CN115261219A - Green and efficient refining system and method for biomass resource utilization - Google Patents

Green and efficient refining system and method for biomass resource utilization Download PDF

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CN115261219A
CN115261219A CN202210567215.6A CN202210567215A CN115261219A CN 115261219 A CN115261219 A CN 115261219A CN 202210567215 A CN202210567215 A CN 202210567215A CN 115261219 A CN115261219 A CN 115261219A
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organic acid
biomass
des
fermentation
solution
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张栩
张立鹤
陈琳
李晨曦
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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    • C12P7/06—Ethanol, i.e. non-beverage
    • C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
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    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The invention relates to a biomass pretreating agent which is an organic acid-based eutectic solvent and comprises organic acid, choline chloride and Lewis acid. The invention also relates to a green high-efficiency refining system and method for pretreating biomass based on the organic acid-based eutectic solvent. The system and the method comprise a resource utilization scheme of biomass, realize the all-component green high-efficiency refining of the biomass, and provide a new idea of green high-efficiency utilization of biomass resource. Experiments prove that the biomass refining method provided by the application not only realizes the full-component high-value utilization of biomass raw materials such as straws, energy grass, forest trees and the like, but also overcomes the defects of difficult recovery and treatment and high cost of an extraction solvent, so that the method has great values in large-scale industrial production and practical application.

Description

Green and efficient refining system and method for biomass resource utilization
Technical Field
The invention belongs to the field of biomass energy and biological fermentation, and relates to a green efficient refining system and method for biomass resource utilization.
Background
Lignocellulose as an important renewable resource, its efficient resource utilization has been widely studied and paid attention. But the complex structure prevents the effective separation and utilization of each component, so that most comprehensive utilization researches still do not reach the industrial application level. The current main comprehensive utilization scheme is divided into cellulose priority, hemicellulose priority, lignin priority and the like, wherein products with the hemicellulose priority mainly comprise xylose, arabinose, furfural and the like; the preferential utilization strategy product of the lignin comprises an emulsifier, a dye dispersant, a degradable plastic bag, phenolic resin, military aviation kerosene and the like; the utilization strategy mainly based on cellulose utilization can be used for producing paper pulp, dissolving pulp for fibers, nano cellulose, fuel ethanol, biomass graphene and the like, and the paper pulp is used for further producing degradable green products such as paper pulp molding and the like. However, the utilization strategy only focuses on partial utilization of lignocellulose resources, and reasonable resource utilization of the whole process is not realized. Therefore, the comprehensive utilization scheme of cellulose, hemicellulose and lignin which accords with the green processing concept needs to be researched and developed urgently.
At present, the production process and part of fuel ethanol mainly based on cellulose utilization enter the industrialization stage, the market has good reverberation, but the problems of low efficiency of five-carbon sugar and six-carbon sugar cooperative utilization, large enzyme dosage, difficult treatment of process wastewater and the like still exist, so that the resource waste is caused, and the industrial application is restricted. Particularly, currently, in order to realize the cooperative utilization of pentose and hexose, genetic engineering strains are mostly adopted, which not only brings about the problem of genetic safety, but also limits the application in other fields.
A new generation of green solvent-eutectic solvent (DES) has attracted extensive attention in recent years, and the hydrolysis efficiency of pretreated DES waste liquid is greatly improved while lignin is preferentially extracted.
Therefore, the proposal of resource comprehensive utilization of cellulose and hemicellulose which does not depend on genetic engineering bacteria has very important significance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a green high-efficiency refining system and method for pretreating biomass based on an organic acid-based eutectic solvent. Experiments prove that the production process provided by the application not only realizes the full-component high-value utilization of biomass raw materials such as straws, energy grass, forest trees and the like, but also overcomes the defects of difficult recovery and treatment and high cost of an extraction solvent, so that the production process has the value of large-scale industrial production and practical application.
To this end, the invention provides a biomass pretreating agent which is an organic acid-based eutectic solvent and comprises an organic acid, choline chloride and a lewis acid, wherein the organic acid comprises one or more of formic acid, acetic acid and lactic acid, preferably acetic acid, and the lewis acid comprises one or more of aluminum chloride, ferric chloride and manganese chloride, preferably ferric chloride.
In some preferred embodiments of the present invention, the pretreatment agent comprises, based on the total mass of the pretreatment agent:
40% -75%, preferably 60% -75%, more preferably 60%;
choline chloride 20% -40%, preferably 20-36%, more preferably 36%;
the Lewis acid is 1% to 20%, preferably 4% to 16%, more preferably 4%.
The invention provides a green and efficient biomass refining system which comprises a material mixing tank, a high-temperature reaction kettle, a solid residue separation device, an organic acid base DES solution storage tank, a lignin separation device, a DES solution storage tank, a low organic acid concentration solution fermentation tank, a second fermentation product separation device and a second fermentation product storage tank which are sequentially connected;
the refining system also comprises a first water supply pipeline connected with the organic acid-based DES solution storage tank;
the refining system also comprises a second water supply pipeline connected with the low organic acid concentration solution storage tank;
the refining system also comprises a lignin storage tank, and a feed inlet of the lignin storage tank is connected with a lignin discharge port of the lignin separation device;
the refining system also comprises a high organic acid concentration solution pipeline, one end of the high organic acid concentration solution pipeline is connected with a discharge hole of the DES aqueous solution storage tank, and the other end of the high organic acid concentration solution pipeline is connected with a feed hole of the low organic acid concentration solution storage tank.
According to some embodiments of the present invention, the system further comprises an enzymolysis tank, an enzymolysis liquid fermentation tank, an I fermentation product separation device and an I fermentation product storage tank which are connected with the solid residue discharge port of the solid residue separation device.
In a third aspect of the present invention, there is provided a method for green and high-efficiency refining of biomass by using the green and high-efficiency refining system of biomass according to the second aspect of the present invention, comprising:
step A, mixing a pretreating agent and a biomass raw material in a material mixing tank, and then sending the mixture into a high-temperature reaction kettle for high-temperature pretreatment to obtain a high-temperature pretreatment product;
step B, separating the high-temperature pretreatment product by using a solid residue separation device to obtain an organic acid-based DES solution and solid residues;
step C, adding water into the organic acid-based DES solution, uniformly mixing to obtain an organic acid-based DES suspension, and separating the organic acid-based DES suspension by using a lignin separation device to obtain a DES aqueous solution and lignin;
d, diluting and sterilizing a part of DES aqueous solution to obtain a low organic acid concentration solution, fermenting the low organic acid concentration solution by using a low organic acid concentration solution fermentation tank to obtain a DES fermentation culture product, and separating the DES fermentation culture product by using a second fermentation product separation device to obtain a second fermentation product;
wherein the pretreatment agent is the biomass pretreatment agent of claim 1 or 2.
According to the invention, in step D, another part of the DES aqueous solution is used as a high organic acid concentration solution without sterilization for adjusting the pH value of the low organic acid concentration solution, preferably, the organic acid content in the high organic acid concentration solution is 80-400g/L.
In some embodiments of the invention, in step C, water is used in an amount of 1 to 5 times, preferably 1 to 3 times, more preferably 3 times the volume of the organic acid based DES solution.
According to the invention, in step A, the temperature of the reaction is between 100 and 300 ℃, preferably between 140 and 160 ℃.
According to the invention, the reaction temperature is between 10min and 10h, preferably between 50 and 70min.
In some embodiments of the invention, the mass of the pretreatment agent and the biomass feedstock is 1 (4-20), preferably 1 (5-10), and more preferably 1:5.
In some embodiments of the invention, in step D, the organic acid content of the low organic acid concentration solution is 10 to 15g/L.
In some embodiments of the invention, the method for green and efficient refining of biomass further comprises a step E of performing enzymolysis on the solid residue through an enzymolysis tank, performing sugar liquor fermentation treatment on the obtained enzymolysis liquid through an enzymolysis liquid fermentation tank, and then performing separation treatment on a sugar liquor fermentation product through an I fermentation product separation device to obtain an I fermentation product.
The invention achieves the following beneficial effects:
(1) The invention provides a pretreatment method for respectively utilizing pentose and hexose based on organic acid by combining the current utilization situation of lignocellulose, after pretreatment, most of hemicellulose is degraded into pentose which is dissolved in an organic acid eutectic solvent, the cellulose content of a solid part rich in cellulose can reach more than 90 percent, and the dosage of cellulase is greatly reduced.
(2) According to the invention, the high-concentration acid solution based on organic acid consumption as a driving force is established as the pH regulating solution, the continuous carbon source supplement in the fermentation process is indirectly realized through pH regulation, the inhibition effect of the high-concentration organic acid on microorganisms is relieved, and the bulk bio-based chemicals are produced through co-fermentation of the organic acid and the pentose, so that the resource utilization of the solvent in the pretreatment process is realized, and the pretreatment cost is greatly reduced.
(3) When the solid part rich in cellulose is subjected to ethanol fermentation, safe non-genetic engineering strains such as commercial Angel yeast and the like are adopted, so that the problem caused by gene safety is avoided.
(4) The solvent used in the invention is green and environment-friendly, has low price, is easy to obtain raw materials, and has no toxicity and harm in the process.
Drawings
In order that the invention may be readily understood, a more particular description of the invention briefly described above will be rendered by reference to the appended drawings.
FIG. 1 is a schematic view of a process flow of green and efficient refining of full components of biomass.
FIG. 2 is a schematic diagram of green high-efficiency refining system of biomass.
FIG. 3 is a schematic diagram of a green high-efficiency refining system for biomass.
The reference numerals in fig. 2 and 3 are explained as follows: 1, a material mixing tank; 2, a high-temperature reaction kettle; 3 solid-liquid residue separation device; 4, an organic acid-based DES solution storage tank; 5, an I water supply pipeline (abbreviated as PII water); 6 the II water supply pipeline (abbreviated as PII water); 7 a III water supply pipeline (abbreviated as PIII water); 10 solid-liquid residue storage tank; 11, an enzymolysis tank; 12 an enzymatic hydrolysate storage tank; 13 an enzymatic hydrolysate fermentation device; 14 a first fermentation product separation device; 15 a first fermentation product storage tank; 20, an organic acid-based DES suspension storage tank; 21 lignin separation unit; 22DES aqueous solution storage tank; 23, a low organic acid concentration solution storage tank; 24 fermentation tank for low organic acid concentration solution; 25 the second fermentation product separation device; 26 a second fermentation product storage tank; 27 high organic acid concentration solution three-way valve; 28 high organic acid concentration solution pipeline; 29 storage tank for solution with high organic acid concentration; 30 lignin storage tank.
Detailed Description
In order that the invention may be readily understood, a more particular description thereof will be rendered by reference to the appended drawings. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, to the extent that there is no stated or intervening value in that stated range, to the extent that there is no such intervening value, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where a specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
Term (I)
The term "green and efficient refining method of biomass" in the invention specifically refers to a method for realizing effective separation of lignin, cellulose and hemicellulose after biomass is pretreated, products with high added values are respectively obtained after processing, all components of lignocellulose are effectively utilized, and the solvent and the like used in the pretreatment process are also processed to obtain products with high added values, so that no waste is discharged in the whole process, and the method accords with the concept of green processing.
The term "biomass full-component green efficient refining process" in the invention specifically refers to a specific means and a process route for realizing a "biomass green efficient refining method", relates to the connection and the sequence of each processing link, and adds the steps of solvent circulation, water resource recycling, heat recovery and the like, and can refer to a process flow chart specifically.
The term "biomass" as used herein mainly refers to plant-based lignocellulose-based biomass, the main effective components of which are cellulose, hemicellulose, and lignin, among other components.
The term "full component" in the full-component high-value utilization in the present invention is the sum of three biomass components of lignin, cellulose and hemicellulose contained in the biomass raw material, and does not include other components in the biomass, such as ash, grease, and the like.
The term "biomass feedstock" as used herein refers to plant material containing biomass components, including straw, energy grasses, forest trees, and the like.
The term "water" as used herein means tap water, deionized water or distilled water, unless otherwise specified or indicated.
Embodiments II
As mentioned above, the current solution of comprehensive utilization of cellulose, hemicellulose and lignin according to the concept of green processing is not satisfactory, and there are always problems of this kind or others. For example, although part of the fuel ethanol production process mainly using cellulose utilization enters the industrialization stage, the problems of low efficiency of cooperative utilization of pentose and hexose, large enzyme dosage, difficult treatment of process wastewater and the like still exist, so that resource waste is caused, and the industrial application is restricted. Particularly, currently, in order to realize the cooperative utilization of pentose and hexose, genetic engineering strains are mostly adopted, which not only brings about the problem of gene safety, but also limits the application in other fields; for another example, although a new generation of green solvent-eutectic solvent (DES) has greatly improved lignocellulose enzymolysis efficiency after pretreatment while preferentially extracting lignin, there are few problems in the prior art such as how to treat the DES waste liquid after pretreatment.
In view of the above problems in the prior art, the present inventors have conducted extensive and intensive studies on a comprehensive resource utilization technique of cellulose and hemicellulose that is independent of genetically engineered bacteria, and have studied and designed a resource-oriented green and efficient refining method of biomass such as cellulose and hemicellulose that is independent of genetically engineered bacteria, and a process flow diagram thereof is shown in fig. 1. Experiments prove that the biomass refining method provided by the application not only realizes the full-component high-value utilization of biomass raw materials such as straws, energy grass, forest trees and the like, but also overcomes the defects of difficult recovery and treatment and high cost of an extraction solvent, so that the method has great values in large-scale industrial production and practical application.
In order to achieve the technical scheme, in a first aspect of the invention, the biomass pretreating agent is an organic acid-based eutectic solvent and specifically comprises an organic acid, choline chloride and a lewis acid, wherein the organic acid comprises one or more of formic acid, acetic acid and lactic acid, preferably acetic acid, and the lewis acid comprises one or more of aluminum chloride, ferric chloride and manganese chloride, preferably ferric chloride.
In some preferred embodiments of the present invention, the pretreatment agent comprises, based on the total mass of the pretreatment agent:
40% -75%, preferably 60% -75%, more preferably 60%;
choline chloride 20% -40%, preferably 20-36%, more preferably 36%;
the Lewis acid is 1% to 20%, preferably 4% to 16%, more preferably 4%.
In some particularly preferred embodiments of the present invention, the pretreatment agent comprises, based on the total mass of the pretreatment agent: 60% of ethyl acid, 36% of choline chloride and 4% of ferric chloride.
The second aspect of the invention provides a green high-efficiency refining system of biomass, which can be understood as a green high-efficiency refining system for pretreating biomass based on an organic acid-based eutectic solvent, and the process flow schematic diagram is shown in figure 2. As can be seen from fig. 2, the green and efficient refining system for biomass comprises a material mixing tank 1, a high-temperature reaction kettle 2, a solid residue separation device 3, an organic acid base DES solution storage tank 4, a lignin separation device 21, a DES solution storage tank 22, a low organic acid concentration solution storage tank 23, a low organic acid concentration solution fermentation tank 24, a second fermentation product separation device 25 and a second fermentation product storage tank 26 which are connected in sequence;
the refining system also comprises a first water supply pipeline 5 connected with the organic acid-based DES solution storage tank 4 and used for supplying water to the organic acid-based DES solution storage tank;
the refining system also comprises a water supply pipeline II 6 connected with a low organic acid concentration solution storage tank 23 and used for supplying water to the low organic acid concentration solution storage tank;
the refining system further comprises a lignin storage tank 30, the inlet of which is connected to the lignin outlet of the lignin separation unit 21.
The refining system also comprises a high organic acid concentration solution pipeline 28, one end of which is connected with the discharge hole of the DES aqueous solution storage tank 22 through a high organic acid concentration solution three-way valve 27, and the other end is connected with the feed hole of the low organic acid concentration solution storage tank 24.
According to some embodiments of the present invention, the system further comprises an enzymolysis tank 11, an enzymolysis liquid fermentation tank 13, an I fermentation product separation device 14 and an I fermentation product storage tank 15 which are sequentially connected with the solid residue discharge port of the solid residue separation device 3.
It will be appreciated by those skilled in the art that in the process flow illustrated in figure 2 above, the function of the organic acid based DES solution reservoir 4 includes: (1) before adding water, the organic acid-based DES solution storage tank is used; (2) In the process of adding water and mixing, the organic acid base DES solution is used as a mixing tank for the organic acid base DES solution and water; (3) And adding water to mix the mixture to form an organic acid-based DES suspension, and then using the organic acid-based DES suspension as a storage tank.
Preferably, a solid-liquid residue storage tank 10 is additionally arranged between the solid-liquid residue separation device 3 and the enzymolysis tank 11 in the process flow shown in the figure 2; an enzymolysis liquid storage tank 12 is additionally arranged between the enzymolysis tank 11 and the enzymolysis liquid fermentation device 13; an organic base DES suspension storage tank 20 is additionally arranged between the organic base DES solution storage tank 4 and the lignin separation device 21, and a water supply pipeline 5I is correspondingly changed into a water supply pipeline connected with a feed inlet of the organic acid base DES suspension storage tank 20 and used for supplying water to the organic acid base DES suspension storage tank 20; a high organic acid concentration solution storage tank 29 is additionally arranged between the three-way valve 27 and the low organic acid concentration solution fermentation tank 24; the solid-liquid residue storage tank 10, the enzymatic hydrolysate storage tank 12, the organic-based DES suspension storage tank 20 and the high organic acid concentration solution storage tank 29 are used as buffer storage tanks for corresponding materials, so that the operation flexibility and the flexibility are improved, as shown in FIG. 3.
It is further preferable that a third water supply pipeline 7 for supplying water to the high organic acid concentration solution storage tank 29 is connected to the high organic acid concentration solution storage tank 29 in the above-described process flow shown in fig. 3.
It will be appreciated by those skilled in the art that in the process flow illustrated in fig. 3, the function of the organic acid-based DES suspension tank 20 includes: (1) In the process of adding water and mixing, the organic acid-based DES solution is used as a mixing tank for water; (2) And adding water to mix the mixture to form an organic acid-based DES suspension, and then using the organic acid-based DES suspension as a storage tank.
It will also be appreciated by those skilled in the art that in the process flow illustrated in FIG. 3 above, the function of the high organic acid concentration solution tank 29 includes: (1) a high organic acid concentration solution storage tank; (2) For controlling the high organic acid concentration in the high organic acid concentration solution in a suitable range by adding water through the III water supply pipe 7.
In a third aspect of the present invention, there is provided a method for green and high-efficiency refining of biomass by using the green and high-efficiency refining system of biomass according to the second aspect of the present invention, which can be understood as a process for green and high-efficiency refining of biological lignin by using the green and high-efficiency refining system of biomass according to the second aspect of the present invention, as shown in fig. 1, it includes:
step A, mixing a pretreating agent and a biomass raw material (namely lignocellulose) in a material mixing tank 1, and then sending the mixture into a high-temperature reaction kettle 2 for high-temperature pretreatment to obtain a high-temperature pretreatment product;
step B, separating the high-temperature pretreatment product by using a solid residue separation device 3 to obtain an organic acid-based DES solution and solid residues;
step C, adding water into the organic acid-based DES solution, uniformly mixing to obtain an organic acid-based DES suspension, and separating the organic acid-based DES suspension by a lignin separation device 21 to obtain a DES aqueous solution and lignin;
d, adding water into a part of DES aqueous solution to dilute and sterilize to obtain a low organic acid concentration solution, fermenting the low organic acid concentration solution through a low organic acid concentration solution fermentation tank 24 to obtain a DES fermentation culture product, and separating the DES fermentation culture product through a second fermentation product separation device 25 to obtain a second fermentation product;
wherein the pretreatment agent is a biomass pretreatment agent according to the first aspect of the present invention.
According to the invention, in step D, another part of the DES aqueous solution is used as a solution with a high organic acid concentration directly without sterilization to adjust the pH of a solution with a low organic acid concentration.
In some embodiments of the present invention, the method for green and efficient refining of biomass further comprises a step E of performing enzymolysis on the solid residue by using the enzymolysis tank 11, performing sugar liquor fermentation treatment on the obtained enzymolysis liquid by using the enzymolysis liquid fermentation tank 13, and then performing separation treatment on the sugar liquor fermentation product by using the first fermentation product separation device 14 to obtain the first fermentation product.
It is easily understood that the above process is realized based on the biomass pretreatment agent (i.e. the organic acid-based eutectic solvent) according to the first aspect of the present invention and the biomass green high-efficiency refining system according to the second aspect of the present invention, and therefore the biomass green high-efficiency refining system and method provided by the present invention can be understood as a biomass green high-efficiency refining system and method based on the organic acid-based eutectic solvent.
From the above, it can be seen that the biomass green high-efficiency refining system and method of the invention provide a means for effectively separating biomass (including cellulose, hemicellulose and lignin), and realize the respective utilization of each component. Especially, the cellulose independent fermentation independent of the genetic engineering bacteria capable of utilizing five-carbon sugar and six-carbon sugar can be realized, and the production of the cellulose ethanol can be realized by common commercial saccharomyces cerevisiae (such as Angel yeast) and the like; hemicellulose can be converted into high value-added products, such as microbial oils, by other microorganisms.
Furthermore, the green and efficient biomass refining system and method also provide a production process for preparing the microbial oil by high-concentration fed-batch fermentation with organic acid as a carbon source. Based on a pH adjusting system of a fermentation tank, high-concentration organic acid is used as a solution for adjusting the pH, the pH rises after organic acid radicals are consumed by microorganisms, the pH adjusting system is stimulated to continuously supplement the high-concentration organic acid, and therefore the high-concentration organic acid is utilized.
Furthermore, the green and efficient refining system and method for biomass also provide a resource utilization scheme for the lignocellulose biorefinery process, and except for lignocellulose, other solvents used in the production process and the like are all resource utilized. The method comprises the steps of taking lignocellulose biomass as a raw material, firstly carrying out high-temperature pretreatment on the lignocellulose biomass by using an organic acid-based eutectic solvent to realize separation of lignin, hemicellulose and cellulose, wherein the lignin is sold as a product or is further utilized in a high-value mode, the hemicellulose and the organic acid-based eutectic solvent are fermented together by rhodotorula glutinis used for preparing microbial oil, and the cellulose is subjected to enzymolysis and then is fermented by using a commercial saccharomyces cerevisiae microbial inoculum to produce ethanol.
In some specific embodiments of the present invention, the biomass green high-efficiency refining method specifically comprises the following steps:
(1) Pulverizing raw materials and removing impurities
The production process is suitable for most of lignocellulose biomass, the specific crushing and impurity removing processes are slightly different along with different raw materials, and different crushers and crushing processes are selected according to the raw materials. Raw materials include, but are not limited to, forest, grasses, agricultural crops, industrial waste lignocelluloses, and the like.
(2) Preparation of organic acid base eutectic solvent
The organic acid-based eutectic solvent according to the present invention mainly comprises 3 types of effective components including organic acids (formic acid, acetic acid, lactic acid, preferably acetic acid), choline chloride, and lewis acids (aluminum chloride, ferric chloride, manganese chloride, etc., preferably ferric chloride). The 3 components are mixed according to a certain proportion to form uniform transparent liquid at 90 ℃.
(3) Biomass (lignocellulose) pretreatment
And (3) uniformly mixing the prepared raw materials and the organic acid-based eutectic solvent prepared in the step (2) according to a certain proportion, and then reacting in a reaction kettle, wherein the reaction requires high temperature. And after the reaction is finished, centrifuging or filtering to realize solid-liquid separation. A solid fraction (solid residue) rich in cellulose and a liquid fraction (organic acid based DES solution) with dissolved lignin were obtained separately.
(4) Lignin extraction
And (3) adding a certain amount of water into the liquid part (organic acid-based DES solution) dissolved with the lignin obtained in the step (3), without adjusting the pH, standing to form a precipitate, wherein the precipitate is a lignin solid, and then obtaining the lignin solid and a solution (DES aqueous solution) after extracting the lignin by a centrifugal or filtration mode. Drying the lignin to obtain a lignin product (lignin), and using the solution (DES aqueous solution) after the lignin is extracted for subsequent microbial fermentation.
(5) Fermenting lignin extractive solution (DES aqueous solution)
And (3) adding a nitrogen source, inorganic salt and the like which are necessary for the growth of microorganisms into the low organic acid concentration solution obtained after the solution (DES aqueous solution) obtained in the step (4) after the lignin extraction is finished is diluted, preparing a culture medium for microbial fermentation, and adjusting the pH value to be between 5 and 7 according to the requirements of different microorganisms. Adding Rhodotorula glutinis (CGMCC No. 2258) for fermentation.
(6) Cellulose ethanol fermentation
And (3) carrying out enzymolysis or acidolysis on the solid part (solid residue) rich in cellulose obtained in the step (3) to obtain an enzymolysis liquid, and then adding commercial Angel alcohol yeast for fermentation to produce ethanol.
In the preferable technical scheme of the invention, the organic acid used in the step (2) mainly comprises formic acid, acetic acid or lactic acid, and the Lewis acid mainly comprises one or more of aluminum chloride, ferric chloride or manganese chloride. Further preferred combinations are acetic acid, choline chloride and ferric chloride. Preferably, the organic acid-based eutectic solvent component ratio is: 40-75% of acetic acid, 20-40% of choline chloride and 1-20% of ferric chloride. More preferably, the content of each component is as follows: 60-75% of acetic acid, 20-36% of choline chloride and 4-16% of ferric chloride. Still more preferably, the fermentable solvent system comprises the following components in percentage by weight: acetic acid (60%): choline chloride (36%): ferric chloride (4%).
Preferably, the reaction temperature of the step (3) is 100-300 ℃, and the extraction temperature is 140-160 ℃. The high-temperature extraction time in the step (3) is 10min-10h, and the preferred extraction time is 50min-70min. The ratio of the liquid (pretreatment agent) and the solid (biomass raw material) in the step (3) is 1 (4-20), preferably 1 (5-10), and more preferably 1:5.
Preferably, the amount of water added in step (4) is 1 to 5 times, preferably 1 to 3 times, and more preferably 3 times that of the organic acid-based DES solution.
The microorganism used in step (5) must be a microorganism capable of fermenting at least formic acid, acetic acid or lactic acid as a carbon source and also a five-carbon sugar as a carbon source. The preferred microorganism is oleaginous yeast Rhodotorula glutenins, the products being microbial oils and carotenes. Preferably, in order to reduce the problem of the inhibition of microorganisms by high-concentration acid and the problem of large alkali consumption for adjusting pH, two solutions of organic acid with different concentrations are required to be prepared, wherein one solution is low-acetic acid concentration solution, and the other solution is high-acetic acid concentration solution. The concentration of the initial low-acetic acid concentration solution is below 20g/L, the prepared high-organic-acid-concentration solution is used as an acid solution for adjusting pH, and the characteristic that the pH rises after organic acid radicals are consumed by microorganisms is utilized to excite a pH adjusting system to continuously supplement high-concentration organic acid, so that the utilization of the high-concentration organic acid is realized. Preferably, diluting the obtained solution (DES aqueous solution) after lignin extraction to acetic acid concentration of 10-15g/L to obtain low organic acid concentration solution, and adding nitrogen source and other nutrients to obtain initial low concentration culture medium; and directly sterilizing the undiluted solution after lignin extraction to obtain a high-acetic-acid-concentration solution for adjusting the pH, wherein the concentration of the organic acid is 80-400g/L according to different proportions of acetic acid in the initial DES.
The inventors have found that since the result of each pretreatment varies depending on the initial acetic acid concentration (acetic acid concentration in a solution having a high organic acid concentration), it is preferable to control the acetic acid concentration of the solution having a high organic acid concentration within a suitable range in order to ensure stability between fermentations, which is more advantageous for fermentations.
For example, in the case of Rhodotorula glutinis fermentation, since the result of each pretreatment varies depending on the initial acetic acid concentration (acetic acid concentration in a high organic acid concentration solution), it is preferable to adjust the acetic acid concentration of the high organic acid concentration solution by adding a part of water to adjust the acetic acid concentration of the high organic acid concentration solution to 150 to 180g/L for the purpose of ensuring stability between fermentations, which is more advantageous for fermentation.
The specific process flow diagram is shown in figure 1, wherein, the first fermentation product includes but is not limited to grease, the first fermentation product includes but is not limited to acetone, butanol and ethanol, and the second fermentation product includes but is not limited to grease.
The preferable embodiment is an optimized scheme provided by the inventor for the full-component green high-efficiency refining process of biomass, and the preferable process conditions are provided by carrying out amplification and optimization on the process through a simulation experiment. The process scheme is according to the chemical engineering safety requirement, the whole process does not relate to toxic and harmful solvents, and the process is green and environment-friendly and accords with corresponding laws and regulations.
Example III
In order that the invention may be more readily understood, the invention will now be described in further detail with reference to the accompanying drawings and examples, which are given by way of illustration only and are not limiting to the scope of the invention. The starting materials or components used in the present invention can be obtained commercially or by conventional methods unless otherwise specified.
The strain for producing the microbial oil used in the embodiment of the invention is Rhodotorula glutinis (CGMCC No. 2258), and the yeast for producing the ethanol is Saccharomyces cerevisiae active dry yeast agent which is purchased from Angel yeast (yeast X1 special for Angel ethanol).
Oil initial fermentation medium: diluting the extracted acetoxy DES with water to adjust acetic acid concentration to 15g/L,1g/L urea, 2g/L yeast powder, and 5g/L dipotassium hydrogen phosphate.
Acetic acid-based DES feed medium (for pH adjustment) was adjusted to 150-180g/L acetic acid concentration with appropriate amount of water.
The biomass raw materials mainly used in the following examples were pennisetum, poplar and corn stover.
Example 1: determination of main components of pennisetum alopecuroides, poplar and corn straw
The component determination of each raw material is carried out by adopting a two-step sulfuric acid method. Firstly, 0.2g of poplar, corn straw and pennisetum alopecuroides are accurately weighed respectively and placed in a pressure-resistant pipe, 3mL of 72% concentrated H2SO4 solution prepared in advance is added, and water bath is carried out immediately for 1H at 30 ℃. After the completion, deionized water is added into the pressure-resistant pipe to dilute the sulfuric acid-resistant concentration to 4%, and then the hydrolysis is carried out for 1h at 121 ℃. After completion, the mixture was cooled for about 1 hour, and the supernatant was filtered through a 0.22. Mu.L filter and placed in a sample bottle for HPLC analysis. And finally, filtering the hydrolyzed system in the pressure-resistant test tube, putting the obtained solid residue into an oven for drying, and measuring the dried mass of the solid residue.
TABLE 1 determination of various Biomass feedstock Components
Figure RE-GDA0003874280190000111
Example 2:
acetic acid, choline chloride and ferric chloride as acetic acid (60%): choline chloride (36%): preparing 500g of pretreatment solvent according to the proportion of ferric chloride (4%), weighing 100g of poplar, reacting for 3 hours at 140 ℃, performing suction filtration and drying to obtain 44.9g of solid rich in cellulose, adding water into the liquid part to fix the volume to 1.5L, and performing precipitation treatment to obtain 13.5g of lignin. The content of cellulose, hemicellulose and lignin in the residue was determined to be 83.1%, 1.8% and 4.4%, respectively. And carrying out enzymolysis on the solid rich in cellulose according to the concentration of 6% of solid content to obtain an enzymolysis liquid with the glucose concentration of 42.4 g/L. Adding Angel yeast into the enzymatic hydrolysate according to one thousandth of the concentration of the glucose for ethanol fermentation, and finally obtaining the ethanol with the concentration of 20.6g/L. Wherein the liquid part after lignin extraction is determined to have the concentration of acetic acid of 198g/L, the concentration of choline chloride of 114g/L, the concentration of glucose of 4.3g/L and the concentration of xylose of 10.3g/L. Respectively diluting the solution to acetic acid concentrations of 10g/L, 15g/L, 20g/L, 30g/L and 50g/L, then preparing a culture medium according to a culture medium formula for oil fermentation, sterilizing, and performing shake flask fermentation culture at a culture temperature of 30 ℃. And (4) measuring the bacterial quantity and the oil quantity after the fermentation is finished. When the concentration of acetic acid exceeds 20g/L, the microorganism hardly grows, and thus batch fermentation is performed, and the concentration of acetic acid in the initial culture medium should be lower than 20g/L. The specific results are as follows:
TABLE 2 fermentation results of oils and fats with acetic acid as carbon source
Figure RE-GDA0003874280190000121
Example 3:
acetic acid, choline chloride and ferric chloride as per acetic acid (60%): choline chloride (36%): preparing 500g of pretreatment solvent according to the proportion of ferric chloride (4%), weighing 100g of pennisetum alopecuroides, reacting for 80min at 160 ℃, performing suction filtration and drying to obtain 38.2g of solid rich in cellulose, adding water into the liquid part to fix the volume to 2L, and performing precipitation treatment to obtain 14.5g of lignin. The determination shows that the content of cellulose, hemicellulose and lignin in the residue are 87.1%, 0.8% and 3.4%, respectively. And carrying out enzymolysis on the solid rich in cellulose according to the concentration of 6% of solid content to obtain an enzymolysis liquid with the glucose concentration of 49.4 g/L. Adding Angel yeast into the enzymolysis solution according to 0.5 thousandth of the glucose concentration for ethanol fermentation, and finally obtaining the ethanol with the concentration of 24.6g/L. Wherein the liquid part after lignin extraction is determined to have acetic acid concentration of 146g/L, choline chloride concentration of 88.2g/L, glucose concentration of 2.3g/L and xylose concentration of 9.3g/L. Diluting the solution until the concentration of acetic acid is 15g/L, then preparing a culture medium according to a culture medium formula for oil fermentation, taking the culture medium as an initial culture medium of a fermentation tank, wherein the total volume of the fermentation tank body is 5L, the initial liquid-filled culture medium is 2L, and performing fermentation culture after sterilization. The solution after lignin extraction is directly used as a solution for adjusting pH after being sterilized, the pH is controlled to be 6.5 in the fermentation process, and the fermentation is finished when the volume of the final fermentation liquor reaches 3L. The culture temperature was 30 ℃. After the fermentation, the measured bacterial quantity is 33.2g/L, and the oil quantity is 7.1g/L.
Example 4:
formic acid, choline chloride and ferric chloride as formic acid (60%): choline chloride (36%): preparing 500g of pretreatment solvent according to the proportion of ferric chloride (4%), weighing 100g of straws, reacting for 90min at 160 ℃, performing suction filtration and drying to obtain 40.2g of solid rich in cellulose, adding water into the liquid part to fix the volume to 2L, and performing precipitation treatment to obtain 16.5g of lignin. The determination shows that the content of cellulose, hemicellulose and lignin in the residue is 80.1%, 1.6% and 2.4%, respectively. And carrying out enzymolysis on the solid rich in cellulose according to the concentration of 6% of solid content to obtain an enzymolysis liquid with the glucose concentration of 45.4 g/L. Adding the enzymatic hydrolysate into Angel yeast agent according to one thousandth of the concentration of glucose for ethanol fermentation, and finally obtaining the ethanol with the concentration of 21.3g/L. Wherein the liquid part after lignin extraction is determined to have the concentration of formic acid of 144g/L, the concentration of choline chloride of 87.7g/L, the concentration of glucose of 1.1g/L and the concentration of xylose of 8.3g/L. Respectively diluting the solution to formic acid concentration of 10g/L, 15g/L, 20g/L, 30g/L and 50g/L, then preparing culture medium according to the formula of the culture medium for oil fermentation, sterilizing, and performing shake flask fermentation culture at the culture temperature of 30 ℃. And (4) measuring the bacterial quantity and the oil quantity after the fermentation is finished. The specific results are as follows:
TABLE 3 fermentation results of oils and fats with formic acid as carbon source
Figure RE-GDA0003874280190000131
Example 5:
acetic acid, choline chloride and ferric chloride as acetic acid (60%): choline chloride (36%): preparing 500g of pretreatment solvent according to the proportion of ferric chloride (4%), weighing 100g of straws, reacting for 60min at 160 ℃, performing suction filtration and drying to obtain 39.1g of solid rich in cellulose, adding water into the liquid part to fix the volume to 2L, and performing precipitation treatment to obtain 14.1g of lignin. The determination shows that the content of cellulose, hemicellulose and lignin in the residue is 80.1%, 2.8% and 4.9%. And carrying out enzymolysis on the solid rich in cellulose according to the concentration of 6% of solid content to obtain an enzymolysis liquid with the glucose concentration of 45.1 g/L. Adding the enzymatic hydrolysate into Angel yeast agent according to one thousandth of the concentration of glucose for ethanol fermentation, and finally obtaining the ethanol with the concentration of 21.6g/L. Wherein the concentration of acetic acid is 144g/L, the concentration of choline chloride is 86.2g/L, the concentration of glucose is 1.3g/L, and the concentration of xylose is 8.3g/L after the liquid part after the lignin is extracted is measured. Diluting the solution until the concentration of acetic acid is 15g/L, then preparing a culture medium according to a culture medium formula for oil fermentation, taking the culture medium as an initial culture medium of a fermentation tank, wherein the total volume of the fermentation tank body is 5L, the initial liquid-filled culture medium is 1L, and performing fermentation culture after sterilization. The solution after lignin extraction is directly used as a solution for adjusting pH after being sterilized, the pH is controlled to be 6.5 in the fermentation process, and the fermentation is finished when the volume of the final fermentation liquor reaches 3L. The culture temperature was 30 ℃. After the fermentation, the measured bacterial quantity is 41.2g/L, and the oil quantity is 10.3g/L.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A biomass pretreating agent is an organic acid-based eutectic solvent and comprises organic acid, choline chloride and Lewis acid, wherein the organic acid comprises one or more of formic acid, acetic acid and lactic acid, preferably acetic acid, and the Lewis acid comprises one or more of aluminum chloride, ferric chloride and manganese chloride, preferably ferric chloride.
2. The biomass pretreatment agent of claim 1, wherein the pretreatment agent comprises, based on the total mass of the pretreatment agent:
40% -75%, preferably 60% -75%, more preferably 60%;
choline chloride 20% -40%, preferably 20-36%, more preferably 36%;
the Lewis acid is 1% to 20%, preferably 4% to 16%, more preferably 4%.
3. A green efficient refining system for biomass comprises a material mixing tank, a high-temperature reaction kettle, a solid residue separation device, an organic acid base DES solution storage tank, a lignin separation device, a DES solution storage tank, a low organic acid concentration solution fermentation tank, a II fermentation product separation device and a II fermentation product storage tank which are sequentially connected;
the refining system also comprises a first water supply pipeline connected with the organic acid-based DES solution storage tank;
the refining system also comprises a second water supply pipeline connected with the low organic acid concentration solution storage tank;
the refining system also comprises a lignin storage tank, and a feed inlet of the lignin storage tank is connected with a lignin discharge hole of the lignin separation device;
the refining system also comprises a high organic acid concentration solution pipeline, wherein one end of the high organic acid concentration solution pipeline is connected with a discharge port of the DES aqueous solution storage tank, and the other end of the high organic acid concentration solution pipeline is connected with a feed port of the low organic acid concentration solution storage tank.
4. The green high-efficiency refining system for biomass according to claim 3, further comprising an enzymolysis tank, an enzymolysis liquid fermentation tank, an I fermentation product separation device and an I fermentation product storage tank which are connected with a solid residue discharge hole of the solid residue separation device.
5. A green high-efficiency refining method of biomass by using the green high-efficiency refining system of biomass as claimed in claim 3 or 4, which comprises the following steps:
step A, mixing a pretreating agent and a biomass raw material in a material mixing tank, and then sending the mixture into a high-temperature reaction kettle for high-temperature pretreatment to obtain a high-temperature pretreatment product;
step B, separating the high-temperature pretreatment product by using a solid residue separation device to obtain an organic acid-based DES solution and solid residues;
step C, adding water into the organic acid-based DES solution, uniformly mixing to obtain an organic acid-based DES suspension, and separating the organic acid-based DES suspension by using a lignin separation device to obtain a DES aqueous solution and lignin;
d, diluting and sterilizing a part of DES aqueous solution to obtain a low organic acid concentration solution, fermenting the low organic acid concentration solution by using a low organic acid concentration solution fermentation tank to obtain a DES fermentation culture product, and separating the DES fermentation culture product by using a second fermentation product separation device to obtain a second fermentation product;
wherein the pretreatment agent is the biomass pretreatment agent of claim 1 or 2.
6. The green high-efficiency refining method of biomass according to claim 5, characterized in that in the step D, another part of DES aqueous solution is used as high organic acid concentration solution to adjust the pH value of low organic acid concentration solution directly without sterilization; preferably, the organic acid content in the high organic acid concentration is 80-400g/L.
7. The green high-efficiency refining method of biomass according to claim 5 or 6, characterized in that in the step C, the amount of water is 1-5 times, preferably 1-3 times, and more preferably 3 times of the volume of the organic acid-based DES solution.
8. The green high-efficiency refining method of biomass according to any one of claims 5 to 7, characterized in that, in the step A, the temperature of the reaction is 100-300 ℃, preferably 140-160 ℃; and/or the reaction temperature is 10min-10h, preferably 50-70min; and/or the mass of the pretreating agent and the biomass raw material is 1 (4-20), preferably 1 (5-10), and more preferably 1:5.
9. The green high-efficiency refining method for biomass according to any one of claims 5 to 8, characterized in that in the step D, the content of organic acid in the low organic acid concentration solution is 10 to 15g/L.
10. The green high-efficiency refining method of biomass according to any one of claims 5 to 9, characterized in that the green high-efficiency refining method of biomass comprises a step E of performing enzymolysis on the solid residue through an enzymolysis tank, performing sugar liquor fermentation treatment on the obtained enzymolysis liquid through an enzymolysis liquid fermentation tank, and then performing separation treatment on the sugar liquor fermentation product through a first fermentation product separation device to obtain a first fermentation product.
CN202210567215.6A 2022-05-23 2022-05-23 Green and efficient refining system and method for biomass resource utilization Pending CN115261219A (en)

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