CN102060662B - Chemical power poly-generation energy system and method for recycling CO2 - Google Patents

Chemical power poly-generation energy system and method for recycling CO2 Download PDF

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CN102060662B
CN102060662B CN2010105844287A CN201010584428A CN102060662B CN 102060662 B CN102060662 B CN 102060662B CN 2010105844287 A CN2010105844287 A CN 2010105844287A CN 201010584428 A CN201010584428 A CN 201010584428A CN 102060662 B CN102060662 B CN 102060662B
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gas
gasification
reactions
building
internal
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CN2010105844287A
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CN102060662A (en
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冯杰
易群
李文英
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太原理工大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/16Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/16Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

Abstract

The invention relates to the technical fields of energy sources and environment and discloses chemical power poly-generation energy system and method for recycling CO2. In the system, coal gas obtained by gasifying a carbon-rich raw material, and a hydrogen-rich raw material, namely, coke oven gas, are mixed and subjected to a reforming reaction and a chemical synthesis reaction to obtain a reaction product, the reaction product is processed in a flash evaporation process and a rectification process for separation to obtain CO2 gas and a final product, one part of the CO2 gas separated from a rectifying tower is delivered to take part in the gasification process of the carbon-rich raw material, and the other part of the CO2 is delivered to take part in the reforming reaction. By means of the system and the method provided by the invention, the CO2 separated in the rectifying process is used as feed gas to be directly recycled by the system so that a water gas shift reaction, chemical-looping combustion and other methods with higher energy-consumption performance for improving the chemical concentration of the CO2 are avoided, the problems of reduced energy system efficiency caused by the separation of CO2 and difficulties in transporting and storing large amount of CO2 are solved, and thus, a dual-effect production mode for energy-saving and environmental-protection utilization of resources is realized.

Description

A kind of recyclable CO that utilizes 2Chemical industry power Poly-generation energy resource system and method

Technical field

The present invention relates to derived energy chemical and environmental technology field, particularly relate to a kind of chemical industry power Poly-generation energy resource system and method for energy-conserving and environment-protective.

Background technology

China's energy structure is based on coal, and coal is as the fossil energy of high carbon emission, and its traditional direct burning utilizes mode and transformation technology efficiency of energy utilization low (being about 35%-38%), CO 2Discharging is serious, and China was as far back as CO in 2007 2Quantity discharged has just surpassed the U.S., ranks first in the world.In the Kyoto Protocol agreement, and in " Copenhagen meeting ", China all represents to play an active part in CO 2Reduce discharging, and China is in industrial great development period, this makes China bear huge pressure aspect politics, economy and the environment undoubtedly.The energy general layout of the rich charcoal oil starvation of China, make the liquid fuel critical shortage again, China just became net oil importer from oil exportiog countries from 1993, and demand increases always, higher threat is to national energy security, and it is very urgent to seek new coal-based liquid alternative fuel.On the other hand,, but seem obviously not enough for the utilization of coke-oven gas as coking big country, basically based on burning (29,000,000,000 Nm3,2004), in the coke-oven gas hydrogen content up to 60%, CH 4Content is about 25%, and this direct incendiary utilizes mode, and not only energy utilization efficiency is low, and has wasted valuable hydrogen resource.Therefore, how to realize the reasonable trans-utilization of coal resources and coke-oven gas, low to solve energy utilization efficiency, problems such as environmental pollution is serious, liquid fuel shortage just merit attention.

In the face of the pressure of the above energy and environmental problem, new coal utilization technology obtains extensive concern and development.Whole coal gas combined cycle (IGCC) power generation system, and the chemical-power multi-combined production system that grows up on this basis promoted the degree of utilizing of the energy to a great extent, makes energy utilization efficiency improve 7%-10% on the original basis.At present, existing in the world many commercial demonstration projects, although improved utilization efficiency of energy in technology and technologic improvement,, for reducing CO significantly 2Discharging seem that still some is powerless.For this reason, based on CO 2The IGCC polygenerations systeme that captures storing technology (Carbon Capture and Storage is called for short CCS) obtains further research and development.Most of at present CO that reduces discharging 2Approach mostly is to utilize methods such as water gas shift reaction, membrane separation technique, chemical chain burning technology to improve CO 2Concentration, thereby reach CO 2Isolating purpose.Although these technology can reduce CO to a great extent 2Discharging, but CO 2The energy consumption of separating energy consumption and air separation facility is also quite big, as the CO of system's reduction of discharging more than 70% 2The time, the system capacity utilising efficiency only is 35%-37%.These reduction of discharging approach all are earlier CO to be converted into CO 2, and then carry out CO 2Separate, not only wasted valuable CO resource, also increased separating energy consumption.In addition, isolated a large amount of CO 2Processing also need to consider the present CO of China 2Annual requirement is 1,000,000 tons/year of less thaies also, the CO that separates 2Far above the demand ability to bear, for CO 2Although underground processing of sealing up for safekeeping obtains the approval of a plurality of countries in the world, also only rest on simulation and laboratory stage at present, and the risk of ground storage is bigger, CO 2Pipeline transportation equipment harshness, the cost height does not obtain the approval of developed countries such as the European Union and the U.S..

From top progress as can be seen, the improvement by technology can improve the system capacity utilising efficiency, but keeps away unavoidable CO 2Emission problem.Otherwise, can realize CO by the improvement of technology 2Reduction of discharging, but make the system capacity utilising efficiency descend, the CO that separates simultaneously 2Handle and also have some technical difficult problems.Be not difficult to obtain energy utilization efficiency and CO 2Reduction of discharging is an opposition, paradox, how to solve this contradiction, when reaching system's greater efficiency, realizes CO 2Reduction of discharging, avoid CO 2Separate, and CO 2Problems such as subsequent disposal realize that finally production system energy-saving and emission-reduction double effects just seems particularly crucial and important.

Summary of the invention

The object of the present invention is to provide a kind of recyclable CO of utilization 2Chemical industry power Poly-generation energy resource system and method, to solve separation of C O 2The energy consumption height, transport and bury CO 2Problems such as difficulty and safety coefficient are low.

For achieving the above object, the invention provides a kind of recyclable CO of utilization 2Chemical industry power Poly-generation energy resource system, this system comprises: gasification unit is used for receiving unit from this internal system round-robin CO 2Gas, and will comprise this CO 2Gas, oxygen, water vapour and carbon-rich materials are made raw gas at interior mixture; The synthetic gas sensible heat reclaims and clean unit, is used for most of sensible heat is lowered the temperature, reclaimed to this raw gas and being refined into clean gasification gas; Reformer unit is used for receiving unit from this internal system round-robin CO 2Gas, and will comprise this CO 2The mixed gas of the gasification gas of gas and described cleaning carries out reforming reaction and prepares the new gas of building-up reactions; The chemical industry synthesis unit is used for the new gas of this building-up reactions is carried out building-up reactions preparation feedback product; Flasher is used for this reaction product is isolated thick product stream; Rectifying tower is used for making with extra care this thick product stream for chemical end-products and isolating CO 2Gas, wherein, this isolated CO 2Gas is described internal system round-robin CO 2Gas is again with this CO 2Gas separates according to a certain percentage, is sent to reformer unit and gasification unit respectively, finishes described CO 2Gas is in the recycle of internal system.

Preferably, this system is methyl alcohol-electric power polygenerations systeme or dimethyl ether-electric power polygenerations systeme, and described carbon-rich materials is coal, heavy oil, refinery coke or biological particles.

Preferably, the mixed gas of described participation reforming reaction comprises the gasification gas and the described internal system round-robin of the part CO of coke-oven gas, described cleaning 2Gas, wherein, reforming reaction is with the CH in the described gas mixture 4And CO 2Be converted into CO and H 2

For achieving the above object, the invention provides a kind of recyclable CO of utilization 2Chemical industry power Poly-generation method, this method comprises: steps A, will the part from internal system round-robin CO 2Gas, oxygen, water vapour and carbon-rich materials are in interior mixture gasification and be refined into purified gasification gas; Step B will comprise that described purified gasification gas and part are from internal system round-robin CO 2The mixed mixed gas of gas carries out reforming reaction and prepares the new gas of building-up reactions; Step C carries out building-up reactions preparation feedback product with the new gas of described building-up reactions, more described reaction product is isolated thick product stream; Step D, described thick product stream is refining for chemical end-products and isolate CO 2Gas, this isolated CO 2Gas is described internal system round-robin CO 2Gas is again with described CO 2Gas separates according to a certain percentage, and with internal system round-robin CO 2Gas is sent to respectively participates in described reforming reaction and described gasification, finishes this CO 2Gas is in the recycle of internal system.

Preferably, adopt rectifying that described thick product stream is isolated chemical end-products and CO among the described step D 2Gas.

Preferably, the described mixed gas that carries out reforming reaction among the described step B comprises the gasification gas of coke-oven gas, described cleaning and the CO that the described systemic circulation of part is utilized 2, wherein, reforming reaction is with the CH in the described mixed gas 4And CO 2Be converted into CO and H 2

Preferably, described step C comprises flash vaporization process, this flash vaporization process is isolated thick product stream and unreacting gas logistics with described reaction product, described unreacting gas logistics is further divided into circulation gas and circulation gas two portions not, wherein, circulation gas returns continue to participate in building-up reactions, and circulation gas does not act as a fuel directly burning providing reforming reaction required heat, or the combustion power generation that acts as a fuel.

Preferably, be sent to the CO that participates in reforming reaction and described gasification described in the step D respectively 2Molar flow is than being 0.2-4.5.

More preferably, in the aforesaid method, the molar ratio of described gasification gas and coke-oven gas is by CO and H in the new gas of the desired building-up reactions of described chemical end-products 2Mol ratio size decision.

More preferably, in the aforesaid method, the described molar flow of the circulation gas of building-up reactions and circulation gas not of participating in again is than being 0.3-4.2.

The invention has the advantages that and cancelled traditional skill upgrading CO such as water gas shift reaction, burning chemistry chains that utilize 2Concentration and separation of C O 2Production model, make the CO that produces in the system 2Can turn back to recycle in the unit of system, overcome at present owing to reclaim CO 2The defective that the energy utilization efficiency that causes descends has significantly been avoided recovery CO especially 2Storage, the risk of burying, truly realized the multiple effect of production system energy-saving and emission-reduction economy; In addition, the present invention has cancelled the water gas shift reaction adjustment synthetic gas CO/H that present chemical-process generally adopts 2The production model of ratio is used CO instead 2/ CH 4Reforming reaction is with CO 2And CH 4Be converted into CO and H 2, rationally utilized the characteristics of rich hydrogen of coke-oven gas and the rich carbon of gasification gas, with the two organic coupling and trans-utilization, reduced the consumption of water resources and the discharging of greenhouse gases, increased synthetic new gas active principle (CO+H 2) content, realized that coal and coke-oven gas efficiently utilize.

Description of drawings

Fig. 1 is a kind of recyclable CO that utilizes provided by the invention 2Chemical industry power Poly-generation energy resource system structural representation.

Fig. 2 is a kind of recyclable CO that utilizes provided by the invention 2Chemical industry power Poly-generation energy resource system process flow sheet.

Fig. 3 is for the invention provides a kind of recyclable CO of utilization 2Coal-based dimethyl ether-electric power Poly-generation energy resource system process flow diagram.

Embodiment

The purpose, technical solutions and advantages of the present invention are more clear understands that below in conjunction with instance analysis, and with reference to accompanying drawing, the present invention is described in more detail in order to make.

Fig. 1 is a kind of recyclable CO that utilizes provided by the invention 2Chemical industry power Poly-generation energy resource system structural representation, this system has comprised that gasification unit 1, synthetic gas sensible heat reclaim and clean unit 2, reformer unit 3, chemical industry synthesis unit 4, flasher 5, rectifying tower 6, reformation auxiliary unit 7, combined cycle generation unit 8.Wherein, reformer unit 3 comprises first interchanger and reforming reactor.Chemical industry synthesis unit 4 comprises new air compressor, recycle compressor, second interchanger and chemical industry synthesis reactor.

Wherein, gasification unit 1 is used to receive the CO of a part of recycle 2Gas and carbon-rich materials.With carbon-rich materials, oxygen, materials such as water vapour gasification preparation raw gas, and the raw gas that makes is exported to the synthetic gas sensible heat reclaim and clean unit 2.The synthetic gas sensible heat reclaims with clean unit 2 and is used for the raw gas that receives is lowered the temperature and reclaimed most of sensible heat and purify, and then the clean gas that makes is exported to reformer unit 3.First interchanger in the reformer unit 3 is to the coal gas of cleaning and the CO of coke-oven gas and recycle 2Mixed gas carries out exporting to reforming reactor after the preheating, and the product from reforming reactor is carried out exporting to chemical industry synthesis unit 4 after heat release is handled, and reforming reactor carries out reforming reaction to the gas mixture that carries out after the thermal pretreatment, with CH 4And CO 2Be converted into CO and H 2, the new gas of building-up reactions that obtains is exported to chemical industry synthesis unit 4 after by the interchanger heat release.The new air compressor of chemical industry synthesis unit 4 is to the acting of boosting of the new gas of building-up reactions, the gas of recycle compressor after and the reaction gas that obtains required chemical industry synthesis pressure from the further compressed action of the circulation gas of not participating in building-up reactions of flasher to mixed boosting, described reaction gas being exported to second interchanger carries out exporting to the chemical industry synthesis reactor after the thermal pretreatment again, this chemical industry synthesis reactor is carried out chemosynthesis reaction to the gas mixture that carries out after the thermal pretreatment, and the building-up reactions product that obtains is exported to flasher 5 after by the second interchanger heat release.Flasher 5 is used for the reaction product of chemical industry synthesis unit 4 outputs is separated into unreacting gas logistics and thick product stream, wherein thick product stream is sent to rectifying tower 6, the unreacting gas logistics is further divided into circulation gas and circulation gas two portions not, circulation gas with enter chemical industry synthesis unit 4 after the new gas of building-up reactions mixes once more and participate in building-up reactionss, a unreacting gas part is sent to the reformation auxiliary unit 7 directly burning that acts as a fuel, providing reforming reaction required heat, another part is sent to combined cycle generation unit 8 gas that acts as a fuel and carries out combustion power generation.Rectifying tower 6 is used for the thick product stream of flasher input is chemical end-products through refining purification of rectifying, and isolates CO 2Gas, a part of CO 2Gas is sent to reformer unit 3, and another part enters gasification unit 1.Reformation auxiliary unit 7 is used for the directly burning that acts as a fuel of part unreacting gas is reacted required heat so that reformer unit to be provided.Combined cycle generation unit 8 is used for the fuel gas of input is carried out combustion power generation.

Wherein said chemical industry power Poly-generation energy resource system can be methyl alcohol-electric power polygenerations systeme or dimethyl ether-electric power polygenerations systeme, and described carbon-rich materials is coal, heavy oil, refinery coke or biological particles.

Fig. 2 is a kind of recyclable CO that utilizes provided by the invention 2Chemical industry power Poly-generation energy resource system process flow sheet.

Its concrete technical process is as follows: coal, air, water vapour, O 2With CO from the isolated a part of recycle of rectifying tower 223 make raw gas 9 in gasification unit 1, and raw gas 9 reclaims with clean unit 2 cooling earlier through sensible heat and reclaims most of sensible heat, purifies and removes H 2Sour gas such as S and NOx is to satisfy the synthetic requirement of producing of subsequent chemicals.The CO that the clean gas 11 that obtains after the purification, purified coke-oven gas 10 reach from the recycle of rectifying tower 6 222 mixing backs become to enter reformer unit 3 carries out reforming reaction, and reforming reaction is about to the CH in the gas mixture 4And CO 2Under the effect of catalyzer, directly reform altogether and be converted into CO and H 2The synthetic new gas 12 that obtains enters chemical industry synthesis unit 4 with the circulation gas 16 from flasher 5 and carries out the DME building-up reactions, and the building-up reactions product that obtains is exported to flasher 5.Flasher 5 is divided into unreacting gas logistics 14 and thick product stream 15 with the building-up reactions product, and wherein thick product stream 15 is sent to rectifying tower 6 refining purifications becomes final product DME/ methyl alcohol 21 and CO 220, and CO 220 are divided into tributary CO 222 and tributary CO 223, CO wherein 223 get back to gasification unit, CO 222 are sent to reformer unit, wherein, and CO 222 and CO 223 molar flow is than being 0.2-4.5.Unreacting gas logistics 14 is further divided into circulation gas 16 and circulation gas 17 not, and the molar flow of participating in the circulation gas of building-up reactions and circulation gas not again is than being 0.3-4.2.Circulation gas 16 returns and carries out DME (dme) building-up reactions at chemical industry synthesis unit 4 after chemical industry synthesis unit 4 mixes with the new gas 12 of building-up reactions, a circulation gas part 18 does not enter reformation auxiliary unit 7 burning that acts as a fuel and provides heat for reformer unit 3 reaction, and circulation gas another part 19 is not sent to the combined cycle generation unit of being made up of internal combustion turbine and steam turbine 8 and carries out combustion power generation.The hot-fluid of native system and merit stream are as shown in Figure 2.

The used coal of embodiment is analyzed as shown in table 1, and table 2 is system's main streams data results, and table 3 is new system performance information.Associative list 2 and Fig. 2 be not if there is CO 2The flow scheme of recycling, the CO that produces in the system 2Finally be discharged in the atmosphere is CO in the logistics 18,19,20 2, from table 2, can see the CO in the logistics 20 2The quality percentage composition surpasses 90%, and logistics 18,19 relatively, the CO in the logistics 20 2Content surpasses CO 21/2 of total content can cause severe contamination if directly be discharged in the atmosphere.Therefore, with this part CO 2Recycle, not only reduce CO 2Discharging also is stored into its indirect reformer in the chemical, has improved the element utilization ratio.Because the CO of designed system 2It is less that the recycle conversion process is formed influence to system's synthetic gas, and system flow technology is constant substantially, as can be seen from Table 3, under same energy input condition, has recycle CO 2System with respect to no recycle CO 2System; about 5 percentage points on the element utilization ratio, have been promoted; up to 70%; and the energy utilization efficiency reduction is less than 1 percentage point; still have 59.83%, its emission reduction effect also all has corresponding lifting, on the technical scale basis of designed in an embodiment 1,200,000 tons of dme of annual output; through conversion, this CO 2The production system of recycle is with respect to no CO 2The production system of recycle will reduce discharging about 170,000 tons of CO every year 2Be not difficult to find out that from above data and analysis the system that the present invention proposes utilizes the energy of the minimum part of system self to remove to have realized CO 2Recycling transform, solved because CO 2The problem that the system capacity utilization ratio that separating energy consumption causes descends has improved the element utilization ratio of system and has reduced CO 2Discharging, have higher energy utilization efficiency, also avoided simultaneously CO 2Transportation, store and a series of technical barriers and risk such as to bury, from truly having realized the multiple effect of utilization of resources maximization, energy-saving and emission-reduction.

Coal-based dimethyl ether-electric power Poly-generation energy resource system process flow diagram that Fig. 3 proposes for the present invention.The principle of this technology is described identical with Fig. 1 and Fig. 2, repeats no more herein.At this, mainly to the further detailed explanation of the actually operating technical process of coal-based dimethyl ether-electric power Poly-generation energy resource system.At first, the CO of part recycle 2Gas and broken coal, oxygen and water vapour generate and contain CO, H at the vapourizing furnace internal reaction 2, CO 2, H 20 and a small amount of CH 4, H 2The raw gas of composition such as S, COS, lime-ash reunion balling-up is discharged with solid form.High temperature rough gas (about 1050 ℃) enters first waste heat boiler, makes feedwater (0.7MPa, 20 ℃) become saturation steam and send into vapourizing furnace so that required steam to be provided; Raw gas is recycled cooling water temperature to 371 ℃, and it is separated from the gas to enter the flying dust that cyclonic separator will be wherein, and flying dust returns vapourizing furnace workshop section and utilizes the back to discharge with the lime-ash form again.Raw gas after separation, dedusting is not with flying dust substantially, and sulphur in the raw gas and nitrogen compound have been converted to gaseous sulphide, ammonia and prussic acid etc.; Again by spray NaHCO 3Absorption equipment, removing halogenide, and the absorption agent that lost efficacy separated; Adopt high temperature desulfuration agent to remove the H in the gasification raw gas at last 2S and COS are to satisfy the requirement of subsequent technique building-up reactions.Will be through the coke-oven gas and the gasification gas that comes from high temperature purification and the CO of part recycle of purifying treatment 2Gas mixes, and wherein the molar ratio of gasification gas (GG) and coke-oven gas (COG) is according to CO in the reforming reactor exit gas and H 2Molar ratio adjust, to satisfy the required optimum response synthesis gas components of follow-up synthetic DME ratio, here GG/COG is 0.78-1.05, mixed gas and reforming reaction exit gas carry out entering reforming reactor after the heat exchange.In reforming reactor, CH takes place in mixed gas under the effect of catalyzer 4/ CO 2Directly be total to reforming reaction, with the H in the synthetic gas 2/ CO transfers to about 1.0-1.5, and reforming reactor exit gas (about 980 ℃) further makes synthetic gas be cooled to 60 ℃ by water recirculator after heat exchange, enters gas/water separator the condensed water in the gas is separated.Clean building-up reactions gas adopts the compression of the cold geometric ratio of three inter-stages, boosts to 6.5MPa with the part unreacting gas of recycle and enters synthesis reactor, at 260 ℃, carries out the dme building-up reactions under the 6.0MPa.Because building-up reactions is an exothermic process, after waste heat recovery, can partly separate as rectifying; Be rich in the gas cooling to 40 ℃ of methyl alcohol/dme after will reacting then, under 5.40MPa pressure, enter flasher, the gas delivery that flasher will be rich in methyl alcohol/dme becomes unreacting gas logistics and thick product stream, the unreacting gas logistics is further divided into circulation gas and circulation gas not, and the molar flow of participating in the circulation gas of building-up reactions and circulation gas not again is than being 0.3-4.2.The thick product of separating at flasher enters rectifying tower and further separates purification, adopts three-tower rectification, CO in the isolated light constituent of first tower 2Content up to 90% (massfraction), also contain a spot of CH 4, do not need to purify, directly recycle and reuse, a part turns back to vapourizing furnace, and another part turns back in the reforming reaction process, wherein is sent to the CO that participates in reforming reaction and described vapourizing furnace 2Molar flow is than being 0.2-4.5.Heavy constituent then in the back two rectifying tower isolate dme and methyl alcohol successively.The unreacting gas that flashes off then the part recycle to improve the transformation efficiency of building-up reactions, a remaining unreacting gas part is sent into the burning of reformation auxiliary unit, providing reformer unit to react needed heat, another part gas gas that acts as a fuel after steam-laden directly enters gas turbine combustion acting generating.The high-temperature tail gas of reformation auxiliary unit and internal combustion turbine outlet produces (537 ℃, 10MPa) high temperature and high pressure steam after waste heat recovery, promote the steam turbine acting.Table 1 Table 2 Table 3

Based on Fig. 1, Fig. 2 and a kind of recyclable CO that utilizes shown in Figure 3 2Chemical industry power Poly-generation energy resource system and technical process, the present invention has provided a kind of recyclable CO of utilization provided by the invention 2The Poly-generation method, this method comprises: steps A, will the part from internal system round-robin CO 2Gas, oxygen, water vapour and carbon-rich materials are in interior mixture gasification and be refined into purified gasification gas; Step B will comprise that described purified gasification gas and part are from internal system round-robin CO 2The mixed mixed gas of gas carries out reforming reaction and prepares the new gas of building-up reactions; Step C carries out building-up reactions preparation feedback product with the new gas of described building-up reactions, more described reaction product is isolated thick product stream; Step D, described thick product stream is refining for chemical end-products and isolate CO 2Gas, this isolated CO 2Gas is described internal system round-robin CO 2Gas is again with described CO 2Gas separates according to a certain percentage, and with internal system round-robin CO 2Gas is sent to respectively participates in described reforming reaction and described gasification, finishes this CO 2Gas is in the recycle of internal system.

Preferably, adopt rectifying that described thick product stream is isolated chemical end-products and CO among the described step D 2Gas.

Preferably, the described mixed gas that carries out reforming reaction among the described step B comprises the gasification gas of coke-oven gas, described cleaning and the CO that the described systemic circulation of part is utilized 2. wherein, reforming reaction is with the CH in the described mixed gas 4And CO 2Be converted into CO and H 2

Preferably, described step C comprises flash vaporization process, this flash vaporization process is isolated thick product stream and unreacting gas logistics with described reaction product, described unreacting gas logistics is further divided into circulation gas and circulation gas two portions not, wherein, circulation gas returns continue to participate in building-up reactions, and circulation gas does not act as a fuel directly burning providing reforming reaction required heat, or the combustion power generation that acts as a fuel.

Preferably, be sent to the CO that participates in reforming reaction and described gasification described in the step D respectively 2Molar flow is than being 0.2-4.5.

More preferably, the molar ratio of gasification gas described in the aforesaid method and coke-oven gas is by CO and H in the new gas of the desired building-up reactions of described chemical end-products 2Mol ratio size decision.

More preferably, in the aforesaid method, the described molar flow of the circulation gas of building-up reactions and circulation gas not of participating in again is than being 0.3-4.2.

The present invention, has cancelled the water gas shift reaction that present chemical-process generally adopts simultaneously and has adjusted synthetic gas CO/H as raw material with coal and coke-oven gas 2The production model of ratio is used CO instead 2/ CH 4Reforming reaction is with CO 2And CH 4Be converted into CO and H 2, rationally utilized the characteristics of rich hydrogen of coke-oven gas and the rich carbon of gasification gas, with the two organic coupling and trans-utilization, reduced the consumption of water resources and the discharging of greenhouse gases, increased synthetic new gas active principle (CO+H 2) content, realized that coal and coke-oven gas efficiently utilize.By the circulation of unreacting gas appropriateness, remedied the synthetic in the past low excessively defective of One-through design transformation efficiency, by finding best unreacting gas circulation ratio, under the prerequisite that guarantees higher chemical industry transformation efficiency, lifting system capacity usage ratio and element utilization ratio have realized the raising of entire system efficient simultaneously.

The present invention has removed traditional skill upgrading CO such as water gas shift reaction, burning chemistry chains that utilize from 2Concentration, and separation of C O 2Production model, on the one hand these The Application of Technology are transformed into CO again with the CO resource of preciousness 2, consume great amount of water resources and O simultaneously 2, reduced the system element utilization ratio.On the other hand, CO 2Separation increased the facility investment expense, and separating energy consumption is huge, a large amount of CO that separate simultaneously 2Processing, transportation stores and all to have certain technical barrier and potential safety hazard, has influenced the energy utilization efficiency of system and the safe reliability of subsequent processes, has increased extra investment costs.For the decarburization sepn process, no matter be decarburization before the burning, the still decarburization production model after the burning all can not be avoided the problem of above existence.Therefore, really can realize CO 2The reduction of discharging approach be to improve production technique, reduce CO in the production process 2Generation; Improve production technology, with CO 2Rational trans-utilization.At present, at first with CO 2Be converted into CO, carry out oxo process chemical and liquid fuel again and be undoubtedly CO 2The optimum utilization approach.But CO 2Stability is strong, make it be converted into CO and need consume lot of energy, consider that the vapourizing furnace gasification produces a large amount of heats, also improved in the time of the raising of gasification temperature coal chemically reactive (coal tar and different gasifying mediums as: interactional response capacitys such as carbonic acid gas, oxygen, water vapor).Therefore, can be with CO 2Feed vapourizing furnace as vaporized chemical and react, carbon in the coal and the carbonic acid gas generation reduction reaction that enters in the vapourizing furnace can make CO 2Be reduced into CO, not only increased the content of CO in the raw gas, and CO 2Play the effect of vaporized chemical, can reduce the needed water vapour of gasification reaction.At reformer unit, CO takes place 2/ CH 4Reforming reaction, CO 2In reaction process, serve as reactant, with the CO of system's generation 2Turn back to reformer unit, can be with CO 2As prepared using, not only reduce 'inertia' gas CO 2And CH 4Content has also increased CO and H in the synthetic new gas 2Content, improved the utilization ratio of system C element.For this reason, the present invention has rationally utilized the function of each technique unit of system, with the isolated a large amount of CO of rectifying 2Be sent to gasification unit respectively and reformer unit reacts.CO 2Turn back to vapourizing furnace reaction, make that CO content increases in the raw gas, but excessive CO 2Can reduce the temperature of outlet raw gas, can make that also CO content increasing degree is bigger in the raw gas, can suppress the carrying out of reformer unit reforming reaction, reduce CO 2+ CH 4Transformation efficiency, system CO 2Emission reduction effect can not get guaranteeing.Because CO 2/ CH 4Reforming reaction is a strong endothermic reaction, if a large amount of CO 2All turn back to reformer unit, no doubt can increase CO 2Trans-utilization, reduce CO 2Gas purging, but certainly will also can increase the energy expenditure of system, the energy utilization efficiency of system will can not get guaranteeing.Therefore, take into account the capacity usage ratio and the CO of system 2Emission reduction effect, the present invention has provided CO 2Turn back to the ratio of the best of vapourizing furnace and reformer unit,, can improve the energy utilization efficiency and the CO of system simultaneously by seeking the optimal allocation ratio 2Emission reduction effect.From system in its entirety, system has cancelled water gas shift reaction, burning chemistry chains etc. and has promoted CO 2The transformation technology of concentration does not have extra CO 2Separating unit more need not be considered CO 2Storage, problem such as bury.System architecture is simple, has reduced the extras investment cost.

Utilize the present invention, with the CO of system's generation 2Turn back to gasification unit and reformer unit and carry out recycle, overcome at present owing to reclaim CO 2The defective that the energy utilization efficiency that causes descends has significantly been avoided recovery CO especially 2Storage, the risk of burying, simplified system, reduced investment cost, truly realized production system energy-saving and emission-reduction, economic multiple effect.Reclaiming 70% above CO 2Situation under, the energy utilization efficiency of process system of the present invention will be higher than and reclaims CO 2CCS-IGCC system (about 36%), also be higher than and do not have reclaim CO 2IGCC system (about 45%), even be higher than and reclaim CO 2Chemical industry and the polygenerations systeme (about 48%) produced of IGCC coupling.Above data are at the CO that does not consider to separate 2Store, bury etc. under technical problem and the security risk prerequisite, in case these problems are included limit of consideration in, process system energy utilization efficiency of the present invention, emission reduction effect and economy will have bigger advantage and potentiality.

Above-described specific examples is only for detailed explanation useful achievement of the present invention and special technology scheme; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (9)

1. chemical industry power Poly-generation energy resource system, this system comprises:
Gasification unit is used for receiving unit from this internal system round-robin CO 2Gas, and will comprise this CO 2Gas, oxygen, water vapour and carbon-rich materials are made raw gas at interior mixture;
The synthetic gas sensible heat reclaims and clean unit, is used for most of sensible heat is lowered the temperature, reclaimed to this raw gas and being refined into clean gasification gas;
Reformer unit is used for receiving unit from this internal system round-robin CO 2Gas, and will comprise this CO 2The mixed gas of the gasification gas of gas and described cleaning carries out reforming reaction and prepares the new gas of building-up reactions;
The chemical industry synthesis unit is used for the new gas of this building-up reactions is carried out building-up reactions preparation feedback product;
Flasher is used for this reaction product is isolated thick product stream;
Rectifying tower is used for making with extra care this thick product stream for chemical end-products and isolating CO2 gas, wherein, and this isolated CO 2Gas is described internal system round-robin CO 2Gas is again with this CO 2Gas is that the 0.2-4.5 branch is opened according to molar ratio, is sent to reformer unit and gasification unit respectively, finishes described CO 2Gas is in the recycle of internal system.
2. a kind of chemical industry power Poly-generation energy resource system according to claim 1 is characterized in that,
This system is methyl alcohol-electric power polygenerations systeme or dimethyl ether-electric power polygenerations systeme, and described carbon-rich materials is coal, heavy oil, refinery coke or biological particles.
3. a kind of chemical industry power Poly-generation energy resource system according to claim 1 is characterized in that,
The mixed gas of described participation reforming reaction comprises the gasification gas and the described internal system round-robin of the part CO of coke-oven gas, described cleaning 2Gas, wherein, reforming reaction is with the CH in the described gas mixture 4And CO 2Be converted into CO and H 2
4. chemical industry power Poly-generation method, this method comprises:
Steps A will be partly from internal system round-robin CO 2Gas, oxygen, water vapour and carbon-rich materials are in interior mixture gasification and be refined into purified gasification gas;
Step B will comprise that described purified gasification gas and part are from internal system round-robin CO 2The mixed mixed gas of gas carries out reforming reaction and prepares the new gas of building-up reactions;
Step C carries out building-up reactions preparation feedback product with the new gas of described building-up reactions, more described reaction product is isolated thick product stream;
Step D, described thick product stream is refining for chemical end-products and isolate CO 2Gas, this isolated CO 2Gas is described internal system round-robin CO 2Gas is again with described CO 2Gas is that 0.2-4.5 divides and to open according to molar ratio, and the CO that the internal system round-robin has been separated 2Gas is sent to respectively participates in described reforming reaction and described gasification, finishes this CO 2Gas is in the recycle of internal system.
5. a kind of chemical industry power Poly-generation method according to claim 4 is characterized in that,
Adopt rectifying that described thick product stream is isolated chemical end-products and CO among the described step D 2Gas.
6. a kind of chemical industry power Poly-generation method according to claim 4 is characterized in that,
The described mixed gas that carries out reforming reaction among the described step B comprises coke-oven gas, described purified gasification gas and the described internal system round-robin of part CO 2, wherein, reforming reaction is with the CH in the described mixed gas 4And CO 2Be converted into CO and H 2
7. a kind of chemical industry power Poly-generation method according to claim 4 is characterized in that:
Described step C comprises flash vaporization process, this flash vaporization process is isolated thick product stream and unreacting gas logistics with described reaction product, described unreacting gas logistics is further divided into circulation gas and circulation gas two portions not, wherein, circulation gas returns and continues to participate in building-up reactions, circulation gas does not act as a fuel directly burning providing reforming reaction required heat, or the combustion power generation that acts as a fuel.
8. a kind of chemical industry power Poly-generation method according to claim 6 is characterized in that, the molar ratio of described purified gasification gas and coke-oven gas is by CO and H in the new gas of the desired building-up reactions of described chemical end-products 2Mol ratio size decision.
9. a kind of chemical industry power Poly-generation method according to claim 7 is characterized in that, described continuation is participated in the molar flow of the circulation gas of building-up reactions and circulation gas not than being 0.3-4.2.
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