CN107416767B - A method of hydrogen and carbon electrode material are prepared using biomass - Google Patents
A method of hydrogen and carbon electrode material are prepared using biomass Download PDFInfo
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- CN107416767B CN107416767B CN201710702918.4A CN201710702918A CN107416767B CN 107416767 B CN107416767 B CN 107416767B CN 201710702918 A CN201710702918 A CN 201710702918A CN 107416767 B CN107416767 B CN 107416767B
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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Abstract
The invention discloses a kind of methods for preparing hydrogen and carbon electrode material using biomass, preparation process is as follows: biomass of the crushing after dry is sufficiently mixed with green activating dose, under the action of vapor and green activating dose, multiple gasification priming reaction occurs for biomass, obtains the porous carbon electrode material of porosity prosperity；The gasification gas of generation obtains hydrogen-rich gas product through subsequent methane reforming reaction and water-gas shift reaction.For the present invention during preparing hydrogen, gasification temperature is lower, reduces energy consumption, and subsequent further catalysis purification processes, promotes density of hydrogen and yield, provides basis for later period separation；Gas coke switchs to improve the utilization rate of biomass for porous carbon electrode material through green activating.Entire gasification activation process is environmentally protective, easy to operate, less energy consumption, at low cost.The method of the present invention is advantageously implemented the higher value application of biomass.
Description
Technical field
The present invention relates to biomass economy fields, and in particular to a kind of to prepare hydrogen and carbon electrode material using biomass
Method.
Background technique
Biomass is a kind of important renewable energy, has the characteristics that green, low-carbon, cleaning, unique renewable carbon source,
Resource problem is very rich, is world's fourth largest energy.But since its energy density is low, the utilization efficiency directly burnt is very low,
In order to improve its utilization rate, it usually needs carry out thermochemical study to it.Biomass gasification technology is current biomass energy
One of main path utilized, it can convert biomass into the gaseous fuel of high-quality, mainly there is air gasification, oxygen rich air
Change, steam gasification etc..Wherein, for steam gasification because of its simple process and low cost, the gas calorific value that gasifies is high, and hydrogen output height etc. is excellent
Point, and be widely studied and apply.
Currently, biomass steam gasification technology, main target is the synthesis gas for obtaining hydrogen product or high heating value.
In order to improve H2 yield, gasification temperature is improved, the methods of de- CO2 of In-sltu reinforcement gasification has obtained extensive research.But these sides
Method all can cause carbon atom utilization rate sharply to decline, and reduce so as to cause the utilization rate of biomass.It is burnt in biomass gasification process
Charcoal formation is inevitable, and gasification of biomass coke is a kind of porous carbon material, is a kind of very promising platform material
Material, can be widely applied to the fields such as electrode material, adsorbent, catalyst.
And the porosity that carbon electrode material often uses the activators such as KOH, ZnCl2 and H3PO4 to improve carbon is prepared at present, but due to
It easily causes equipment to corrode, therefore need to be found novel green in high reaction temperatures with stronger alkalinity or acidity
Color activator is reduced to equipment corrosion.
In conclusion current biomass steam gasification process, is concerned only with single gas products, STRENGTH ON COKE byproduct benefit
It is not high with rate, biomass economy rate is significantly reduced, while gasification temperature is higher, energy consumption is larger, and raw materials are also
Equipment can be caused corrosion-damaged, therefore need to find new and effective biomass preparation method.
Summary of the invention
For disadvantages described above and Improvement requirement, the present invention is directed to propose a kind of prepare hydrogen and carbon electrode material using biomass
The method of material realizes that biomass under the conditions of vapor and green activating dose are common existing, prepares the hydrogen rich gas of high added value
The porous carbon electrode material of body and porosity prosperity, it is small to equipment corrosion, greatly improve biomass economy value.The present invention
Method solves the problems, such as biomass high value added utilization and equipment corrosion.
S1: the biomass after crushing and drying being sufficiently mixed with green activating dose, obtains reaction raw materials,
S2: reach 550 DEG C~650 DEG C of reaction temperature to level-one fixed bed reactors, vapor and inert gas are led to
Enter in reactor, and reaction raw materials be put into reactor, biomass fermentation anger priming reaction, the reaction time be 20min~
60min,
S3: being passed through second level fixed bed reactors for the gasification gas that step S2 is obtained, and under the action of catalyst, carries out methane two
Carbonoxide reforming reaction, reaction temperature are 400~500 DEG C, and the reaction time is 20~60min, the step for reducing methane and
Carbon dioxide content promotes density of hydrogen and yield,
S4: the gasification gas after step S3 is reformed is passed through three-stage fixed bed reactor, under the action of catalyst, carries out aqueous vapor
Conversion reaction, reaction temperature are 400~500 DEG C, and the reaction time is 20~60min, the step for reducing carbon monoxide content,
Density of hydrogen and yield are further promoted,
S5: the hydrogen-rich gasification gas that step S4 is obtained after cooling, obtains to obtain hydrogen-rich gas product,
S6: the step S2 solid product obtained is porous carbon, after the reaction was completed, through naturally cooling to environment temperature,
S7: carrying out pickling for the porous carbon in step S6, then with excessive deionized water filtration and washing, until filtrate at
Re-dry after neutrality obtains porous carbon electrode material,
Wherein, step S3, S4 and S5 is hydrogen-rich porous carbon electrode material bar line gas products bar line, and step S6, S7 is
Porous carbon electrode material bar line, hydrogen-rich gas product bar line and porous carbon electrode material bar line are in no particular order.
The principle of the above inventive concept of the present invention is: the priming reaction that consumingly gasifies occurs for biomass, greatly improves
The porosity of hydrogen content and gas coke in gasification gas.Effect is mainly reflected in two aspects: on the one hand, vapor is both
Gasifying agent, and be gas activation agent, the raw gasification reaction of biomass fermentation can be promoted, while reaming is carried out to gas coke；It is another
Aspect, green activating dose while carrying out chemical activation to gas coke, can also generate a large amount of hydrogen；So as to compared with
A large amount of hydrogen is generated at a temperature of low and obtains the porous carbon electrode material with flourishing pore structure, and reaction temperature is lower same
When apply green activating dose, greatly reduce corrosion to equipment.In addition, the gasification gas generated is made by subsequent catalyst
Methane reforming reaction under reduces methane and carbon dioxide content, hydrogen content and water-gas shift reaction is promoted, into one
Step reduces carbon monoxide content, to be greatly improved the concentration and yield of hydrogen, and then obtains hydrogen-rich gas product, passes through
After separating treatment, clean hydrogen product can be obtained, finally realize the high value added utilization of biomass.
Further, the biomass in the step S1 includes: one of bamboo, sawdust, rice husk or a variety of, and green is living
Agent includes KHCO3、NaHCO3、CaCl2One of or it is a variety of, the quality of green activating dose of addition is made a living material mass
10%~50%.
Further, the drying temperature of the biomass in the step S1 is 100~110 DEG C, and drying time is 12
~for 24 hours.
Further, the flow velocity of vapor is 0.2mL/min~0.5mL/min in the step S2, and inert gas is nitrogen
Gas or argon gas, flow velocity are 100mL/min~200mL/min.
Further, the catalyst in the step S3 is Ni/NiO2、Ni/Al2O3、Ni/TiO2One of or it is a variety of.
Further, the catalyst in the step S4 is one of Cu-Zn, Fe-Cr, Co-Mo or a variety of.
Further, the concentration of hydrochloric acid of pickling is 1mol/L~2mol/L, drying temperature and time point in the step S7
It Wei not 100C~110 DEG C and 12h~for 24 hours.
Further, the hydrogen-rich gas that the present invention obtains has high hydrogen content, and carbon electrode material has flourishing hole
Structure and good chemical property.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) in method of the invention, green activating dose is introduced in biomass steam gasification, promotes biomass same
Shi Fasheng gasification priming reaction, on the one hand, vapor is both gasifying agent and gas activation agent, can promote biomass
Gasification reaction, while reaming is carried out to gas coke；On the other hand, chemical activation is being carried out to gas coke green activating dose
Meanwhile it can also generate a large amount of hydrogen；So as to generate a large amount of hydrogen at a lower temperature and obtain that there is flourishing hole
The porous carbon electrode material of gap structure, reaction temperature is lower while applying green activating dose, greatly reduces the corruption to equipment
Erosion.
(2) the gasification gas generated in method of the invention is by the methane reforming reaction under subsequent catalyst action, drop
Low-methoxyl alkane and carbon dioxide content promote hydrogen content using water-gas shift reaction and further decrease carbon monoxide content, from
And it is greatly improved the concentration and yield of hydrogen, and then obtain hydrogen-rich gas product, after separating treatment, it can be obtained clean
Net hydrogen product.
(3) porous carbon materials obtained in method of the invention have flourishing pore structure, can be used as chemical property
Excellent electrode material.
(4) method coproduction of the invention hydrogen product and porous carbon electrode material, realizes the high added value of biomass
It utilizes, improves the utilization rate of biomass.
Detailed description of the invention
Fig. 1 is the artwork for preparing the method for hydrogen and carbon electrode material in the embodiment of the present invention using biomass.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of methods for preparing hydrogen and carbon electrode material using biomass, as shown in Figure 1, specific packet
Include following steps:
(1) biomass after crushing and drying is sufficiently mixed with green activating dose, obtains reaction raw materials；
(2) reach reaction temperature (reaction temperature be 550~650 DEG C) to level-one fixed bed reactors, by vapor with it is lazy
Property gas is passed through in reactor, and reaction raw materials is put into reactor, biomass fermentation anger priming reaction, and the reaction time is
20~60min；
(3) the gasification gas that step (2) obtains is passed through second level fixed bed reactors, under the action of catalyst, carries out methane two
Carbonoxide reforming reaction, reaction temperature are 400~500 DEG C, and the reaction time is 20~60min, reduce methane and carbon dioxide and contain
Amount promotes density of hydrogen and yield；
(4) the gasification gas after step (3) is reformed is passed through three-stage fixed bed reactor, under the action of catalyst, carries out aqueous vapor
Conversion reaction, reaction temperature are 400~500 DEG C, and the reaction time is 20~60min, reduce carbon monoxide content, are further promoted
Density of hydrogen and yield；
(5) the hydrogen-rich gasification gas that step (4) obtains obtains hydrogen-rich gas product after mixture of ice and water is fully cooled；
(6) solid product that step (2) obtains is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
(7) porous carbon in step (6) is subjected to pickling, then with excessive deionized water filtration and washing, until filtrate
At re-dry after neutrality, carbon electrode material is obtained.
Wherein, the biomass in the step (1) includes: one of bamboo, sawdust, rice husk or a variety of, green activating
Agent includes one of KHCO3, NaHCO3, CaCl2 or a variety of, and it is 10 that green activating dose of addition quality, which is biomass gross mass,
~50%.
The drying temperature of biomass in step (1) is 100~110 DEG C, and drying time is 12~for 24 hours.
The flow velocity of vapor is 0.2~0.5mL/min in step (2), and inert gas is nitrogen or argon gas, flow velocity 100
~200mL/min.
Catalyst in step (3) is one of Ni/NiO2, Ni/Al2O3, Ni/TiO2 or a variety of.
Catalyst in step (4) is one of Cu-Zn, Fe-Cr, Co-Mo or a variety of.
The concentration of hydrochloric acid of pickling is 1~2mol/L in step (7), and drying temperature and time are respectively 100~110 DEG C and 12
~for 24 hours.
The principle of the above inventive concept of the present invention is: the priming reaction that consumingly gasifies occurs for biomass, greatly improves
The porosity of hydrogen content and gas coke in gasification gas.Effect is mainly reflected in two aspects: on the one hand, vapor is both
Gasifying agent, and be gas activation agent, the raw gasification reaction of biomass fermentation can be promoted, while reaming is carried out to gas coke；It is another
Aspect, green activating dose while carrying out chemical activation to gas coke, can also generate a large amount of hydrogen；So as to compared with
A large amount of hydrogen is generated at a temperature of low and obtains the porous carbon electrode material with flourishing pore structure, reaction temperature of the present invention
It is lower while applying green activating dose, greatly reduce the corrosion to equipment.In addition, the gasification gas generated is urged by subsequent
Methane reforming reaction under agent effect, reduces methane and carbon dioxide content, promotes hydrogen content and aqueous vapor conversion is anti-
It answers, further decreases carbon monoxide content, to be greatly improved the concentration and yield of hydrogen, and then obtain hydrogen-rich gas production
Product finally realize the high value added utilization of biomass.
It, can be with by the way that biomass is carried out gasification priming reaction under vapor and green activating dose in the method for the present invention
Obtain the hydrogen-rich gas of high yield, can be obtained hydrogen product by later separation, and hydrogen be a kind of calorific value height, zero-emission,
Light weight gas can be converted to various energy resources, be a kind of green energy resource being concerned；Flourishing porous of obtained porosity
Carbon material can be widely applied to electrode material, the fields such as adsorbent, to greatly improve the utility value of biomass.
For more detailed description the method for the present invention, further illustrated below with reference to specific embodiment:
Embodiment 1
The embodiment of the present invention illustrates that a kind of method for preparing hydrogen and carbon electrode material using biomass, the method are specific
Include the following steps:
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, the green of biomass gross mass 50% will be accounted for
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 600 DEG C of assigned temperature, being passed through vapor flow is 0.2mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 30min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 65%, yield is up to 300mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1900m2/g
Ultimate ratio capacitor is up to 270F/g.
Embodiment 2
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 50%
Chemical agent agent NaHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 600 DEG C of assigned temperature, being passed through vapor flow is 0.2mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 30min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/Al2O3
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Cu-Zn effect, water-gas shift reaction is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 62%, yield is up to 290mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 2000m2/g
Ultimate ratio capacitor is up to 280F/g.
Embodiment 3
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 50%
Chemical agent CaCl2 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 600 DEG C of assigned temperature, being passed through vapor flow is 0.2mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 30min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/TiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Co-Mo effect, water-gas shift reaction is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 60%, yield is up to 280mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1800m2/g
Ultimate ratio capacitor is up to 260F/g.
Embodiment 4
S1: after being put into 100 DEG C of oven dryings after sawdust is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 10%
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 600 DEG C of assigned temperature, being passed through vapor flow is 0.5mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 30min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 55%, yield is up to 250mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1500m2/g
Ultimate ratio capacitor is up to 230F/g.
Embodiment 5
S1: after being put into 110 DEG C of oven drying 12h after rice husk is crushed and screened, with the green for accounting for biomass gross mass 30%
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 600 DEG C of assigned temperature, being passed through vapor flow is 0.5mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 30min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 500 DEG C, reaction time 30min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 60%, yield is up to 280mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1700m2/g
Ultimate ratio capacitor is up to 250F/g.
Embodiment 6
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 50%
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 650 DEG C of assigned temperature, being passed through vapor flow is 0.5mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 20min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 500 DEG C, reaction time 20min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 500 DEG C, reaction time 20min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 62%, yield is up to 290mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1900m2/g
Ultimate ratio capacitor is up to 270F/g.
Embodiment 7
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 50%
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 550 DEG C of assigned temperature, being passed through vapor flow is 0.5mL/min, argon flow 200mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 60min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 400 DEG C, reaction time 60min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 400 DEG C, reaction time 60min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 60%, yield is up to 280mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1800m2/g
Ultimate ratio capacitor is up to 260F/g.
Embodiment 8
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 50%
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 550 DEG C of assigned temperature, being passed through vapor flow is 0.5mL/min, nitrogen flow 100mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 60min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 450 DEG C, reaction time 60min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 450 DEG C, reaction time 60min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 58%, yield is up to 270mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (1mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (110 DEG C, for 24 hours) afterwards obtain carbon electrode material, and specific surface area is up to 1700m2/ g, is prepared into super capacitor electrode
Ultimate ratio capacitor is up to 250F/g.
Embodiment 9
S1: after being put into 105 DEG C of oven dryings after bamboo is crushed and screened for 24 hours, with the green for accounting for biomass gross mass 50%
Chemical agent KHCO3 is sufficiently mixed to obtain gasification reaction raw material；
S2: being 45mm using diameter, and the level-one fixed bed reactors that length is 60mm carry out gasification reaction, by reactor plus
After heat arrives 600 DEG C of assigned temperature, being passed through vapor flow is 0.5mL/min, nitrogen flow 100mL/min, by the biology of 2g
Matter mixture is rapidly feeding in the middle part of reactor, reaction time 60min, and biomass is made to carry out adequately gasification priming reaction；
S3: gasification gas is passed through second level fixed bed reactors (diameter 45mm, length 60mm), in catalyst n i/NiO2
Under effect, methane reforming with carbon dioxide is carried out, reaction temperature is 450 DEG C, reaction time 60min, reduces methane and two
Content of carbon oxide promotes density of hydrogen and yield；
S4: the gasification gas after reformation is passed through three-stage fixed bed reactor (diameter 45mm, length 60mm), in catalyst
Under Fe-Cr effect, water-gas shift reaction is carried out, reaction temperature is 450 DEG C, reaction time 60min, reduces carbon monoxide and contains
Amount further promotes density of hydrogen and yield；
S5: obtained hydrogen-rich gasification gas obtains hydrogen-rich gas product, density of hydrogen can after mixture of ice and water is fully cooled
Up to 58%, yield is up to 270mL/g；
S6: the solid product of acquisition is porous carbon, after the reaction was completed, through naturally cooling to environment temperature；
S7: porous carbon carries out pickling (2mol/L), then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry (100 DEG C, 12h) afterwards, obtain carbon electrode material, and specific surface area is prepared into super capacitor electrode up to 1700m2/g
Ultimate ratio capacitor is up to 250F/g.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of method for preparing hydrogen and carbon electrode material using biomass, which is characterized in that it includes the following steps:
S1: the biomass after crushing and drying being sufficiently mixed with green activating dose, obtains reaction raw materials,
S2: reaching 550 DEG C~650 DEG C of reaction temperature to level-one fixed bed reactors, and vapor and inert gas are passed through instead
Answer in device, and reaction raw materials be put into reactor, biomass fermentation anger priming reaction, the reaction time be 20min~
60min,
S3: being passed through second level fixed bed reactors for the gasification gas that step S2 is obtained, and under the action of catalyst, carries out methane titanium dioxide
Carbon reforming reaction, reaction temperature are 400 DEG C~500 DEG C, and the reaction time is 20min~60min,
S4: the gasification gas after step S3 is reformed is passed through three-stage fixed bed reactor, under the action of catalyst, carries out aqueous vapor conversion
Reaction, reaction temperature are 400 DEG C~500 DEG C, and the reaction time is 20min~60min,
S5: the hydrogen-rich gasification gas that step S4 is obtained after cooling, obtains to obtain hydrogen-rich gas product,
S6: the step S2 solid product obtained is porous carbon, after the reaction was completed, through naturally cooling to environment temperature,
S7: the porous carbon in step S6 is subjected to pickling, then with excessive deionized water filtration and washing, until filtrate is at neutrality
Re-dry afterwards obtains porous carbon electrode material,
Wherein, the preparation of hydrogen-rich porous carbon electrode material and porous carbon electrode material are prepared in no particular order,
Green activating dose includes KHCO3、NaHCO3、CaCl2One of or it is a variety of, it is total that green activating dose of additional amount accounts for biomass
The ratio of quality is 10%~50%.
2. a kind of method for preparing hydrogen and carbon electrode material using biomass according to claim 1, which is characterized in that
Biomass in the step S1 includes: one of bamboo, sawdust, rice husk or a variety of.
3. a kind of method for preparing hydrogen and carbon electrode material using biomass according to claim 1, which is characterized in that
The drying temperature of biomass in the step S1 is 100 DEG C~110 DEG C, and drying time is 12h~for 24 hours.
4. a kind of method for preparing hydrogen and carbon electrode material using biomass according to claim 1, which is characterized in that
The flow velocity of vapor is 0.2mL/min~0.5mL/min in the step S2, and inert gas is nitrogen or argon gas, inert gas
Flow velocity be 100mL/min~200mL/min.
5. a kind of method for preparing hydrogen and carbon electrode material using biomass according to claim 1, which is characterized in that
Catalyst in the step S3 is Ni/NiO2、Ni/Al2O3、Ni/TiO2One of or it is a variety of.
6. a kind of method for preparing hydrogen and carbon electrode material using biomass according to claim 1, which is characterized in that
Catalyst in the step S4 is one of Cu-Zn, Fe-Cr, Co-Mo or a variety of.
7. a kind of method for preparing hydrogen and carbon electrode material using biomass according to claim 1, which is characterized in that
The concentration of hydrochloric acid of pickling is 1mol/L~2mol/L in the step S7, drying temperature and time be respectively 100 DEG C~110 DEG C and
12h~for 24 hours.
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