CN103373705B - Method and device for improving grade of medium-and-low-temperature solar thermal power and integrally separating CO2 - Google Patents

Abstract

The invention discloses a method and a device for improving the grade of medium-and-low-temperature solar thermal power and integrally separating CO2. According to the method, a palladium base alloy membrane structure with very strong hydrogen permeation property is introduced into a methane/water vapor reforming reaction, thereby greatly improving reaction conditions, increasing percent conversion rate of methane and realizing CO2 separation. 200 DEG C cyclone separator trench type solar is used for providing latent heat of vaporization for reforming vapor, the latent heat of vaporization is converted into vapor internal energy, and the vapor internal energy is converted into synthesis gas chemical energy. 550 DEG C light-concentrating tower-type solar is used for providing reaction heat needed by the reforming reaction and the reaction heat is directly converted into synthesis gas chemical energy. Thus, grade is improved. Finally, conversion of heat into power is realized in a high-efficiency fuel gas-vapor combined circulating system. By the method and the device provided by the invention, the high-efficiency conversion of medium-and-low-temperature solar thermal power and comprehensive gradient utilization of medium-and-low-temperature solar thermal power and fossil fuel which are complementary to each other are realized; moreover, the integral separation of CO2 is also realized.

Description

Middle low-grade solar thermal energy grade promotes and CO 2the method and apparatus that integration is separated

Technical field

The present invention relates to energy technology field, particularly in one, low-grade solar thermal energy grade promotes and CO ₂the method that integration is separated and device.

Background technology

Technology related to the present invention at present mainly comprises middle low-temperature solar energy and utilizes CO in technology, membrane reactor technology and energy resource system ₂isolation technique, its separately the Status of development of technology and feature as follows:

1. in, low-temperature solar energy utilizes technology

In view of fossil energy finiteness and utilize in process the seriousness producing pollution, effective utilization of the novel clean energy (as sun power, wind energy, Geothermal energy etc.) is become to an importance of Sustainable development.In recent years, sun power obtains extensive concern with advantages such as its unique reserves unlimitedness, the ubiquity of existence, the spatter property of exploitation and the economy that progressively promotes, becomes one of the effective way solving energy shortage, environmental pollution and Greenhouse effect.

Current, the main development direction of solar utilization technique is that solar photoelectric transforms and photothermal conversion, and wherein the solar dynamic power system of photothermal conversion is again the heliotechnics of following twenty or thirty year most magnetism.But on the one hand solar energy density is low, spatial and temporal distributions is discontinuous, the huge and energy storage equipment of costliness need be configured; Solar energy heating efficiency increases along with heat-collecting temperature and reduces on the other hand, and the hot growth turning effect rate of power cycle needs the basis that rises to working medium initial temperature, this contradiction makes solar energy thermal-power-generating efficiency be difficult to improve (existing only about 10%), also cause higher cost for solar power generation thus, seriously constrain photo-thermal power generation extensive development and engineer applied.Current solar energy thermal-power-generating technology and emerging thermochemistry energy conversion technique (the thermochemistry energy conversion system etc. as gas renormalizing) research focus mostly in the transformation of energy of high temperature solar heat and utilization, and mostly are the raising of the component capabilities such as high-temperature heat-gathering and thermochemical conversion and the research and development of relevant novel material.The high-temperature heat-gathering of more than 1000 DEG C invariably complicated with equipment, cost of investment is high and photo-thermal conversion efficiency is low for cost.

Comparatively speaking, the middle low-temperature solar energy thermal utilization technology of current less than 300 DEG C obtains large-scale commercial with its good solar collecting performance and the simple heat collector of economy.The heat collector of this temperature range, focusing ratio is low, and solar collecting performance is good, and collecting efficiency generally can reach more than 60%, effectively prevent the high cost cost of high temperature solar energy conversion system.But the temperature of working medium is lower, realizes heat to power output more difficult, the direct utilization of current centering low temperature heat energy still lacks effective technology.And conventional energy resources utilizes systems technology and technique to become better and approaching perfection day by day, the combined cycle working medium initial temperature as advanced person has reached 1600 DEG C.If the renewable energy sources such as imagination sun power are able to realize energy transformation and release in general energy system, not only can Substitute For Partial fossil energy consume, reduce corresponding pollutant emission, more will greatly improve renewable energy source fault offset grade and heat turns effect rate, alleviate that it is unstable, a discontinuous supply difficult problem simultaneously.The complementary cascade utilization of middle low-temperature solar energy and fossil oil is expected to provide a brand-new approach for solving the clean utilization that is low and that realize fossil oil of solar energy transformation efficiency simultaneously.

In multi-energy complementation system, middle low-temperature solar energy can mutually integrated with some physics endothermic process in therrmodynamic system (warm integrated), as evaporative process, heat recovery process; Also can mutually integrated with some endothermic chemical reaction (thermochemistry be integrated), as pyrolytic reaction and reforming reaction etc.The steam Rankine cycle complementary system that the former proposes as N.Lior and K.Koai, low-temperature zone working-medium water absorbs about 100 DEG C of solar heat evaporations, high temperature section combustion of fossil fuel provides heat to make steam superheating, form different heat sources to utilize in the coupling of differing temps section, solar heat input share is up to 80%, and system thermal efficiency can reach 18%.The combined cycle system of a kind of middle low-temperature solar energy that the latter proposes as H.Hong and H.Jin and the complementation of fossil oil thermochemistry, utilize the pyrolysis characteristics of methanol fuel under middle cold condition, with the Driven by Solar Energy methyl alcohol thermal desorption thermal response of 200 ~ 300 DEG C, generate with H ₂be the synthetic gas of main component with CO, thus make low-grade sun power be converted into higher-grade syngas chemistry energy; Synthetic gas drives Gas-steam Combined Cycle work done, achieves the lifting of middle low-temperature solar energy grade and its Efficient Conversion in power system.In its case analysis, solar heat input ratio is 18%, solar electrical energy generation net efficiency and system efficiency reaches 35% and 60.7% respectively, but this calculating have ignored turbine blade cooling impact.The system that a kind of sun power grade that and for example N.Zhang proposes promotes indirectly, middle low-temperature solar energy is first by the integrated latent heat of vaporization providing steam needed for methane reforming reaction of heat, the steam produced reacts with methane generation high temperature reformation again, in thermal chemical reaction, low-grade sun power is carrier with internal steam work, is converted into higher-grade syngas chemistry energy, achieves the indirect lifting of grade, synthetic gas drives combustion gas circulation work done afterwards, finally achieves the efficient heat-work conversion of sun power.Compared with conventional chemical extraction cycle, fossil energy saving rate reaches 20% ~ 30%.

2. membrane reactor technology

Due to thermodynamical restriction, methane and water vapor need could fully react under the high temperature conditions (750 ~ 920 DEG C).When temperature of reaction is more than 850 DEG C, the methane conversion of more than 80% can be obtained.From thermodynamic equilibrium theory, as obtaining higher transformation efficiency under lower temperature of reaction, must break original thermodynamic(al)equilibrium, the direction that chemical equilibrium can be made to generate to product as reduced resultant concentration is moved.Experiment shows, when temperature of reaction is 500 DEG C, as removed the hydrogen of 90%, methane conversion can reach 94%.Therefore, how while reforming reaction is carried out, constantly resultant to be shifted out from reaction system the focus becoming research.Palladium base alloy films (being generally palladium-silver alloy), a kind of permeable membrane with high hydrogen permeability, start to be applied in reforming reaction, the membrane reactor constructed integrates catalyzed reaction and isolation technique, the purification that can realize hydrogen in reformation hydrogen production system be separated, thus obtain highly purified hydrogen, improve reforming conversion, can also control CO content, prevent poisoning of catalyst, obtain the CO of high density simultaneously ₂gas, realizes CO ₂separation.

Palladium-base alloy membrane reactor ultimate principle is: because film has very high hydrogen permeation selectivity and saturating hydrogen speed, and other gas almost can not penetrate film, or only there is extremely low penetrance, therefore, under the promotion of film both sides hydrogen partial pressure difference, react the opposite side of hydrogen-permeable to film of side, along with the intermembranous flowing of hydrogen, reaction side density of hydrogen reduces, break original thermodynamic(al)equilibrium, the direction of reacting to generating hydrogen is moved, and reaction conversion ratio improves, and can obtain highly purified hydrogen and high concentration CO respectively in film both sides ₂synthetic gas.

It is generally acknowledged that hydrogen follows dissolving-flooding mechanism through the process of palladium basement membrane, meet fluid transport equation F=BA [(P _h) ⁿ-(P _l) ⁿ], wherein F is the molar flow rate that hydrogen passes film, and B, A are respectively the useful area of rate of permeation and film, P _h, P _lrepresent the dividing potential drop of hydrogen in film reaction side and per-meate side respectively, for hydrogen is through the motivating force of film, index n is difference to some extent because of the difference of membrane structure, material, and in palladium-base alloy membrane structure, n is taken as 0.5.Key step is as follows: step 1, hydrogen molecule are at palladium film chemical absorption of surface and be dissociated into hydrogen atom; Step 2, Surface Hydrogen atom are dissolved in palladium film; Step 3, in film, be ionized into proton and electronics is diffused into opposite side from side; Step 4, hydrogen ion are received electronics again to become atom and are separated out from palladium film, in chemical adsorption states; Step 5, Surface Hydrogen atomize synthesize hydrogen molecule and desorption.Step 1,5 is surface process, and step 3 is bulk diffusion process.Total speed of hydrogen infiltration is controlled by wherein the slowest step or multiple step.

Separation factor is the important parameter of characterization of membrane performance, represents the selective penetrated property energy of film.Under being generally defined as the same terms, the ratio of pure hydrogen and rare gas element transit dose, weighs the separation efficiency of film with this.Experimental results demonstrate, the alloy lattice of palladium basement membrane only allows hydrogen molecule dissolve and diffuse through, and retain other Inert gas molecule, further demonstrate that first hydrogen molecule is dissociated absorption on palladium film surface, then proton and electronics is ionized at palladium film internal diffusion, at the opposite side of film, proton has received electronics to become hydrogen ion adsorption from metal grid again, associates for hydrogen atom is by desorption.Only be dissociated absorption become the hydrogen of protic state could diffuse transmission palladium film, and other gas that can not become proton can not be through, and this is also that the hydrogen of palladium membrane diffusion is containing the reason of other impurity.Under normal circumstances, hydrogen permeation rate is relevant with the hydrogen partial pressure difference of temperature of reactor and film both sides.

The structured material of methane/water vapor film reforming reaction performance and film, catalyst type, reaction conditions (as temperature of reaction, reaction pressure, reactant intake velocity, water carbon mol ratio, gas scavenging flow and flow pattern) are relevant.Generally, the structured material of film, catalyst type pre-determines, and reaction conditions is the key factor of restriction methane conversion, selectivity of product and hydrogen yield.By reaction kinetics and the durothermic dual restriction of mould material, film reaction temperature general control is within the scope of 450 ~ 600 DEG C; From thermodynamic(al)equilibrium, improve reaction pressure, methane conversion reduces, but hydrogen partial pressure improves simultaneously, add the motivating force (partial pressure difference) flowed between hydrogen membrane, can promote again the conversion of methane, therefore reaction pressure will consider many-sided factor such as reaction pressure, temperature to the impact of methane conversion; For preventing carbon deposition phenomenon, water carbon mol ratio is higher than 2.5 usually, and too high water carbon mol ratio can reduce the dividing potential drop of hydrogen, and then reduces the perviousness of hydrogen, and general control is in 2.5 ~ 3.5 scopes.

3. CO in energy resource system ₂isolation technique

The integrated CO of energy resource system ₂the major way of sepn process can according to CO ₂the difference of sepn process position in systems in which (in other words separation point) is divided into four classes such as " being separated before burning ", " being separated in burning ", " being separated after burning " and " burning chemistry chains ".

1) be separated before burning

This technology be utilize suitable carbon method for transformation carbon-based fuel to be converted into synthetic gas (main component is CO and H ₂), further by transformationreation, the CO in synthetic gas is converted into CO ₂and H ₂, then by separating technology by CO ₂separate, cleaner hydrogen-enriched fuel gas can be obtained.Due to CO ₂separation is carried out before combustion processes, the CO in synthetic gas to be separated ₂concentration is higher, decreases after separating energy consumption relative combustion.But fuel chemical energy reduces, the driven power generation system heat be usually separated before burning turns merit decrease in efficiency 7 ~ 10 percentage points.

2) be separated in burning

This technology utilizes space division system to produce oxygen enrichment or pure oxygen gas, then fuel and oxygen is together transported to special pure oxygen burning stove and burns, and the main component generating flue gas is CO ₂and water vapor.Partial fume after burning is re-injection roasting kiln again, reduces temperature of combustion on the one hand; Improve CO in tail gas further on the other hand ₂mass concentration, generally can reach more than 95%, and the main component due to flue gas is CO ₂and H ₂o, can be separated and direct weighting liquefaction recycling.But be separated O ₂time need the electric work expending flood tide, the wasted work of air separation unit, make system output work reduce 0.22 ~ 0.25kWh/kg O ₂left and right.

3) be separated after burning

Separation of C O after burning ₂be the most common be also the separating measure the most easily expected, because the CO of the flue gas after burning ₂concentration is general all lower, and the general chemical absorption method that adopts is separated, due in tail gas except CO ₂sour gas also has nitrogen and sulfur oxide and metal pollutant outward, brings very burden to absorption below.And separation of C O ₂concentration is low, and process tail is large-minded, separation of C O ₂energy consumption is very large on the impact of system performance, generally makes system efficiency decline 10 ~ 15%;

4) burning chemistry chains

This technology comprises two continuous print redox reactions, and in reduction reaction process, fuel and metal oxide react, and while generating metal, fuel is oxidized to CO ₂and H ₂o; Metal and air reaction regenerate metal oxide in the oxidation reaction, its process has the advantage of natural separating carbon dioxide, namely products of combustion only needs water in simple cooling mixture just can separating carbon dioxide, does not need extra separating energy consumption.Also the feature less than general combustion process combusts irreversible loss is embodied in combustion.

Summary of the invention

(1) technical problem that will solve

Main purpose of the present invention is to provide low-grade solar thermal energy grade in one and promotes and CO ₂the method that integration is separated and device, efficiently change with low-grade solar thermal energy in realizing and and the comprehensive cascade utilization of fossil oil complementation, and realize CO ₂integration be separated.

(2) technical scheme

For achieving the above object, the invention provides low-grade solar thermal energy grade in one to promote and CO ₂the method that integration is separated, the method is in methane/steam reforming reaction, introduce the extremely strong palladium-base alloy membrane structure of hydrogen permeability energy, thus significantly improves reaction conditions, improves methane conversion, realizes CO ₂be separated.

The method also comprises: utilize the parabolic trough type sun power of 200 DEG C to provide the latent heat of vaporization of reforming steam, be converted into internal steam work, is converted into syngas chemistry energy by participating in reforming reaction.

The method also comprises while utilizing the parabolic trough type sun power of 200 DEG C: utilize the light-focusing type tower type solar of 550 DEG C to provide the reaction heat needed for reforming reaction to be converted into syngas chemistry energy, realize grade to promote, finally in high efficiency burnt gas-steam combined cycle system, realize heat to power output.

For achieving the above object, present invention also offers one and realize described middle low-grade solar thermal energy grade lifting and CO ₂the device of integration separation method, comprising:

Air compressor 1, for air S1 being boosted to the top pressure of Brayton circulation, forming pressurized air S2 and exporting to combustion chamber 2;

, there is combustion reactions for the synthesis of fuel gas S25 and pressurized air S2, obtain high-temperature gas S26 in combustion chamber 2;

Gas turbine 3, for realizing high-temperature fuel gas S26 expansion working;

Fuel compressor 4, for boosting to reforming reaction pressure by fuel gas S3;

First boosting pump 5, for boosting to reforming reaction pressure by water S5;

Economizer 6, for by reformate (S14, S15) heat supply, heats freshet stock S7 to the saturated aquosity under reforming reaction pressure;

Solar still 7, evaporates the saturation water S8 under reforming reaction pressure for utilizing solar thermal energy;

Trough type solar heat-collector 8, for assemble required in low-temperature solar energy, and export to solar still 7;

Regenerator 9, heats for utilizing the gas mixture S10 of reformate (S12, S13) to water vapor S9 and compressed fuel gas S4;

Tower type solar heat collector 10, for warm solar thermal energy in collection, exports to reformer 11;

Film reformer 11, for by tower type solar heat collector 10 heat supply, makes fuel and water vapor carry out film reforming reaction under a certain pressure;

First condenser 12, for being rich in CO ₂synthetic gas S16 cool, and remove water of condensation S18;

Hydrogen gas compressor 13, the hydrogen S17 for reforming reaction being obtained boosts to the top pressure of Brayton circulation;

Second boosting pump 14, for boosting to reforming reaction pressure by water of condensation S18;

CO ₂physical absorption unit 15: for by the CO in synthol gas S21 ₂be separated;

Gas compressor 16: for will CO be removed ₂clean fuel gas S22 boost to Brayton circulation top pressure;

Three-pressure reheat boiler 17: by gas turbine smoke evacuation S27 heat supply, complete the preheating of different pressures feedwater in bottoming cycle, evaporation, superheating process;

Steam turbine 18: the superheated vapour S32 expansion working that waste heat boiler produces;

Second condenser 19: steam turbine steam discharge S29 is condensed to saturation water S30 state, so that recycle;

3rd boosting pump 20: water of condensation S30 is boosted to pressure needed for steam cycle; And

Generator (21,22): be connected with combustion gas and steam turbine respectively, is converted into electric energy by the mechanical work that turbine produces and exports.

In the apparatus, feedwater feeding economizer after pressurization is heated to the saturated aquosity under reforming pressure, enter solar still evaporation, water vapor mixes with the fuel gas after compression to be sent into regenerator and heats further, enter the film reforming reactor generation thermo-negative reaction of solar-heating subsequently, obtain respectively being rich in CO in reactor film both sides ₂synthol gas and highly purified hydrogen; Synthol gas enters CO after condensation dehydration ₂physical absorption unit, water of condensation is reused as reforming reactants, isolated CO ₂through four inter-stage cold reduction liquefaction, to seal up for safekeeping, the clean fuel gas after decarburization is compressed into combustion reactions pressure, and the hydrogen after compression together enters combustion chamber as fuel and pressurized air burns, the high-temperature flue gas generated drives Gas-steam Combined Cycle work done, realizes Power output.

In such scheme, described reformer 11 heat requirements are provided by tower type solar heat collector 10, import and export and are all connected with regenerator 9.

In such scheme, the hot side-entrance of described regenerator 9 is connected with reformer 11, and outlet connects economizer 6, and cold side import is connected with the mixing section of water vapor with fuel gas, and outlet connects reformer 11.

In such scheme, described vaporizer 7 heat requirements are provided by trough type solar heat-collector 8, and import is connected with economizer 6, and outlet vapor S9 mixes with compressed fuel gas S4.

In such scheme, the hot side-entrance of described economizer 6 is connected with regenerator 9, and outlet connects the first condenser 12 and hydrogen gas compressor 13 respectively, and cold side import and pump (5,14) are connected, and outlet connects vaporizer 7.

In such scheme, introduce palladium-base alloy membrane structure in described reformer 11, exit gas is for being rich in CO ₂synthetic gas S12 and highly purified hydrogen S13 two bursts of logistics.

In such scheme, needed for described reforming reaction, a water vapor part comes from the water of condensation S18 in synthetic gas S16, and all the other supplement S5 by moisturizing.

In such scheme, described steam turbine 18 high pressure cylinder exit portion gas is used for gas turbine 3 blade cooling, draws and mix with reheated steam after cooling, enters intermediate pressure cylinder and continues expansion working.

(3) beneficial effect

As can be seen from technique scheme, the present invention has following beneficial effect:

1, middle low-grade solar thermal energy grade provided by the invention promotes and CO ₂the method that integration is separated and device, owing to introducing palladium-base alloy membrane reactor, improve methane/steam reforming reaction condition, the intermembranous flowing of hydrogen constantly makes the hydrogen of generation from reaction sidesway to per-meate side, in reaction zone, chemical reaction will continue to generation H ₂direction carry out, increased substantially methane conversion, finally obtained highly purified hydrogen fuel and be rich in CO respectively in per-meate side and reaction side ₂gas, achieve middle low-grade solar thermal energy efficiently change and and the comprehensive cascade utilization of fossil oil complementation, and achieve CO ₂integration be separated.

2, middle low-grade solar thermal energy grade provided by the invention promotes and CO ₂the method that integration is separated and device, the introducing of sun power, internal combustion turbine smoke discharging residual heat can be used for driving bottoming cycle, and the heat coupling of reformate waste heat recovery part have also been obtained improvement, adds system output work; Due to the increase of sun power input share, reduce fossil energy consumption, improve circulation thermal performance further.In system, solar heat input share is 28.2%, CO ₂when capture rate is 90.97%, equivalent efficiency reaches 57.97%; Conventional gas-the Steam Combined Cycle inputted with identical fossil oil and tail gas collecting CO ₂conventional gas-Steam Combined Cycle compare, sun power only turns effect rate and reaches 19.2% and 36.4% respectively, and fossil oil saving rate is respectively 16.4% and 31.2%, unit generating CO ₂discharge reduces 92.5% and 38% respectively.Visible, present method achieves solar energy highly effective heat to power output and utilizes with the complementation of fossil oil, and by CO ₂be separated and utilize integrated with high efficiency of energy, there is good development prospect.

3, middle low-grade solar thermal energy grade provided by the invention promotes and CO ₂the method that integration is separated and device, achieve the efficient heat-work conversion of middle low-grade solar thermal energy and the integrated complementary cascade utilization with fossil oil, and high efficiency of energy utilized and CO ₂isolation integral is integrated, and heating power, the feature of environmental protection are all good, has good future in engineering applications.

Accompanying drawing explanation

Fig. 1 is that middle low-grade solar thermal energy grade provided by the invention promotes and CO ₂the schematic diagram of the device that integration is separated.

Embodiment

For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.

This middle low-grade solar thermal energy grade provided by the invention promotes and CO ₂the method that integration is separated and device, be in methane/steam reforming reaction, introduce the extremely strong palladium-base alloy membrane structure of hydrogen permeability energy, thus significantly improve reaction conditions, improve methane conversion, realize CO ₂be separated.Utilizing the parabolic trough type sun power of 200 DEG C to provide the latent heat of vaporization of reforming steam, be converted into internal steam work, being converted into syngas chemistry energy by participating in reforming reaction.Meanwhile, utilize the light-focusing type tower type solar of 550 DEG C to provide the reaction heat needed for reforming reaction to be converted into syngas chemistry energy, realize grade and promote, finally in high efficiency burnt gas-steam combined cycle system, realize heat to power output.

The application of palladium-base alloy membrane reactor, has increased substantially methane conversion under mesophilic condition, has realized CO ₂integration be separated; Parabolic trough type sun power (200 DEG C) provides the latent heat of vaporization of reforming steam, is converted into internal steam work, is converted into syngas chemistry energy by participating in reforming reaction; Meanwhile, light-focusing type tower type solar (550 DEG C) provides the reaction heat needed for reforming reaction to be converted into syngas chemistry energy, realizes grade and promotes, finally in high efficiency burnt gas-steam combined cycle system, realize heat to power output.

This middle low-grade solar thermal energy grade provided by the invention promotes and CO ₂the device that integration is separated, comprising:

Air compressor 1: top pressure air S1 being boosted to Brayton circulation, forms pressurized air S2 and exports to combustion chamber 2;

Combustion chamber 2: combustion reactions occurs synthol gas S25 and pressurized air S2, obtains high-temperature gas S26;

Gas turbine 3: high-temperature fuel gas S26 expansion working;

Fuel compressor 4: fuel gas S3 is boosted to reforming reaction pressure;

First boosting pump 5: moisturizing S5 is boosted to reforming reaction pressure;

Economizer 6: by reformate (S14, S15) heat supply, heating freshet stock S7 is to the saturated aquosity under reforming reaction pressure;

Solar still 7: utilize solar thermal energy to be evaporated by the saturation water S8 under reforming reaction pressure;

Trough type solar heat-collector 8: the middle low-temperature solar energy needed for gathering, and export to solar still 7;

Regenerator 9: utilize reformate (S12, S13) to heat water vapor S9 and the gas mixture S10 of the rear fuel gas S4 of compression;

Tower type solar heat collector 10: warm solar thermal energy in collection, exports to reformer 11;

Film reformer 11: by tower type solar heat collector 10 heat supply, makes fuel and water vapor carry out film reforming reaction under a certain pressure;

First condenser 12: will CO be rich in ₂synthetic gas S16 cool, and remove water of condensation S18;

Hydrogen gas compressor 13: hydrogen fuel S17 reforming reaction obtained boosts to the top pressure of Brayton circulation;

Second boosting pump 14: for water of condensation S18 is boosted to reforming reaction pressure;

CO ₂physical absorption unit 15: for by the CO in synthol gas S21 ₂be separated;

Gas compressor 16: will CO be removed ₂clean fuel gas S22 boost to Brayton circulation top pressure;

Three-pressure reheat boiler 17: by gas turbine smoke evacuation S27 heat supply, complete the preheating of different pressures feedwater in bottoming cycle, evaporation, superheating process;

Steam turbine 18: the superheated vapour S32 expansion working that waste heat boiler produces;

Second condenser 19: steam turbine steam discharge S29 is condensed to saturation water S30 state, so that recycle;

3rd boosting pump 20: water of condensation S30 is boosted to pressure needed for steam cycle;

Generator (21,22): be connected with combustion gas and steam turbine respectively, is converted into electric energy by the mechanical work that turbine produces and exports.

Connection between above-mentioned each equipment is the pipeline usually adopted and connects.

Low CO of the present invention ₂the groove tower combined type sun power of discharge and fossil energy complementary system, its flow process is: the water feeding economizer after pressurization is heated to the saturated aquosity under reforming pressure, enter solar still evaporation, mix with the fuel gas after compression and send into regenerator and heat further, enter the film reforming reactor generation thermo-negative reaction of solar-heating subsequently, obtain respectively being rich in CO in reactor film both sides ₂synthol gas and highly purified hydrogen.Synthol gas enters CO after condensation dehydration ₂physical absorption unit, water of condensation is reused as reforming reactants, isolated CO ₂through four inter-stage cold reduction liquefaction, to seal up for safekeeping, the clean fuel gas after decarburization is compressed into combustion reactions pressure, and the hydrogen after compression together enters combustion chamber as fuel and pressurized air burns, the high-temperature flue gas generated drives Gas-steam Combined Cycle work done, realizes Power output.

Promote and CO in this middle low-grade solar thermal energy grade provided by the invention ₂in the device that integration is separated, reformer 11 heat requirements are provided by tower type solar heat collector 10, import and export and are all connected with regenerator 9; The hot side-entrance of regenerator 9 is connected with reformer 11, and outlet connects economizer 6, and cold side import is connected with the mixing section of water vapor with fuel gas, and outlet connects reformer 11; Vaporizer 7 heat requirements are provided by trough type solar heat-collector 8, and import is connected with economizer 6, and outlet vapor S9 mixes with fuel gas S4 after compression; The hot side-entrance of economizer 6 is connected with regenerator 9, and outlet connects the first condenser 12 and hydrogen gas compressor 13 respectively, and cold side import and pump (5,14) are connected, and outlet connects vaporizer 7; Introduce palladium-base alloy membrane structure in reformer 11, exit gas is for being rich in CO ₂synthetic gas S12 and highly purified hydrogen S13 two bursts of logistics; Needed for reforming reaction, a water vapor part comes from the water of condensation S18 in synthetic gas S16, and all the other supplement S5 by moisturizing; Steam turbine 18 high pressure cylinder exit portion gas is used for gas turbine 3 blade cooling, draws and mix with reheated steam after cooling, enters intermediate pressure cylinder and continues expansion working.

Please referring again to Fig. 1, major portion of the present invention is low CO ₂the groove tower combined type sun power of discharge and fossil energy complementary system.Wherein: 1-air compressor; 2-combustion chamber; 3-gas turbine; 4-fuel compressor; 5-pump; 6-economizer; 7-solar still; 8-trough type solar heat-collector; 9-regenerator; 10-tower type solar heat collector; 11-film reformer; 12-condenser; 13-hydrogen gas compressor; 14-pump; 15-CO ₂physical absorption unit; 16-gas compressor; 17-three-pressure reheat boiler; 18-steam turbine; 19-condenser; 20-pump; 21,22-generator.

Connection in said system is known technology, and the present invention is not described specifically at this.

System flow describes: this system mainly comprises low CO ₂the groove tower combined type sun power of discharge and fossil energy complementary system.Water feeding economizer after pressurization is heated to the saturated aquosity under reforming pressure, enter solar still evaporation, mix with the fuel gas after compression and send into regenerator and heat further, enter the film reforming reactor generation thermo-negative reaction of solar-heating subsequently, obtain respectively being rich in CO in reactor film both sides ₂synthol gas and highly purified hydrogen.Synthol gas enters CO after condensation dehydration ₂physical absorption unit, water of condensation is reused as reforming reactants, isolated CO ₂through four inter-stage cold reduction liquefaction, to seal up for safekeeping, the clean fuel gas after decarburization is compressed into combustion reactions pressure, and the hydrogen after compression together enters combustion chamber as fuel and pressurized air burns, the high-temperature flue gas generated drives Gas-steam Combined Cycle work done, realizes Power output.

Simulate system with ASPEN PLUS software, the physical property of gas and water adopts RK-SOAVE, STEAM-TA equation respectively, CO before burning ₂be separated and adopt physical method, its physical absorbent selects SELEXOL (polyoxyethylene glycol dimethylether), tail gas CO ₂be separated the method adopting chemical absorption, its chemical absorber selects MEA, middle low-temperature solar energy is according to commercial applications maturation parabolic trough type solar energy thermal-power-generating heat-absorption subsystem design widely the most now, middle temperature solar is according to the subsystem design in the tower type solar energy thermal power generation station run in the world at present, fuel reforming selects Pd-Ag alloy membrane reactor, and turbine cooling adopts enclosed steam cooling mode.

Specific embodiment in balance condition performance perameter in table 1.Main related conditions is: under systematic steady state operation conditions, compressor efficiency 89%; Combustion efficiency of combustion chamber 100%, crushing is 3%; Gas turbine isentropic efficiency 88%; Interchanger minimum temperature difference 15 DEG C, crushing 1%; Steam initial temperature 600 DEG C, reheat temperature 560 DEG C, waste heat boiler pinch-point temperature difference 15 DEG C, minimum funnel temperature 100 DEG C.

Specific embodiment cyclic balance operating mode thermal performance and balance, respectively referring to table 2, table 3, (comprises turbine initial temperature 1308 DEG C, pinch-point temperature difference and component capabilities etc.), simultaneously to conventional gas-Steam Combined Cycle CC, tail gas collecting CO under identical assumed condition ₂conventional gas-Steam Combined Cycle CC-Post and native system LEHSOLRGT to have carried out simulating contrast.Visible, be 91% in carbon capture rate, solar heat input share is under the base regime of 28.2%, inputs, same CO with same fuel ₂the CC-Post system of trapping level is compared, LEHSOLRGT system CO ₂quantity discharged reduce by 38%, thermo-efficiency and efficiency improves 4.2% and 17.6% respectively, and due to the input of solar thermal energy, the clean output work of system significantly improves, and sun power only turns effect rate and fossil energy saving rate is respectively 36.4% and 31.2%; Compared with CC system, the clean output work of LEHSOLRGT system improves 19.7%, but because of solar heat share large percentage (28.2%), heat source temperature is lower, and its direct efficiency of utilization is low, is separated simultaneously and compresses CO ₂bring inevitable energy consumption and power loss, therefore complementary system thermo-efficiency decrease to some degree (14.1%), but efficiency is identical, and achieves CO ₂integration be separated.Sun power only turns effect rate and fossil energy saving rate is respectively 19.2% and 16.4%.

From can find out in analysis, the maximum advantage of LEHSOLRGT system is the integrated of tower type solar and methane film reforming reaction, middle temperature solar thermal energy grade is promoted, capacity for work increases, the transformation efficiency of methane increases substantially, chemical energy in process combustion is fully utilized, combustion reactions loss reduces 25.1% than traditional direct burning.CO ₂adding of sepn process, except separating energy consumption itself, other performance of system is also affected, and without CO ₂the CC system of trapping is compared, each elementary cell loss all slightly increase, but with tail gas collecting CO ₂cC-Post system compare, separating unit loss be only its 11.5%, clean output work also obviously increases.Its reason is, separation of C O in tail gas ₂time, flue gas flow is large, CO ₂concentration low (5%), and need from steam turbine, to draw a large amount of steam as CO ₂the reboiler thermal source of desorption tower, adds energy consumption and the irreversible loss of separating unit, and the clean output work of bottoming cycle also significantly reduces, the penalty of circulation.

Compared with reference system, native system needs to set up middle low-temperature solar energy collecting apparatus and middle temperature solar heat collecting equipment.For middle low-temperature heat collection, the groove type heat collector that technology relative maturity, cost are lower can be adopted.Groove type heat collector has excellent solar collecting performance in middle cryogenic applications, even if at 100W/m ²solar irradiation intensity under also can reach more than 50% collecting efficiency.For middle temperature thermal-arrest, can adopt tower-type heat collector, due to heat-collecting temperature only ~ 550 DEG C, solar collecting performance can maintain a good state, and it should be noted that, the lifting that system efficiency and solar heat turn effect rate improves directly related with system economy.

The present invention is as the low CO of one ₂the sun power of discharge and the gas-steam combined cycle system of fossil energy complementation, not only achieve the lifting of middle low-grade solar thermal energy grade and efficient conversion and the comprehensive cascade utilization with fossil oil complementation, and achieve CO with less energy-consumption cost ₂integration is separated, and heating power, the feature of environmental protection are all good, have wide future in engineering applications.

Table 1 system Specifeca tion speeification

Table 2 system thermal performance

Table 3 system balance sheet

In table 2, because system has sun power and the input of fossil energy two kinds difference, therefore efficiency is comparatively suitable interpretational criteria.Approximate think fuel approximate its net calorific value of 1.04 times, define system equivalent efficiency is as follows:

${\mathrm{\η}}_e=\frac{W_{\mathrm{net}}}{E_f+Q_{\mathrm{sol}}(1-T_0/T_{\mathrm{sol}})}=\frac{W_{\mathrm{net}}}{1.04m_f\·\mathrm{LHV}+Q_{\mathrm{sol}}(1-T_0/T_{\mathrm{sol}})}$

Wherein T ₀for envrionment temperature.When solar heat input share is zero, above-mentioned equivalent efficiency then equals system efficiency.

Solar heat input share and effect rate that only turns (the latter considers heat collector loss) thereof are defined as:

$X_{\mathrm{sol}}=\frac{Q_{\mathrm{sol}}}{Q_f+Q_{\mathrm{sol}}}=\frac{Q_{\mathrm{sol}}}{m_f\·\mathrm{LHV}+Q_{\mathrm{sol}}}$

${\mathrm{\η}}_{\mathrm{sol}}=\frac{W_{\mathrm{net}}-W_{\mathrm{ref}}}{Q_{\mathrm{rad}}}=\frac{W_{\mathrm{net}}-Q_f{\mathrm{\η}}_{\mathrm{th},\mathrm{ref}}}{Q_{\mathrm{rad}}}$

Wherein, W _reffor the lower reference system generated energy of identical fossil oil input, W _ref=Q _fη _{th, ref}two reference systems chosen are respectively conventional gas-steam combined cycle system CC and tail gas collecting CO ₂conventional gas-steam combined cycle system CC-Post.Q _radfor considering sun power always projection amount during heat collector loss, Q _rad=Q _sol/ η _col, η _colfor collector efficiency.

When fossil energy saving rate is identical with reference system amount of work, the relative reduction of fossil energy in native system:

${\mathrm{SR}}_f=\frac{W_{\mathrm{net}}/{\mathrm{\η}}_{\mathrm{th},\mathrm{ref}}-Q_f}{W_{\mathrm{net}}/{\mathrm{\η}}_{\mathrm{th},\mathrm{ref}}}=1-\frac{Q_f\·{\mathrm{\η}}_{\mathrm{th},\mathrm{ref}}}{W_{\mathrm{net}}}$

Symbol table

Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (11)

1. low-grade solar thermal energy grade promotes and CO in one kind ₂the method that integration is separated, is characterized in that, the method is in methane/steam reforming reaction, introduce the extremely strong palladium-base alloy membrane structure of hydrogen permeability energy, thus significantly improves reaction conditions, improves methane conversion, realizes CO ₂separation;

The method also comprises: utilize the parabolic trough type sun power of 200 DEG C to provide the latent heat of vaporization of reforming steam, be converted into internal steam work, being converted into syngas chemistry energy, realizing grade and promoting by participating in reforming reaction.

2. middle low-grade solar thermal energy grade according to claim 1 promotes and CO ₂the method that integration is separated, it is characterized in that, the method also comprises while utilizing the parabolic trough type sun power of 200 DEG C:

Utilize the light-focusing type tower type solar of 550 DEG C to provide the reaction heat needed for reforming reaction to be converted into syngas chemistry energy, realize grade and promote, finally in high efficiency burnt gas-steam combined cycle system, realize heat to power output.

3. realize a device for method described in claim 1, it is characterized in that, comprising:

Air compressor (1), for air (S1) being boosted to the top pressure of Brayton circulation, forming pressurized air (S2) and exporting to combustion chamber (2);

, there is combustion reactions for the synthesis of fuel gas (S25) and pressurized air (S2), obtain high-temperature gas (S26) in combustion chamber (2);

Gas turbine (3), for realizing high-temperature fuel gas (S26) expansion working;

Fuel compressor (4), for boosting to reforming reaction pressure by fuel gas (S3);

First boosting pump (5), for boosting to reforming reaction pressure by water (S5);

Economizer (6), for by reformate (S14, S15) heat supply, heats freshet stock (S7) to the saturated aquosity under reforming reaction pressure;

Solar still (7), for utilizing solar thermal energy by saturation water (S8) evaporation under reforming reaction pressure;

Trough type solar heat-collector (8), for assemble required in low-temperature solar energy, and export to solar still (7);

Regenerator (9), heats the gas mixture (S10) of water vapor (S9) with compressed fuel gas (S4) for utilizing reformate (S12, S13);

Tower type solar heat collector (10), for warm solar thermal energy in collection, exports to film reformer (11);

Film reformer (11), for by tower type solar heat collector (10) heat supply, makes fuel and water vapor carry out film reforming reaction under a certain pressure;

First condenser (12), for being rich in CO ₂synthetic gas (S16) cool, and remove water of condensation (S18);

Hydrogen gas compressor (13), the hydrogen (S17) for reforming reaction being obtained boosts to the top pressure of Brayton circulation;

Second boosting pump (14), for boosting to reforming reaction pressure by water of condensation (S18);

CO ₂physical absorption unit (15): for by the CO in synthol gas (S21) ₂be separated;

Gas compressor (16): for will CO be removed ₂clean fuel gas (S22) boost to Brayton circulation top pressure;

Three-pressure reheat boiler (17): by gas turbine smoke evacuation (S27) heat supply, complete the preheating of different pressures feedwater in bottoming cycle, evaporation, superheating process;

Steam turbine (18): superheated vapour (S32) expansion working that waste heat boiler produces;

Second condenser (19): steam turbine steam discharge (S29) is condensed to saturation water (S30) state, so that recycle;

3rd boosting pump (20): water of condensation (S30) is boosted to pressure needed for steam cycle; And

Generator (21,22): be connected with combustion gas and steam turbine respectively, is converted into electric energy by the mechanical work that turbine produces and exports.

4. device according to claim 3, it is characterized in that, in the apparatus, feedwater feeding economizer after pressurization is heated to the saturated aquosity under reforming pressure, enter solar still evaporation, water vapor mixes with the fuel gas after compression to be sent into regenerator and heats further, enters the film reforming reactor generation thermo-negative reaction of solar-heating subsequently, obtains respectively being rich in CO in reactor film both sides ₂synthol gas and highly purified hydrogen; Synthol gas enters CO after condensation dehydration ₂physical absorption unit, water of condensation is reused as reforming reactants, isolated CO ₂through four inter-stage cold reduction liquefaction, to seal up for safekeeping, the clean fuel gas after decarburization is compressed into combustion reactions pressure, and the hydrogen after compression together enters combustion chamber as fuel and pressurized air burns, the high-temperature flue gas generated drives Gas-steam Combined Cycle work done, realizes Power output.

5. device according to claim 3, is characterized in that, described film reformer (11) institute heat requirement is provided by tower type solar heat collector (10), imports and exports and is all connected with regenerator (9).

6. device according to claim 3, it is characterized in that, described regenerator (9) hot side-entrance is connected with film reformer (11), outlet connects economizer (6), cold side import is connected with the mixing section of water vapor with fuel gas, outlet junctional membrane reformer (11).

7. device according to claim 3, it is characterized in that, described solar still (7) institute heat requirement is provided by trough type solar heat-collector (8), import is connected with economizer (6), and outlet vapor (S9) mixes with compressed fuel gas (S4).

8. device according to claim 3, it is characterized in that, described economizer (6) hot side-entrance is connected with regenerator (9), outlet connects the first condenser (12) and hydrogen gas compressor (13) respectively, cold side import is connected with the first boosting pump (5), the second boosting pump (14), and outlet connects solar still (7).

9. device according to claim 3, is characterized in that, introduce palladium-base alloy membrane structure in described film reformer (11), exit gas is reformate (S12, S13) two bursts of logistics.

10. device according to claim 3, is characterized in that, a water vapor part needed for described reforming reaction comes from and is rich in CO ₂synthetic gas (S16) in water of condensation (S18), all the other by moisturizing supplement (S5).

11. devices according to claim 3, it is characterized in that, described steam turbine (18) high pressure cylinder exit portion gas is used for gas turbine (3) blade cooling, draws and mix with reheated steam after cooling, enters intermediate pressure cylinder and continues expansion working.