CN101565725B - Maize straw pretreatment method - Google Patents
Maize straw pretreatment method Download PDFInfo
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- CN101565725B CN101565725B CN2009100691047A CN200910069104A CN101565725B CN 101565725 B CN101565725 B CN 101565725B CN 2009100691047 A CN2009100691047 A CN 2009100691047A CN 200910069104 A CN200910069104 A CN 200910069104A CN 101565725 B CN101565725 B CN 101565725B
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Abstract
The invention relates to a maize straw pretreatment method that is a new method for using supercritical or subcritical fluid technology to pretreat the maize straw. The new method improves the enzymolysis efficiency of cellulose in the maize straw, removes lignin that has inhibiting effect on the further fermentation process while improving the sugar yield of the straw, and provides an effective way for further cleanly and highly efficiently producing products such as fuel ethanol and the like. The method is characterized in that the pretreatment temperature is 50-250 DEG C; the operation pressure is 10-20MPa; the reaction time is 0.1-5h; and the solvent is the mixed solvent of CO2, water and one of or more of methanol, ethanol, butanol, pentanol and the like. The sugar yield of the cellulose in the maize straw is 40-95 percent.
Description
Technical field
The present invention relates to a kind of maize straw pretreatment method, the method is used overcritical or the sub-critical flow body technique carries out pretreated novel method to maize straw, improves cellulosic enzymolysis efficiency in maize straw.
Background technology
Maize straw is a kind of a large amount of agricultural waste, and main component is Mierocrystalline cellulose, hemicellulose, xylogen and some soluble substances.Wherein, Mierocrystalline cellulose is the main source of fermentable sugars, content accounts for 35%～45% (oven dry weight of cellulose raw material), and fermentable sugars can be further converted to liquid fuel or the industrial chemicals such as ethanol, acetone, butanols, acetic acid, butyleneglycol through microbial fermentation; Also can be used as the fermentation raw material of microbiotic, organic acid, single cell protein (SCP), zymin.When adopting the cellulase hydrolysis maize straw to produce glucose, cellulase must just can make reaction carry out on cellulosic substrate by Contact-sorption.And the multiple component structure of the condition of surface of cellulosic crystallizing field, Woody Biomass, Woody Biomass, xylogen are caused Woody Biomass to be difficult to hydrolysis to cellulosic provide protection and Mierocrystalline cellulose by the factor of the structure such as hemicellulose covering and chemical composition.Therefore, must carry out pre-treatment to the maize straw raw material, Mierocrystalline cellulose, hemicellulose and xylogen are separated, break cellulosic crystalline texture, improve Mierocrystalline cellulose to the accessibility of enzyme, make cellulase penetrate into Mierocrystalline cellulose, thereby effectively improve enzymolysis efficiency.
Existing maize straw pretreatment technology comprises physical method, chemical process, physico-chemical process, several large classes such as biological method, tens groups.The main processing intent of each treatment process all is to increase the several respects such as raw material endoporus area, reduction cellulose crystallity, removal xylogen, removal hemicellulose.Following table has been summarized the relative merits of each treatment process.
Each pretreatment process of table 1-1 relatively
As seen from the above table, above each separation method respectively has relative merits, but all introduces the unfriendly reagent of several environment to I haven't seen you for ages, makes preprocessing process be mixed with impurity or causes environmental pollution.
Summary of the invention
The invention provides a kind of novel maize straw pretreatment method.The present invention adopts CO take maize straw as raw material
2, the alcohols such as water and methyl alcohol, ethanol, butanols, amylalcohol is as single or hybrid reaction extraction solvent, under overcritical or undercritical conditions, maize straw carried out pre-treatment.
Maize straw mainly is comprised of plant cell wall, and the cell walls essentially consist is Mierocrystalline cellulose, hemicellulose, xylogen, and some soluble componentss.At supercritical CO
2Under condition, water solvent enters in fibrous material, and the space of infiltrated fiber inside.Due to water and CO
2The combined action acid degradation and the thermal destruction that produce fibrous material, the lower-molecular substance stripping, the fiber polymerization degree descends.Simultaneously, high temperature, high pressure, moisture condition can be aggravated again the destruction to Mierocrystalline cellulose inside hydrogen bond, and the free hydroxyl that makes new advances has increased the binding site of cellulase.Can dissolve the low molecule solute that is decomposed into fragment and take away the solid materials system the adding of alcohols entrainment agent such as methyl alcohol, ethanol, butanols, amylalcohol, reaches to improve fiber sugar yield in maize straw, removes simultaneously the purpose of the impurity such as hemicellulose, xylogen.
Technology of the present invention is as follows:
Maize straw pretreatment method of the present invention is to adopt CO
2Or CO
2With water or CO
2Mix as the reaction, extraction solvent with one or more in water, methyl alcohol, ethanol, butanols, amylalcohol, under overcritical or undercritical conditions, maize straw is carried out pre-treatment.
Raw material mass mixture ratio is as follows:
Raw material: CO
2Solvent: other solvents=1: 0.5～100: 0～50; Other solvents are one or more mixing in water, methyl alcohol, ethanol, butanols or amylalcohol.
The pretreatment operation mode adopts intermittently or is continuous; Periodical operation is that reaction mass and solvent once are packed in reactor, namely takes out after reaction is completed; The continous way operating characteristics is with in the disposable reactor of packing into of stalk, and to end, Continuous Flow adds to reactor to solvent from the operation beginning, and the reaction, extraction product also flows out from reactor continuously with solvent.
Pretreatment process processing condition of the present invention are: temperature is 50～250 ℃; Working pressure is 10～20MPa; Reaction times is 0.1～5 hour.
When treatment capacity hour, can adopt andnon-continuous operation manner, when treatment capacity is larger, can adopt the operate continuously mode.
Periodical operation of the present invention can be adopted technological process shown in Figure 1, uses CO
2, water and alcoholic solution as follows as the step of supercritical solvent pre-treatment maize straw:
(1) take stalk, water and alcoholic solution after a certain amount of pulverizing and sieving, add in reactor 9, open reactor;
(2) check that thermopair 14 is connected with agitator and whether correctly connect, whether normally rotate, then open CO
2Fresh feed pump 5 is squeezed into quantitative CO in reactor
2
(3) air inlet complete after, with controller general supply, display screen power supply, magnetic stirring apparatus electric power starting, adjust agitator speed to certain rotating speed successively, set temperature of reaction according to temperature regulator 14, then begin reaction, by tensimeter 17 observing response pressure at any time;
(4) after reaction is completed, close heating unit.Reactor is taken out in heating tank, naturally be cooled to below 30 ℃, open CO
2Air outlet valve cuts out water of condensation, agitator after the still internal pressure is down to normal pressure, open kettle cover, takes out reaction product, analyzes.
Operate continuously of the present invention can be adopted technological process shown in Figure 2, uses CO
2, water and alcoholic solution as follows as the step of overcritical or subcritical solvent pre-treatment maize straw:
(1) stalk after pulverizing and sieving is put into the reaction, extraction device, connects pipeline according to Fig. 2, opens general supply and each instrument power source;
(2) open the experimental installation Controlling System, input extracting pressure, extraction temperature, CO
2The experimental implementation values such as flow and added solvent flow;
(3) start CO
2Fresh feed pump 5, system boosts, and starts simultaneously temperature control system, and system heats up;
(4) after system temperature reaches design temperature, start water, alcohols fresh feed pump 7, the beginning timing;
(5) to setting-up time, reaction, extraction is complete, closes successively temperature control system 14, solvent feed pump 7, CO
2Fresh feed pump 5, CO
2Steel cylinder 1 and automatic back pressure valve 10, system's cooling pressure release;
(6) pressure release complete after, close instrument, take out material and analyze.
Adopt CO
2, the alcohols such as water and methyl alcohol, ethanol, butanols, amylalcohol is as overcritical or subcritical hybrid reaction extraction solvent, after under critical or subcritical solvent condition, maize straw being carried out pre-treatment, the Mierocrystalline cellulose sugar yield in maize straw is 40～95%.
Supercritical process is applied in the pre-treatment of lignocellulose as a kind of emerging green chemistry process, can environmental contamination reduction, and make product more easily separated, be a kind of promising pretreatment technology that has modern environmental consciousness.The overcritical pretreatment process of lignocellulose is the special property of utilizing supercutical fluid, passes through CO under super critical condition
2The effect of equal solvent and properties-correcting agent destroys crystal structure of cellulose, and increased fiber element accessibility is broken the connecting key between Mierocrystalline cellulose and hemicellulose, xylogen, thereby reaches the effect that improves the maize straw sugar yield.
The present invention adopts overcritical or the subcritical abstraction reaction technology carries out pre-treatment to maize straw, when improving the stalk sugar yield, removal is to the inhibited xylogen of further fermenting process, for the clean and effective production of further carrying out the products such as alcohol fuel provides an effective way.Adopt overcritical or subcritical technology is carried out the technical superiority of pretreated novel method to maize straw:
(1) overcritical or subcritical system is not introduced the organic and inorganic solvent of the non-close friend of environment, and can realize the recycle of solvent, has environmental consciousness.
(2) overcritical or subcritical pretreatment process is temperature required with respect to steam explosion, pressure condition is lower, and equipment is relatively simple.
(3) utilize the subtle change of temperature and pressure can cause the larger difference of dissolving power, can pass through transformation temperature, pressure is realized adjustment and control to preprocessing process.
Description of drawings
Fig. 1: periodical operation schema;
Fig. 2 operate continuously schema;
Wherein: 1-CO
2Steel cylinder 2-stopping valve 3-CO
2Water cooler 4-mass flowmeter 5-CO
2The manual back pressure valve 13-of fresh feed pump 6-solvent 7-solvent feed pump 8-preheater 9-reactor 10-automatic back pressure valve 11-gas-liquid separator 12-agitator 14-temperature regulator 9-tensimeter 15-safety valve 16-rupture disk 17-tensimeter.
Embodiment
Below in conjunction with the drawings and specific embodiments, method of the present invention is described in further detail.
Embodiment 1:
Take the maize straw complete feed as raw material, get 5g and put into reactor.Operational condition is: temperature 50 C, pressure are 10MPa, CO
2Amount is 100 times of material quantity, and the water yield is 50 times of material quantity, 5 hours reaction times.The solid materials saccharification is analyzed after pretreatment, and the stalk sugar yield is 58%, and lignin removing rate is 30%.
The present embodiment adopts technological process shown in Figure 1, uses CO
2As follows as the step of overcritical or subcritical solvent pre-treatment maize straw with water:
(1) take 5g through pulverizing air-dry maize straw, distilled water 250ml adds in reactor 9, opens reactor;
(2) open CO
2Fresh feed pump 5 is beaten the CO of 500g in the reactor
2
(3) air inlet complete after, successively with controller general supply, display screen power supply, magnetic stirring apparatus electric power starting, adjust agitator speed to 300rpm, set temperature of reaction;
(4) reaction 5h, close heating unit.Reactor is taken out in heating tank, naturally be cooled to below 30 ℃, open CO
2Air outlet valve cuts out water of condensation, agitator after the still internal pressure is down to normal pressure, open kettle cover, takes out reaction product and analyzes.
Embodiment 2:
Take the maize straw complete feed as raw material, get 5g and put into reactor, butanols, aqueous solution 200ml, wherein butanol content is 33%.Operational condition is: 180 ℃ of temperature, pressure are 15MPa, CO
2Amount is 40 times of material quantity, 1 hour reaction times.The solid materials saccharification is analyzed after pretreatment, stalk sugar yield 95%.Lignin removing rate is 90%.
The present embodiment adopts technological process shown in Figure 1, uses CO
2As follows as the step of overcritical or subcritical solvent pre-treatment maize straw with the butanols aqueous solution:
(1) take 5g through pulverizing air-dry maize straw, volume ratio is that distilled water and the butanols of 2: 1 is total to 200ml, adds in reactor 9, opens reactor;
(2) open CO
2Fresh feed pump 5 is squeezed into 200gCO in reactor
2
(3) air inlet complete after, successively with controller general supply, display screen power supply, magnetic stirring apparatus electric power starting, adjust agitator speed to 300rpm, set temperature of reaction;
(4) after reaction 1h, close heating unit.Reactor is taken out in heating tank, naturally be cooled to below 30 ℃, open CO
2Air outlet valve cuts out water of condensation, agitator after the still internal pressure is down to normal pressure, open kettle cover, takes out reaction product.
Embodiment 3:
Take the maize straw complete feed as raw material, get 5g and put into reactor.Operational condition is: 250 ℃ of temperature, pressure are 20MPa, CO
2Amount is 40 times of material quantity, 0.1 hour reaction times.The solid materials saccharification is analyzed after pretreatment, stalk sugar yield 40%, and lignin removing rate is 60%.
The present embodiment adopts technological process shown in Figure 1, uses CO
2Step as overcritical or subcritical solvent pre-treatment maize straw is as follows:
(1) take 5g through pulverizing air-dry maize straw, add in reactor 9, open reactor;
(2) open CO
2Fresh feed pump 5 is squeezed into 200gCO in reactor
2
(3) air inlet complete after, successively with controller general supply, display screen power supply, magnetic stirring apparatus electric power starting, adjust agitator speed to 300rpm, set temperature of reaction;
(4) after reaction 0.1h, close heating unit.Reactor is taken out in heating tank, naturally be cooled to below 30 ℃, open CO
2Air outlet valve cuts out water of condensation, agitator after the still internal pressure is down to normal pressure, open kettle cover, takes out reaction product.
Embodiment 4:
Take the maize straw complete feed as raw material, get 500g, add in reactor.CO
2Flow 20g/min, other solvent are the water amylalcohol mixing solutions of 33% amylalcohol, flow 2g/min.180 ℃ of temperature, pressure are 15MPa, and the solid materials saccharification is analyzed after pretreatment, and the stalk sugar yield brings up to 93% by undressed 8%.Lignin removing rate is 90%.
The present embodiment adopts technological process shown in Figure 2, uses CO
2As follows as the step of overcritical or subcritical solvent pre-treatment maize straw with amylalcohol, the aqueous solution:
(1) stalk after pulverizing and sieving is put into the reaction, extraction device, connects pipeline according to Fig. 2, opens general supply and each instrument power source;
(2) open the experimental installation Controlling System, input extracting pressure, extraction temperature, CO
2The experimental implementation such as flow and solvent flux value;
(3) start CO
2Fresh feed pump, system boosts, and starts simultaneously temperature control system, and system heats up;
(4) after system temperature reaches design temperature, start the solvent feed pump, the beginning timing;
(5) to setting-up time, extract completely, close successively temperature control system, solvent feed pump, CO
2Fresh feed pump, CO
2Steel cylinder and automatic back pressure valve, system's cooling pressure release;
(6) pressure release complete after, take out material analyzing, close instrument.
Open and a kind of maize straw pretreatment method that proposes of the present invention, those skilled in the art can be by using for reference this paper content, and the links such as appropriate change raw material, processing parameter, structure design realize.Method of the present invention and technology are described by preferred embodiment, person skilled obviously can not break away from that the present invention third holds, in spirit and scope to method as herein described with technology is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and content.
Claims (2)
1. a maize straw pretreatment method, is characterized in that the reaction, extraction solvent adopts CO
2, water and alcoholic solvent, wherein alcoholic solvent is the mixed solvent of one or more solvents in methyl alcohol, ethanol, butanols, amylalcohol, under overcritical or undercritical conditions, maize straw is carried out pre-treatment; Pretreatment process is, temperature is 50～250 ℃, and working pressure is 10～20MPa, and the reaction times is 0.1～5 hour.
2. a kind of maize straw pretreatment method as claimed in claim 1, is characterized in that the pretreatment operation mode adopts intermittence or continuous; Periodical operation is that reaction mass and solvent once are packed in reactor, namely takes out after reaction is completed; The continous way operating characteristics is with in the disposable reactor of packing into of stalk, and to end, Continuous Flow adds to reactor to solvent from the operation beginning, and the reaction, extraction product also flows out from reactor continuously with solvent.
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| CN2009100691047A CN101565725B (en) | 2009-06-02 | 2009-06-02 | Maize straw pretreatment method |
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| CN102198387B (en) * | 2010-03-24 | 2014-06-11 | 淮北中润生物能源技术开发有限公司 | Continuous reaction system taking subcritical or supercritical liquid as solvent and solid as reactant |
| WO2011126654A2 (en) | 2010-03-30 | 2011-10-13 | Cornell University | Biphasic supercritical carbon dioxide-water pretreatment of lignocellulosic biomass |
| CN102605020B (en) * | 2012-03-29 | 2013-07-31 | 天津大学 | Method for improving lignocellulose enzymolysis and saccharification efficiency |
| CN103966877B (en) * | 2013-01-24 | 2017-04-12 | 财团法人金属工业研究发展中心 | Processing method for bio-based materials containing cellulose |
| CN104073532A (en) * | 2014-06-09 | 2014-10-01 | 华南理工大学 | Method for preparing xylose and glucose by pre-treating bagasse materials |
| CN106497987A (en) * | 2016-11-07 | 2017-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of combined method for pre-processing microcrystalline cellulose of meto-super-critical |
| CN108033864B (en) * | 2017-12-08 | 2021-06-15 | 山东农业大学 | Bio-based fiber silicone resin coated controlled release fertilizer special for wedge-shaped flowers and preparation method thereof |
| CN111979820A (en) * | 2020-08-28 | 2020-11-24 | 扬州交石新材料科技有限公司 | Method for preparing straw nano cellulose dispersion liquid by supercritical-high pressure homogenization technology |
| CN112553269A (en) * | 2020-12-24 | 2021-03-26 | 安徽工业大学 | Pretreatment and enzymolysis method of corn straw |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113348A (en) * | 2007-09-06 | 2008-01-30 | 昆明理工大学 | Process for preparing bio-fuel by high-pressure fluid transformation technique |
| CN101362827A (en) * | 2008-09-26 | 2009-02-11 | 复旦大学 | Method for processing cellulose by supercritical carbon dioxide, products and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113348A (en) * | 2007-09-06 | 2008-01-30 | 昆明理工大学 | Process for preparing bio-fuel by high-pressure fluid transformation technique |
| CN101362827A (en) * | 2008-09-26 | 2009-02-11 | 复旦大学 | Method for processing cellulose by supercritical carbon dioxide, products and use thereof |
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