CN101191084A - Multi-coproduction energy method and system by using coal gasification heat with methane reforming manner - Google Patents
Multi-coproduction energy method and system by using coal gasification heat with methane reforming manner Download PDFInfo
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- CN101191084A CN101191084A CNA200710177471XA CN200710177471A CN101191084A CN 101191084 A CN101191084 A CN 101191084A CN A200710177471X A CNA200710177471X A CN A200710177471XA CN 200710177471 A CN200710177471 A CN 200710177471A CN 101191084 A CN101191084 A CN 101191084A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000002309 gasification Methods 0.000 title claims abstract description 91
- 238000002407 reforming Methods 0.000 title claims abstract description 52
- 239000003245 coal Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 153
- 239000000126 substance Substances 0.000 claims abstract description 66
- 238000006057 reforming reaction Methods 0.000 claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 claims abstract description 49
- 239000003034 coal gas Substances 0.000 claims abstract description 28
- 239000003345 natural gas Substances 0.000 claims abstract description 28
- 239000002918 waste heat Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 239000012495 reaction gas Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 115
- 238000010248 power generation Methods 0.000 claims description 26
- 235000009508 confectionery Nutrition 0.000 claims description 24
- 239000000446 fuel Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 238000002485 combustion reaction Methods 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 3
- 238000005261 decarburization Methods 0.000 claims description 2
- 238000013022 venting Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 15
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000000629 steam reforming Methods 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000004939 coking Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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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]
-
- 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
-
- 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
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a polygeneration energy method and system using coal gasification sensible heat with methane reforming and relates to the electrical power and chemical industry production technical field. The system comprises a gasification subsystem, a methane reforming subsystem, a waste heat recovery subsystem, a chemical industrial synthesis subsystem and an electric power production subsystem. In the system and method, the high temperature gasification coal gas produced by a gasification furnace provides a methane steam reforming reactor with reaction heat in heat exchange mode; the heat transfer type reforming reactor replaces the prior radiating heat exchanger, converts the partial high-grade physical energy into the chemical energy of synthesis gas, mixes the gasification coal gas and the reforming reaction gas in different proportions according to the production requirement of chemical products by taking advantage of the characteristics that the gasification coal gas is rich in carbon and the reforming reaction gas is rich in hydrogen, saves the conversion flow in the prior production process of coal-based chemical industrial products, and decreases the energy consumption used for treating the methane in natural gas/coke-oven gas. The invention combines the chemical industry production and the electric power production, and effectively avoids the disadvantageous factors on the mutual energy utilization.
Description
Technical field
The present invention relates to a kind of based on coal, with the Poly-generation energy resource system of coal and Sweet natural gas, coal and two kinds of raw material production electric power of coke-oven gas and Chemicals, belong to electric power and chemical production technical field.
Background technology
High pressure, jumbo air flow bed coal gasification not only can clean, be that (integrated gasification combined cycle plants IGCC), also makes coal become a reality as the raw materials for production of Chemicals to electric power efficiently with coal conversion.Because the current resources situation of the rich coal weak breath of China, from the eighties in last century, China just notes introducing coal gasification production chemical product, and synthetic ammonia is a kind of.Pay attention to the application of coal gasification in recent years especially in chemical industry, except that original Texaco (now being the GE technology) gasification technology of introducing, successively introduce nearly 20 Shell vapourizing furnaces and GSP gasification technology again, being used to produce with methyl alcohol is end product or the Chemicals of intermediate product (as C-1 chemistry industry such as dme, various alkene).In addition, China also begins to drop into huge resource to quicken its development at gasification of coal clean electric power generation technical elements, in " optimal development energy industry " chapter of " China's national economy and social development 11th Five-Year Plan outline ", clearly proposed in 2006, " advance the clean coal generating, start integral coal gasification combustion gas one steam combined cycle engineering ".These effort that drop in advance all are coal-based or have laid a good foundation based on the development of the polygenerations systeme of coal.
The synthetic gas temperature that vapourizing furnace is produced is very high, has a large amount of high-grade heat energy, for the utilization of this part heat energy, and in the per unit area yield system of present different production purposes, people's treatment process difference.For being the energy resource system (IGCC) of purpose to produce electric power, whether the synthetic gas that comes out from vapourizing furnace is with sensible heat utilization, can influence the efficient of entire I GCC system, in general, can make entire I GCC system efficiency maximum differ about 3 to 4 percentage points.People do a lot of work at this problem, for example merely Texaco and Shell arranged with the physics mode utilization, the Texaco vapourizing furnace has a kind of flow process that has adopted the design of radiation recuperator and convection recuperator, produces steam with the sensible heat of synthetic gas and is sent to waste heat boiler exerting oneself with the increase steam cycle.Because the restriction of steam cycle initial temperature, the temperature of the water vapour that produces is usually below 600 ℃, and owing to ash fusion point, the synthetic gas temperature of vapourizing furnace outlet is usually more than 1300 ℃, exist huge heat transfer temperature difference, this part sensible heat to fail to obtain good utilization in the middle of the heat transfer process.Synthetic gas blending refrigerative method behind Shell stove employing high-temperature synthesis gas and the low temperature purification, make high-temperature synthesis gas be cooled to (in fact this cause very big available energy loss) about 900 ℃, again with waste heat boiler in water/water vapour heat exchange, because the steam that produces is sent to the steam turbine generating, therefore vapor temperature is usually also below 600 ℃, and heat transfer temperature difference is also very big.And two-stage gasifier (as the air gasification stove of Mitsubishi and the pure oxygen gasification stove of Xi'an thermal technology institute), the method that has partly adopted the sensible heat chemistry to utilize, promptly the high-temperature synthesis gas of first section outlet is used for providing part or all of gasification heat to second section, but vapourizing furnace syngas outlet temperature still about 1100 ℃, still need be provided with interchanger and add hot water/water vapour.These methods are not all utilized high-grade energy well.And for being for the per unit area yield system of purpose with the production chemical product, because Chemical Manufacture is more paid attention to material composition and high conversion (being the utilization of chemical energy) thereof for a long time, utilization to physical energy in the chemical system is paid little attention to, chemical process flow institute's heat requirement and steam are all from the lower general facilities of efficient, therefore in the system of per unit area yield Chemicals, angle from the investment of saving system, do not establish interchanger behind the vapourizing furnace, the vapourizing furnace high-temperature synthesis gas with a large amount of waste heats all discarded in vain.
Methyl alcohol is important chemical material, can produce numerous downstream Chemicals, as acetic acid, dme and MTBE etc.In addition, methyl alcohol also might become the vehicle fuel that accounts for lion's share and the fuel of distributed power supply.The main raw material that is used to produce methyl alcohol is Sweet natural gas, coal (containing coke(oven)gas) and oil, at present worldwide, is that the methyl alcohol of raw material production has comparative advantage with the Sweet natural gas, in the 31Mt methyl alcohol of producing in 2002, and the 91%th, with the Sweet natural gas raw material.Although China is the country of rich coal, production capacity of methanol reached 5Mt in 2003, with the Sweet natural gas be raw material account for 41%, this makes China's methyl alcohol industry rise under the situation present Gas Prices one tunnel young tiger and is faced with severe tests.Therefore develop the national conditions that the methyl alcohol industry must be considered the rich coal weak breath of China, should greatly develop with the coal is the methanol production system of raw material, originally is that the production system of raw material also should progressively be drawn close to coal-based system with the Sweet natural gas.Methyl alcohol-electric polygenerations systeme can improve the production model of the high as far as possible transformation efficiency of pursuit traditional in the Chemical Manufacture in addition, and can be low with parameter in the higher therrmodynamic system replacement chemical plant of parameter, inefficient power plant for self-supply improves the big present situation of chemical system energy consumption.
Sweet natural gas base methanol production present situation: be that raw material is produced in the process of methyl alcohol with the Sweet natural gas, at first needing Sweet natural gas (main component is a methane) is changed into synthetic gas (CO+H
2), method for transformation mainly is divided three classes: 1. one section steam reforming is traditional method, but because the synthetic gas hydrogen-carbon ratio after transforming is higher, so some factory can mend carbonic acid gas again; 2. steam reforming reaction is promptly carried out in two sections conversions of hot type (method that can realize domesticizing) in primary reformer, adds pure oxygen and carry out the part catalytic oxidation in the autothermal secondary reformer, to reach suitable hydrogen-carbon ratio; 3. two sections conversions of heat exchange type (advanced method that needs further exploitation or introduce), promptly the high-temperature gas by the secondary reformer outlet directly provides one section heat that steam reforming is required, and primary reformer does not need extraneous heating basically.Above-mentioned this three classes technology all needs to consume the Sweet natural gas that a part acts as a fuel, and provides compression work for natural gas conversion processes provides heat and various unstripped gas, recycle gas compressor.
One section conversion of Sweet natural gas steam is the method for raw materials for production gas traditional in the Sweet natural gas base methanol process flow process, but owing to need to adopt a part of Sweet natural gas to act as a fuel, and gained synthetic gas hydrogen content is higher, so energy consumption is bigger.In patent is called with " hydrocarbon gas and coal are the method (CN1699316) of raw material production methyl methanol syngas ", though also considered rich carbon of producing synthesis gas from coal and the hydrogen-rich characteristics of hydrocarbon gas preparing synthetic gas it is mixed and made into the methyl alcohol synthetic raw gas, this method still needs the carbon monodixe conversion process.
Coke-oven gas utilizes present situation: according to statistic data, the coke output of China in 2003 has reached 1.6 hundred million tons, account for three/the last one of whole world coke output, the 1-10 month in 2006, Chinese coke output was 22,620 ten thousand tons, increase by 17.2% compared with the same period of last year, the high speed development like this of China's coking industry causes China's coking industry to show Three Difficult Issues especially, and the utilization of coke-oven gas is exactly one of them.Different according to the coking type of furnace and ature of coal condition, when raw coal was converted into coke, coal tar per ton can produce 300 ~ 400m
3Coke-oven gas is by 320 m
3/ ton coal tar calculates, and produces coke-oven gas 86,400,000,000 m per year
3, only the coke-oven gas of association in coking in Shanxi Province's every year just reaches 270-360 hundred million m
3, most coke-oven gas are directly burnt or emptying, and this is contaminate environment not only, also causes the huge waste of the energy, is hydrogen because the coke-oven gas mole is formed over half, and hydrogen is important chemical material, and is as shown in table 1.
Table 1 coke-oven gas is formed
The dry gas mole is formed (%) | Calorific value | |||||
H 2 | CH 4 | CO | C mH n | CO 2 | N 2 | |
56-60 | 23-27 | 5-8 | 2-4 | 1.5-3.0 | 0.3-0.8 | kJ/m 3 |
Impurity mass concentration (g/m 3) | ||||||
Tar | Clumsy | Cyanogen | HS | HCN | Naphthalene | 17000-18000 |
Trace | 2-5 | 0.05 | 0.02 | 0.3 | 0.3 |
If can rationally utilize coke-oven gas, can reduce the raw material consumption and the energy consumption of chemical industry greatly.People recognize this problem gradually, have proposed some one after another and have utilized approach, and are as shown in table 2.As seen from table, primary CO and H in the coke-oven gas
2Molar ratio be about 1: 10, therefore, must adopt the reformation technology with the CH in the coke-oven gas if utilize Chemicals in the synthetic table 2 of coke-oven gas
4Be converted into CO and H
2, as transforming or steam reforming by pure oxygen.
Table 2 Chemicals
CO∶H 2 | Product |
1∶3 | Methane |
1: 1 or 1: 2 | Alkane and |
1∶1 | The branched-chain hydrocarbon of gas and |
1∶1 | |
1∶2-1∶3 | |
1∶1.5-1∶2 | The mixture of alcohol, aldehyde, ketone, ester, acid |
In Chemical Manufacture, usually adopt and pursue the production model of high conversion as far as possible, i.e. the unstripped gas synthesizing methanol that all circulates, the indifferent gas in the circulation gas is constantly accumulated, need often discharging in order to avoid influence transformation efficiency, so the indifferent gas content in the fresh feed gas can not be too high.The molar percentage of methane accounts for about 25% in the coke-oven gas, and reaction is quite disadvantageous to methyl alcohol for this, and methane must change into synthetic gas.From the angle of chemical reaction, what methane was transformed is thorough more good more, therefore will pay a high price.With two patents of utilizing coke-oven gas to produce synthetic gas is that example-heat exchange type coke-oven gas pressurized catalysis partial oxidation is produced the technology (01116056.X) of synthetic gas and hydrocarbon gas is the apparatus and method (03115819.6) that raw material non-catalytic partial oxidation method is produced synthetic gas, in order not introduce inert nitrogen gas, all adopt to coke-oven gas and feed pure oxygen, with hydrogen in the coke-oven gas and methane generation oxidizing reaction to provide reforming reaction required heat.Adopt this class technology, except will expending a large amount of pure oxygens, also will increase air separation plant, converter (similar) and heat-exchange equipment with vapourizing furnace.
And exist a large amount of high temperature sensible heats to remain to be utilized in the gasification system, therefore take all factors into consideration from above two aspects, the present invention is from the angle of coal and Sweet natural gas/coke-oven gas comprehensive utilization, with chemical system and power generation system organic combination, a kind of polygenerations systeme method of utilizing the gasification sensible heat in the methane reforming mode has been proposed, be a kind of, can comprehensively, efficiently utilize the new system of coal and Sweet natural gas/coke-oven gas based on coal.
Summary of the invention
The objective of the invention is the problem of utilizing at present gasification of coal high temperature sensible heat, and the higher drawback of gas/water steam chemical industry production energy consumption, a kind of Poly-generation energy resource system that utilizes the gasification sensible heat in the methane reforming mode is proposed, this system can chemical mode reclaims the sensible heat of high-temperature coal gasification synthetic gas, Chemical Manufacture and electrical production are combined, thereby avoid energy each other to utilize the unfavorable factor of aspect.
Technical scheme of the present invention is as follows:
Utilize the Poly-generation energy resource system of gasification sensible heat in the methane reforming mode, it is characterized in that this system comprises:
A) the gasification subsystem 1, is used to produce high-temperature gasification coal gas 8;
B) methane reforming subsystem 2, this subsystem comprises reforming reactor and interchanger, the high-temperature gasification coal gas 8 that is come out by the gasification subsystem provides reaction heat for reforming reactor;
C) waste heat recovery subsystem, the sensible heat and the high-temperature gasification coal gas remaining sensible heat after the reforming reaction heat exchange that are used for reforming reaction gas 12 that the methane reforming subsystem is made reclaim, produce middle pressure steam 10 and high pressure steam 18, middle pressure steam is sent into the methane reforming subsystem;
D) Chemical Manufacture subsystem 4, partial gasification coal gas 14 after reforming reaction subsystem and the heat exchange of waste heat recovery subsystem is raw material to this subsystem through gas after the heat exchange of waste heat recovery subsystem and high-temperature gasification coal gas 8 with reforming reaction gas 12, produces needed Chemicals;
E) power generation sub-system 5, this subsystem adopts the combustion and steam association circulating power generation system, internal combustion turbine with high-temperature gasification coal gas 8 after reforming reaction subsystem and the heat exchange of waste heat recovery subsystem residue gasification gas 14 and speeding of producing of chemical industry subsystem to exit 19 be fuel, the high-temperature vapor that is produced by the waste heat recovery subsystem is sent to the steam turbine of power generation sub-system.
Provided by the inventionly a kind ofly utilize the gasification sensible heat to produce the processing method of carbon one Chemicals and electric power simultaneously, it is characterized in that this method comprises the steps: in the methane reforming mode
1) utilizes coal 6 and pure oxygen 7 in gasification subsystem 1, to gasify and produce high-temperature gasification coal gas 8, enter methane reforming subsystem 2 then, provide reaction institute heat requirement to the methane reforming reaction that with Sweet natural gas/coke-oven gas and middle pressure steam is raw material in the mode of heat exchange; The pressure of described middle pressure steam is 15~20bar; The reforming reaction temperature is 850 ℃~920 ℃;
2) utilize sensible heat and high-temperature gasification coal gas remaining sensible heat after the reforming reaction heat exchange of the reforming reaction gas 12 that the waste heat recovery subsystem makes the methane reforming subsystem to reclaim, production high pressure steam 18 supplies with power generation sub-system, produce middle pressure steam 10 offers reformation subsystem 2 as reactant;
3) the partial gasification coal gas 14 of high-temperature gasification coal gas 8 after reforming reaction subsystem and the heat exchange of waste heat recovery subsystem, mix with the reaction gas of reforming reaction gas 12 after the heat exchange of waste heat recovery subsystem, unstripped gas as Chemical Manufacture, the component of unstripped gas is according to the production requirement of specific product, allocate in proportion by reforming reaction gas and gasification gas, after the part unreacting gas mixes, carry out building-up reactions through decarburization, pressurization back; Another part gasification gas is sent to power generation sub-system, exits with speeding as the fuel of power generation sub-system internal combustion turbine, and the high-temperature vapor that is produced by the waste heat recovery subsystem is sent to the power generation sub-system steam turbine.
Carbon one Chemicals described in the present invention are methyl alcohol, dme or alkene.
The present invention has the following advantages and the high-lighting effect: this system replaces traditional radiation recuperator with heat exchange type methane vapor reforming reactor, part higher-grade physical energy is converted into the chemical energy of synthetic gas, and utilize rich carbon of gasification gas and the hydrogen-rich characteristics of reforming reaction gas, according to the production requirement of Chemicals the two being pressed different ratios mixes, remove the shift process in traditional coal-based Chemicals production process from, and reduced the energy consumption that Sweet natural gas/coke-oven gas is handled.In this polygenerations systeme, the sensible heat of coal gas of high temperature is recycled with chemical mode, provide reaction institute heat requirement to methane reforming, need not other consume fuel and produce high-temperature flue gas.In addition, the rich carbon synthetic gas of reformation gained hydrogen-rich synthetic gas (reformation afterreaction gas) and gasification of coal gained (gasification gas) is according to the different ratios blending, can provide synthetic raw gas to the chemical industry synthesis system according to optimal proportion, and hydrogen-rich synthetic gas need not to mend carbon, and rich carbon synthetic gas need not conversion.Chemical Manufacture and electrical production are combined, and effectively having avoided each other, energy utilizes the aspect unfavorable factor.
Description of drawings
Fig. 1 the present invention is with the polygenerations systeme schematic flow sheet of coal and Sweet natural gas/coke-oven gas while production chemical product and electric power.
Fig. 2 methane reforming subsystem of the present invention synoptic diagram.
Fig. 3 is the process flow sheet of chemical industry synthon system specific embodiment.
Among the figure: 1-gasification subsystem; 2-methane reforming subsystem; 3-waste heat recovery subsystem; 4-chemical industry synthon system; The 5-power generation sub-system; The 6-coal; 7-oxygen; The 8-gasification gas; Press steam among the 10-; 11-Sweet natural gas or coke-oven gas; 12-reforming reaction gas; The 14-gasification gas; The 17-water coolant; 18-high-temperature vapor 19-off-gas; The 20-flue gas; The 21-methanol product; 22-; The 23-reforming reactor; 25-reforming reaction pipe; The 26-decarbonizing tower; The 27-carbonic acid gas; 28-fresh feed gas; 29-virgin gas compressor; The 30-recycle gas compressor; 31-circulation gas; The 32-synthetic raw gas; The 33-synthetic tower; The 34-interchanger; The 35-refined unit
Embodiment
Provided by the inventionly utilize the Poly-generation energy method of gasification sensible heat and system mainly to comprise following five subsystems: gasification subsystem 1, methane reforming subsystem 2, waste heat recovery subsystem 3, chemical industry synthon system 4 and power generation sub-system 5 in the methane reforming mode.
The present invention is further described below in conjunction with drawings and Examples.
See also Fig. 1, provided by the inventionly utilize the Poly-generation energy method of gasification sensible heat and system mainly to comprise following five subsystems: gasification subsystem 1, methane reforming subsystem 2, waste heat recovery subsystem 3, chemical industry synthon system 4 and power generation sub-system 5 in the methane reforming mode.After gasifying, coal 6 and pure oxygen 7 produce high-temperature gasification coal gas 8 in gasification subsystem 1, enter methane reforming subsystem 2 then, methane reforming reaction in Sweet natural gas/coke-oven gas provides heat, gasification gas after reacted reforming reaction gas 12 and the heat exchange enters 3 heat releases of waste heat recovery subsystem respectively, and production high pressure steam 18 is supplied with power generation sub-system 5 generatings, a small amount of middle pressure steam 10 of production offers reformation subsystem 2 as reactant.Cooled reforming reaction gas is all sent into chemical industry synthon system 4, cooled gasification gas 14 component and quantity according to reforming reaction gas, part is sent into production chemical product 21 in the chemical industry synthon system 4, then off-gas 19 is sent into power generation sub-system 5, as the fuel of power generation sub-system.
Figure 2 shows that the schematic flow sheet of methane reforming subsystem 2 provided by the invention.Sweet natural gas or coke-oven gas 11 and mix the back from the middle pressure steam 10 of waste heat recovery subsystem 3 and form unstripped gass, unstripped gas enters reforming reactor 23 and carries out reforming reaction then, and the gasification gas 8 that is come out by gasification subsystem 1 provides reforming reaction heat.Reforming reactor is a heat exchange type, is made of reforming reaction pipe 25 and burner hearth, is filled with catalysts in the pipe.Methane/the steam reforming reaction that takes place in the reaction tubes, reforming reaction pressure are 15~20bar; The reforming reaction temperature is 850 ℃~920 ℃.Its reaction equation is:
CH
4+H
2O→3H
2+CO
CO+H
2O →H
2+CO
2
Methane/steam reforming reaction is a strong endothermic reaction, and reforming reaction institute heat requirement is provided with heat exchange mode by the high-temperature synthesis gas of gasification subsystem outlet.
Waste heat recovery subsystem provided by the invention, reaction gas sensible heat that the methane reforming subsystem is made and gasification gas remaining sensible heat after the reforming reaction heat exchange reclaims, and is used for preheating reforming reactants and production high pressure superheated steam and supplies with power generation sub-system, produces middle pressure steam and be used for reforming reaction.
Chemical industry synthon provided by the invention system can produce multiple Chemicals, its unstripped gas is formed and can be allocated in proportion by reforming reaction gas and gasification gas according to the production requirement of specific product, to satisfy concrete production requirement, methyl alcohol-electric polygenerations systeme for example, dme-electric polygenerations systeme.Reforming reaction gas is because rich hydrogen (hydrogen is the valuable raw material during chemical industry synthesizes), therefore all be sent to chemical industry synthon system, the rich carbon of gasification gas, according to the reforming reaction tolerance of gained, according to the synthetic best hydrogen-carbon ratio that requires of chemical industry, part is sent to the chemical industry subsystem, after the two mixing, the purification, compressed machine carries out building-up reactions after being compressed to the synthetic required pressure of chemical industry, and thick product is separated off-gas supply capability subsystem from refined unit.
Figure 3 shows that methyl alcohol synthon system schematic of the present invention.Reforming reaction gas after the heat exchange and partial gasification coal gas are sloughed the fresh feed gas 28 behind the carbonic acid gas 27 in decarbonizing tower 26, send into fresh feed air compressor 29 boost the back with send into recycle gas compressor 30 after recycle feed gas 31 mixes and boost, reach synthetic raw gas 32 behind the methyl alcohol synthesis pressure and pass through and send into synthetic tower 33 behind the preheaters and carry out methyl alcohol and synthesize.Sintetics is through the refining methanol product 21 that obtains, and part unreacting gas 31 continues to participate in building-up reactions as circulation gas, and off-gas 19 outputs to power generation sub-system and acts as a fuel.
Power generation sub-system provided by the invention, be the combustion and steam association circulating power generation system, internal combustion turbine is a fuel with the residue gasification gas and the venting of speeding, and the high-temperature vapor that water vapour that combustion turbine exhaustion produces and waste heat recovery subsystem produce is sent into the steam turbine generating.
Embodiment:
Table 3 reforming reactor exit gas composition (gas renormalizing)
Project name | CO | H 2 | CO 2 | H 2O | CH 4 |
Molar content (%) | 9.0 | 48.4 | 5.4 | 33.8 | 3.5 |
Because the rich hydrogen of the synthetic gas behind the methane reforming, therefore the rich CO of gasification gained synthetic gas can access the two during by the different ratios blending synthetic raw gas of different hydro carbon ratio.What the restriction of coal gas high-temperature sensible heat because the synthetic gas quantity that is obtained by methane reforming is gasified, comparatively small amt, therefore all synthetic with methyl alcohol, carry out blending and from gasification gas, extract part or all of synthetic gas, the definition splitting ratio
Under the methane reforming reaction condition that this paper adopts, the H2/CO value after the blending and the relation of splitting ratio as shown in Figure 4, splitting ratio is big more, the H2/CO value is more little, this is owing to the higher reason of carbon monoxide content in the gasification gas institute preparing synthetic gas.
The contrast of coal and natural gas double-fuel methyl alcohol-electric power polygenerations systeme and branch product system is as shown in table 4, when the methyl alcohol of producing as much and electric power, because it is the system for methanol synthesis comparison minimum with present energy consumption that methyl alcohol divides the product system, therefore the gas consumption in the polygenerations systeme is slightly high, adds up to fuel consumption but the total fuel consumption of system still is lower than branch product system.
Table 4 coal and Sweet natural gas polygenerations systeme contrast with dividing the product system
Project | Polygenerations systeme | Coal-based IGCC | Sweet natural gas base methyl alcohol | Divide to produce and add up to |
Total fuel consumption (MW) | 745 | 658 | 117 | 775 |
Consume Sweet natural gas (MW) | 123 | 0 | 117 | 117 |
The consumption of coal that disappears (MW) | 622 | 658 | 0 | 658 |
Methanol output (MW) | 92 | 0 | 92 | 92 |
Output net work (MW) | 279 | 279 | 0 | 279 |
Table 5 reforming reactor exit gas composition (coke-oven gas reformation)
Project name | CO | H 2 | CO 2 | H 2O | CH 4 |
Molar content (%) | 7.9 | 53.1 | 3.5 | 27.3 | 3.2 |
Fig. 5 is with behind the methane reforming utilization gasification sensible heat in the coke-oven gas, the relation of splitting ratio and hydrogen-carbon ratio, because coke-oven gas itself contains a large amount of hydrogen, therefore identical gasification sensible heat can be handled more coke-oven gas, so comparison diagram 4 and Fig. 5 are as can be known, under identical hydrogen-carbon ratio, the splitting ratio of coal and coke-oven gas system is bigger, be that more gasification gas can participate in blending and prepares unstripped gas, it is synthetic to carry out methyl alcohol.
With the coke-oven gas is the methanol production system of raw material, owing to contain the methane of 25% volume fraction of having an appointment in the coke-oven gas, in the methyl alcohol building-up process, methane belongs to rare gas element, be unfavorable for building-up process, especially in traditional vapor phase process flow process, because unreacting gas circulates in a large number, methane can build up in unstripped gas, need be useful gas composition with methane conversion therefore.In two kinds of patents that methane is handled at coke-oven gas, because non-catalytic partial oxidation method oxygen-consumption is smaller, so coke-oven gas base methyl alcohol reference system adopts method in the patent (03115819.6) in the table 6.
The contrast of coal and coke-oven gas methyl alcohol-electric power polygenerations systeme and reference system is as shown in table 6, and when the methyl alcohol of exporting as much and electric power, the polygenerations systeme fuel consumption is less than the total fuel consumption of branch product system.
Table 6 coke-oven gas/coal polygenerations systeme contrasts with dividing the product system
Project | Polygenerations systeme | Coal-based IGCC | Coke(oven)gas base methyl alcohol | Divide to produce and add up to |
Total fuel consumption (MW) | 910 | 728 | 247 | 975 |
Consume coke(oven)gas (MW) | 288 | 0 | 247 | 247 |
The consumption of coal that disappears (MW) | 622 | 728 | 0 | 728 |
Methanol output (MW) | 92 | 0 | 92 | 92 |
Output net work (MW) | 279 | 279 | 0 | 279 |
Claims (3)
1. utilize the Poly-generation energy resource system of gasification sensible heat in the methane reforming mode, it is characterized in that this system comprises:
A) gasification subsystem (1) is used to produce high-temperature gasification coal gas (8);
B) a methane reforming subsystem (2), this subsystem comprises reforming reactor and interchanger, the high-temperature gasification coal gas (8) that is come out by the gasification subsystem provides reaction heat for reforming reactor;
C) waste heat recovery subsystem, the sensible heat and the high-temperature gasification coal gas remaining sensible heat after the reforming reaction heat exchange that are used for reforming reaction gas (12) that the methane reforming subsystem is made reclaim, produce middle pressure steam (10) and high pressure steam (18), middle pressure steam is sent into the methane reforming subsystem;
D) a Chemical Manufacture subsystem (4), partial gasification coal gas (14) after reforming reaction subsystem and the heat exchange of waste heat recovery subsystem is raw material to this subsystem through gas after the heat exchange of waste heat recovery subsystem and high-temperature gasification coal gas (8) with reforming reaction gas (12), produces needed Chemicals;
E) power generation sub-system (5), this system adopts the combustion and steam association circulating power generation system, internal combustion turbine be a fuel with the residue gasification gas (14) and the venting (19) of speeding that produces of chemical industry subsystem of high-temperature gasification coal gas (8) after reforming reaction subsystem and the heat exchange of waste heat recovery subsystem, is sent to the steam turbine of power generation sub-system by the high-temperature vapor of waste heat recovery subsystem generation.
2. adopt according to claim 1 that a kind of of system utilizes the gasification sensible heat to produce the processing method of carbon one Chemicals and electric power simultaneously in the methane reforming mode, it is characterized in that this method comprises the steps:
1) utilizes coal (6) and pure oxygen (7) in gasification subsystem (1), to gasify and produce high-temperature gasification coal gas (8), enter methane reforming subsystem (2) then, provide reaction institute heat requirement to the methane reforming reaction that with Sweet natural gas/coke-oven gas and middle pressure steam is raw material in the mode of heat exchange; The pressure of described middle pressure steam is 15~20bar; The reforming reaction temperature is 850 ℃~920 ℃;
2) utilize sensible heat and high-temperature gasification coal gas remaining sensible heat after the reforming reaction heat exchange of the reforming reaction gas (12) that the waste heat recovery subsystem makes the methane reforming subsystem to reclaim, production high pressure steam (18) supplies with power generation sub-system, produce middle pressure steam (10) offers reformation subsystem (2) as reactant;
3) the partial gasification coal gas (14) of high-temperature gasification coal gas (8) after reforming reaction subsystem and the heat exchange of waste heat recovery subsystem, mix with the reaction gas of reforming reaction gas (12) after the heat exchange of waste heat recovery subsystem, unstripped gas as Chemical Manufacture, the component of unstripped gas is according to the production requirement of specific product, allocate in proportion by reforming reaction gas and gasification gas, after the part unreacting gas mixes, carry out building-up reactions through decarburization, pressurization back; Another part gasification gas is sent to power generation sub-system, exits with speeding as the fuel of power generation sub-system internal combustion turbine, and the high-temperature vapor that is produced by the waste heat recovery subsystem is sent to the power generation sub-system steam turbine.
3. utilize the gasification sensible heat processing method of production chemical product and electric power simultaneously according to claim 2 is described in the methane reforming mode, it is characterized in that: described carbon one Chemicals are methyl alcohol, dme, alkene.
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