RENEWABLE CARBON CONTENT IN METHANOL AND OTHER PRODUCTS FROM GASIFICATION OF BIOMASS

• US 20140080928A1
• Filed: 09/13/2013
• Published: 03/20/2014
• Est. Priority Date: 09/14/2012
• Status: Active Grant

• Current Assignee: Sundrop IP Holdings, LLC
• Original Assignee: Sundrop Fuels, Inc.
• Inventors: Kelfkens, Renus Constantyn, Kosstrin, Herbert Mark
• Granted Patent: US 9,416,077 B2
• Time in Patent Office: Days
• US Class Current: 518/704
• CPC Class Codes: C07C 29/1518 one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

An integrated plant is provided to improve carbon utilization of carbon molecules from gasified woody biomass to be converted into methanol. Detectors ensure a minimized sulfur content of less than 0.05% by dry weight of the woody biomass. A biomass gasifier reacts woody biomass in a rapid gasification reaction to produce a syngas composition having a ratio of hydrogen to carbon dioxide that is higher than needed for methanol synthesis. Parallel to the gasifier, a hydrocarbon reforming reactor provides a syngas composition having a ratio of hydrogen to carbon monoxide that is higher than needed for methanol synthesis. The combined syngas mixture from the biomass gasifier and the hydrocarbon reforming reactor comprises feed to a methanol synthesis plant, such that a majority of the carbon dioxide produced by the biomass gasification reaction and the hydrogen produced by the hydrocarbon reforming reactor are synthesized into methanol.

Claims

1. An integrated plant to improve carbon utilization of carbon molecules from gasified woody biomass to be converted into methanol, comprising:

a biomass gasifier comprising a radiant high heat-flux reactor configured to react woody biomass received from a biomass feed system in moist fine particle form at a temperature of at least 950 degrees C., where the biomass gasifier has a steam supply input and one or more heat sources, and in the presence of the steam the woody biomass in moist fine particle form is reacted in the radiant high heat-flux reactor in a rapid biomass gasification reaction to produce at least syngas components, including hydrogen (H2), carbon dioxide (CO2), and carbon monoxide (CO);

a hydrocarbon reforming reactor configured to receive a methane-based gas, where the hydrocarbon reforming reactor is in parallel to and cooperates with the radiant high heat-flux reactor to produce a high quality combined syngas mixture for methanol synthesis between the resultant reactant products coming from the two reactors, wherein the hydrocarbon reforming reactor provides

     1) hydrogen gas,

     2) a hydrogen-rich syngas composition, in which a ratio of hydrogen (H2) to carbon monoxide (CO) is higher than a ratio generally needed for methanol synthesis, and

     3) any combination of the two, to be mixed with a potentially carbon dioxide (CO2) rich syngas composition produced by the biomass gasifier, in which a ratio of hydrogen to carbon dioxide (H2;

CO2) is higher than the ratio generally needed for methanol synthesis in order to convert greater than 60% of the carbon-based molecules in the woody biomass received from a biomass feed system into methanol by way of a methanol synthesis plant;

one or more detectors that are geographically located on the same site as the radiant high heat-flux reactor, wherein the one or more detectors are configured to measure a sulfur content of the woody biomass and are configured to ensure a minimized sulfur content of the woody biomass to less than 0.05% by weight such that the integrated plant operates without a water-gas-shift unit and without an acid gas removal unit because the methanol synthesis plant converts the carbon dioxide into methanol and the detectors ensure that biomass has a minimized sulfur content;

a sulfur removal unit configured to remove at least sulfur-based gas contaminants from the syngas coming from the radiant high heat-flux reactor, where the sulfur removal unit is downstream of the biomass gasifier and the hydrocarbon reforming reactor and are upstream of the methanol synthesis plant; and

where the combined syngas mixture from the biomass gasifier and the hydrocarbon reforming reactor are fed to the methanol synthesis plant, such that a majority of the carbon dioxide (CO2) produced by the biomass gasification reaction and the hydrogen (H2) produced by the hydrocarbon reforming reactor are synthesized into methanol.

2. The integrated plant of claim 1, wherein the one or more detectors are configured to perform chromatography so as to measure the sulfur content of the woody biomass and ensure that the minimized sulfur content of the woody biomass is less than the 0.05% by dry weight of the woody biomass, where the woody biomass in moist fine particle form is characterized by a decreased particle size and an overall increase in surface area due to being processed in a steam explosion unit, which is in the biomass feed system, where the steam explosion unit, the hydrocarbon reforming reactor, and the biomass gasifier are part of the integrated plant.

3. The integrated plant of claim 1, wherein the one or more detectors are configured to work in conjunction with a stored database which maintains a listing of all those certain varieties of trees that are suitable for creating woody biomass, where the stored database lists at least a sulfur content and geographical location for each variety of tree, such that the woody biomass feed produced from each variety of tree possesses the minimized sulfur content of less than the 0.05% by dry weight of the woody biomass.

4. The integrated plant of claim 1, wherein the one or more detectors that ensure the minimized sulfur content of less than the 0.05% by dry weight of the woody biomass further ensure that the woody biomass to be fed for the biomass gasifier possesses a minimized sulfur content of less than 0.01% by dry weight of the woody biomass.

5. The integrated plant of claim 1, where the radiant high heat-flux reactor comprising the biomass gasifier is configured to react the woody biomass received from the biomass feed system in an oxidation free environment to produce the at least syngas components, including hydrogen (H2), carbon dioxide (CO2), and carbon monoxide (CO), where the carbon dioxide (CO2) comprises less than 50% by volume of the syngas.

6. The integrated plant of claim 1, where the hydrocarbon reforming reactor is configured to supply a volume of hydrogen (H2) to the combined syngas mixture such that a ratio of the hydrogen to the sum of the carbon monoxide and the carbon dioxide (H2:

(CO+CO2)) of the combined syngas mixture is between 2.1 and 2.8.

7. The integrated plant of claim 1, where the hydrocarbon reforming reactor is configured to supply a volume of hydrogen (H2) to the combined syngas mixture such that a majority of the carbon dioxide (CO2) entering the methanol synthesis plant is utilized in the synthesis of methanol.

8. The integrated plant of claim 1, where the hydrocarbon reforming reactor is configured to supply a quantity of hydrogen (H2) to the combined syngas mixture such that an exit flue gas from the methanol synthesize plant contains less than 3% of a total quantity of carbon-based molecules fed into the biomass gasifier.

9. The integrated plant of claim 1, where the hydrocarbon reforming reactor is configured to supply the quantity of hydrogen (H2) to the combined syngas mixture such that most of total quantity of carbon-based molecules fed into the biomass gasifier are converted into methanol and subsequently gasoline, where less than 9% of the total quantity of carbon-based molecules fed into the biomass gasifier are not converted into gasoline.

10. The integrated plant of claim 1, where the sulfur recovery unit may be comprised of one or more sulfur guard fixed beds or an amine unit or a combination and configured to remove sulfur and other gas contaminants from the combined syngas mixture.

11. The integrated plant of claim 1, wherein the biomass feed system comprises a steam explosion unit comprising an input cavity to receive woody biomass as a feedstock, one or more steam supply inputs, and two or more stages to pre-treat the woody biomass for subsequent supply to the biomass gasifier, where the two or more stages use a combination of heat, pressure, and moisture that are applied to the woody biomass to make the woody biomass into the moist fine particle form, where a steam explosion process breaks down a bulk structure of the received woody biomass, at least in part, by applying low-pressure steam through a first steam supply input to begin degrading bonds between lignin and hemi-cellulose from cellulose fibers of the woody biomass and increase a moisture content of the received woody biomass, then applying high-pressure steam by way of a second steam supply input at a pressure of at least ten times atmospheric pressure to heat and pressurize any gases and fluids present within the woody biomass, and then rapidly depressurizing the woody biomass with the increased moisture content and degraded bonds so as to internally blow apart the bulk structure of the woody biomass, thereby placing the woody biomass into the moist fine particle form, where the woody biomass in the moist fine particle form is subsequently fed to a feed section of the biomass gasifier.

12. The integrated plant of claim 1, where the hydrocarbon reforming reactor is a Steam Methane Reformer (SMR), where the radiant high heat-flux reactor has the biomass feed system, a first steam supply inlet, a first set of sensors to measure a chemical composition of produced product gases from the radiant high heat-flux reactor, and a gasifier reactor control system to cause the biomass gasification reaction of the woody biomass in moist fine particle form at a temperature of at least 950 degrees C., the SMR reactor has a methane-based gas feed system, a second steam supply inlet, a second set of sensors to measure a chemical composition of produced product gases from the SMR reactor, and an SMR control system, and both the SMR control system and the gasifier reactor control system are part of one or more control systems, wherein the gasifier reactor control system and the SMR control system interact to control an amount of hydrogen (H2) and carbon monoxide and carbon dioxide (CO+CO2) gases supplied to the combined syngas mixture to achieve a proper ratio of hydrogen (H2) to carbon monoxide and carbon dioxide (CO+CO2) that is higher than a ratio generally needed for methanol synthesis from 1) a first stream of the syngas components from the SMR reactor, 2) a separate second stream of the syngas components from the high radiant high heat-flux reactor and 3) a flow of hydrogen gas from a separator off a purge gas line coming out of the methanol synthesis plant, and any of these three sources are mixed together prior to feeding the combined syngas mixture at the proper ratio into the methanol synthesis plant.

13. The integrated plant of claim 1, where the radiant high heat-flux reactor is configured to react woody biomass in the moist fine particle form in the rapid biomass gasification reaction at a temperature of at least 950 degrees C. primarily by way of a radiant heat emitted from the radiant high heat-flux reactor to produce reactant products including ash and syngas components of hydrogen and carbon monoxide exiting the radiant high heat-flux reactor.

14. A method in an integrated plant of improving carbon utilization of carbon molecules from gasified woody biomass to be converted into methanol, comprising:

using one or more detectors to measure a sulfur content of the woody biomass, where the one or more detectors are configured to ensure a minimized sulfur content of the woody biomass of less than 0.05% by weight, such the integrated plant operates without a water-gas-shift unit and without an acid gas removal unit, where the one or more detectors are geographically located on the same site as the integrated plant;

feeding the woody biomass with the minimized sulfur content as a feedstock into a biomass feed system that includes a steam explosion unit configured to apply a combination of heat, pressure, and moisture to the woody biomass to make the woody biomass into a moist fine particle form;

receiving the woody biomass in moist fine particle form from the biomass feed system into a biomass gasifier comprising a radiant high heat-flux reactor configured to react woody biomass at a temperature of at least 950 degrees C., where the biomass gasifier has a steam supply input and one or more heat sources, and in the presence of the steam the woody biomass in moist fine particle form is reacted in the radiant high heat-flux reactor in a rapid biomass gasification reaction to produce at least syngas components, including hydrogen (H2);

carbon dioxide (CO2), and carbon monoxide (CO, where the steam explosion unit and the biomass gasifier are part of the integrated plant;

receiving a methane-based gas into a hydrocarbon reforming reactor which is in parallel to and cooperates with the radiant high heat-flux reactor to produce a high quality combined syngas mixture for methanol synthesis between the resultant reactant products coming from the two reactors, wherein the hydrocarbon reforming reactor provides

     1) hydrogen gas,

     2) a hydrogen-rich syngas composition, in which a ratio of hydrogen (H2) to carbon monoxide (CO) is higher than a ratio generally needed for methanol synthesis, and

     3) any combination of the two, to be mixed with a potentially carbon dioxide (CO2) rich syngas composition produced by the biomass gasifier, in which a ratio of hydrogen to carbon dioxide (H2;

CO2) is higher than the ratio generally needed for methanol synthesis in order to convert greater than 60% of the carbon-based molecules in the woody biomass received from the biomass feed system into methanol by way of a methanol synthesis plant;

removing at least sulfur-based contaminants from the combined syngas mixture by passing the combined syngas mixture through one or more sulfur guard fixed beds that are downstream of the biomass gasifier and the hydrocarbon reforming reactor and are upstream of the methanol synthesis plant, where the sulfur removal unit is configured to remove gas contaminants from the combined syngas mixture; and

feeding the combined syngas mixture to the methanol synthesis plant, such that a majority of the carbon dioxide (CO2) produced by the radiant high heat-flux reactor and the hydrogen (H2) produced by the hydrocarbon reforming reactor are synthesized into methanol.

15. The method of claim 14, wherein feeding the woody biomass with the minimized sulfur content as a feedstock into a biomass feed system further comprises:

receiving the woody biomass as a feedstock though an input cavity into the steam explosion unit comprising one or more steam supply inputs and two or more stages to pre-treat the woody biomass for subsequent supply to the biomass gasifier, where the two or more stages apply the combination of heat, pressure, and moisture to the woody biomass to configure the woody biomass into the moist fine particle form;

breaking down a bulk structure of the received woody biomass, at least in part, by applying low-pressure steam through a first steam supply input to the steam explosion unit so as to begin degrading bonds between lignin and hemi-cellulose from cellulose fibers of the woody biomass and increase a moisture content of the received woody biomass;

applying high-pressure steam by way of a second steam supply input to the steam explosion unit at a pressure of at least ten times atmospheric pressure to heat and pressurize any gases and fluids present within the woody biomass, and

rapidly depressurizing the woody biomass with the increased moisture content and degraded bonds so as to internally blow apart the bulk structure of the woody biomass, thereby placing the woody biomass into the moist fine particle form, where the woody biomass in the moist fine particle form is subsequently fed to a feed section of the biomass gasifier.