CN105255956A - Method for removing fermentation inhibitor from straw hydrolysate - Google Patents
Method for removing fermentation inhibitor from straw hydrolysate Download PDFInfo
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- CN105255956A CN105255956A CN201510649653.7A CN201510649653A CN105255956A CN 105255956 A CN105255956 A CN 105255956A CN 201510649653 A CN201510649653 A CN 201510649653A CN 105255956 A CN105255956 A CN 105255956A
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Abstract
The invention discloses a method for removing a fermentation inhibitor from straw hydrolysate. At first, CaO is utilized for adjusting the pH value of the hydrolysate to be 3.0-7.0; then activated carbon and organic modified attapulgite are mixed according to the mass ratio of 3:1-1:3, and adsorb and treat the straw hydrolysate with the mass accounting for 0.5-3.0% of the mass of the hydrolysate; after detoxification treatment is finished, the mixture is cooled to normal temperature, and solid and liquid separation is carried out. According to the method, less activated carbon is used, the organic modified attapulgite low in cost is used, and the detoxification cost of the straw hydrolysate is reduced; meanwhile, content of the phenols inhibitor, hydroxymethyl furfural and furfural is greatly reduced, coordinate repression of the follow-up microorganism fermentation inhibitor is weakened, the fermenting property of carbohydrates in the straw hydrolysate is improved, and a new way is provided for reducing the detoxification cost of the straw hydrolysate.
Description
Technical field
The invention belongs to straw lignocellulose raw material comprehensive development and utilization field, be specifically related to a kind of method of gac and recessed native complex treatment stalk hydrolyzed solution fermentation inhibitor.
Background technology
Along with traditional fossil energy is day by day exhausted, problem of environmental pollution increasingly sharpens, and people focus on sight on new and renewable sources of energy gradually.Lignocellulose-like biomass resource has the outstanding advantages such as source is wide, quantity is large, renewable, becomes study hotspot.China, as traditional large agricultural country, has abundant straw lignocellulose biomass; The universal way of vast Rural areas process agricultural wastes straw is directly burned by stalk, and not only utilising efficiency is low, and contaminate environment, the harm eubiosis.Lignocellulose material mainly comprises Mierocrystalline cellulose, hemicellulose and xylogen.Mierocrystalline cellulose is the crystalline structure of queueing discipline, forms primarily of glucose polymerisation, and hemicellulose is polymerized primarily of wood sugar, pectinose and seminose.By hydrolysis, Mierocrystalline cellulose and hemicellulose can discharge sugar unit, most of microbe can the sugar unit such as these glucose of metabolism, wood sugar, pectinose and seminose, converts it into important Chemicals as microbial oil, bacteria cellulose, butanols, ethanol, hydrogen, biogas etc.Biochemical conversion method utilizes lignocellulose to become the important subject of technical field of biomass chemical engineering.Under acid hydrolysis conditions, the hemicellulose in stalk and cellulose hydrolysis can obtain pentose and hexose, and the xylogen in stalk DeR then can occur and obtains complicated phenolic compound (Vanillin, syringic aldehyde etc.); Can be there is degraded to a certain degree in pentose and hexose simultaneously, produces many fermentation inhibitors, mainly include machine acids (formic acid, acetic acid, levulinic acid etc.), the large class of aldehydes (5 hydroxymethyl furfural, furfural etc.) two.The existence of these by products, has strong restraining effect for follow-up biological fermentation.
Summary of the invention
The object of the invention is to: provide a kind of stalk hydrolyzed solution to remove the method for fermentation inhibitor, gac and the composite hydrolyzed solution to preparing of organically-modified recessed soil carry out detoxification treatment, remove most fermentation inhibitor, the hydrolyzed solution obtained, as the fermention medium of microorganism growth, provides a feasible approach for reducing fermentable cost.
Technical solution of the present invention is that the method that this stalk hydrolyzed solution removes fermentation inhibitor comprises the following steps:
(1) utilize CaO that stalk hydrolyzed solution pH before treatment is adjusted to 3.0-7.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation;
(2) weigh gac and organically-modified recessed soil, mixing, its mixing quality is than being 3:1 ~ 1:3; Wherein, organically-modified recessed soil adopts octadecyl trimethyl ammonium chloride to carry out modification;
(3) the stalk hydrolyzed solution after step (1) process is got, the mixture of gac/organically-modified recessed soil adds in hydrolyzed solution with 0.5% ~ 3.0% of hydrolyzed solution quality, being placed in temperature is that the water bath with thermostatic control shaking table of 25 ° of C ~ 80 ° C carries out absorption detoxification, and the detoxification time is 0.5h ~ 3h;
(4) after detoxification treatment completes, normal temperature is cooled to, solid-liquid separation.
Wherein, in handled stalk hydrolyzed solution, stalk is the one in wheat stalk, bagasse, maize straw, straw.
Advantage of the present invention is: carry out detoxification treatment to stalk hydrolyzed solution, remove most fermentation inhibitor, decrease the content of cellulose biomass dilute acid hydrolysis by product, little to the glucide loss in stalk hydrolyzed solution, the hydrolyzed solution obtained is as the fermention medium of microorganism growth, shorten fermentation period, improve fermentation efficiency, reduce stalk hydrolyzed solution detoxification cost and fermentable cost.
Accompanying drawing explanation
Fig. 1 is the impact of different detoxification order on wheat-straw hydrolyzed solution detoxification efficiency.
Embodiment
Further illustrate technical solution of the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as it is restriction to technical scheme.
embodiment 1:utilize CaO that wheat stalk hydrolyzed solution pH before treatment is adjusted to 5.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 1:1; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 1.0% of hydrolyzed solution quality, temperature 50 ° of C adsorb 1h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 61.5%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 92.3%, formic acid, acetic acid and levulinic acid clearance are respectively 9.4%, 8.6% and 9.3%, HMF and furfural clearance is respectively 10.0% and 13.6%.
embodiment 2:utilize CaO that corn stalk hydrolysis pH before treatment is adjusted to 3.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 3:1; Measure 40g hydrolyzed solution, gac and organically-modified recessed earth mixtures are added in stalk hydrolyzed solution, be placed in water-bath with 0.5% of hydrolyzed solution quality, temperature 25 ° of C adsorb 3h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 30.1%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 93.4%, formic acid, acetic acid and levulinic acid clearance are respectively 6.8%, 4.6% and 7.2%, HMF and furfural clearance is respectively 5.1% and 6.9%.
embodiment 3:utilize CaO that bagasse hydrolyzed solution pH before treatment is adjusted to 7.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and the recessed soil of Organic, mix with mass ratio 1:3; Measure 40g hydrolyzed solution, gac and organically-modified recessed earth mixtures are added in stalk hydrolyzed solution, be placed in water-bath with 3.0% of hydrolyzed solution quality, temperature 80 ° of C adsorb 0.5h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 80.4%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 88.2%, formic acid, acetic acid and levulinic acid clearance are respectively 12.5%, 15.4% and 18.1%, HMF and furfural clearance is respectively 19.2% and 30.7%.
embodiment 4:utilize CaO that bagasse hydrolyzed solution pH before treatment is adjusted to 5.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 1:2; Measure 40g hydrolyzed solution, gac and organically-modified recessed earth mixtures are added in stalk hydrolyzed solution, be placed in water-bath with 1.4% of hydrolyzed solution quality, temperature 55 ° of C adsorb 1h; Normal temperature is cooled to, solid-liquid separation after having adsorbed.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 60.9%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 95.2%, formic acid, acetic acid and levulinic acid clearance are respectively 1.8%, 6.5% and 7.2%, HMF and furfural clearance is respectively 8.3% and 17.8%.
embodiment 5:utilize CaO that straw hydrolyzed solution pH before treatment is adjusted to 6.3, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 2:1; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 1.8% of hydrolyzed solution quality, temperature 50 ° of C adsorb 1h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 89.1%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 95.4%, formic acid, acetic acid and levulinic acid clearance are respectively 17.9%, 5.4% and 7.1%, HMF and furfural clearance is respectively 26.1% and 5.3%.
embodiment 6:utilize CaO that straw hydrolyzed solution pH before treatment is adjusted to 5.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 1:1; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 2.2% of hydrolyzed solution quality, temperature 45 ° of C adsorb 1.5h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 82.3%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 97.2%, formic acid, acetic acid and levulinic acid clearance are respectively 4.1%, 6.5% and 7.9%, HMF and furfural clearance is respectively 19.9% and 28.6%.
embodiment 7:utilize CaO that corn stalk hydrolysis pH before treatment is adjusted to 5.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 1:1; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 0.5% of hydrolyzed solution quality, temperature 50 ° of C adsorb 2.5h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 18.6%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 98.5%, formic acid, acetic acid and levulinic acid clearance are respectively 1.4%, 3.7% and 4.3%, HMF and furfural clearance is respectively 4.0% and 6.6%.
embodiment 8:utilize CaO that corn stalk hydrolysis pH before treatment is adjusted to 5.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 1:3; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 2.0% of hydrolyzed solution quality, temperature 50 ° of C adsorb 1h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 81.5%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 91.1%, formic acid, acetic acid and levulinic acid clearance are respectively 8.4%, 8.6% and 10.9%, HMF and furfural clearance is respectively 22.7% and 31.2%.
embodiment 9:utilize CaO that wheat stalk hydrolyzed solution pH before treatment is adjusted to 6.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 2:1; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 2.2% of hydrolyzed solution quality, temperature 55 ° of C adsorb 1.5h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 95.2%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 89.5, formic acid, acetic acid and levulinic acid clearance are respectively 10.9%, 15.0% and 18.3%, HMF and furfural clearance is respectively 39.8% and 27.6%.
embodiment 10:utilize CaO that wheat stalk hydrolyzed solution pH before treatment is adjusted to 3.8, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Weigh gac and organically-modified recessed soil, mix with mass ratio 1:2; Measure 40g hydrolyzed solution, added in stalk hydrolyzed solution by the mixture of gac and organically-modified recessed soil, be placed in water-bath with 1.8% of hydrolyzed solution quality, temperature 50 ° of C adsorb 1h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilizing ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate is 61.5%, the liquid chromatography for measuring total reducing sugar rate of recovery is utilized to be 91.6%, formic acid, acetic acid and levulinic acid clearance are respectively 15.8%, 12.9% and 12.3%, HMF and furfural clearance is respectively 16.5% and 43.4%.
embodiment 11:utilize CaO that straw hydrolyzed solution pH before treatment is adjusted to 3.8, staticly settle rear vacuum filtration method and carry out solid-liquid separation; Gac and organically-modified recessed soil is weighed with mass ratio 1:2; Measure 40g hydrolyzed solution, gac/organically-modified recessed soil is 1.8% of hydrolyzed solution quality, according to: add organically-modified recessed soil after 1. first adding gac, 2. gac is added after first adding organically-modified recessed soil, 3. add organically-modified recessed soil and gac simultaneously, three kinds of orders add in stalk hydrolyzed solution, are placed in water-bath, and temperature 50 ° of C adsorb 1h; After having adsorbed, be cooled to normal temperature, solid-liquid separation.
Utilize ultraviolet-visible spectrophotometer to measure hydrolyzate decolorizing rate and be respectively 77.5%, 75.6% and 74.0%, utilize the liquid chromatography for measuring total reducing sugar rate of recovery, formic acid, acetic acid and levulinic acid clearance, HMF and furfural clearance are shown in Fig. 1.
Claims (3)
1. stalk hydrolyzed solution removes the method for fermentation inhibitor, it is characterized in that this removal methods comprises the following steps:
(1) utilize CaO that stalk hydrolyzed solution pH before treatment is adjusted to 3.0-7.0, staticly settle rear vacuum filtration method and carry out solid-liquid separation;
(2) weigh gac and organically-modified recessed soil, mixing, its mixing quality is than being 3:1 ~ 1:3; Wherein, organically-modified recessed soil adopts octadecyl trimethyl ammonium chloride to carry out modification;
(3) hydrolyzed solution after step (1) process is got, the mixture of gac/organically-modified recessed soil adds in hydrolyzed solution with 0.5% ~ 3.0% of hydrolyzed solution quality, being placed in temperature is that the water bath with thermostatic control shaking table of 25 ° of C ~ 80 ° C carries out absorption detoxification, and the detoxification time is 0.5h ~ 3h;
After detoxification treatment completes, be cooled to normal temperature, solid-liquid separation.
2. stalk hydrolyzed solution according to claim 1 removes the method for fermentation inhibitor, it is characterized in that: in handled stalk hydrolyzed solution, stalk is the one in wheat stalk, bagasse, maize straw, straw.
3. stalk hydrolyzed solution according to claim 1 removes the method for fermentation inhibitor, it is characterized in that: carry out solid-liquid separation after detoxification completes, and separation method is the one in centrifugal, vacuum filtration, filter press.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801633A (en) * | 2016-03-25 | 2016-07-27 | 中国科学院大学 | Method for detoxifying cellulosic pyrolysate hydrolysate |
| CN108821467A (en) * | 2018-05-29 | 2018-11-16 | 中科院广州能源所盱眙凹土研发中心 | The purified treatment and circulation utilization method of alcohol fermentation wastewater |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1377874A (en) * | 2002-04-12 | 2002-11-06 | 浙江大学 | Process for preparing sorbic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1377874A (en) * | 2002-04-12 | 2002-11-06 | 浙江大学 | Process for preparing sorbic acid |
Non-Patent Citations (3)
| Title |
|---|
| 张良等: "凹凸棒土有机表面改性的工艺研究", 《江苏工业学院学报》 * |
| 彭芬等: "凹凸棒土热改性对玉米秸秆稀酸水解液脱色的研究", 《应用化工》 * |
| 葛菁萍等: "活性炭对玉米芯半纤维素稀硫酸水解液的脱毒效果", 《微生物学通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801633A (en) * | 2016-03-25 | 2016-07-27 | 中国科学院大学 | Method for detoxifying cellulosic pyrolysate hydrolysate |
| CN108821467A (en) * | 2018-05-29 | 2018-11-16 | 中科院广州能源所盱眙凹土研发中心 | The purified treatment and circulation utilization method of alcohol fermentation wastewater |
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