CN107987856A - Method for preparing biological fuel gas, activated carbon and products thereof - Google Patents

Method for preparing biological fuel gas, activated carbon and products thereof Download PDF

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Publication number
CN107987856A
CN107987856A CN201610634658.7A CN201610634658A CN107987856A CN 107987856 A CN107987856 A CN 107987856A CN 201610634658 A CN201610634658 A CN 201610634658A CN 107987856 A CN107987856 A CN 107987856A
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China
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minutes
activated carbon
lignin
plant
fermentation
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CN107987856B (en
Inventor
赵鹏翔
卜令习
刘彦涛
赵正凯
蒋建新
赵锦
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STATE GRID ENERGY SAVING SERVICE Co Ltd
State Grid Corp of China SGCC
Beijing Forestry University
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STATE GRID ENERGY SAVING SERVICE Co Ltd
State Grid Corp of China SGCC
Beijing Forestry University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The invention belongs to chemical industry and biomass energy source domain, more particularly to biomass economy field, a kind of method for preparing biological fuel gas is more particularly to, is included the following steps, the raw material that will be enriched in lignin carbonizes 10 90 minutes at 400 DEG C 600 DEG C, obtains lignin carbide and isolates gas.The invention further relates to method, obtained activated carbon and the method for the combustion gas of co-producing bio matter and activated carbon for preparing activated carbon.The method obtains the biological fuel gas of high burning-value and the activated carbon of high-specific surface area, moreover, the method realizes effective degraded regeneration of straw, alleviates the dual-pressure of environment and the energy.

Description

Method for preparing biological fuel gas, activated carbon and products thereof
Technical field
The invention belongs to chemical industry and biomass energy biomass economy field, it is related to biomass economy field, and in particular to A kind of method for preparing biological fuel gas, a kind of method and product for preparing activated carbon, and the combustion gas of co-producing bio matter and activity The method of charcoal.
Background technology
The annual whole nation has a large amount of straw dead meals to need to be degraded and handled.Wherein, maize straw occupies agricultural solid Body dead meal is the first, and the annual output in China is more than 200,000,000 tons/year.Straw is mainly by cellulose, hemicellulose and lignin Composition；Wherein, hemicellulose is easier to be hydrolyzed to pentose, and cellulose is more difficult to be hydrolyzed to hexose, and lignin is generally as combustion Material.From the point of view of by taking maize straw as an example, its degradation treatment mode mainly includes being converted into feed, being degraded to fertilizer and biomass at present Power generation etc., but the straw utilization rate of these methods is very low, less than 10%.Therefore, a large amount of maize straws still using directly burning or The mode of discarding is handled, and causes great environmental pollution and energy waste.In face of the dual-pressure of environment and the energy, by biology Matter is converted into the energy, the exploitation of chemicals has caused extensive concern, wherein, straw is former as extensive and cheap biomass Material, it, which will efficiently be utilized, to have great importance to alleviating environment and Pressure on Energy.
Biological fuel gas (biogas) be using agricultural crop straw, forest tree castoff, edible fungi residues, fowl and animal excrement and all The imflammable gas that inflammable substance is converted into as raw material.At present, the main method for preparing biological fuel gas is by crops Stalk carries out charing process when 3 to 4 is small when inflammable substance under 680-700 DEG C of high temperature, and gas is then demultiplex out simultaneously Purification.But the carbonization temperature of this method is high, carbonization time length, energy consumption is excessive.
Activated carbon has special microstructure, flourishing pore structure, huge specific surface area and stronger adsorption energy Power, can effectively remove colourity, stink and most organic pollutants and some inorganic matters, be widely used at present environment, chemical industry, The fields such as medicine, food, national defence, agricultural, especially usage amount is increasing in environmental protection, has fabulous development prospect. The traditional preparation method of activated carbon includes charing and activation step.Charing is to carbonize carbon raw material in aerobic environment high temperature, No matter raw material belongs to aromatic compound or chain compound, and phenyl ring planar molecule is all obtained after charing and is condensed the three-dimensional to be formed Net structure carbide.Activation can use Physical or chemical method, and activation is activated carbon pore-forming, abundant surface group, expansion table The process of area and burning-off disordered carbon, is the committed step for preparing activated carbon；Wherein, activation temperature and time are to surface oxygen-containing group The type and quantity of group have a direct impact, and then have impact on the performance of activated carbon.Current activation method is mainly by carbide After being impregnated in lye, roasted at a high temperature of 850 DEG C.But the specific surface area of activated carbon is relatively low prepared by the activation method.
Still need at present a kind of to straw progress effectively degraded and the method handled, to alleviate the social energy and environment Dual-pressure.
The content of the invention
The present inventor obtains a kind of method for preparing high burning-value biological fuel gas, will be enriched in lignin raw material medium temperature, Fast charring, the gas isolated can be used as biological fuel gas.The present inventors have additionally discovered that by carbide with soda-dip, then successively Roasted in two temperature sections, can obtain the activated carbon of high-specific surface area.Based on this, the combustion of co-producing bio matter is also obtained in the present inventor The method of gas and activated carbon.Meanwhile the present invention realizes effective degradation treatment of straw, pair of the energy and resource is alleviated Weight power.Also, the preparation method of the present invention is succinctly efficient, easy to operation.
First aspect present invention is related to a kind of method for preparing biological fuel gas, includes the following steps：
The raw material that will be enriched in lignin carbonizes 10-90 minutes at 400 DEG C -600 DEG C, obtains lignin carbide and separates Go out gas.
In one embodiment of first aspect present invention, the charing carries out in nitrogen atmosphere.
In one embodiment of first aspect present invention, the step of gas that will be isolated is purified is further included；It is excellent The step of selection of land, the purification include separating the gas cyclone isolated, cooling.
In one embodiment, the gas and/or purified gas isolated are biological fuel gas.
In one embodiment of first aspect present invention, in the raw material weight percentage of lignin for >= , >=80%, >=90%, >=95%, >=99% or 100% 50%, >=70%.
In one embodiment of first aspect present invention, carbonization temperature is 420 DEG C -570 DEG C, 430 DEG C -550 DEG C or 480 DEG C -500 DEG C, be preferably 420 DEG C, 430 DEG C, 445 DEG C, 470 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 550 DEG C, 560 DEG C or 570 DEG C.
In one embodiment of first aspect present invention, carbonization time is 15-75 minutes, 20-60 minutes or 30-40 points Clock, is preferably 15 minutes, 18 minutes, 20 minutes, 24 minutes, 30 minutes, 36 minutes, 40 minutes, 47 minutes, 52 minutes, 60 points Clock or 75 minutes.
In one embodiment of first aspect present invention, the raw material is prepared by a method comprising the following steps Arrive：
1) part containing lignin of plant is subjected to stream explosion process；
2) steaming for obtaining step 1), which is disclosed, synchronizes diastatic fermentation, removes ethanol and Yeast protein in fermentate, As described raw material.
In one embodiment of first aspect present invention, including any one or multinomial in following A to I：
A. the cellulase dosage of simultaneous saccharification and fermentation is 16-28FPU/ (g celluloses) in step 2), is preferably 20- 25FPU/ (g celluloses), more preferably 22FPU/ (g celluloses)；
B. the yeast concentration of simultaneous saccharification and fermentation is 2-9g/ (L fermentation systems cumulative volume) in step 2), is preferably 3-7g/ (L fermentation systems cumulative volume), more preferably 5g/ (L fermentation systems cumulative volume)；
C. the temperature of simultaneous saccharification and fermentation is 28 DEG C -50 DEG C in step 2), when the time is 85-110 small；Preferably, temperature For 30 DEG C -40 DEG C, when the time is 90-100 small；It is highly preferred that temperature is 35 DEG C, when the time is 96 small；
D. the concentration of substrate of simultaneous saccharification and fermentation is 5%-25% (w/w) in step 2), is preferably 10%-20% (w/w), More preferably 10% (w/w)；
E. the part containing lignin of the plant is crop material (such as maize straw)；Preferably, the plant Water content≤12% (w/w) of part containing lignin ,≤10% (w/w) ,≤8% (w/w) or≤5% (w/w)；
F. the temperature of stream explosion process is 180-210 DEG C in step 1), and the time is 3-15 minutes；Preferably, temperature 190 DEG C -200 DEG C, the time is 5-10 minutes；It is highly preferred that temperature is 195 DEG C, the time is 6 minutes；
G. before being additionally included in stream explosion process, the step of with the part containing lignin of acid solution infiltration of plants；Preferably, acid solution Dosage be 0.3-0.6kg/ (part containing lignin of kg plants), more preferably 0.4-0.45kg/ (kg plants containing wooden The part of element)；Preferably, the concentration of the acid solution is 0.1%-1% (w/w), more preferably 0.1%-0.5% (w/w), into one Step is preferably 0.25% (w/w)；
H. in step 2), the method for removing ethanol is distillation, is preferably continuous still；
I. in step 2), the step of method of Yeast protein is including settling, then removing light phase component is removed, is preferably settled Method is centrifugal sedimentation.
Second aspect of the present invention is related to a kind of method for preparing activated carbon, including the step that lignin carbide is activated Suddenly；
Preferably, lignin carbide method as any one of first aspect present invention is made；
Alternatively, the activation includes lignin carbide being impregnated in lye, isolates solid, then by the solid into The step of row roasting.
In one embodiment, the material that the activated carbon obtains after being activated for lignin carbide.
In one embodiment of second aspect of the present invention, including any one or multinomial in following a to g：
A. described be roasted to first roasts 20-40 minutes at 500 DEG C -650 DEG C, then roasts 40-80 at 670 DEG C -930 DEG C Minute；Preferably, first roast 25-35 minutes at 570 DEG C -630 DEG C, then roasted 50-70 minutes at 690 DEG C -900 DEG C；More Preferably, first roast 30 minutes at 600 DEG C, then at 700 DEG C -900 DEG C roast 1 it is small when；
B. the weight ratio of the lye and lignin carbide is (0.2-1):1, be preferably (0.3-0.8):1, more preferably For 0.5:1；
C. one or more of the lye in potassium hydroxide solution, sodium hydroxide solution and calcium hydroxide solution； Preferably, the lye is potassium hydroxide solution；
D. the concentration of the lye is 45%-70% (w/w), is preferably 50%-65% (w/w), more preferably 60% (w/ w)；
E. the temperature impregnated is room temperature, is preferably 10-35 DEG C；
F. when the time impregnated is 2-4 small, when being preferably 3 small；
G. the step that the material after activation is washed, is dried is further included.
Third aspect present invention is related to the activated carbon as made from second aspect the method；Preferably, the activated carbon Specific surface area >=700m2/ g, more preferably >=750m2/g、≥900m2/g、≥1100m2/ g or >=1300m2/ g, further preferably For 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2/ g or 1320m2/g。
Fourth aspect present invention is related to the method selected from following (1) to any one of (6), including appoints in claim 1 to 8 Method described in one；
Preferably, the part containing lignin of the plant is crop material (such as maize straw)；
Preferably, combustion value >=11000kJ/m of the biological fuel gas3, more preferably >=12000kJ/m3, it is further excellent Elect 11000kJ/m as3、11800kJ/m3、12000kJ/m3Or 12200kJ/m3；
Preferably, specific surface area >=700m of the activated carbon2/ g, more preferably >=750m2/g、≥900m2/g、≥ 1100m2/ g or >=1300m2/ g, more preferably 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2/ g or 1320m2/g；
(1) method for handling the part containing lignin of plant；
(2) method that the steaming of the part containing lignin of plant is disclosed is handled；
(3) method for the simultaneous saccharification and fermentation residue that the steaming of the part containing lignin of processing plant is disclosed；
(4) by part co-producing bio matter combustion gas of the plant containing lignin and the method for activated carbon；
(5) method that the combustion gas of co-producing bio matter and activated carbon are disclosed by the steaming of the part containing lignin of plant；With
(6) the co-producing bio matter combustion gas of simultaneous saccharification and fermentation residue and work disclosed by the steaming of the part containing lignin of plant The method of property charcoal.
In the present invention,
Unless otherwise instructed, " stream explosion process " refers to Steam explosion treatment, in particular to that raw material is inserted steam blasting is anti- Answer in device, be passed through high temperature, high steam and maintain certain time at a certain temperature, then moment (less than 0.5 second) opening valve Door, during material sudden pressure reduction full of steam, the acute expansion of gas in hole is so as to producing " explosion " effect.
Unless otherwise instructed, in addition to lignin carbonizes the material to be formed, " lignin carbide " can also be included in raw material Other components carbonize the material to be formed.
Unless otherwise instructed, " the containing lignin portion of plant " refers to the part containing lignin in plant, such as stalk (including maize straw), root, stem, leaf, pericarp etc..
The beneficial effect that the present invention obtains：
1st, the present invention is prepared in the method for biological fuel gas, and the raw material that will be enriched in lignin carries out medium temperature fast charring, obtains Obtained the biological fuel gas of high burning-value.
2nd, the present invention is prepared in the method for activated carbon, and the carbide after steeping liquor roasts under two temperature sections successively Burn, obtain the activated carbon of high-specific surface area.
3rd, The inventive method achieves the coproduction of high burning-value biological fuel gas and active carbon with high specific surface area.
4th, effective degraded The inventive method achieves straw utilizes, and alleviates the dual pressure of the energy and environment Power.
5th, method of the invention obtains cellulose ethanol and Yeast protein at the same time, takes full advantage of raw material resources, significantly The production cost of cellulose ethanol, Yeast protein is reduced, improves the overall economic efficiency of biomass material.
6th, method of the invention isolates Yeast protein, has not only obtained the chemicals of economic value, but also significantly reduce Protein component is to preparing the interference of activated carbon.
7th, the simultaneous saccharification and fermentation in the method for the present invention, makes the conversion ratio of cellulose in straw reach more than 90%, Content of lignin in residue is high, impurity content is extremely low, be conducive to follow-up charing process obtain high burning-value biological fuel gas and The activated carbon of high-specific surface area.
8th, method of the invention, carbonizes in nitrogen atmosphere, is conducive to obtain the biological fuel gas of high burning-value.
9th, in method of the invention, carbide is impregnated with high-concentration alkali liquor, reduces the dosage and subsequent wash water of lye Dosage, saved cost.
10th, in method of the invention, on the one hand steam blasting pretreatment can improve the yield of cellulose ethanol, on the other hand may be used The specific surface area of raw material is improved, the easy pore-forming of material, can produce activated carbon, while eliminate other under more temperate condition The interference of component.
Brief description of the drawings
In order to make the content of the present invention more clearly understood, the specific embodiment below according to the present invention and combination Attached drawing, the present invention is described in further detail, wherein：
Fig. 1 is the present invention by maize straw co-producing bio matter combustion gas and the flow chart of activated carbon.
Embodiment
Embodiment 1
The flow by maize straw co-producing bio matter combustion gas and activated carbon with reference to shown in Fig. 1 is operated.
The particle diameter of maize straw is between 20 millimeters~30 millimeters, water content≤12% (w/w).It is with mass concentration When 0.25% sulfuric acid solution infiltration maize straw 2 is small, the dosage of sulfuric acid solution is 0.40~0.45kg/ (kg maize straws). Then, maize straw is continued steam blasting at 195 DEG C to pre-process 6 minutes.Obtained steaming is disclosed and synchronizes saccharification hair Ferment reacts, wherein, substrate mass concentration is 10%, and cellulase dosage is 22FPU/ (g celluloses), yeast concentration 5g/L, 35 DEG C of reaction temperature, when the simultaneous saccharification and fermentation time 96 is small.Reaction product removes cellulose ethanol through continuous still, then through centrifugation After sedimentation, the light phase component-Yeast protein on top is removed, remaining diastatic fermentation residue passes through pneumatic conveying drying.Will be dried Diastatic fermentation residue, in 480 DEG C of fast charrings 30 minutes, is isolated gas and through cyclonic separation and cooling, is obtained in nitrogen atmosphere To biological fuel gas 1.At room temperature, by carbide be immersed in the KOH solution of 60% (w/w) keep 3 it is small when, KOH solution with The weight ratio of carbide is 0.5:1.Carbide after dipping is first roasted 30 minutes at 600 DEG C, then 1 is roasted at 800 DEG C Hour, it is washed, dry, obtain activated carbon 1.
Embodiment 2
The flow by maize straw co-producing bio matter combustion gas and activated carbon with reference to shown in Fig. 1 is operated.
The particle diameter of maize straw is between 20 millimeters~30 millimeters, water content≤12% (w/w).It is with mass concentration When 0.25% sulfuric acid solution infiltration maize straw 2 is small, the dosage of sulfuric acid solution is 0.40~0.45kg/ (kg maize straws). Then, maize straw is continued steam blasting at 195 DEG C to pre-process 6 minutes.Obtained steaming is disclosed and synchronizes saccharification hair Ferment reacts, wherein, substrate mass concentration is 10%, and cellulase dosage is 22FPU/ (g celluloses), yeast concentration 5g/L, 35 DEG C of reaction temperature, when the simultaneous saccharification and fermentation time 96 is small.Reaction product removes cellulose ethanol through continuous still, then through centrifugation Sedimentation, removes the light phase component-Yeast protein on top, and remaining diastatic fermentation residue passes through pneumatic conveying drying.By dried sugar Change fermentation residue in nitrogen atmosphere in 500 DEG C of fast charrings 40 minutes, isolate gas and through cyclonic separation and cooling, obtain Biological fuel gas 2.At room temperature, by carbide be immersed in 60% (w/w) KOH solution keep 3 it is small when, KOH solution with charing Thing weight ratio is 0.5:1.Carbide after dipping first roast 30 minutes at 600 DEG C, then when roasting 1 is small at 800 DEG C, is passed through Washing, drying, obtain activated carbon 2.
Embodiment 3
The flow by maize straw co-producing bio matter combustion gas and activated carbon with reference to shown in Fig. 1 is operated.
The particle diameter of maize straw is between 20 millimeters~30 millimeters, water content≤12% (w/w).It is with mass concentration When 0.25% sulfuric acid solution infiltration maize straw 2 is small, the dosage of sulfuric acid solution is 0.40~0.45kg/ (kg maize straws). Then, maize straw is continued steam blasting at 195 DEG C to pre-process 6 minutes.Obtained steaming is disclosed and synchronizes saccharification hair Ferment reacts, wherein, substrate mass concentration is 10%, and cellulase dosage is 22FPU/ (g celluloses), yeast concentration 5g/L, 35 DEG C of reaction temperature, when the simultaneous saccharification and fermentation time 96 is small.Reaction product removes cellulose ethanol through continuous still, then through centrifugation After sedimentation, the light phase component-Yeast protein on top is removed, remaining diastatic fermentation residue passes through pneumatic conveying drying.Will be dried Diastatic fermentation residue, in 500 DEG C of fast charrings 40 minutes, is isolated gas and through cyclonic separation and cooling, is obtained in nitrogen atmosphere To biological fuel gas 3.At room temperature, carbide is immersed in 60% (w/w) KOH solution keep 3 it is small when, KOH solution and charcoal The weight ratio of compound is 0.5:1.Carbide after dipping is first roasted 30 minutes at 600 DEG C, then roasting 1 is small at 700 DEG C When, it is washed, dry, obtain activated carbon 3.
Embodiment 4
The flow by maize straw co-producing bio matter combustion gas and activated carbon with reference to shown in Fig. 1 is operated.
The particle diameter of maize straw is between 20 millimeters~30 millimeters, water content≤12% (w/w).It is with mass concentration When 0.25% sulfuric acid solution infiltration maize straw 2 is small, the dosage of sulfuric acid solution is 0.40~0.45kg/ (kg maize straws). Then, maize straw is continued steam blasting at 195 DEG C to pre-process 6 minutes.Obtained steaming is disclosed and synchronizes saccharification hair Ferment reacts, wherein, substrate mass concentration is 10%, and cellulase dosage is 22FPU/ (g celluloses), yeast concentration 5g/L, 35 DEG C of reaction temperature, when the simultaneous saccharification and fermentation time 96 is small.Reaction product removes cellulose ethanol through continuous still, then through centrifugation After sedimentation, the light phase component-Yeast protein on top is removed, remaining diastatic fermentation residue passes through pneumatic conveying drying.Will be dried Diastatic fermentation residue, in 500 DEG C of fast charrings 40 minutes, is isolated gas and through cyclonic separation and cooling, is obtained in nitrogen atmosphere To biological fuel gas 4.At room temperature, by carbide be immersed in the KOH solution of 60% (w/w) keep 3 it is small when, KOH solution with The weight ratio of carbide is 0.5:1.Carbide after dipping is first roasted 30 minutes at 600 DEG C, then 1 is roasted at 900 DEG C Hour, it is washed, dry, obtain activated carbon 4.
Comparative example 1
Between 20 millimeters~30 millimeters, water content≤12% (w/w), maize straw particle is existed the particle diameter of maize straw At 500 DEG C in nitrogen atmosphere fast charring 40 minutes, isolate gas and purify and to obtain biological fuel gas A.At room temperature, by charcoal Compound be immersed in the KOH solution of 60% (w/w) keep 3 it is small when, the weight ratio of KOH solution and carbide is 0.5:1.Will dipping Rear carbide first roast 30 minutes at 600 DEG C, then when roasting 1 is small at 800 DEG C, washed, dry, and obtains activated carbon A.
Comparative example 2
The particle diameter of maize straw is between 20 millimeters~30 millimeters, water content≤12% (w/w).It is with mass concentration When 0.25% sulfuric acid solution infiltration maize straw 2 is small, the dosage of sulfuric acid solution is 0.40~0.45kg/ (kg maize straws). Then, maize straw is continued steam blasting at 195 DEG C to pre-process 6 minutes, obtained steaming is disclosed.Steaming is disclosed at 500 DEG C Under in nitrogen atmosphere fast charring 40 minutes, isolate gas and purify obtain biological fuel gas B.At room temperature, will carbonize Thing be immersed in the KOH solution of 60% (w/w) keep 3 it is small when, the weight ratio of KOH solution and carbide is 0.5:1.After impregnating Carbide first roast 30 minutes at 600 DEG C, then at 800 DEG C roasting 1 it is small when, it is washed, dry, obtain activated carbon B.
Test case
Measure embodiment 1-4, the combustion value of biological fuel gas of comparative example 1-2, the specific surface area of activated carbon, biological fuel gas Yield, activated carbon yield and cellulose ethanol yield, the results are shown in Table 1.
The combustion value of biological fuel gas and the specific surface area of activated carbon, unit are respectively kJ/m3And m2/g。
Biological fuel gas yield：Prepared biological fuel gas, divided by the weight of used maize straw are collected, is given birth to Substance combustible gas yield, m3/ (kg maize straws).
Activated carbon yield：Collect and weigh the weight of prepared activated carbon, divided by the weight of used maize straw, obtain Activated carbon yield, %.
Cellulose ethanol yield：Collect and weigh the weight of cellulose ethanol, divided by the weight of used maize straw, obtain fibre Tie up alcohol getting rate, %.
Table 1
As shown in Table 1, compared with comparative example 1-2, specific surface area higher, the biomass of the activated carbon that the method for the present invention obtains The combustion value higher of combustion gas.Moreover, the present invention is disclosed with simultaneous saccharification and fermentation processing steaming, while prepare cellulose ethanol and yeast egg In vain, the production cost of cellulose ethanol, Yeast protein is considerably reduced, takes full advantage of raw material resources.
Obviously, the above embodiments are merely examples for clarifying the description, and the restriction not to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (10)

1. a kind of method for preparing biological fuel gas, includes the following steps：
The raw material that will be enriched in lignin carbonizes 10-90 minutes at 400 DEG C -600 DEG C, obtains lignin carbide and separates outlet Body；
Preferably, the charing carries out in nitrogen atmosphere；
Alternatively, the step of gas that will be isolated is purified is further included；Preferably, the purification includes the gas that will be isolated The step of body cyclonic separation, cooling.
2. according to the method described in claim 1, wherein, in the raw material weight percentage of lignin be >=50%, >= , >=90%, >=95%, >=99% or 100% 70%, >=80%.
3. according to the method described in claim 1, wherein, carbonization temperature for 420 DEG C -570 DEG C, 430 DEG C -550 DEG C or 480 DEG C - 500 DEG C, be preferably 420 DEG C, 430 DEG C, 445 DEG C, 470 DEG C, 480 DEG C, 500 DEG C, 520 DEG C, 550 DEG C, 560 DEG C or 570 DEG C.
4. according to the method described in claim 1, wherein, carbonization time is 15-75 minutes, 20-60 minutes or 30-40 minutes, Preferably 15 minutes, 18 minutes, 20 minutes, 24 minutes, 30 minutes, 36 minutes, 40 minutes, 47 minutes, 52 minutes, 60 minutes or 75 minutes.
5. method according to any one of claim 1 to 4, wherein, method of the raw material by including the following steps It is prepared：
1) part containing lignin of plant is subjected to stream explosion process；
2) steaming for obtaining step 1), which is disclosed, synchronizes diastatic fermentation, removes ethanol and Yeast protein in fermentate, is The raw material.
6. according to the method described in claim 5, it is characterized in that any one or multinomial in following A to I：
A. in step 2), the cellulase dosage of simultaneous saccharification and fermentation is 16-28FPU/ (g celluloses), is preferably 20-25FPU/ (g celluloses), more preferably 22FPU/ (g celluloses)；
B. in step 2), the yeast concentration of simultaneous saccharification and fermentation is 2-9g/ (L fermentation systems cumulative volume), is preferably that (L is sent out 3-7g/ Ferment system cumulative volume), more preferably 5g/ (L fermentation systems cumulative volume)；
C. in step 2), the temperature of simultaneous saccharification and fermentation is 28 DEG C -50 DEG C, when the time is 85-110 small；Preferably, temperature 30 DEG C -40 DEG C, the time for 90-100 it is small when；It is highly preferred that temperature is 35 DEG C, when the time is 96 small；
D. in step 2), the concentration of substrate of simultaneous saccharification and fermentation is 5%-25% (w/w), is preferably 10%-20% (w/w), more Preferably 10% (w/w)；
E. the part containing lignin of the plant is crop material (such as maize straw)；Preferably, the plant containing wood Water content≤12% (w/w) of the part of quality ,≤10% (w/w) ,≤8% (w/w) or≤5% (w/w)；
F. in step 1), the temperature of stream explosion process is 180-210 DEG C, and the time is 3-15 minutes；Preferably, temperature for 190 DEG C- 200 DEG C, the time is 5-10 minutes；It is highly preferred that temperature is 195 DEG C, the time is 6 minutes；
G. before being additionally included in stream explosion process, the step of with the part containing lignin of acid solution infiltration of plants；Preferably, the use of acid solution Measure as 0.3-0.6kg/ (part containing lignin of kg plants), more preferably 0.4-0.45kg/ (kg plants containing lignin Part)；Preferably, the concentration of the acid solution is 0.1%-1% (w/w), more preferably 0.1%-0.5% (w/w), further excellent Elect 0.25% (w/w) as；
H. in step 2), the method for removing ethanol is distillation, is preferably continuous still；
I. in step 2), the step of method of Yeast protein is including settling, then removing light phase component is removed, the method preferably settled For centrifugal sedimentation.
7. a kind of method for preparing activated carbon, including the step of lignin carbide is activated；
Preferably, lignin carbide method as any one of claim 1 to 6 is made；
Alternatively, the activation includes lignin carbide being impregnated in lye, isolates solid, then the solid is roasted The step of burning.
8. according to the method described in claim 7, it is characterized in that any one or multinomial in following a to g：
A. described be roasted to first roasts 20-40 minutes at 500 DEG C -650 DEG C, then 40-80 points are roasted at 670 DEG C -930 DEG C Clock；Preferably, first roast 25-35 minutes at 570 DEG C -630 DEG C, then roasted 50-70 minutes at 690 DEG C -900 DEG C；It is more excellent Selection of land, first roast 30 minutes at 600 DEG C, then at 700 DEG C -900 DEG C roast 1 it is small when；
B. the weight ratio of the lye and lignin carbide is (0.2-1):1, be preferably (0.3-0.8):1, more preferably 0.5:1；
C. one or more of the lye in potassium hydroxide solution, sodium hydroxide solution and calcium hydroxide solution；It is preferred that Ground, the lye are potassium hydroxide solution；
D. the concentration of the lye is 45%-70% (w/w), is preferably 50%-65% (w/w), more preferably 60% (w/w)；
E. the temperature impregnated is room temperature, is preferably 10-35 DEG C；
F. when the time impregnated is 2-4 small, when being preferably 3 small；
G. the step that the material after activation is washed, is dried is further included.
9. the activated carbon as made from 7 or 8 the method for claim；
Preferably, specific surface area >=700m of the activated carbon2/ g, more preferably >=750m2/g、≥900m2/g、≥1100m2/g Or >=1300m2/ g, more preferably 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2/ g or 1320m2/g。
10. the method selected from following (1) to any one of (6), including method described in any item of the claim 1 to 8；
Preferably, the part containing lignin of the plant is crop material (such as maize straw)；
Preferably, combustion value >=11000kJ/m of the biological fuel gas3, more preferably >=12000kJ/m3, more preferably 11000kJ/m3、11800kJ/m3、12000kJ/m3Or 12200kJ/m3；
Preferably, specific surface area >=700m of the activated carbon2/ g, more preferably >=750m2/g、≥900m2/g、≥1100m2/g Or >=1300m2/ g, more preferably 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2/ g or 1320m2/g；
(1) method for handling the part containing lignin of plant；
(2) method that the steaming of the part containing lignin of plant is disclosed is handled；
(3) method for the simultaneous saccharification and fermentation residue that the steaming of the part containing lignin of processing plant is disclosed；
(4) by part co-producing bio matter combustion gas of the plant containing lignin and the method for activated carbon；
(5) method that the combustion gas of co-producing bio matter and activated carbon are disclosed by the steaming of the part containing lignin of plant；With
(6) the simultaneous saccharification and fermentation residue co-producing bio matter combustion gas disclosed by the steaming of the part containing lignin of plant and activated carbon Method.
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