an alkali metal levulinate, an alkali metal valerate, an alkali metal 5-hydroxy pentanoate, or an alkali metal 5-alkoxy pentanoate. - An anolyte will then be prepared 912. The anolyte comprises a quantity of the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate. Once prepared, the anolyte may be placed 920 in an electrolytic cell, such as those described herein.
- After placing the anolyte in the cell, the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate is decarboxylated 924. This decarboxylation may involve electrolysis. Such decarboxylation forms one or more radicals that react to form a hydrocarbon fuel product such as, for example, octane, octadione, 1,8-hydroxy octane, and/or 1,8-dialkoxy octane.
- Tests were run in order to test the decarboxylation of products. In order to perform this testing, an electrochemical cell was prepared. This cell consisted of a two compartment electrochemical cell with minimal membrane-anode gap. The minimal gap is necessary for creating optimum mass transfer conditions in the anolyte compartment. A smooth platinum anode was used where decarboxylation occurs. A 1″ (one inch) diameter and 1 mm thick NaSICON ceramic membrane was used between the anode and cathode compartment. The NaSICON membrane was obtained from the Ceramatec company of Salt Lake City, Utah. A nickel cathode was used in the cathode compartment.
- The test set up consisted of 1 liter glass flasks sealed with 3 holed rubber stoppers as anolyte and catholyte reservoirs. Each reservoir was placed on a hot plate and thermocouples were placed in each of the reservoirs. About 300 mL of anolyte (18.6% (wt/wt) sodium levulinate in methanol) and catholyte (15 wt. % aqueous NaOH) were used. The temperature was controlled by a temperature controller to maintain the temperature of feed solutions to the anolyte, and catholyte at 45° C. Pumps were used to circulate the anolyte and catholyte solutions.
- Test Summary: Electrochemical decarboxylation was conducted at a current density of ˜50 mA per cm2 of membrane area for 7 hours. The cell was operated until 20% (wt/wt) of the starting available sodium content was removed. The voltage profile for this constant current test data is shown in
FIG. 10 . The voltage stayed constant during the sodium removal and decarboxylation process. - Results: The post-reaction anolyte solution was analyzed by GC-MS analysis. 2,7-octanedione was the predominant product along with a minor unknown bi-product and traces of methyl levulinate and levulinic acid. The GC chromatogram is shown as
FIG. 11 . - All of the articles/papers mentioned in this disclosure are expressly incorporated herein by reference.
- The present invention may be embodied in other specific forms without departing from its structures, methods, or other essential characteristics as broadly described herein and claimed hereinafter. The described embodiments are to be considered in all respects only as illustrative, and not restrictive. The scope of the invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (9)
1. A method of forming a hydrocarbon fuel compound comprising:
obtaining a quantity of a hexose sugar;
reacting the hexose sugar to form an alkali metal levulinate, an alkali metal valerate, an alkali metal 5-hydroxy pentanoate, or an alkali metal 5-alkoxy pentanoate;
preparing an anolyte comprising the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate; and
decarboxylating the alkali metal levulinate, the alkali metal valerate, the alkali metal 5-hydroxy pentanoate, or the alkali metal 5-alkoxy pentanoate to form radicals, wherein the radicals react to form a hydrocarbon fuel compound.
2. A method as claimed in claim 1 , wherein the fuel compound is a gasoline additive.
3. A method as claimed in claim 1 , wherein the hexose sugar is reacted to form an alkali metal valerate, wherein the decarboxlation of the alkali metal valerate produces radicals that react to form octane.
4. A method as claimed in claim 1 , wherein the hexose sugar is reacted to form an alkali metal levulinate, wherein the decarboxlation of the alkali metal levulinate produces radicals that react to form 2,7-octadione.
5. A method as claimed in claim 1 , wherein the hexose sugar is reacted to form an alkali metal 5-hydroxy pentanoate, wherein the decarboxlation of the alkali metal 5-hydroxy pentanoate produces radicals that react to form 1,8-hydroxy octane.
6. A method as claimed in claim 1 , wherein the hexose sugar is reacted to form an alkali metal 5-alkoxy pentanoate, wherein the decarboxlation of the alkali metal 5-alkoxy pentanoate produces radicals that react to form 1,8-dialkoxy octane.
7. A method as claimed in claim 1 , wherein the decarboxylation occurs in an electrolytic cell, wherein the electrolytic cell comprises an anolyte compartment that houses the anolyte, a catholyte compartment that houses a catholyte, and an alkali ion conducting membrane that separates the anolyte compartment from the catholyte compartment.
8. A method as in claim 7 , wherein the alkali ion conducting membrane is a NaSICON membrane.
9. A method as claimed in claim 1 , further comprising the steps of:
obtaining a quantity of biomass;
converting the biomass into a carbohydrate; and
converting the carbohydrate into the hexose sugar.
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WO2012103135A2 (en) | 2012-08-02 |
US20140360866A1 (en) | 2014-12-11 |
JP5897039B2 (en) | 2016-03-30 |
EP2668250B1 (en) | 2019-04-24 |
US8821710B2 (en) | 2014-09-02 |
US9677182B2 (en) | 2017-06-13 |
WO2012103135A3 (en) | 2012-11-22 |
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