CN107987856B - Method for preparing biomass gas and active carbon and products thereof - Google Patents

Method for preparing biomass gas and active carbon and products thereof Download PDF

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CN107987856B
CN107987856B CN201610634658.7A CN201610634658A CN107987856B CN 107987856 B CN107987856 B CN 107987856B CN 201610634658 A CN201610634658 A CN 201610634658A CN 107987856 B CN107987856 B CN 107987856B
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activated carbon
item
lignin
fermentation
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CN107987856A (en
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赵鹏翔
卜令习
刘彦涛
赵正凯
蒋建新
赵锦
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State Grid Corp of China SGCC
Beijing Forestry University
State Grid Energy Conservation Service Co Ltd
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State Grid Corp of China SGCC
Beijing Forestry University
State Grid Energy Conservation Service Co Ltd
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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

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  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention belongs to the fields of chemical industry and biomass energy, particularly relates to the field of biomass utilization, and more particularly relates to a method for preparing biomass gas. The invention also relates to a method for preparing the activated carbon, the prepared activated carbon and a method for co-producing biomass gas and activated carbon. The method obtains the biomass fuel gas with high fuel value and the activated carbon with high specific surface area, and the method realizes the effective degradation and regeneration of the plant straws and relieves the double pressure of environment and energy.

Description

Method for preparing biomass gas and active carbon and products thereof
Technical Field
The invention belongs to the field of chemical industry and biomass energy biomass utilization, relates to the field of biomass utilization, and particularly relates to a method for preparing biomass gas, a method for preparing activated carbon, a product of the method, and a method for co-producing biomass gas and activated carbon.
Background
A large amount of plant straw waste materials need to be degraded and treated every year. Wherein, the corn straw is the first agricultural solid waste material, and the annual output in China is more than 2 hundred million tons per year. The plant straw mainly comprises cellulose, hemicellulose and lignin; among them, hemicellulose is easily hydrolyzed into pentose, cellulose is hardly hydrolyzed into hexose, and lignin is generally used as fuel. Taking corn straws as an example, the degradation treatment modes of the method mainly comprise conversion into feed, degradation into fertilizer, biomass power generation and the like at present, but the utilization rate of the straws of the methods is low and is less than 10 percent. Therefore, a large amount of corn straws are still treated by direct burning or discarding, which causes great environmental pollution and energy waste. In the face of the dual pressure of environment and energy, the development of converting biomass into energy and chemicals has attracted extensive attention, wherein, plant straws are used as a wide and cheap biomass raw material, and the efficient utilization of the plant straws has important significance for relieving the pressure of environment and energy.
The biomass gas (biogas) is a combustible gas converted from crop straws, forest and wood wastes, edible fungus residues, livestock and poultry manure and all combustible substances as raw materials. At present, the main method for preparing biomass gas is to carry out carbonization treatment on combustible substances such as crop straws and the like at the high temperature of 680-700 ℃ for 3 to 4 hours, and then separate and purify the gas. But the method has high carbonization temperature, long carbonization time and overhigh energy consumption.
The activated carbon has a special microcrystalline structure, a developed pore structure, a huge specific surface area and a strong adsorption capacity, can effectively remove chromaticity, odor, most organic pollutants and certain inorganic substances, is widely used in the fields of environment, chemical industry, medicines, food, national defense, agriculture and the like at present, is particularly used in increasingly large amount in environmental protection, and has a very good development prospect. The traditional preparation method of the activated carbon comprises the steps of carbonization and activation. The carbonization is to carbonize the carbon-containing raw material at high temperature in an aerobic environment, and the carbonized material with a three-dimensional network structure formed by condensation of benzene ring plane molecules is obtained after carbonization no matter the raw material belongs to an aromatic compound or a chain compound. The activation can adopt a physical method or a chemical method, and is a process of forming holes, enriching surface groups, enlarging the surface area and burning out disordered carbon by the activated carbon, which is a key step for preparing the activated carbon; wherein, the activation temperature and the activation time directly influence the type and the number of the surface oxygen-containing groups, thereby influencing the performance of the activated carbon. The existing activation method is mainly to immerse the carbide in alkali liquor and then roast the carbide at a high temperature of 850 ℃. But the specific surface area of the activated carbon prepared by the activation method is lower.
At present, a method for effectively degrading and treating plant straws is needed to relieve the dual pressure of social energy and environment.
Disclosure of Invention
The inventor obtains a method for preparing high-fuel-value biomass gas, the lignin-rich raw material is carbonized at medium temperature and fast, and the separated gas can be used as the biomass gas. The inventor also finds that the activated carbon with high specific surface area can be obtained by impregnating the carbide with alkali liquor and then sequentially roasting at two temperature sections. Based on the method, the inventor also obtains a method for co-producing the biomass fuel gas and the activated carbon. Meanwhile, the invention realizes the effective degradation treatment of the plant straws and reduces the double pressure of energy and resources. Moreover, the preparation method is simple and efficient, and is convenient to operate.
The first aspect of the invention relates to a method for preparing biomass fuel gas, which comprises the following steps:
carbonizing the raw material rich in lignin at 400-600 ℃ for 10-90 minutes to obtain lignin carbide and separating gas.
In one embodiment of the first aspect of the present invention, the carbonization is performed in a nitrogen atmosphere.
In one embodiment of the first aspect of the present invention, the method further comprises the step of purifying the separated gas; preferably, the purification comprises the steps of cyclone separation of the separated gas, cooling.
In one embodiment, the separated gas and/or the purified gas is biomass fuel gas.
In one embodiment of the first aspect of the present invention, the weight percentage content of the lignin in the raw material is equal to or more than 50%, equal to or more than 70%, equal to or more than 80%, equal to or more than 90%, equal to or more than 95%, equal to or more than 99%, or 100%.
In one embodiment of the first aspect of the present invention, the carbonization temperature is 420 ℃ to 570 ℃, 430 ℃ to 550 ℃, or 480 ℃ to 500 ℃, preferably 420 ℃, 430 ℃, 445 ℃, 470 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 560 ℃ or 570 ℃.
In one embodiment of the first aspect of the present invention, the charring 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.
In one embodiment of the first aspect of the present invention, the starting material is prepared by a process comprising the steps of:
1) steaming and exploding the part containing the lignin of the plant;
2) and (2) carrying out synchronous saccharification and fermentation on the steam exploded material obtained in the step 1), and removing ethanol and yeast protein in a fermentation product to obtain the raw material.
In one embodiment of the first aspect of the present invention, any one or more of the following a to I is included:
A. the dosage of the cellulase for simultaneous saccharification and fermentation in the step 2) is 16-28FPU/(g cellulose), preferably 20-25FPU/(g cellulose), and more preferably 22FPU/(g cellulose);
B. the concentration of the yeast for synchronous saccharification and fermentation in the step 2) is 2-9g/(L of the total volume of the fermentation system), preferably 3-7g/(L of the total volume of the fermentation system), and more preferably 5g/(L of the total volume of the fermentation system);
C. the temperature of the synchronous saccharification and fermentation in the step 2) is 28-50 ℃, and the time is 85-110 hours; preferably, the temperature is 30-40 ℃, and the time is 90-100 hours; more preferably, the temperature is 35 ℃ and the time is 96 hours;
D. the substrate concentration of the simultaneous saccharification and fermentation in the step 2) is 5-25% (w/w), preferably 10-20% (w/w), and more preferably 10% (w/w);
E. the lignin-containing part of the plant is crop straw (such as corn stover); preferably, the lignin-containing portion of the plant has a moisture content of less than or equal to 12% (w/w), < 10% (w/w), < 8% (w/w) or < 5% (w/w);
F. the temperature of the steam explosion treatment in the step 1) is 180-210 ℃, and the time is 3-15 minutes; preferably, the temperature is 190 ℃ -200 ℃, and the time is 5-10 minutes; more preferably, the temperature is 195 ℃ and the time is 6 minutes;
G. further comprising the step of infiltrating the lignin-containing part of the plant with an acid solution before the steam explosion treatment; preferably, the acid liquor is used in an amount of 0.3-0.6kg/(kg lignin-containing parts of the plant), more preferably 0.4-0.45kg/(kg lignin-containing parts of the plant); preferably, the acid solution has a concentration of 0.1% to 1% (w/w), more preferably 0.1% to 0.5% (w/w), and even more preferably 0.25% (w/w);
H. in the step 2), the method for removing the ethanol is distillation, preferably continuous distillation;
I. in step 2), the method for removing the yeast protein comprises the steps of settling and then removing the light phase component, and the preferred settling method is centrifugal settling.
The second aspect of the present invention relates to a method for producing activated carbon, comprising the step of activating lignin char;
preferably, the lignin char is produced by a method according to any one of the first aspect of the invention;
optionally, the activating comprises the steps of immersing the lignin char in a lye, separating out the solids, and roasting the solids.
In one embodiment, the activated carbon is the material obtained after activation of lignin char.
In one embodiment of the second aspect of the present invention, any one or more of the following a to g is included:
a. the roasting is carried out for 20-40 minutes at 500-650 ℃ and then for 40-80 minutes at 670-930 ℃; preferably, the raw materials are firstly roasted at 570-630 ℃ for 25-35 minutes and then roasted at 690-900 ℃ for 50-70 minutes; more preferably, the mixture is roasted at 600 ℃ for 30 minutes and then at 700-900 ℃ for 1 hour;
b. the weight ratio of the alkali liquor to the lignin carbide is (0.2-1) to 1, preferably (0.3-0.8) to 1, more preferably 0.5: 1;
c. the alkali liquor is selected from one or more of potassium hydroxide solution, sodium hydroxide solution and calcium hydroxide solution; preferably, the alkali liquor is potassium hydroxide solution;
d. the concentration of the alkali liquor is 45-70% (w/w), preferably 50-65% (w/w), more preferably 60% (w/w);
e. the dipping temperature is room temperature, preferably 10-35 ℃;
f. the dipping time is 2 to 4 hours, preferably 3 hours;
g. also comprises the steps of washing and drying the activated substance.
A third aspect of the invention relates to an activated carbon produced by the method of the second aspect; preferably, the specific surface area of the activated carbon is more than or equal to 700m2/g, more preferably 750m or more2/g、≥900m2/g、≥1100m2/g or more than or equal to 1300m2(ii) g, more preferably 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2Per g or 1320m2/g。
The fourth aspect of the present invention relates to a method selected from any one of the following (1) to (6), including the method of any one of claims 1 to 8;
preferably, the lignin-containing part of the plant is crop straw (such as corn stover);
preferably, the fuel value of the biomass fuel gas is more than or equal to 11000kJ/m3More preferably 12000kJ/m or more3More preferably 11000kJ/m3、11800kJ/m3、12000kJ/m3Or 12200kJ/m3；
Preferably, the specific surface area of the activated carbon is more than or equal to 700m2/g, more preferably 750m or more2/g、≥900m2/g、≥1100m2/g or more than or equal to 1300m2(ii) g, more preferably 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2Per g or 1320m2/g；
(1) A method of treating a lignin-containing part of a plant;
(2) a method of treating a deflagration material of a lignin-containing portion of a plant;
(3) a method for treating simultaneous saccharification and fermentation residues of a steamed and exploded material of a lignin-containing part of a plant;
(4) a method for co-producing biomass gas and activated carbon from lignin-containing parts of plants;
(5) a method for co-producing biomass gas and activated carbon from a steam exploded material of a lignin-containing part of a plant; and
(6) a method for co-producing biomass gas and activated carbon from simultaneous saccharification and fermentation residues of steam-exploded material of lignin-containing parts of plants.
In the present invention,
if not stated otherwise, "steam explosion" refers to steam explosion, specifically, the raw material is put into a steam explosion reactor, high-temperature and high-pressure steam is introduced and maintained at a certain temperature for a certain time, then a valve is opened instantaneously (less than 0.5 second), and when the pressure of the material filled with the pressure steam is suddenly reduced, the gas in the pores expands sharply, thereby generating "explosion" effect.
Unless otherwise specified, the "lignin char" may include, in addition to the material formed by carbonization of lignin, materials formed by carbonization of other components in the raw material.
Unless otherwise specified, "lignin-containing parts of a plant" refers to parts of a plant that contain lignin, such as straw (including corn stover), roots, stems, leaves, pericarp, and the like.
The invention has the following beneficial effects:
1. in the method for preparing the biomass gas, the raw material rich in lignin is subjected to medium-temperature rapid carbonization, so that the biomass gas with high combustion value is obtained.
2. In the method for preparing the activated carbon, the carbide after being soaked in the alkali liquor is roasted at two temperature sections in sequence to obtain the activated carbon with high specific surface area.
3. The method realizes the co-production of the biomass gas with high fuel value and the activated carbon with high specific surface area.
4. The method of the invention realizes the effective degradation and utilization of the plant straws and relieves the dual pressure of energy and environment.
5. The method of the invention simultaneously obtains the cellulosic ethanol and the yeast protein, fully utilizes the raw material resources, greatly reduces the production cost of the cellulosic ethanol and the yeast protein, and improves the comprehensive economic benefit of the biomass raw material.
6. The method of the invention separates out the yeast protein, which not only obtains the chemical with economic value, but also greatly reduces the interference of the protein component to the preparation of the active carbon.
7. The synchronous saccharification and fermentation in the method of the invention enables the conversion rate of cellulose in the plant straws to reach more than 90%, the lignin content in the residue is high, the impurity content is extremely low, and the subsequent carbonization treatment is facilitated to obtain the biomass fuel gas with high combustion value and the activated carbon with high specific surface area.
8. The method of the invention is carbonized in nitrogen atmosphere, which is beneficial to obtaining biomass gas with high burning value.
9. In the method, the carbide is impregnated by the high-concentration alkali liquor, so that the use amount of the alkali liquor and the use amount of subsequent washing water are reduced, and the cost is saved.
10. In the method, the steam explosion pretreatment can improve the yield of the cellulosic ethanol on one hand, improve the specific surface area of the raw material on the other hand, facilitate pore formation of the material, produce the active carbon under mild conditions and simultaneously eliminate the interference of other components.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a flow chart of the present invention for co-production of biomass gas and activated carbon from corn stover.
Detailed Description
Example 1
The operation is carried out by referring to the flow of the co-production of the biomass fuel gas and the activated carbon by the corn straws shown in the figure 1.
The grain diameter of the corn straw is between 20 and 30 millimeters, and the water content is less than or equal to 12 percent (w/w). Soaking the corn straws for 2 hours by using a sulfuric acid solution with the mass concentration of 0.25%, wherein the dosage of the sulfuric acid solution is 0.40-0.45 kg/(kg of corn straws). Then, the corn stover was pretreated for 6 minutes at 195 ℃ by continuous steam explosion. And carrying out synchronous diastatic fermentation reaction on the obtained steam exploded material, wherein the mass concentration of a substrate is 10%, the dosage of cellulase is 22FPU/(g cellulose), the concentration of yeast is 5g/L, the reaction temperature is 35 ℃, and the synchronous diastatic fermentation time is 96 hours. The reaction product is continuously distilled to remove the cellulosic ethanol, then is centrifugally settled, the upper light phase component, namely the yeast protein is removed, and the residual saccharification fermentation residue is dried by airflow. And (3) quickly carbonizing the dried saccharification fermentation residues at 480 ℃ for 30 minutes in a nitrogen atmosphere, separating gas, and performing cyclone separation and cooling to obtain the biomass gas 1. The char was immersed in a 60% (w/w) KOH solution at room temperature for 3 hours at a weight ratio of KOH solution to char of 0.5: 1. And roasting the impregnated carbide at 600 ℃ for 30 minutes, then roasting at 800 ℃ for 1 hour, washing and drying to obtain the activated carbon 1.
Example 2
The operation is carried out by referring to the flow of the co-production of the biomass fuel gas and the activated carbon by the corn straws shown in the figure 1.
The grain diameter of the corn straw is between 20 and 30 millimeters, and the water content is less than or equal to 12 percent (w/w). Soaking the corn straws for 2 hours by using a sulfuric acid solution with the mass concentration of 0.25%, wherein the dosage of the sulfuric acid solution is 0.40-0.45 kg/(kg of corn straws). Then, the corn stover was pretreated for 6 minutes at 195 ℃ by continuous steam explosion. And carrying out synchronous diastatic fermentation reaction on the obtained steam exploded material, wherein the mass concentration of a substrate is 10%, the dosage of cellulase is 22FPU/(g cellulose), the concentration of yeast is 5g/L, the reaction temperature is 35 ℃, and the synchronous diastatic fermentation time is 96 hours. The reaction product is continuously distilled to remove the cellulosic ethanol, then is centrifugally settled to remove the upper light phase component, namely the yeast protein, and the residual saccharification fermentation residue is dried by airflow. And (3) quickly carbonizing the dried saccharification fermentation residues at 500 ℃ for 40 minutes in a nitrogen atmosphere, separating gas, and performing cyclone separation and cooling to obtain the biomass gas 2. The char was immersed in a 60% (w/w) KOH solution at room temperature for 3 hours at a KOH solution to char weight ratio of 0.5: 1. And roasting the impregnated carbide at 600 ℃ for 30 minutes, then roasting at 800 ℃ for 1 hour, washing and drying to obtain the activated carbon 2.
Example 3
The operation is carried out by referring to the flow of the co-production of the biomass fuel gas and the activated carbon by the corn straws shown in the figure 1.
The grain diameter of the corn straw is between 20 and 30 millimeters, and the water content is less than or equal to 12 percent (w/w). Soaking the corn straws for 2 hours by using a sulfuric acid solution with the mass concentration of 0.25%, wherein the dosage of the sulfuric acid solution is 0.40-0.45 kg/(kg of corn straws). Then, the corn stover was pretreated for 6 minutes at 195 ℃ by continuous steam explosion. And carrying out synchronous diastatic fermentation reaction on the obtained steam exploded material, wherein the mass concentration of a substrate is 10%, the dosage of cellulase is 22FPU/(g cellulose), the concentration of yeast is 5g/L, the reaction temperature is 35 ℃, and the synchronous diastatic fermentation time is 96 hours. The reaction product is continuously distilled to remove the cellulosic ethanol, then is centrifugally settled, the upper light phase component, namely the yeast protein is removed, and the residual saccharification fermentation residue is dried by airflow. And (3) quickly carbonizing the dried saccharification fermentation residues at 500 ℃ for 40 minutes in a nitrogen atmosphere, separating gas, and performing cyclone separation and cooling to obtain the biomass gas 3. The char was immersed in a 60% (w/w) KOH solution at room temperature for 3 hours at a weight ratio of KOH solution to char of 0.5: 1. And roasting the impregnated carbide at 600 ℃ for 30 minutes, then roasting at 700 ℃ for 1 hour, washing and drying to obtain the activated carbon 3.
Example 4
The operation is carried out by referring to the flow of the co-production of the biomass fuel gas and the activated carbon by the corn straws shown in the figure 1.
The grain diameter of the corn straw is between 20 and 30 millimeters, and the water content is less than or equal to 12 percent (w/w). Soaking the corn straws for 2 hours by using a sulfuric acid solution with the mass concentration of 0.25%, wherein the dosage of the sulfuric acid solution is 0.40-0.45 kg/(kg of corn straws). Then, the corn stover was pretreated for 6 minutes at 195 ℃ by continuous steam explosion. And carrying out synchronous diastatic fermentation reaction on the obtained steam exploded material, wherein the mass concentration of a substrate is 10%, the dosage of cellulase is 22FPU/(g cellulose), the concentration of yeast is 5g/L, the reaction temperature is 35 ℃, and the synchronous diastatic fermentation time is 96 hours. The reaction product is continuously distilled to remove the cellulosic ethanol, then is centrifugally settled, the upper light phase component, namely the yeast protein is removed, and the residual saccharification fermentation residue is dried by airflow. And (3) quickly carbonizing the dried saccharification fermentation residues at 500 ℃ for 40 minutes in a nitrogen atmosphere, separating gas, and performing cyclone separation and cooling to obtain the biomass gas 4. The char was immersed in a 60% (w/w) KOH solution at room temperature for 3 hours at a weight ratio of KOH solution to char of 0.5: 1. And roasting the impregnated carbide at 600 ℃ for 30 minutes, then roasting at 900 ℃ for 1 hour, washing and drying to obtain the activated carbon 4.
Comparative example 1
The particle size of the corn straw is between 20 and 30 millimeters, the water content is less than or equal to 12 percent (w/w), the crushed corn straw is quickly carbonized for 40 minutes in nitrogen atmosphere at 500 ℃, gas is separated and purified to obtain the biomass fuel gas A. The char was immersed in a 60% (w/w) KOH solution at room temperature for 3 hours at a weight ratio of KOH solution to char of 0.5: 1. And roasting the impregnated carbide at 600 ℃ for 30 minutes, then roasting at 800 ℃ for 1 hour, washing and drying to obtain the activated carbon A.
Comparative example 2
The grain diameter of the corn straw is between 20 and 30 millimeters, and the water content is less than or equal to 12 percent (w/w). Soaking the corn straws for 2 hours by using a sulfuric acid solution with the mass concentration of 0.25%, wherein the dosage of the sulfuric acid solution is 0.40-0.45 kg/(kg of corn straws). Then, the corn straws are subjected to continuous steam explosion pretreatment for 6 minutes at the temperature of 195 ℃ to obtain the steam explosion material. And (3) quickly carbonizing the explosion-steaming material in a nitrogen atmosphere at 500 ℃ for 40 minutes, separating gas and purifying to obtain the biomass gas B. The char was immersed in a 60% (w/w) KOH solution at room temperature for 3 hours at a weight ratio of KOH solution to char of 0.5: 1. And roasting the impregnated carbide at 600 ℃ for 30 minutes, then roasting at 800 ℃ for 1 hour, washing and drying to obtain the activated carbon B.
Test example
The fuel value, the specific surface area of the activated carbon, the biomass gas yield, the activated carbon yield and the cellulosic ethanol yield of the biomass gas of examples 1 to 4 and comparative examples 1 to 2 were measured, and the results are shown in Table 1.
The fuel value of the biomass fuel gas and the specific surface area of the active carbon are respectively kJ/m3And m2/g。
The biomass gas yield is as follows: collecting the prepared biomass gas, and dividing the biomass gas by the weight of the used corn straws to obtain the biomass gas yield m3/(kg corn stover).
The yield of the activated carbon is as follows: the weight of the prepared activated carbon was collected and weighed, and divided by the weight of the corn stover used to obtain the yield,%.
The yield of the cellulosic ethanol is as follows: the weight of the cellulosic ethanol was collected and weighed, divided by the weight of the corn stover used, to obtain the cellulosic ethanol yield,%.
TABLE 1
Figure BDA0001070399410000111
As can be seen from table 1, the activated carbon obtained by the method of the present invention has a higher specific surface area and a higher fuel value of biomass fuel gas than those of comparative examples 1 to 2. In addition, the method treats the steam explosion material by synchronous saccharification and fermentation, prepares the cellulosic ethanol and the yeast protein simultaneously, greatly reduces the production cost of the cellulosic ethanol and the yeast protein, and fully utilizes raw material resources.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (62)

1. A method for preparing biomass fuel gas comprises the following steps:
1) infiltrating crop straws with acid liquor;
2) carrying out steam explosion treatment on the crop straws obtained in the step 1), wherein the temperature of the steam explosion treatment is 180-210 ℃, and the time is 3-15 minutes to obtain a steam explosion material;
3) carrying out synchronous saccharification and fermentation on the steamed and exploded material, and removing ethanol and yeast protein in a fermentation product to obtain a lignin-rich raw material; wherein the dosage of the cellulase for synchronous diastatic fermentation is 16-28FPU/g cellulose, the yeast concentration is 2-9g/L total volume of the fermentation system, the substrate concentration is 5-25% (w/w), the temperature for synchronous diastatic fermentation is 28-50 ℃, and the time is 85-110 hours;
4) carbonizing the raw material rich in lignin at 400-600 ℃ in a nitrogen atmosphere for 10-90 minutes to obtain lignin carbide and separating gas.
2. The method of claim 1, further comprising the step of purifying the separated gas.
3. The method of claim 2, wherein the purifying comprises cyclonic separating the separated gas, cooling.
4. The method as claimed in claim 1, wherein the weight percentage of lignin in the raw material obtained in step 3) is not less than 50%.
5. The method as claimed in claim 1, wherein the weight percentage of lignin in the raw material obtained in step 3) is not less than 70%.
6. The method as claimed in claim 1, wherein the weight percentage of lignin in the raw material obtained in step 3) is not less than 80%.
7. The method as claimed in claim 1, wherein the weight percentage of lignin in the raw material obtained in step 3) is not less than 90%.
8. The method as claimed in claim 1, wherein the weight percentage of lignin in the raw material obtained in step 3) is not less than 95%.
9. The method as claimed in claim 1, wherein the raw material obtained in step 3) has a lignin content of 99% by weight or more.
10. The method of claim 1, wherein the weight percentage of lignin in the feedstock from step 3) is 100%.
11. The method as claimed in claim 1, wherein, in the step 4), the carbonization temperature is 420-570 ℃.
12. The method as claimed in claim 1, wherein, in the step 4), the carbonization temperature is 430-550 ℃.
13. The method as claimed in claim 1, wherein, in the step 4), the carbonization temperature is 480 ℃ to 500 ℃.
14. The method according to claim 1, wherein in step 4), the carbonization temperature is 420 ℃, 430 ℃, 445 ℃, 470 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 560 ℃ or 570 ℃.
15. The method as claimed in claim 1, wherein the carbonization time in the step 4) is 15 to 75 minutes.
16. The method as claimed in claim 1, wherein the carbonization time in the step 4) is 20 to 60 minutes.
17. The method as claimed in claim 1, wherein the carbonization time is 30 to 40 minutes in the step 4).
18. The method of claim 1, wherein in step 4), the carbonization time is 15 minutes, 18 minutes, 20 minutes, 24 minutes, 30 minutes, 36 minutes, 40 minutes, 47 minutes, 52 minutes, 60 minutes, or 75 minutes.
19. The method according to claim 1, characterized by any one or more of the following a to I:
A. in the step 3), the dosage of the cellulase for synchronous saccharification and fermentation is 20-25FPU/g cellulose;
B. in the step 3), the concentration of yeast for synchronous saccharification and fermentation is 3-7g/L of the total volume of the fermentation system;
C. in the step 3), the temperature of the synchronous saccharification and fermentation is 30-40 ℃, and the time is 90-100 hours;
D. in the step 3), the substrate concentration of the synchronous saccharification and fermentation is 10-20% (w/w);
E. the crop straw is corn straw;
F. in the step 2), the temperature of the steam explosion treatment is 190-200 ℃, and the time is 5-10 minutes;
G. in the step 1), the dosage of the acid liquor is 0.3-0.6kg/kg of crop straws;
H. in the step 3), the method for removing the ethanol is distillation;
I. in the step 3), the method for removing the yeast protein comprises the steps of settling and then removing the light phase component.
20. The process of claim 19, wherein in step 3), the cellulase amount for simultaneous saccharification and fermentation is 22FPU/g cellulose.
21. The method of claim 19, wherein in step 3) the yeast concentration for simultaneous saccharification and fermentation is 5g/L of the total volume of the fermentation system.
22. The method of claim 19, wherein in step C), the temperature of simultaneous saccharification and fermentation is 35 ℃ and the time is 96 hours.
23. The process of claim 19, wherein in item D, the substrate concentration of the simultaneous saccharification and fermentation in step 3) is 10% (w/w).
24. The method of claim 19, wherein in item E, the crop straw has a moisture content of less than or equal to 12% (w/w).
25. The method of claim 19, wherein in item E, the crop straw has a moisture content of 10% (w/w) or less.
26. The method of claim 19, wherein in item E, the crop straw has a moisture content of 8% (w/w) or less.
27. The method of claim 19, wherein in item E, the crop straw has a moisture content of less than or equal to 5% (w/w).
28. The method according to claim 19, wherein in item F, the temperature of the steam explosion treatment in step 2) is 195 ℃ for 6 minutes.
29. The method as claimed in claim 19, wherein in item G, the amount of acid solution used in step 1) is 0.4-0.45kg/kg crop straw.
30. The method as claimed in claim 19, wherein in item G, the acid solution has a concentration of 0.1-1% (w/w) in step 1).
31. The method as claimed in claim 19, wherein in item G, the acid solution has a concentration of 0.1-0.5% (w/w) in step 1).
32. The method as claimed in claim 19, wherein in item G, the acid solution has a concentration of 0.25% (w/w) in step 1).
33. The process of claim 19, wherein in item H, the ethanol removal process in step 3) is a continuous distillation.
34. The method according to claim 19, wherein in item I, in step 3), the method of sedimentation is centrifugal sedimentation.
35. A method of producing activated carbon comprising the step of activating lignin char produced by the method of any one of claims 1 to 34; wherein the activation comprises the steps of dipping the lignin carbide in alkali liquor, separating out solid, roasting the solid for 20-40 minutes at 500-650 ℃, and roasting for 40-80 minutes at 670-930 ℃.
36. The method of claim 35, characterized by any one or more of the following a to g:
a. roasting the solid at 570-630 ℃ for 25-35 minutes, and then roasting at 690-900 ℃ for 50-70 minutes;
b. the weight ratio of the alkali liquor to the lignin carbide is (0.2-1) to 1;
c. the alkali liquor is selected from one or more of potassium hydroxide solution, sodium hydroxide solution and calcium hydroxide solution;
d. the concentration of the alkali liquor is 45-70% (w/w);
e. the dipping temperature is room temperature;
f. the dipping time is 2-4 hours;
g. also comprises the steps of washing and drying the activated substance.
37. The process of claim 36, wherein in item a, the solid is calcined at 600 ℃ for 30 minutes and then at 700 ℃ to 900 ℃ for 1 hour.
38. The method of claim 36, wherein in item b, the weight ratio of the alkali liquor to the lignin char is (0.3-0.8): 1.
39. The method of claim 36, wherein in item b, the weight ratio of the lye to the lignin char is 0.5: 1.
40. The method of claim 36, wherein in item c, the lye is a potassium hydroxide solution.
41. The method of claim 36, wherein the concentration of the lye is 50% -65% (w/w) in item d.
42. The method of claim 36, wherein the concentration of the lye is 60% (w/w) in item d.
43. The method of claim 36, wherein the temperature of the impregnation is 10-35 ℃ in item e.
44. The method of claim 36, wherein in item f, the time of immersion is 3 hours.
45. Activated carbon made by the process of any one of claims 35 to 44; the specific surface area of the activated carbon is more than or equal to 700m2/g。
46. The activated carbon according to claim 45, having a specific surface area of 750m or more2/g。
47. The activated carbon according to claim 45, having a specific surface area of 900m or more2/g。
48. The activated carbon according to claim 45, having a specific surface area of 1100m or more2/g。
49. The activated carbon according to claim 45, having a specific surface area of 1300m or more2/g。
50. The activated carbon according to claim 45, having a specific surface area of 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2Per g or 1320m2/g。
51. A method of treating crop straw comprising the steps of the method of any one of claims 1 to 44.
52. A method for co-producing biomass fuel gas and activated carbon from crop straw, comprising the steps of any one of claims 35 to 44.
53. The method of claim 51 or 52, wherein the crop straw is corn stover.
54. The method of claim 51 or 52, wherein the biomass fuel gas has a fuel value of 11000kJ/m or more3。
55. The method of claim 51 or 52, wherein the biomass fuel gas has a fuel value of 12000kJ/m or more3。
56. The method of claim 51 or 52, wherein the biomass fuel gas has a fuel value of 11000kJ/m3、11800kJ/m3、12000kJ/m3Or 12200kJ/m3。
57. The method of claim 52, wherein the activated carbon has a specific surface area of 700m or more2/g。
58. The method of claim 52, wherein the activated carbon has a specific surface area of 750m or more2/g。
59. The method of claim 52, wherein the activated carbon has a specific surface area of 900m or more2/g。
60. The method of claim 52, wherein the activated carbon has a specific surface area of 1100m or more2/g。
61. The method of claim 52, wherein the activated carbon has a specific surface area of 1300m or more2/g。
62. The method of claim 52, wherein the activated carbon has a specific surface area of 900m2/g、930m2/g、1000m2/g、1160m2/g、1190m2Per g or 1320m2/g。
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