CN102408918A - High-quality high-efficiency water-gas shift method and device - Google Patents
High-quality high-efficiency water-gas shift method and device Download PDFInfo
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- CN102408918A CN102408918A CN2010102943308A CN201010294330A CN102408918A CN 102408918 A CN102408918 A CN 102408918A CN 2010102943308 A CN2010102943308 A CN 2010102943308A CN 201010294330 A CN201010294330 A CN 201010294330A CN 102408918 A CN102408918 A CN 102408918A
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Abstract
The invention discloses a high-quality high-efficiency water-gas shift method and a device. The invention adopts domestic wastes, kitchen wastes, municipal sludge, biomass and other carbon-containing substances or carbon-containing wastes as raw materials, and realizes a high-quality high-efficiency water-gas shift reaction by introducing water vapor under an air-isolated (oxygen-free) condition and performing microwave induction. The invention has a simple process, convenient operations, low running cost, short reaction time, low energy consumption, a high conversion rate, and widely-applicable raw materials; no catalyst is required; no coking phenomenon occurs; the prepared water gas has high quality, that is, a high H2 content; the H2/CO (volume ratio) is almost maintained to be about 2:1, which greatly reduces the purification and refining cost in subsequent procedures; biological fuel oil with low cost and high quality is prepared through FT (Fischer-Tropsch) synthesis, which can substitute scarce petroleum resources.
Description
Technical field
The present invention relates to the energy and energy-conserving and environment-protective field, specifically be meant a kind of high-quality high-level efficiency water-gas shift method and device.
Background technology
Along with China's rapid development of economy, energy consumption also grows with each passing day, and China has become the power consumption big country in the world, and the exhausted problem of the energy has seriously hampered the sound development of China's economy.According to estimates, will be 2.5 hundred million tons to the supply breach of the year two thousand twenty China's oil, externally interdependency is up to more than 54%, and oil crisis will become the major issue of the affairs that threaten the national security inevitably.A large amount of exploitations of the limited resources-mineral fuel of the earth (oil, coal, Sweet natural gas etc.) are used, and have accelerated global energy dilemma process on the one hand, have destroyed the ecotope of human society on the other hand, have also brought global environmental pollution (like SO
x, NO
xDeng a large amount of dischargings).The basic outlet that solves energy dilemma and environmental pollution is to develop the various renewable energy sources that comprise biomass energy.
At present, produce the strategic development direction that high-quality liquids and gases fuel has also become various countries' 21 century new energy development by biomass.In the research that in the past utilizes biomass exploitation biofuel; Raw material concentrates on higher plant; Especially the grain and oil plant as soybean, corn etc.; But face the facts such as world food is in short supply, ecosystem destruction, the route of being produced biofuel by the traditional grain crop suffers countries in the world scientist's query, forces people that eye is turned to the method with other development of raw materials biofuels.The nontoxic odorless of hydrogen itself generates water, no CO during burning
2Discharging is to solve one of effective cleaning energy of global greenhouse effect.Therefore, be raw material with domestic refuse, changing food waste, municipal sludge, biomass waste etc., the high water-gas of preparation hydrogen content is used to produce the high-quality biological fuel oil or relevant Chemicals have important strategic meaning and economic results in society.
Up to the present, the patent about high hydrogen richness water gas shift reaction has: " a kind of method of producing hydrogen by catalytic cracking of biologic matter and device thereof " (CN1435369), " method and the technology of rubbish, biomass low temperature electrocatalytic gasification and liquefaction " (CN1995285), " electrocatalysis water vapour recapitalization biological oil is produced the device and method of hydrogen " (CN101177239), " biomass hydrogen-rich combustion gas preparation method and device " (CN101100621), " a kind of is the method for raw material for preparing hydrogen with biomass " (CN101348234).These patents all must be used catalyzer, and catalyzer is prone to poison, and raw material and processing condition are all had the strict requirement of comparison, are difficult to be applicable to various raw materials (like domestic refuse, changing food waste, municipal sludge, biomass waste etc.) hydrogen manufacturing or water-gas.
In addition; Patent " a kind of biomass and coal mixed fluidized bed gasification process and device thereof " (CN1557919); Though do not use catalyzer; But because vapourizing furnace has adopted the air feed burning and supplied the alternative expression mode of operation at intermittence of steam gasification, the water-gas quality that generates on the one hand is unstable, and heat exchanger effectiveness is low on the other hand.Patent " a kind of coal gas internal heating low-temperature cracking temperature control with improving quality of coal gas method " (CN101497802) needs to adopt the oxygen-enriched combusting heat supply, and production cost is high, and hydrogen richness is the highest in the water-gas also can only reach 40-50vol%.Patent " method of preparing biodiesel from sludge by microwave radiation " (CN1850943) though adopted microwave, needs in raw material, to add the suction ripple medium of 1-10wt%, and water-gas productive rate not high (major part of raw material is converted into solid carbon).
Summary of the invention
The object of the invention is exactly the deficiency that exists in the prior art in order to overcome, and a kind of high-quality high-level efficiency water-gas shift method and device are provided.With domestic refuse, changing food waste, municipal sludge, biomass and other carbon containing things or carbonaceous refuse is raw material; Under secluding air (anaerobic), catalyst-free condition; Feed water vapour,, make it under lower temperature conditions, promptly have high reaction activity and high through microwave induced even heating; Realize the water gas shift reaction of high-quality high-level efficiency (high conversion), for the synthetic of high-quality biological fuel oil of new generation contributed.
The object of the invention is realized through following technical scheme:
After domestic refuse, changing food waste, municipal sludge, biomass and other carbon containing things or carbonaceous refuse carried out drying and dehydrating, pulverize, drop in the vapourizing furnace.With the air in the displacement vapourizing furnaces such as water vapour or water-gas or nitrogen, itself and air are completely cut off.Feed water vapour (keeping faint malleation in the stove), use microwave induced heating, raw material and water vapour thermally equivalent in the stove, (than about the temperature required low 100-300 of common water-gas shift ℃) promptly realized water gas shift reaction at a lower temperature.High-temperature water gas after reaction finishes is through heat exchanger heats soft water, and the steam of generation supplies the water-gas shift of vapourizing furnace to use.Technology of the present invention is simple, easy to operate, running cost is low, the reaction times is short, energy consumption is low, transformation efficiency is high; Raw material is applied widely, need not to use catalyzer, and no coking phenomenon takes place; And the water-gas hydrogen content that makes is high, and H2/CO (volume ratio) almost remains on about 2: 1.Through synthetic low cost, the high-quality bio-fuel-oil of can preparing of FT (Fischer-Tropsch) to replace rare petroleum resources.
The present invention compared with prior art has following advantage and beneficial effect:
1, the present invention uses microwave induced even heating, promptly realizes water gas shift reaction at a lower temperature, and temperature of reaction is than low about 100-300 ℃ of common electrically heated, combustion gas heating.Reaction times is short, energy consumption is low, transformation efficiency is high.
2, the present invention need not to use catalyzer, and no coking phenomenon takes place.
3, raw material of the present invention is applied widely, can use domestic refuse, changing food waste, municipal sludge, biomass and other various carbon containing things or carbonaceous refuse.
4, the water-gas hydrogen content that makes of the present invention is high, H
2/ CO (volume ratio) almost remains on about 2: 1, is suitable for preparing low cost, high-quality bio-fuel-oil.
Description of drawings
Fig. 1 is apparatus of the present invention figure.Domestic refuse, changing food waste, municipal sludge, biomass and other carbon containing things or carbonaceous refuse drop in the former hopper 1 after drying, pulverizing, send into vapourizing furnace 3 through screw conveyor 2.In vapourizing furnace 3, raw material and water vapour meet, and through the heating of inducing of microwave tube 4, water gas shift reaction take place.The high-temperature water gas that generates gets into heat exchanger 6 and carries out heat exchange system water vapour with soft water behind baffle plate 5, water vapour imports vapourizing furnace 3 water supply gas shift reactions and uses.Water-gas after the waste heat recovery is looked its quality height, can partly or all return vapourizing furnace and react, and high-quality water-gas send follow-up refining step, FT (Fischer-Tropsch) synthetic etc.Unreacted high-temp solid resistates in vapourizing furnace 3 (like charcoal etc.) after water seal cooling (water vapour of generation is introduced vapourizing furnace 3), importing solid residue groove 7, the charcoal that from solid residue groove 7, takes out etc. after treatment can recycling.Before the device operation, can be with the air in the displacement vapourizing furnaces 3 such as nitrogen or water vapour or water-gas.
Embodiment
Below in conjunction with embodiment, the present invention is done further detailed description:
Embodiment 1
The first step is with the air in the water vapour displacement gas stove 3.
Second step was a raw material with the straw, was dried to water-content less than 20wt%, was crushed to size less than 2cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 980 ℃ of conditions.
H in the water-gas that generates
2: 61.8vol%, CO:30.1vol%, other (are mainly CO
2, CH
4Deng): 8.1vol%.Solid residue production rate (the dry method mass percent of solid residue and raw material input amount): 1.8%.
The first step is with the air in the water-gas displacement gas stove 3.
Second step was a raw material with the apple branch, was dried to water-content less than 15wt%, was crushed to size less than 1cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 1100 ℃ of conditions.
H in the water-gas that generates
2: 62.6vol%, CO:29.7vol%, other: 7.7vol%.Solid residue production rate: 4.6%.
The first step is with the air in the nitrogen replacement vapourizing furnace 3.
Second step was a raw material with the straw, was dried to water-content less than 25wt%, was crushed to size less than 2cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 790 ℃ of conditions.
H in the water-gas that generates
2: 52.4vol%, CO:24.9vol%, other: 22.7vol%.Solid residue production rate: 3.5%.
Embodiment 4
The first step is with the air in the water-gas displacement gas stove 3.
Second step was a raw material with the plastic waste, washed, is dried to water-content less than 5wt%, was crushed to size less than 0.5cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 610 ℃ of conditions.
H in the water-gas that generates
2: 63.2vol%, CO:29.7vol%, other: 7.1vol%.Solid residue production rate: 5.3%.
Embodiment 5
The first step is with the air in the nitrogen replacement vapourizing furnace 3.
Second step was a raw material with the changing food waste, was dried to water-content less than 12wt%, was crushed to size less than 0.5cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 450 ℃ of conditions.
H in the water-gas that generates
2: 48.4vol%, CO:25.4vol%, other: 26.2vol%.Solid residue production rate: 9.4%.
Embodiment 6
The first step is with the air in the water vapour displacement gas stove 3.
Second step was a raw material with the domestic refuse, removed foreign material such as metal, glass, pottery, was dried to water-content less than 8wt%, was crushed to size less than 1cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 300 ℃ of conditions.
H in the water-gas that generates
2: 44.5vol%, CO:23.1vol%, other: 32.4vol%.Solid residue production rate: 7.8%.
Embodiment 7
The first step is with the air in the nitrogen replacement vapourizing furnace 3.
Second step was a raw material with the municipal sludge, was dried to water-content less than 15wt%, was crushed to size less than 0.5cm, sent into vapourizing furnace 3 through former hopper 1 with screw conveyor 2.
The 3rd microwave induced heating of step issues the unboiled water gas shift reaction 870 ℃ of conditions.
H in the water-gas that generates
2: 46.1vol%, CO:24.7%, other: 29.2vol%.Solid residue production rate: 13.6%.
Claims (9)
1. high-quality high-level efficiency water-gas shift method and device; It is characterized in that; With domestic refuse, changing food waste, municipal sludge, biomass and other carbon containing things or carbonaceous refuse is raw material, under secluding air (anaerobic) condition, feeds water vapour; Through microwave induced, water gas shift reaction takes place.
2. a kind of high-quality high-level efficiency water-gas shift method according to claim 1 and device; It is characterized in that; After domestic refuse, changing food waste, municipal sludge, biomass and other carbon containing things or carbonaceous refuse drop into vapourizing furnace; Air with in the displacement vapourizing furnaces such as water vapour or water-gas or nitrogen makes it reach the purpose of secluding air.
3. a kind of high-quality high-level efficiency water-gas shift method according to claim 1 and device is characterized in that, can add catalyzer or absorbing material in the raw material, also can not add catalyzer or absorbing material.
4. a kind of high-quality high-level efficiency water-gas shift method according to claim 1 and device; It is characterized in that; The water vapour that feeds both can be saturation steam, also can be the overheated steam after thermal source heating (the waste heat heating that exports like electrically heated, microwave heating, vapourizing furnace etc.).
5. a kind of high-quality high-level efficiency water-gas shift method according to claim 1 and device is characterized in that, through microwave induced, water gas shift reaction take place.
6. a kind of high-quality high-level efficiency water-gas shift method according to claim 1 and device is characterized in that water gas shift reaction both can be a continous way, also can be intermittent types.
7. a kind of high-quality high-level efficiency water-gas shift method according to claim 1 and device is characterized in that gasification system or device.
8. system according to claim 7 both can be a thermopnore, also can be fixed bed.
9. device according to claim 7 both can be horizontal, also can be vertical.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719277A (en) * | 2012-04-27 | 2012-10-10 | 四川绿冶科技有限责任公司 | Closed, continuous high purity water gas generator |
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN114958434A (en) * | 2021-12-24 | 2022-08-30 | 昆明理工大学 | Method and equipment for producing hydrogen by biomass microwave pyrolysis and gasification |
| CN116144411A (en) * | 2023-01-04 | 2023-05-23 | 中国煤层气集团有限公司 | High-temperature steam generation method for preparing natural gas by high-temperature water activated hydrocarbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850585A (en) * | 2006-05-08 | 2006-10-25 | 鲍涛 | Process for reforming and gasifying several carbon-base compounds by electromagnetic wave coupling steam |
| CN101307259A (en) * | 2008-07-01 | 2008-11-19 | 广东科达机电股份有限公司 | Gas producing device and method |
| CN101357750A (en) * | 2008-09-11 | 2009-02-04 | 鲍涛 | Method and device of microwave excitation molten salt catalytic reforming gasification carbon group compound |
-
2010
- 2010-09-26 CN CN2010102943308A patent/CN102408918A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850585A (en) * | 2006-05-08 | 2006-10-25 | 鲍涛 | Process for reforming and gasifying several carbon-base compounds by electromagnetic wave coupling steam |
| CN101307259A (en) * | 2008-07-01 | 2008-11-19 | 广东科达机电股份有限公司 | Gas producing device and method |
| CN101357750A (en) * | 2008-09-11 | 2009-02-04 | 鲍涛 | Method and device of microwave excitation molten salt catalytic reforming gasification carbon group compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719277A (en) * | 2012-04-27 | 2012-10-10 | 四川绿冶科技有限责任公司 | Closed, continuous high purity water gas generator |
| CN102963866A (en) * | 2012-11-30 | 2013-03-13 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN102963866B (en) * | 2012-11-30 | 2015-01-21 | 安徽理工大学 | Method for preparing hydrogen-rich synthesis gas via biomass pyrolysis |
| CN114958434A (en) * | 2021-12-24 | 2022-08-30 | 昆明理工大学 | Method and equipment for producing hydrogen by biomass microwave pyrolysis and gasification |
| CN116144411A (en) * | 2023-01-04 | 2023-05-23 | 中国煤层气集团有限公司 | High-temperature steam generation method for preparing natural gas by high-temperature water activated hydrocarbon |
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Application publication date: 20120411 |