US20130326953A1 - Gasification Method for Reducing Emission of Carbon Dioxide - Google Patents

Gasification Method for Reducing Emission of Carbon Dioxide Download PDF

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US20130326953A1
US20130326953A1 US13/992,859 US201113992859A US2013326953A1 US 20130326953 A1 US20130326953 A1 US 20130326953A1 US 201113992859 A US201113992859 A US 201113992859A US 2013326953 A1 US2013326953 A1 US 2013326953A1
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carbon
carbon dioxide
gasification
syngas
catalyst
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Jin Hong Kim
Ja Hyun Yang
Il Yong Jeong
Dae Hee CHO
Jeong Mook Kim
Ok Youn Kim
Jong Chan Lee
Gyoo Tae Kim
Joo Won Park
Sam Ryong Park
Sun Choi
Seung Hoon Oh
Hyun Min Shim
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SK Innovation Co Ltd
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Assigned to SK INNOVATION CO., LTD. reassignment SK INNOVATION CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHOI, SUN, KIM, JIN HONG, OH, SEUNG HOON, PARK, JOO WON, PARK, SAM RYONG, KIM, GYOO TAE, SHIM, HYUN MIN, CHO, DAE HEE, JEONG, IL YONG, KIM, JEONG MOOK, KIM, OK YOUN, LEE, JONG CHAN, YANG, JA HYUN
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    • 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
    • C01B3/34—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 by reaction of hydrocarbons with gasifying agents
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    • C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
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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
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Definitions

  • the present invention relates to a gasification method of a carbon-containing material such as coal, biomass or petroleum coke, and more particularly, to a gasification method capable of increasing a gasification rate and reducing an amount of carbon dioxide to be generated by using a catalyst at a low temperature.
  • gasification means that solid or liquid fuel which basically contains carbon such as coal, petroleum coke, and biomass is reacted with gas such as oxygen, steam, carbon dioxide, and hydrogen to produce combustible gases such as CO, H 2 and CH 4 .
  • gas such as oxygen, steam, carbon dioxide, and hydrogen
  • the process is performed primarily at a high temperature and high pressure in order to maximize capacity and efficiency of a gasification treatment.
  • the resultant combustible gases are used as a plant fuel gas, as chemicals or synthetic petroleum through a methanol synthesis process, an NH 3 synthesis process and a Fischer-Tropsch synthesis process, or as a hydrogen generation source for a hydro-desulphurisation process and a hydrocracking process of crude oil by maximizing hydrogen production.
  • syngas by reacting coal or other carbon-containing materials with steam and oxygen (or air).
  • the “syngas” of the present invention is mainly formed of hydrogen and carbon monoxide, but the present invention is not limited thereto, and may additionally include components such as carbon dioxide and methane.
  • FIG. 3 schematically shows the conventional gasification process.
  • H 2 O, oxygen and a carbon-containing material are introduced to a gasifier.
  • the carbon-containing material introduced to a gasifier is reacted with H 2 O and oxygen both with a kind of catalysts and without catalysts, thus generating a product containing H 2 , CO, CO 2 , and the like. Then, the following main reactions occur in the gasifier.
  • the product thus generated in the gasifier is subjected to a removal process of particular materials, Hg, and NOx, and then an acidic gas removal process of H 2 S and CO 2 . Subsequently, the resultant gas is selectively used for Fischer-Tropsch (F-T) reaction or MeOH reaction through the following water gas shift reaction, or may be used without changing excess H 2 .
  • F-T Fischer-Tropsch
  • MeOH MeOH
  • Carbon efficiency (%) (the sum of the mole number of carbon monoxide and the mole number of methane in syngas having a H 2 /CO of 2 to 2.1) ⁇ 100/mole number of carbon in raw materials introduced for gasification
  • Such low carbon efficiency reduces economic efficiency of a Coal-to-Liquids (CTL) process, or the like. Further, in order to reduce CO 2 that is a greenhouse gas, additional facilities are required, high costs are required to collect and store carbon, and it is difficult to construct commercial plants with economic efficiency.
  • CTL Coal-to-Liquids
  • Korean patent Laid-open Publication No. 10-2008-0041635 discloses an alkaline metal catalytic steam gasification method which uses CO 2 trapping materials and/or mineral binder materials in a gas generation apparatus.
  • the Patent Document discloses CO 2 trapping materials for converting CO 2 into solid carbonate or bicarbonate in order to improve catalyst activity.
  • CO 2 may not be converted into substantially available materials such as CO.
  • this Patent Document is limited to the specific catalyst and should additionally include CO 2 trapping materials such as CaO.
  • the present inventors found that, there is no net generation of carbon dioxide, and efficiency of gasification process is increased, when the amount of carbon dioxide consumed by the C—CO 2 reaction is equal to the sum of the amount of carbon dioxide produced during the combustion of syngases and the amount of carbon dioxide produced by the water gas shift reaction. Thus, the present invention was accomplished.
  • an object of the present invention is to provide a gasification method of carbon-containing materials, which may reduce a CO 2 generation amount, as well as achieve high carbon efficiency from carbon-containing materials such as coal, petroleum coke, and biomass at a low temperature.
  • a gasification method of carbon-containing materials includes:
  • step (b) generating a carbon dioxide rich gas including at least one selected from i) introducing a portion of the syngas that has been produced in step (a) into the combustion process, and
  • step (c) recycling, to step (a), the carbon dioxide rich gas that has been produced in step (b).
  • Examples of the catalysts that may be used in step (a) include general catalysts that may be used for the gasification reaction of carbon-containing materials, and preferably transition metal catalysts, or catalysts containing alkaline metals or alkaline earth metals.
  • Examples of the alkaline metal components that may be used include Li, Na, K, Rb, Cs, Fr, and the like.
  • Examples of the alkaline earth metal components that may be used include Mg, Ca, and the like.
  • Examples of the transition metal catalysts that may be used include Fe, Ni, Co, Cu, Zn, and the like.
  • the present invention is not limited thereto. Other metal components which is suitable to the object of the present invention may be used, which is evident to those skilled in the art.
  • the catalyst which may be used includes one or a mixture of at least two, of hydrates, oxides, and metal salts of the metal.
  • the metal may be mixed with general gasification reaction catalysts.
  • the carbon-containing materials to be treated in step (a) may be used without limitation as long as they may be a material which is suitable to the object of the present invention. Typical examples thereof include coal, biomass, coke, or the like, but the present invention are not limited thereto.
  • step (b) in order to generate the carbon dioxide rich gas in step (b), one selected from introducing a portion of the syngas that has been produced in step (a) to the combustion process and separating hydrogen and carbon monoxide from the syngas may be used, or two processes thereof may be used at the same time. A portion of the syngas that has been produced in step (b) is introduced to the combustion process and thereby a heating value which is required for the gasification of carbon-containing materials according to the present invention may be supplied.
  • a combustion method includes general flame combustion, catalyst combustion, and the like. In order to control conditions at the time of introduction to a gasifier, methods such as Chemical Looping Combustion may be used. Two or more combustion methods may be combined for a higher effect.
  • the present invention may further include:
  • step (d) separating carbon dioxide from the syngas that has not been not introduced at the time of the combustion process in step (b).
  • present invention may further include:
  • step (e) recycling, to step (a), the carbon dioxide that has been separated in step (d); or
  • step (f) recycling, to the combustion process of step (b), the carbon dioxide that has been separated in step (d).
  • the present invention may further include separating and recovering the catalyst used for the purpose of gasification.
  • the catalyst may be separated and recovered at any time during the gasification according to the present invention, if necessary.
  • the catalyst recovery is performed such that effective catalyst components are recovered in liquid or solid state from the mixture of catalyst and ash.
  • the catalyst may be recovered from the mixture of catalyst and ash emitted from the lower portion of the gasifier; or from the entrainment material in gas flow, by using an apparatus separately provided or integrally equipped with the gasifier.
  • gasification method of the invention a gasification method in which carbon dioxide that is a greenhouse gas is not generated may be implemented. Also, carbon efficiency may be maximized, when chemicals such as methanol or production of synthetic oil are produced through the consecutive Fischer-Tropsch process after the gasification, and thus economic efficiency of the entire process may be improved.
  • CCS Carbon Capture & Storage
  • FIG. 1 shows the process of a gasification method according to a preferable specific example of the present invention
  • FIGS. 2 a and 2 b show graphs showing a composition example of the syngas emitted from a gasifier
  • FIG. 2 a is a graph showing the composition of the syngas at the time of steam-carbon dioxide gasification with use of a catalyst
  • FIG. 2 b is a graph showing the composition of the syngas at the time of steam-carbon dioxide gasification of lignite without use of a catalyst;
  • FIG. 3 shows a general process of high temperature steam-oxygen gasification
  • FIG. 4 shows a general CTL process made of a high temperature steam-oxygen gasifier.
  • the present invention basically includes separating and recycling carbon dioxide after gasification using a catalyst, which promotes the C—CO 2 gasification reaction in a gasifier.
  • the gasification method according to the present invention discloses (a) reacting carbon-containing materials to be treated, such as coal, petroleum coke, biomass, and the like under the presence of a catalyst with steam to produce a syngas containing hydrogen, carbon monoxide and carbon dioxide.
  • coal, petroleum coke, biomass, and the like along with a catalyst are added to a gasifier 1 .
  • the reactions in the gasifier 1 result in production of a syngas containing hydrogen, carbon monoxide and carbon dioxide.
  • the reaction rate of the C—CO 2 reaction known as a carbon dioxide gasification reaction is generally slower than that of the steam gasification reaction at a low temperature.
  • a catalyst is used to supplement the slower reaction rate of CO 2 reaction.
  • the catalyst that may be used in the present invention may include general catalysts that may be used for the gasification reaction of carbon-containing materials, and preferably include catalysts containing alkaline metals or alkaline earth metals. Examples of the alkaline metal components that may be used include Li, Na, K, Rb, Cs, Fr, and the like.
  • the alkaline earth metals examples include Mg, Ca, and the like.
  • the catalyst which may be used includes one or a mixture of at least two, of hydrates, oxides, and metal salts of the metal.
  • the metal may be mixed with general gasification reaction catalysts.
  • the gasification may be preferably performed at a temperature of 750 to 850° C.
  • the syngas generated from the gasifier 1 is subjected to separation of carbon dioxide from the syngas containing H 2 and carbon monoxide in a CO 2 separation section 3 .
  • the carbon dioxide thus separated may be recycled to a recycled line and supplied directly to the gasifier 1 , or may be supplied to a catalytic combustion section 4 along with a portion of the syngas which has been emitted from the gasifier 1 and recycled to the recycled line. Then, the syngas that has been emitted from the gasifier 1 and recycled is burned in the catalytic combustion section 4 , and thus a heating value required for the reaction, steam and carbon dioxide are supplied.
  • the carbon dioxide that has been produced by the combustion of carbon monoxide is converted into carbon monoxide through the C—CO 2 reaction in the gasifier 1 , a portion of the generated carbon monoxide is converted into hydrogen and carbon dioxide through the water gas shift reaction.
  • the amount of carbon dioxide consumed by the C—CO 2 reaction is equal to the sum of the amount of carbon dioxide produced during the combustion of the syngases and the amount of carbon dioxide produced by the water gas shift reaction, there is no net generation of carbon dioxide, and therefore efficiency of gasification process is increased.
  • the carbon dioxide that has been recycled and steam that has been supplied to the gasifier 1 are allowed to increase a partial pressure of carbon dioxide and a partial pressure of steam as a gasification agent, which serves to promote the gasification reaction with steam and the gasification reaction with carbon dioxide.
  • FIG. 2 shows the composition of the syngas generated by the steam-carbon dioxide gasification of lignite containing 10 wt % of a K 2 CO 3 catalyst and catalyst-free lignite.
  • the composition of the syngas proceeded at the temperature of 800° C., the atmospheric pressure and the gage pressure of 1 Kg f /cm 2 . Then, a partial pressure of steam was about 0.36 Kg f /cm 2 and a partial pressure of carbon dioxide was 0.19 Kg f /cm 2 .
  • the catalyst is used as shown in FIG. 2 a , carbon dioxide is converted into carbon monoxide by reaction with the carbon of coal, whereas carbon monoxide is not almost produced by the C—CO 2 reaction at the time of the gasification of catalyst-free coal.
  • the effect is not limited to a K 2 CO 3 catalyst.
  • the catalyst that has been subjected to gasification is recovered, and is supplied to the gasifier 1 again along with carbon-containing materials.
  • a stoichiometric formula of the steam gasification reaction to 1 g-mol of bituminous coal, calculated from the composition of the syngas generated from a GE-TEXACO gasifier [see DOE/NETL-2008/1331] is as follows:
  • the maximum theoretical heat efficiency calculated using the following formula is about 70%.
  • 0.23 mol of carbon dioxide is emitted per 1 g-mol of the carbon included in bituminous coal, and therefore 77% of the carbon may be used effectively.
  • Heat efficiency (%) [(mole number of H 2 ⁇ unit heating value of H 2 )+(mole number of CO ⁇ unit heating value of CO) ⁇ 100 (%)/[g-mol of coal ⁇ unit heating value of coal]
  • the heat efficiency calculated using the calculation equation of heat efficiency is about 96%.
  • the Air Separation Unit (ASU) that separates oxygen from air and supplied to a gasifier has a very large effect on heat efficiency of the entire gasification process.
  • a supplied oxygen amount according to the gasification method described in the present Example corresponds to about 44%, compared to Comparative Example 1, and thus energy supplied for ASU operation is considerably low.
  • a heat of reaction required for gasification is supplied by the combustion of coal that is a solid state, whereas a heat of reaction required for gasification is supplied by burning the syngas that is a gas state in the present invention, thus obtaining high combustion efficiency.
  • the effect obtained from the present invention may be further improved by using a catalyst at the time of burning the syngas. In other words, combustion of the syngas is performed by using a catalyst, and thereby it is expected that a ratio of oxygen to fuel may be minimized.
  • a ratio of hydrogen to carbon monoxide may be controlled by the water gas shift reaction.
  • the syngas produced through a GE-TEXACO gasifier of Comparative Example 1 is converted such that a ratio of hydrogen to carbon monoxide is 2 to 1 through the water gas shift reaction.
  • the water gas shift reaction is performed in a gasifier, and thereby an additional reactor is not needed. Then, the steam gasification reaction and the C—CO 2 gasification reaction are preferably carried out by about 1 to 0.33, respectively. About 39% is converted into hydrogen and carbon dioxide through the water gas shift reaction, with respect to the total amount of carbon monoxide produced by the gasification reaction.
  • the carbon efficiency improved by the present invention may significantly reduce an amount of raw materials such as coal to be used.
  • the cost of raw materials, the apparatus cost and operation cost for drying, grinding, transfer and storage of raw material (coal) may be reduced significantly.
  • the ASU apparatus cost and operation cost may be improved by 50% or more through catalytic combustion of the syngas.
  • the amount of carbon dioxide to be emitted is reduced significantly, the used energy amount and costs of apparatus such as a CO 2 separation process, for example, an amine absorption process are improved significantly, and therefore economic efficiency of the entire process may be further improved.

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EP2650258A2 (en) 2013-10-16
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CN103261089A (zh) 2013-08-21
CA2820859A1 (en) 2012-06-14
WO2012077978A3 (ko) 2012-08-02
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AU2011339160A1 (en) 2013-07-11
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