CN102268295A - Method for producing hydrogen-enriched fuel gas by gasification of biomass high-temperature steam and device for same - Google Patents
Method for producing hydrogen-enriched fuel gas by gasification of biomass high-temperature steam and device for same Download PDFInfo
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Abstract
The invention discloses a method for producing a hydrogen-enriched fuel gas by gasification of biomass high-temperature steam and a device for the same. The method comprises the following steps: overheating and warming steam to above 900 DEG C in the absence of catalyst based on pure steam as a gasification medium, wherein the amount of the steam adding to a high-temperature gasification reactor is controlled, regulated and metered by using a constant flow pump and a steam generation device; and carrying out high-temperature steam gasifying reaction in a fixed bed gasification reactor at the temperature of 900-1050 DEG C, so that the high-heat-value hydrogen-enriched fuel gas is produced under the process conditions of proper reaction temperature, steam flow rate, raw material particle size, reaction time and the like. According to the invention, the heat value of the hydrogen-enriched fuel gas produced by using the method is 11-14MJ/Nm<3>, the hydrogen content of the hydrogen-enriched fuel gas is above 45%-51%. The method has the advantages that any catalyst is not used, the high-heat-value hydrogen-enriched fuel gas is obtained, the utilization ratio of energy is improved, low-grade biomass energy can be converted to high-grade hydrogen energy, and the like.
Description
Technical field
The present invention relates to biomass gasification technology, relate in particular to method and device thereof that a kind of biomass high-temperature steam gasification is produced hydrogen-rich combustion gas.
Background technology
Hydrogen burning product environmentally safe; Calorific value height (143 MJ/kg are about 3 times of gasoline, coke 4.5 times); Be used as low-temperature fuel cell and can not produce NO
XAnd CO
2Can store cost-effectively and carry; Be a kind of safe energy, do not have the follow-up injury of secular unknown range.The hydrogen of present 96 % comes from the high-temperature vapor reforming reaction of fossil oil, and wherein Sweet natural gas is that topmost raw material accounts for 48 %, and heavy oil and petroleum naphtha take second place and account for 30 %, and coal accounts for 18 %.By fossil oil hydrogen manufacturing, not only consume a large amount of Nonrenewable resources, production process also can pollute environment.Water electrolysis hydrogen production also is a kind of very proven technique, but will consume a large amount of electric power during because of electrolysis, and the heat that is produced than burning hydrogen itself is also many.If directly utilize the electric power of thermal power plant's supply to come brine electrolysis, be worthless economically.
Biomass are elementary composition by carbon, hydrogen, oxygen, nitrogen, sulphur etc., compare with fossil oil, and the volatile matter height, ash content is little, and sulphur, nitrogen content are low, and environmental pollution is little during burning, and can have reproducibility, and resource distribution is wide, and reserves are big, and the title of " green coal " is arranged.It self still is the carrier of hydrogen simultaneously, and wherein the components by weight percent of protium is 6%, accounts for more than 40 % of biomass total energy.In reaction process, the CO of generation
2With the CO that absorbs in the biomass process of growth
2On total amount, realize balance, can not cause Greenhouse effect, can reach truly " zero release ".Has cleaning, energy-conservation and do not consume outstanding advantages such as mineral wealth with biomass for raw material hydrogen manufacturing.It is very attractive and development prospect that the biomass energy that utilization has a recyclability is produced hydrogen.
The thermochemical method hydrogen manufacturing of biomass is considered to have economy and technology vitality most in nearly mid-term.The gasification biomass hydrogen preparation is comparatively harsh for reactor and reaction conditions under condition of supercritical water, and system's control is comparatively complicated.At present both at home and abroad the biomass gasifying hydrogen making technology mainly adopts the catalytic gasification method, but this technology is to having proposed than higher requirement in activity of such catalysts, heat resistance, physical strength and work-ing life etc., and causes gasification furnace structure more complicated.If gasifying biomass and catalytic pyrolysis are made as two section reactor, then both increase systemic resistance in addition, increased cost of investment again.It is gasifying medium that traditional biomass gasification technology adopts air, oxygen, water vapour-air, water vapour-oxygen usually.When being vaporized chemical with the air, N
2The diluting effect that has to comhustible component has reduced fuel gases calorific value; With oxygen is that gasifying medium then needs oxygen generating plant, makes the gasifying process complexity and has increased facility investment.
Summary of the invention
For solve that prior art exists use air, oxygen etc. as gasifying medium the time, gasifying process complexity, the problem that facility investment is big, the invention provides a kind of biomass high-temperature steam gasification and produce the method and the device thereof of hydrogen-rich combustion gas, the hydrogen-rich combustion gas hydrogen content height that makes, tar content is low, and calorific value is high and clean.
Technical scheme of the present invention is: a kind of biomass high-temperature steam gasification is produced the method for hydrogen-rich combustion gas, with pure water vapor as gasifying medium, with water vapour is overheated is warming up to 〉=900 ℃, control water vapour flow is 1 ~ 600 g/h, constant current is injected into to be carried out the steam gasification reaction with biomass in the high temperature fixed bed gasifying reactor and obtains hydrogen-rich combustion gas under 900~1050 ℃ high temperature, the particle diameter of biomass is 40~80 orders, reaction times is 30min, hydrogen volume mark in the hydrogen-rich combustion gas of producing is 45 ~ 51%, and fuel gases calorific value is at 11~14MJ/Nm
3
Described biomass are wood chip or rice husk.
When described biomass are wood chip, when control water vapour flow is 1.05g/min, H in the hydrogen-rich combustion gas that obtains under the differing temps
2The volume ratio of/CO is 0.92<H
2/ CO<2.61; When controlled temperature is 850 ℃, the next 0.46<H of different water vapour flows
2/ CO<2.53;
When described biomass are rice husk, control water vapour flow is 1.05g/min, 0.52<H under the then differential responses temperature
2/ CO<1.99, if controlled temperature is 850 ℃, 0.39<H under the then different water vapour flows
2/ CO<2.47.
Be used for described biomass high-temperature steam gasification and produce the device of the method for hydrogen-rich combustion gas, form by water vapor generation device, tube furnace, condensing works, be provided with the high temperature fixed bed gasifying reactor in the tube furnace, the inlet end of high temperature fixed bed gasifying reactor is connected with water vapor generation device, and the exit end of high temperature fixed bed gasifying reactor is connected with condensing works.
Described water vapor generation device is composed in series by constant current volume pump and water vapour producer, and the insulation pipeline that is connected by having heat tape of water vapor generation device and high temperature fixed bed gasifying reactor connects.
Described condensing works is composed in series by prolong and cryosel water-bath condenser.
The add-on of water vapour is measured and regulating and controlling with the water that enters the liquid state before the water vapour producer, compares with adopting the water vapour metering, and is more accurate and convenient, makes the steam gasification reaction be easy to control, and the target of hydrogen-rich combustion gas is produced in realization.
Beneficial effect:
(1) gasification reaction carries out under 900~1050 ℃ high temperature, and adopting the high temperature pure water vapor is gasifying medium, and gasification reaction is at high temperature carried out, and speed of response is significantly accelerated, and has dwindled the reactor reaction space; The N that has brought when having avoided with the air to vaporized chemical
2Dilution to comhustible component has improved fuel gases calorific value; Simultaneously, do not need oxygen gasified required oxygen generating plant, simplified reactive system;
(2) be gasifying medium with the high temperature pure water vapor, because the transformationreation of reduction reaction, carbon monoxide and the water vapour of carbon and water vapour can greatly improve the productive rate and the hydrogen productive rate of combustion gas.
(3) in the gasification reaction process, do not use any catalyzer, avoid owing to use problems such as the recovery of device complicacy that catalyzer brought and catalyzer and regeneration, make the simple in structure of reaction unit and be easy to safeguard, simplified technological process;
(4) fuel gases calorific value improves, and tar content significantly reduces, and improves combustion gas quality.900~1050 ℃ high temperature can promote the cracking of benzene in the tar and derivative thereof, and makes a large amount of carbon blacks and high-temperature vapor reaction generation combustion gas that coke tar cracking generates; In addition, hydrocarbon polymer and water vapour generation reforming reaction and make it be converted into small molecules inflammable gass such as hydrogen and carbon monoxide, the hydrogen-rich combustion gas of producing, and can effectively solve the tar problem.Under laboratory condition, can prepare calorific value at 11~14 MJ/Nm
3, the hydrogen-rich combustion gas of hydrogen content more than 45~51 %.
(5) provide a kind of water vapour preparation facilities that can accurately measure the water vapour flow, made simple and easyly, stability of flow can produce the water vapour that temperature is higher than 120 ℃ continuously.The add-on of water vapour is measured and regulating and controlling with the water that enters the liquid state before the water vapour producer, compares with adopting the water vapour metering, and is more accurate and convenient, makes the steam gasification reaction be easy to control, and the target of hydrogen-rich combustion gas is produced in realization.
(6) reaction process can be regulated H in the combustion gas by control reaction temperature and the add-on that changes water vapour
2The ratio of/CO.
Description of drawings
Fig. 1 is that biomass high-temperature steam gasification of the present invention prepares hydrogen-rich combustion gas experimental system synoptic diagram.
Wherein, 1. nitrogengas cylinder 2. variable valve 3. under meters 4. constant current volume pumps 5. water vapour producers 6. tube furnaces 7. high temperature fixed bed gasifying reactors 8. prolongs 9. cryosel water-bath condensers 10. wet flow indicators 11. gas-chromatographies.
Fig. 2 is the detected result that biomass high-temperature steam gasification of the present invention prepares hydrogen-rich combustion gas gas-chromatography TCD detector.
Fig. 3 prepares the detected result of hydrogen-rich combustion gas gas-chromatography fid detector for biomass high-temperature steam gasification of the present invention.
The experiment condition of Fig. 2 Fig. 3 all is 1000 ℃, and the flow rate of water vapour is 1.02 g/min.
Fig. 4 is that temperature is to H
2The influence of/CO.
Fig. 5 is that the flow of water vapour is to H
2The influence of/CO.
Embodiment
Further specify actual content of the present invention below in conjunction with accompanying drawing.
As shown in Figure 1, be used for described biomass high-temperature steam gasification and produce the device of the method for hydrogen-rich combustion gas, form by water vapor generation device, tube furnace 6, condensing works, be provided with high temperature fixed bed gasifying reactor 7 in the tube furnace 6, the inlet end of high temperature fixed bed gasifying reactor 7 is connected with water vapor generation device, and the exit end of high temperature fixed bed gasifying reactor 7 is connected with condensing works.Described water vapor generation device is composed in series by constant current volume pump 4, water vapour producer 5, and the insulation pipeline that is connected by having heat tape of water vapor generation device and high temperature fixed bed gasifying reactor 7 connects.Described condensing works is composed in series by prolong 8 and cryosel water-bath condenser 9.Wherein tube furnace 6 can provide enough heating powers, guarantees that high temperature fixed bed gasifying reactor 7 can keep constant temperature.The body of high temperature fixed bed gasifying reactor 7 is internal diameter 57 mm, the stainless steel tube of length overall 1160 mm, and the highest design temperature is 1100 ℃.Regulate and metering is injected into discharge in the water vapour producer 5 by constant current volume pump 4, the range of constant current volume pump 4 is 1~600 g/h.Water is heated to be water vapour fully in water vapour producer 5, the insulation pipeline through having heat tape is injected in the high temperature fixed bed gasifying reactor 7 again.Have temperature that the insulation pipeline of heat tape can keep transfer line more than 120 ℃, can guarantee the temperature of overheated steam in entering high temperature fixed bed gasifying reactor 7 like this.The nitrogen that can be earlier in the high temperature fixed bed gasifying reactor 7 be provided by the nitrogen supply (NS) device is with the air emptying in the system.The nitrogen supply (NS) device mainly is composed in series by nitrogengas cylinder 1, variable valve 2 and spinner-type flowmeter 3, by variable valve 2 control nitrogen flows.The overheated steam and the biomass that enter in the high temperature fixed bed gasifying reactor 7 are carried out gasification reaction under 900~1050 ℃ high temperature.Biomass material heats up rapidly through heat, and heat scission reaction at first takes place, and volatile matter is separated out, and generates H
2, CO, CO
2, CH
4With other gaseous state small molecules (CnHm), hydrocarbons (lightH/C), tar heavy hydrocarbon and coke (char) such as (tar) have been generated simultaneously.Under the effect of steam gasification medium, pyrolysis product further reacts, the main transformationreation of reduction reaction, carbon monoxide and water vapour between carbon and the water vapour and the steam reforming reaction of hydrocarbon polymer of taking place in reaction process.Remove wherein unreacted water by the hydrogen-rich combustion gas that comes out in the high temperature fixed bed gasifying reactor 7 process prolong 8 preliminary condensations earlier, enter the tar of isolating in the cryosel water-bath condenser 9 in the combustion gas then.Under laboratory condition, can prepare calorific value at 11~14 MJ/Nm
3, the hydrogen-rich combustion gas of hydrogen content more than 45~51 %.
It is a kind of fixed bed gasification reactor that the present invention develops biomass gasifying hydrogen making reactor voluntarily, be the core apparatus of gasification hydrogen-producing, the gasification reaction process is carried out in airtight space, and temperature of reaction is even, gasifying medium contacts with solid biomass well, and the mass-and heat-transfer effect is good;
It is a kind of quick-heating type water vapour producer that the present invention develops the water vapour producer voluntarily, it is the key equipment of preparation steam gasification agent, the water that enters the water vapour producer the utmost point in the short period of time (in 1~2 second) vaporize fully and become water vapour, and continuation heat temperature raising, water vapour is heated to more than 120 ℃, satisfies the required steam gasification agent of biomass gasification process.
And can regulate H in the hydrogen-rich combustion gas of acquisition by control raw material and reaction conditions
2/ CO volume ratio.When described biomass are wood chip, when control water vapour flow is 1.05g/min, regulate H in the hydrogen-rich combustion gas that obtains under the differing temps
2The volume ratio of/CO is 0.92<H
2/ CO<2.61; When controlled temperature is 850 ℃, regulate the next 0.46<H of different water vapour flows
2/ CO<2.53;
When described biomass are rice husk, control water vapour flow is 1.05g/min, then regulates 0.52<H under the differential responses temperature
20.39<H under the different water vapour flows if controlled temperature is 850 ℃, is then regulated in/CO<1.99
2/ CO<2.47.
Embodiment 1: be raw material with the pine sawdust, the reaction raw materials amount is 3 ± 0.2 g, and particle diameter is 40 ~ 80 orders.Before the experiment beginning, the nitrogen purging reactor is used in the connection of check test system, and the proofing unit resistance to air loss.The experiment beginning, the setting tube furnace is heated to 1000 ℃ with the temperature rise rate of 10 ℃/min with reactor.After treating that temperature reaches steady state, stop to feed nitrogen, open constant flow pump and water vapour producer, the output flow of regulating constant flow pump is 1.02 g/min, stablizes the required water vapour flow of output-response.Treat system stability after for some time, the quartz boat that fills wood chip is pushed the reactor middle part, the residence time of reacting in stove is 30 min, is gasified totally to guarantee raw material.Combustion gas is passed through wet flow indicator measuring products gas cumulative volume after condensed water and tar are removed in the condenser system cooling, and collects on-condensable product gas with the aluminium foil sampler bag.Experimental result sees Table 1.
Table 1 wood chip is in the experimental result of 1000 ℃ of following steam gasifications
1.
1. the amount of water vapour is 1.02g/min; 2. dry base is denitrogenated.
Claims (6)
1. a biomass high-temperature steam gasification is produced the method for hydrogen-rich combustion gas, it is characterized in that, with pure water vapor as gasifying medium, with water vapour is overheated is warming up to 〉=900 ℃, control water vapour flow is 1 ~ 600 g/h, constant current is injected into to be carried out the steam gasification reaction with biomass in the high temperature fixed bed gasifying reactor (7) and obtains hydrogen-rich combustion gas under 900~1050 ℃ high temperature, the particle diameter of biomass is 40~80 orders, reaction times is 30min, hydrogen volume mark in the hydrogen-rich combustion gas of producing is 45 ~ 51%, and fuel gases calorific value is at 11~14MJ/Nm
3
2. biomass high-temperature steam gasification according to claim 1 is produced the method for hydrogen-rich combustion gas, it is characterized in that: described biomass are wood chip or rice husk.
3. biomass high-temperature steam gasification according to claim 2 is produced the method for hydrogen-rich combustion gas, it is characterized in that: when described biomass are wood chip, and when control water vapour flow is 1.05g/min, H in the hydrogen-rich combustion gas that obtains under the differing temps
2The volume ratio of/CO is 0.92<H
2/ CO<2.61; When controlled temperature is 850 ℃, the next 0.46<H of different water vapour flows
2/ CO<2.53;
When described biomass are rice husk, control water vapour flow is 1.05g/min, 0.52<H under the then differential responses temperature
2/ CO<1.99, if controlled temperature is 850 ℃, 0.39<H under the then different water vapour flows
2/ CO<2.47.
4. be used for the arbitrary described biomass high-temperature steam gasification of claim 1 ~ 3 and produce the device of the method for hydrogen-rich combustion gas, it is characterized in that: form by water vapor generation device, tube furnace (6), condensing works, be provided with high temperature fixed bed gasifying reactor (7) in the tube furnace (6), the inlet end of high temperature fixed bed gasifying reactor (7) is connected with water vapor generation device, and the exit end of high temperature fixed bed gasifying reactor (7) is connected with condensing works.
5. according to claim 4ly be used for the device that the biomass high-temperature steam gasification is produced the method for hydrogen-rich combustion gas, it is characterized in that: described water vapor generation device is composed in series by constant current volume pump (4) and water vapour producer (5), and the insulation pipeline that is connected by having heat tape of water vapor generation device and high temperature fixed bed gasifying reactor (7) connects.
6. according to claim 4ly be used for the device that the biomass high-temperature steam gasification is produced the method for hydrogen-rich combustion gas, it is characterized in that: described condensing works is composed in series by prolong (8) and cryosel water-bath condenser (9).
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CN114752720A (en) * | 2022-05-18 | 2022-07-15 | 北京高创智信冶金科技有限公司 | Hydrogen-rich thermal reduction blowing gas, preparation method thereof and application thereof in blast furnace iron making |
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Application publication date: 20111207 |