CN102585247A - Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose - Google Patents
Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose Download PDFInfo
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Abstract
The invention relates to a method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose. The method comprises the following steps of: performing pretreatment on a lignocellulose raw material through a diluted acid method to get the residue from acid hydrolysis, performing enzymolysis with cellulase and xylanase to get the residue from the enzymatic hydrolysis, and further performing steam boiling and sulfonation on the residue from the enzymatic hydrolysis through a hydrosulphite process steam boiling technology to prepare a lignin sulfonate product. According to the method disclosed by the invention, the utilization rate of the lignocellulose raw material is improved, and the method further has better economic and social benefits.
Description
Technical field
The invention belongs to the biological fermentation engineering field, specifically, relate to a kind of method of utilizing lignocellulose enzymic hydrolysis residue to prepare sulfonated lignin.
Background technology
The lignocellulose resource is a renewable resources the abundantest on the earth,, accumulates and is storing up huge biomass energy up to 1,500 hundred million tons according to measuring and calculating gross annual output amount.China is a large agricultural country; The YO of crop material (like straw, straw etc.) very huge (annual output can reach about 700,000,000 tons, is equivalent to 500,000,000 tons of mark coals), according to statistics; Present straw utilization rate 33%; But only account for 2.6% through what utilize after certain technical finesse, all the other major parts just act as a fuel and wait directly utilization, and DEVELOPMENT PROSPECT is boundless.If can a lignocellulose resource part wherein be converted into the chemical or the energy, with producing huge economic and social benefit.Traditional lignocellulose utilization of resources approach is more single, and except going back the field, mainly utilizing approach is burning, gasification and hydrolysis.
At present for the utilization of lignocellulose, using more is to be raw material with the lignocellulose, and hydrolysis semicellulose and cellulosic component wherein prepares sugar alcohol product or fermentative production of ethanol and other organic acid product.Industrial lignin receives the influence of factors such as fibrous material, pulping process and process for extracting, and physicochemical property differ greatly, and acid hydrolysis xylogen, alkali lignin, sulfonated lignin, enzymic hydrolysis xylogen etc. are generally arranged.The enzymic hydrolysis xylogen is owing to having higher activity near the initial wood mass procatarxis.Can produce a large amount of hydrolytic residues after the semicellulose of lignocellulose and cellulosic component are utilized, the lignin component of the overwhelming majority is still wherein residual, as not being used, will cause significant wastage.Therefore, further utilize the hydrolytic residue Development and Production lignosulfonic acid salt product of lignocellulose very necessary.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing lignocellulose enzymic hydrolysis residue to prepare sulfonated lignin.
Lignocellulose enzymic hydrolysis residue can adopt sulfite cooking to prepare the lignosulfonic acid product salt.The purpose of sulphite boiling is with the xylogen effect in sulfite cooking liquor and the raw material, generates lignosulfonic acid and sulfonated lignin, thereby realizes the separation of feed composition.In the sulfite cooking process, whole physical-chemical reaction is divided into two kinds of effects substantially.First kind of infiltration and sulfonation that act as cooking liquor to raw material, second kind of stripping and raw material that act as resultant of reaction separates into fibrous paper pulp.Two kinds of effects take place simultaneously, are not well-separated.Cooking liquor had both relied on the diffusion of cooking liquor itself and the capillary action of raw material to the infiltration of raw material, also forced by means of digestion process pressure raises to infiltrate.Cooking liquor infiltrates after the raw material, and lignin generation sulfonation reaction generation lignosulfonic acid or Sulfite lignin in main and the raw material are referred to as sulfonated lignin, are dissolved in the acid solution.
The method of utilizing lignocellulose enzymic hydrolysis residue to prepare sulfonated lignin of the present invention may further comprise the steps:
(1) diluted acid method pre-treatment: under diluted acid, coldcondition, lignocellulosic material is carried out pre-treatment, solid-liquid separation obtains the acid hydrolysis residue;
(2) enzymolysis: utilize cellulase and zytase that the acid hydrolysis residue is carried out enzymolysis, remove most of Mierocrystalline cellulose and remaining semicellulose, obtain the enzymic hydrolysis residue;
(3) boiling, sulfonation: adopt hydrosulphite method digesting technoloy that the enzymic hydrolysis residue is carried out boiling, sulfonation, the preparation sulfonated lignin.
Above-mentioned steps also comprises the concentrated back of the reaction product after boiling, sulfonation spraying drying, obtains the sulfonated lignin powder-like product.
Said lignocellulosic material can be in corn cob, corn straw, wheat stalk, broomcorn straw, cotton stalk, soybean stalks, sunflower stalk, sesame stalk, peanut stalk, rape stalk, Ipomoea batatas rattan and the rice straw one or more.
Wherein, in the said step (1), diluted acid low temperature pretreatment condition is: acid concentration 0.1%～2.0%, and liquid-solid ratio 10～4: 1,100～150 ℃ of temperature, time 10～180min; Acid hydrolysis residue component is: content of cellulose: 40%～70%, and hemicellulose level: 1%～15%, the Kelly Clarkson content of lignin: 15%～30%, ash oontent: 1%～5%.
In the said step (1), what described acid can be in sulfuric acid, hydrochloric acid, phosphoric acid, the formic acid is a kind of; Dry substance concentration can be adjusted to 15%-18% through adding water.
In the said step (2), the cellulase consumption is 10～30FPIU/ gram substrate, and the zytase consumption is 10～30FPIU/ gram substrate.
In the said step (2), enzymatic hydrolysis condition is: pH is 4.5～5.2, rotating speed 50～200r/min, and temperature is at 46～50 ℃, and enzymolysis time is at 24～72h.
Kelly Clarkson lignin content >=40% in the enzymic hydrolysis residue.
In the said step (3), it is 5%～20% slurry that enzymic hydrolysis residue water is adjusted to concentration of substrate, adds sealed reactor behind the sodium sulfite anhy 96, is warming up to temperature required picking up counting.
In the said step (3), sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 1%～20% during boiling.
In the said step (3), boiling, sulfonation condition are: temperature of reaction is 120～180 ℃, and the reaction times is 1～10h.
The present invention is a raw material with lignocellulose enzymic hydrolysis residue; Adopt hydrosulphite method digesting technoloy to prepare the lignosulfonic acid product salt; Improved in the lignocellulose fermentation production process the utilization ratio of lignocellulosic material, realized the recycle of trade refuse, reduced cost; Also being significant aspect the minimizing water environment pollution, have remarkable economic efficiency and social benefit.PH value when the pH value of the inventive method enzymic hydrolysis and boiling is more approaching, and the enzymic hydrolysis residue can directly carry out boiling and need not regulate pH, and technology is simple, is convenient to operation.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.Under the situation that does not deviate from the present invention's spirit and essence, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.If do not specialize the conventional means that used technique means is well known to those skilled in the art among the embodiment.
Embodiment 1
1.5kg corn cob joins in the 9kg dilution heat of sulfuric acid, boiling 120min under 1.2%, 118 ℃ of condition of sulfuric acid concentration.Reaction finishes the back and adopts the cloth bag whizzer to carry out solid-liquid separation, obtains the acid hydrolysis residue.The acid hydrolysis residue adds in the reactor drum of band stirring, adds water and regulates dry concentration to 16%, regulates pH to 4.8; 50 ℃ of temperature add cellulase (20FPIU/ restrains Mierocrystalline cellulose) and zytase (15FPIU/ restrains Mierocrystalline cellulose), mixing speed 200r/min; Adopt the cloth bag whizzer to carry out solid-liquid separation behind the enzymolysis 48h; It is for use to filtrate, and filter residue is the enzymic hydrolysis residue, is used to prepare sulfonated lignin.Concentration of substrate is 20% during boiling, and sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 10%, and temperature of reaction is 160 ℃, and the reaction times is 5h.It is 1.89mmol/CLS that reaction finishes back detection sulfonation degree, concentrates the back spraying drying and obtains tawny sodium lignosulfonate powder-like product.Through measuring, the sodium lignosulfonate water-reducing rate is 10.47%, meets the national salable product standard (GB8076-1997) of efficient retarding and water reducing agent in " concrete admixture ".
Embodiment 2
1.5kg corn straw joins in the 15kg dilution heat of sulfuric acid, boiling 90min under 0.8%, 125 ℃ of condition of sulfuric acid concentration.Reaction finishes the back and adopts the cloth bag whizzer to carry out solid-liquid separation, gets the acid hydrolysis residue.The acid hydrolysis residue is gone in the reactor drum of band stirring, adds water and regulates dry concentration to 18%, regulates pH to 5.1; 49 ℃ of temperature; Add cellulase (15FPIU/ restrains Mierocrystalline cellulose) and zytase (20FPIU/ restrains Mierocrystalline cellulose), mixing speed 150r/min adopts the cloth bag whizzer to carry out solid-liquid separation behind the enzymolysis 36h; It is for use to filtrate, and filter residue is that the enzymic hydrolysis residue is used to prepare sulfonated lignin.Concentration of substrate is 10% during boiling, and sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 20%, and temperature of reaction is 140 ℃, and the reaction times is 2h.It is 1.37mmol/CLS that reaction finishes back detection sulfonation degree, concentrates the back spraying drying and obtains Vandyke brown sodium lignosulfonate powder-like product.Through measuring, the sodium lignosulfonate water-reducing rate is 10.62%, meets the national salable product standard (GB8076-1997) of efficient retarding and water reducing agent in " concrete admixture ".
Embodiment 3
Wheat stalk 1.5kg joins in the 10.5kg dilution heat of sulfuric acid, boiling 150min under 2.0%, 105 ℃ of condition of sulfuric acid concentration.Reaction finishes the back and adopts the cloth bag whizzer to carry out solid-liquid separation, gets the acid hydrolysis residue.The acid hydrolysis residue is gone in the reactor drum of band stirring, adds water and regulates dry concentration to 15%, regulates pH to 4.6; 48 ℃ of temperature; Add cellulase (10FPIU/ restrains Mierocrystalline cellulose) and zytase (30FPIU/ restrains Mierocrystalline cellulose), mixing speed 50r/min adopts the cloth bag whizzer to carry out solid-liquid separation behind the enzymolysis 72h; It is for use to filtrate, and filter residue is that the enzymic hydrolysis residue is used to prepare sulfonated lignin.Concentration of substrate is 5% during boiling, and sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 15%, and temperature of reaction is 150 ℃, and the reaction times is 3h.It is 1.76mmol/CLS that reaction finishes back detection sulfonation degree, concentrates the back spraying drying and obtains Vandyke brown sodium lignosulfonate powder-like product.Through measuring, the sodium lignosulfonate water-reducing rate is 11.29%, meets the national salable product standard (GB8076-1997) of efficient retarding and water reducing agent in " concrete admixture ".
Embodiment 4
1.5kg rice straw joins in the 6kg dilute hydrochloric acid solution, boiling 180min under 2.0%, 100 ℃ of condition of concentration of hydrochloric acid.Reaction finishes the back and adopts the cloth bag whizzer to carry out solid-liquid separation, obtains the acid hydrolysis residue.The acid hydrolysis residue adds in the reactor drum of band stirring, adds water and regulates dry concentration to 16%, regulates pH to 4.5; 50 ℃ of temperature add cellulase (30FPIU/ restrains Mierocrystalline cellulose) and zytase (10FPIU/ restrains Mierocrystalline cellulose), mixing speed 180r/min; Adopt the cloth bag whizzer to carry out solid-liquid separation behind the enzymolysis 24h; It is for use to filtrate, and filter residue is the enzymic hydrolysis residue, is used to prepare sulfonated lignin.Concentration of substrate is 5% during boiling, and sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 1%, and temperature of reaction is 120 ℃, and the reaction times is 10h.It is 1.58mmol/CLS that reaction finishes back detection sulfonation degree, concentrates the back spraying drying and obtains tawny sodium lignosulfonate powder-like product.Through measuring, the sodium lignosulfonate water-reducing rate is 10.98%, meets the national salable product standard (GB8076-1997) of efficient retarding and water reducing agent in " concrete admixture ".
Embodiment 5
1.5kg broomcorn straw joins in the 15kg dilute phosphoric acid solution, boiling 90min under 2%, 150 ℃ of condition of phosphoric acid concentration.Reaction finishes the back and adopts the cloth bag whizzer to carry out solid-liquid separation, gets the acid hydrolysis residue.The acid hydrolysis residue is gone in the reactor drum of band stirring, adds water and regulates dry concentration to 14%, regulates pH to 5.2; 47 ℃ of temperature; Add cellulase (20FPIU/ restrains Mierocrystalline cellulose) and zytase (20FPIU/ restrains Mierocrystalline cellulose), mixing speed 100r/min adopts the cloth bag whizzer to carry out solid-liquid separation behind the enzymolysis 36h; It is for use to filtrate, and filter residue is that the enzymic hydrolysis residue is used to prepare sulfonated lignin.Concentration of substrate is 13% during boiling, and sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 17%, and temperature of reaction is 180 ℃, and the reaction times is 1h.It is 1.37mmol/CLS that reaction finishes back detection sulfonation degree, concentrates the back spraying drying and obtains Vandyke brown sodium lignosulfonate powder-like product.Through measuring, the sodium lignosulfonate water-reducing rate is 10.31%, meets the national salable product standard (GB8076-1997) of efficient retarding and water reducing agent in " concrete admixture ".
Embodiment 6
Soybean stalks 1.5kg joins in the 9kg dilute hydrochloric acid solution, boiling 140min under 2.0%, 121 ℃ of condition of concentration of hydrochloric acid.Reaction finishes the back and adopts the cloth bag whizzer to carry out solid-liquid separation, gets the acid hydrolysis residue.The acid hydrolysis residue is gone in the reactor drum of band stirring, adds water and regulates dry concentration to 17%, regulates pH to 4.7; 46 ℃ of temperature; Add cellulase (10FPIU/ restrains Mierocrystalline cellulose) and zytase (25FPIU/ restrains Mierocrystalline cellulose), mixing speed 80r/min adopts the cloth bag whizzer to carry out solid-liquid separation behind the enzymolysis 60h; It is for use to filtrate, and filter residue is that the enzymic hydrolysis residue is used to prepare sulfonated lignin.Concentration of substrate is 15% during boiling, and sodium sulfite anhy 96 quality and enzymic hydrolysis residue mass ratio are 8%, and temperature of reaction is 170 ℃, and the reaction times is 8h.It is 6.83mmol/CLS that reaction finishes back detection sulfonation degree, concentrates the back spraying drying and obtains Vandyke brown sodium lignosulfonate powder-like product.Through measuring, the sodium lignosulfonate water-reducing rate is 11.73%, meets the national salable product standard (GB8076-1997) of efficient retarding and water reducing agent in " concrete admixture ".
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (10)
1. method of utilizing lignocellulose enzymic hydrolysis residue to prepare sulfonated lignin may further comprise the steps:
(1) diluted acid method pre-treatment: under diluted acid, coldcondition, lignocellulosic material is carried out pre-treatment, solid-liquid separation obtains the acid hydrolysis residue;
(2) enzymolysis: utilize cellulase and zytase that the acid hydrolysis residue is carried out enzymolysis, centrifugal, filtration, it is for use to filtrate, and filter residue is the enzymic hydrolysis residue;
(3) boiling, sulfonation: adopt the hydrosulphite method that the enzymic hydrolysis residue is carried out boiling, sulfonation, the preparation sulfonated lignin.
2. the method for claim 1; It is characterized in that in the step (1) that said lignocellulosic material is one or more in corn cob, corn straw, wheat stalk, broomcorn straw, cotton stalk, soybean stalks, sunflower stalk, sesame stalk, peanut stalk, rape stalk, Ipomoea batatas rattan and the rice straw.
3. the method for claim 1; It is characterized in that in the step (1) that said diluted acid low temperature pretreatment condition is: acid concentration 0.1%～2.0%, the volume mass ratio of diluted acid and lignocellulose is 10～4: 1; 100～150 ℃ of temperature, time 90～180min.
4. the method for claim 1 is characterized in that in the step (1), and described acid is a kind of in sulfuric acid, hydrochloric acid, phosphoric acid, the formic acid, through adding water dry substance concentration is adjusted to 15%-18%.
5. the method for claim 1; It is characterized in that in the step (1) that said acid hydrolysis residue component is following: content of cellulose: 40%～70%, hemicellulose level: 1%～15%; The Kelly Clarkson content of lignin: 15%～30%, ash oontent: 1%～5%.
6. like the arbitrary described method of claim 1-5, it is characterized in that in the step (2), said cellulase consumption is 10～30FPIU/g substrate, the zytase consumption is 10～30FPIU/g substrate.
7. like the arbitrary described method of claim 1-5, it is characterized in that said enzymatic hydrolysis condition is in the step (2): pH 4.5～5.2, rotating speed 50～200r/min, 46～50 ℃ of temperature, enzymolysis time 24～72h.
8. like the arbitrary described method of claim 1-5, it is characterized in that in the step (2), in the said enzymic hydrolysis residue, Kelly Clarkson lignin content >=40%.
9. like the arbitrary described method of claim 1-5, it is characterized in that in the step (3), enzymic hydrolysis residue mass percent is 5%～20% during boiling, sodium sulfite anhy 96 and enzymic hydrolysis residue mass ratio are 1%～20%.
10. like the arbitrary described method of claim 1-5, it is characterized in that in the step (3), said boiling, sulfonation reaction condition are: 120～180 ℃ of temperature, the reaction times is 1～10h.
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| CN109251700A (en) * | 2018-07-05 | 2019-01-22 | 北京林业大学 | Multi-functional wooden cellulase hydrolysed ferment residue filler, preparation method and applications |
| CN109503859A (en) * | 2018-12-06 | 2019-03-22 | 齐鲁工业大学 | A method of highly sulfonated sodium lignosulfonate is prepared using wheat stalk |
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| CN112442519A (en) * | 2019-09-05 | 2021-03-05 | 中国石油天然气股份有限公司 | Method for pretreating corn straw and corn straw pretreatment |
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| CN110616237A (en) * | 2019-10-22 | 2019-12-27 | 天津科技大学 | Method for preparing xylo-oligosaccharide from steam-exploded plant fiber raw material |
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