CN109809407A - CO in a kind of biomass pyrolytic tail gas2Utilization method - Google Patents
CO in a kind of biomass pyrolytic tail gas2Utilization method Download PDFInfo
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- CN109809407A CN109809407A CN201711155756.3A CN201711155756A CN109809407A CN 109809407 A CN109809407 A CN 109809407A CN 201711155756 A CN201711155756 A CN 201711155756A CN 109809407 A CN109809407 A CN 109809407A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The present invention provides CO in a kind of biomass pyrolytic tail gas2Utilization method, the method includes use biomass pyrolysis process generate charcoal for reducing agent, by catalysis reaction will be pyrolyzed tail gas in the higher CO of content2It is reduced to CO, preferably can add alkaline metal catalysts into reaction system to accelerate CO2Reduction rate.Wherein, the alkaline metal catalysts are one or more of alkali metal, alkaline-earth metal or rare earth metal.Using method of the invention, the greenhouse gases CO that biomass pyrolytic can be generated2It is converted into the CO of high added value, while converting CO for the charcoal that pyrolytic process generates, the utilization rate of carbon resource in biomass pyrolytic technique is improved, reduces the discharge of greenhouse gases, there is good prospects for commercial application.
Description
Technical field
The present invention relates to CO2Trans-utilization, in particular to CO in a kind of biomass pyrolytic tail gas2Utilization method.
Background technique
With the aggravation of the conventional fossils resource consumption such as petroleum, increasingly harsh, the research of renewable energy of environmental requirement
It receives significant attention.Lignocellulose biomass is the most abundant renewable resource on the earth, is the energy, material by its Efficient Conversion
Material and high valuable chemicals are current alleviating energy crisis and the most effective approach of environmental pressure.Wherein, biomass pyrolytic quilt
It is considered one of most effective way in biomass transformation technology, the extensive concern by academia and industrial circle.
Biomass pyrolytic refers to biomass material under the conditions of completely cutting off existing for air or a small amount of air, using medium reaction
Temperature, the process that biomass is pyrolyzed.The technology is to produce based on bio oil, while a certain amount of pyrolytic carbon of by-product and heat
It vents one's spleen.Wherein, bio oil obtains fuels and chemicals by catalytic refining, and pyrolytic carbon may be used as soil conditioner or activity
Charcoal raw material.Pyrolysis gas is mainly by CO, CO2、CH4、H2And C2-C4Hydro carbons forms, wherein CO2Content may be up to 50% or more.Such as
The higher CO of content in what trans-utilization pyrolysis gas2Become one of the development bottleneck of biomass pyrolytic technology.If can be by suitable
The technology of conjunction is by CO2It is converted into the CO of high added value, biomass pyrolysis process carbon atom utilization rate not only can be improved, but also subtract
Lack greenhouse gas emission, improved the economy of biomass pyrolysis process, more meets biomass renewable resource clean utilization
Requirement.
Currently, CO2Trans-utilization route mainly have methane carbon dioxide reformation, Reversed Water-gas Shift and add hydrogen.In addition,
Have some about CO2The report of coal gasification is carried out as oxidant, this is CO2Utilization provide an other route, that is, use
Carbonaceous material is as reducing agent to CO2Carry out electronation.
Chinese patent CN 1060802216A discloses a kind of device of carbon dioxide reduction carbon monoxide, described in the patent
Device can use coke, charcoal, coal, blue carbon and/or petroleum coke reduction carbon dioxide.Chinese patent CN 1800009A is announced
A kind of novel process for preparing carbon monoxide from carbon dioxide.The invention is pointed out, under oxygen-free environment, coke can be by carbon dioxide
It is reduced to CO.Chinese patent CN 101665721A discloses the technique that carbon monoxide is separated from carbon dioxide.The invention passes through
Use scorching hot coke by the carbon dioxide reduction in power plant flue gas for carbon monoxide.
Mentioning in published patent and document and can use carbonaceous resource for carbon dioxide reduction is carbon monoxide, still
Without reference to the process reaction performance improvement and the technology biomass pyrolytic field application.So far, it has no
CO is restored about the by-product charcoal generated using biomass pyrolytic2Report, have no and utilize biomass pyrolysis system itself
The charcoal of generation restores CO in pyrolysis gas under self-catalysis or extra catalyst effect2Prepare the report of CO.
Summary of the invention
The object of the present invention is to provide CO in a kind of biomass pyrolytic tail gas2Utilization method, generated using pyrolytic process
Charcoal be reducing agent by CO2It is reduced to CO.It, can be by the greenhouse gases of biomass pyrolytic by-product using method of the invention
CO2With charcoal synchronize be converted into CO, while reform remove pyrolysis gas in remaining a small amount of tar, improve biomass fast pyrogenation
The carbon resource utilization rate of system.
CO in a kind of biomass pyrolytic tail gas2Utilization method, use biomass pyrolysis process generate charcoal be and also
Former agent is by CO2It is reduced to CO.
Preferably alkaline metal catalysts can be added into reaction system to accelerate CO2Reduction rate.It is described to
The alkalinous metal mass content added in reaction system is the 0.1~20% of biological carbonaceous amount.
The biomass pyrolysis process includes biomass fast pyrogenation, biomass slow pyrolysis or biomass flash heat
Solution.
The alkaline metal catalysts are alkali metal (Li, Na, K, Rb, Cs), alkaline-earth metal (Mg, Ca, Sr, Ba) or rare earth
One or more of metal (La, Ce, Sm).
The alkalinous metal form added into reaction system be nitrate, acetate, carbonate, hydroxide and
Oxide.
The addition manner of the alkaline metal catalysts has following a few classes: directly by alkalinous metal predecessor in biomass
It is added in biomass material when pyrolysis stock；Alkalinous metal predecessor is added in thermal decomposition product charcoal by dipping；
Alkaline metal oxide or load are had to the catalyst and charcoal physical mixed of alkaline metal oxide.
The biomass includes but are not limited to agricultural crop straw, trees, agriculture and forestry organic waste material, processing of farm products leftover bits and pieces
Material, bagasse, furfural dregs, corncob, rice husk, shell, reed etc..
The charcoal restores CO2Reaction carries out in fixed bed reactors or fluidized-bed reactor.
The charcoal restores CO2Reaction carries out under the following conditions: reaction temperature is 773K~1473K, reaction pressure
For 0.01~8.0MPa, pyrolysis gas air speed is 0.1~20L/g- charcoal h, and pyrolytic carbon air speed is 0.1-100.0g/h.
The invention discloses CO in a kind of biomass pyrolytic tail gas2Utilization method.The life generated using biomass pyrolytic
Object charcoal is reducing agent, under relatively mild reaction conditions, by the CO in pyrolysis system2It is converted into CO, it is synchronous to turn charcoal
The CO with more high added value is turned to, while reducing the tar content in pyrolysis gas, promotes the further utilization of final CO, the skill
The use of art improves the carbon utilisation rate of entire biomass pyrolysis system reducing while greenhouse gas emission, improve biology
The economy of matter pyrolysis system.
It is that reducing agent can be by the CO in pyrolysis gas using charcoal using method of the invention2It is reduced to CO, is reformed simultaneously
Remaining a small amount of tar in pyrolysis gas is removed, CO can be improved by way of adding alkaline metal catalysts2Reduction reaction
Activity.The carbon resource utilization rate of biomass pyrolysis system not only can be improved in the application of the technology, reduces greenhouse gas emission, subtracts
Few CO needed due to environmental requirement2Seal processing investment up for safekeeping, tar is to equipment and catalysis used during reducing subsequent CO utilization
The damage of agent improves the economy and the feature of environmental protection of whole process.When charcoal neutral and alkali tenor is more than 3wt%, heat
CO in venting one's spleen2Can at relatively low temperature (900 DEG C), one way is fully converted to CO.It realizes compared under low energy consumption, biology
The pyrolysis gas of matter pyrolysis system by-product and the synchronous of charcoal utilize, and the alkalinous metal that process uses can be recycled and be continued to use.
The CO in green high-efficient conversion pyrolysis gas may be implemented in the use of the technology2。
Specific embodiment
Below by specific embodiment and comparative example, the present invention will be further described.
Embodiment 1
The charcoal for weighing the generation of 5g corncob fast pyrogenation is loaded into the middle part of fixed bed reactors, is passed through N2Room temperature purging
Air in 10min removing system, is then warming up to 900 DEG C.After reactor bed reaches goal response temperature, by N2It is switched to
95%CO2- 5%N2Gaseous mixture, the variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Embodiment 2
The charcoal for weighing the generation of 5g rice husk fast pyrogenation is loaded into the middle part of fixed bed reactors, is passed through N2Room temperature purging
Air in 10min removing system, is then warming up to 1200 DEG C.After reactor bed reaches goal response temperature, by N2Switching
For 95%CO2- 5%N2Gaseous mixture, the variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Embodiment 3
The charcoal for weighing the generation of 5g rice straw fast pyrogenation is loaded into the middle part of fixed bed reactors, is passed through N2Room temperature purging
Air in 10min removing system, is then warming up to 700 DEG C.After reactor bed reaches goal response temperature, by N2It is switched to
95%CO2- 5%N2Gaseous mixture, the variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Embodiment 4
The charcoal for weighing the generation of 5g corncob fast pyrogenation is loaded into the middle part of fixed bed reactors, is passed through N2Room temperature purging
Air in 10min removing system, is then warming up to 900 DEG C.After reactor bed reaches goal response temperature, by N2It is switched to
Simulate biomass pyrolytic gas mixture (5%N2- 5%CH4- 47%CO-43%CO2), the variation of gas chromatographic detection tail gas.Detection
The results are shown in Table 1.
Embodiment 5
The charcoal for weighing the generation of 5g corncob fast pyrogenation, takes 0.21g K2CO3It is dissolved in 12g deionized water and obtains
Potassium precursor solution impregnates charcoal G using the solution, dries in the shade at room temperature overnight, then 393K is dry in air atmosphere
12h.Then 873K roasts 3h in an ar atmosphere.Obtain additional 3wt%K2The charcoal H of O.A certain amount of H is taken to be loaded into fixation
In bed reactor, it is passed through N2Room temperature purges the air in 10min removing system, is then warming up to 900 DEG C.Reactor bed reaches
After goal response temperature, by N2It is switched to simulation biomass pyrolytic gas mixture (5%N2- 5%CH4- 47%CO-43%CO2),
The variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Embodiment 6
In addition to weighing 0.033g KNO3Instead of K2CO3, obtain additional 0.1wt%K2Except the charcoal L of O, other steps
With embodiment 5.Testing result is as shown in table 1.
Embodiment 7
In addition to weighing 1.32g calcium nitrate instead of K2CO3, obtain except the charcoal M of additional 6wt%CaO, other steps are same
Embodiment 5.Testing result is as shown in table 1.
Embodiment 8
The charcoal for weighing the generation of 5g rice husk fast pyrogenation, takes 0.21g K2CO3It is dissolved in 12g deionized water and obtains potassium
Precursor solution impregnates charcoal G using the solution, dries in the shade at room temperature overnight, then 393K dries 12h in air atmosphere.
Then 873K roasts 3h in an ar atmosphere.Obtain additional 3wt%K2The charcoal N of O.
It takes a certain amount of N to be loaded into fixed bed reactors, is passed through N2Room temperature purges the air in 10min removing system,
Then 900 DEG C are warming up to.After reactor bed reaches goal response temperature, by N2It is switched to simulation biomass pyrolytic gas mixture
(5%N2- 5%CH4- 47%CO-43%CO2), the variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Embodiment 9
In addition to the pyrolysis gas substitution simulation pyrolysis gas of biomass mixing for using true corncob fast pyrogenation process to generate
Except object, other steps are the same as embodiment 5.Testing result is as shown in table 1.
Comparative example 1
Take a certain amount of corncob fast pyrogenation charcoal, the corncob successively washed using acetone, dilute hydrochloric acid and deionized water
Pyrolytic carbon obtains charcoal G through 120 DEG C of drying.It takes 5g charcoal G to be loaded into fixed bed reactors, is passed through N2Room temperature purging
Air in 10min removing system, is then warming up to 900 DEG C.After reactor bed reaches goal response temperature, by N2It is switched to
95%CO2- 5%N2Gaseous mixture, the variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Comparative example 2
It takes 5g charcoal G to be loaded into fixed bed reactors, is passed through N2Room temperature purges the air in 10min removing system,
Then 900 DEG C are warming up to.After reactor bed reaches goal response temperature, by N2It is switched to simulation biomass pyrolytic gas mixture
(5%N2- 5%CH4- 47%CO-43%CO2), the variation of gas chromatographic detection tail gas.Testing result is as shown in table 1.
Reaction described in above-described embodiment and comparative example carries out in fixed bed reactors without specified otherwise.The dress of charcoal
Amount is 0.5g, and the internal diameter of fixed bed reactors is 6mm, length 400mm.It is finished to charcoal loading, is passed through N2Room temperature purging
Air in 10min removing system, is then warming up to reaction temperature.After reactor bed reaches goal response temperature, by N2It cuts
It is changed to reaction gas, by gas chromatographic detection tail gas composition with the situation of change of reaction process.The target temperature is
773-1473K, reaction pressure 0.1-1.0MPa, air speed 4L/g-Ch.
Table 1: embodiment and comparative example reaction result
By above-mentioned result it is found that the charcoal of the present invention for using biomass pyrolysis process to generate is reducing agent,
The higher CO of content in tail gas will be pyrolyzed by catalysis reaction2It is feasible for being reduced to CO, while can by addition alkalinous metal
To accelerate charcoal and CO2Reaction speed.The invention is suitable for pure CO2And CO in pyrolysis gas2Trans-utilization.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright range is defined by the following claims.
Claims (10)
1. CO in a kind of biomass pyrolytic tail gas2Utilization method, it is characterised in that the method be using biomass pyrolysis process
The charcoal of generation is reducing agent, by CO2It is reduced to CO.
2. CO in a kind of biomass pyrolytic tail gas according to claim 12Utilization method, it is characterised in that reactant
Alkaline metal catalysts are added in system to accelerate CO2Reduction rate；The alkalinous metal matter added into reaction system
Measure 0.1~20% that content is biological carbonaceous amount.
3. CO in a kind of biomass pyrolytic tail gas according to claim 12Utilization method, it is characterised in that the life
Material pyrolysis process includes biomass fast pyrogenation, biomass slow pyrolysis or biomass flash pyrolysis.
4. CO in a kind of biomass pyrolytic tail gas according to claim 12Utilization method, it is characterised in that the life
Substance include but are not limited to agricultural crop straw, trees, agriculture and forestry organic waste material, processing of farm products leftover bits and pieces, bagasse, furfural dregs,
Corncob, rice husk, shell or reed.
5. CO in a kind of biomass pyrolytic tail gas according to claim 22Utilization method, it is characterised in that the alkali
Property metal is the one or more of alkali metal, alkaline-earth metal or rare earth metal.
6. CO in a kind of biomass pyrolytic tail gas according to claim 22Utilization method, it is characterised in that the alkali
Metal is Li, Na, K, Rb or Cs, and the alkaline-earth metal is Mg, Ca, Sr or Ba；The rare earth metal is La, Ce or Sm.
7. CO in a kind of biomass pyrolytic tail gas according to claim 22Utilization method, it is characterised in that the alkali
Property metallic catalyst addition manner have following a few classes: directly by alkalinous metal predecessor biomass pyrolytic stock up when be added to
In biomass material；Alkalinous metal predecessor is added in thermal decomposition product charcoal by dipping；By alkaline metal oxide
Or load has the catalyst and charcoal physical mixed of alkaline metal oxide.
8. CO in a kind of biomass pyrolytic tail gas according to claim 22Utilization method, it is characterised in that alkalinous metal
Predecessor are as follows: nitrate, acetate, carbonate, hydroxide or the oxide of alkalinous metal.
9. CO in a kind of biomass pyrolytic tail gas according to claim 12Utilization method, which is characterized in that the biology
Charcoal restores CO2Reaction carries out under the following conditions: reaction temperature is 773K~1473K, and reaction pressure is 0.01~8.0MPa, heat
Air speed of venting one's spleen is 0.1~20L/g- charcoal h, and pyrolytic carbon air speed is 0.1-100.0g/h.
10. CO in a kind of biomass pyrolytic tail gas according to claim 12Utilization method, which is characterized in that it is described
Charcoal restores CO2Reaction carries out in fixed bed reactors or fluidized-bed reactor.
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| CN112090397A (en) * | 2020-09-08 | 2020-12-18 | 浙江工业大学 | Method for improving heat value of blast furnace tail gas by using biochar and obtaining carbon with high specific surface area |
| CN114736700A (en) * | 2022-04-18 | 2022-07-12 | 中国科学院工程热物理研究所 | Pyrolysis system and pyrolysis method |
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