CN106520845B - Surfactant recovery technology in lignocellulose synchronous saccharification and fermentation process - Google Patents
Surfactant recovery technology in lignocellulose synchronous saccharification and fermentation process Download PDFInfo
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- CN106520845B CN106520845B CN201510586230.5A CN201510586230A CN106520845B CN 106520845 B CN106520845 B CN 106520845B CN 201510586230 A CN201510586230 A CN 201510586230A CN 106520845 B CN106520845 B CN 106520845B
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention provides a surfactant recovery technology in a lignocellulose synchronous saccharification and fermentation process, and belongs to the field of fuel ethanol production through biomass degradation and fermentation. The technology comprises the steps of carrying out acidolysis, steam explosion pretreatment on lignocellulose, directly adding a surfactant and a buffer solution without detoxification for carrying out enzymolysis, and then inoculating saccharomyces cerevisiae for ethanol fermentation; after fermentation, ethanol is distilled, and simultaneously, enrichment of a surfactant, a fermentation inhibitor and a buffering agent is realized; the coupling separation and recovery of the surfactant, the buffering agent and the fermentation inhibitor are realized by extracting the fermentation inhibitor. The invention has the advantages that: the recovered surfactant and the fermentation inhibitor can be reused, so that the pollution is reduced, and the cost is effectively reduced; the recovered toxicity inhibitor can also be used for preparing high-value chemicals through chemical conversion, so that the atom utilization rate in the biomass conversion process is improved. In a word, the surfactant recycling technology in the synchronous saccharification and fermentation process of lignocellulose further promotes the industrialization process of cellulosic ethanol.
Description
Technical Field
The invention relates to the field of producing fuel ethanol by biomass raw material degradation through a fermentation process, in particular to a surfactant recovery technology in a lignocellulose synchronous saccharification and fermentation process.
Background
Lignocellulose is the most abundant biomass resource in the world, and the production of fuel ethanol by using lignocellulose as a raw material not only can effectively relieve the energy crisis and reduce the environmental pollution, but also meets the sustainable development target of large-scale petroleum substitution of fuel ethanol in the future, and has great economic value and social significance. Currently, the Simultaneous saccharification and fermentation (SSCF) process of lignocellulose is widely used for the production of cellulosic ethanol. However, the lignocellulose for producing the fuel ethanol must be pretreated, and the lignocellulose is partially degraded under the conditions of high temperature, high pressure and the like in the pretreatment process, so that various organic acids, furans, phenols and other compounds are released. The compounds have obvious inhibiting effect on the activity of cellulase and the growth and fermentation of saccharomycetes in the enzymolysis process, so that the cellulase and the saccharomyces cerevisiae cannot work normally and become a main obstacle for producing cellulosic ethanol. According to the laboratory, a nonionic surfactant is added in the synchronous saccharification and fermentation process of the lignocellulose raw material for in-situ detoxification, the fermentation strain is subjected to chemical external protection while ethanol fermentation is carried out, and the tolerance of yeast cells to a fermentation inhibitor is improved, so that the cellulose ethanol fermentation efficiency is improved (CN 201410668100.1).
However, in the ethanol separation process, the discharge of wastewater containing nonionic surfactant and fermentation inhibitor causes environmental pollution; the surfactant is fine chemical, the toxicity inhibitor can also be used for preparing high-value chemical through chemical conversion, and the recovered surfactant and the fermentation inhibitor can not only reduce pollution, but also effectively reduce cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a surfactant recovery technology in a lignocellulose synchronous saccharification and fermentation process.
The invention provides a surfactant recovery technology in a lignocellulose synchronous saccharification and fermentation process, which is basically characterized in that firstly, solid-liquid separation is carried out on fermentation liquor; then distilling the supernatant to separate ethanol and simultaneously realizing enrichment of the surfactant and the fermentation inhibitor; and finally, the fermentation inhibitor is extracted by an organic solvent to realize the coupling separation and recovery of the surfactant and the fermentation inhibitor.
The recovered surfactant and buffer can be directly used in the next fermentation process, and the fermentation inhibitor is extracted and collected for preparing high-value chemicals by chemical conversion.
A technology for recovering surfactant in a lignocellulose synchronous saccharification and fermentation process comprises the following specific steps: taking pretreated lignocellulose as a raw material, directly adding a surfactant, cellulase and a buffer solution, and carrying out enzymolysis at high temperature; then reducing the temperature, inoculating saccharomyces cerevisiae, performing solid-liquid separation after ethanol fermentation, and evaporating supernatant to enrich the surfactant, the fermentation inhibitor and the buffer; and then the coupling separation and recovery of the fermentation inhibitor surfactant, the buffering agent and the fermentation inhibitor are realized through the extraction of an organic solvent.
In the fermentation system: the solid-to-liquid ratio of the pretreated lignocellulose to the buffer solution is 0.1-0.3 g/mL; the concentration of the water-soluble surfactant is 0-0.4 g/mL; the addition amount of the cellulase is 10-30FPU/g raw material; the cell concentration of the saccharomyces cerevisiae is as follows: 0.1*108-1.0*108Per mL;
the pre-enzymolysis temperature is 45-60 ℃, and the pre-enzymolysis time is 2-48 hours; the temperature for synchronous saccharification and ethanol fermentation production is 30-39 ℃; the synchronous saccharification and ethanol fermentation time is 16-96 hours at 150-300 rpm.
The surfactant is subjected to coupling separation and recovery, namely the enrichment of the surfactant, a fermentation inhibitor and a buffering agent is simultaneously realized in the process of distilling ethanol after the solid-liquid separation is carried out on the fermentation liquor; and then the coupling separation and recovery of the surfactant, the buffering agent and the fermentation inhibitor are completed by extracting the fermentation inhibitor by the organic solvent.
The distillation temperature is 30-100 ℃, the distillation pressure is-0.01 MPa to-0.1 MPa, and the distillation time is 10 minutes to 120 minutes.
The lignocellulose is selected from agricultural wastes, forestry wastes, special energy crops or/and various wastes containing cellulose;
the agricultural wastes are wheat straws, corn straws or/and rice straws;
the forestry waste is branches and leaves generated by felling, waste wood or/and wood chips;
the special energy crops are sweet sorghum or/and willow branches;
the various cellulose-containing wastes are municipal solid waste, waste paper or/and bagasse.
The surfactant is at least one of polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polydimethylsiloxane and Tween; preferably polyethylene glycol.
The molecular weight of the surfactant polyethylene glycol is 200-; preferably 200-.
The organic solvent is as follows: benzene, toluene, diethyl ether, ethyl acetate, n-butyl ether, petroleum ether, dimethyl sulfoxide or methyl isobutyl ketone.
The pH value of the buffer solution is 4.0-5.5, and the pH buffer solution is as follows: acetic acid-sodium acetate, citric acid-sodium citrate, phosphoric acid-sodium phosphate and sulfuric acid solution.
Compared with the prior art, the method for recovering the surfactant in the synchronous saccharification and fermentation process of the lignocellulose, provided by the invention, has the following advantages: the invention synchronously realizes the enrichment of the surfactant, the buffer and the yeast cells in the process of separating the ethanol without increasing any additional energy consumption; then the enriched surfactant is extracted to realize the coupling separation and recovery of the surfactant, the buffer and the fermentation inhibitor. The fermentation inhibitor can be used for producing high-value chemicals, and further improves the atom utilization rate of the lignocellulose raw material. In conclusion, the recovery technology of the surfactant in the cellulose production process further promotes the industrialization process of the cellulose ethanol, and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a surfactant, yeast, buffer coupled cycle.
FIG. 2 surfactant, yeast, buffer coupled cycle.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited by the embodiments, and the following embodiments and descriptions are only illustrative of the principle of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
In addition, in the following examples, the content of each component in the fermentation broth was measured by using a high performance liquid chromatograph (Agilent 1260), and the conversion rate and ethanol yield were calculated from the amount of the substrate charged, and the ethanol concentration was calculated from the mass of ethanol in the fermentation broth, the volume of activated water and pH liquid.
The chromatographic conditions are as follows: an ion exchange column with a column temperature of 65 ℃, a parallax refraction detector and a detector of 50 ℃; mobile phase: 5Mm H2SO4The flow rate was 0.6ml/min, and the amount of sample was 25 uL.
The specific surfactant recovery process can be seen in figure 1. Examples are shown below.
Example 1
Mixing the pretreated fast-growing poplar powderMixing 1.5g as substrate, 0.2g/ml PEG-1000, 12ml buffer solution, and cellulase 20FPU/g raw material, performing enzymolysis at 50 deg.C for 24 hr, cooling to 33 deg.C, and adding Saccharomyces cerevisiae to maintain cell concentration of 0.8 x 108SSF fermentation was carried out for 72 hours/mL. Performing solid-liquid separation after fermentation, distilling the supernatant, extracting, and distilling the residual liquid to obtain surfactant and buffer which can be directly used in the next fermentation process (see figure 1). The results of 4 cycles of PEG-1000 are shown in FIG. 2. As can be seen from the figure, PEG-1000 can be recycled, ethanol concentration is basically constant.
Example 2
The experimental procedure is the same as that of example 1, except that PEG-200 is used, and the ethanol concentration is shown in Table 1. it can be seen from the table that PEG-200 can be recycled.
TABLE 1 ethanol concentration data
| PEG-200 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 17.0 | 18.25 | 16.20 | 15.08 |
Example 3
The experimental procedure was the same as in example 1, except that 0.2g/ml PEG-400 was added, and the ethanol concentration is shown in Table 2. it can be seen from the table that PEG-400 can be recovered and reused.
TABLE 2 ethanol concentration data
| PEG-400 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 21.20 | 20.35 | 18.51 | 19.68 |
Example 4
The experimental procedure is the same as that of example 1, except that the pre-enzymolysis is carried out at 50 ℃ for 4 hours, and the ethanol concentration is shown in Table 3. it can be seen from the table that PEG-1000 can be recycled.
TABLE 3 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 14.02 | 13.90 | 15.83 | 12.30 |
Example 5
The experimental procedure is the same as that of example 1, except that the pre-enzymolysis is carried out at 50 ℃ for 48 hours, and the ethanol concentration is shown in Table 4.
TABLE 4 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 26.80 | 25.89 | 26.12 | 24.88 |
Example 6
The experimental procedure is the same as that of example 1, except that the pre-enzymolysis is carried out at 45 ℃ and the ethanol concentration is shown in Table 5.
TABLE 5 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 15.02 | 14.80 | 13.83 | 14.60 |
Example 7
The experimental procedure is the same as that of example 1, except that the pre-enzymolysis is carried out at 60 ℃, and the ethanol concentration is shown in Table 6.
TABLE 6 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 14.02 | 13.50 | 14.63 | 13.82 |
Example 8
The experimental procedure was the same as in example 1, except that the cellulase concentration was 30FPU/g lignocellulose and the ethanol concentration was shown in Table 7. it can be seen from the table that PEG-1000 can be recovered and reused.
TABLE 7 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 28.30 | 27.89 | 26.12 | 27.43 |
Example 9
The experimental procedure was the same as in example 1, except that the cellulase was 10FPU/g lignocellulose and the ethanol concentration was as shown in Table 8. it can be seen from the Table that PEG-1000 could be recovered and reused.
TABLE 8 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 15.02 | 14.80 | 13.83 | 14.38 |
Example 10
The experimental procedure was the same as in example 1, except that the fermentation time was 48 hours, and the ethanol concentration was shown in Table 9. it can be seen from the table that PEG-1000 can be recovered and reused.
TABLE 9 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 11.02 | 11.90 | 10.83 | 11.28 |
Example 11
The experimental procedure was the same as in example 1, except that the fermentation time was 96 hours, and the ethanol concentration was shown in Table 10. it can be seen from the table that PEG-1000 can be recovered and reused.
TABLE 10 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 21.12 | 20.50 | 18.22 | 19.78 |
Example 12
The experimental procedure was the same as in example 1, except that Saccharomyces cerevisiae was added to maintain the cell concentration at 0.1 x 108The ethanol concentration is shown in Table 11 when the fermentation time is 96 hours per mL, and it can be seen from the table that PEG-1000 can be recovered and reused.
TABLE 11 ethanol concentration data
| PEG-200 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 10.02 | 9.90 | 9.83 | 10.22 |
Example 13
The experimental procedure was the same as in example 1, except that Saccharomyces cerevisiae was added to maintain the cell concentration at 1.0 x 108The ethanol concentration is shown in Table 12 when the fermentation time is 96 hours per mL, and it can be seen from the table that PEG-1000 can be recovered and reused.
TABLE 12 ethanol concentration data
| PEG-1000 | Fresh and | Cycle | 1 | |
|
| Ethanol concentration [ g/l] | 20.12 | 21.28 | 19.22 | 18.78 |
Examples 14 to 17
The experimental procedure is the same as that of example 1, except that the concentration of PEG-1000 is different, and the ethanol concentration is shown in Table 13. it can be seen from the table that PEG-1000 can be recycled.
TABLE 13 ethanol concentration data
| Examples | PEG-1000[g/ml] | Fresh and | Cycle | 1 | |
|
| 14 | 0.05 | 8.12 | 9.08 | 7.99 | 8.53 | |
| 15 | 0.10 | 11.88 | 12.23 | 11.79 | 12.02 | |
| 17 | 0.15 | 20.12 | 21.28 | 19.22 | 18.78 |
Examples 18 to 20
The experimental procedure was the same as in example 1, except that different surfactants were added, and the ethanol concentration is shown in Table 14.
TABLE 14 ethanol concentration data
| Examples | Surface active agent | Fresh and | Cycle | 1 | |
|
| 18 | PEG-2000 | 20.12 | 21.28 | 19.22 | 18.78 | |
| 19 | Polyethylene glycol monomethyl ether | 8.32 | 8.08 | 8.99 | 7.53 | |
| 20 | Polyethylene glycol dimethyl ether | 7.12 | 7.08 | 7.09 | 8.12 |
Claims (10)
1. A method for recovering surfactant in a lignocellulose synchronous saccharification and fermentation process is characterized by comprising the following steps: taking pretreated lignocellulose as a substrate, directly adding a surfactant, cellulase and a buffer solution for carrying out pre-enzymolysis without detoxification treatment, then adding saccharomyces cerevisiae for carrying out synchronous diastatic fermentation, and simultaneously realizing enrichment of the surfactant, a fermentation inhibitor and a buffer agent in the process of distilling ethanol after carrying out solid-liquid separation on fermentation liquor; then the coupling separation and recovery of the surfactant, the buffering agent and the fermentation inhibitor are completed by extracting the fermentation inhibitor by an organic solvent;
the surfactant is at least one of polyethylene glycol, polyethylene glycol monomethyl ether and polyethylene glycol dimethyl ether;
in the fermentation system: the solid-to-liquid ratio of the pretreated lignocellulose to the buffer solution is (0.1-0.3) g: 1 mL; the addition amount of the cellulase is 10-30FPU/g raw material; the cell concentration of the saccharomyces cerevisiae is as follows: 0.5X 108-1.8×108Per mL; the concentration of the surfactant is 0.05-0.4 g/mL;
the pre-enzymolysis temperature is 45-60 ℃, and the pre-enzymolysis time is 2-48 hours; the temperature for synchronous saccharification and ethanol fermentation production is 30-39 ℃; the time for simultaneous saccharification and ethanol fermentation is 16-96 hours, 150-.
2. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 1, wherein: the distillation temperature is 30-100 ℃, the distillation pressure is-0.01 MPa to-0.1 MPa, and the distillation time is 10 minutes to 120 minutes.
3. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 1, wherein: the lignocellulose is selected from agricultural wastes, forestry wastes, special energy crops, municipal solid wastes, waste paper or/and bagasse.
4. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 3, wherein: the agricultural waste is wheat straw, corn straw or/and rice straw.
5. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 3, wherein: the forestry waste is branches and leaves generated by felling, waste wood or/and wood chips.
6. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 3, wherein: the special energy crops are sweet sorghum or/and willow branches.
7. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 1, wherein: the molecular weight of the surfactant polyethylene glycol is 200-8000.
8. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 1, wherein: the molecular weight of the surfactant polyethylene glycol is 200-2000.
9. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 1, wherein: the organic solvent is as follows: benzene, toluene, diethyl ether, ethyl acetate, n-butyl ether, petroleum ether, dimethyl sulfoxide or methyl isobutyl ketone.
10. The method for recovering the surfactant in the simultaneous saccharification and fermentation process of lignocellulose as recited in claim 1, wherein: the pH value of the buffer solution is 4.0-5.5; the buffer solution is acetic acid-sodium acetate, citric acid-sodium citrate or phosphoric acid-sodium phosphate.
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| CN102154381A (en) * | 2010-12-17 | 2011-08-17 | 清华大学 | Method for joint production of ethanol and microbial lipid by using methyl cellulose as raw material |
| CN103255185A (en) * | 2012-02-21 | 2013-08-21 | 华东理工大学 | Method for producing microbial oil through lignocellulose simultaneous saccharification and fermentation, and for recycling cellulase |
| CN103923949A (en) * | 2014-03-13 | 2014-07-16 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method and apparatus for producing ethanol through synchronous saccharification and fermentation of lignocellulose |
| CN104846033A (en) * | 2015-05-14 | 2015-08-19 | 天津大学 | Method for preparing bioethanol by recovering and reusing resistant cellulase of coupling surface active agents of recombinant bacteria |
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| CN102154381A (en) * | 2010-12-17 | 2011-08-17 | 清华大学 | Method for joint production of ethanol and microbial lipid by using methyl cellulose as raw material |
| CN103255185A (en) * | 2012-02-21 | 2013-08-21 | 华东理工大学 | Method for producing microbial oil through lignocellulose simultaneous saccharification and fermentation, and for recycling cellulase |
| CN103923949A (en) * | 2014-03-13 | 2014-07-16 | 中国石油集团东北炼化工程有限公司吉林设计院 | Method and apparatus for producing ethanol through synchronous saccharification and fermentation of lignocellulose |
| CN104846033A (en) * | 2015-05-14 | 2015-08-19 | 天津大学 | Method for preparing bioethanol by recovering and reusing resistant cellulase of coupling surface active agents of recombinant bacteria |
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