CN109402196A - A method of biological liquid fuel is produced using biomass - Google Patents
A method of biological liquid fuel is produced using biomass Download PDFInfo
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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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- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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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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Abstract
The present invention provides a kind of methods using biomass production biological liquid fuel, while preparing high-concentration biological liquid fuel, can obtain the solid-state fertilizer or liquid fertilizer of high added value；The step of the method use, includes at least, sulphite or bisulfites are added in biomass material, heat temperature raising carries out boiling, material after boiling is separated by solid-liquid separation, liquid phase and cellulose-containing solid phase are obtained, auxiliary material is added in the liquid phase, form solid-state fertilizer or liquid fertilizer, enzyme preparation is added in cellulose-containing solid phase, production sugar is hydrolyzed, strain is accessed in liquid glucose and is fermented, biological liquid fuel is obtained.Method of the invention can be used for biological liquid fuel and organic fertilizer Joint Production, have broad application prospects.
Description
Technical field
The invention belongs to biological fields, and in particular to a method of biological liquid fuel is produced using biomass.
Background technique
Human society enters from 20th century using petroleum as main energy sources and the epoch of chemicals raw material, with industrial technology
Development and the improvement of people's living standards, automobile demand amount are consequently increased.Thus two serious problems: 1, petroleum are brought
For non-renewable energy resources, reserves are limited, and due to largely exploiting, consumption is too fast, faced the state of imbalance of supply and demand；2, petroleum is used
The serious destruction of environment, the especially carbon dioxide and particulate matter of oil combustion discharge are caused as fuel and chemicals raw material
Serious greenhouse effects and air pollution are resulted in, serious environment and social concern have been caused.Based on above-mentioned two o'clock, Ren Menzheng
Making great efforts to develop clean renewable new energy.Alcohol fuel is one of the clean energy resource by more and more concerns in recent years.
It is added in gasoline, can be improved the octane number of gasoline, dilute the toxic compounds such as Benzene In Gasoline and aromatic hydrocarbons, facilitate vapour
Oily full combustion significantly reduces air pollutant emission, is the renewable energy with great potential.
Traditional alcohol fuel (that is, first generation alcohol fuel) is main to produce mainly with the production of corn and other starches based raw material
Process route are as follows: raw material crushing-thinning-fermentation-distillation-ethyl alcohol-dehydration-denaturation-alcohol fuel.In the technique
Thinning concentration of substrate is more than 25%, even as high as 30%, and the concentration of alcohol in fermenting-ripening mash reaches 12-15% even more
Height, corresponding ethanol distillation energy consumption are lower (1.5-3 tons-steam/ton ethyl alcohol).Since concentration of alcohol is high and fermentation residue evaporation is solidifying
Liquid reuse keeps total water consume relatively low, and only 1.5-4 tons/ton ethyl alcohol, entire production process has the spy of significant clean energy resource
Point.Currently, Corn Fuel Ethanol is obtained going deep into development and be widely applied in the U.S., significant economic and social benefit is achieved.
However, corn alcohol there are problems that competing raw material with feeding grain in regular period and a given area, development is subject to certain restrictions.
Alcohol fuel (that is, second generation alcohol fuel) is produced with lignocellulosic materials such as stalks, can make full use of agricultural wastes,
It ensures national energy security, reduce environmental pollution and the wasting of resources, pull employment, farmers' income is improved, in recent years by extensive
Concern.
CN107446957A discloses a kind of alcohol fuel and preparation method thereof, wraps up fiber for lignin in stalk
Element is unfavorable for enzyme hydrolysis and fermentation process among them there is key is connected chemically, and reduces the conversion ratio that cellulose becomes ethyl alcohol
The problem of, but the concentration of alcohol that preparation method of the invention obtains only has 0.05mg/ml, it is low that ethyl alcohol produces concentration.
CN105060621B discloses a kind of method for strengthening biochemical treatment cellulose fuel ethanol waste water, and discloses every 1 ton of production
Cellulose fuel ethanol will generate about 25~35t industrial wastewater.It is high that cellulose fuel ethanol produces organic concentration in waste water.
CN104986855B discloses a kind of cellulose fuel ethanol waste water processing method, and it is raw to specifically disclose cellulose fuel ethanol
Sulfate and ammonia nitrogen concentration are high in waste water caused by during producing, 1 ton of cellulose fuel ethanol of every production, will generation about 25~
35t industrial wastewater, sulfate and ammonia nitrogen concentration are high in generated waste water in cellulose fuel ethanol production process, restrict significantly
The development of cellulose fuel ethanol industry.
Lignocellulosic structure is complicated, and degradation is difficult, it usually needs chemical reagent is added and is pre-processed, can produce accordingly
Raw a large amount of non-saccharide catabolite and mortifier, hinder subsequent enzymatic hydrolysis and fermentation efficiency.In existing preprocess method, diluted acid
Method (mainly sulfuric acid) is more commonly used engineering selection scheme.But dilute sulfuric acid meeting severe corrosion equipment in thermophilic digestion, makes
At security risk and increase plant investment and maintenance cost.Especially under the high temperature conditions, such as temperature is greater than 140 DEG C), metal
Corrosion rate will increase 10 times or more, substantially reduce the service life of material.Moreover, during the cooking process, as material is in hurricane band
It is pushed ahead under dynamic, friction is generated between stalk particle and metal inner surface, this can destroy the passivation protection film of metal inner surface, accelerate
Corrosion.In order to improve equipment life, can also be used the metals such as the stronger steel alloy of corrosion resistance, Hastelloy, but equipment at
This will be correspondingly improved 5-10 times, dramatically increase production cost, and industry is hard to carry on.
Secondly because lignocellulosic conversion ratio is lower, often make its COD high containing a large amount of undegradable organic matters in waste water
Up to 40000 or even 100000, sewage treatment difficulty is big.The use of sulfuric acid will cause sulfate radical in waste water concentration height again, generally all
Very big pressure is brought to wastewater treatment in 3000mg/l or more, high even more than 15000mg/l.Sulfate radical is in anaerobic condition
It is lower to be easy to be reduced into hydrogen sulfide by sulfate reducing bacteria；And hydrogen sulfide exists in water phase, can inhibit the life of anaerobic methanogens
Long, serious person also results in it and is poisoned to death, so that the removal efficiency of organic matter is decreased obviously, wastewater treatment difficulty and cost are big
It is big to improve.Due to needing to adjust pH value in enzymolysis process, ammonium hydroxide neutralization is generallyd use, to avoid soluble metal ion is introduced,
But this also results in that the ammonia-nitrogen content in waste water is excessively high, equally increases the difficulty of sewage treatment, dramatically increases operating cost,
It is less economical.
Further, since ligocellulose degradation's property is poor, usually used hydrolyzation system concentration of substrate is lower, generally 10-
15%, corresponding fermentation liquid concentration of alcohol is relatively low, generally 3-5% (v/v).So low concentration of alcohol proposes distillation
Steam consumption during taking is more than 6 ton/ton ethyl alcohol, and water consume is up to 25 ton/ton ethyl alcohol or more, with 1st generation cornstarch ethyl alcohol
It is dramatically increased compared to cost.Moreover, because being difficult to reuse after fermentation residue liquid waste processing, economy and the feature of environmental protection of product do not have
Competitiveness causes the industrialization of cellulosic ethanol to be slowly difficult to realize.
There are the low distillation energy consumption height of equipment burn into maturation wine with dregs concentration of alcohol, water for existing cellulosic ethanol mainstream production technology
Consume the reluctant problem of high sewage.Especially wastewater discharge is big in production, and Organic substance in water, sulfate, ammonia nitrogen concentration
Height, processing difficulty is big, and direct emission is again serious to pollute environment, this constrains the development of cellulosic ethanol industry significantly.And this hair
It is bright to have developed a kind of new process by a large amount of creative labour for the problems in prior art, it is of the invention public
The new process opened does not use sulfuric acid, has both solved equipment etching problem, and waste water and dregs can be added directly concentration and evaporation production height again
It is worth product Fulvic acid organic fertilizer, evaporation lime set can save water consume, it is often more important that greatly reduce sewage treatment with reuse
Cost.In addition, the concentration of alcohol of this technique fermenting-ripening mash is more than 7.6%, it might even be possible to reach 10%, be higher than existing industry
Industrialization technology.Entire production process cleaning, environmental protection, both significantly reduce water consume, have been greatly reduced evaporation and separation rectifying
Steam consumption, significantly improve equipment efficiency of usage and device capbility, be there is good development potentiality and application prospect can
Renewable sources of energy new technology.
It can be seen that existing cellulosic ethanol production complex process, at high cost, water consumption is big, and sewage treatment difficulty is big,
So that the Progress in industrialization of this technology is slow.
Summary of the invention
Summary of the invention
To solve the above-mentioned problems, present inventor have surprisingly found that using the method for the invention on the one hand can be big
Amplitude improves ethyl alcohol production efficiency, on the other hand solves the problems, such as the waste water and dregs generated in current biofuel production process,
High added value fertilizer is converted by original waste water and dregs.
Semantic interpretation:
Auxiliary material: auxiliary material described herein refers to the solid matter packet for being added to and producing organic fertilizer in pretreated waste liquid
Include but be not limited to a) biomass ferment residue, b) biomass stock, crushing, removal of impurities, the available screenings of wash phase or separation
Object, c) humic acid or the material after d) fermentation residue continues with.Wherein, fermentation residue can extract for biological liquid fuel
Residue afterwards.Biomass: include but is not limited to the raw material of lignocellulosic, can be forestry crop and be also possible to crops straw
Stalk etc., such as rice straw, corn stover, maize peel, corncob, straw, cotton stalk, wood chip, sawdust etc..
Humic acid: humic acid is one kind of multiple class molecules that organic substance is formed through a series of decomposition of microorganism and synthesis
Organic matter is widely present in soil, lignite, peat, weathered coal, river, lake, ocean and marsh.It can after through processing
It is widely used in agricultural and forestry as organic fertilizer.
Fulvic acid: being a kind of humic acid of small molecule, be mainly used as production foliar fertilizer, punching fertilising, agricultural fertilizer synergist,
Plant growth regulator etc..
Biological liquid fuel: referring to the liquid fuel or liquable gaseous fuel for being converted by biomass or being extracted, can be with
The gasoline and diesel oil produced by petroleum are partly or entirely substituted, is the important directions of renewable energy development and utilization.Including biology
Ethyl alcohol, butanol, methane etc..
The beneficial effects of the present invention are:
1, it can get concentracted sugar solution (130-235g/l) using this technology, hence it is evident that be higher than existing industry industrialization technology.
When for producing ethyl alcohol, the alcohol fermentation mash that concentration is higher than 7.6% (v/v) can be obtained, cellulosic ethanol is substantially increased
Economy.
2, equipment efficiency of usage is significantly improved, water consume is reduced, save evaporation and separates the steam consumption of rectifying.
3, bio-fuel production is carried out using sulphite or bisulfites, the pollution sources in the production of original ethyl alcohol is turned
Change the Yellow humic acid fertilizer for obtaining high added value, pollution is reduced, after technical solution of the present invention eats up part of cellulosic ethanol cost
With competitiveness, large-scale production is feasible.
4, this technique uses less chemicals, shorter reaction time, obtains the ethyl alcohol of higher yield.
Detailed description of the invention
The present invention relates to a kind of methods using biomass production biological liquid fuel, which is characterized in that highly concentrated obtaining
While spending biological liquid fuel, the solid-state fertilizer or liquid fertilizer of high added value can be obtained；The step of the method uses is at least
Include: step 1: sulphite or bisulfites being added in biomass material, heat temperature raising carries out boiling, wherein described
The w/w concentration of biomass material is 10-45%, and sulphite or bisulfites w/w concentration are 0.1-15%；Step 2: will
Material after boiling is separated by solid-liquid separation, and liquid phase and cellulose-containing solid phase are obtained；Step 3: it is added in the liquid phase auxiliary
Material forms solid-state fertilizer or liquid fertilizer；Step 4: enzyme preparation is added in cellulose-containing solid phase, production sugar is hydrolyzed；Step 5:
Strain is accessed in liquid glucose to ferment, and obtains biological liquid fuel.
Particularly, present inventors have surprisingly found that, high-concentration biological liquid can be obtained using the method for the invention and is fired
Material, high-concentration biological liquid fuel are the biofluid combustion that biological liquid fuel v/v concentration reaches 7.6% or more in fermentation liquid
Material.
Preferably, step 1 further includes oxygenation pretreatment or low-kappa number step, the step are as follows: a) uses lye and sulfurous
Hydrochlorate or bisulfites add simultaneously perhaps b) to be added or c) using lye before sulphite or bisulfites
Added after sulphite or bisulfites using lye or d) using acid solution sulphite or bisulfites it
Preceding addition perhaps e) uses acid solution that acid solution and sulphite are added or f) used after sulphite or bisulfites
Or bisulfites adds simultaneously.
Sulphite or bisulfites are monovalent soluble salt or bivalent soluble salt；Preferably, the sulphite
Or bisulfites is selected from Na2SO3、K2SO3、MgSO3、CaSO3、(NH4)2SO3、NaHSO3、KHSO3Or NH4HSO3One of
Or it is a variety of；It is furthermore preferred that the sulphite or bisulfites are monovalent soluble salt.
The w/w concentration of sulphite or bisulfites can any concentration between 0%-30%, specific sulfurous
The w/w concentration of hydrochlorate or bisulfites be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%,
0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%,
2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%,
3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%,
4.8%, 4.9%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%,
19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%.
Sulphite or bisulfites w/w concentration are 0.1-15% in a particular embodiment, and preferred concentration is
0.5-10%, more preferably 1-5%.
Alkali used in alkaline boiling is monovalent soluble alkali or bivalent soluble alkali；Preferably, the alkali be selected from KOH,
One of NaOH or ammonium hydroxide or a variety of.
The w/w concentration of lye or acid solution can any concentration between 0%-20%, the w/w of specific lye or acid solution
Concentration can for 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%,
1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%,
2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%,
3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%,
6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%.
The acid solution w/w concentration that a specific embodiment always uses be 0.1-5%, concentration of lye 0.1-10%, more
Preferably 0.3-5%.
The w/w concentration of substrate can any concentration between 1%-45%, the w/w concentration of specific substrate can be
1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%,
18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%,
33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%.
In a specific embodiment, the condition of heat temperature raising described in step 1 are as follows: be heated to 140-200
DEG C, preferably 150-190 DEG C, more preferably 158-180 DEG C, soaking time be 15-200 minutes, preferably 30-120 minutes,
The time is 35-100 minutes in one embodiment.
It further include washing step after the separation of solid and liquid in step 2 in another specific embodiment, the washing
Step includes that water is added in obtained solid phase to be washed, and solid content is 12-30%, preferably 15-25% when washing；Into one
Step is preferred, and washing the water used is hot water, it is furthermore preferred that the water that washing uses is 50-90 DEG C of hot water.
In another specific embodiment, the ratio for the auxiliary material that liquid phase described in step 3 is added is 1:10-10:1,1:
9-9:1、1:8-8:1、1:7-7:1、1:6-6:1、1:5-5:1、1:4-4:1、1:3-3:1、1:2-4:1。
In a specific embodiment, auxiliary material used in step 3 is selected from: a) biomass ferment residue, b) biology
Matter stock crushes, removal of impurities, the available screenings of wash phase or isolate or washery slag, c) humic acid or d) fermentation residue continues
Treated material.Preferably, the auxiliary material are as follows: a) biomass ferment residue, the fermentation residue are biological fluids in step 5
Residue after fluid fuel extraction；Or b) biomass stock, crush, removal of impurities, the available screenings of wash phase or isolate or
Washery slag, the screenings or isolate are the available waste obtained after being crushed biomass；Or the washery slag is that will give birth to
Substance carries out the solid phase residue for being separated by solid-liquid separation acquisition after being washed under conditions of 20-80 DEG C when cleaning；C) fermentation residue after
Continuous treated material, it is preferred that material is that sulphite is added or using alkali/oxygen method treated material in fermentation residue.
Biomass is the cellulosic material containing lignin, it is preferred that biomass is rice straw, corn stover, maize peel, wheat
Stalk, corncob, cotton stalk, wood chip, sawdust, bagasse etc..
In a specific embodiment of the invention, the solid-state fertilizer or liquid fertilizer of acquisition are the fertilizer containing fulvic acid.
In a specific embodiment, it after being separated by solid-liquid separation the material after boiling in step 2, directly digests,
Or hot water is added in solids, it after being sufficiently mixed, then is separated by solid-liquid separation, which can be repeated several times, and separating for several times is obtained
The liquid mixing arrived, the production for solid-state fertilizer or liquid fertilizer in step 3；
Preferably, after the material after boiling being separated by solid-liquid separation in the step 2, be added hot water, sufficiently in solids
It after mixing, is separated by solid-liquid separation again, isolated twice liquid is mixed, for solid-state fertilizer in step 3 or liquid fertilizer
Production.
It is furthermore preferred that the solid-phase material after being separated by solid-liquid separation described in step 2 is ground, it is preferred that use high shear mill
Broken equipment is ground, it is furthermore preferred that the high shear pulverising apparatus is colloid mill, mill, sledge mill etc..
Material or the material pH to 4.0-6.0 after grinding, concentration of substrate 15%-30% after adjusting pretreatment boiling add
After entering complex enzyme formulation, is reacted at a temperature of 40-60 DEG C 24-72 hours, the use of concentration is in one embodiment 0.5-5%w/
The complex enzyme formulation of w.
The complex enzyme formulation that the present invention uses includes cellulase, hemicellulose enzyme and/or beta-glucosidase, the half fiber
Tieing up plain enzyme includes zytase, galactosidase, mannosidase, arabinofuranosidase and/or xylobiase etc..
In a specific embodiment of the invention, pentose/hexose common fermentation bacterial strain is accessed in enzymolysis liquid, inoculum concentration is
0.05-5g/l reacts 24-72 hours at a temperature of 30-40 DEG C.
In a specific embodiment of the invention, biological liquid fuel is ethyl alcohol, butanol or methane.
In a specific embodiment, while preparing high-concentration biological liquid fuel, height can be obtained
The solid-state fertilizer or liquid fertilizer of added value；The step of the method use, includes at least: step 1: biomass material is located in advance
Reason；Step 2: being added sulphite in biomass material, and the w/w concentration of the biomass material is 10-45%, and heating rises
Temperature carries out boiling, wherein sulphite w/w concentration is 0.1-15%；Step 3: by step 2 products therefrom be added enzyme preparation into
Row enzymatic hydrolysis；Step 4: step 3 products therefrom is fermented, and production obtains biological liquid fuel and fermentation residue；Step 5:
Fermentation residue is further processed and obtains solid-state fertilizer or liquid fertilizer.
Method of the present invention is in the application for alcohol fuel and in the fertilizer Joint Production containing fulvic acid.
Alcohol fuel prepared by method of the present invention or the fertilizer containing fulvic acid.
It is above only to summarise some aspects of the invention, it is not that should not be regarded as limiting the present invention in any way yet
All patents and publications that this specification is mentioned all is as a whole and incorporated in the present invention by reference to document.
It will be recognized by one skilled in the art that certain changes can be made without departing from design or range of the invention to the present invention.Below
Embodiment present invention be described in more detail, be not construed as limitation the present invention or the present invention illustrated by specific method model
It encloses.
Specific embodiment
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary for these, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art
Member it should be understood that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form into
Row modifications or substitutions, but these modifications and replacement are fallen within the protection scope of the present invention.
In the following Examples and Comparative Examples, ethanol content is measured using HPLC method, actual conditions are as follows:
BIO-RAD analytical column HPX-87H
Sampling volume: 20 μ L
Mobile phase: 0.005M sulfuric acid is filtered and is deaerated by 0.2 μm of filter membrane
Flow velocity: 0.5mL/min
Column temperature: 55-65 DEG C
Detector temperature: as far as possible close to column temperature
Detector: refractive index detector
Runing time: 50min.
In the following Examples and Comparative Examples, fulvic acid content is according to HG/T 3276-2012 " ammonium humate fertilizer analysis
Method " in volumetric method be measured.
Enzyme preparation is purchased from commercial enzyme preparation company, wherein cellulase is purchased from especially that；Hemicellulose enzyme is believed purchased from Novi；
Beta-glucosidase enzyme product is believed purchased from Novi；Beta galactosidase is purchased from especially that；Seminase is contained purchased from the summer；Arabinofuranosidase
Glycosidase is purchased from especially that；Xylobiase is believed purchased from Novi；Zytase is purchased from especially that.
Pentose/hexose common fermentation bacterial strain (also known as C5 bacterial strain) is according to embodiment in the specification of CN201310752782.X
The saccharomyces cerevisiae that 1 method is prepared.
C5 strain culturing method are as follows: by fermented yeast be inoculated in YEPD culture medium (yeast extract 10g/L, peptone 20g/L,
Glucose 20g/L, remaining is water, pH value 6) in, culture to cell density is 2 × 10 under the conditions of 20 DEG C, 200rpm8A/
ML, to obtain the yeast juice of C5 bacterial strain.
Enzymolysis liquid is putted into fermenter, also, by the yeast juice of C5 bacterial strain after brine, centrifugation, will be sent out
Ferment yeast accesses in YEPD culture medium, and the urea of 500ppm, anaerobic fermentation is added.
The direct boiling of 1 sodium sulfite of embodiment prepares ethyl alcohol
(1) by corn stover sodium sulfite boiling
Sodium sulfite is added in corn stover and carries out boiling, concentration of substrate 20%, concentration of sodium sulfite is 2% (w/
w).It is sufficiently mixed, boiling is heated after sealing, temperature is 165 DEG C, and the time is 90 minutes.After boiling, material is squeezed
Pressure is separated by solid-liquid separation.80 DEG C of hot water are added in solid, after being thoroughly mixed, carries out second and is separated by solid-liquid separation.
(2) organic fertilizer is produced using separation liquid phase
Liquid isolated twice is merged, fermentation residue is added, after being sufficiently mixed, is concentrated by evaporation, solid-state Huang is obtained
Rotten acid fertilizer.The ratio of mixed liquor and the fermentation residue of addition is 1:1.Fulvic acid w/w content is 21.6% in gained fertilizer.
(3) solid is digested and is fermented
It is added water and cellulase into isolated solid, enzyme preparation concentration is 4%w/w, concentration of substrate 20%, and pH is
5.0, in 50 DEG C of shaking tables, digest 72 hours.
After enzymatic hydrolysis, C5 yeast is inoculated in enzymolysis liquid, inoculum concentration 3g/l, 32 DEG C ferment 72 hours.Fermentation ends
Afterwards, concentration of alcohol is 5.86% (v/v).
The direct boiling of 2 ammonium sulfite of embodiment prepares ethyl alcohol
(1) by corn stover ammonium sulfite cooking
Ammonium sulfite is added in corn stover and carries out boiling, concentration of substrate 20%, ammonium sulfite concentration is 2% (w/
w).It is sufficiently mixed, boiling is heated after sealing, temperature is 185 DEG C, and the time is 90 minutes.After boiling, material is squeezed
Pressure is separated by solid-liquid separation.80 DEG C of hot water are added in solid, after being stirred, carries out second and is separated by solid-liquid separation.
(2) organic fertilizer is produced using separation liquid phase
Liquid isolated twice is merged, after fermentation residue is added, is concentrated by evaporation, obtains solid-state Yellow humic acid fertilizer.
The ratio of mixed liquor and the fermentation residue of addition is 1:1.Fulvic acid content is 19.7% in gained fertilizer.
(3) solid is digested and is fermented
It is added water and cellulase into isolated solid, enzyme preparation concentration is 4%w/w, concentration of substrate 20%, and pH is
5.0, in 50 DEG C of shaking tables, digest 72 hours.
After enzymatic hydrolysis, C5 yeast is inoculated in enzymolysis liquid, inoculum concentration 3g/l, 32 DEG C ferment 72 hours.Fermentation ends
Afterwards, concentration of alcohol is 4.35% (v/v).
3 alkali process of embodiment prepares ethyl alcohol
(1) sodium hydroxide is added simultaneously and ammonium sulfite carries out boiling
Sodium hydroxide is added simultaneously in corn stover and ammonium sulfite carries out boiling, concentration of substrate 20%, hydroxide
Na concn is 3% (w/w), and ammonium sulfite concentration is 2% (w/w).Boiling is heated after sealing, temperature is 185 DEG C, and the time is 90 points
Clock.After boiling, material is squeezed, is separated by solid-liquid separation.80 DEG C of hot water are added in solid, after being stirred, carry out second
Secondary separation of solid and liquid.
(2) organic fertilizer is produced using separation liquid phase
Liquid isolated twice is merged, after fermentation residue is added, is concentrated by evaporation, obtains solid-state Yellow humic acid fertilizer.
The ratio of mixed liquor and the fermentation residue of addition is 1:1.Fulvic acid content is 29.5% in gained fertilizer.
(3) solid is digested and is fermented
It is added water and cellulase into isolated solid, enzyme preparation concentration is 4%w/w, concentration of substrate 20%, and pH is
5.0, in 50 DEG C of shaking tables, digest 72 hours.
After enzymatic hydrolysis, C5 yeast is inoculated in enzymolysis liquid, inoculum concentration 3g/l, 32 DEG C ferment 72 hours.Fermentation ends
Afterwards, concentration of alcohol is 7.78% (v/v).
Addition sulphite prepares ethyl alcohol after the first alkali process of embodiment 4
(1) by corn stover sodium hydroxide solution pre-cooked
Sodium hydroxide is added in corn stover and carries out pre-cooked, concentration of substrate 20%, naoh concentration 3%
(w/w), temperature is 80 DEG C, and the time is 50 clocks.
(2) corn stover is continued with sodium sulfite boiling
2% (w/w) ammonium sulfite is added in material after pre-cooked and carries out boiling, is sufficiently mixed, heats and steam after sealing
It boils, temperature is 185 DEG C, and the time is 90 minutes.
Remaining step is the same as embodiment 2.
Obtaining fulvic acid content in solid fertilizer is 33.6%, and concentration of alcohol is 8.42% (v/v).
Alkali process prepares ethyl alcohol after embodiment 5 first adds sulphite
Ammonium sulfite, concentration of substrate 20% are added in corn stover, ammonium sulfite concentration is 2% (w/w).Sealing
Afterwards, boiling 50 minutes at 80 DEG C add 3% (w/w) sodium hydroxide later, continue boiling 90 minutes at 185 DEG C.
Remaining step is the same as embodiment 2.
Obtaining fulvic acid content in solid fertilizer is 30.4%, and concentration of alcohol is 7.93% (v/v).
Embodiment 6 first adds and prepares ethyl alcohol using low-kappa number after sulphite
Ammonium sulfite, concentration of substrate 20% are added in corn stover, ammonium sulfite concentration is 2% (w/w).Sealing
Afterwards, boiling 50 minutes at 80 DEG C add 3% (w/w) acetic acid later, continue boiling 90 minutes at 185 DEG C.
Remaining step is the same as embodiment 2.
Finally obtained concentration of alcohol is 7.25% (v/v).
Embodiment 7 adds sulphite simultaneously and sour processing prepares ethyl alcohol
In corn stover, concentration of substrate 20%, while ammonium sulfite and acetic acid is added, ammonium sulfite concentration is 2%
(w/w), acetic acid dosage is 3% (w/w).After sealing, boiling 90 minutes at 185 DEG C.
Remaining step is the same as embodiment 2.
Finally obtained concentration of alcohol is 6.86% (v/v).
Ethyl alcohol is prepared using sulphite after the first acid adding of embodiment 8
In corn stover, concentration of substrate 20%, 3% (w/w) acetic acid of addition, boiling 50 minutes at 80 DEG C, later
Ammonium sulfite 2% (w/w) is added, is continued boiling 90 minutes at 185 DEG C.After boiling, material is squeezed, solid-liquid
Separation.
Remaining step is the same as embodiment 2.
Finally obtained concentration of alcohol is 7.75% (v/v).
The optimization experiment of 9 biomass concentration of substrate of embodiment
The present embodiment is carried out according to the method for embodiment 4, is not both to change simultaneously substrate when boiling using potassium sulfite
Concentration.It the results are shown in Table 1.
1 experimental result of table
10 pre-cooked condition optimizing of embodiment --- lye selection
Different lye are added in cotton stalk (concentration of substrate 18%) to optimize, the concentration of lye is 3%, and lye is pre-
Boiling temperature is 100 DEG C, and digestion time is 50 minutes.Sodium sulfite, concentration 2% are added later.Boiling is heated after sealing, temperature
Degree is 160 DEG C, and the time is 60 minutes.After boiling, material is squeezed, is separated by solid-liquid separation, 60 DEG C of hot water are added in solid,
After being stirred, carries out second and be separated by solid-liquid separation.Later, according to step described in embodiment 1, the fertilizer containing fulvic acid is prepared
Material, extrusion liquid and auxiliary material adding proportion are 2:1.Later by enzymatic hydrolysis and fermentative production of ethanol, as a result referring to table 2.
2 pre-cooked condition optimizing experimental result of table
11 pre-cooked condition optimizing of embodiment
The sodium hydroxide solution that 2.5% (w/w) is added in straw (concentration of substrate 18%) carries out pre-cooked, to pre-cooked
Condition optimizes.The sodium sulfite of 4% (w/w) is added later, continues boiling, temperature is 160 DEG C, and the time is 80 minutes.It steams
After boiling, material is squeezed, is separated by solid-liquid separation, 60 DEG C of hot water are added in solid, after being stirred, carries out second of solid-liquid
Separation.Later, according to step described in embodiment 1, the solid fertilizer containing fulvic acid, extrusion liquid and auxiliary material adding proportion are prepared
It is 2:3.Later by enzymatic hydrolysis and fermentative production of ethanol, as a result referring to table 3.
3 pre-cooked condition optimizing experimental result of table
The optimization experiment of 12 sulphite type of embodiment
The addition potassium hydroxide progress pre-cooked in corn stover (concentration of substrate 20%), concentration of potassium hydroxide 4%,
Pre-cooked temperature is 100 DEG C, and digestion time is 50 minutes.Sulphite, concentration 3% are added later.Boiling is heated after sealing,
Temperature is 170 DEG C, and the time is 90 minutes.After boiling, material is squeezed, is separated by solid-liquid separation.80 DEG C of heat are added in solid
Water after being stirred, carries out second and is separated by solid-liquid separation.Later, according to step described in embodiment 1, prepare ethyl alcohol, as a result referring to
Table 4.
4 pre-cooked condition optimizing experimental result of table
13 pre-cooked condition optimizing of embodiment --- sodium hydroxide additive amount
Sodium hydroxide is added in rice straw (concentration of substrate 20%) and carries out pre-cooked, optimizes sodium hydroxide dosage, boiling
Temperature is 90 DEG C, and digestion time is 50 minutes.Ammonium sulfite is added later, concentration is 4% (w/w).Boiling is heated after sealing, temperature
Degree is 165 DEG C, and the time is 60 minutes.After boiling, material is squeezed, is separated by solid-liquid separation, 90 DEG C of hot water are added in solid,
After being stirred, carries out second and be separated by solid-liquid separation.Later, according to step described in embodiment 1, the solid-state containing fulvic acid is prepared
Fertilizer, extrusion liquid and auxiliary material adding proportion are 1:1.Later by enzymatic hydrolysis and fermentative production of ethanol, as a result referring to table 5.
5 pre-cooked condition optimizing experimental result of table
The optimization of 14 sulphite additive amount of embodiment is tested
The potassium hydroxide that 1% is added in bagasse (concentration of substrate 17%) carries out pre-cooked, and boiling temperature is 80 DEG C, steams
It boils the time 70 minutes, ammonium sulfite concentration is optimized, boiling is heated after sealing, temperature is 165 DEG C, and the time is 50 minutes.
After boiling, material is squeezed, is separated by solid-liquid separation.90 DEG C of hot water are added in solid, after being sufficiently mixed, carry out second admittedly
Liquid separation.Later, according to step described in embodiment 2, the solid fertilizer containing fulvic acid is prepared, extrusion liquid and auxiliary material add ratio
Example is 1:1.Later by enzymatic hydrolysis and fermentative production of ethanol, as a result referring to table 6.
6 experimental result of table
Influence experiment of the 15 sulphite boiling temperature of embodiment to pretreating effect
The sodium hydroxide that 2% (w/w) is added in corn stover (solid content 25%) carries out pre-cooked, and boiling temperature is
90 DEG C, digestion time is 50 minutes.Potassium sulfite is added later, concentration is 5% (w/w), heats boiling after sealing.By boiling temperature
Degree optimizes, and the time is 30 minutes.After boiling, material is squeezed, is separated by solid-liquid separation, 80 DEG C of hot water are added in solid
It is washed, is separated by solid-liquid separation.Later, according to step described in embodiment 1, the solid fertilizer containing fulvic acid is prepared, is squeezed
Liquid and auxiliary material adding proportion are 4:1 out.Pass through enzymatic hydrolysis and fermentative production of ethanol later, as a result referring to table 7.
7 experimental result of table
Influence experiment of the 16 sulphite digestion time of embodiment to pretreating effect
The sodium hydroxide that 1% is added in corncob (concentration of substrate 30%) carries out pre-cooked, boiling temperature 100
DEG C, digestion time is 50 minutes.7% ammonium sulfite is added later, heats boiling after sealing, 150 DEG C of boiling temperature, to boiling
Time optimizes.After boiling, material is squeezed, is separated by solid-liquid separation, 60 DEG C of hot water are added in solid and are washed, into
Row is separated by solid-liquid separation.Later, according to step described in embodiment 2, solid fertilizer and ethyl alcohol containing fulvic acid are prepared, as a result referring to
Table 8.
8 experimental result of table
Embodiment 17 digests concentration of substrate experiment
(1) by straw ammonium sulfite cooking
4.5% sodium hydroxide is added in straw stalk (concentration of substrate 17%) and carries out pre-cooked, boiling temperature 80
DEG C, digestion time is 50 minutes.Later be added 4% sodium sulfite, continue after sealing heat boiling, 190 DEG C of boiling temperature, when
Between 30 minutes.After boiling, material is squeezed, is separated by solid-liquid separation.Hot water is added in solid to be washed, to hot water temperature
It optimizes, is separated by solid-liquid separation again later.
(2) organic fertilizer is produced using separation liquid phase
Liquid isolated twice is merged, fermentation residue is added, after being sufficiently mixed, is concentrated by evaporation, obtains fulvic acid
Solid fertilizer.The ratio of mixed liquor and the fermentation residue of addition is 1:1.Fulvic acid content is 38.4% (w/w) in gained fertilizer.
(3) solid is digested and is fermented
Water and enzyme are added into isolated solid, enzyme preparation is to contain cellulase, hemicellulase and beta-glucosidase
The complex enzyme of enzyme, enzyme preparation concentration are 5%w/w, are optimized to enzymatic hydrolysis concentration of substrate, pH 4.8, in 52 DEG C of shaking tables, enzyme
Solution 60 hours.
After enzymatic hydrolysis, C5 yeast is inoculated in enzymolysis liquid, inoculum concentration 3g/l, 33 DEG C ferment 60 hours.Fermentation ends
Afterwards, concentration of alcohol is measured.As a result referring to table 10.
10 experimental result of table
The experiment of 18 defibrination of embodiment
The potassium hydroxide that 1% is added in bagasse (concentration of substrate 17%) carries out pre-cooked, and boiling temperature is 80 DEG C, steams
Boil the time 70 minutes.5% ammonium sulfite solution is added later, continues to heat boiling after sealing, temperature is 165 DEG C, and the time is
50 minutes.After boiling, material is squeezed, is separated by solid-liquid separation.Hot water is added in solid to be washed, carries out again later
It is separated by solid-liquid separation.The solid that a part is isolated is taken out, after carrying out defibrination using mill, squeezes and is separated by solid-liquid separation, solid is subjected to enzyme
Solution and ethyl alcohol.The solid of remaining non-defibrination carries out enzymatic hydrolysis and alcohol fermentation under identical condition.Enzyme preparation is to contain fiber
The complex enzyme of plain enzyme, hemicellulase and beta-glucosidase.Enzymatic hydrolysis and fermentation condition are the same as embodiment 4.
Under the conditions of not defibrination, fermenting alcohol concentration is 7.88% (v/v)；After defibrination, fermenting alcohol concentration is 8.76%
(v/v), 11% is improved.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (22)
1. a kind of method using biomass production biological liquid fuel, which is characterized in that obtaining the combustion of high-concentration biological liquid
While material, the solid-state fertilizer or liquid fertilizer of high added value can be obtained；The step of the method use, includes at least:
Step 1: being added sulphite or bisulfites in biomass material, and heat temperature raising carries out boiling, wherein described
The w/w concentration of biomass material is 10-45%, and sulphite or bisulfites w/w concentration are 0.1-15%；
Step 2: the material after boiling is separated by solid-liquid separation, and obtains liquid phase and cellulose-containing solid phase；
Step 3: being added auxiliary material in the liquid phase, forms solid-state fertilizer or liquid fertilizer；
Step 4: enzyme preparation is added in cellulose-containing solid phase, production sugar is hydrolyzed；
Step 5: strain is accessed in liquid glucose and is fermented, biological liquid fuel is obtained.
2. the method as described in claim 1, which is characterized in that the high-concentration biological liquid fuel refers to biological in fermentation liquid
Liquid fuel v/v concentration reaches 7.6% or more.
3. such as the described in any item methods of the claims, which is characterized in that the step 1 further includes oxygenation pretreatment or acid
Pre-treatment step, the step are as follows:
A) it is added simultaneously using lye and sulphite or bisulfites, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of lye are 0.1-10%；Or
B) it is added before sulphite or bisulfites using lye, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of lye are 0.1-10%；Or
C) it is added after sulphite or bisulfites using lye, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of lye are 0.1-10%；Or
D) it is added before sulphite or bisulfites using acid solution, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of acid solution are 0.1-5%；Or
E) it is added after sulphite or bisulfites using acid solution, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of acid solution are 0.1-5%；Or
F) it is added simultaneously using acid solution and sulphite or bisulfites, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of acid solution are 0.1-5%.
4. such as the described in any item methods of the claims, which is characterized in that the sulphite or bisulfites w/w are dense
Degree is 0.5-10%, and more preferable w/w concentration is 1-5%.
5. such as the described in any item methods of the claims, which is characterized in that the condition of heat temperature raising described in step 1 are as follows:
It is heated to 140-200 DEG C, preferably 150-190 DEG C, more preferably 158-180 DEG C, soaking time is 15-200 minutes, excellent
It is selected as 30-120 minutes, more preferably 35-100 minutes.
6. such as the described in any item methods of the claims, which is characterized in that in step 2, further include after the separation of solid and liquid
Washing step, the washing step include that water is added in obtained solid phase to be washed, and solid content is 12-30% when washing,
Preferably 15-25%；It is further preferred that the water that washing uses is hot water, it is furthermore preferred that the water that washing uses is 50-90 DEG C
Hot water.
7. such as the described in any item methods of the claims, which is characterized in that the auxiliary material that liquid phase described in step 3 is added
Ratio is 1:10-10:1.
8. such as the described in any item methods of the claims, which is characterized in that auxiliary material used in step 3 is selected from:
A) biomass ferment residue, b) it biomass stock, crushes, removal of impurities, the available screenings of wash phase or isolate or wash
Slag, c) humic acid or the material after d) fermentation residue continues with；Wherein,
Preferably, the auxiliary material are as follows:
A) biomass ferment residue, the biomass ferment residue are that biological liquid fuel mentions in step 5 described in claim 1
Residue after taking；Or
B) biomass stock, crush, removal of impurities, the available screenings of wash phase or isolate or washery slag, the screenings or point
It is the available waste obtained after being crushed biomass from object；Or the washery slag is when biomass cleans at 20-80 DEG C
Under conditions of washed after carry out again be separated by solid-liquid separation acquisition solid phase residue；
D) material after fermentation residue continues with, it is preferred that the material is that sulphite or use is added in fermentation residue
Alkali/oxygen method treated material.
9. such as the described in any item methods of the claims, which is characterized in that the biomass is the fiber containing lignin
Plain raw material；Preferably, the biomass is rice straw, corn stover, maize peel, straw, corncob, cotton stalk, wood chip, sawdust, sugarcane
Slag etc..
10. such as the described in any item methods of the claims, which is characterized in that the sulphite or bisulfites are one
Valence soluble-salt or bivalent soluble salt；Preferably, the sulphite or bisulfites are selected from Na2SO3、K2SO3、Mg
(HSO3)2、Ca(HSO3)2、(NH4)2SO3、NaHSO3、KHSO3Or NH4HSO3One of or it is a variety of；It is furthermore preferred that the sulfurous
Hydrochlorate or bisulfites are monovalent soluble salt.
11. such as the described in any item methods of the claims, which is characterized in that the solid-state fertilizer or liquid fertilizer is containing fulvic acids
Fertilizer.
12. such as the described in any item methods of the claims, which is characterized in that alkali used in the alkaline boiling is monoacidic base
Or diatomic base；Preferably, the alkali is selected from one of KOH, NaOH or ammonium hydroxide or a variety of.
13. such as the described in any item methods of the claims, which is characterized in that in the step 2 by the material after boiling into
After row is separated by solid-liquid separation, directly digests, or hot water is added in solids, after being sufficiently mixed, then be separated by solid-liquid separation, the solid-liquid point
It can be repeated several times from step, the liquid that separating for several times is obtained mixes, the production for solid-state fertilizer or liquid fertilizer in step 3；It is excellent
Choosing, after the material after boiling being separated by solid-liquid separation in the step 2, be added hot water in solids, after being sufficiently mixed, then
It is secondary to be separated by solid-liquid separation, liquid isolated twice is mixed, the production for solid-state fertilizer or liquid fertilizer in step 3.
14. such as the described in any item methods of the claims, which is characterized in that the solid phase after being separated by solid-liquid separation described in step 2
Material is ground.
15. such as the described in any item methods of the claims, which is characterized in that material or grinding after adjusting pretreatment boiling
Material pH to 4.0-6.0 afterwards, concentration of substrate 15%-30% react 24- at a temperature of 40-60 DEG C after complex enzyme formulation is added
72 hours.
16. such as the described in any item methods of the claims, it is characterised in that the complex enzyme formulation include cellulase,
Hemicellulose enzyme and/or beta-glucosidase, the hemicellulase include zytase, galactosidase, mannosidase, Ah
Draw primary furanoside enzyme and/or xylobiase etc..
17. such as the described in any item methods of the claims, which is characterized in that access pentose/hexose into enzymolysis liquid and send out altogether
Yeast-like fungi strain, inoculum concentration 0.05-5g/l react 24-72 hours at a temperature of 30-40 DEG C.
18. such as the described in any item methods of the claims, which is characterized in that the biological liquid fuel is ethyl alcohol, butanol
Or methane.
19. such as the described in any item methods of the claims, which is characterized in that preparing high-concentration biological liquid fuel
While, the solid-state fertilizer or liquid fertilizer of high added value can be obtained；The step of the method use, includes at least:
Step 1: biomass material is pre-processed；
Step 2: being added sulphite in biomass material, and the w/w concentration of the biomass material is 10-45%, and heating rises
Temperature carries out boiling, wherein sulphite w/w concentration is 0.1-15%；
Step 3: step 2 products therefrom addition enzyme preparation is digested；
Step 4: step 3 products therefrom is fermented, and production obtains biological liquid fuel and fermentation residue；
Step 5: fermentation residue is further processed and obtains solid-state fertilizer or liquid fertilizer；
Preferably, pre-treatment step in the step 1 are as follows:
A) it is added simultaneously using lye and sulphite or bisulfites, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of lye are 0.1-10%；Or
B) it is added before sulphite or bisulfites using lye, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of lye are 0.1-10%；Or
C) it is added after sulphite or bisulfites using lye, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of lye are 0.1-10%；Or
D) it is added before sulphite or bisulfites using acid solution, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of acid solution are 0.1-5%；Or
E) it is added after sulphite or bisulfites using acid solution, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of acid solution are 0.1-5%；Or
F) it is added simultaneously using acid solution and sulphite or bisulfites, sulphite or bisulfites w/w concentration are
0.1-15%, the w/w concentration of acid solution are 0.1-5%.
20. such as the described in any item methods of the claims, which is characterized in that the fermentation residue to be further processed
Solid-state fertilizer or liquid fertilizer are obtained, the treating method comprises and sulphite is added in the fermentation residue or using alkali/oxygen method
Processing.
21. a kind of described in any item methods of the claims are for alcohol fuel and the fertilizer Joint Production containing fulvic acid
In application.
22. a kind of alcohol fuel of described in any item method preparations of the claims or the fertilizer containing fulvic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114075579A (en) * | 2020-08-13 | 2022-02-22 | 国投生物科技投资有限公司 | Method for preparing organic fertilizer and biological liquid fuel by using lignocellulose |
| CN115341004A (en) * | 2021-05-12 | 2022-11-15 | 国投生物科技投资有限公司 | Method for preparing monosaccharide from biomass raw material |
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