SE2250333A1 - Biomass hydroliquefaction - Google Patents
Biomass hydroliquefactionInfo
- Publication number
- SE2250333A1 SE2250333A1 SE2250333A SE2250333A SE2250333A1 SE 2250333 A1 SE2250333 A1 SE 2250333A1 SE 2250333 A SE2250333 A SE 2250333A SE 2250333 A SE2250333 A SE 2250333A SE 2250333 A1 SE2250333 A1 SE 2250333A1
- Authority
- SE
- Sweden
- Prior art keywords
- reactor
- feedstock
- biomass
- wood
- temperature
- Prior art date
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000007787 solid Substances 0.000 claims abstract description 38
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000002199 base oil Substances 0.000 claims description 33
- 239000002023 wood Substances 0.000 claims description 27
- 239000011859 microparticle Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 241000196324 Embryophyta Species 0.000 claims description 9
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- -1 logging residue Substances 0.000 claims description 5
- 241000609240 Ambelania acida Species 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 239000002154 agricultural waste Substances 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 239000004463 hay Substances 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000000047 product Substances 0.000 description 51
- 238000002474 experimental method Methods 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 14
- 239000012263 liquid product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 150000001735 carboxylic acids Chemical class 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 150000001336 alkenes Chemical group 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- YKJSOAKPHMIDLP-UHFFFAOYSA-J 2-ethylhexanoate;molybdenum(4+) Chemical compound [Mo+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O YKJSOAKPHMIDLP-UHFFFAOYSA-J 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/06—Sulfides
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
Abstract
A process is disclosed for liquefying solid biomass by a catalytic process, and an organic liquefaction product obtained by the process.
Description
BIOMASS HYDROLIQUEFACTION TECHNICAL FIELD The present disclosure generally relates to Iiquefying solid biomass. The disclosure relates particularly, though not exclusively, to a process for Iiquefying solid biomass by a catalytic hydroprocessing process to provide an organic liquefaction product, and to said organic liquefaction product.
BACKGROUND This section illustrates useful background information without admission of any technique described herein being representative of the state of the art.
Biological materials such as solid biomass have been proposed as an alternative hydrocarbon source for manufacturing fuels, chemicals, and polymers. A problem when converting solid biomass is that the obtained product is often a solid or multi- phase product containing a large amount of oxygen and being acidic, which makes further processing difficult and costly.
When biomass is converted, it is typically transferred by using a carrier oil containing tetralin, which is a known hydrogen donor due to one naphthenic ring. According to Burton et al 1986, "Catalytic Hydroliquefaction of Lignocellulosic Biomass", International Journal of Solar Energy tetralin is used typically in coal liquefaction process and Burton et al. utilizes the tetralin also in biomass liquefaction experiments.
There is therefore a need to develop processes for producing from biomass products in which at least some of the above problems are at least partially alleviated. Additionally, there is a need for renewable products that can be further converted to fuels and be used in chemical industry.
SUMMARY The appended claims define the scope of protection. Any example and/or technical description of an apparatus, system, product and/or process in the description and/or drawing which is not covered by the claims, is presented herein not as an embodiment of the invention but as background art or as an example useful for understanding the invention.
According to a first aspect is provided a process for Iiquefying solid biomass comprising: a. providing in a reactor a feedstock comprising solid biomass; and b. hydroprocessing the feedstock at a temperature selected from the range 250-400°C in the presence of catalytic microparticles comprising MoS, wherein the molar ratio of S to Mo is 1-3, to provide an organic liquefaction product.
With the present process it is possible to convert solid biomass to an organic liquefaction product with a high yield. Another advantage is that the process can be run under operating conditions in which there is no significant thermal cracking of the biomass and/or a carrier oil which may be used in the process. ln an embodiment the feedstock comprises solid biomass dispersed in a carbonaceous carrier oil.
The solid biomass can be dispersed in the carrier oil as a particulate material. The particles in the particulate material may be of any suitable size, but it is preferred that the particles have a mesh size of less than 7, preferably less than 10. A suitably small mesh size allows efficient dispersion of the biomass particles in the carrier oil, easy transfer by pumping, and enhanced reactive surface area for the hydroprocessing. ln an embodiment the carrier oil has a viscosity of 8 mPas or less at 100°C. Said viscosity allows efficient transfer of the feedstock by pumping. Additionally, the solid biomass is efficiently dispersed in the carrier oil when using a carrier oil with such a viscosity, which also enhances heat transfer during the hydroprocessing. ln an embodiment the carrier oil is a renewable carrier oil, or a partially or fully renewable carrier oil. A renewable carrier in this context means that it does not contain fossil hydrocarbons more than in trace amounts. ln another embodiment the carrier oil is a fossil carrier oil. ln an embodiment the carrier oil is selected to be inert in the reaction, i.e. it does not significantly react with the biomass or the hydrogen during the hydroprocessing. Examples of inert carrier oils include paraffinic hydrocarbons, preferably paraffinic hydrocarbons having at least 10 carbon atoms, more preferably 10-22 carbon atoms. An example of a suitable carrier oil is dodecane. ln an embodiment the inert carrier oil is recycled in the process. ln an embodiment the carrier oil is used to transfer the biomass to the reactor and to help in hydrogen mass transfer. ln an embodiment the carrier oil is thermally stable during the transfer or storage of the feedstock. ln another embodiment the carrier oil is thermally stable during the transfer but may react in the reactor. ln a preferred embodiment the carrier oil is free from oxygen.
The carrier oil may alternatively contain oxygen, in which case it reacts during the hydroprocessing. Examples of oxygen containing carrier oils include triglycerides, fatty acids, hydrothermal liquefaction oil, and tall oil and its derivatives. ln an embodiment the carrier oil contains at least partially the organic liquefaction product obtained in the present process. When some of the obtained organic liquefaction product is recycled as a carrier oil, there is less need for feeding external carrier oil into the process. Such an embodiment is particularly useful when running the process as a continuous process. ln an embodiment no hydrogen donating oil, such as tetralin, is added or present in the process, and/or in the feedstock, and/or in the carrier oil. ln the present process the carrier oil does not have to contain any hydrogen donating oil. Advantageously with the present process, the hydroprocessing is efficient even without tetralin or other hydrogen donating oil. Therefore, addition of hydrogen donating oils can be omitted, which provides an economical advantage and simplifies the present process. ln an embodiment the feedstock contains 5-90% solid biomass, preferably 10-85%, more preferably 10-35% or 60-85%, expressed as the wt-% of the solids of the biomass in the feedstock. Preferably, the remaining part of the feedstock substantially consists of the carrier oil. ln an embodiment the feedstock contains 10-35% solid biomass, preferably 10-35%. ln this amount the feedstock, and the solid biomass contained in it, can be more easily transferred to the reactor by pumping. ln another embodiment the feedstock contains 60-85% solid biomass, expressed as the wt-% of the solids of the biomass in the feedstock. ln an embodiment the water content of the biomass is not more than 50 wt-%, more preferably the water content is between 5 and 25 wt-%, and most preferably between 8 and 20 wt-%. ln an embodiment in the process at least 90% of the number of the catalytic microparticles have a size below 7um, wherein the size of a microparticle is expressed as an average of the longest dimension and the shortest dimension of the microparticle. ln an embodiment in the process at least 90% of the catalytic microparticles have a size below 50um, wherein the size of a microparticle is expressed as an average of the longest dimension and the shortest dimension of the microparticle. ln an embodiment no other catalyst than the catalytic microparticles is used in the hydroprocessing process.
With the present catalytic microparticles surprisingly high biomass concentration in the feedstock can be used with high carbon efficiency.
Further, the present catalytic microparticles are advantageous because they provide a high yield with a catalyst that contains only one metal, thereby simplifying the process and providing an economic advantage. ln an embodiment at least 90% of the microparticles have an aspect ratio of 0.40- 1.0, as analysed from SEM micrographs. ln an embodiment the distribution of the aspect ratios of the microparticles is such that at least 90% of the microparticles have an aspect ratio in the range 0.40 - 1.0 um/um, at least 80% of the microparticles have an aspect ratio in the range 0.50 - 1.0 um/um and at least 65% of the microparticles have an aspect ratio in the range 0.60 - 1.0 um/um. ln another embodiment 94 % of the microparticles have an aspect ratio within the range 0.40 - 1.0, 84% of the microparticles within 0.50 - 1.0 and 69% of the microparticles have an aspect ratio within 0.60 - 1.0. The aspect ratio is expressed as the ratio between the width and the length of the microparticle. The dimensions of the particles can be measured e.g. from SEM micrographs. ln an embodiment the microparticles have at least partially crysta||ine structure. ln an embodiment the crystallinity is at least 10%, at least 15%, at least 20% or at least 30%. For catalytic efficiency it may be advantageous to have partially non-crysta||ine catalyst. The degree of crystallinity can be determined by X-ray diffraction analysis. ln an embodiment the catalytic microparticles are dispersed in a fluid, preferably in the liquid phase, inside the reactor, and wherein said fluid comprises the carrier oil and reaction products formed during the process. This is advantageous to ensure that in the catalytic hydroprocessing the feedstock is reacted with the hydrogen dissolved in the feedstock, and that no catalytic reactions occur in a gas phase. ln an embodiment the solid biomass comprises at least one cellulose containing material such as wood, logging residue, wood chips, wood sawdust, wood bark, construction wood, demolition wood, paper, recycled paper, plant part, fruit, vegetable, plant processing waste, grain, grass, corn, corn husks, hay, bagasse, straw, bamboo, and agricultural waste. Preferably the biomass comprises wood saw dust, logging residue, or their combination. ln an embodiment the solid biomass may be selected from a cellulose containing material such as wood, logging residue, wood chips, wood sawdust, wood bark, construction wood, demolition wood, paper, recycled paper, plant part, fruit, vegetable, plant processing waste, grain, grass, corn, corn husks, hay, bagasse, straw, bamboo, and agricultural waste. ln an embodiment the solid biomass comprises wood, logging residue, wood chips, sawdust, wood bark, wood saw dust, construction wood, demolition wood, or any combination thereof. ln another embodiment the solid biomass comprises construction wood, demolition wood, or their combination. ln an embodiment the biomass comprises paper, recycled paper, or a combination thereof. ln an embodiment the biomass comprises plants, plant parts, fruit, vegetable, plant processing waste, grain, grass, corn, corn husks, hay, bagasse, straw, bamboo, agricultural waste, or their combination. ln an embodiment the hydroprocessing comprises or consists of reacting the biomass in the presence of hydrogen gas and the catalytic microparticles. ln an embodiment the present hydroprocessing process is carried out in a temperature and pressure wherein the carrier oil is in liquid phase. ln an embodiment the hydroprocessing is carried out at a temperature below 400°C, preferably at a temperature selected from the range 250-400°C, more preferably 270-390°C; and/or at a pressure selected from the range 30-300 bar, preferably 70- 170 bar, more preferably 80-150 bar. Preferably these conditions are selected such that hydrocracking does not significantly occur. ln an embodiment the molar ratio of hydrogen gas to feedstock oxygen is at least 2. When this amount of the hydrogen gas as H2 is used inside the reactor during the hydroprocessing, the liquefaction is efficient. As hydrogen is consumed during the hydroprocessing, additional hydrogen gas is preferably fed into the reactor during hydroprocessing. ln an embodiment the hydroprocessing is carried out in two or more reactors in a series. ln a preferred embodiment the hydroprocessing is carried out in two or more reactors in a series, in which each subsequent reactor is operated at a higher temperature than the first reactor. Optionally the process is carried out with three reactors in a series, and the temperature of the first reactor is selected from the range 270-350°C, the temperature of the second reactor is selected from the range 340-400°C, and the temperature of the third reactor is selected from the range 380- 400°C. ln an embodiment the process further comprises fractionating a light product having a boiling point below 360°C from the organic liquefaction product of the first reactor, and feeding the remaining feed to at least one subsequent reactor. Preferably the heavy product is fed to the second reactor. 7 According to a second aspect is provided an organic Iiquefaction product produced by the present process and having a lower oxygen content than the solid biomass.
BRIEF DESCRIPTION OF THE FIGURES Some example embodiments will be described with reference to the accompanying figures, in which: Fig. 1 shows TGA-data for the organic Iiquefaction product obtained in experiment 1.
Fig. 2 shows TGA-data for the organic Iiquefaction product obtained in experiment 2.
Fig. 3 shows TGA-data for the THF-soluble phase obtained in experiment 1.
Fig. 4 shows TGA-data for the THF-soluble phase obtained in experiment 2.
DETAILED DESCRIPTION As used herein, the term "comprising" includes the broader meanings of "including", "containing", and "comprehending", as well as the narrower expressions "consisting of' and "consisting only of". ln an embodiment the process steps are carried out in the sequence identified in any aspect, embodiment, or claim. ln another embodiment any process step specified to be carried out to an organic Iiquefaction product or an intermediate obtained in a preceding process step is carried out directly to said product or intermediate, i.e. without additional, optional or auxiliary processing steps that may chemically and/or physically alter the product or intermediate between said two consecutive steps. ln an embodiment the present process is an industrial process. ln another embodiment the industrial process may exclude small scale methods such as laboratory scale methods that are not scaled up to volumes used in industry. ln an embodiment the present process is a continuous process. ln an embodiment the boiling point refers to a boiling point at atmospheric pressure. ln an embodiment the present feedstock, and/or the present Iiquefaction product, is 8 renewable and has a higher content of 146 isotopes than chemically corresponding components derived from fossil sources. Said higher content of 146 isotopes is an inherent feature of the present product, and it distinguishes it from fossil materials. Thus, the carbon atoms of the present renewable products comprise a higher number of 146 isotopes compared to carbon atoms of fossil materials. The isotope ratio of renewable carbon does not change in the course of chemical reactions and therefore the origin of the carbon can be analysed from products that are chemically synthesized or catalytically converted from renewable materials. lt is thus possible to distinguish between a carbonaceous compound or composition derived from renewable sources, and a similar carbonaceous compound or composition derived from fossil sources by analysing their 126 and 146 isotope content. The 146 isotope content can be measured and quantified by standard methods, such as ASTM D 6866 or DIN 51637. Typically, in a component or composition derived completely from renewable sources the measured 146 content of the total carbon content is 100% (i measurement accuracy). The carbon isotope profile can thus be used to determine the nature and origin for example to distinguish between renewable and fossil products. Renewable products have inherently for example a lower carbon footprint and are a technically advantageous alternative for fossil products. The nature and origin of feedstocks and products manufactured in the present processes can thus be confirmed and distinguished by carbon isotope analysis. Thus, a product manufactured with the present process from renewable feedstock has a 146 content which corresponds to the portion of renewable feedstock in the product. When a fully renewable feedstock is used as a feedstock, the resulting reaction product has a 146 content of about 100%. ln an embodiment the obtained organic liquefaction product is further upgraded. Preferably the organic liquefaction product is upgraded by hydrogenating to at least partially remove heteroatoms and to at least partially saturate aromatics. ln an embodiment the pressure is controlled by feeding hydrogen gas into the hydroprocessing reactor. ln an embodiment the hydroprocessing is carried out in one single reactor. Advantageously the present process provides a good yield and efficiently liquefies the biomass already in a one pass of the feedstock through the process. ln an embodiment the hydroprocessing is carried out in two or more reactors. When two or more reactors are used, they can be arranged in parallel or in a series. When using a configuration with two or more reactors in a series, in the first reactor it may be useful to operate at a lower temperature than in the later reactor or reactors. ln an embodiment, when two or more reactors are used in a series, the second reactor and/or the further reactor is operated at a higher temperature than the first reactor. ln another embodiment the temperature is substantially the same in the two or more reactors.
When two or more reactors are used in a series, a light product can be fractionated from the organic liquefaction product, and the remaining feed is fed to a subsequent reactor. ln an embodiment the light product obtained after the first reactor comprises compounds having a boiling point <150°C.
When a light product is separated from the organic liquefaction product obtained in the first reactor, the remaining feed which is fed to a subsequent reactor contains less light product. Cracking of components in the light product can also be avoided as they are removed before entering the second reactor, which is optionally operated at a highertemperature, which increases yield of the organic liquefaction product. Further, there is a less mass transferred to the second reactor which causes less heating in case the feed is heated, thereby increasing energy efficiency. An additional advantage is that as there is less mass transferred to the second reactor, the relative catalyst loading is increased in the second reactor and the optional subsequent reactors.
The organic liquefaction product obtained with the present process contains more middle distillate than what can be achieved with previous methods.
The organic liquefaction product obtained may be liquid from room temperature, and up to 500°C. The organic liquefaction product may comprise one or more organic liquid phases. ln an embodiment at least 10 wt-%, preferably at least 12 wt-%, more preferably at least 13 wt-%, of the organic liquefaction product has a boiling point above 180°C. ln an embodiment at least 60 wt-%, preferably at least 65 wt-%, more preferably at least 70 wt-%, of the organic Iiquefaction product has a boiling point in the range 180-360°C. ln an embodiment at least 90 wt-%, preferably at least 95 wt-%, more preferably at least 97 wt-%, of the organic Iiquefaction product has a boiling point below 500°C.
EXAMPLES The following examples are provided to better illustrate the claimed invention. They are not to be interpreted as limiting the scope of the invention, which is determined by the claims. To the extent that specific materials are mentioned, it is merely for purposes of illustration and is not intended to limit the invention. One skilled in the art may develop equivalent means or reactants without exercising inventive capacity and without departing from the scope of the invention. lt shall be understood that many variations can be made in the procedures described herein while remaining within the scope of the present invention. Analytical methods Determination of hydroxyl numbers analyzing amounts of hydroxyl groups belonging to aliphatic alcohols (aliphatic OH), phenols (aromatic OH) and OH-groups of carboxylic acids, was performed by "P-NMR on a Bruker Avance 500 UltraShield NMR spectrometer using methodology described for instance in L. Akim et al. Holzforschung 2001, 55, 386-390. 1H-NMR was used to characterize relative amounts of protons being part of aromatic, aliphatic, ether/alcohol, aldehyde, ketone, carboxylic acid and olefin functionalities of the obtained product mixtures.
Boiling point ranges were determined using thermogravimetric analysis on a Mettler- Toledo TGA/SDTA851 e instrument.
Example 1. Preparation of active molybdenum sulfide catalyst.
Molybdenum 2-ethylhexanoate (15.01 g, assay 15% Mo w/w), was mixed with dodecane (100 mL) and dimethyl disulfide (DMDS, 11 mL) in a 300 mL pressure stainless steel reactor. An inert nitrogen atmosphere was established using three vacuum - nitrogen cycles (nitrogen at 3 bars) before the autoclave was pressurized with hydrogen to 120 bar at room temperature. The mixture was then agitated during 11 heating to 300 °C and then kept at this temperature for 4 h. After cooling, part of the liquid was removed by vacuum distillation on a rotary evaporator. The molybdenum sulfide catalyst slurry had a dry weight assay of 19.3% w/w.
Example 2. Lignocellulose Iiquefaction experiments 1 and 2 Sawdust (<0.28 mm particle size) was mixed with the catalyst slurry prepared as described in Example 1 in a 300 ml autoclave. The starting materials for the experiments are shown in Table 1.
Table 1. Reactor feed Experiment1 Experiment2 sawdust g 26.09 30.00 Moisture wt% 8.50 % 8.50 % content of I I sawdust i iii5¿¿;¿¿¿5¿ iiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiii i iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiii i The autoclave was inerted with Ng and pressurized to 120 bar with H2 and heated to 320°C in experiment 1 and to 380°C in experiment 2. The reaction time at the reaction temperature was 4 h in experiment 1 and 2 h in experiment 2. After the reactor had cooled to room temperature it was depressurised and the liquid products were collected from the reactor. After the main liquid product was collected, the reactor was rinsed with pentane and the liquid obtained by pentane wash was included in the liquid product amount. The solids including the catalyst were separated from the liquid product by centrifugation. ln addition, to solids organic liquid and aqueous phase were separated. Finally, the reactor and solid residues were rinsed with tetrahydrofuran (THF, 2 x 40 mL) and the amount of THF-soluble phase was determined by evaporation of the THF. The solid residue was weighed after drying in a vacuum oven at 40°C overnight. 12 The amounts of reaction products and mass balance are shown in Table 2. The yields shown in table 2 include the dodecane that was part of the reaction mixture. ln both experiments, the aqueous phase formation is indicating remarkable hydrodeoxygenation activity of the catalyst.
Table 2. Products and mass balance Experiment 1 Experiment 2 2222222222222222222222222222222222222222222222222222222 iiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iååó llllllllllllllllllllllllllllllllllllllllllllll 3333:56 llllllllllllllllllllllll i Liquid g 32.3 41 9 llllllllllllllllllllllllllllllllllllllllllllllllllllllllllll dig iiiiiiiiiii iiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii à lllllllllllllllllllllllll i Aqueous phase (including g 7.3 i 5.0 the water from biomass å moisture) iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii g iiiiiiiiiii iiiiiiiiiiiiiiiiiiii 36335 iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii 36.225 iiiiiiiiiiiiiiiiiiiiiii i Mass balance f wt% 92 % 82 % §TTL¿¿¿LJ;T¿Q¿T|T¿ iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiii iiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiii U THF soluble yield wt% 23 % f 11 % Nuclear magnetic resonance spectroscopy (1H- and 31P-NMR-) data for the liquid products of experiments 1 and 2 are found below (Tables 3A, 3B and 3C, 3D, respectively) and thermogravimetric analysis (TGA-) data are shown in Figures 1 and 2, respectively. 1H- and "P-NMR-data for the THF-soluble phases are found below (Tables 4A, 4B and 4C, 4D, respectively) and TGA-data are shown in Figures 3 and 4. The NMR data indicate that the THF-soluble phases have a higher oxygen content. Additionally, it can be noted that most of the oxygen in the reaction products is in phenolic OH groups. TGA for THF soluble phase was made until 600 oC, at 600 oC the atmosphere was changed from nitrogen to air. The residual that was left 13 after the air treatment was considered to be inorganics.
Table 3A. 1H-NMR (CDClg) data for the liquid product of experiment 1 (normalized integrals). lH-NMR signals ppm lntegral Carboxylic acid H (COOH) and 12-9 0 aldehyde H (CHO) Aromatic H 9-6.2 0.5 Olefin H 6.2-4.5 0.1 Aliphatic alcohol H, -CHOH or 4.5-3.3 <0.1 aliphatic ether -CHOR Aliphatic H 3.3-0 99.4 Table 3B. Hydroxyl numbers measured by "P-NMR for the liquid product of experiment 1.
Aliphatic OH Aromatic OH Carboxylic acid (mmol/g) (mmol/g) 0.02 0.12 0.08 Table 3C. 1H-NMR (CDClg) data for the liquid product of experiment 2 (normalized integrals). lH-NMR signals ppm lntegral Carboxylic acid H (COOH) and 12-9 0 aldehyde H (CHO) Aromatic H 9-6.2 1.0 Olefin H 6.2-4.5 0.1 Aliphatic alcohol H, -CHOH or 4.5-3.3 <0.1 aliphatic ether -CHOR Aliphatic H 3.3-0 98.8 14 Table 3D. Hydroxyl numbers measured by slP-NMR for the liquid product of experiment 2.
Aliphatic OH Aromatic OH Carboxylic acid (mmol/g) (mmol/g) 0.01 0.25 0.04 Table 4A. lH-NMR (DMSO-d6) data for the THF-soluble phase of experiment 1 (normalized integrals). lH-NMR signals ppm lntegral Carboxylic acid H (COOH) and 12-9 1 .3 aldehyde H (CHO) and phenol (OH) Aromatic H 9-6.2 11.2 Olefin H 6.2-4.5 Not detected Aliphatic alcohol H, -CHOH or 4.5-3.3 10.0 aliphatic ether -CHOR Aliphatic H 3.3-0 77.5 Table 4B. Hydroxyl numbers measured by "P-NMR for the THF-soluble phase of experiment 1.
Aliphatic OH Aromatic OH Carboxylic acid (mmol/g) (mmol/g) 0.03 2.47 0.32 Table 4C. lH-NMR (DMSO-d6) data for the THF-soluble phase of experiment 2 (normalized integrals). lH-NMR signals ppm lntegral Carboxylic acid H (COOH) and 12-9 1 .5 aldehyde H (CHO) and phenol (OH) Aromatic H 9-6.2 16.7 Olefin H 6.2-4.5 Not detected Aliphatic alcohol H, -CHOH or 4.5-3.3 4.6 aliphatic ether -CHOR Aliphatic H 3.3-0 77.2 Table 4D. Hydroxyl numbers measured by "P-NMR for the THF-soluble phase of experiment 2.
Aliphatic OH Aromatic OH Carboxylic acid (mmol/g) (mmol/g) 0.04 2.56 0.12 ln the yields presented in table 5, it has been assumed that the dodecane was inert and the amount of dodecane loaded to the reactor has been subtracted from the liquid product amount. TGA data for the THF soluble phase shows that 65% of THF soluble phase of experiment 1 (Fig 3) and 71% of THF soluble phase of experiment 2 (Fig 4) is volatile below 500 oC. Thus, the organic liquefaction product yield on a dry biomass basis is for both experiments 38%. The solid yield includes the solids separated from the reaction product and the amount of inorganics in the THF phase as defined by TGA. The amount of solids was very low indicating that almost all biomass was converted and almost no char was formed. Table 6 presents the boiling point regions of the organic liquefaction product with dodecane included.
Table 5. Product yields on a dry biomass basis Experiment1 Experiment2 Temperature °C 320 380 åiLiggj¿yii¿i¿iiffggifiiigiiiyiißigagigi; iiiiiiiiiiiiiiiiiiiii iiii iiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiii iiiiiiiiiiiiiiiii ål % i šOrganic liquefaction producti wt% 38% 38% Éunciuding liquid and <5oo oc THFÉ soluble phase) 16 Solid yield from dry biomass basis wt% 2% 1% Table 6. Boiling point fractions of organic liquid product including dodecane Boiling point regions Experiment 1 Experiment 2 iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii ii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii Xi 360-500 °C 12 % i 9 % iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii i ginigåfigigiinii; iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii i The foregoing description has provided by way of non-limiting examples of particular implementations and embodiments a full and informative description of the best mode presently contemplated by the inventors for carrying out the invention. lt is however clear to a person skilled in the art that the invention is not restricted to details of the embodiments presented in the foregoing, but that it can be implemented in other embodiments using equivalent means or in different combinations of embodiments without deviating from the characteristics of the invenfion.
Claims (13)
1. A process for Iiquefying solid biomass comprising: a. providing in a reactor a feedstock comprising solid biomass; and b. hydroprocessing the feedstock at a temperature selected from the range 250-400°C in the presence of catalytic microparticles comprising MoS, wherein the molar ratio of S to Mo is 1-3, to provide an organic Iiquefaction product.
2. The process of claim 1, in which the feedstock comprises solid biomass dispersed in a carbonaceous carrier oil.
3. The process of claim 1 or 2, in which the carrier oil has a viscosity of 8 mPas or less at 100°C.
4. The process of any one of claims 1-3, in which the feedstock contains 5-90% solid biomass, preferably 10-85%, more preferably 10-35% or 60-85%, expressed as the wt-% of the solids of the biomass in the feedstock
5. The process of any one of claims 1-4, in which the water content of the biomass is not more than 50 wt-%, more preferably between 5 and 25 wt-%, most preferably between 8 and 20 wt-%.
6. The process of any one of claims 1-5, in which at least 90% of the number of the catalytic microparticles have a size below 7um, and wherein the size of a microparticle is expressed as an average of the longest dimension and the shortest dimension of the microparticle.
7. The process of any one of claims 1-6, in which the solid biomass comprises at least one cellulose containing material such as wood, logging residue, wood chips, sawdust, wood bark, wood saw dust, construction and demolition wood, paper, recycled paper, plant part, fruit, vegetable, plant processing waste, grain, grass, corn, corn husks, hay, bagasse, straw, bamboo, and agricultural waste, preferably wood saw dust and/or logging residue.
8. The process of any one of claims 1-7, in which the hydroprocessing is carried out at a temperature below 400°C, preferably at a temperature selected from the
9.range 250-400°C, more preferably 270-390°C; and at a pressure selected from therange 30-300 bar, preferably 70-170 bar, more preferably 80-150 bar.
10. The process of any one of claims 1-8, in which the molar ratio of hydrogen gas to feedstock oxygen is at least
11. The process of any one of claims 1-10, in which the hydroprocessing is carried out in two or more reactors in a series in which each subsequent reactor is operated at a higher temperature than the first reactor, preferably such that the temperature of the first reactor is selected from the range 270-350°C, the temperature of the second reactor is selected from the range 340-400°C, and the temperature of the third reactor is selected from the range 380-400°C.
12. The process of claim 11 further comprising fractionating a light product having a boiling point below 360°C from the organic liquefaction product of the first reactor, and feeding the remaining feed to at least one subsequent reactor.
13. An organic liquefaction product produced by the process of any one of claims 1-11 and having a lower oxygen content than the solid biomass.
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A. Burton, et al. "Catalytic Hydroliquefaction of Lignocellulosic Biomass" In: Int. J. Solar Energy, 1986, Vol. 4, No. 2, pp. 67-80. * |
M. Grilc, et al. "Hydrodeoxygenation of solvolysed lignocellulosic biomass by unsupported MoS2, MoO2, Mo2C and WS2 catalysts", 2015, vol 163, pp 467-477, DOI: 10.1016/j.apcatb.2014.08.032 * |
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