CN103667389A - Method for combinatively pre-treating cellulose biomass raw material by hydrogen peroxide and liquefied ammonia - Google Patents
Method for combinatively pre-treating cellulose biomass raw material by hydrogen peroxide and liquefied ammonia Download PDFInfo
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- CN103667389A CN103667389A CN201310645094.3A CN201310645094A CN103667389A CN 103667389 A CN103667389 A CN 103667389A CN 201310645094 A CN201310645094 A CN 201310645094A CN 103667389 A CN103667389 A CN 103667389A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a method for combinatively pre-treating a cellulose biomass raw material by hydrogen peroxide and liquefied ammonia. The invention is intended to provide the method for combinatively pre-treating the cellulose biomass raw material by hydrogen peroxide and liquefied ammonia, in order to raise enzymatic hydrolysis efficiency and the yield of monosaccharide and ethanol of the treated biomass. A technology scheme provided by the invention is characterized by: mixing and uniformly stirring the biomass raw material with 10-100 meshes of particle sizes and 30% by weight of aqueous hydrogen peroxide solution under normal temperature, wherein the dosage of the aqueous hydrogen peroxide solution is 0.2-2.0 times that of the biomass raw material; and then adding the obtained mixture into a pressure reaction container, injecting liquefied ammonia with the dosage being 0.2-5 times that of the biomass raw material, heating until 70-190 DEG C, maintaining the temperature for 2-30min, then releasing ammonia in a gas manner, and taking out the treated raw material after cooling to finish. The method provided by the invention is suitable for helping cellulase to digest glycan, to convert the glycan into monosaccharide, for cellulose ethanol production or as a forage additive.
Description
Technical field
The present invention relates to a kind of method of hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, for auxiliary fiber element enzymic digestion glycan, make it be converted into monose, for cellulosic ethanol production or as feed additive.
Background technology
Cellulose biomass refers to that cellulose, hemicellulose and xylogen are main raw material, and main source has timber, bamboo, agricultural crop straw, shell etc.Mierocrystalline cellulose in cellulose biomass raw material and hemicellulose obtain fermentable monose by enzymic hydrolysis, through fermentation, obtain ethanol again, be broadly divided into the steps such as pre-treatment, enzymolysis, fermentation, have that theoretical yield is high, a reaction temperature and and without advantages such as extra disposals of pollutants.The monose obtaining after the raw material enzymolysis such as stalk also can directly add in feed, can directly by animal, be absorbed.
The pre-treatment of biomass is that preparing essential in cellulose ethanol is also the step of most critical, and how it will directly have influence on enzymolysis and the fermenting process in downstream to the treatment effect of biomass material.Pretreated object is to remove xylogen to cellulosic sealing, removes part xylogen, disintegrates the crystalline structure of Mierocrystalline cellulose densification, improves the accessibility of enzyme, makes glycan be converted into this process of monose and carries out smoothly.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of method that hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material are provided for the problem of above-mentioned existence, take hydrogen peroxide and ammonia as medium, in pressurized vessel, heat and control aqueous hydrogen peroxide solution ratio, temperature, retention time, ammonia consumption, to significantly improve enzymolysis efficiency and monose and the ethanol production of processing artifact matter.
The technical solution adopted in the present invention is: the method for hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the aqueous hydrogen peroxide solution that is first 30% by particle diameter 10-100 object biomass material with mass percent mixes and mixes thoroughly at normal temperatures, wherein aqueous hydrogen peroxide solution consumption be biomass material consumption 0.2-2.0 doubly; Again gained mixture is put into pressure reacting container, inject biomass material consumption 0.2-5 liquefied ammonia doubly, be heated to 70-190 ℃, and keep 2-30 minute, ammonia is discharged, take out after cooling the raw material after processing.
The method of hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the aqueous hydrogen peroxide solution that is first 30% by particle diameter 10-100 object biomass material with mass percent mixes and mixes thoroughly at normal temperatures, wherein aqueous hydrogen peroxide solution consumption be biomass material consumption 0.5-1.5 doubly; Again gained mixture is put into pressure reacting container, inject biomass material consumption 1-3 liquefied ammonia doubly, be heated to 90-150 ℃, and keep 5-15 minute, ammonia is discharged, take out after cooling the raw material after processing.
The method of hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the aqueous hydrogen peroxide solution that is first 30% by particle diameter 10-100 object biomass material with mass percent mixes and mixes thoroughly at normal temperatures, wherein aqueous hydrogen peroxide solution consumption be biomass material consumption 0.8-1.2 doubly; Again gained mixture is put into pressure reacting container, inject biomass material consumption 1.5-2.5 liquefied ammonia doubly, be heated to 110-130 ℃, and keep 8-12 minute, ammonia is discharged, take out after cooling the raw material after processing.
Described biomass material is the mixture of Mierocrystalline cellulose and xylogen, and its raw material comprises a kind of or any several mixture in timber, bamboo, agricultural crop straw, shell.
The water ratio of described biomass material is not higher than 25%.
Described pressure reacting container is that pressure is adjustable or controlled, and adopts the pressurized vessel of external electric method or the heating of internal electrical heating method, and its withstand voltage is 20MPa, generally can select pressure reaction still.
The invention has the beneficial effects as follows: 1, the present invention selects in the treating processes of hydrogen peroxide-liquefied ammonia combined pretreatment biomass material, destroyed cellulosic crystallization combination, changed lignin structure, removed xylogen to cellulosic sealing, removed part xylogen, thereby improved the accessibility of enzyme, made the monose enzymolysis yield of pre-treatment artifact raw material processed can improve 1 ~ 7 times, improved the output of monose and ethanol.2, most of Mierocrystalline cellulose and hemicellulose non-degradable, do not need neutralization or clean, do not produce fermentation inhibitor, residual ammonium salt can be used as the nutrition of microorganism, has environment friendly.3, with respect to other reagent, to have cost lower and to features such as human body have no side effect for hydrogen peroxide used in the present invention and ammonia, and the ammonia in gaseous state after decompression can, by pressurization lowered temperature reclamation, continue recycle.4, reaction conditions of the present invention is gentle, lower to equipment and materials performance requriements, and reagent does not have very strong corrosive nature to reaction unit.
Embodiment
Embodiment 1: utilize hydrogen peroxide-liquefied ammonia to combine take the pretreatment process that mao bamboon is biomass material.
Annual whole strain mao bamboon is sawed-off, cutting, pulverizing 40 mesh sieves divides, after dry, record water ratio 8% left and right, under normal temperature, adding mass percent is that 30% aqueous hydrogen peroxide solution (hydrogen peroxide) mixes with its (mao bamboon powder), wherein the ratio (mass ratio) of aqueous hydrogen peroxide solution consumption and biomass material (mao bamboon powder) consumption is 0.7:1, after mixing thoroughly, put into pressure reaction still, after sealing, inject liquefied ammonia, ammonia consumption is 2 times (mass ratioes) of biomass material (mao bamboon powder), control reactor and be heated to 150 ℃ and keep 10 minutes, then opening valve makes excess of ammonia with gas form, discharge that (ammonia is mainly to make filament expansion, change the effects such as lignin structure, a small amount of meeting exists or reacts with the form of hydration ammonia, excess of ammonia makes to keep certain pressure in reaction vessel, can improve the perviousness of ammonia in biomass material, so ammonia is always excessive), the raw material taking out after processing is dried.The complete bamboo of pre-treatment carries out enzymic hydrolysis in 72 hours, and biomass material per ton (mao bamboon powder) can obtain approximately 480 kilograms of glucose and xyloses, compares with the bamboo not dealing with, and under same enzymatic hydrolysis condition, its transformation efficiency improves 6 times of left and right.
After liquefied ammonia heating in pressure reaction still self-assembling formation pressure, the factors such as this pressure and liquefied ammonia injection rate, Heating temperature are relevant.
Embodiment 2: utilize hydrogen peroxide-liquefied ammonia to combine the pretreatment process with maize straw.
Maize straw is cut, be crushed to 50-100 order particle, after dry, record water ratio 10% left and right, under normal temperature, adding mass percent is that 30% aqueous hydrogen peroxide solution (hydrogen peroxide) mixes with its (mao bamboon powder), wherein the ratio (mass ratio) of aqueous hydrogen peroxide solution consumption and biomass material (mao bamboon powder) consumption is 0.5:1, after mixing thoroughly, put into pressure reaction still, after sealing, inject liquefied ammonia, ammonia consumption is 1 times (mass ratio) of biomass material (mao bamboon powder), control reactor and be heated to 130 ℃ and keep 10 minutes, then open valve and discharge gas, the raw material taking out after processing is dried.The complete stalk of pre-treatment carries out enzymic hydrolysis in 72 hours, biomass material per ton (mao bamboon powder) can obtain approximately 559 kilograms of glucose and xyloses, compare with the stalk not dealing with, under same enzymatic hydrolysis condition, its transformation efficiency improves 2 times of left and right, and wherein the transformation efficiency of glucose and xylose is respectively 88% and 91% of contained glycan theoretical value in raw material.
Embodiment 3: utilize hydrogen peroxide-liquefied ammonia to combine the pretreatment process to straw.
Straw is cut, is crushed to 50-100 order particle, after dry, record water ratio 10% left and right, under normal temperature, adding mass percent is that 30% aqueous hydrogen peroxide solution (hydrogen peroxide) mixes with straw, wherein aqueous hydrogen peroxide solution consumption is 1:1 with the ratio (mass ratio) of biomass material consumption, after mixing thoroughly, put into pressure reaction still, after sealing, inject liquefied ammonia, ammonia consumption is 3 times (mass ratioes) of biomass material, control reactor and be heated to 90 ℃ and keep 10 minutes, then open valve and discharge gas, the raw material taking out after processing is dried.The complete stalk of pre-treatment carries out enzymic hydrolysis in 144 hours, and biomass material per ton can obtain approximately 523 kilograms of glucose and xyloses, compares with the stalk not dealing with, and under same enzymatic hydrolysis condition, its transformation efficiency improves 2.4 times of left and right.
Embodiment 4: utilize hydrogen peroxide-liquefied ammonia to combine the pretreatment process to mixtures such as straw, broomcorn straw, Alfalfas.
Three kinds of agricultural crop straws are cut, be crushed to 50-100 order particle, 1:1:1 mixes in mass ratio again, mixed water ratio is through measuring not higher than 15%, under normal temperature, adding mass percent is that 30% aqueous hydrogen peroxide solution (hydrogen peroxide) mixes with stalk, wherein aqueous hydrogen peroxide solution consumption is 1:1 with the ratio (mass ratio) of biomass material consumption, after mixing thoroughly, put into pressure reaction still, after sealing, inject liquefied ammonia, ammonia consumption is 1 times (mass ratio) of biomass material, control reactor and be heated to 170 ℃ and keep 5 minutes, then open valve and discharge gas, the raw material taking out after processing is dried.The complete stalk of pre-treatment carries out enzymic hydrolysis in 144 hours, and biomass material per ton can obtain approximately 364 kilograms of glucose and xyloses, compares with the stalk not dealing with, and under same enzymatic hydrolysis condition, its transformation efficiency improves 1.6 times of left and right.
In the various embodiments described above, if raw material is originally as the materials such as sawdust below 100 orders, can saves and shatter step.
Claims (6)
1. the method for a hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the aqueous hydrogen peroxide solution that is first 30% by particle diameter 10-100 object biomass material with mass percent mixes and mixes thoroughly at normal temperatures, wherein aqueous hydrogen peroxide solution consumption be biomass material consumption 0.2-2.0 doubly; Again gained mixture is put into pressure reacting container, inject biomass material consumption 0.2-5 liquefied ammonia doubly, be heated to 70-190 ℃, and keep 2-30 minute, then make ammonia discharge with gas form, take out after cooling the raw material after processing.
2. the method for a hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the aqueous hydrogen peroxide solution that is first 30% by particle diameter 10-100 object biomass material with mass percent mixes and mixes thoroughly at normal temperatures, wherein aqueous hydrogen peroxide solution consumption be biomass material consumption 0.5-1.5 doubly; Again gained mixture is put into pressure reacting container, inject biomass material consumption 1-3 liquefied ammonia doubly, be heated to 90-150 ℃, and keep 5-15 minute, ammonia is discharged, take out after cooling the raw material after processing.
3. the method for a hydrogen peroxide and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the aqueous hydrogen peroxide solution that is first 30% by particle diameter 10-100 object biomass material with mass percent mixes and mixes thoroughly at normal temperatures, wherein aqueous hydrogen peroxide solution consumption be biomass material consumption 0.8-1.2 doubly; Again gained mixture is put into pressure reacting container, inject biomass material consumption 1.5-2.5 liquefied ammonia doubly, be heated to 110-130 ℃, and keep 8-12 minute, ammonia is discharged, take out after cooling the raw material after processing.
4. according to the method for the hydrogen peroxide described in claim 1 or 2 or 3 and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: described biomass material is the mixture of Mierocrystalline cellulose and xylogen, its raw material comprises a kind of or any several mixture in timber, bamboo, agricultural crop straw, shell.
5. according to the method for the hydrogen peroxide described in claim 1 or 2 or 3 and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: the water ratio of described biomass material is not higher than 25%.
6. according to the method for the hydrogen peroxide described in claim 1 or 2 or 3 and liquefied ammonia combined pretreatment cellulose biomass raw material, it is characterized in that: described pressure reacting container is that pressure is adjustable or controlled, and the pressurized vessel that adopts external electric method or the heating of internal electrical heating method, its withstand voltage is 20MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838608A (en) * | 2015-12-02 | 2016-08-10 | 华中农业大学 | Method for segment pretreatment on straws through ammonia water and hydrogen peroxide |
| CN110241156A (en) * | 2019-07-03 | 2019-09-17 | 上海中溶科技有限公司 | A kind of preprocess method extracting cellulose and hemicellulose from stalk |
-
2013
- 2013-12-05 CN CN201310645094.3A patent/CN103667389A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| KIM J.S ET AL: "Pretreatment of wastepaper and pulp mill sludge by aqueous ammonia and hydrogen peroxide", 《APPL BIOCHEM BIOTECHNOL》 * |
| 刘建军等: "斑茅酶解转化可发酵单糖的液氨预处理以参数优化", 《生物工程学报》 * |
| 苏茂尧等: "纤维素经液氨处理对其结构和晶型的影响", 《纤维素科学与技术》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105838608A (en) * | 2015-12-02 | 2016-08-10 | 华中农业大学 | Method for segment pretreatment on straws through ammonia water and hydrogen peroxide |
| CN110241156A (en) * | 2019-07-03 | 2019-09-17 | 上海中溶科技有限公司 | A kind of preprocess method extracting cellulose and hemicellulose from stalk |
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Application publication date: 20140326 |