EP2199366A1 - Verfahren zur Umwandlung von Biomasse in Bio-Öl mit anorganischen Kohlenstoffen und Zerlegung und Regeneration von anorganischen Kohlenstoffen - Google Patents
Verfahren zur Umwandlung von Biomasse in Bio-Öl mit anorganischen Kohlenstoffen und Zerlegung und Regeneration von anorganischen Kohlenstoffen Download PDFInfo
- Publication number
- EP2199366A1 EP2199366A1 EP08171260A EP08171260A EP2199366A1 EP 2199366 A1 EP2199366 A1 EP 2199366A1 EP 08171260 A EP08171260 A EP 08171260A EP 08171260 A EP08171260 A EP 08171260A EP 2199366 A1 EP2199366 A1 EP 2199366A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbonate
- biomass
- inorganic
- solid
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 229910052806 inorganic carbonate Inorganic materials 0.000 title claims abstract description 25
- 239000012075 bio-oil Substances 0.000 title claims abstract description 14
- 230000008929 regeneration Effects 0.000 title description 8
- 238000011069 regeneration method Methods 0.000 title description 8
- 238000000354 decomposition reaction Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002956 ash Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000005677 organic carbonates Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
-
- 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
Definitions
- the invention relates generally to the use of inorganic carbonates in the conversion of biomass, and more specifically to the decomposition and regeneration of such inorganic carbonates.
- Inorganic carbonates in particular sodium carbonate and potassium carbonate, have been proposed as catalysts for the conversion of biomass. It is also known that carbonates, in particular potassium carbonate, are formed as a byproduct of the conversion of certain types of biomass.
- carbonates in particular potassium carbonate
- the role of inorganic carbonates in biomass conversion has been poorly understood, which has led to on the one hand a sub-optimal use of these carbonates and, on the other hand, to an undesirable accumulation of carbonates in biomass conversion reactors due to the formation of carbonates as a byproduct.
- the present invention addresses these problems by providing a process for the catalytic conversion of solid biomass material, said process comprising the steps of:
- Another aspect of the invention comprises a method for recovering heat from char and coke that are formed during the biomass conversion.
- the step of regenerating the hydroxide to the corresponding carbonate is combined with the step of recovering heat from char and coke.
- the present invention is based on the discovery that inorganic carbonates decompose to the corresponding metal oxide and carbon dioxide under conditions that are suitable for their catalytic conversion of biomass material to a bio-oil.
- the temperature in step (i) is generally in the range of from 200°C to 500°C, more preferably in the range of from 350°C to 450°C. These temperatures are normally not considered high enough to cause the decomposition of inorganic carbonates. However, due to interactions that exist between the carbonate and the biomass material, at least partial decomposition of the organic carbonates occurs at these temperatures.
- bio-oil that is formed in the conversion of biomass is highly acidic, due to the presence of organic acids such as carboxylic acids.
- bio-oils produced in these reactions have a pH of less than 3. This is low enough to convert an inorganic carbonate to the corresponding hydrogen carbonate, or bicarbonate.
- the bicarbonates are thermally considerably less stable than the carbonates from which they derive.
- the reaction is self catalyzed.
- the formation of a small amount of a bio-oil lowers the pH, thereby accelerating the decomposition of the carbonate.
- the metal hydroxide resulting from the decomposition of the carbonate access a sink for the acidic bio-oil compounds that are formed. The presence of the metal hydroxide thereby facilitates the formation of the acidic bio-oil.
- regeneration of the hydroxide to the carbonate may take place in situ , as sufficient CO 2 may be formed in the biomass conversion to react at least some of the hydroxide back to the corresponding carbonate. This may be a reason why the need for regeneration is not generally recognized by those active in this field.
- biomass material from most sources contains considerable amounts of inorganic materials, which form a solid byproduct generally referred to as "ash".
- ash a solid byproduct
- at least part of the ash will be in the form of inorganic carbonates.
- the process of the present invention addresses the former issue by providing a regeneration step in which hydroxide is converted to the corresponding carbonate.
- the process of the invention addresses the latter issue by recovering carbonates present in the ash by-product and recycling them back into the process to the extent required.
- the process of the invention is suitable for conversion of any type of solid biomass material to form a bio-oil.
- the process is particularly suitable for the conversion of biomass comprising cellulose.
- the biomass feedstock used in the process may further comprise lignin.
- An important aspect of the process of invention is the formation of bio-oil.
- part of the biomass is converted to non-condensable gases.
- the solid residue may contain any unconverted solid biomass material.
- the solid residue further comprises solid reaction products of the biomass conversion reaction, in general coke and char.
- the inorganic materials present in the biomass feedstock to some extent end up in the gas phase in the form of fly ash; for the most part, however, the ash is present in the solid residue, generally embedded in the char.
- any inorganic carbonate that was added to the reaction mixture will also find its way to the solid residue of the biomass conversion reaction.
- at least some of the inorganic carbonate may be present in the solid residue in the form of the hydroxide.
- a suitable example of an oxygen containing gas is air.
- Heat generated by burning the char and/or coke can be used to supply heat to the biomass conversion step.
- Significant amounts of CO 2 are formed during the burning of the char and coke.
- Any metal hydroxide or metal oxide present in the solid residue is converted to the corresponding carbonate during this regeneration step.
- a suitable regeneration temperature is in the range of from 550°C to 800°C, typically around 650°C.
- Regenerated carbonate is recycled back into step (i).
- the carbonate particles may be used to carry heat from the regeneration reaction to the biomass conversion step.
- any inorganic carbonate is suitable for use as a catalyst in step (i) of the process.
- Particularly suitable are the carbonates of the monovalent and divalent metals.
- the monovalent alkali metals are particularly preferred, especially sodium and potassium.
- the ash formed in the solid residue of the biomass conversion reaction may comprise the oxide, the hydroxide or the carbonate of alkali metals and earth alkaline metals.
- the ash can be converted to the carbonate ash in step (ii), and the carbonate ash can be recycled to step (i).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Processing Of Solid Wastes (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08171260A EP2199366A1 (de) | 2008-12-10 | 2008-12-10 | Verfahren zur Umwandlung von Biomasse in Bio-Öl mit anorganischen Kohlenstoffen und Zerlegung und Regeneration von anorganischen Kohlenstoffen |
| PCT/US2009/067543 WO2010068784A1 (en) | 2008-12-10 | 2009-12-10 | Decomposition and regeneration of inorganic carbonates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08171260A EP2199366A1 (de) | 2008-12-10 | 2008-12-10 | Verfahren zur Umwandlung von Biomasse in Bio-Öl mit anorganischen Kohlenstoffen und Zerlegung und Regeneration von anorganischen Kohlenstoffen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2199366A1 true EP2199366A1 (de) | 2010-06-23 |
Family
ID=40612894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08171260A Withdrawn EP2199366A1 (de) | 2008-12-10 | 2008-12-10 | Verfahren zur Umwandlung von Biomasse in Bio-Öl mit anorganischen Kohlenstoffen und Zerlegung und Regeneration von anorganischen Kohlenstoffen |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP2199366A1 (de) |
| WO (1) | WO2010068784A1 (de) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2581130A (en) * | 1947-09-10 | 1952-01-01 | Standard Oil Dev Co | Process for converting carbohydrates into bituminous substances |
| US3553279A (en) * | 1968-03-29 | 1971-01-05 | Texas Instruments Inc | Method of producing ethylene |
| US4266083A (en) * | 1979-06-08 | 1981-05-05 | The Rust Engineering Company | Biomass liquefaction process |
| US4421631A (en) * | 1981-10-02 | 1983-12-20 | Rockwell International Corporation | Hydrocarbon treatment process |
| EP0121343A1 (de) * | 1983-03-03 | 1984-10-10 | Pentanyl Technologies, Inc. | Integriertes ionisches Verflüssigungsverfahren |
| WO2008098358A1 (en) * | 2007-02-18 | 2008-08-21 | David Rendina | Liquid fuel feedstock production process |
| EP1970425A1 (de) * | 2007-02-20 | 2008-09-17 | BIOeCON International Holding N.V. | Verbessertes Verfahren zum Umwandeln von Energieträgermaterial auf Kohlenstoffbasis |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101481049B1 (ko) * | 2005-04-29 | 2015-01-21 | 알타카 인사트 베 디스 티카레트 에이.에스. | 유기 물질 전환 방법 및 장치 |
| CA2555135C (en) * | 2005-08-02 | 2012-04-03 | Alberta Research Council Inc. | Method of treatment of wood ash residue |
-
2008
- 2008-12-10 EP EP08171260A patent/EP2199366A1/de not_active Withdrawn
-
2009
- 2009-12-10 WO PCT/US2009/067543 patent/WO2010068784A1/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2581130A (en) * | 1947-09-10 | 1952-01-01 | Standard Oil Dev Co | Process for converting carbohydrates into bituminous substances |
| US3553279A (en) * | 1968-03-29 | 1971-01-05 | Texas Instruments Inc | Method of producing ethylene |
| US4266083A (en) * | 1979-06-08 | 1981-05-05 | The Rust Engineering Company | Biomass liquefaction process |
| US4421631A (en) * | 1981-10-02 | 1983-12-20 | Rockwell International Corporation | Hydrocarbon treatment process |
| EP0121343A1 (de) * | 1983-03-03 | 1984-10-10 | Pentanyl Technologies, Inc. | Integriertes ionisches Verflüssigungsverfahren |
| WO2008098358A1 (en) * | 2007-02-18 | 2008-08-21 | David Rendina | Liquid fuel feedstock production process |
| EP1970425A1 (de) * | 2007-02-20 | 2008-09-17 | BIOeCON International Holding N.V. | Verbessertes Verfahren zum Umwandeln von Energieträgermaterial auf Kohlenstoffbasis |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010068784A1 (en) | 2010-06-17 |
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| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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Extension state: AL BA MK RS |
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| AKY | No designation fees paid | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
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| 18D | Application deemed to be withdrawn |
Effective date: 20101224 |