CN110004196B - Process for co-producing fuel ethanol and DDGS by using straw and corn - Google Patents

Process for co-producing fuel ethanol and DDGS by using straw and corn Download PDF

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CN110004196B
CN110004196B CN201910285646.1A CN201910285646A CN110004196B CN 110004196 B CN110004196 B CN 110004196B CN 201910285646 A CN201910285646 A CN 201910285646A CN 110004196 B CN110004196 B CN 110004196B
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corn
ddgs
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fuel ethanol
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CN110004196A (en
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金明杰
霍俊呈
褚荣浩
胡雨蝶
林嘉鑫
赖沁烜
陈相雪
王盛炜
袁也
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Nanjing University of Science and Technology
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/10—Animal feeding-stuffs obtained by microbiological or biochemical processes
    • A23K10/12—Animal feeding-stuffs obtained by microbiological or biochemical processes by fermentation of natural products, e.g. of vegetable material, animal waste material or biomass
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    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides
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    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • 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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    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
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    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • 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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    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

The invention discloses a process for co-producing fuel ethanol and DDGS by using straw and corn. The process combines the first-generation fuel ethanol technology and the second-generation fuel ethanol technology, and the mass ratio of the straw to the corn flour is controlled to be 1: 3-4, mixing the straw hydrolysate with the corn liquefied liquid, regulating the pH to the optimal pH range of the fermentation strain, adding the fermentation strain, and fermenting to obtain the fuel ethanol and the high-quality DDGS. The invention coproduces the first-generation ethanol and the second-generation ethanol, and the produced DDGS contains the xylooligosaccharide with high nutritive value, so that the product quality is improved, and the invention has potential market application prospect.

Description

Process for co-producing fuel ethanol and DDGS by using straw and corn
Technical Field
The invention belongs to the technical field of lignocellulose hydrolysis, and relates to a process for co-producing fuel ethanol and high-quality distillers' grains with protein (DDGS) from straw and corn.
Background
Biomass energy is one of the most potential ways to address real and future energy crisis and environmental pollution. The first generation fuel ethanol technology for producing fuel ethanol based on starch and sugar fermentation has the problem of 'competing with people for food and competing with food for land', and does not accord with the strategy of sustainable development. The rest mass biomass energy of straw class that produces in the agricultural production is mainly burnt, and the utilization ratio is extremely low. The cellulose ethanol technology can not only utilize waste crop straws, but also can produce renewable clean energy, namely ethanol, and has more advantages than the first-generation fuel ethanol technology. The second generation fuel ethanol technology using cellulose as a raw material has become one of the main flows of new energy sources in the new century, but the cellulose ethanol technology cannot be applied in large-scale commercialization due to the immature and economical limitations of key technologies.
The problems mainly existing in the current cellulosic ethanol technology include: (1) At present, the production intensity and the ethanol concentration of lignocellulose ethanol are generally low, and only 0.3-0.5g.L -1 ·h -1 . The production strength of the corn ethanol can reach 1.6-2.0g.L -1 ·h -1 Is approximately 4 times the production intensity of lignocellulose ethanol. This means that the equipment cost of the lignocellulose process is 4 times that of the corn process, and the energy consumption, labor cost and the like for producing ethanol of unit mass are also greatly higher than those of the corn ethanol process; (2) Lignocellulosic ethanol does not produce high value added byproduct DDGS as corn ethanol, but corn ethanol alone technology cannot produce high quality DDGS that can be rich in xylooligosaccharides.
Disclosure of Invention
The invention aims to provide a process for co-producing fuel ethanol and high-quality DDGS by using straw and corn. The technology combines the first-generation fuel ethanol technology and the second-generation fuel ethanol technology, improves the ethanol production strength, simultaneously produces DDGS containing high-value xylooligosaccharide, reduces the production cost and improves the product income.
The technical scheme for realizing the purpose of the invention is as follows:
the technology for co-producing fuel ethanol and high-quality DDGS by using straw and corn comprises the following specific steps:
step 1, carrying out acidic pretreatment on crushed straws, and drying to obtain pretreated straws;
step 2, adding hydrolase and water into the pretreated straw, adjusting the pH to the optimal pH range of the enzyme, hydrolyzing, and centrifuging to obtain straw hydrolysate;
step 3, adding liquefying enzyme alpha-amylase into the corn flour, adjusting the pH value to 4.0-7.0, and liquefying to obtain corn liquefied liquid;
step 4, the mass ratio of the straw to the corn flour is 1: 3-4, mixing the straw hydrolysate with the corn liquefied liquid, regulating the pH to the optimal pH range of the fermentation strain, adding the fermentation strain, and fermenting to obtain the fuel ethanol and the high-quality DDGS.
In the step 1, the straw is one or more selected from wheat straw, corn straw, agriculture and forestry waste, rice straw, sorghum straw, soybean straw and forestry waste.
In the invention, in the step 1, the pretreatment can be dilute acid pretreatment, alkaline pretreatment, hot water pretreatment, steam explosion pretreatment and the like.
In the step 2, the hydrolase is one or a mixture of several of cellulase, xylanase, trichoderma reesei and the like which are conventionally used in the field.
In the present invention, in the step 2, the pH is in an optimal pH range of the enzyme, and is generally 3.0 to 10.0.
In the invention, in the step 3, the liquefying temperature is 85 ℃.
In the present invention, in step 4, the fermentation strain adopts ethanol fermentation strain which is conventionally used in the art and is selected from yeast, bacteria or mold, etc.
Compared with the prior art, the invention has the following advantages:
(1) The corn and straw co-production improves the production strength of the ethanol, saves the time required by enzymolysis, improves the ethanol production efficiency, reduces the manpower and material resources required by production, and greatly reduces the cost.
(2) The method has less inhibitor generated in the pretreatment process, and obviously improves enzymolysis and fermentation efficiency.
(3) Compared with the lignocellulose ethanol technology, the technology of the invention not only greatly improves the production strength of ethanol, but also can produce high-quality DDGS rich in high-value xylo-oligosaccharide.
Drawings
Fig. 1 is a diagram of mixed fermentation results of a dilute acid pretreated straw hydrolysate and a corn liquefied solution according to different proportions, wherein the proportion of the corn straw hydrolysate to the corn liquefied solution is 1:2 (A), 1:3 (B), 1:4 (C), 0:1 (D).
Fig. 2 is a graph of the detection result of the content of xylooligosaccharide in DDGS obtained by the ratio of corn stalk hydrolysate to corn liquefier at 1:4.
Detailed Description
The invention is further described in detail below with reference to examples and figures.
Example 1
Influence of mixing straw hydrolysate and corn liquefied liquid according to different proportions on DDGS quality of product
1. Obtaining straw hydrolysate. 10% of straw (wt/wt) and 1% of dilute sulfuric acid (wt/wt) are put into a 2L reaction kettle, the reaction kettle is raised to 160 ℃, the temperature is reduced after the reaction kettle is maintained for 10min, and the obtained product is put into an oven (60 ℃) to be dried until the moisture content is between 10 and 20 percent. Placing the straw treated by dilute acid into a conical flask, adding cellulase and xylanase according to 22% of dry matter (wt/wt), wherein the proportion of the cellulase to the xylanase is 7:3, regulating ph to 4.0-7.0, placing into a shaking table at 50 ℃ and 250rpm for enzymolysis, separating solid from liquid by a centrifugal machine after the enzymolysis is finished, and taking supernatant after centrifugation as hydrolysate of the straw.
2. Obtaining the corn liquefied liquid. Preparing a corn liquefied solution with a substrate concentration of 30%, placing sterile water into a conical flask, adding alpha-amylase and corn flour, shaking uniformly, adjusting ph to 5.7, placing into a water bath, and preserving heat for 4 hours at 85 ℃ to obtain the corn liquefied solution.
3. And (5) mixing and fermenting. Mixing the corn liquefied liquid and the hydrolysis liquid of the straw according to different proportions. Mixing the corn liquefied liquid and the straw hydrolysate according to the proportion of 1:2,1:3,1:4 and 0:1, inoculating yeast, and putting into a shaking table at 30 ℃ for fermentation at 150 rpm. And obtaining the fuel ethanol and DDGS products after fermentation.
Detection of DDGS. And distilling the mixture obtained by fermentation to obtain four different DDGS, drying the DDGS, and comparing the colors of the DDGS, wherein the DDGS quality is obviously higher than that of the other two DDGS when the ratio of the straw hydrolysate to the corn liquefied liquid is 1:3 and 1:4.
The influence of different proportions of straw hydrolysate and corn liquefied liquid on fermentation is studied. And (3) carrying out dilute acid pretreatment on the straws, and mixing the hydrolysis liquid with the corn liquefaction liquid to carry out the mixing proportion of fermentation experiments. The results of the experiment are shown in FIG. 1 and Table 1, and the fermentation was completed within 72 hours at all mixing ratios (FIG. 1). When the ratio of the corn stalk hydrolysate to the corn liquefied liquid is 1:4, the final ethanol concentration reached 118.80g/L (FIG. 2). Corn stalk hydrolysate and corn liquefier in the ratio of 1:2, the final ethanol concentration was 104.89g/L. As can be seen from table 1, the production intensity of ethanol is different in different ratios, and the method of combining the corn fuel ethanol technology and the lignocellulose fuel ethanol technology improves the production intensity of ethanol in comparison with the lignocellulose ethanol technology, and the quality color of DDGS obtained according to different ratios is shown in fig. 2, wherein the color of DDGS obtained by 1:3 and 1:4 accords with the national standard. Compared with the corn fuel ethanol technology, the mixed fermentation method is rich in xylo-oligosaccharide, and the quality of DDGS is improved.
TABLE 1 data obtained when mixed fermentation of dilute acid pretreated straw hydrolysate and corn steep liquor was performed for 96 hours
Figure GDA0004146859090000031
In summary, the mixture of corn stalks and corn treated with dilute acid has excellent fermentation performance, and the ethanol productivity reaches more than 1.94g/L/h in 48 hours. The mixture of corn and dilute acid pretreated corn stover achieves better fermentation performance than dilute acid pretreated corn stover alone. Fig. 2 shows DDGS produced from different ratios of straw hydrolysate to corn liquefier. The ratio of the straw hydrolysate to the corn liquefied liquid is 1:3 and 1:4, the DDGS obtained by the method has higher quality, wherein the ratio of the straw hydrolysate to the corn liquefied liquid is 1: the content of xylo-oligosaccharide in the DDGS produced in the process of the invention is 10859.32mg/kg, the total phosphorus content is 0.62%, the crude ash content is 12.5%, the crude protein content is 19.3%, and other indexes all meet the national standard, which indicates that the DDGS produced by the process of the invention is a qualified high-quality DDGS with xylo-oligosaccharide.

Claims (4)

1. The process for co-producing fuel ethanol and DDGS by using straw and corn is characterized by comprising the following specific steps:
step 1, carrying out acidic pretreatment on crushed straws, and drying to obtain pretreated straws;
step 2, adding cellulase, xylanase and water into the pretreated straw according to the dry matter concentration of 22%, wherein the proportion of the cellulase to the xylanase is 7:3, regulating the pH to the optimal pH range of the enzyme, hydrolyzing, and centrifuging to obtain straw hydrolysate;
step 3, adding alpha-amylase into the corn flour, adjusting the pH to 4.0-7.0, and liquefying to obtain corn liquefied liquid;
step 4, the mass ratio of the straw to the corn flour is 1: 3-4, mixing the straw hydrolysate with the corn liquefied liquid, regulating the pH to the optimal pH range of the yeast, adding the yeast, and fermenting to obtain the fuel ethanol and the DDGS.
2. The process according to claim 1, wherein in step 1, the straw is selected from one or more of wheat straw, corn straw, rice straw, sorghum straw, soybean straw.
3. The process of claim 1, wherein in step 2, the pH is 3.0 to 10.0.
4. The process of claim 1 wherein in step 3, the liquefaction temperature is 85 ℃.
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CN110468161B (en) * 2019-08-08 2021-05-04 国投生物科技投资有限公司 Application of corn and rice in wheat ethanol fermentation process and method for producing ethanol by fermenting raw materials by using mixed raw materials
CN114807245A (en) * 2021-01-18 2022-07-29 中国石油天然气股份有限公司 Method for improving DDGS quality in corn ethanol process through secondary fermentation of vinasse
CN114794308A (en) * 2021-01-18 2022-07-29 中国石油天然气股份有限公司 Method for improving DDGS color in corn ethanol process based on vinasse pH regulation

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