CA2199435C - Method of producing hydrogen from biomass - Google Patents
Method of producing hydrogen from biomass Download PDFInfo
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- CA2199435C CA2199435C CA002199435A CA2199435A CA2199435C CA 2199435 C CA2199435 C CA 2199435C CA 002199435 A CA002199435 A CA 002199435A CA 2199435 A CA2199435 A CA 2199435A CA 2199435 C CA2199435 C CA 2199435C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical Kinetics & Catalysis (AREA)
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- Combustion & Propulsion (AREA)
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Abstract
A method of producing hydrogen from a cellulose-containing biomass is disclosed, which includes the steps of:
(a) forming a liquid phase containing the biomass, water and a catalyst in a reaction chamber such that an upper space is defined above the liquid phase in the chamber;
(b) heating the liquid phase at a temperature of 250-374°C while maintaining the upper space at a pressure higher than the saturated vapor pressure of water, so that hydrogen is formed and collected in the upper space; and (c) discharging part of the collected hydrogen during step (b).
(a) forming a liquid phase containing the biomass, water and a catalyst in a reaction chamber such that an upper space is defined above the liquid phase in the chamber;
(b) heating the liquid phase at a temperature of 250-374°C while maintaining the upper space at a pressure higher than the saturated vapor pressure of water, so that hydrogen is formed and collected in the upper space; and (c) discharging part of the collected hydrogen during step (b).
Description
This invention relates to a method of producing hydrogen from a cellulose-containing biomass.
One known method for the production of hydrogen from wood chips includes subjecting the wood chips to water gas shift reactions in which the wood chips are converted into hydrogen and carbon monoxide and the carbon monoxide in turn is converted into hydrogen and carbon dioxide. Since the above reactions should be performed at a high temperature of about 1,000°C, it is a general practice to burn part of the wood chips to supply the heat for the reactions. Thus, the Efficiency of the above method is not satisfactory. Further, the above method is not applicable to a wet cellulose-containing biomass.
The present invention has be<=_n made in view of the above problems. In accordance wii~h one aspect of the present invention there is provided a method of producing hydrogen from a cellulose-containing biomass, comprising a method of producing hydrogen from a cellulose-containing biomass, comprising forming a liquid phase containing the biomass, water and a catalyst in a reaction chamber such that an upper space is defined above the liquid phase in the chamber, feeding an inert gas to said reaction chamber to maintain the upper space at a pressure higher than the saturated vapour pressure of water, heating the liquid phase at a temperature of 250-374°~~ while maintaining the upper space at a pressure higher than the saturated vapour pressure of water, so that hydrogen is formed and collected in the upper space, and discharging part of the collected hydrogen during heating.
In another aspect, the present invention provides a method of producing hydrogen from a cellulose-containing biomass, comprising a method of p-~oducing hydrogen from a cellulose containing biomass, comprising forming a liquid phase containing the biomass, water and a cat=aly~;t in a first chamber of a reaction zone having a gas-:Liquid separating membrane disposed to partition the reaction zone into t:he first chamber and a second chamber, heating the liquid phase i~o a temperature of 250-374°C, feeding a pressurized inert gas to the second chamber to maintain the first chamber at a pressure higher than the saturated vapour pressure of water during 1_he heating, so that the biomass is decomposed to produce hydrogen which passes through the membrane to the second chamber, and, during the feeding of the pressurized inert gas, discharging part of the hydrogen from the second chamber together with inert gas.
The present invention will be described in detail below with reference to the accompanying drawings, in which:
Fig. 1 is a schematic illustration of one embodiment of an apparatus useful for carrying oui; the method of the present invention;
Fig. 2 is a vertical cross-sectional view diagrammatically showing an embodiment of a :reactor for the apparatus of Fig. 1;
Fig. 3 is a sectional view diagrammatically showing a tubular reactor useful for carrying out the method of the present invention;
Fig. 4 is a sectional view taken on line IV-IV in Fig. 3;
and Fig. 5 is a schematic illustr<~tion of another embodiment of an apparatus useful for carrying out the method of the present invention.
In accordance with one embodiment of the present invention, cellulose-containing biomass is heat-treated in the presence of water and a metal catalyst at a temperature of 250-374°C and a pressure higher than the saturated vapor pressure of water.
The term "cellulose-cc>ntainin<~ biomass" used in the present specification is intended to refer to various kinds of materials containing cellulose. Examples of the cellulose-containing biomass include wood, wood chips, wood powder, bark, baggasse, bamboo, wastes of agricult:ura.L products, paper, peat, sewage, soil, city wastes and other cellulose-containing waste materials.
The metal catalyst may be Fe, Ni, Co, Mo, W, Pt and Cu.
These metals may be used as various forms such as 2~~9~35 elemental metals, oxides and sulfides. A supported catalyst containing a porous carrier and the above catalytic metal supported thereon may also be suitably used. Illustrative of suitable carriers are silica, alumina, silica-alumina, zirconia, titania, zeolite, sepiolite, kieselguhr (diatomacous earth) and clay. If desired, a co-catalyst such as a hydroxide, a carbonate or a formate of an alkali metal or an alkaline earth metal, e.g: sodium,, potassium, lithium or magnesium, may be used in conjunction with the above metal catalyst. The metal catalyst is generally used in an amount of 0.01-10 parts by weight, preferably 0.1-1 part by weight, per part by weight of the cellulose-containing biomass on the dry basis.
Water is generally present in an amount of 2-100 parts by weight, preferably 4-10 parts by weight, per part by weight of the cellulose-containing biomass on the dry basis.
The heat treatment is performed at a temperature of 250-374°C, preferably 300-370°C, at a pressure higher than the saturated water vapor pressure at the heat treatment temperature. The treatment time is generally 5-18O minutes:
If desired, an inert gas such as nitrogen, argon or helium may be used to maintain the desired treatment pressure. An organic solvent such as an alcohol, a ketone or a phenol compound may be present in the reaction system Referring now to Fig. 1, designated as 1 is a reaction vessel having a lower part in which a metal catalyst is packed. R feed containing biomass, water and, optionally, a co-catalyst is fed to the reaction vessel 1 by a pump 2 to form a liquid phase 3 within the reaction vessel l so that a space 4 is defined above the liquid phase 3 and the packed metal catalyst is immersed in the liquid phase 3. The reaction vessel 1 is surrounded by a jacket 5 to which a heating medium is fed to heat the liquid phase 3 by indirect heat exchange therewith. A pressurized inert gas is fed through a valve 6 to the upper space 4 to maintain the pressure in the space 4 higher than the saturated vapor pressure of water.
_ 4 _ ~'~9~4~3a The biomass in the liquid phase 3 is decomposed to form hydrogen which is collected in the upper space 4. The hydrogen in the upper space. is continuously or intermittently discharged for recovery through a valve 7 to maintain the hydrogen partial pressure below a predetermined level. By this expedient, the yield of methane by-product is minimized.
The pressure in the upper space 4 is monitored by a sensor 9 having an output coupled with the valve 6, so that the inert gas is fed to the upper space 4 to maintain the upper space 4 at a pressure higher than a predetermined level. The liquid phase 3 after the completion of the reaction is discharged through a valve 8.
In Fig. 2, component parts similar to those in Fig.
1 are designated by the same reference numerals. Designated as 1 is a reaction vessel surrounded by a heating jacket 5.
A packed bed of a metal catalyst is disposed in the reaction vessel 1. In the embodiment shown in Fig. 2, the reaction vessel 1 is vertically elongated to ensure a long residence time of the biomass feed in the reaction vessel 1. However, whilst a long residence time is desirable from the standpoint of improved gasification rate, the yield of hydrogen has been found to decrease as the residence time increases.
To cope with this problem, an inert gas is fed from the bottom of the reaction vessel 1 so as to maintain an upper space 4 above a liquid phase 3 at a pressure higher than a predetermined level and to sweep hydrogen formed in the liquid phase 3. Further, a plurality of funnel-like gas flow control members 11-l3 having riser tubes 14-16 are disposed to minimize the contact of the hydrogen formed in the liquid phase 3 with the catalyst. Thus, the hydrogen produced is swept by the inert gas and collected in the flow control members 11-13. The collected hydrogen successively ascends through the riser pipes 14-16 and is passed to the upper space 4 with minimum contact with the catalyst bed. As a consequence, a high yield of hydrogen is attained while ensuring a high rate of gasification.
Referring to Figs. 3 and 4, designated as 21 is a tubular reactor surrounded by a jacket 25. A tubular gas-liquid separating membrane 22 defining therewithin a second chamber 23 is disposed in the reactor 21 to define an annular first chamber 24 between them. A metal catalyst is packed in the first chamber 24. A raw material feed containing biomass, water and, optionally, a co-catalyst is fed to the first chamber 24 and is contacted with the metal catalyst. A heating medium is fed to the jacket 25 to heat the liquid phase 3 by indirect heat exchange therewith.
A pressurized inert gas is fed to the second chamber 23 to maintain the pressure within the first chamber 24 higher than the saturated vapor pressure of water. The biomass in the first chamber 24 is decomposed to form hydrogen which is diffused through the membrane 22 into the second chamber 23. The hydrogen in the second chamber 23 is discharged continuously or intermittently from the reactor together with the inert gas.
The membrane 22 permits the passage of a gas therethrough but prevents the passage of a liquid therethrough. A membrane formed of a metal or a ceramic is suitably used.
Since the above method uses a lower temperature than that in the conventional method, solar energy can be utilized to carry out the method according to the present invention. Fig. 5 depicts a system flow chart for the production of hydrogen from biomass using solar energy.
Designated as 30 is a reactor which may be similar to that shown in Figs. 1-4. The reactor 30, in which a packed bed of a catalyst is disposed, is surrounded by a heating jacket 31 through which a heating medium is recirculated. The heating medium is heated in a solar concentrator 32 and is fed to a heat storage device 33 through a line 42. The medium in the device 33 is introduced through a line 43 to the jacket 31 to heat the reactor 30 at 250-374°C by indirect heat exchange therewith. The heating medium is discharged through a line 41 and recycled to the solar concentrator 32.
Biomass and make-up water are fed to a preparation tank 35 to which a liquid recovered in a solid-liquid separator 3 is also fed through a line 49. The mixture is then introduced into heat exchangers 34a and 34b through a line 46 and is fed through line 45 to the reactor 30.
An inert gas is also fed to the reactor 30 to maintain the mixture fed through the line 45 so that the decomposition of the biomass resulting in the formation of hydrogen is performed at a pressure higher than the saturated vapor pressure of water. The inert gas and the product gas including hydrogen are discharged from the reactor through a line 44a, introduced into the heat exchanger 34a to heat the biomass feed, and then fed to a gas separator 38 where hydrogen is isolated for recovery. The liquid phase in the reactor 30 is introduced through a line 44b to the heat exchanger 34b to heat the biomass feed and is then fed to a solid-liquid separator 36, where it is separated into a solid residue and the liquid which is recovered and recycled to the preparation tank 35 as described previously.
The following examples will further illustrate the present invention.
Example 1 A commercially available nickel catalyst (NI-3288 (trade name) manufactured by Engelhard Inc.) was used as the metal catalyst. Prior to use, the nickel catalyst was ground to 60-100 mesh (Tyler) and reduced with hydrogen gas. A
mixture of 5 g of cellulose (fine crystals, product of E.
Merck Inc.), 30 g of water, 2 g of the nickel catalyst and 0.5 g of sodium carbonate was charged in a reactor (inside volume: 100 ml). The reactor was heated at 300°C. The product gas was discharged at a rate of 2 liters per minute.
To maintain inside of the reactor at a pressure higher than the saturated vapor pressure of water at 300°C, pressurized nitrogen gas was fed to the reactor. The product gas was cooled and measured for the amount thereof with a gas meter _7_ ~~99435 and for the composition thereof with gas chromatography. The yields of hydrogen, carbon dioxide and methane are shown in Table 1. The production of carbon monoxide and hydrocarbons having 2 or more carbon atoms was only trace. The gasification rate was 83 ~ based on carbon.
Comparative Example 1 In the same manner as that in Example 1, a mixture of 5 g of cellulose (fine crystals, product of E. Merck Inc.), 30 g of water, 2 g of the nickel catalyst and 0.5 g of sodium carbonate was charged in a reactor (inside volume: 100 ml). The reactor was pressurized with nitrogen gas to 3 MPa so that the reaction pressure was the same as that in Example 1. The reactor was heated to 300°C and maintained at that temperature for 30 minutes. Then, the reactor was cooled to room temperature. The product gas was measured for the amount thereof with a gas meter and for the composition thereof with gas chromatography. The yields of hydrogen, carbon dioxide and methane are shown in Table 1. The production of carbon monoxide and hydrocarbons having 2 or more carbon atoms was only trace. The gasification rate was g0 ~ based on carbon.
Table 1 Yield of Gas (mmol) Example 1 79.0 101.4 33.9 Comparative Example 1 16.2 74.8 52.8 As will be appreciated from the results shown above, when the biomass decomposition is carried out without removing produced HZ from the reaction zone, the yield of H2 is 16.2 mmol under the conditions where the gasification rate is 80 $. In contrast, in the method according to the present invention, the yield of Hz is 79.0 mmol under the conditions providing a gasification rate of 83 ~.
One known method for the production of hydrogen from wood chips includes subjecting the wood chips to water gas shift reactions in which the wood chips are converted into hydrogen and carbon monoxide and the carbon monoxide in turn is converted into hydrogen and carbon dioxide. Since the above reactions should be performed at a high temperature of about 1,000°C, it is a general practice to burn part of the wood chips to supply the heat for the reactions. Thus, the Efficiency of the above method is not satisfactory. Further, the above method is not applicable to a wet cellulose-containing biomass.
The present invention has be<=_n made in view of the above problems. In accordance wii~h one aspect of the present invention there is provided a method of producing hydrogen from a cellulose-containing biomass, comprising a method of producing hydrogen from a cellulose-containing biomass, comprising forming a liquid phase containing the biomass, water and a catalyst in a reaction chamber such that an upper space is defined above the liquid phase in the chamber, feeding an inert gas to said reaction chamber to maintain the upper space at a pressure higher than the saturated vapour pressure of water, heating the liquid phase at a temperature of 250-374°~~ while maintaining the upper space at a pressure higher than the saturated vapour pressure of water, so that hydrogen is formed and collected in the upper space, and discharging part of the collected hydrogen during heating.
In another aspect, the present invention provides a method of producing hydrogen from a cellulose-containing biomass, comprising a method of p-~oducing hydrogen from a cellulose containing biomass, comprising forming a liquid phase containing the biomass, water and a cat=aly~;t in a first chamber of a reaction zone having a gas-:Liquid separating membrane disposed to partition the reaction zone into t:he first chamber and a second chamber, heating the liquid phase i~o a temperature of 250-374°C, feeding a pressurized inert gas to the second chamber to maintain the first chamber at a pressure higher than the saturated vapour pressure of water during 1_he heating, so that the biomass is decomposed to produce hydrogen which passes through the membrane to the second chamber, and, during the feeding of the pressurized inert gas, discharging part of the hydrogen from the second chamber together with inert gas.
The present invention will be described in detail below with reference to the accompanying drawings, in which:
Fig. 1 is a schematic illustration of one embodiment of an apparatus useful for carrying oui; the method of the present invention;
Fig. 2 is a vertical cross-sectional view diagrammatically showing an embodiment of a :reactor for the apparatus of Fig. 1;
Fig. 3 is a sectional view diagrammatically showing a tubular reactor useful for carrying out the method of the present invention;
Fig. 4 is a sectional view taken on line IV-IV in Fig. 3;
and Fig. 5 is a schematic illustr<~tion of another embodiment of an apparatus useful for carrying out the method of the present invention.
In accordance with one embodiment of the present invention, cellulose-containing biomass is heat-treated in the presence of water and a metal catalyst at a temperature of 250-374°C and a pressure higher than the saturated vapor pressure of water.
The term "cellulose-cc>ntainin<~ biomass" used in the present specification is intended to refer to various kinds of materials containing cellulose. Examples of the cellulose-containing biomass include wood, wood chips, wood powder, bark, baggasse, bamboo, wastes of agricult:ura.L products, paper, peat, sewage, soil, city wastes and other cellulose-containing waste materials.
The metal catalyst may be Fe, Ni, Co, Mo, W, Pt and Cu.
These metals may be used as various forms such as 2~~9~35 elemental metals, oxides and sulfides. A supported catalyst containing a porous carrier and the above catalytic metal supported thereon may also be suitably used. Illustrative of suitable carriers are silica, alumina, silica-alumina, zirconia, titania, zeolite, sepiolite, kieselguhr (diatomacous earth) and clay. If desired, a co-catalyst such as a hydroxide, a carbonate or a formate of an alkali metal or an alkaline earth metal, e.g: sodium,, potassium, lithium or magnesium, may be used in conjunction with the above metal catalyst. The metal catalyst is generally used in an amount of 0.01-10 parts by weight, preferably 0.1-1 part by weight, per part by weight of the cellulose-containing biomass on the dry basis.
Water is generally present in an amount of 2-100 parts by weight, preferably 4-10 parts by weight, per part by weight of the cellulose-containing biomass on the dry basis.
The heat treatment is performed at a temperature of 250-374°C, preferably 300-370°C, at a pressure higher than the saturated water vapor pressure at the heat treatment temperature. The treatment time is generally 5-18O minutes:
If desired, an inert gas such as nitrogen, argon or helium may be used to maintain the desired treatment pressure. An organic solvent such as an alcohol, a ketone or a phenol compound may be present in the reaction system Referring now to Fig. 1, designated as 1 is a reaction vessel having a lower part in which a metal catalyst is packed. R feed containing biomass, water and, optionally, a co-catalyst is fed to the reaction vessel 1 by a pump 2 to form a liquid phase 3 within the reaction vessel l so that a space 4 is defined above the liquid phase 3 and the packed metal catalyst is immersed in the liquid phase 3. The reaction vessel 1 is surrounded by a jacket 5 to which a heating medium is fed to heat the liquid phase 3 by indirect heat exchange therewith. A pressurized inert gas is fed through a valve 6 to the upper space 4 to maintain the pressure in the space 4 higher than the saturated vapor pressure of water.
_ 4 _ ~'~9~4~3a The biomass in the liquid phase 3 is decomposed to form hydrogen which is collected in the upper space 4. The hydrogen in the upper space. is continuously or intermittently discharged for recovery through a valve 7 to maintain the hydrogen partial pressure below a predetermined level. By this expedient, the yield of methane by-product is minimized.
The pressure in the upper space 4 is monitored by a sensor 9 having an output coupled with the valve 6, so that the inert gas is fed to the upper space 4 to maintain the upper space 4 at a pressure higher than a predetermined level. The liquid phase 3 after the completion of the reaction is discharged through a valve 8.
In Fig. 2, component parts similar to those in Fig.
1 are designated by the same reference numerals. Designated as 1 is a reaction vessel surrounded by a heating jacket 5.
A packed bed of a metal catalyst is disposed in the reaction vessel 1. In the embodiment shown in Fig. 2, the reaction vessel 1 is vertically elongated to ensure a long residence time of the biomass feed in the reaction vessel 1. However, whilst a long residence time is desirable from the standpoint of improved gasification rate, the yield of hydrogen has been found to decrease as the residence time increases.
To cope with this problem, an inert gas is fed from the bottom of the reaction vessel 1 so as to maintain an upper space 4 above a liquid phase 3 at a pressure higher than a predetermined level and to sweep hydrogen formed in the liquid phase 3. Further, a plurality of funnel-like gas flow control members 11-l3 having riser tubes 14-16 are disposed to minimize the contact of the hydrogen formed in the liquid phase 3 with the catalyst. Thus, the hydrogen produced is swept by the inert gas and collected in the flow control members 11-13. The collected hydrogen successively ascends through the riser pipes 14-16 and is passed to the upper space 4 with minimum contact with the catalyst bed. As a consequence, a high yield of hydrogen is attained while ensuring a high rate of gasification.
Referring to Figs. 3 and 4, designated as 21 is a tubular reactor surrounded by a jacket 25. A tubular gas-liquid separating membrane 22 defining therewithin a second chamber 23 is disposed in the reactor 21 to define an annular first chamber 24 between them. A metal catalyst is packed in the first chamber 24. A raw material feed containing biomass, water and, optionally, a co-catalyst is fed to the first chamber 24 and is contacted with the metal catalyst. A heating medium is fed to the jacket 25 to heat the liquid phase 3 by indirect heat exchange therewith.
A pressurized inert gas is fed to the second chamber 23 to maintain the pressure within the first chamber 24 higher than the saturated vapor pressure of water. The biomass in the first chamber 24 is decomposed to form hydrogen which is diffused through the membrane 22 into the second chamber 23. The hydrogen in the second chamber 23 is discharged continuously or intermittently from the reactor together with the inert gas.
The membrane 22 permits the passage of a gas therethrough but prevents the passage of a liquid therethrough. A membrane formed of a metal or a ceramic is suitably used.
Since the above method uses a lower temperature than that in the conventional method, solar energy can be utilized to carry out the method according to the present invention. Fig. 5 depicts a system flow chart for the production of hydrogen from biomass using solar energy.
Designated as 30 is a reactor which may be similar to that shown in Figs. 1-4. The reactor 30, in which a packed bed of a catalyst is disposed, is surrounded by a heating jacket 31 through which a heating medium is recirculated. The heating medium is heated in a solar concentrator 32 and is fed to a heat storage device 33 through a line 42. The medium in the device 33 is introduced through a line 43 to the jacket 31 to heat the reactor 30 at 250-374°C by indirect heat exchange therewith. The heating medium is discharged through a line 41 and recycled to the solar concentrator 32.
Biomass and make-up water are fed to a preparation tank 35 to which a liquid recovered in a solid-liquid separator 3 is also fed through a line 49. The mixture is then introduced into heat exchangers 34a and 34b through a line 46 and is fed through line 45 to the reactor 30.
An inert gas is also fed to the reactor 30 to maintain the mixture fed through the line 45 so that the decomposition of the biomass resulting in the formation of hydrogen is performed at a pressure higher than the saturated vapor pressure of water. The inert gas and the product gas including hydrogen are discharged from the reactor through a line 44a, introduced into the heat exchanger 34a to heat the biomass feed, and then fed to a gas separator 38 where hydrogen is isolated for recovery. The liquid phase in the reactor 30 is introduced through a line 44b to the heat exchanger 34b to heat the biomass feed and is then fed to a solid-liquid separator 36, where it is separated into a solid residue and the liquid which is recovered and recycled to the preparation tank 35 as described previously.
The following examples will further illustrate the present invention.
Example 1 A commercially available nickel catalyst (NI-3288 (trade name) manufactured by Engelhard Inc.) was used as the metal catalyst. Prior to use, the nickel catalyst was ground to 60-100 mesh (Tyler) and reduced with hydrogen gas. A
mixture of 5 g of cellulose (fine crystals, product of E.
Merck Inc.), 30 g of water, 2 g of the nickel catalyst and 0.5 g of sodium carbonate was charged in a reactor (inside volume: 100 ml). The reactor was heated at 300°C. The product gas was discharged at a rate of 2 liters per minute.
To maintain inside of the reactor at a pressure higher than the saturated vapor pressure of water at 300°C, pressurized nitrogen gas was fed to the reactor. The product gas was cooled and measured for the amount thereof with a gas meter _7_ ~~99435 and for the composition thereof with gas chromatography. The yields of hydrogen, carbon dioxide and methane are shown in Table 1. The production of carbon monoxide and hydrocarbons having 2 or more carbon atoms was only trace. The gasification rate was 83 ~ based on carbon.
Comparative Example 1 In the same manner as that in Example 1, a mixture of 5 g of cellulose (fine crystals, product of E. Merck Inc.), 30 g of water, 2 g of the nickel catalyst and 0.5 g of sodium carbonate was charged in a reactor (inside volume: 100 ml). The reactor was pressurized with nitrogen gas to 3 MPa so that the reaction pressure was the same as that in Example 1. The reactor was heated to 300°C and maintained at that temperature for 30 minutes. Then, the reactor was cooled to room temperature. The product gas was measured for the amount thereof with a gas meter and for the composition thereof with gas chromatography. The yields of hydrogen, carbon dioxide and methane are shown in Table 1. The production of carbon monoxide and hydrocarbons having 2 or more carbon atoms was only trace. The gasification rate was g0 ~ based on carbon.
Table 1 Yield of Gas (mmol) Example 1 79.0 101.4 33.9 Comparative Example 1 16.2 74.8 52.8 As will be appreciated from the results shown above, when the biomass decomposition is carried out without removing produced HZ from the reaction zone, the yield of H2 is 16.2 mmol under the conditions where the gasification rate is 80 $. In contrast, in the method according to the present invention, the yield of Hz is 79.0 mmol under the conditions providing a gasification rate of 83 ~.
Claims (7)
1. A method of producing hydrogen from a cellulose-containing biomass, comprising forming a liquid phase containing the biomass, water and a catalyst in a reaction chamber such that an upper space is defined above the liquid phase in the chamber, feeding an inert gas to said reaction chamber to maintain the upper space at a pressure higher than the saturated vapour pressure of water, heating the liquid phase at a temperature of 250-374°C while maintaining the upper space at a pressure higher than the saturated vapour pressure of water, so that hydrogen is formed and collected in the upper space, and discharging part of the collected hydrogen during heating.
2. A method as claimed in claim 1 in which the inert gas is fed directly to the upper space.
3. A method as claimed in claim 1 in which the inert gas is fed to a bottom portion of the liquid phase.
4. A method as claimed in any one of claims 1, 2 or 3 which further comprises heating a heating medium with solar energy and feeding the said heated heating medium to the reaction chamber for heating the liquid phase by indirect heat exchange therewith.
5. A method of producing hydrogen from a cellulose-containing biomass, comprising forming a liquid phase containing the biomass, water and a catalyst in a first chamber of a reaction zone having a gas-liquid separating membrane disposed to partition the reaction zone into the first chamber and a second chamber, heating the liquid phase to a temperature of 250-374°C, feeding a pressurized inert gas to the second chamber to maintain the first chamber at a pressure higher than the saturated vapour pressure of water during the heating, so that the biomass is decomposed to produce hydrogen which passes through the membrane to the second chamber, and, during the feeding of the pressurised inert gas, discharging part of the hydrogen from the second chamber together with inert gas.
6. A method as claimed in claim 5 in which the reaction zone is a tubular reactor and the membrane is a tubular membrane defining therewith the second chamber, the tubular membrane being coaxially disposed in the tubular reactor to define the first chamber between the membrane and the tubular reactor.
7. A method as claimed in claim 5 or 6 which further comprises heating a heating medium with solar energy and feeding the said heated heating medium to the reactor for heating the liquid phase by indirect heat exchange therewith.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8051816A JP2736330B2 (en) | 1996-03-08 | 1996-03-08 | Method for producing hydrogen from cellulosic biomass |
| JP8-051816 | 1996-03-08 | ||
| JP8-064304 | 1996-03-21 | ||
| JP8064304A JP2736331B2 (en) | 1996-03-21 | 1996-03-21 | Method for producing hydrogen from cellulosic biomass using solar heat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2199435A1 CA2199435A1 (en) | 1997-09-08 |
| CA2199435C true CA2199435C (en) | 2002-01-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002199435A Expired - Fee Related CA2199435C (en) | 1996-03-08 | 1997-03-07 | Method of producing hydrogen from biomass |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2199435C (en) |
| GB (1) | GB2310865B (en) |
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| EP1862527B1 (en) * | 2006-05-30 | 2011-01-19 | Environmental Consulting Catalysts & Processes for a Sustainable Development | A process for the production of light hydrocarbons from natural bitumen or heavy oils |
| EP1878695A1 (en) | 2006-07-14 | 2008-01-16 | BIOeCON International Holding N.V. | Processing of biomass-derived oxygenates with particles comprising a coke deposit |
| EP1889870A1 (en) * | 2006-08-16 | 2008-02-20 | BIOeCON International Holding N.V. | Stable suspensions of biomass comprising inorganic particulates |
| US8303676B1 (en) * | 2008-02-19 | 2012-11-06 | Proton Power, Inc. | Conversion of C-O-H compounds into hydrogen for power or heat generation |
| US9698439B2 (en) | 2008-02-19 | 2017-07-04 | Proton Power, Inc. | Cellulosic biomass processing for hydrogen extraction |
| US8475722B2 (en) | 2010-04-08 | 2013-07-02 | Toyota Jidosha Kabushiki Kaisha | Hydrogen generation device and method of using same |
| US8657920B2 (en) | 2010-04-08 | 2014-02-25 | Toyota Jidosha Kabushiki Kaisha | Apparatus for purifying hydrogen and method for using the same |
| JP5737407B2 (en) * | 2011-08-11 | 2015-06-17 | トヨタ自動車株式会社 | Hydrogen generator and method of using the same |
| US10005961B2 (en) | 2012-08-28 | 2018-06-26 | Proton Power, Inc. | Methods, systems, and devices for continuous liquid fuel production from biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113446A (en) * | 1975-07-22 | 1978-09-12 | Massachusetts Institute Of Technology | Gasification process |
| GB2089831B (en) * | 1980-12-18 | 1984-10-31 | Univ Salford Ind Centre | Conversion of municipal waste to fuel |
| US5019135A (en) * | 1987-10-13 | 1991-05-28 | Battelle Memorial Institute | Method for the catalytic conversion of lignocellulosic materials |
| DE3806732A1 (en) * | 1988-03-02 | 1989-11-09 | Andersen Kjeld | METHOD FOR GASIFICATION OF ORGANIC MATERIAL IN SYNTHESEGAS OR GASOFMY OR LIQUID HYDROCARBONS OR FOR REMOVING ORGANIC MATERIAL IN WASTEWATER |
| NZ253874A (en) * | 1992-06-05 | 1996-04-26 | Battelle Memorial Institute | Catalytic conversion of liquid organic materials into a product gas of methane, carbon dioxide and hydrogen |
-
1997
- 1997-03-07 CA CA002199435A patent/CA2199435C/en not_active Expired - Fee Related
- 1997-03-07 GB GB9704772A patent/GB2310865B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2199435A1 (en) | 1997-09-08 |
| GB2310865B (en) | 2000-02-09 |
| GB2310865A (en) | 1997-09-10 |
| GB9704772D0 (en) | 1997-04-23 |
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