CN101245262B - Gas-steam combined cycle system and technique based on coal gasification and methanation - Google Patents
Gas-steam combined cycle system and technique based on coal gasification and methanation Download PDFInfo
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- CN101245262B CN101245262B CN2008100566199A CN200810056619A CN101245262B CN 101245262 B CN101245262 B CN 101245262B CN 2008100566199 A CN2008100566199 A CN 2008100566199A CN 200810056619 A CN200810056619 A CN 200810056619A CN 101245262 B CN101245262 B CN 101245262B
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
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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
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Abstract
A combined cycle system based on coal gasification and methanation gas-steam and a technique thereof, wherein, the method comprises the following steps: oxygen produced by an air separation unit and coal powder or water-coal-slurry are sent into coal gasification equipment, the produced crude gasification gas is sent to a carbon monoxide sulfur-tolerant shift reactor to adjust the ratio of hydrogen and carbon after the sensible heat recollecting, and is then sent into sulfur-tolerant methanation reactor to produce methane and carbon dioxide, then the reaction product is sent into desulfurization and decarbonization equipment so that element sulfur can be recovered and carbon dioxide can be separated so as to obtain substitute natural gas with high content of methane, part of which is sentto the gas-steam combined cycle equipment while the other part is sent to a urban gas system. The enriched CO2 density of the system can reach 50 to 60 percent, technical probability is provided for reasonably realizing low-energy-consumption reduced exhaust of CO2, no change needs to be done with gas turbines, each chemical unit operates according to established rated condition and needs not to change load owing to power conditioning so as to improve the economy of the operation of power plants; compared with the prior art, the energy utilization efficiency of the whole system is improved soas to realize the efficient clean utilization of coal.
Description
Technical field
The present invention relates generally to a kind of CO of novelty
2High density enriching method and electricity-substitute natural gas co-generation system and processing method, particularly relating to the coal is the gas-steam combined cycle system and the processing method based on gasification and methanation of raw material.
Background technology
In recent years, because the obvious aggravation of Greenhouse effect to weather and ecological impact added in rising violently of world wide internal combustion oil and gas price.According to the resource situation of the rich coal weak breath of China, IGCC relies on its higher power supplying efficiency and potential CO as a kind of novel clean coal power generation technology
2The reduction of discharging advantage, the arena of history has been gone up at the station again.But it still faces following three problems: at first, the economy in IGCC power station, the cost in IGCC power station are 2 times of common coal power station cost at present; Secondly, IGCC power station variable load operation ability; The 3rd, internal combustion turbine changes the renovation technique of low-heat value gas in the burning.
Gasification is to be most important core technology and key equipment in the chemical system of the energy with coal-based, the energy and chemical system based on it can not only solve efficient and pollutant emission problem in the coal conversion process preferably, and can produce liquid fuel and electric power equal energy source product, important meaning be arranged solving the coal resources comprehensive utilization and alleviating Chinese hydrocarbon resources shortage problem.
When Chemicals such as synthetic F-T liquid fuel, methyl alcohol and DME, need adjust the ratio of hydrogen and carbon monoxide by the CO transformationreation, to satisfy the requirement of production technique.In the industry, the CO transformationreation is all carried out in the presence of catalyzer, mainly contains Fe-Cr, Cu-Zn and Co-Mo three big series catalysts.The purpose of exploitation Co-Mo series catalysts can directly be carried out the CO conversion with sulfurous gas in order to satisfy in heavy oil, the gasification inhibition and generation chemical product flow process with exactlying, the needs of desulfurization and decarburization again, thereby simplification operational path.The transformationreation of carbon monoxide and water vapour is a reversible exothermic process, and reaction equation is as follows:
CO+H
2O
CO
2+H
2 (1)
Usually contain more CO in the coal gas that gasification produced, this kind coal gas is low toxic with CO because of its calorific value, is unsuitable for direct fuel as gas and circulating power station and uses; In the presence of catalyzer, CO all can be converted into methane, substitute natural gas that Here it is (SNG).With gas reforming is the process (namely for methane reaction process) of methane, can carry out according to following dual mode:
2CO+2H
2 
CH
4+CO
2 (2)
CO+3H
2 
CH
4+H
2O (3)
Peggy Y.Hou thinks CO and H
2On molybdenum sulfide catalyst, carry out, and done relevant research according to reaction (2).And research is at present mostly carried out according to reaction (3) with practice, use to contain cobalt or nickel-containing catalyst, and be methane at 200～350 ℃ of following CO shortenings, be a kind of Special Circumstances of F-T method synthin.Tradition as a kind of purification techniques is applied as: (A) be used for removing process gas (as refining H
2Or ammonia synthesis gas) a spot of CO and CO in
2(B) town gas is detoxified by the CO methanation, and the calorific value of unit volume increases.And large-scale application is the production substitute natural gas, go into operation in 1984 as U.S. Great plains natural gas plant, and 18500 tons of Japanese consumpting coal amounts, available rate is greater than 98.7%, CO
2CER reaches 5000 tons/day.
Summary of the invention
The objective of the invention is to fully utilize the gasification of large-scale application and according to reaction 2CO+2H
2 
CH
4+ CO
2The methanation technology that carries out solves existing coal high-efficiency and utilizes the problem that technology exists and a kind of coal-based gas-steam combined cycle system and the processing method that proposes, and realizes a kind of CO of high density
2The beneficiation technologies scheme changes the single power supply form in traditional power station, produces electric power and substitute natural gas simultaneously.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of gas-steam combined cycle system based on coal-gasification methaneization is characterized in that this system comprises:
A) combustion and steam combined cycle power plant 25;
B) one produces oxygen and the air separation plant 26 of nitrogen, and the nitrogen 17 that this air separation plant makes is connected with combustion and steam combined cycle power plant 25 by pipeline;
C) coal gasification apparatus 21 that produces high pressure steam and thick gasification gas, this coal gasification apparatus is connected by the oxygen 3 that pipeline and air separation plant 26 make, and the high pressure steam 5 of generation is connected with combustion and steam combined cycle power plant 25 by pipeline;
D) carbon monoxide sulfur-tolerant water gas shift device 22, the thick gasification gas 4 that this carbon monoxide sulfur-tolerant water gas shift device makes coal gasification apparatus 21 are adjusted into and are fit to methane synthetic conversion gas 6;
E) methanation in presence of sulfur reactor 23, the reaction back generates the mixed gas 7 of methane and carbonic acid gas, pipeline by conversion gas 6 is connected with described carbon monoxide sulfur-tolerant water gas shift device 22, and the middle pressure steam 8 of generation is connected with combustion and steam combined cycle power plant 25 with desulfurization and decarburization equipment 24 by pipeline respectively;
F) desulfurization and decarburization equipment 24, this equipment removes organosulfur, inorganic sulfur and the carbonic acid gas the mixed gas 7 of the methane that comes out from the methanation in presence of sulfur reactor and carbonic acid gas, be connected with described methanation in presence of sulfur reactor 23 by pipeline, to reclaim elemental sulfur 11 and separating carbon dioxide 10, the substitute natural gas 12 that obtains is connected with combustion and steam combined cycle power plant 25 with gas system 13 respectively by pipeline.
A kind of gas-steam combined circulation technology method based on coal-gasification methaneization provided by the invention is characterized in that this method carries out as follows:
1) oxygen 3 that is made by air separation plant 26 and dry coal powder or coal water slurry 2 enter coal gasification apparatus 21 together, and the thick gasification gas 4 of generation reclaims through sensible heat, and the high pressure steam 5 that produces 8～14MPa is sent into combustion and steam combined cycle power plant 25 to produce electric power 15; The nitrogen 17 that air separation plant 26 makes is sent into the combustion chamber in the combustion and steam combined cycle power plant 25;
2) temperature after sensible heat reclaims is reduced to 150～220 ℃ thick gasification gas 4 and is entered carbon monoxide sulfur-tolerant water gas shift device 22 transformationreations take place, and adjusting hydrogen-carbon ratio is 1: 1; Conversion gas 6 after adjusting enters methanation in presence of sulfur reactor 23, according to 2CO+2H
2 
CH
4+ CO
2Reaction formula generates the mixed gas 7 of methane and carbonic acid gas, and produces the middle pressure steam of 2～6MPa; The mixed gas of methane and carbonic acid gas is sent into desulfurization and decarburization equipment 24, and the middle pressure steam 8 of generation is divided into two strands, and one is sent into combustion and steam combined cycle power plant 25 and changes electric power 15 into, and one sends into desulfurization and decarburization equipment 24 as the absorbent regeneration thermal source;
3) make the mixed gas 7 of the methane that enters desulfurization and decarburization equipment 24 and carbonic acid gas remove wherein organosulfur, inorganic sulfur and carbonic acid gas, obtain containing the substitute natural gas 12 that volumetric molar concentration is 86%～96% methane, part is sent into gas system 13 as gas, and part acts as a fuel and 14 sends into combustion and steam combined cycle power plant 25 to produce electric power 15; And reclaiming elemental sulfur 11, separating carbon dioxide 10 is to realize reduction of discharging.
In above-mentioned processing method of the present invention, the catalyzer that described carbon monoxide sulfur-tolerant water gas shift device uses is the Co-Mo catalyzer; The vapor pressure of described coal gasification apparatus is 3～6.5MPa.The catalyzer that described methanation in presence of sulfur reactor uses is a molybdenum sulfide catalyst, and reaction process is carried out in 210～280 ℃ isothermal reactor, and reaction pressure is 2.5～6MPa.
The present invention has the following advantages and the high-lighting effect: the 1. methanation reaction enrichment CO that is undertaken by reaction formula (2)
2Concentration (50%～60%) than by transformationreation enrichment CO
2Concentration (30%～40%) height, thus CO reduced
2The energy consumption of absorption process; And CO
2The rate of recovery (～90%) also will be higher than general system (～70%), because can utilize products C H in stripping
4Carry out, the gas after gas is carried enters absorption process again, thereby has increased CO
2Yield, therefore, be the reduction of discharging CO of less energy-consumption
2New technique direction is provided, and has made reduction of discharging CO
2Purpose and quantity more reasonable.2. electric power and substitute natural gas are born the cost of equipment of processes such as gasification, desulfurization and decarburization jointly, thereby make the specific investment expense descend.The diversity of product has changed the supplying mode of the single energy carrier in traditional power station, can promote enterprise competitiveness and economic benefit.3. substitute natural gas is as the fuel of internal combustion turbine, and its composition satisfies the requirement of conventional gas turbine fully, so need not transform internal combustion turbine.4. electric power and substitute natural gas production process are coupled, when electric power needs varying load, only need the methanation reaction substitute natural gases of producing are sent into the gas system more, each chemical unit need not be the electric adjustment change of load according to set declared working condition operation; And the thermo-efficiency of production substitute natural gas also is higher than gas-steam combined circulating generation process, so from the angle of efficient, when this system will be no matter all will remain on higher level.5. coal (particularly high sulphur coal etc.) can be converted into electricity and substitute natural gas energy carrier clean, high added value.So can have coal resources and electricity-substitute natural gas combination producing factory is set up in the place of natural gas source scarcity at each big city periphery,, provide civilian substitute natural gas again both for the city provides electric power.Organically gasification, methanation and combustion and steam combined cycle are combined, realized the high-efficiency cleaning utilization of coal.
Description of drawings
Fig. 1 is the gas-steam combined cycle system process flow sheet that the present invention is based on coal-gasification methaneization.
Fig. 2 is the principle schematic of coal gasification apparatus.
Among the figure: the 1-air; 2-dry coal powder/coal water slurry; 3-oxygen; The thick gasification gas of 4-; The 5-high pressure steam; 6-conversion gas; The gas mixture of 7-methane and carbonic acid gas; The 8-middle pressure steam; The 10-carbonic acid gas; The 11-elemental sulfur; The 12-substitute natural gas; 13-gas system; 14-fuel; 15-electric power; The 16-flue gas; 17-nitrogen; The 21-coal gasification apparatus; 22-carbon monoxide sulfur-tolerant water gas shift device; 23-methanation in presence of sulfur reactor; 24-desulfurization and decarburization equipment; 25-gas-steam combined circulation device; The 26-air separation plant.
Embodiment
Be further described by 1,2 pair of system architecture of the present invention of accompanying drawing and embodiment below.
The system that the present invention proposes mainly comprises coal gasification apparatus 21, carbon monoxide sulfur-tolerant water gas shift device 22, methanation in presence of sulfur reactor 23, desulfurization and decarburization equipment 24, combustion and steam combined cycle power plant 25 and air separation plant 26; Described air separation plant 26 links to each other with combustion and steam combined cycle power plant 25 by the pipeline of nitrogen 17; Described coal gasification apparatus 21 is connected with air separation plant 26 by the pipeline of oxygen 3, and the pipeline by high pressure steam 5 is connected with combustion and steam combined cycle power plant 25; The thick gasification gas that described carbon monoxide sulfur-tolerant water gas shift device 22 makes coal gasification apparatus is adjusted into and is fit to methane synthetic conversion gas 6; Described methanation in presence of sulfur reactor 23, the reaction back generates the mixed gas 7 of methane and carbonic acid gas, this reactor is connected with described carbon monoxide sulfur-tolerant water gas shift device 22 by the pipeline of conversion gas 7, and the pipeline by middle pressure steam 8 is connected with desulfurization and decarburization equipment 24 with combustion and steam combined cycle power plant 25 respectively; Organosulfur, inorganic sulfur and CO2 removal the methane that described desulfurization and decarburization equipment 24 will come out from methanation in presence of sulfur reactor 23 and the mixed gas 7 of carbonic acid gas, and reclaiming elemental sulfur and separating carbon dioxide, the substitute natural gas 12 of generation is connected with combustion and steam combined cycle power plant 25 with gas system 13 respectively by pipeline.
Technological process of the present invention is as follows: air 1 enters oxygen 3 that air separation plant 26 makes and dry coal powder or coal water slurry 2 and enters coal gasification apparatus 21 together, coal gasification apparatus 21 is made up of vapourizing furnace main body and waste heat boiler, as shown in Figure 2, the pressure of coal gasification course is 3～6.5MPa, the thick gasification gas that produces reclaims sensible heat through waste heat boiler, and the high pressure steam 5 that produces 8～14MPa is sent into combustion and steam combined cycle power plant 25; Thick gasification gas 4 temperature after the cooling are 150～220 ℃, enter carbon monoxide sulfur-tolerant water gas shift device 22 transformationreation takes place, the purpose of transformationreation is owing to the content of carbon monoxide in the coal gas is higher, more complete in order to make that follow-up methanation reaction carries out, just the volume ratio (being hydrogen-carbon ratio) of hydrogen and carbon monoxide in the needs adjustment coal gas is reacted with Co-Mo as catalyzer, reaction is adiabatic reaction, temperature range is 210～420 ℃, and pressure is 2.5～6MPa, according to reaction formula CO+H
2O
CO
2+ H
2Carry out, the hydrogen-carbon ratio of adjusting in the coal gas is 1: 1, makes it to be fit to methane synthetic needs; Conversion gas 6 after adjusting enters methanation in presence of sulfur reactor 23, and as catalyzer, temperature of reaction is 210～280 ℃ with moly-sulfide, and pressure is 2.5～6MPa, according to reaction formula 2CO+2H
2 
CH
4+ CO
2Carry out, generate the mixed gas 7 of methane and carbonic acid gas, by the methanation that this reaction formula carries out, CO in the mixed gas that obtains
2Concentration (50%～60%) than the CO that obtains by transformationreation
2Concentration (30%～40%) height, thus CO reduced
2The energy consumption of sepn process, the methanation reaction process is emitted a large amount of heat and is taken away by high temperature water-supply, make temperature of reaction maintain in 210～280 ℃ the scope, and the middle pressure steam 8 that produces 2～6MPa is divided into two strands, one is sent into combustion and steam combined cycle power plant 25 and changes electric power 15 into, and another strand sent into desulfurization and decarburization equipment 24 and provided heat for the regeneration of absorption agent; The mixed gas of methane and carbonic acid gas enters desulfurization and decarburization equipment 24, is absorption agent with MDEA, NHD or low-temp methanol, to remove wherein main organosulfur (H
2S) and inorganic sulfur (COS), reclaim elemental sulfur (S) 11, and separating carbon dioxide 10 reduces discharging realizing by Claus or complexing iron sulphur technology; The methane molar content can reach 86～96% in the substitute natural gas 12 that obtains, being divided into two parts utilizes, part substitute natural gas 14 is sent into combustion and steam combined cycle power plant 25 and is acted as a fuel, to produce electric power 15, part substitute natural gas 13 is sent into the gas system as the city domestic gas.
The invention will be further described below by embodiment and accompanying drawing, but the present invention is not limited to embodiment.
Embodiment: with 5000 tons/day of raw coal consumptions with internal combustion turbine is that the combustion and steam combined cycle of siemens V94.3a is the calculating of basis entire system performance when coming that embodiment carried out base load.
Present embodiment 1 used gasification coal adopts Shaanxi Bin County bituminous coal, and its composition and Lower heat value see Table 1.
Table 1 feed coal composition and calorific value
| Ultimate analysis | LHV | ||||||
| Mad 2.52 | Had 3.85 | Oad 12.73 | Nad 0.36 | Sad 0.46 | Cad 69.94 | Aad 10.14 | (MJ/kg) 27.7 |
Table 2 embodiment overall performance data
| System schema | Embodiment 1 | Embodiment 2 |
| Coal-supplying amount (t/d) vapor pressure (MPa) high-pressure steam pressure (MPa) raw gas temperature (℃) methanation in presence of sulfur reaction pressure (MPa) methanation in presence of sulfur temperature of reaction (℃) the empty branch scale of middle pressure steam pressure (MPa) (tO 2/ d) delivery (MWe) substitute natural gas (SNG) output (Nm 3/ d) substitute natural gas efficient (LHV) power supplying efficiency (LHV) system efficiency (LHV) | 5000 3 8 150 2.5 210 2 3651 358.1 559527 67.4％ 38.3％ 54.0％ | 5000 6.5 14 220 6 280 6 3651 365.3 559492 69.2％ 39.4％ 55.7％ |
Substitute natural gas efficient=substitute natural gas Lower heat value/raw material calorific value;
Power supplying efficiency=substitute natural gas efficient * combustion and steam combined cycle efficiency;
System efficiency=(substitute natural gas Lower heat value * substitute natural gas output+clean delivery)/raw material calorific value.
Claims (4)
1. gas-steam combined circulation technology method based on gasification and methanation is characterized in that this method carries out as follows:
1) oxygen (3) that is made by air separation plant (26) and dry coal powder or coal water slurry (2) enter coal gasification apparatus (21) together, the thick gasification gas (4) that produces reclaims through sensible heat, and the high pressure steam (5) that produces 8～14MPa is sent into combustion and steam combined cycle power plant (25) to produce electric power (15); The nitrogen (17) that air separation plant (26) makes is sent into the combustion chamber in the combustion and steam combined cycle power plant (25);
2) temperature after sensible heat reclaims is reduced to 150～220 ℃ thick gasification gas (4) and is entered carbon monoxide sulfur-tolerant water gas shift device (22) transformationreation takes place, and adjusts that the volume ratio of hydrogen and carbon monoxide is 1: 1 in the coal gas; Conversion gas (6) after adjusting enters methanation in presence of sulfur reactor (23), according to
Reaction formula generates the mixed gas (7) of methane and carbonic acid gas, and produces the middle pressure steam of 2～6MPa; The mixed gas of methane and carbonic acid gas is sent into desulfurization and decarburization equipment (24), the middle pressure steam (8) that produces is divided into two strands, one is sent into combustion and steam combined cycle power plant (25) and changes electric power (15) into, and one sends into desulfurization and decarburization equipment (24) as the absorbent regeneration thermal source; The catalyzer that described methanation in presence of sulfur reactor uses is molybdenum sulfide catalyst, and reaction process is carried out in 210～280 ℃ isothermal reactor, and reaction pressure is 2.5～6MPa;
3) make the mixed gas (7) of the methane that enters desulfurization and decarburization equipment (24) and carbonic acid gas remove wherein organosulfur, inorganic sulfur and carbonic acid gas, obtain containing the substitute natural gas that volumetric molar concentration is 86%～96% methane (12), part is sent into gas system (13) as gas, and partly act as a fuel (14) send into combustion and steam combined cycle power plant (25) to produce electric power (15); And reclaiming elemental sulfur (11), separating carbon dioxide (10) is to realize reduction of discharging.
2. the gas-steam combined circulation technology method based on gasification and methanation as claimed in claim 1 is characterized in that: the catalyzer that described carbon monoxide sulfur-tolerant water gas shift device uses is the Co-Mo catalyzer.
3. the gas-steam combined circulation technology method based on gasification and methanation as claimed in claim 1, it is characterized in that: step 2) catalyzer that uses of described methanation in presence of sulfur reactor is molybdenum sulfide catalyst, reaction process is carried out in 210～280 ℃ isothermal reactor, and reaction pressure is 2.5～6MPa.
4. the gas-steam combined circulation technology method based on gasification and methanation as claimed in claim 1, it is characterized in that: the vapor pressure of described coal gasification apparatus is 3～6.5MPa.
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