CN107829104A - A kind of method for obtaining hydrogen and biomass fuel rod simultaneously with biomass material - Google Patents
A kind of method for obtaining hydrogen and biomass fuel rod simultaneously with biomass material Download PDFInfo
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- CN107829104A CN107829104A CN201711068860.9A CN201711068860A CN107829104A CN 107829104 A CN107829104 A CN 107829104A CN 201711068860 A CN201711068860 A CN 201711068860A CN 107829104 A CN107829104 A CN 107829104A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The present invention relates to biomass by hydro-thermal carbonization and the method for electrolytic hydrogen production combined cycle, and in particular to the method for obtaining hydrogen and biomass fuel rod simultaneously with biomass material.Including step：(1) biomass material, oxidant and water are mixed, at the uniform velocity heated up, carry out hydro-thermal reaction；(2) by the product after hydro-thermal reaction, separation of solid and liquid is carried out；(3) using the liquid after hydro-thermal reaction in step (2) as positive pole, it is electrochemically reacted, collects hydrogen, the anode electrolyte after being electrolysed；(4) anode electrolyte after being electrolysed in step (3) is mixed with solid matter after hydro-thermal reaction in step (2), carries out hydro-thermal reaction again；(5) repeat step (2)~(4), untill being collected in step (3) less than hydrogen；(6) after the solid product cleaning, drying of hydro-thermal reaction in step (4), it is pressed into fuel rod.Biomass material is directly utilized, innovatively opens the approaches and methods of a biomass energy clean utilization.
Description
Technical field
The present invention relates to biomass by hydro-thermal carbonization and the method for electrolytic hydrogen production combined cycle, and in particular to uses biomass material
The method for obtaining hydrogen and biomass fuel rod simultaneously.
Background technology
As human society from current carbon economy era is progressively transitioned into low-carbon economy and hydrogen economy epoch, Ren Menxi
Prestige is broken away to be depended on unduly to carbon fuel, to solve the related social concern for the environmental pollution and initiation being on the rise, therefore,
It has developed a series of regenerative resources such as solar energy, wind energy, biomass energy, and the new skill such as electric car and fuel-cell vehicle
Art, meet pursuit of the mankind to quality life.
Hydrogen Energy is used as " secondary energy sources ", and current Hydrogen Energy is mainly derived from fossil fuels, biomass and water, and technique mainly has
Electrolytic hydrogen production, pyrolysis hydrogen manufacturing, photochemical hydrogen manufacturing, radiant hydrolytic hydrogen production, the hydrogen manufacturing of plasma electric chemical method and biological hydrogen production etc..At this
In a little methods, in addition to biomass and water hydrogen producing technology, other methods are all by existing nytron in nature
Extracted in the primary energy such as thing --- natural gas, coal, oil, these methods produce the hydrogen of gained, not only need quite
Big energy consumption, and gained efficiency is at a fairly low；And pollution is also generated to environment in its producing process.
Water electrolysis hydrogen production technology is current using relatively wide and one of method of comparative maturity.Hydrogen production process using water as raw material
The inverse process for fuel cell power generation that to be hydrogen formed with oxygen, as long as therefore electric energy is provided, then water can be made to resolve into hydrogen and oxygen.Work
Skill process is fairly simple, will not also produce pollution, but it is big to consume electricity.
Normal temperature water electrolysis process usually requires noble metal, such as platinum, iridium etc. and is used as catalyst, due to electrode mistake caused by oxygen
Journey dynamic process is slower, and overpotential is larger, and in general water electrolysis voltage will reach 2V or so, therefore to electrolytic cell
Material and life-span are all greatly affected, and its application is subject to certain restrictions.The technique of current electrolysis water, equipment are continuous
Improve, but water electrolysis hydrogen production energy consumption is still very high.
Using technology is bakeed, biomass material is dried, then by adding bonding agent, biomass processing be molded,
Obtaining being easy to store, transport and the higher fuel rod of calorific value, are the currently used technological means for preparing biomass fuel rod, but
Equally there is also energy consumption it is higher the problem of, the fuel rod that is obtained with this method, due to nothing contained in no removal biomass
Machine salt, bonding agent is with the addition of again in forming process, stove coking can be made in use, influence the life-span of combustion furnace；And
With biomass by hydro-thermal carbonization technology, relatively low energy consumption can be used, carbon is directly hydrolyzed in the higher biomass material of water content
Change, the inorganic salts contained in biomass are dissolved in water, therefore,, can be direct without adding bonding agent after solid matter is dried
The fuel rod of high heating value is pressed into, its hydrophobicity performance is more preferable, is more convenient for storing and transports, and burner hearth will not be caused to damage using process
Wound.
But needed to consume substantial amounts of water with hydro-thermal method, and largely water can be discharged after need to handling, and be added
Cost of investment, it also have impact on the technological industrialization process.
China Patent Publication No. CN107012195A " a kind of method using agricultural crop straw as fermenting raw materials hydrogen manufacturing ", use
Agricultural crop straw is that raw material carries out fermentation generation hydrogen.This innovation and creation have carried out pre-treatment for farming stalk, make
Obtain agricultural crop straw on composition and pore passage structure to be changed, beneficial to the quick progress of fermentation, solve the pollution of stalk
With the problem of waste, while cheap raw material is provided for biological hydrogen preparation field, agricultural crop straw is turned waste into wealth.Although the invention is led to
The pre-treatment of stalk is crossed, improves the speed of fermentation, still, culture production hydrogen mixed bacteria, handles agricultural crop straw, and finally
Fermentation process, it is all very time-consuming, meanwhile, the product of fermentation is the mixture of hydrogen and carbon dioxide, it is also necessary to passes through it
His technological means, pure hydrogen is obtained after removing removing carbon dioxide.
China Patent Publication No. CN107128874A " a kind of water device for producing hydrogen and its method ", using carbon dioxide as raw material,
By be catalyzed, synthesize be converted into required for C/Hratio hydrocarbon CO+2H2Gaseous mixture, CO is then made by conversion2+
3H2Gaseous mixture, after separating water outlet, water circulation uses, CO2+3H2Through separation, CO2Raw material use is made in return.Consumed in course of reaction
Resource is water, and it is hydrogen to produce resource.But pass through CO2Recycle, its process is more complicated, and energy consumption
Suitable height, total hydrogen generation efficiency is relatively low, equally, it is also desirable to obtains pure hydrogen after removing removing carbon dioxide.
The bright spot of above-mentioned two patent of invention is all to prepare hydrogen as raw material without using fossil fuel, is replaced
, with biomass, water and carbon dioxide realize recyclability prepared by hydrogen as raw material.But both there is
Above-mentioned weak point.
The content of the invention
The present invention, as raw material, by hydrothermal carbonization method and electrolytic hydrogen production method, while is obtained using biomass resource
The fuel rod and pure hydrogen of high-quality high fuel value, but the problem of be that of avoiding encountered in above-mentioned technical background.
In hydro-thermal reaction, the method by adding oxidant, the progress of hydrolysis is accelerated, having in biomass
Machine functional group is oxidized to acid, turns into the hydrionic source in electrolytic hydrogen production, and oxidant is reduced in itself；It is molten after hydro-thermal reaction
Liquid, turn into the reactant of cell reaction, reduce the usage amount of water, eliminate the post-processing step of complexity；It is electrolysed hydro-thermal reaction
Solution afterwards, pure hydrogen is obtained in negative pole, pure water electricity is substituted with the fast oxidation-reduction pair of course of reaction kinetic rate
The oxygen evolution reaction of solution reaction positive pole, in positive pole side, it is not necessary to using noble metal catalyst, meanwhile, decomposition voltage is by original
More than the 2V come, drops to below 2V, greatly reduces the energy consumption that electrolysis needs.Positive pole is passed through by the oxidant of biomass reduction
Cell reaction, it is oxidized once more, the anode electrolyte is returned in hydrothermal reaction kettle and the solids after original separation of solid and liquid
Matter is reacted, and is so moved in circles, untill electrolysis can not produce hydrogen again.Last solid constituent can be with biomass
The biomass fuel rod of high quality is prepared, energy is fully utilized.
In whole process, innovatively oxidant is put into biomass solution, by the oxidant in hydro-thermal reaction
In be reduced with electrolytic process be oxidized, dexterously hydrothermal carbonization technology and electrolysis tech are coupled together, solve list
One technology using when run into the problem of.Raw material is only biomass and water, can but produce the hydrogen that can be stored and utilize respectively
And biomass fuel, realize the effective utilization and cleaning discharge of biomass, the particularly utilization to regenerative resource, biomass
The efficient utilization of energy, opens a technical strategies.
The present invention provides a kind of method for obtaining hydrogen and biomass fuel rod simultaneously with biomass material.
The present invention includes two independent operating units, and one is biomass hydro-thermal reaction, secondly being cell reaction.It is above-mentioned
Two independent operation units, the positive pole of electrolyte is used as by the product liquid of hydro-thermal reaction, also or electrolyte positive pole conduct
The liquid reactants of hydro-thermal reaction and circulated.Comprise the following steps that：
(1) biomass material, oxidant and water are mixed, at the uniform velocity heated up, carry out hydro-thermal reaction；In hydrothermal reaction kettle,
The redox reaction that the hydrolysis of biomass and the product of hydrolysis and oxidant are carried out is carried out simultaneously.It is although raw
The hydrolysis of material, with the species of biomass and the difference of reaction condition, very big difference is had, still, it reacts
Product majority is carbohydrate, and glucide contains abundant hydroxyl and aldehyde radical, can be oxidized agent, for example be oxidized agent Fe3+Oxidation
For carboxyl, and oxidant itself has then been reduced into Fe2+。
(2) by the product after hydro-thermal reaction, separation of solid and liquid is carried out, obtains the solid matter after hydro-thermal reaction and hydro-thermal reaction
Liquid afterwards；Solid matter can be deposited in hydrothermal reaction kettle, liquid substance is transported to the positive pole of electrolytic cell；
(3) using the liquid after hydro-thermal reaction in step (2) as positive pole, it is electrochemically reacted.In positive pole, hydro-thermal reaction
Fe is obtained in the oxidant being reduced afterwards such as (1)2+, oxidant Fe is oxidized into again after electrolysis3+, in the organic acid in solution
Hydrogen ion, negative pole is transported to by dielectric film, and after negative pole obtains electronics, produces hydrogen.The electricity of the electrolysis of the present invention
Pressure, can be according to the difference of oxidant, in 0.8-1.5V, the electrochemical reaction with regard to that can carry out hydrogen precipitation, moreover, positive pole does not have
Use noble metal catalyst.
Wherein, the cell reaction carried out in step (3) is as follows：
Positive pole：2Fe2+——2Fe3++2e-；
Negative pole：2H++2e-——H2。
Its standard reaction electromotive force is 0.77V.
And conventional water electrolysis reaction is
Positive pole：2H2O——O2+4H+4e-；
Negative pole：4H++4e-——2H2。
Standard reaction electromotive force is 1.23V.
The standard reaction electromotive force of the latter is higher than the former 0.46V, moreover, Fe3+/Fe2+The oxidation-reduction dynamic of electricity pair
Learning speed will be apparently higher than O2/H2O, therefore, catalyst can be used as without using noble metal such as platinum, ruthenium etc..Such cell reaction
Hydrogen production process, considerably reduce consumption and the material cost of electric energy.
In this process, regenerated by the oxidant of biomass reduction by electrolysis, and the H that electrolytic hydrogen production needs+
There is provided by the organic acid generated in hydrothermal reaction kettle.
(4) anode electrolyte after being electrolysed in step (3) is mixed with solid matter after hydro-thermal reaction in step (2), entered
The hydro-thermal reaction of row again；
(5) repeat step (2)~(4), untill being collected in step (3) less than hydrogen；The principle that step (5) is carried out is such as
It is upper described, biomass is simply carried out to the hydrolysis and reaction of gradation, until reaction is properly completed.
(6) after the solid product cleaning, drying of hydro-thermal reaction in step (4), it is pressed into fuel rod.
Wherein, the biomass material in the step (1) is that the lignin in agriculture and forestry production process (removes grain, fruit
The lignocellulosics such as stalk in addition, trees), farming industry leftover bits and pieces, during agriculture and forestry organic waste material and Animal husbandry production
Fowl and animal excrement and discarded object.
Wherein, the oxidant in the step (1) is the metallic compound for the multivalent state that can carry out redox reaction.
Such as potassium permanganate, potassium bichromate, vanadic sulfate, vanadium trichloride, ferric sulfate, iron chloride etc..
Wherein, the part by weight of the biomass material in the step (1) and water is 1~100:100, the oxidant
Final concentration of 0.01~2mol/L.
Wherein, the reaction temperature of step (1) hydro-thermal reaction is at 120~380 DEG C, 0.1~8MPa of pressure, the reaction time
For 0.1~6 hour.
Compared with prior art, the present invention has the advantages that：
Biomass material is directly utilized, the biomass material even can be without efflorescence and baking process, without addition
Bonding agent, it is possible to obtain the biomass fuel rod of high quality；Water required for water-heat process is greatly reduced, solution discharge
Last handling process is more convenient；In the side of the positive electrode of electrolytic cell, conventional hydropower can be compared without using noble metal catalyst, decomposition voltage
The voltage of solution is lower, and power consumption is less, prepares pure hydrogen at low cost.The process meanses of use are conventional hydro-thermals
Reaction and the organic coupling of cell reaction, environmentally friendly carry out the utilization of biomass energy, are easy to industrialization and scale very much,
Innovatively open the approaches and methods of a biomass energy clean utilization.
Brief description of the drawings
Fig. 1 is the comparison diagram of biomass fuel rod and biomass straw made from embodiment 1；
Fig. 2 is biomass straw FTIR spectrum figure in embodiment 1；
Fig. 3 is the FTIR spectrum figure of biomass fuel rod in embodiment 1；
Fig. 4 is the Faradaic current and time graph of 1-7 circulation in embodiment 1.
Embodiment
It is that the present invention will be further described for embodiment with lower part, but implementation below is only to this hair
Bright is explained further, and does not represent the scope of the present invention and is only limitted to this, the equivalence replacement that every thinking with the present invention is done,
In protection scope of the present invention.
Embodiment 1
(1) 5 grams of the maize straw dried is added in 100 milliliters of aqueous solution, while adds 3 grams of Fe2(SO4)3·7H2O,
Mixed liquor is placed into pressure-resistant hydrothermal reaction kettle, with 5 DEG C of min-1Programming rate, reactor is heated to 150 DEG C, at this
At a temperature of stop 1 hour after, Temperature fall to room temperature；
(2) by the product after hydro-thermal reaction, separation of solid and liquid is carried out, solid matter is deposited in hydrothermal reaction kettle, liquids
Matter is as anode electrolyte；
(3) using the liquid after hydro-thermal reaction as the anode electrolyte of electrolytic cell, by the use of copolymer solid electrolyte as every
Film, plus 1V voltage, constant-potential electrolysis is carried out, until current density≤1mA cm-2, while collect hydrogen in negative pole；
(4) anode electrolyte after being electrolysed mixes with the solid matter after previous hydro-thermal reaction, and the hydro-thermal carried out again is anti-
Should, equally with 5 DEG C of min-1Programming rate, reactor is heated to 150 DEG C, at such a temperature stop 1 hour after, Temperature fall
To room temperature；
(5) repeat step (2)~(4), untill being collected in step (3) less than hydrogen；
(6) after the solid product cleaning, drying of the hydro-thermal reaction of last time, it is pressed into fuel rod.
By the biomass straw of the present embodiment, originally sheet, after hydrothermal carbonization, powder, nothing have just been directly changed
Milled processed need to be passed through again；This becomes easily stored and transport biomass fuel rod, as shown in Figure 1.Simultaneously compare Fig. 2 and
The FTIR spectrum figure of Fig. 3 biomass straws before and after the processing, it can be seen that in the stalk after processing, 3440cm-1O-H's
Stretching vibration peak and 1120-1050cm-1The stretching vibration peak C-O at place is significantly reduced, and this is due to hydro-thermal reaction and oxidant
Collective effect, the oxygen-containing group in biomass is oxidized to organic acid, hydrogen ion is provided for follow-up electrolytic hydrogen production.
Embodiment 2
(1) 3 grams of the pine powder dried is added in 100 milliliters of aqueous solution, while adds 5 grams of FeCl3·6H2O, mixing
Liquid is placed into pressure-resistant hydrothermal reaction kettle, with 4 DEG C of min-1Programming rate, reactor is heated to 200 DEG C, at such a temperature
After stopping 2 hours, Temperature fall to room temperature；
(2) by the product after hydro-thermal reaction, separation of solid and liquid is carried out, solid matter is deposited in hydrothermal reaction kettle, liquids
Matter is as anode electrolyte；
(3) using the liquid after hydro-thermal reaction as the anode electrolyte of electrolytic cell, by the use of copolymer solid electrolyte as every
Film, plus 0.9V voltage, constant-potential electrolysis is carried out, until current density≤1mA cm-2, while collect hydrogen in negative pole；
(4) anode electrolyte after being electrolysed mixes with the solid matter after previous hydro-thermal reaction, and the hydro-thermal carried out again is anti-
Should, equally with 4 DEG C of min-1Programming rate, reactor is heated to 200 DEG C, at such a temperature stop 1 hour after, Temperature fall
To room temperature；
(5) repeat step (2)~(4), untill being collected in step (3) less than hydrogen；
(6) after the solid product cleaning, drying of the hydro-thermal reaction of last time, it is pressed into fuel rod.
By the implementation of the present embodiment, it can be seen that, under constant pressure 0.9V electrolytic condition, hydrogen can be also carried out with reference to Fig. 4
The electrochemical reaction of the precipitation of gas, moreover, positive pole does not use noble metal catalyst.
Embodiment 3
(1) 10 grams of the turfgrass directly gathered in is added in 100 milliliters of aqueous solution, while adds 3 grams of VOSO4·3H2O,
Mixed liquor is placed into pressure-resistant hydrothermal reaction kettle, with 3 DEG C of min-1Programming rate, reactor is heated to 180 DEG C, in the temperature
After the lower stop of degree 3 hours, Temperature fall to room temperature；
(2) by the product after hydro-thermal reaction, separation of solid and liquid is carried out, solid matter is deposited in hydrothermal reaction kettle, liquids
Matter is as anode electrolyte；
(3) using the liquid after hydro-thermal reaction as the anode electrolyte of electrolytic cell, by the use of copolymer solid electrolyte as every
Film, plus 1.5V voltage, constant-potential electrolysis is carried out, until current density≤1mA cm-2, while collect hydrogen in negative pole；
(4) anode electrolyte after being electrolysed mixes with the solid matter after previous hydro-thermal reaction, and the hydro-thermal carried out again is anti-
Should, equally with 3 DEG C of min-1Programming rate, reactor is heated to 180 DEG C, at such a temperature stop 1 hour after, Temperature fall
To room temperature；
(5) repeat step (2)~(4), untill being collected in step (3) less than hydrogen；
(6) after the solid product cleaning, drying of the hydro-thermal reaction of last time, it is pressed into fuel rod.
Biomass material is needed not move through conventional baking process, it is possible to directly in hydrothermal reaction kettle by the present embodiment
Reaction, reduces the pre-treatment step during biomass economy.
Claims (7)
- A kind of 1. method for obtaining hydrogen and biomass fuel rod simultaneously with biomass material, it is characterised in that methods described bag Include following steps：(1) biomass material, oxidant and water are mixed, at the uniform velocity heated up, carry out hydro-thermal reaction；(2) by the product after hydro-thermal reaction, separation of solid and liquid is carried out, obtains after hydro-thermal reaction liquid after solid matter and hydro-thermal reaction Body；(3) using the liquid after hydro-thermal reaction in step (2) as positive pole, it is electrochemically reacted, hydrogen is collected, after obtaining electrolysis Anode electrolyte；(4) anode electrolyte after being electrolysed in step (3) is mixed with solid matter after hydro-thermal reaction in step (2), carried out again Secondary hydro-thermal reaction；(5) repeat step (2)~(4), untill being collected in step (3) less than hydrogen；(6) after the solid product cleaning, drying of hydro-thermal reaction in step (4), it is pressed into fuel rod.
- 2. according to the method for claim 1, it is characterised in that the biomass material in the step (1) is given birth to for agriculture and forestry Fowl and animal excrement during lignin, farming industry leftover bits and pieces, agriculture and forestry organic waste material and Animal husbandry production during production and Discarded object.
- 3. according to the method for claim 1, it is characterised in that the oxidant in the step (1) is to be aoxidized The metallic compound of the multivalent state of reduction reaction.
- 4. according to the method for claim 1, it is characterised in that the weight of biomass material and water in the step (1) Ratio is 1~100:100, final concentration of 0.01~2mol/L of the oxidant.
- 5. according to the method for claim 1, it is characterised in that the reaction temperature of the hydro-thermal reaction in the step (1) exists 120~380 DEG C, 0.1~8MPa of pressure, the reaction time is 0.1~6 hour.
- 6. according to the method for claim 1, it is characterised in that the electrochemical reaction in the step (3) is anti-with hydro-thermal Anode electrolyte of the liquid as electrolytic cell after answering, by the use of copolymer solid electrolyte as barrier film, it is electrolysed, is received in negative pole Collect hydrogen.
- 7. according to the method for claim 6, it is characterised in that the voltage of the electrolysis is 0.8-1.5V.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305745A (en) * | 2018-11-22 | 2019-02-05 | 湖南农业大学 | A kind of method of cow dung deep dehydration |
| CN111206256A (en) * | 2020-02-27 | 2020-05-29 | 上海理工大学 | Biochar electrochemical reforming hydrogen production method based on biomass multistage utilization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102381820A (en) * | 2011-09-20 | 2012-03-21 | 福州开发区三水环保科技有限公司 | Sludge treatment process based on hydrothermal modification technology |
| CN106676564A (en) * | 2017-01-18 | 2017-05-17 | 邓渝林 | Method and system for preparing hydrogen by electrolyzing biomass directly |
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2017
- 2017-11-03 CN CN201711068860.9A patent/CN107829104A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381820A (en) * | 2011-09-20 | 2012-03-21 | 福州开发区三水环保科技有限公司 | Sludge treatment process based on hydrothermal modification technology |
| CN106676564A (en) * | 2017-01-18 | 2017-05-17 | 邓渝林 | Method and system for preparing hydrogen by electrolyzing biomass directly |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109305745A (en) * | 2018-11-22 | 2019-02-05 | 湖南农业大学 | A kind of method of cow dung deep dehydration |
| CN111206256A (en) * | 2020-02-27 | 2020-05-29 | 上海理工大学 | Biochar electrochemical reforming hydrogen production method based on biomass multistage utilization |
| CN111206256B (en) * | 2020-02-27 | 2021-04-30 | 上海理工大学 | Biochar electrochemical reforming hydrogen production method based on biomass multistage utilization |
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Application publication date: 20180323 |