CN110026071A - It is a kind of that the carbon cycle system and method utilized is restored based on ammonia process decarburization and electro-catalysis - Google Patents
It is a kind of that the carbon cycle system and method utilized is restored based on ammonia process decarburization and electro-catalysis Download PDFInfo
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Abstract
It is a kind of that the carbon cycle system and method utilized is restored based on ammonia process decarburization and electro-catalysis, belong to green energy resource applied technical field.The present invention is trapping utilization and the conversion storage problem for solving carbon dioxide.Including ammonia process decarbonization system, electro-catalysis also original system, clean energy resource recovery system and melt down regulator control system；The boiler tail end flue gas of fired power generating unit is passed through ammonia process decarbonization system and carries out CO2 removing, the ammonium bicarbonate crystal and carbodiimide solution of generation, through generating the clean energy resourcies such as CO, formic acid by electro-catalysis reduction system catalytic reduction after processing；After the recovery processing of clean energy resource recovery system, for melting down regulation and for providing chemical industry raw material；Regulator control system is melted down when fired power generating unit is in heavy-duty service, clean energy resource is provided and enters furnace, and superfluous electric energy is supplied to electro-catalysis also original system when underrun.The present invention solves the problem of excess production capacity that power plant generates because clean energy resource networks, and is capable of forming effective carbon cycle system.The present invention can be used for all kinds of fired power generating units.
Description
Technical field
The present invention relates to a kind of ammonia process decarburizations and electro-catalysis to restore the carbon cycle system and method utilized, is related to decarburization, carbon
Circulation and green energy resource applied technical field.
Background technique
According to statistics, the consumption of fossil energy in 2016 still accounts for the 85.5% of global Energy Consumption total amount, and short-term
Significant change is not had inside.The mankind lead to greenhouse gas emission for depending on unduly for fossil energy (coal, petroleum, natural gas)
Middle CO2 emission concentration rises to the highest level over 800,000 years, reaches 3.3 million tons.In recent years, the row of carbon dioxide
Although high-volume growth rate slows down, whole still linear ascendant trend.2016, China had become the big carbon of the first in the world
State is discharged, carbon discharge capacity accounting 27.3% is more than that (BP world energy sources count year to nearly 11.3 percentage points of the deputy U.S. within 2016
Mirror).In order to solve this status, in signature " Paris agreement " in 2015, protocol target is the dioxy in the year two thousand thirty China in China
Change than 2005 decline 60%-65% of carbon emission amount.Therefore, the trapping for developing carbon dioxide utilizes and conversion memory technology,
As greenhouse effects are solved the problems, such as, reach the important outlet of protocol target.
Ammonia process decarburization technique is all CO all the time2One of important process of trapping.Its advantage is that: 1, absorbent be not easy by
Oxidative degradation；2, CO with higher2Absorb load；3, low energy consumption；4, corrosion-free problem.But there are still many problems, such as:
1, the escaping of ammonia 2, regeneration energy consumption are high 3, reaction later period absorptivity is low etc..And novel ammonia process decarbonization process can solve traditional handicraft and deposit
The problem of, which makes it be more than solution degree of supersaturation using ethyl alcohol as dissolved agent, to reduce the solubility of carbodiimide solution, generates brilliant
Body product.The low energy consumption parsing for realizing carbon dioxide is regenerated with crystallized product.There are mainly two types of implementation method, respectively mixing is inhaled
Agent method and dissolved method are received, being distinguished as composite absorber method is that dissolved agent is added in absorption tower and crystallizes, and dissolved method is to inhale
It receives and is crystallized outside tower.Dissolved method advantage: 1, process can be individually operated, convenient for strengthening crystallization；2, crystallization yield is high；3, crystal grain
Diameter is small, is conducive to reduce decompression energy consumption.The crystalline product of both implementation methods is mainly ammonium hydrogen carbonate, the main component of waste liquid
For ammonium hydrogen carbonate, ammonium carbonate, aminoquinoxaline and ethyl alcohol etc..
It is very promising in conjunction with China's present power status processing decarburization product.Chinese petroleum economics Institute for Research and Technology pair
It in the prediction of the year two thousand fifty China's power generation energy resource, is shown under the support energetically that China networks to clean energy resource, clean energy resource power generation
Ratio is by 50% or more accounting.China constantly find reinforce power grid dissolve clean energy resource, be effectively relieved " abandon water, abandonment,
The method of abandoning light " situation.Up to now, China's fired power generating unit checks and approves building scale and has been up to 1.9 hundred million kilowatts, obvious confession occurs
The phenomenon that greater than asking.Coal fired power generation installation is up to peak value after scholarly forecast the year two thousand twenty, will there is more than one hundred million kilowatts of fired power generating units at that time
As superfluous production capacity, this will cause the Thermal generation unit idleness of equipment largely created or low power run.Meanwhile it can also be serious
Influence the production and operation of clean energy resource electricity power enterprise.
Electro-catalysis restores in the technology of carbon dioxide, based on the exploitation of Different electrodes material, is often used three-electrode system.
By different electrodes, i.e., carbon dioxide electro-catalysis is converted the cleanings energy such as CO, formic acid, methane, methanol by different catalyst
Source.Because required electric energy is larger, economy is restricted, and the feed carbon dioxide for being catalyzed reduction need to be the titanium dioxide of high-purity
Carbon.Therefore, technology is confined on laboratory research and mechanism study.In conjunction with the above status, a kind of novel ammonia process decarburization of proposition
And the carbon cycle technology that electro-catalysis reduction utilizes is imperative.
Summary of the invention
The present invention is to solve the trapping of carbon dioxide to utilize and conversion storage problem, provide it is a kind of based on ammonia process decarburization and
Electro-catalysis restores the carbon cycle system and method utilized.
The present invention solves the technical solution that above-mentioned technical problem uses are as follows:
A kind of to restore the carbon cycle system utilized based on ammonia process decarburization and electro-catalysis, the carbon cycle system includes: ammonia process
Decarbonization system, electro-catalysis also original system, clean energy resource recovery system and melt down regulator control system；
The ammonia process decarbonization system includes cooler (flue gas cooling device), CO2Absorption tower, dissolved method strengthen system of crystallization
System and solid-liquid separator (equipment for separating liquid from solid)；Boiler smoke enters CO after cooler is cooling2Absorption tower, it is strong by dissolved method
Change crystal system and removes CO2And ammonium bicarbonate crystal and carbodiimide solution are formed, after product is separated by solid-liquid separator, it is respectively fed to electricity
The electric catalyticing system 1 and electric catalyticing system 2 of catalyst reduction system；Remaining flue gas is by CO2The exhanst gas outlet on absorption tower is discharged；
The electro-catalysis also original system raw material by processed ammonium bicarbonate crystal and carbodiimide solution, as consumption respectively
Electro-catalysis reduction is carried out, clean energy resource CO or formic acid are formed；Required electric energy via melt down regulator control system judgement after provide；
The clean energy resource recovery system by electro-catalysis reduction system outlet clean energy resource by processing classification after, one
Divide to be supplied to and melt down regulator control system, another part is stored in industrial storage device for industrial application；
The regulator control system that melts down is for judging boiler operatiopn state and whether for electric catalyticing system providing electric energy, if into
Row clean energy resource melts down；In fired power generating unit underrun, system controls the electricity for being supplied to electric catalyticing system, carries out electricity and urges
Change reduction；When heavy-duty service, the clean energy resource CO that will be recycled from clean energy resource recovery system melts down combustion-supporting and inhibits NOx
Generate situation.
Further, the CO2Absorption tower absorbs CO using ammonia process decarbonization method2, and solution is passed through dissolved method and strengthens knot
Crystallographic system system, carries out CO2The reinforcing crystallization of absorption and the cycle applications of absorbent；The crystal and carbodiimide solution of product are via separation of solid and liquid
Electro-catalysis also original system is sent into after device separation.
Further, the electro-catalysis also original system is divided into electric catalyticing system 1 and electric catalyticing system 2,1 electricity of electric catalyticing system
Ammonium bicarbonate aqueous solution after being catalyzed reduction treatment, the carbodiimide solution after 2 electro-catalysis reduction treatment of electric catalyticing system.
Two systems used catalyst is based on metallic catalyst, with metal Zn, Ag, Au and through other metals of overdoping
Based on Zn, Ag, Au electrode after changing performance, it is intended in not being passed through CO2Under conditions of, by ammonium hydrogen carbonate or carbodiimide solution electrolyte
Direct electrochemistry is reduced to CO and H2Equal clean energy resourcies；Based on the electrodes such as Bi or Sn with metal Bi and Sn etc. and after processing,
In not being passed through CO2Under conditions of, electrolyte direct electrochemistry is reduced to the clean energy resourcies such as formic acid；Electric energy is sentenced by regulator control system
Disconnected conveying.
Further, the clean energy resource recovery system includes product separator, liquid products conversion device and liquid
Loop back device, product separator by generation predominantly formic acid product liquid and predominantly CO and H2Gaseous product point
From；Product liquid formic acid etc. is converted CO and H by liquid products conversion device2Gas；Liquid loop back device returns remaining liquid
It send to liquid handling device, is re-supplied to electro-catalysis also original system after processing.
Further, the regulator control system that melts down includes judgment means and melts down control device, and the judgment means are used for
Fired power generating unit is judged for high load capacity or underrun, and regulation is conveyed to electricity and the action time of electric catalyticing system；Described time
Furnace control device is for regulating and controlling the clean energy resource gas flow of recycling and melting down the time.
A kind of to restore the carbon cycle method utilized based on ammonia process decarburization and electro-catalysis, the method is based on above system come real
Existing, the realization process of the method are as follows:
Firstly, boiler smoke is passed through in ammonia process decarbonization system, after flue gas is via flue gas cooling device cooling, it is passed through CO2
Absorption tower carries out ammonia absorption, and the dissolved method of absorption tower lower end connection strengthens crystal system, strengthens CO2Arresting efficiency, generation are caught
Carbon product ammonium bicarbonate crystal and carbodiimide solution；The product of generation is separated by equipment for separating liquid from solid, and extra ammonium hydroxide is returned and is absorbed
Tower, crystal and carbodiimide solution are sent into electro-catalysis also original system 1 and system 2 after handling respectively；
In electro-catalysis also original system, different voltage is controlled, product is subjected to electro-catalysis using different elctro-catalysts
The clean energy resource of reduction, generation is sent into clean energy resource recovery system；Product separation is carried out first, gaseous product is a certain proportion of
CO and H2Gas collection, product liquid are delivered to reforming unit, are partially converted into clean energy resource gas, part industry storage；Its
Extraction raffinate body is recycled to electro-catalysis also original system；
The effect for melting down regulator control system always exists in the whole process, melts down the judgment means of regulator control system, can
Judge fired power generating unit status for high load capacity or underload；To which control device is melted down in control, under high loads, cleaned
The energy melts down operation, and controls the amount of melting down and melt down the time；At low load, control is conveyed to the electricity and work of electric catalyticing system
With the time, the mechanism of flexible modulation is realized.
Present invention feature the most prominent and significant beneficial effect are:
A kind of novel ammonia process decarburization and electro-catalysis according to the present invention restore the carbon cycle technical method utilized, original
Ammonia process decarburization on the basis of, establish more efficiently novel C O2Capture method improves CO2Arresting efficiency.Meanwhile passing through electricity
The method for being catalyzed reduction, the CO that will be trapped2It is converted into storable such as formic acid, CO clean energy resource, forms effective carbon
The circulatory system.The technical method not only can solve the application problem of novel ammonia process decarburization product, also can solve fired power generating unit
Problem of excess production capacity can also solve electro-catalysis reduction CO2Electric energy and CO in the process2The offer problem in source.Clean energy resource melts down
Regulator control system, the not only electric energy supply of adjustable electric catalyticing system, (idle) can also utilize in performing low-load running of machine set
Remaining electricity, CO etc. is melted down raising efficiency by (busy) when heavy-duty service reduces the discharge of the pollutants such as NOx, is formed a kind of controllable
Flexibility adjustment mechanism, realize and the offer of fuel be provided.
The present invention includes ammonia process decarbonization system, electro-catalysis also original system, clean energy resource recovery system and melts down regulator control system.
The boiler tail end flue gas of fired power generating unit is passed through ammonia process decarbonization system and carries out CO2 removing, the ammonium bicarbonate crystal and carbodiimide solution of generation
(ammonium hydrogen carbonate and ammonium carbonate etc.), through generating the clean energy resourcies such as CO, formic acid by electro-catalysis reduction system catalytic reduction after processing；
After the recovery processing of clean energy resource recovery system, a part is for melting down regulation, and another part is for providing chemical industry raw material；
Regulator control system is melted down when fired power generating unit is in heavy-duty service, and clean energy resource is provided and enters furnace, it will be superfluous when underrun
Electric energy is supplied to electro-catalysis also original system.The present invention solves the problem of excess production capacity that power plant generates because clean energy resource networks,
And it is capable of forming effective carbon cycle system.The present invention can be used for all kinds of fired power generating units.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of system of the present invention.
Specific embodiment
A kind of carbon cycle system utilized based on ammonia process decarburization and electro-catalysis reduction of the present invention includes: ammonia process decarburization
System, electro-catalysis also original system, clean energy resource recovery system and melt down regulator control system；
The novel ammonia process decarbonization system includes flue gas cooling device, CO2Absorption tower, dissolved method strengthen crystal system and
Equipment for separating liquid from solid；Boiler smoke enters CO after cooler is cooling2Absorption tower, CO2Absorption tower uses novel ammonia process decarbonization method
Absorb CO2, and solution is passed through dissolved method and strengthens crystal system, carry out CO2The reinforcing crystallization of absorption and the circulation of absorbent are answered
With；The crystal and carbodiimide solution of product are separated via equipment for separating liquid from solid, are respectively fed to electric catalyticing system 1 and electric catalyticing system 2.Its
Remaining flue gas is discharged by absorption tower gas vent；
The electric catalyticing system is divided into system 1 and system 2, the ammonium bicarbonate aqueous solution after 1 electro-catalysis reduction treatment of system,
Carbodiimide solution after 2 electro-catalysis reduction treatment of system.Form the clean energy resourcies such as CO or formic acid；Required electric energy is via melting down regulator control system
It is provided after judgement；Two systems used catalyst is different.
The clean energy resource recovery system includes product separator, liquid products conversion device and liquid loop back device,
Separator can be by the cleaning liquid energy (predominantly formic acid) of generation and gas clean energy resource (predominantly CO and H2) separation；Liquid
Body product reforming unit can convert CO and H for product liquid formic acid etc.2Gas；Remaining liquid is recycled to by liquid loop back device
Electric catalyticing system.The clean energy resource of generation is stored in industrial storage device, and a part, which is supplied to, melts down regulator control system, another portion
Divide and is used for industrial application；
It is described to melt down regulator control system judgment means and melt down control device, for judging boiler operatiopn state and whether being electricity
Catalysis system provides electric energy, if carries out clean energy resource and melts down.The judgment means are born for judging that fired power generating unit is locating for height
Lotus operation or underrun, in underrun, system controls the electricity for being supplied to electric catalyticing system, carries out electro-catalysis also
Original, and control action time；The clean energy resourcies such as the CO recycled from clean energy resource recovery system are melted down when heavy-duty service
It is combustion-supporting and reduce NOx emission.It is described to melt down control device, for regulating and controlling the clean energy resource gas flow of recycling and melting down the time.
A kind of ammonia process decarburization is illustrated to specific embodiment in conjunction with Fig. 1 and electro-catalysis restores the carbon cycle side utilized
Method:
Firstly, boiler smoke is passed through in novel ammonia process decarbonization system, after flue gas is via flue gas cooling device cooling, it is passed through
CO2Absorption tower carries out ammonia absorption, and the dissolved method of absorption tower lower end connection strengthens crystal system, strengthens CO2Arresting efficiency generates
Catch carbon product ammonium bicarbonate crystal and carbodiimide solution.The product of generation is separated by equipment for separating liquid from solid, and extra ammonium hydroxide is returned and is inhaled
Tower is received, crystal and carbodiimide solution are sent into electro-catalysis also original system 1 and system 2 after handling respectively.
In electro-catalysis also original system, different voltage is controlled, product is subjected to electro-catalysis using different elctro-catalysts
The clean energy resource of reduction, generation is sent into clean energy resource recovery system.Product separation is carried out first, gaseous product is a certain proportion of
CO and H2Gas collection, product liquid are delivered to reforming unit, are partially converted into clean energy resource gas, part industry storage.Its
Extraction raffinate body is recycled to electro-catalysis also original system.
The effect for melting down regulator control system always exists in the whole process, judgment means, it can be determined that fired power generating unit
Status is high load capacity or underload.To which control device is melted down in control, under high loads, carries out clean energy resource and melt down behaviour
Make, and controls the amount of melting down and melt down the time.Under underload, control is conveyed to electricity and the action time of electric catalyticing system.It realizes
A kind of mechanism of flexible modulation.
Verification the verifying results explanation of the invention:
Ammonia process decarbonization system of the present invention is to CO2Removal efficiency up to 98.5%, the crystal of ammonium hydrogen carbonate receives brilliant feelings
Condition is good, replaces rich solution to regenerate with crystal regeneration, substantially reduces regeneration energy consumption.From integrated results as can be seen that integration after heat
Force system has the effect of depth energy saving, can recycle low temperature complementary energy 48.62MW.And in electric catalyticing system, electrode used therein is to electricity
Solve liquid NH4HCO3Deng reduction efficiency in, CO and H2Ratio 1:1- can be reached in lower overpotential (- 1.5vs.Ag/AgCl)
1:2 realizes that generation water-gas simultaneously utilizes again compared under low energy consumption.Novel ammonia process decarbonization system cooperates with work with electric catalyticing system
With, and the intelligence by melting down regulator control system is adjusted, and realizes that entire unit energy regulatory mechanism is established, it is preliminary realize the energy with
The fusion of information.
Claims (6)
1. a kind of restore the carbon cycle system utilized based on ammonia process decarburization and electro-catalysis, which is characterized in that the carbon cycle system
Include: ammonia process decarbonization system, electro-catalysis also original system, clean energy resource recovery system and melts down regulator control system；
The ammonia process decarbonization system includes cooler, CO2Absorption tower, dissolved method strengthen crystal system and solid-liquid separator；Boiler
Flue gas enters CO after cooler is cooling2Absorption tower strengthens crystal system by dissolved method and removes CO2And form ammonium bicarbonate crystal
And carbodiimide solution, after product is separated by solid-liquid separator, it is respectively fed to electric catalyticing system 1 and the electro-catalysis system of electro-catalysis also original system
System 2；Remaining flue gas is by CO2The exhanst gas outlet on absorption tower is discharged；
Respectively by processed ammonium bicarbonate crystal and carbodiimide solution, the raw material as consumption carries out the electro-catalysis also original system
Electro-catalysis reduction, forms clean energy resource CO or formic acid；Required electric energy via melt down regulator control system judgement after provide；
By the clean energy resource of electro-catalysis reduction system outlet after processing classification, a part mentions the clean energy resource recovery system
Regulator control system is melted down in supply, and another part is stored in industrial storage device for industrial application；
The regulator control system that melts down is for judging boiler operatiopn state and whether for electric catalyticing system providing electric energy, if carries out clear
The clean energy melts down；In fired power generating unit underrun, system controls the electricity for being supplied to electric catalyticing system, carries out electro-catalysis also
It is former；When heavy-duty service, the clean energy resource CO that will be recycled from clean energy resource recovery system melts down combustion-supporting and NOx is inhibited to generate
Situation.
2. a kind of carbon cycle system utilized based on ammonia process decarburization and electro-catalysis reduction according to claim 1, feature
It is, the CO2Absorption tower absorbs CO using ammonia process decarbonization method2, and solution is passed through dissolved method and strengthens crystal system, it carries out
CO2The reinforcing crystallization of absorption and the cycle applications of absorbent；After the crystal and carbodiimide solution of product are separated via equipment for separating liquid from solid
It is sent into electro-catalysis also original system.
3. a kind of carbon cycle system utilized based on ammonia process decarburization and electro-catalysis reduction according to claim 1 or 2, special
Sign is that the electro-catalysis also original system is divided into electric catalyticing system 1 and electric catalyticing system 2,1 electro-catalysis of electric catalyticing system also original place
Ammonium bicarbonate aqueous solution after reason, the carbodiimide solution after 2 electro-catalysis reduction treatment of electric catalyticing system.
4. a kind of carbon cycle system utilized based on ammonia process decarburization and electro-catalysis reduction according to claim 3, feature
It is, the clean energy resource recovery system includes product separator, liquid products conversion device and liquid loop back device, product
Separator by generation predominantly formic acid product liquid and predominantly CO and H2Gaseous product separation；Liquid products conversion
Product liquid formic acid etc. is converted CO and H by device2Gas；Remaining liquid is recycled to liquid handling dress by liquid loop back device
It sets, is re-supplied to electro-catalysis also original system after processing.
5. a kind of according to claim 4 restore the carbon cycle system utilized based on ammonia process decarburization and electro-catalysis, feature exists
In the regulator control system that melts down includes judgment means and melts down control device, and the judgment means are for judging that fired power generating unit is
High load capacity or underrun, regulation are conveyed to electricity and the action time of electric catalyticing system；The control device that melts down is used for
Regulate and control the clean energy resource gas flow of recycling and melts down the time.
6. a kind of restore the carbon cycle method utilized based on ammonia process decarburization and electro-catalysis, which is characterized in that the realization of the method
Process are as follows:
Firstly, boiler smoke is passed through in ammonia process decarbonization system, after flue gas is via flue gas cooling device cooling, it is passed through CO2Absorption tower
Ammonia absorption is carried out, the dissolved method of absorption tower lower end connection strengthens crystal system, strengthens CO2Carbon product is caught in arresting efficiency, generation
Ammonium bicarbonate crystal and carbodiimide solution；The product of generation is separated by equipment for separating liquid from solid, and extra ammonium hydroxide is returned to absorption tower, crystal
And carbodiimide solution handle respectively after be sent into electro-catalysis also original system 1 and system 2；
In electro-catalysis also original system, different voltage is controlled, product is subjected to electro-catalysis reduction using different elctro-catalysts,
The clean energy resource of generation is sent into clean energy resource recovery system；First carry out product separation, by a certain proportion of CO of gaseous product with
H2Gas collection, product liquid are delivered to reforming unit, are partially converted into clean energy resource gas, part industry storage；Remaining fluid
Body is recycled to electro-catalysis also original system；
The effect for melting down regulator control system always exists in the whole process, melts down the judgment means of regulator control system, can determine whether
Fired power generating unit status is high load capacity or underload；To which control device is melted down in control, under high loads, clean energy resource is carried out
Operation is melted down, and controls the amount of melting down and melts down the time；At low load, when control is conveyed to electricity and the effect of electric catalyticing system
Between, realize the mechanism of flexible modulation.
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| CN201910342579.2A CN110026071A (en) | 2019-04-25 | 2019-04-25 | It is a kind of that the carbon cycle system and method utilized is restored based on ammonia process decarburization and electro-catalysis |
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| CN201910342579.2A CN110026071A (en) | 2019-04-25 | 2019-04-25 | It is a kind of that the carbon cycle system and method utilized is restored based on ammonia process decarburization and electro-catalysis |
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| CN201910342579.2A Pending CN110026071A (en) | 2019-04-25 | 2019-04-25 | It is a kind of that the carbon cycle system and method utilized is restored based on ammonia process decarburization and electro-catalysis |
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| WO2023184637A1 (en) * | 2022-03-28 | 2023-10-05 | 势加透博（北京）科技有限公司 | Carbon dioxide capture method and system capable of co-producing carbon monoxide and hydrogen |
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| CA2833889A1 (en) * | 2012-11-30 | 2014-05-30 | Alstom Technology Ltd | Electroylytic reduction of carbon capture solutions |
| CN106693648A (en) * | 2016-12-08 | 2017-05-24 | 华电电力科学研究院 | Carbon dioxide capture system by employing ammonia process of strengthening crystallization and method of carbon dioxide capture system |
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| WO2023184637A1 (en) * | 2022-03-28 | 2023-10-05 | 势加透博（北京）科技有限公司 | Carbon dioxide capture method and system capable of co-producing carbon monoxide and hydrogen |
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