CN101074397A - Combined system and process for producing electric-substituted natural gas based on coal gasification and methanation - Google Patents

Combined system and process for producing electric-substituted natural gas based on coal gasification and methanation Download PDF

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CN101074397A
CN101074397A CN 200710117724 CN200710117724A CN101074397A CN 101074397 A CN101074397 A CN 101074397A CN 200710117724 CN200710117724 CN 200710117724 CN 200710117724 A CN200710117724 A CN 200710117724A CN 101074397 A CN101074397 A CN 101074397A
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gas
gasification
natural gas
coal
sulfur
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CN100582201C (en
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李政
王明华
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Tsinghua University
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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]
    • 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]

Abstract

An electric-substituting natural gas combined system and process based on coal gasification and methanation are disclosed. The process is carried out by delivering oxygen, powdered coal or water-gas slurry into gasified apparatus, recovering for crude gasified gas by wet heat, delivering into sulfur-resisting carbon monoxide carbon reactor, adjusting hydrogen-carbon ratio, entering into desulfurizing decarbonizer, recovering elementary sulfur while enriching carbon dioxide, delivering synthetic gas into methane reactor to generate substituted natural gas as domestic gas partially, entering into gas and steam combined circulator partially, and entering into substituted natural gas storage tank partially. It integrates coal gasified, methanation and gas steam combined circulation together, it's efficient and clean, has better utilizing rate, no CO2 discharge and need for changing gas turbine or load.

Description

Electric-substituted natural gas co-generation system and technology based on gasification and methanation
Technical field
The present invention relates generally to a kind of electric-substituted natural gas co-generation system and processing method of novelty, particularly relate to co-generation system and processing method, the invention still further relates to and utilize said system and processing method to realize that a kind of brand-new coke-oven gas utilizes mode based on gasification and methanation.
Background technology
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.
Methanation is applied as a kind of tradition of purification techniques: (1) is used for removing process gas (as refining H 2Or ammonia synthesis gas) a spot of CO and CO in 2(2) town gas is detoxified by the CO methanation, and the calorific value of unit volume increases.And the large-scale application of methanation is the production instead of 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.
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.
In addition, the coke production amount of China, consumption, export volume all rank first in the world, but a large amount of coke-oven gas can not get effective utilization, and valuable resource has not only been wasted in directly emptying burning, also severe contamination environment.
Summary of the invention
The objective of the invention is to fully utilize the gasification and the methanation technology of large-scale application, solve existing coal high-efficiency and utilize the problem that technology exists and a kind of coal-based electric-substituted natural gas co-generation system and the processing method that proposes, change the single power supply form in traditional power station, produce electric power and instead of natural gas simultaneously; Simultaneously provide a kind of brand-new solution for the utilization of coke-oven gas, made it change the higher instead of natural gas of energy density into by this system and processing method.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of electric-substituted natural gas co-generation system based on coal-gasification methaneization is characterized in that this system comprises:
A) combustion and steam combined cycle power plant;
B) oxygenous air separation plant;
C) coal gasification apparatus that produces high pressure steam and raw gas, this coal gasification apparatus is connected with air separation plant by oxygen channel, is connected with the combustion and steam combined cycle power plant by the high pressure steam pipeline;
D) carbon monoxide sulfur-tolerant water gas shift device, the thick gasification gas that this carbon monoxide sulfur-tolerant water gas shift device makes coal gasification apparatus are adjusted into and are fit to methane synthetic gasification gas;
E) desulfurization and decarburization equipment, organosulfur and inorganic sulfur that this equipment removes from the gasification gas that carbon monoxide sulfur-tolerant water gas shift device comes out take off, be connected with described carbon monoxide sulfur-tolerant water gas shift device and reclaim elemental sulfur, carbon dioxide-enriched by the gasification gas pipeline;
F) methanator, the reaction back generates instead of natural gas, this reactor is connected with described carbon monoxide sulfur-tolerant water gas shift device by the gasification gas pipeline, be connected with domestic fuel pipeline, instead of natural gas storage tank and combustion and steam combined cycle power plant respectively by the instead of natural gas pipeline, by steam-pipe be connected with desulfurization and decarburization equipment with combustion and steam combined cycle power plant, carbon monoxide sulfur-tolerant water gas shift device respectively.
A kind of electric-substituted natural gas joint process method based on coal-gasification methaneization provided by the invention is characterized in that this method carries out as follows:
1) oxygen that makes of air admission air separation plant and coal dust or coal water slurry enter coal gasification apparatus together, and the thick gasification gas of generation reclaims through sensible heat, produce high pressure steam and send into the combustion and steam combined cycle power plant to produce electric power;
2) the thick gasification gas after the cooling enters carbon monoxide sulfur-tolerant water gas shift device generation transformationreation, is fit to methane synthetic hydrogen-carbon ratio to adjust; Gasification gas after adjusting enters desulfurization and decarburization equipment, removes wherein organosulfur and inorganic sulfur, obtains clean synthetic gas, and reclaims elemental sulfur, obtains carbon dioxide-enriched to realize reduction of discharging;
3) the clean synthetic gas that will obtain is sent into methanator and is generated instead of natural gas, and part is as domestic gas, and part is sent into the combustion and steam combined cycle power plant and acted as a fuel to produce electric power, and part is sent into the instead of natural gas storage tank in case of need; Reaction process is emitted a large amount of heat to produce middle pressure steam, and part is sent into the combustion and steam combined cycle power plant and changed electric power into, and part is sent into carbon monoxide sulfur-tolerant water gas shift device, and part is sent into desulfurization and decarburization equipment.
Described electric-substituted natural gas joint process method based on gasification and methanation is characterized in that: the catalyzer that described carbon monoxide sulfur-tolerant water gas shift device uses is cobalt one molybdenum catalyst, and regulating suitable methane synthetic hydrogen-carbon ratio is 3: 1.
Described electric-substituted natural gas joint process method based on gasification and methanation, it is characterized in that: the reaction process in the described methanator of step 3) is carried out in two steps, the first step is carried out in temperature 500-600 ℃ adiabatic reactor, second step carried out in 250-300 ℃ isothermal reactor, and reaction pressure is 50-60bar; The heat that reaction process is emitted is 40-60bar with the middle pressure steam pressure that produces.
Described electric-substituted natural gas joint process method based on gasification and methanation, it is characterized in that: described coal gasification apparatus adopts coal dust or coal water slurry charging and sensible heat way of recycling, vapor pressure is 55-65bar, the high-pressure steam pressure that produces is 80-140bar, and the temperature of the thick gasification gas after the cooling is 150-400 ℃.
Described electric-substituted natural gas joint process method based on gasification and methanation is characterized in that: when when coal gasification apparatus breaks down, the instead of natural gas that stores in the instead of natural gas storage tank is sent into the combustion and steam combined cycle power plant to produce electric power.
Described electric-substituted natural gas joint process method based on gasification and methanation is characterized in that: utilize gasification gas after coke-oven gas and the transformationreation directly to mix and regulate hydrogen-carbon ratio.
The present invention has the following advantages and the high-lighting effect: 1. coal (particularly high sulphur coal etc.) can be converted into electricity and instead of natural gas energy carrier clean, high added value.So can have coal resources and electric-substituted natural gas combination producing factory is set up in the place of natural gas source scarcity at each big city periphery,, provide civilian instead of 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, and need not transform internal combustion turbine.2. coke-oven gas be can fully utilize efficiently, coking plant, particularly medium and small coking plant coke-oven gas problem of outlet solved.3. electric power and instead of natural gas are born the cost of equipment of processes such as gasification, purification 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.4. electric power and instead of natural gas production process are coupled, when electric power needs varying load, only need the methanation reaction instead of natural gas of producing are sent into city natural gas pipe network more, each chemical unit need not be the electric adjustment change of load according to set declared working condition operation.5. instead of 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.6. hydrogen-carbon ratio need be adjusted owing to the instead of natural gas production process, thereby CO can be reduced discharging 2, and the purpose that reduces discharging is more reasonable.
Description of drawings
Fig. 1 is the electricity one instead of natural gas co-generation system process flow sheet that the present invention is based on coal-gasification methaneization.
Embodiment
By accompanying drawing system architecture of the present invention and embodiment are further described below.
The system that the present invention proposes mainly comprises combustion and steam combined cycle power plant 20, air separation plant 21, coal gasification apparatus 15, carbon monoxide sulfur-tolerant water gas shift device 16, desulfurization and decarburization equipment 17, methanator 18, instead of natural gas storage tank 19; Described coal gasification apparatus is connected with air separation plant by oxygen channel, is connected with the combustion and steam combined cycle power plant by the high pressure steam pipeline; The thick gasification gas that described carbon monoxide sulfur-tolerant water gas shift device makes coal gasification apparatus is adjusted into and is fit to methane synthetic gasification gas; Described desulfurization and decarburization equipment will remove from organosulfur and the inorganic sulfur the gasification gas that carbon monoxide sulfur-tolerant water gas shift device comes out, be connected with described carbon monoxide sulfur-tolerant water gas shift device and reclaim elemental sulfur, carbon dioxide-enriched by the gasification gas pipeline; Described methanator, the reaction back generates instead of natural gas, this reactor is connected with described carbon monoxide sulfur-tolerant water gas shift device by the gasification gas pipeline, be connected with domestic fuel pipeline, instead of natural gas storage tank and combustion and steam combined cycle power plant respectively by the instead of natural gas pipeline, by steam-pipe be connected with desulfurization and decarburization equipment with combustion and steam combined cycle power plant, carbon monoxide sulfur-tolerant water gas shift device respectively.
Concrete technology of the present invention is as follows:
Air 1 enters oxygen 3 that air separation plant 21 makes and coal dust or coal water slurry 2 and enters coal gasification apparatus 15 together, and the thick gasification gas of generation reclaims through sensible heat, produces high pressure steam 5 and sends into combustion and steam combined cycle power plant 20; Thick gasification gas 4 after the cooling enters carbon monoxide sulfur-tolerant water gas shift device 16 transformationreation takes place, and as catalyzer, adjusts suitable methane synthetic hydrogen-carbon ratio with cobalt-molybdenum; Gasification gas 6 after adjusting enters desulfurization and decarburization equipment 17, to remove organosulfur and inorganic sulfur wherein, obtains clean synthetic gas 7, and reclaims elemental sulfur 9, and carbon dioxide-enriched 8 is to realize reduction of discharging; The clean synthetic gas 7 that obtains is sent into methanator 18 generate instead of natural gas 10, part is as domestic gas, part is sent into combustion and steam combined cycle power plant 20 and is acted as a fuel to produce electric power 12, and part is sent into instead of natural gas storage tank 19 in case of need; Reaction process is emitted a large amount of heat and is taken away by high temperature water-supply, make temperature of reaction maintain a certain scope, and generation middle pressure steam 11, part is sent into combustion and steam combined cycle power plant 20 and is changed electric power 12 into, part is sent into carbon monoxide sulfur-tolerant water gas shift device 16 as reaction raw materials, and part is sent into desulfurization and decarburization equipment 17 and provided heat for the regeneration of absorption agent; When coal gasification apparatus 15 grades break down, the instead of natural gas 13 that stores in the instead of natural gas storage tank 19 can be sent into combustion and steam combined cycle power plant 20 to produce electric power 12.
The invention will be further described below by embodiment and accompanying drawing, but the present invention is not limited to embodiment.
Embodiment 1: 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.
Air 1 enters the oxygen 3 that air separation plant 21 makes, after being forced into 60-70bar and concentration be that the coal water slurry 2 of 60-70% enters coal gasification apparatus 15 together, coal gasification apparatus can adopt multiple structure formation, for example two-part, four nozzle opposed types or Texaco's form etc., vapor pressure is 55-65bar, temperature is 1300-1500 ℃, and the thick gasification gas of generation reclaims through sensible heat, and the high pressure steam 5 that produces 80-140bar is sent into combustion and steam combined cycle power plant 20; Thick gasification gas 4 after the cooling is 150-400 ℃, enters carbon monoxide sulfur-tolerant water gas shift device 16 transformationreation takes place, and used catalyzer is the cobalt-molybdenum catalyzer, hydrogen-carbon ratio is adjusted into be fit to methane synthetic 3: 1; Gasification gas 6 after adjusting enters desulfurization and decarburization equipment 17, is absorption agent with MDEA or NHD, removes wherein main organosulfur (H 2S) and inorganic sulfur (COS), reclaim elemental sulfur (S) 9 by Claus technology, carbon dioxide-enriched 8 is injected the oil field through pressurized liquefied back or is buried in the seabed to realize reduction of discharging; The clean synthetic gas 7 that obtains enters methanator 18 and generates instead of natural gas, the methane molar content can reach 93-96% in the instead of natural gas 10 behind the methanation reaction, being divided into three parts utilizes, part is sent into combustion and steam combined cycle power plant 20 and is acted as a fuel, to produce electric power 12, part is sent into gas distributing system as the city domestic gas, and there is small portion to deliver to instead of natural gas storage tank 19, in order to when coal gasification apparatus breaks down, from it instead of natural gas 13 is supplied with combustion and steam combined cycle power plant 20 and use, improve the available rate of full factory; The heat of the high-temperature gas after the adiabatic reaction and reaction process are emitted a large amount of heat and are taken away by high temperature water-supply, and make the isothermal reaction temperature maintenance at 250-300 ℃, the middle pressure steam 11 of the 40-60bar that produces, be divided into three strands, one is sent into combustion and steam combined cycle power plant 20 and changes electric power 12 into, one sends into carbon monoxide sulfur-tolerant water gas shift device 16 as reaction raw materials, and another strand sent into desulfurization and decarburization equipment 17 and provided heat for the regeneration of absorption agent.
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 (MJ/kg)
Mad Had Oad Nad Sad Cad Aad
2.52 3.85 12.73 0.36 0.46 69.94 10.14 27.7
Embodiment 2: directly mixing the adjusting hydrogen-carbon ratio with gasification gas 6 and coke-oven gas 14 is that 3: 1 these situations are example, thereby alleviate the load that carbon monoxide sulfur-tolerant water gas shift device carries out transformationreation, other organizational forms of technical process and processing parameter limit as embodiment 1.In embodiment 2,, calculate raw material consumption amount and entire system performance based on the product production that embodiment 1 calculates.
Present embodiment 2 used coke-oven gas composition and Lower heat value see Table 2.
Table 2 coke-oven gas composition and Lower heat value
H 2 CH 4 CO CO 2 N 2 O 2 H 2O C mH n LHV(MJ/kg)
58.10 24.90 5.86 2.35 3.90 0.39 2.35 2.15 37.9
Even if by, obtain system of the present invention and the processing method overall performance in embodiment 1 and embodiment 2 shown in the data of table 3.As can be seen from the table, based on the electric-substituted natural gas co-generation system and the technology of gasification of the present invention and methanation, except aforesaid advantage, system efficiency also increases than prior art.
Table 3 embodiment 1 and embodiment 2 overall performance data
System schema Embodiment 1 Embodiment 2
Coal-supplying amount (t/d) coke-oven gas consumption (Nm 3/ d) empty branch scale (tO 2/ d) delivery (MWe) instead of natural gas output (Nm 3/ d) instead of natural gas efficient (LHV) power supplying efficiency (LHV) system efficiency (LHV) 5000 0 3651 365.3 509492 73.2％ 37.4％ 45.1％ 683 4562096 472 348.2 509817 85.8％ 38.6％ 48.8％
Instead of natural gas efficient=instead of natural gas Lower heat value/raw material calorific value;
Power supplying efficiency=instead of natural gas efficient * combustion and steam combined cycle efficiency;
System efficiency=(instead of natural gas Lower heat value * instead of natural gas output+clean delivery)/raw material heat

Claims (7)

1. electric-substituted natural gas co-generation system based on coal-gasification methaneization is characterized in that this system comprises:
A) a combustion and steam combined cycle power plant (20);
B) an oxygenous air separation plant (21);
C) coal gasification apparatus (15) that produces high pressure steam and raw gas, this coal gasification apparatus is connected with air separation plant (21) by oxygen channel, by high pressure steam pipeline and combustion and steam combined cycle power plant;
D) a carbon monoxide sulfur-tolerant water gas shift device (16), the thick gasification gas that this carbon monoxide sulfur-tolerant water gas shift device makes coal gasification apparatus are adjusted into and are fit to methane synthetic gasification gas;
E) a desulfurization and decarburization equipment (17), this equipment removes organosulfur and the inorganic sulfur from the gasification gas that carbon monoxide sulfur-tolerant water gas shift device comes out, be connected with described carbon monoxide sulfur-tolerant water gas shift device by the gasification gas pipeline, and reclaim elemental sulfur (9), carbon dioxide-enriched (8);
F) methanator (18), the reaction back generates instead of natural gas, this reactor is connected with domestic fuel pipeline, instead of natural gas storage tank (19) and described combustion and steam combined cycle power plant respectively by the instead of natural gas pipeline, by steam-pipe be connected with desulfurization and decarburization equipment with combustion and steam combined cycle power plant, carbon monoxide sulfur-tolerant water gas shift device respectively.
2. one kind is adopted the electric-substituted natural gas joint process method based on coal-gasification methaneization of system according to claim 1, it is characterized in that this method carries out as follows:
1) air (1) enters oxygen (3) that air separation plant (20) makes and coal dust or coal water slurry (2) and enters coal gasification apparatus (15) together, the thick gasification gas (4) that produces reclaims through sensible heat, produces high pressure steam (5) and sends into combustion and steam combined cycle power plant (20) to produce electric power (12);
2) the thick gasification gas (4) after the cooling enters carbon monoxide sulfur-tolerant water gas shift device (16) generation transformationreation, is fit to methane synthetic hydrogen-carbon ratio to adjust; Gasification gas (6) after adjusting enters desulfurization and decarburization equipment (17), removes wherein organosulfur and inorganic sulfur, obtains clean synthetic gas (7), and reclaims elemental sulfur (9), and carbon dioxide-enriched (8) is to realize reduction of discharging;
The clean synthetic gas (7) that 3) will obtain is sent into methanator (18) and is generated instead of natural gas (10), part is as domestic gas, part is sent into combustion and steam combined cycle power plant (20) and is acted as a fuel to produce electric power (12), and part is sent into instead of natural gas storage tank (19) in case of need; The thermogenesis middle pressure steam (11) of emitting in the reaction process, part is sent into combustion and steam combined cycle power plant (20) and is changed electric power (12) into, and part is sent into carbon monoxide sulfur-tolerant water gas shift device (16), and part is sent into desulfurization and decarburization equipment (17).
3. the electric-substituted natural gas joint process method based on gasification and methanation as claimed in claim 2, it is characterized in that: the catalyzer that described carbon monoxide sulfur-tolerant water gas shift device uses is the cobalt-molybdenum catalyzer, and regulating suitable methane synthetic hydrogen-carbon ratio is 3: 1.
4. as claim 2 or 3 described electric-substituted natural gas joint process methods based on gasification and methanation, it is characterized in that: the reaction process in the described methanator of step 3) is carried out in two steps, the first step is carried out in temperature 500-600 ℃ adiabatic reactor, second step carried out in 250-300 ℃ isothermal reactor, and reaction pressure is 50～60bar; The heat that reaction process is emitted is 40-60bar with the middle pressure steam pressure that produces.
5. the electric-substituted natural gas joint process method based on gasification and methanation as claimed in claim 2, it is characterized in that: described coal gasification apparatus adopts coal dust or coal water slurry charging and sensible heat way of recycling, vapor pressure is 55-65bar, the high-pressure steam pressure that produces is 80～140bar, and the temperature of the thick gasification gas after the cooling is 150～400 ℃.
6. the electric-substituted natural gas joint process method based on gasification and methanation as claimed in claim 2, it is characterized in that: when when breaking down, the instead of natural gas (13) that stores in the instead of natural gas storage tank (19) being sent into combustion and steam combined cycle power plant (20) to produce electric power (12) at coal gasification apparatus (15).
7. the electric-substituted natural gas joint process method based on gasification and methanation as claimed in claim 2 is characterized in that: utilize gasification gas (6) after coke-oven gas (14) and the transformationreation directly to mix and regulate hydrogen-carbon ratio.
CN 200710117724 2007-06-22 2007-06-22 Combined system and process for producing electricity-substituted natural gas based on coal gasification and methanation Active CN100582201C (en)

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