CN101747945A - Two-section method for preparing synthetic gas with biomaterial - Google Patents
Two-section method for preparing synthetic gas with biomaterial Download PDFInfo
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Abstract
The invention relates to a two-section method for preparing synthetic gas with biomaterial, which belongs to the technical field of regenerative energy. The method is characterized in that the method comprises the following steps: firstly, thermally cracking the biomaterial to obtain charcoal and biological crude oil; secondly, feeding the biological crude oil or the oil-charcoal slurry prepared by adopting the charcoal and the biological crude oil into a gasification furnace through a delivery pump to prepare synthetic gas. In the method, the biological crude oil or the oil-charcoal slurry entering the gasification furnace has good flowing property and can be delivered through the pump, thereby solving the problems of delivery and quantitative control for solid biomaterial under high pressure in the prior art, helping improve the operation stability of the gasification furnace and facilitating the control of the product quality of the synthetic gas. The gasification furnace can adopt the ordinary air or oxygen enriched air rather than pure oxygen as the gasification agent, thereby saving the air separation equipment, simplifying the flow and reducing the operation cost. The form is especially attractive to small-scale gasification projects.
Description
[technical field]
The present invention relates to field of renewable energy technology, particularly prepare the method for synthetic gas by biomass materials such as stalk, rice husk, wood chip, firewoods.
[background technology]
Biomass energy is one of human energy that utilizes the earliest, still is used to the heat-obtaining that burns in a large number at Chinese countryside at present.Because the restriction of economy, Wood Adhesives from Biomass is that the technology of other high-grade energy products such as electric power or fuel oil never can realize industrialization but for a long time.In recent years, because the worsening shortages of fossil energies such as oil, particularly because the Greenhouse effect that cause of Carbon emission serious threat people's living environment, biomass are this can to realize in systemic circulation that the renewable energy source of carbon dioxide zero discharge enters people's the visual field again.
Utilize biomass materials such as stalk, rice husk, firewood to obtain extensive studies by the technology that the preparation of elevated temperature heat chemical process contains the synthetic gas of hydrogen and carbon monoxide.Influencing the production efficiency of synthetic gas and the factor of composition has a lot, comprises kind, particle diameter, the moisture that contains and the ash of biomass material, type, vapor pressure and temperature of vapourizing furnace or the like.The vapourizing furnace that is used for gasifying biomass at present roughly can be divided into three kinds: fixed bed, fluidized-bed and air flow bed, Higman and van der Burgt are in gasification " (Gasfication, GulfProfessional Publishing, 2003) existing detailed description in the book.Fixed-bed gasification furnace simple in structure, easy to operate, but non-uniform temperature in the stove contain a large amount of tar in the outlet synthetic gas.Temperature distribution uniform in the fluidized-bed gasification furnace stove, but very sensitive to the physical property of raw material operate waywardly, and operating temperature is general also lower, and it is also considerable to export the coal-tar middle oil content of synthetic gas.Owing to all contain a large amount of tar in the gasification product, fixed-bed gasification furnace and fluidized-bed gasification furnace generally all need follow-up equipment to handle the problem of tar, make gasifying process and system all become very complicated.
In comparison, be the problem that the airflow bed gasification furnace of representative can solve tar preferably with shell and Texaco.The operating temperature of air flow bed is higher, and temperature is more even in the stove, and tar is all cracking in air flow bed, and air flow bed has good amplification characteristic simultaneously, is specially adapted to the application of large industrialized.Yet entrained flow gasification is had relatively high expectations to the solid material particle diameter, and the raw material that enters air flow bed need be worn into very tiny particle, and this has proposed the another one technical barrier for the grinding of the biomass material that contains a large amount of fibers.
Is to solve air flow bed to one of method of solid particulate dimensional requirement by the staging treating biomass material to avoid in vapourizing furnace directly carrying biomass solid, and United States Patent (USP) 6863878, United States Patent (USP) 7013816 and Chinese patent 200510043836.0 all put forward similar solution.The charcoal that biomass solid at first prepares splitting gas and is easy to grind by thermo-cracking at a slow speed under this lower temperature in 500 ℃ of left and right sides grinds to form the charcoal off-line then behind the tiny particle and to be sent to vapourizing furnace with splitting gas and to carry out gasification reaction and prepare synthetic gas.What deserves to be mentioned is the three-section type biomass gasification technology that is called the Carbo-V process that German Ke Lin company proposes.Biomass at first under 400-500 ℃ of low temperature carbonization be pyrolysis gas and charcoal, the pyrolysis gas that contains tar is combustion decomposition at high temperature, thus and charcoal is sent into vapourizing furnace reduction burning gas preparation synthetic gas after grinding.In all these methods, all be to be charcoal in principle, then charcoal sent into vapourizing furnace Wood Adhesives from Biomass.
In order to improve the efficient that self and downstream synthetic gas carry out the chemical conversion process, vapourizing furnace generally all moves under the highly compressed condition, adopts pure oxygen as vaporized chemical.No matter adopt the vapourizing furnace of which kind of type, also whether no matter the method for precarburization is adopted in segmentation, and the gasification of biomass generally all relates to two problems, i.e. Solid Conveying and Melting under the high pressure and pure oxygen gasification.Solid Conveying and Melting under the high pressure is a very complicated loaded down with trivial details task in industrial practice, and the quantitative control of solid matter is a harsh challenge especially, and its effect has a strong impact on the steady running of vapourizing furnace and the quality and the production efficiency of synthetic gas.Pure oxygen gasification is helpful technically to improving gasifying biomass efficient, but owing to must adopt expensive air separation plant to prepare pure oxygen, this is concerning the biomass project of the general type less than normal of scale, need carry out the detailed economic assessment, this also is the development of restriction biomass gasification technology, makes it be difficult to realize one of influence factor that industrialization breaks through.
It is to prepare bio-crude oil (D.Mohan et al, Pyrolysis of Wood/Biomass for Bio-oil:A Critical Review, Energy﹠amp by fast pyrolysis that the another kind of biomass utilizes method; Fuels 2006,20,848-889).The composition of bio-crude oil is very complicated, is made up of hundreds of different materials, contains a large amount of oxygen and water, and calorific value is low.In most of the cases, bio-crude oil can only be used as low-grade furnace oil, must just can obtain a small amount of useful chemical through loaded down with trivial details purification process.Bio-crude oil also can be used in diesel power generation through after certain processing treatment, and just off-set facility such as oil pump all needs to a certain degree transformation to adapt to the physical property of bio-crude oil.Synthetic gas can be used for producing liquid fuels such as methyl alcohol, ethanol, dme, alkene, diesel oil, petroleum naphtha after by purifying treatment, belongs to the renewable energy source domain.
[summary of the invention]
The technical barrier of Solid Conveying and Melting under the high pressure provided a kind of two-stage type biomass to prepare the method for synthetic gas when the present invention was intended to solve the preparation synthetic gas.
Above-mentioned purpose is realized by following technical scheme:
A kind of two-stage type biomass prepares the method for synthetic gas, it is characterized in that, comprising: (1) obtains charcoal and bio-crude oil with biomass through pyrolysis; (2) parrot coal slurry that utilizes transferpump that bio-crude oil or charcoal and bio-crude oil are mixed with is sent into vapourizing furnace and is prepared synthetic gas.
Wherein, biomass material is broken into the following particle of 2mm after drying, sends into pyrolysis reactor by spiral conveyer and carries out described thermo-cracking.
Wherein in the thermal cracking processes in the step (1), the control pyrolyzer moves under normal pressure, temperature maintenance is at 450-650 ℃, heat-up rate is per second 200-600 ℃, the residence time of biomass solid in pyrolyzer is 0.5-5 second, the bio-crude oil weight that generates is the 40%-90% of biomass material, and the weight of the charcoal of generation is the 10-40% of biomass material.
The branch road that obtains bio-crude oil in the step (1) after the thermo-cracking specifically comprises: the steam product that will leave pyrolyzer is cooled to 40 ℃, takes out liquid bio crude oil and water, and will not coagulate pyrolysis gas circulation heat recovery cracking reactor and act as a fuel the part supplementing energy is provided.
Utilizing charcoal and bio-crude oil to be mixed with parrot coal slurry in the step (2) specifically comprises: the part of the charcoal that generates is ground to below 200 microns, send into slurry commanding tank and prepare parrot coal slurry with bio-crude oil, slurry commanding tank can add an amount of methyl alcohol or other chemical to reduce parrot coal slurry viscosity, improve its flowing property and storage stability, make parrot coal slurry directly to be delivered into high-pressure gasified stove and prepare synthetic gas with the conventional mud pump.
When preparing described parrot coal slurry, add methyl alcohol in charcoal and the bio-crude oil mixture, improve its flowing property and storage stability to reduce parrot coal slurry viscosity.
In the step (2), the vaporized chemical that adopts when vapourizing furnace prepares synthetic gas adopts normal air or oxygen-rich air.Described normal air or oxygen-rich air were preheated to 250-600 ℃ before entering vapourizing furnace.
Described vapourizing furnace is provided with in order to adjust the standby water vapor feeding line that gasifier temperature or synthetic gas are formed.
Described vapourizing furnace temperature out is controlled at 900 ℃-1400 ℃, is preferably 1000 ℃-1200 ℃.
In the inventive method, the bio-crude oil or the parrot coal slurry that enter vapourizing furnace all have good flowing property, can pass through pump delivery, thereby the conveying and the quantitative control problem of biomass solid under the prior art high pressure have been solved, can help to improve the operational stability of vapourizing furnace, be convenient to control the quality of synthetic gas product.Another characteristics of the present invention be vapourizing furnace adopt normal air or oxygen-rich air but not pure oxygen as vaporized chemical, thereby saved air separation plant, simplified flow process simultaneously and reduced running cost, this mode is especially attractive to the small evaporator project.
[description of drawings]
Fig. 1 is for sending thermo-cracking product charcoal and bio-crude oil into the synoptic diagram that vapourizing furnace is produced the embodiment of synthetic gas simultaneously;
Fig. 2 produces the synoptic diagram that synthetic gas, charcoal are made the embodiment of other purposes for thermo-cracking product bio-crude oil being sent into vapourizing furnace.
[embodiment]
Below in conjunction with process flow diagram practical application of the present invention is described, but the invention is not restricted to content related among the embodiment.
Embodiment one
In conjunction with shown in Figure 1, biomass material is broken into the following particle of 2mm after drying, sends into The normal pressure fluidized bed rapid pyrolysis reactor (hereinafter to be referred as pyrolyzer) by spiral conveyer, and the temperature of pyrolyzer is controlled at 500 ℃.After the steam product of pyrolyzer was cooled to 40 ℃, bio-crude oil and water left condenser with the form of liquid, and noncondensable gas all loops back the pyrolysis device as the required part of fuel of pyrolyzer, and bio-crude oil enters pulping tank with after water separates in decanting vessel.After solid product charcoal after the pyrolysis leaves pyrolyzer, be ground to below 200 microns, send into pulping tank and bio-crude oil is mixed with parrot coal slurry, the weight ratio of bio-crude oil and wood charcoal powder is 3.25: 1.Bio-crude oil water content 20%, butt weight consists of: C 58.4%, and H 6.0%, and N 0.1%, and O 35.4%, and charcoal weight consists of: C 81.9%, and H 1.6%, and O 16.0%, N0.6%.Parrot coal slurry is at room temperature directly sent into air flow bed by slush pump, sends into air in certain amount simultaneously and makes that the mol ratio of oxygen and carbon is 0.84-0.85.The vapourizing furnace operating pressure is 5.0MPa, and temperature out is 1000 ℃, and the synthetic gas that obtains thus consists of: CO 21.0%, H211.2%, and CO2 7.6%, and H2O 7.5%, N251.9%., high-temperature synthesis gas is passed through operations such as dedusting, desulfurization, decarburization again after waste heat boiler reclaims heat, and after conversion adjustment hydrogen-carbon ratio wherein, can obtain clean synthetic gas, can be used for preparing liquid fuels such as Fischer-Tropsch synthesis oil, methyl alcohol, ethanol
Embodiment two
By embodiment one as can be known, the charcoal of acquisition can all be used to prepare parrot coal slurry, also can partly be used to prepare parrot coal slurry, and part is made other purposes, such as the fuel of pyrolyzer to keep pyrolysis temperature.In conjunction with shown in Figure 2, embodiment two is the extension of embodiment one, and the charcoal that is prepared by biomass through pyrolysis all is used for other purposes, does not deliver to gasifier system and is equipped with synthetic gas.For this situation, bio-crude oil need not slurrying and can directly advance vapourizing furnace with pump delivery and gasify.In addition, other aspects and embodiment one flow process are as broad as long.
Characteristics of the present invention are to adopt normal pressure method such as fast pyrolysis that biomass solid is converted into bio-crude oil liquid and charcoal, be suspended in the parrot coal slurry for preparing in the bio-crude oil by the wood charcoal powder after grinding and directly be delivered into high-pressure gasified stove with slush pump, thereby avoided the transportation problem of biomass solid under the high pressure operating mode, simplify techniqueflow and regular job greatly, can improve the stability and the controllability of vapourizing furnace to a great extent.The method that biomass solid is converted into bio-crude oil and charcoal is not limited to fast pyrolysis, and additive method such as microwave thermal cracking also can be used for and vapourizing furnace combined preparation synthetic gas.Any existence that does not rely on vapourizing furnace can independent operating under the normal pressure, with biomass solid be converted into liquid product, then available conventional equipment this liquid product is delivered into vapourizing furnace method all without prejudice to the present invention's spirit.The present invention is example explanation with the fast pyrolysis, only is that fast pyrolysis can produce more liquid bio crude oil, is more suitable for the present invention's target.
Another significance that adopts the two-part process independently to prepare bio-crude oil and synthetic gas respectively is that these two processes need not carried out in same plant area or same place.Because the tap density of biomass is very little, transportation cost is very high, can only utilize the biomass in certain collection radius, has greatly limited the extensive industrialization that biomass are utilized.Adopt the synthesis gas preparation method of this separate type, can build in the different location independently that thermal cracker prepares bio-crude oil liquid, then gasification is concentrated in these highdensity liquid bio carrieds of crude oil to certain central place.So, the scale of gasification installation can significantly improve, thereby reduces the cost of investment and the running cost of device.In addition, agricultural wastes biomass materials such as stalk, rice husk have certain seasonality, and it is mouldy to become damp easily, is unfavorable for standing storage, and storage also needs huge space.Adopt the present invention's separate process, biomass material can be collected the bio-crude oil of producing season and be in store, be evenly dispersed in raw material then and collect gasification preparation in dull season synthetic gas, with the annual basicly stable production of holdout device.
The present invention is to provide and a kind ofly under normal pressure, biomass solid is converted into bio-crude oil liquid and charcoal by segmented mode, under high pressure bio-crude oil and charcoal are converted into the method for synthetic gas then, both operations are independent fully, do not interdepend, its basic goal is to avoid the biomass solid transportation problem under the high pressure, to help the stable operation and the synthetic gas controllable quality of vapourizing furnace.No matter this integrated mode is aspect processing condition, flow arrangement, the working method various variation to be arranged, especially all the more so during biomass material character generation significant change.But no matter how to change on the techniqueflow, all should not run counter to the present invention's spirit.
Claims (12)
1. a two-stage type biomass prepares the method for synthetic gas, it is characterized in that, comprising: (1) obtains charcoal and bio-crude oil with biomass through pyrolysis; (2) parrot coal slurry that utilizes transferpump that bio-crude oil or charcoal and bio-crude oil are mixed with is sent into vapourizing furnace and is prepared synthetic gas.
2. two-stage type biomass according to claim 1 prepares the method for synthetic gas, it is characterized in that: biomass material is broken into the following particle of 2mm after drying, sends into pyrolysis reactor by spiral conveyer and carries out described thermo-cracking.
3. two-stage type biomass according to claim 1 prepares the method for synthetic gas, it is characterized in that: in the thermal cracking processes in the step (1), the control pyrolyzer moves under normal pressure, temperature maintenance is at 450-650 ℃, heat-up rate is per second 200-600 ℃, the residence time of biomass solid in pyrolyzer is 0.5-5 second, and the bio-crude oil weight of generation is the 40%-90% of biomass material, and the weight of the charcoal of generation is the 10-40% of biomass material.
4. two-stage type biomass according to claim 3 prepares the method for synthetic gas, it is characterized in that: the branch road that obtains bio-crude oil in the step (1) after the thermo-cracking specifically comprises: the steam product that will leave pyrolyzer is cooled to 40 ℃, take out liquid bio crude oil and water, and will not coagulate pyrolysis gas circulation heat recovery cracking reactor and act as a fuel the part supplementing energy is provided.
5. two-stage type biomass according to claim 1 prepares the method for synthetic gas, it is characterized in that: utilize charcoal and bio-crude oil to be mixed with parrot coal slurry in the step (2) and specifically comprise: the part of the charcoal that generates is ground to below 200 microns, send into slurry commanding tank and prepare parrot coal slurry with bio-crude oil, slurry commanding tank can add an amount of methyl alcohol or other chemical to reduce parrot coal slurry viscosity, improve its flowing property and storage stability, make parrot coal slurry directly to be delivered into high-pressure gasified stove and prepare synthetic gas with the conventional mud pump.
6. two-stage type biomass according to claim 5 prepares the method for synthetic gas, it is characterized in that: when preparing described parrot coal slurry, add methyl alcohol in charcoal and the bio-crude oil mixture.
7. two-stage type biomass according to claim 6 prepares the method for synthetic gas, it is characterized in that: described parrot coal slurry adopts slush pump to send into high-pressure gasified stove.
8. prepare the method for synthetic gas according to any described two-stage type biomass of claim 1-7, it is characterized in that: in the step (2), the vaporized chemical that adopts when vapourizing furnace prepares synthetic gas adopts normal air or oxygen-rich air.
9. two-stage type biomass according to claim 8 prepares the method for synthetic gas, it is characterized in that: described normal air or oxygen-rich air were preheated to 250-600 ℃ before entering vapourizing furnace.
10. two-stage type biomass according to claim 8 prepares the method for synthetic gas, it is characterized in that: described vapourizing furnace is provided with in order to adjust the standby water vapor feeding line that gasifier temperature or synthetic gas are formed.
11. two-stage type biomass according to claim 8 prepares the method for synthetic gas, it is characterized in that: described vapourizing furnace temperature out is controlled at 900 ℃-1400 ℃.
12. two-stage type biomass according to claim 11 prepares the method for synthetic gas, it is characterized in that: described vapourizing furnace temperature out is controlled at 1000 ℃-1200 ℃.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311743A (en) * | 2011-08-25 | 2012-01-11 | 季天仁 | Microwave pyrolysis based biomass recycling and integrated treatment method and equipment |
| CN103387853A (en) * | 2013-08-06 | 2013-11-13 | 上海中科高等研究院 | Method for producing synthesis gas by microwave gasification of biochar |
| CN103695014A (en) * | 2013-12-11 | 2014-04-02 | 吉林大学 | Method for preparing methyl alcohol biomass oil through rice husk |
| CN104388105A (en) * | 2014-11-06 | 2015-03-04 | 清华大学 | Device and method for producing synthetic gas by continuous two-stage catalytic pyrolysis |
| CN104789270A (en) * | 2015-01-16 | 2015-07-22 | 胜利油田胜利动力机械集团有限公司 | Biomass two-section type dry distillation gasification process and device |
| CN106085469A (en) * | 2011-11-04 | 2016-11-09 | 国际热化学恢复股份有限公司 | The system and method converted to the elasticity that oil is gentle for raw material |
| CN108458345A (en) * | 2018-03-28 | 2018-08-28 | 金华水清清环保科技有限公司 | A kind of house refuse self-pyrolysis processing unit and its processing method |
| CN109280566A (en) * | 2018-11-08 | 2019-01-29 | 广西科技大学 | A method of using bagasse as the extensive producing synthesis gas of raw material |
| CN110436413A (en) * | 2019-08-12 | 2019-11-12 | 中国科学院工程热物理研究所 | A kind of the two-part synthesis gas preparation system and method for biogas and solar energy complementation |
| CN110564432A (en) * | 2019-08-27 | 2019-12-13 | 华中科技大学 | Coal-fired coupling biomass power generation system and method |
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2010
- 2010-01-14 CN CN201010005303A patent/CN101747945A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311743A (en) * | 2011-08-25 | 2012-01-11 | 季天仁 | Microwave pyrolysis based biomass recycling and integrated treatment method and equipment |
| CN106085469A (en) * | 2011-11-04 | 2016-11-09 | 国际热化学恢复股份有限公司 | The system and method converted to the elasticity that oil is gentle for raw material |
| CN106085469B (en) * | 2011-11-04 | 2020-01-17 | 国际热化学恢复股份有限公司 | System and method for the elastic conversion of feedstock to oil and gas |
| CN103387853A (en) * | 2013-08-06 | 2013-11-13 | 上海中科高等研究院 | Method for producing synthesis gas by microwave gasification of biochar |
| CN103695014A (en) * | 2013-12-11 | 2014-04-02 | 吉林大学 | Method for preparing methyl alcohol biomass oil through rice husk |
| CN103695014B (en) * | 2013-12-11 | 2015-08-19 | 吉林大学 | A kind of method of rice husk methanol bio-oil |
| CN104388105A (en) * | 2014-11-06 | 2015-03-04 | 清华大学 | Device and method for producing synthetic gas by continuous two-stage catalytic pyrolysis |
| CN104789270A (en) * | 2015-01-16 | 2015-07-22 | 胜利油田胜利动力机械集团有限公司 | Biomass two-section type dry distillation gasification process and device |
| CN108458345A (en) * | 2018-03-28 | 2018-08-28 | 金华水清清环保科技有限公司 | A kind of house refuse self-pyrolysis processing unit and its processing method |
| CN109280566A (en) * | 2018-11-08 | 2019-01-29 | 广西科技大学 | A method of using bagasse as the extensive producing synthesis gas of raw material |
| CN110436413A (en) * | 2019-08-12 | 2019-11-12 | 中国科学院工程热物理研究所 | A kind of the two-part synthesis gas preparation system and method for biogas and solar energy complementation |
| CN110564432A (en) * | 2019-08-27 | 2019-12-13 | 华中科技大学 | Coal-fired coupling biomass power generation system and method |
| CN110564432B (en) * | 2019-08-27 | 2021-04-20 | 华中科技大学 | Coal-fired coupling biomass power generation system and method |
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Application publication date: 20100623 |