CN101913559A - Zero emission device for preparing hydrogen, generating power and producing carbon - Google Patents
Zero emission device for preparing hydrogen, generating power and producing carbon Download PDFInfo
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- CN101913559A CN101913559A CN2010102504599A CN201010250459A CN101913559A CN 101913559 A CN101913559 A CN 101913559A CN 2010102504599 A CN2010102504599 A CN 2010102504599A CN 201010250459 A CN201010250459 A CN 201010250459A CN 101913559 A CN101913559 A CN 101913559A
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Abstract
The invention relates to a zero emission device for preparing hydrogen, generating power and producing carbon, which comprises three systems of a gas cracking reactor, a PSA (Pressure Swing Adsorption) separating device and a PEM (Proton Exchange Membrane) fuel cell device. Alkane gases, such as natural gas, coal bed gas, methane, and the like are blown into the gas cracking reactor by a fan for carrying out catalytic decomposition; after the decomposed gas enters the PSA separating device after being subjected to heat exchange and cooling; separated hydrogen enters the PEM fuel cell device for generating power; after undecomposed raw gas is mixed with source gas, the mixture gas enters the next catalytic decomposition circulation; the zero-emission low-energy consumption comprehensive utilization on the natural gas, the coal bed gas and the methane is realized; meanwhile, the catalytic cracking temperature can be changed according to catalyst materials in different systems, and a nano carbon material in a product is automatically collected; and the incomplete decomposed raw gas is subjected to secondary catalytic decomposition after PSA separation so as to ensure that zero emission in 100 percent is realized.
Description
Technical field
The present invention relates to a kind of Zero emission device that is used for Sweet natural gas, coal-seam gas, biogas hydrogen production from catalytic pyrolysis generating power and producing carbon, i.e. zero emission device for preparing hydrogen, generating power and producing carbon.
Background technology
So-called " zero release " be meant ad infinitum reduce pollutent and can source emission until the activity that is zero, promptly utilize cleaner production, 3R (Reduce, Reuse, Recycle) and technology such as ecological industry, realization is to the complete recycle of natural resources, thereby do not give atmosphere, water body and soil leaves over any waste.So zero release with regard to its content, on the one hand is will control to have no alternative but the waste discharge that produces in the production process, and it is reduced to zero; Be that the waste of will have no alternative but discharge makes full use of on the other hand, finally eliminate the existence of the Nonrenewable resources and the energy.With regard to its process, be meant that the waste that will discharge in a kind of industry production process becomes the raw material or the fuel of another kind of industry, thereby make related industries form industrial ecosystem by recycle.Technically, in the industry production process, certain natural law is all followed in the conversion of energy, the energy, resource, and resource conversion is that various energy, various energy transform mutually, starting material are converted into product, all can not realize 100% conversion.According to the law of conservation of energy and the law of conservation of matter, the part of its loss finally enters environment with forms such as water, gas, sound, slag, heat.Environmental Protection in China work is started late, and with existing technology, economic condition, accomplishes that really the waste of will have no alternative but discharge reduces to zero, is extremely difficult.Some enterprise has realized so-called " zero release " by to haveing no alternative but making full use of of discharged waste, has also just changed mode, channel and the node of pollutant emission, and some pollutents finally will enter environment.In this sense, real " zero release " be a kind of theory, the ideal state.
Since the seventies in 20th century indivedual industrial sectors just grope " zero release ", mainly referring to does not at that time have waste water to discharge from factory, all waste water are converted into a solid waste residue through secondary or three grades of sewage disposals except reuse is just only remaining.A Belgian entrepreneur Gunter Pauli established " meeting of zero release research innovation funds " ZERI (Zero Emissions Research Initiatives) by 1994, " zero release " was risen to a kind of theoretical system from indivedual dispersive activities.United Nations had been duly admitted " zero release " notion in 1998, and began to carry out pilot with ZERI foundation cooperation.General headquarters in 1999 are built up in Japanese United Nations University and have set up " United Nations University/zero release forum ", this forum in 2007 and China State Development and Reform Commission person understand resources conservation and cooperate with environmental protection department, hold " develop a circular economy, promote the refuse zero release " forum in Beijing.
In view of " zero release " talked about on the current Chinese society main still " discharge of wastewater is zero " on the primitive meaning, be called for short ZLD (Zero Liguid Discharge).Zero-discharge technology is the integrated application membrane sepn, physics such as evaporative crystallization and/or drying, chemistry, biological process, solid impurity in the middle of the waste water is concentrated into very high density, most of water has returned cyclically utilizing, the remaining water of following solid waste on a small quantity, can select in the following outlet a kind of according to each enterprise's particular case, (this " zero release " decision-making should be considered the factor of following three broad aspect at least: environmental requirement-Financial cost (enterprise competitiveness)-production safety) along with expanding economy, the mankind press for the clean free of contamination energy of exploitation and needn't discharge system.
Hydrogen as energy source has been subjected to people's great attention as cleaning secondary energy efficiently as far back as the seventies in 20th century, and its purposes mainly contains the following aspects: hydrogen is used for space flight industries such as space shuttle, rocket as a kind of high energy fuels; Hydrogen has been widely used in electron trade as shielding gas; In fields such as metallurgy, chemical industry, hydrogen is used for the smelting of metal and synthesizing of Chemicals as reductive agent and raw material, is widely used in the hydrogen storage material performance study simultaneously.Along with the fast development of fuel cell technology with and manufacturing technology ripe day by day, highly purified hydrogen is widely used in the fuel of fuel cell.At present, the method of hydrogen manufacturing mainly contains water electrolysis method, photodissociation water law, carbon and hydrocarbon polymer preparing synthetic gas by reforming method and catalystic pyrolysis etc., wherein, the hydrogen manufacturing of hydrocarbon polymer preparing synthetic gas by reforming method is the most frequently used method of current extensive hydrogen manufacturing, yet the shortcoming of synthetic gas method hydrogen manufacturing is to generate CO, CO
2And H
2Mixture, separation difficulty, the hydrogen manufacturing cost is its most fatal weakness, and, for the use (H of hydrogen fuel cell
2Middle CO concentration is less than 20 * 10
-5) and industrial production to the demand of clean hydrogen, CO must be from H
2In remove.In recent years, methane catalytic decomposition hydrogen manufacturing had become the focus of research, by cracking CH
4Can prepare the not H of carbon oxide
2(can directly use) and carbon nanotube (CNTs by the PEMFC fuel cell, have very good physical strength, electroconductibility and thermal conductivity), owing to can obtain this two kinds of very important products simultaneously, so this technological line has caused many investigators' attention.This technology still is in the conceptual phase at present, because problems such as catalyzer and system design, and fail to realize simultaneously the preparing hydrogen, generating power and producing carbon material, and adopt alkanes gas former (Sweet natural gas, coal-seam gas, biogas) catalytic pyrolysis preparing hydrogen production device mostly to be open cracking apparatus, because catalyst life is limited, can not realize serialization production, and transformation efficiency not high (mostly below 60%), after the cracking in the tail gas carbonic acid gas isothermal chamber gas content after residual methane gas and the cracking higher, and truly the zero release of being unrealized.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of alkane hydrogen class gases such as Sweet natural gas, coal-seam gas, biogas that are used for by gas cracking reactor, PSA transformation adsorption separation device and PEM Proton Exchange Membrane Fuel Cells device, can realize catalytic pyrolysis to Sweet natural gas, coal-seam gas, biogas, the hydrogen that produces after to cracking when obtaining the graphitization nano carbon material of high added value generates electricity, and realizes the comprehensive utilization to Sweet natural gas, coal-seam gas, biogas zero release, less energy-consumption.
Zero emission device for preparing hydrogen, generating power and producing carbon is made up of gas cracking reactor, PSA transformation adsorption separation device and PEM Proton Exchange Membrane Fuel Cells device three big systems.
Wherein the unstripped gas storage tank is communicated with exhaust gas heat exchanger by the air inlet blower fan, exhaust gas heat exchanger is communicated with the gas cracking reactor by heat exchange T-valve, T-valve, MFM mass flowmeter, realization is produced the carbon process to the circulation catalytic decomposition hydrogen manufacturing of alkane hydrogen class gas in the unstripped gas storage tank, it is graphitization nano onion carbon that this process produces carbon, the gas cracking reactor is communicated with exhaust gas heat exchanger by exhaust pipe, exhaust pipe is provided with the tail gas T-valve, and the source of the gas gas that exhaust gas heat exchanger is squeezed into the unstripped gas storage tank by the air inlet blower fan carries out heat exchange; Exhaust gas heat exchanger is provided with cooling blower, cooling blower is connected with PSA transformation adsorption separation device by air compressor, main effect is that Sweet natural gas, coal-seam gas, the biogas tail gas after gas cracking reactor catalytic decomposition is passed through exhaust gas heat exchanger after the overcooling blower fan is cooled to below 40 ℃, pass through air compressor then, will enter PSA transformation adsorption separation device behind the tail gas boil down to 10bar; PSA transformation adsorption separation device links to each other with PEM Proton Exchange Membrane Fuel Cells device through the blower fan of giving vent to anger, hydrogen T-valve, realizes that the hydrogen after the separation of PSA transformation adsorption separation device is entered PEM Proton Exchange Membrane Fuel Cells device to generate electricity; PSA transformation adsorption separation device divided gas flow air exhauster on gas exhaust duct communicates with the unstripped gas storage tank, is mixed into next catalytic decomposition process to separating back undecomposed Sweet natural gas, coal-seam gas, biogas through the unstripped gas that divided gas flow air exhauster and unstripped gas storage tank are provided.
On the described gas cracking reactor thermopair is installed, is used for gas cracking reactor furnace temperature is measured.
Described gas cracking reactor links to each other with afterheat heat exchanger by waste heat backheat pipeline, and to fail to reach the gas cracking reactor temperature required when temperature, then passes through waste heat backheat pipeline and enters afterheat heat exchanger and carry out heat exchange to supply catalytic pyrolysis temperature required.
Described gas cracking reactor links to each other with the air inlet blower fan by air intake control valve, is used for providing gas cracking reactor catalytic pyrolysis process required oxygen.
Described PSA transformation adsorption separation device pressure reduction is 3～10bar.
Patent of the present invention combines catalytic pyrolysis process, transformation adsorption separation process and PEM Proton Exchange Membrane Fuel Cells device power generation process, to Sweet natural gas, coal-seam gas, paraffin gass such as biogas blast the gas cracking reactor through blower fan and carry out catalytic decomposition, tail gas after the decomposition enters PSA transformation adsorption separation device through heat exchange with after cooling off, hydrogen after the separation enters PEM Proton Exchange Membrane Fuel Cells device and generates electricity, enter next catalytic decomposition circulation after undecomposed unstripped gas and source of the gas gas mix, realize Sweet natural gas, coal-seam gas, the biogas zero release, the comprehensive utilization of less energy-consumption; Simultaneously,, can change the catalytic pyrolysis temperature, collect the nano-carbon material in the product automatically according to the catalystic material of different systems; For the unstripped gas of not decomposing fully, decompose through carrying out quadric catalysis after the transformation fractionation by adsorption, to guarantee to realize 100% zero release.
Description of drawings
Fig. 1 is a structural representation of the present invention
Wherein, 1, unstripped gas storage tank; 2, air inlet blower fan; 3, the blower fan of giving vent to anger; 4, T-valve; 5, the MFM mass flowmeter 5; 6, gas cracking reactor; 7, tail gas T-valve; 8, exhaust gas heat exchanger; , 9, cooling blower; 10, air compressor; 11, PSA transformation adsorption separation device; 12, divided gas flow air exhauster; 13, hydrogen T-valve; 14, PEM Proton Exchange Membrane Fuel Cells device; 15, thermopair; 16, air inlet blower fan; 17, air intake control valve; 18, heat exchange T-valve; 19, afterheat heat exchanger; 20, waste heat backheat pipeline.
Embodiment
Be performed such in implementation process: source of the gas gas enters exhaust gas heat exchanger 8 by air inlet blower fan 2 in the unstripped gas storage tank 1, carry out heat exchange with the source of the gas gas in the unstripped gas storage tank 1, gas is by heat exchange T-valve 18 after the heat exchange, T-valve 4, MFM mass flowmeter 5 is communicated with gas cracking reactor 6, realization is produced the carbon process to the circulation catalytic decomposition hydrogen manufacturing of alkane hydrogen class gas in the unstripped gas storage tank 1, it is graphitization nano onion carbon that this process produces carbon, tail gas after the catalytic decomposition enters through tail gas T-valve 7 that source of the gas gas carries out heat exchange in exhaust gas heat exchanger 8 and the unstripped gas storage tank 1, finishes the hydrogen manufacturing that once circulates and produces the carbon process; Sweet natural gas, coal-seam gas, the biogas tail gas process exhaust gas heat exchanger 8 after gas cracking reactor 6 catalytic decomposition is after overcooling blower fan 9, after being cooled to below 40 ℃ through air compressor 10, PSA transformation adsorption separation device 11 will be entered behind the tail gas boil down to 10bar, hydrogen after the separation links to each other with PEM Proton Exchange Membrane Fuel Cells device 14 through the blower fan 3 of giving vent to anger, hydrogen T-valve 13, realizes that the hydrogen after 11 separation of PSA transformation adsorption separation device is entered PEM Proton Exchange Membrane Fuel Cells device 14 to generate electricity; Undecomposed Sweet natural gas after 12 pairs of separation of divided gas flow air exhauster on the PSA transformation adsorption separation device 11, coal-seam gas, biogas are mixed into next catalytic decomposition process through the unstripped gas that divided gas flow air exhauster and unstripped gas storage tank 1 are provided.
Source of the gas is measured by thermopair 15 through exhaust gas heat exchanger 8 back temperature in the gas cracking reactor 6,6 warm stoves are temperature required if temperature fails to reach the gas cracking reactor, then enter afterheat heat exchanger 19 through waste heat backheat pipeline 20 and carry out heat exchange to supply catalytic pyrolysis temperature required.
The present invention is the hydrogen production from catalytic pyrolysis generating power and producing carbon Zero emission device that is used for Sweet natural gas, coal-seam gas, biogas, there are not gases such as carbonic acid gas or carbon monoxide to discharge in the whole implementation process, do not have methane isothermal chamber gas to discharge yet, realize real no gaseous emission, realize zero release.Source of the gas gas is example with methane, and at normal pressure, 800 ℃ of following catalytic pyrolysiss, methane conversion is 90%, near theoretical yield (92.9%), is 20.5% according to energy net income in the whole process.The carbon that produces is high-graphitized nano-onions carbon.
Claims (4)
1. zero emission device for preparing hydrogen, generating power and producing carbon is characterized in that: be made up of gas cracking reactor, PSA transformation adsorption separation device and PEM Proton Exchange Membrane Fuel Cells device three big systems;
Wherein the unstripped gas storage tank is communicated with exhaust gas heat exchanger by the air inlet blower fan, exhaust gas heat exchanger is communicated with the gas cracking reactor by heat exchange T-valve, T-valve, MFM mass flowmeter, the gas cracking reactor is communicated with exhaust gas heat exchanger by exhaust pipe, and exhaust pipe is provided with the tail gas T-valve; Exhaust gas heat exchanger is provided with cooling blower, and cooling blower is connected with PSA transformation adsorption separation device by air compressor; PSA transformation adsorption separation device links to each other with PEM Proton Exchange Membrane Fuel Cells device through the blower fan of giving vent to anger, hydrogen T-valve; PSA transformation adsorption separation device divided gas flow air exhauster on gas exhaust duct communicates with the unstripped gas storage tank.
2. zero emission device for preparing hydrogen, generating power and producing carbon as claimed in claim 1 is characterized in that: on the described gas cracking reactor thermopair is installed.
3. zero emission device for preparing hydrogen, generating power and producing carbon as claimed in claim 1 is characterized in that: described gas cracking reactor links to each other with afterheat heat exchanger by waste heat backheat pipeline.
4. zero emission device for preparing hydrogen, generating power and producing carbon as claimed in claim 1 is characterized in that: described PSA transformation adsorption separation device pressure reduction is 3～10bar.
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| CN 201010250459 CN101913559B (en) | 2010-08-02 | 2010-08-02 | Zero emission device for preparing hydrogen, generating power and producing carbon |
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|---|---|---|---|
| CN 201010250459 CN101913559B (en) | 2010-08-02 | 2010-08-02 | Zero emission device for preparing hydrogen, generating power and producing carbon |
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| CN101913559A true CN101913559A (en) | 2010-12-15 |
| CN101913559B CN101913559B (en) | 2013-05-22 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108439336A (en) * | 2018-05-08 | 2018-08-24 | 上海发电设备成套设计研究院有限责任公司 | A kind of zero-emission cogeneration of hydrogen and electricity system |
| CN110090532A (en) * | 2019-04-10 | 2019-08-06 | 大连理工大学 | A kind of near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition |
| CN111232923A (en) * | 2019-12-31 | 2020-06-05 | 四川天采科技有限责任公司 | Hydrogen extraction method capable of adjusting hydrogen-carbon ratio of natural gas direct cracking circulating reaction gas |
| CN114060899A (en) * | 2021-11-29 | 2022-02-18 | 北京华能长江环保科技研究院有限公司 | Distributed energy utilization system for heating and power generation |
| CN114225628A (en) * | 2021-12-20 | 2022-03-25 | 成都珈丰新能源科技有限公司 | Method and device for separation of tail gas in the process of preparing carbon nanotubes by catalytic cracking of hydrocarbons by multistage partial pressure continuous adsorption method |
| CN114725432A (en) * | 2022-05-05 | 2022-07-08 | 成都岷山绿氢能源有限公司 | Zero-carbon power generation system and power generation process of solid oxide fuel cell |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108439336A (en) * | 2018-05-08 | 2018-08-24 | 上海发电设备成套设计研究院有限责任公司 | A kind of zero-emission cogeneration of hydrogen and electricity system |
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| CN110090532A (en) * | 2019-04-10 | 2019-08-06 | 大连理工大学 | A kind of near-zero release carbon material preparation process of UF membrane coupling lighter hydrocarbons thermal decomposition |
| CN111232923A (en) * | 2019-12-31 | 2020-06-05 | 四川天采科技有限责任公司 | Hydrogen extraction method capable of adjusting hydrogen-carbon ratio of natural gas direct cracking circulating reaction gas |
| CN111232923B (en) * | 2019-12-31 | 2021-10-15 | 四川天采科技有限责任公司 | Hydrogen extraction method for adjusting hydrogen-carbon ratio of natural gas direct cracking circulating reaction gas |
| CN114060899A (en) * | 2021-11-29 | 2022-02-18 | 北京华能长江环保科技研究院有限公司 | Distributed energy utilization system for heating and power generation |
| CN114225628A (en) * | 2021-12-20 | 2022-03-25 | 成都珈丰新能源科技有限公司 | Method and device for separation of tail gas in the process of preparing carbon nanotubes by catalytic cracking of hydrocarbons by multistage partial pressure continuous adsorption method |
| CN114225628B (en) * | 2021-12-20 | 2024-10-29 | 成都珈丰新能源科技有限公司 | Method and device for separating tail gas in process of preparing carbon nano tube by catalytically cracking hydrocarbon by multistage pressure-dividing continuous adsorption method |
| CN114725432A (en) * | 2022-05-05 | 2022-07-08 | 成都岷山绿氢能源有限公司 | Zero-carbon power generation system and power generation process of solid oxide fuel cell |
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| CN101913559B (en) | 2013-05-22 |
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