CN101864455A - A kind of oxidative degradation pretreatment enteromorpha as raw material that utilizes carries out the method that alcohol fuel transforms - Google Patents
A kind of oxidative degradation pretreatment enteromorpha as raw material that utilizes carries out the method that alcohol fuel transforms Download PDFInfo
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- CN101864455A CN101864455A CN201010163126A CN201010163126A CN101864455A CN 101864455 A CN101864455 A CN 101864455A CN 201010163126 A CN201010163126 A CN 201010163126A CN 201010163126 A CN201010163126 A CN 201010163126A CN 101864455 A CN101864455 A CN 101864455A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The present invention relates to a kind of is the method for the alcohol fuel conversion of raw material with the oxidative degradation pretreatment enteromorpha as raw material.Oxidative degradation pretreatment process provided by the invention is simple to operate, cost is lower, the while clean reagent treatment, promptly guarantee Enteromorpha xylogen and Mierocrystalline cellulose are effectively peeled off, improve the amorphous conversion of Mierocrystalline cellulose, degraded product is to later stage ethanol conversion unrestraint effect, and this pre-treatment oxidising agent can not have negative impact to follow-up saccharification and fermentation operation by simple operations, removal fast simultaneously.By the abundant enzymolysis of this method be converted into ethanol fermentation reliable, stable glycolysis sugar be provided.This method at first with the Enteromorpha raw material after lixiviate oven dry is pulverized, add clean oxidation reagent and under 50 ℃ of conditions, react; Reaction finishes to add commercially available cellulase and cellobiase prepares glycolysis sugar, and inserting its volume percent after replenishing the necessity inorganic salt in reaction solution is the yeast liquid of 5-10%, carries out anaerobically fermenting and prepares ethanol.By above-mentioned technology, final inversion rate of glucose is 15%, and yeast conversion of glucose ethanol conversion is 40%.
Description
Technical field
The present invention relates to a kind of oxidative degradation pretreatment enteromorpha as raw material that utilizes and carry out the method that alcohol fuel transforms.
Background technology
Ethanol is as the renewable energy source of a kind of economy, cleaning.Especially with corn, sugarcane be raw material production alcohol fuel aspect the production cost substantially and gasoline compare favourably.But this a large amount of with the necessary food crop of the mankind as the alcoholic acid raw materials for production, had influence on the remarkable fluctuation of world food price at present.Caused the extensive concern in the world at present at the act as a fuel novel material of alcohol production of a large amount of those the non-food source property Biological resources that exist of world wide, also met China carries out alcohol production with non-grain raw material strategic planning simultaneously as Mierocrystalline cellulose, hemicellulose one class.Marine alga can be used as the novel alternative materials of bioenergy fully as a kind of a large amount of Biological resources of ocean.
Green damp algae is that a class comprises the macro of outburst easily such as Enteromorpha, sea lettuce.China's immediate offshore area breaks out the green tide of extensive sudden Enteromorpha continuously in recent years, growth and choice seafood aquiculture to marine fishery resources have serious consequences, and human marine activity, seawater utilization, strand view, the marine eco-environment and people's orthobiosis are caused to have a strong impact on simultaneously.At present both at home and abroad for the high-biomass aggregation green tide outburst all do not have emergency disposal way preferably, generally all be by simple process such as burying or make compost, efficient is low, cost is high, causes the wasting of resources and serious environmental to pollute.Outburst in continuous 3 years Enteromorpha green tide in China Huanghai Sea marine site brings for marine ecology and environment and seriously influences.
By the Enteromorpha cellulose raw producing and ethanol technology that the present invention relates to, both cleared up green alga, protect environment again, and increased power supply, widened the raw material range of alcohol fuel, compare existing traditional ethanol conversion method efficient and significantly improve.Simultaneously green damp algae is carried out recycling, not only turn waste into wealth, turn bane into boon, can reduce government simultaneously and drop into protection coastal waters ecology.
Summary of the invention
The present invention is to be that the alcohol fuel method for transformation of raw material is a purpose with the Enteromorpha to provide a kind of, remedies and improves existing be used for the producing raw material sources of alcohol fuel and the deficiency in the operative technique.
A kind of with green damp algae---Enteromorpha is the alcohol fuel method for transformation of raw material, being characterized in selecting for use Enteromorpha is raw material, after the hot water lixiviate, carry out raw materials pretreatment with hydrogen peroxide, by composite cellulase system (cellulase and cellobiase) enzymolysis, the enzymolysis supernatant liquor behind the filtering insoluble composition, supply the necessary inorganic salt of fermentation after, carry out ethanol fermentation under the inoculation yeast bacterium, anaerobic condition.
Preprocessing process of the present invention has improved the conversion of Enteromorpha crystal form Mierocrystalline cellulose to noncrystalline attitude, remove xylogen to cellulosic constraint by the pre-treatment of mild oxidation agent simultaneously, promote contacting between Mierocrystalline cellulose and composite enzyme system, thereby improved cellulosic enzymolysis efficiency; Mierocrystalline cellulose has been removed the feedback inhibition of cellobiose to cellulase effectively through the complex enzyme hydrolysis effect of cellulase and cellobiase, has improved the content of yeast glycolysis sugar, has further improved the yield of ethanol fermentation.
Embodiment
Enteromorpha described in the present invention is that the green damp algae Enteromorpha of the frequent outburst in marine site, Qingdao in recent years is a raw material; Describedly with the hydrogen peroxide under the different condition raw material is carried out pre-treatment and be: with Enteromorpha hot water extraction solubility frond carbohydrate gum after drying and after being crushed to the 20-80 order, adding concentration expressed in percentage by weight is the hydrogen peroxide of 0.1-2%, and reaction is 12 hours under 50 ℃ of conditions; Reaction conditions is according to the concentration of hydrogen peroxide difference, and pH is slightly different.When wherein concentration of hydrogen peroxide was mass percent 0.2%, pH did not need extra adjustment; When concentration of hydrogen peroxide was mass percent 0.5%, pH was adjusted into 9.5.Add commercially available cellulase and cellobiase in the reaction solution after raw materials pretreatment, add-on is that every gram Enteromorpha raw material adds 0.3-0.5ml cellulase, 0.08-0.15ml cellobiase, enzyme digestion reaction pH is 4.5-5.0, hydrolysis temperature 40-50 ℃, and enzymolysis time 24-72 hour; Described inorganic salt are ammonium salt or nitrate; Described ethanol fermentation is: inserting its volume percent in the reaction solution that above-mentioned enzymolysis obtains is the S. cervisiae liquid of 5-20%, carries out anaerobically fermenting, and leavening temperature is 28-40 ℃, and pH is 4-6, and fermentation time is 24-48 hour.
Embodiment 1: slightly acidic condition is used hydrogen peroxide pre-treatment, compound cellulose enzymolysis down
(1) with the raw material Enteromorpha, earlier through hot water lixiviate 1-2 hour, behind the extraction solubility frond polysaccharide, take out solid substance---Enteromorpha, after secondary water washing, it is standby that dry for standby is crushed to the 20-80 order.
(2) zymin and bacterial classification: cellulase is available from the outstanding promise biological enzyme in Shandong company limited, and cellobiase is available from sigma company, and yeast is available from Angel Yeast.
(3) the oxidative degradation pre-treatment of Enteromorpha: the adding concentration expressed in percentage by weight is 0.2% hydrogen peroxide, and solid-liquid ratio is that 5%, 50 ℃ of water bath processing was handled after 12 hours, takes out and is cooled to room temperature, and interpolation Manganse Dioxide leaves standstill and eliminated the residue hydrogen peroxide in 24 hours.By scanning electron microscopic observation, the Enteromorpha quality is loose after the pre-treatment, and pre-treatment can effectively destroy combining of Enteromorpha Mierocrystalline cellulose and other compositions, promotes the amorphous conversion of Mierocrystalline cellulose, raising cellulase hydrolysis yield;
(4) cellulose complex enzyme is separated: add commercially available cellulase and cellobiase in the reaction solution of pretreated raw material, add-on is 45FPU/g (raw material) cellulase, 55CBU/g (raw material) cellobiase, moisturizing to feed liquid weight percent is 2%, regulating the pH value is 4.5, and stirring reaction is 48 hours under 50 ℃ of conditions;
(5) ethanol fermentation: add ammonium sulfate in the reaction solution that enzymolysis obtains, making its concentration in reaction solution is 10-15g/l, makes the saccharomycetes to make fermentation substratum, standby; Its volume percent of access is 8% yeast liquid in fermention medium, 30 ℃ of conditions fermentations, fermentation time 48 hours.
By above-mentioned technology, with green damp algae---Enteromorpha is a raw material, and final inversion rate of glucose is 15%, and yeast conversion of glucose ethanol conversion is 40%, formerly expects that ethanol conversion is 0.06kg/kg.
Embodiment 2: alkaline condition is used hydrogen peroxide pre-treatment, enzymatic hydrolysis down
(1) with the raw material Enteromorpha, earlier through hot water lixiviate 1-2 hour, behind the extraction solubility frond polysaccharide, take out solid substance---Enteromorpha, after secondary water washing, it is standby that dry for standby is crushed to the 20-80 order.
(2) zymin and bacterial classification: cellulase is available from the outstanding promise biological enzyme in Shandong company limited, and cellobiase is available from sigma company, and yeast is available from Angel Yeast.
(the oxidative degradation pre-treatment of (3) Enteromorpha: the adding concentration expressed in percentage by weight is 0.5% hydrogen peroxide, solid-liquid ratio is 5%, and pH adjusts to 9.5,50 ℃ of water bath processing processing after 6 hours by NaOH, taking-up is cooled to room temperature, and interpolation Manganse Dioxide leaves standstill and eliminated the residue hydrogen peroxide in 24 hours.
(4) cellulose complex enzyme is separated: add commercially available cellulase and cellobiase in the reaction solution of pretreated raw material, add-on is 45FPU/g (raw material) cellulase, 55CBU/g (raw material) cellobiase, moisturizing to feed liquid weight percent is 2%, regulating the pH value is 4.5, and stirring reaction is 48 hours under 50 ℃ of conditions;
(5) ethanol fermentation: add ammonium sulfate in the reaction solution that enzymolysis obtains, making its concentration in reaction solution is 10-15g/l, makes the saccharomycetes to make fermentation substratum, standby; Its volume percent of access is 8% yeast liquid in fermention medium, 30 ℃ of conditions fermentations, fermentation time 48 hours.
By above-mentioned technology, with green damp algae---Enteromorpha is a raw material, and final inversion rate of glucose is 15%, and yeast conversion of glucose ethanol conversion is 40%, formerly expects that ethanol conversion is 0.06kg/kg.
Compare terrestrial plant, content of lignin in the Enteromorpha is lower, therefore utilizes the Enteromorpha Mierocrystalline cellulose as the degraded raw material, can reduce the kind and the intensity of pretreating agent in its production process, avoid removing xylogen under the strong condition, cause the degraded product that produces restraining effect follow-up fermentation.In addition, by regulating mild oxidation reagent---the concentration of hydrogen peroxide, not only removed.The present invention sets up the technology at Enteromorpha cellulosic structure characteristics, by the oxygenant pre-treatment under the mild conditions to improve cellulosic saccharification of Enteromorpha and ethanol conversion efficient to greatest extent, can improve sudden green damp algae---the processing efficiency of Enteromorpha, the developing biomass energy transforms the new way of producing alcohol fuel.
Claims (5)
1. one kind is the alcohol fuel method for transformation of raw material with the Enteromorpha, it is characterized in that selecting Enteromorpha is that raw material is through hot water extraction solubility frond carbohydrate gum after drying and after being crushed to the 20-80 order, lower concentration mild conditions hydrogen peroxide carries out pre-treatment, treatment solution is after Manganse Dioxide is removed unnecessary hydrogen peroxide, adding cellulase and cellobiase carry out cellulose complex enzyme to be separated, and the enzymolysis solution supernatant liquor behind the filtering insoluble composition replenishes inorganic salt, carry out ethanol fermentation under the inoculation yeast bacterium, anaerobic condition.
2. according to claim 1 is the alcohol fuel method for transformation of raw material with the Enteromorpha, it is characterized in that all kinds of edge pipe Enteromorphas in the coastal marine site of described Enteromorpha China, flat Enteromorpha, bar Enteromorpha, wherein is rich in the cellulose family component that can carry out ethanol conversion.
3. according to claim 1 is the alcohol fuel method for transformation of raw material with the Enteromorpha, it is characterized in that described elder generation is through the Enteromorpha of hot water (60-100 ℃) after lixiviate 1-6 hour, be added in the aqueous hydrogen peroxide solution that concentration expressed in percentage by volume is 0.05-2%, reaction is 3-18 hour under 40-70 ℃ of condition.Treatment solution is used for composite cellulase system enzymolysis after Manganse Dioxide is removed unnecessary hydrogen peroxide.
4. according to claim 1 is the preparation method of the alcohol fuel of raw material with the Enteromorpha, it is characterized in that described cellulose complex enzyme is separated is to add in the reaction solution after raw materials pretreatment commercially available cellulase and cellobiase, add-on is that every gram Enteromorpha thing adds the 20-200FPU cellulase, the 10-100CBU/g cellobiase, pH 4.0-6.0, hydrolysis temperature 40-55 ℃, enzymolysis time 24-72 hour.
5. according to claim 1 is the preparation method of the alcohol fuel of raw material with the Enteromorpha, it is characterized in that described ethanol fermentation is for to add the cereuisiae fermentum that its volume percent is 5-10% to the enzymolysis supernatant liquor, carry out anaerobically fermenting, leavening temperature is 26-42 ℃, fermentation time 24-72 hour.
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Cited By (5)
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| CN102733219A (en) * | 2012-02-23 | 2012-10-17 | 重庆恒远晋通科技有限公司 | Method for extracting cellulose from tobacco waste based on reductant-oxidant |
| CN102898536A (en) * | 2012-10-19 | 2013-01-30 | 中国科学院海洋研究所 | Method for degrading enteromorpha polysaccharide |
| CN103397054A (en) * | 2013-07-22 | 2013-11-20 | 韩玥君 | Method for producing ethanol by enteromorpha fermentation |
| CN103468751A (en) * | 2013-09-29 | 2013-12-25 | 上海海洋大学 | Method for preparing bioethanol through green tide algae enteromorpha in enzymolysis mode |
| CN103695333A (en) * | 2013-11-21 | 2014-04-02 | 上海海洋大学 | Stenotrophomonas FQ1 strain and its screening method and use |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102733219A (en) * | 2012-02-23 | 2012-10-17 | 重庆恒远晋通科技有限公司 | Method for extracting cellulose from tobacco waste based on reductant-oxidant |
| CN102733219B (en) * | 2012-02-23 | 2015-04-01 | 重庆恒远晋通科技有限公司 | Method for extracting cellulose from tobacco waste based on reductant-oxidant |
| CN102898536A (en) * | 2012-10-19 | 2013-01-30 | 中国科学院海洋研究所 | Method for degrading enteromorpha polysaccharide |
| CN103397054A (en) * | 2013-07-22 | 2013-11-20 | 韩玥君 | Method for producing ethanol by enteromorpha fermentation |
| CN103468751A (en) * | 2013-09-29 | 2013-12-25 | 上海海洋大学 | Method for preparing bioethanol through green tide algae enteromorpha in enzymolysis mode |
| CN103468751B (en) * | 2013-09-29 | 2015-06-10 | 上海海洋大学 | Method for preparing bioethanol through green tide algae enteromorpha in enzymolysis mode |
| CN103695333A (en) * | 2013-11-21 | 2014-04-02 | 上海海洋大学 | Stenotrophomonas FQ1 strain and its screening method and use |
| CN103695333B (en) * | 2013-11-21 | 2015-08-26 | 上海海洋大学 | A kind of Stenotrophomonas FQ1 bacterial strain and application |
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Application publication date: 20101020 |