CN107058426A - A kind of preprocess method of agriculture and forestry organic waste material - Google Patents
A kind of preprocess method of agriculture and forestry organic waste material Download PDFInfo
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- CN107058426A CN107058426A CN201710244091.7A CN201710244091A CN107058426A CN 107058426 A CN107058426 A CN 107058426A CN 201710244091 A CN201710244091 A CN 201710244091A CN 107058426 A CN107058426 A CN 107058426A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- 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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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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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
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
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Abstract
The invention provides a kind of preprocess method of agriculture and forestry organic waste material, it comprises the following steps：A) by agriculture and forestry organic waste material, acid catalyst, water and organic solvent hybrid reaction, reaction solution and residue are obtained；B) by step A) obtained residue and acid liquid reaction, obtain reaction solution and residue；C) by step B) obtained residue digested, and obtains glucose.The application uses two-step method in agriculture and forestry organic waste material preprocessing process, the system removing lignin and hemicellulose of acidic catalyst and organic solvent are utilized first under the conditions of relatively mild, then using the hemicellulose remained in acid solution hydrolytic residue, the enzymolysis efficiency of cellulose is significantly improved after two-step method, can obtain the higher glucose of yield and the xylose yield that can be received.
Description
Technical field
The present invention relates to biomass resource technical field, more particularly to a kind of preprocess method of agriculture and forestry organic waste material.
Background technology
With increasingly in short supply, the appearance of a large amount of various environmental problems using caused by fossil fuel of fossil fuel, make
The demand for obtaining Renewable Energy Development and searching fossil fuel substitute is increasingly urgent.Agriculture and forestry organic waste material is used as biomass resource
A part, because of its aboundresources, there is recyclability, sustainability and room temperature air can be reduced discharge as energy
Source domain and environmental area study new focus.
Traditional agriculture and forestry organic waste material utilization ways mainly have gasifying electricity generation, liquefaction to prepare alcohol fuel and wooden shaping combustion
Material etc., but domestic and international new research shows that it is more economic and practical to prepare chemicals based on biomass sugar molecule platform.Agricultural are given up
In gurry be rich in hemicellulose and cellulose, under suitable conditions it is preprocessed can obtain biomass monose (glucose and
Xylose), using monose as starting material, important platform chemicals furfural and levulinic can be converted under suitable conditions
Acid.Wherein furfural can be converted into furfuryl alcohol, furancarboxylic acid, tetrahydrofuran etc. and extensively should as important furfuran compound presoma
Bulk chemical；And levulic acid is one of 12 kinds of Important Platform compounds being approved by USDOE, extensively should
For industries such as food, medical treatment, cosmetics manufactures.The carbon source needed for hydrolyzing monose as microbial fermentation production, produces fuel
Ethanol, can alleviate dependence of the mankind for fossil fuel, at the same it is consistent with the low-carbon environment-friendly theme of the world today, be conducive to people
The sustainable development of class society.
However, because lignocellulose raw material has highly crystalline body and lignifying so that wood fibre has to pass through pre-
Processing could improve degree of degradation of the cellulase to cellulose, increase the yield of monose.Preprocess method machinery traditional at present
Polishing, steam explosion, diluted a cid method, alkaline process, organic solvent method, ionic liquid etc., although can obtain higher cellulose-
The conversion ratio of glucose, but required pretreatment condition is harsher (high temperature, high pressure and long-time), causes portion of cellulose and wood
Quality is degraded in preprocessing process.Simultaneously high to equipment requirement, energy consumption and cost are higher, and required soda acid can be caused sternly
The environmental pollution of weight.Bioanalysis energy consumption is low, pollution-free, but cost is higher, the action period is long, but lignocellulosic each component yield
Than relatively low.Therefore, separated while single preconditioning technique or can not be difficult and realize hemicellulose and cellulose simultaneously, no
Beneficial to biomass material comprehensive utilization, large-scale industrial production is caused not carry out.
The content of the invention
Present invention solves the technical problem that being to provide a kind of preprocess method of agriculture and forestry organic waste material, it is pre- that the application is provided
Processing method can realize the separation of hemicellulose and lignin in agriculture and forestry organic waste material, and make the yield of glucose higher.
In view of this, this application provides a kind of preprocess method of agriculture and forestry organic waste material, comprise the following steps：
A), by agriculture and forestry organic waste material, acid catalyst, water and organic solvent hybrid reaction, reaction solution and residue are obtained；
B), by step A) obtained residue and acid liquid reaction, obtain reaction solution and residue；
C), by step B) obtained residue digested, and obtains glucose.
It is preferred that, the one kind of the acid catalyst in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid, acetic acid and adipic acid
Or it is a variety of.
It is preferred that, it is different that the organic solvent is selected from gamma-valerolactone, dioxane, dimethyl sulfoxide (DMSO), tetrahydrofuran, methyl
One or more in butyl ketone, methylcellulose, dimethylformamide and 2- methyltetrahydrofurans.
It is preferred that, the volume ratio of the water and organic solvent is 1：(1~12).
It is preferred that, in the system that the agriculture and forestry organic waste material, acid catalyst, water and organic solvent are mixed to get, liquid-solid ratio
For (5~20) mg：1mg, the concentration of acid catalyst is 0.2wt%~1.5wt%.
It is preferred that, the organic solvent is dioxane, and the acid catalyst is hydrochloric acid.
It is preferred that, step A) in, the time of the reaction is 10~50min, and temperature is 60~100 DEG C.
It is preferred that, step B) in, the concentration of the acid solution is 0.4~1.0wt%, and the temperature of the reaction is 100~130
DEG C, the time of the reaction is 20~50min.
It is preferred that, step C) in, the enzymolysis is carried out in the system being made up of enzyme and sodium azide.
It is preferred that, the agriculture and forestry organic waste material is selected from maize straw, corncob, rice straw, broomcorn straw, bagasse, small
One or more in Wheat Straw and microalgae.
This application provides a kind of preprocess method of agriculture and forestry organic waste material, it comprises the following steps：A) by agriculture and forestry organic waste material,
Acid catalyst, water and organic solvent hybrid reaction, obtain reaction solution and residue；B) by step A) obtained residue and acid solution it is anti-
Should, obtain reaction solution and residue；C) by step B) obtained residue digested, and obtains glucose.Locate in advance in agriculture and forestry organic waste material
During reason, alkalescent key and lignin and fiber between lignin and lignin are broken in the presence of acid catalyst first
Effect key between element, hemicellulose, splits away off lignin, in the solution for being dissolved in water and organic solvent formation, so that
The separation of lignin and hemicellulose is realized, then in the presence of acid solution, hemicellulose is hydrolyzed, by two-step method
Afterwards, because most hemicellulose and lignin are removed, originally fine and close destructurized, the enzyme on cellulose of biomass
Action site is exposed, and is finally digested, and improves glucose yield.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of preprocess method of agriculture and forestry organic waste material, comprise the following steps：
A), by agriculture and forestry organic waste material, acid catalyst, water and organic solvent hybrid reaction, reaction solution and residue are obtained；
B), by step A) obtained residue and acid liquid reaction, obtain reaction solution and residue；
C), by step B) obtained residue digested, and obtains glucose.
This application provides a kind of preprocess method of agriculture and forestry organic waste material, it takes off after being pre-processed first through acidic organic solvent
Except substantial amounts of lignin and hemicellulose, the lignin and hemicellulose of removing can be further converted to high add in the system
The chemicals or liquid fuel of value, or xylose and lignin are reclaimed, reacted residue is further pre-processed by diluted acid, to disappear
Except adverse effect of the hemicellulose to enzyme digestion reaction；After above-mentioned two-step method, substantial amounts of hemicellulose and lignin degradation,
The compact texture of cellulose is caused to be destroyed, finally under the conditions of low enzyme, enzymolysis glucose yield is significantly improved, through two-step method
After can reclaim xylose and glucose simultaneously.
When being pre-processed to agriculture and forestry organic waste material, the application first with acidic catalyst organic solvent solution system
The lignin and hemicellulose in agriculture and forestry organic waste material are removed, is specially：By agriculture and forestry organic waste material, acid catalyst, water and organic solvent
Hybrid reaction, obtains reaction solution and residue.Mostly rich in abundant hemicellulose, cellulose and lignin in agriculture and forestry organic waste material,
Connected mode between hemicellulose and lignin is mainly methyl phenyl ethers anisole key, ester bond, phenyl glycoside key and hemiacetal and acetal
Connection；In the system of acid catalyst, water and the organic solvent formation of the application, acid catalyst mainly plays destruction hemicellulose
The effect of α-fragrance ehter bond connection between lignin molecule and between lignin macromolecular structure unit；In sour environment,
Ester bond, ehter bond and glycosidic bond are unstable to be easy to fracture, causes lignin degradation, while the α of lignin-fragrance ehter bond is in acid
Property under the conditions of be also easily broken, partial lignin small molecule of degrading out, be dissolved in acid catalyst, water and organic solvent formation
In solution.
In above process, the agriculture and forestry organic waste material is material well known to those skilled in the art, as long as it is rich in wooden
Element, cellulose and hemicellulose；Example, the agriculture and forestry organic waste material is selected from maize straw, corncob, rice straw, height
One or more in fine strain of millet stalk, bagasse, wheat stalk and microalgae.The acid catalyst is mainly as catalyst, and it is selected from
One or more in sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid, acetic acid and adipic acid, in a particular embodiment, the acid catalysis
Agent is selected from hydrochloric acid, and its concentration is 0.2wt%~1.5wt%, in a particular embodiment, and its concentration can be 0.4~1.0wt%, this
The concentration of the acid catalyst of step is for base in the system being mixed to get with agriculture and forestry organic waste material, acid catalyst, water and organic solvent
, more specifically, the acid catalyst can only be dissolved in the water, therefore its concentration is the amount and the total amount of hydrochloric acid and water by hydrochloric acid
Ratio be worth to.The increase of the acid catalyst concentration can improve the yield of glucose, but work as concentration increase to a certain extent
Glucose yield change is little afterwards, and the degraded of xylose can be caused on the contrary, while concentrated acid understands etching apparatus and brings environmental problem.
In above process, the organic solvent is selected from gamma-valerolactone, dioxane, dimethyl sulfoxide (DMSO), tetrahydrofuran, methyl tert-butyl
One or more in base ketone, dimethylformamide and 2- methyltetrahydrofurans, more specifically, the organic solvent are selected from dioxy
Six rings.The organic solvent can both be realized as xylose again and lignin enter one as the simple dissolved lignin of solvent
Step changes into the chemicals of high added value and the reaction system of liquid fuel.In a particular embodiment, urged in agriculture and forestry organic waste material, acid
In the system that agent, water and organic solvent are mixed to get, liquid-solid ratio is (5~20) mg：1mg；The body of the organic solvent and water
Product is than being 1: (1~12), in a particular embodiment, the volume ratio of the organic solvent and water is 1: (3~9)；Organic solvent and
The ratio of water is bigger within the above range can more to improve Portugal after the yield of glucose, but organic solvent ratio increase to a certain extent
Grape sugar yield change is little.The temperature of above-mentioned reaction is 60~100 DEG C, and the time of reaction is 10~50min；In specific embodiment
In, the temperature of the reaction is 70~90 DEG C, and the time of the reaction is 20~40min.
Above-mentioned pretreatment has obtained reaction solution and residue, and the raw material that wherein residue reacts as next step, reaction solution is divided into
Substantial amounts of water sedimentation lignin is added after two parts, a part of reaction solution revolving, is stored at room temperature overnight, centrifugation, using anhydrous second
After ether extraction, 80 DEG C of drying are weighed, and are dissolved xylose with water after calculating the rate of recovery of lignin, another part reaction solution revolving, are taken out
Filter, filtrate constant volume surveys xylose with Water515HPLC (high performance liquid chromatograph), calculates the yield of hemicellulose.
According to the present invention, then the preprocessing process of cellulose is hydrolyzed, is specially：The residue that upper step is obtained and acid
Liquid reacts, and obtains reaction solution and residue.Dilute acid hydrolysis hemicellulose during this, acid solution also serves as catalyst, main faults
Glycosidic bond between hemicellulose, realizes the degraded of cellulose.The acid solution can be acid solution well known to those skilled in the art,
This application is had no particular limits, example, the acid solution can be hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid etc., and its concentration is
0.2wt%~1.5wt%, in a particular embodiment, the concentration of the acid solution is 0.4~1.0wt%.Acid solution in the step with
The system of acid catalyst, organic solvent and water formation can not be exchanged in upper step, if first removing hemicellulose using acid solution
In element, this environment, condensation polymerization occurs between lignin molecule, and the later lignin of polycondensation is not allowed more in acidic organic solvent
Easily it is depolymerizated, therefore the yield of glucose can be reduced after reaction system exchange.The temperature of the reaction is 100~130 DEG C, described
The time of reaction is 20~50min.After above-mentioned reaction terminates, obtained reaction solution detects containing for xylose using Water515HPLC
Amount, residue then digests raw material as next step.
The residue that the application finally obtains upper step is digested, and obtains glucose.This process is the enzymolysis of cellulose
In the stage, to be broken the glycosidic bond between cellulose, obtain glucose.In enzymolysis process, preferably by enzyme and sodium azide group
Into system in carry out；Wherein, enzyme is broken the glycosidic bond between cellulose, sodium azide is a kind of bacteriostatic agent as catalyst,
Suppress the generation of bacterium in enzymolysis process；Certainly, sodium azide can also be substituted for other antibiotic such as tetracycline.The enzyme
The temperature of solution is 30~80 DEG C, and the time is 36~72h.
The pretreatment that the application carries out agriculture and forestry organic waste material is mainly removal lignin and hemicellulose, reduces the knot of cellulose
The porous of brilliant degree and increase raw material；After the first step is pre-processed, substantial amounts of lignin and part hemicellulose are removed, former
It is broken the natural cover for defense that is formed by lignin, but also has part hemicellulose to remain in residue after step pretreatment, and
Hemicellulose has certain toxic action to cellulase, then further to remove hemicellulose in a subsequent step, warp
Cross after two-step method, most of hemicellulose and lignin are removed, and the action site of cellulose is exposed, more conducively enzyme
The progress of solution, to obtain the glucose that yield is higher.
In the preprocessing process of agriculture and forestry organic waste material, raw material is the agriculture and forestry organic waste material rich in hemicellulose and cellulose, its
Wide variety, rich reserves, and with recyclability, sustainability the features such as.Organic solvent pretreatment reaction does not need high pressure
High temperature, mild condition, the shortcomings of overcoming Several Traditional Preconditioning Methods high energy consumption, reaction harshness can effectively reduce reaction cost；Make
With organic solvent pretreatment, the hemicellulose and lignin of removing can be caused directly further to change into added value in the system
Higher chemicals or liquid fuel, realizes the circulation of acidic organic solvent, it is to avoid pollution environment.The side provided using the present invention
Method can be effectively reduced enzyme dosage, and higher glucose can be obtained simultaneously and the yield of xylose can be received.
Test result indicates that, the method provided using the present invention can obtain the Portugal of more than 90% yield under the conditions of low enzyme
Grape sugar and more than 70% xylose yield.
For a further understanding of the present invention, the pretreatment side of the agriculture and forestry organic waste material provided with reference to embodiment the present invention
Method is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
1) weigh the drying maize straw powder input 40mL after 4.0g is screened through 40 mesh sieve and contain the 9 of 1wt%HCl:1
(v/v) in the dioxane aqueous solution, then obtained solidliquid mixture is placed in 70mL mechanical stirring kettles, adjusts reactor, make
Its rotating speed is 550rpm, and total power keeps 20min after being warming up to 90 DEG C；Power supply is closed in reaction after terminating, and rapid by reactor
It is placed in frozen water and is cooled to room temperature；
2) reaction solution is transferred out of from reactor, filtered, filtrate, which is used, uses Waters 515HPLC (high performance liquid chromatography
Instrument) determine xylose and lignin；Residue is used to further react；
3) upper step residue is placed in 70mL mechanical stirring kettles, adds 40mL 1wt%HCl solution；Reactor is adjusted, is made
Its rotating speed is 550rpm, and total power keeps 40min after being warming up to 120 DEG C；Power supply is closed in reaction after terminating, and rapid by reactor
It is placed in frozen water and is cooled to room temperature；Reaction solution is transferred out of from reactor, filtered, filtrate is used using Waters 515HPLC
(high performance liquid chromatograph) determines xylose, and residue is used for further enzyme digestion reaction；
4) 0.2g steps 3 are weighed) obtained residue added in 4mL ampere bottles, and enzyme dosage is 3FPU, plus sodium azide is buffered
Liquid (pH4.8) causes reaction final volume to be 4mL, and sealing at 50 DEG C, digests 72h in 150r/min shaking tables, after enzymolysis terminates,
Sample is centrifuged into 40s under 10000r/min, supernatant is taken, enzyme is determined using Waters 515HPLC (high performance liquid chromatograph)
Concentration of glucose in hydrolyzate.
As a result show, the yield of the present embodiment xylose is 71.8%, the yield of glucose is 91.5%.
Embodiment 2
Except step 1) in addition to the dioxane and water volume ratio, remaining condition and step are consistent with embodiment 1, this reality
Apply dioxane described in example and take 1 respectively with water volume ratio:Isosorbide-5-Nitrae:1,9:1,12:1, experimental result is shown, the yield of glucose
Respectively 70.7%, 83.7%, 91.5%, 91.8%, the yield of xylose is 60.8%, 62.8%, 71.8%, 56.1%, is examined
Consider energy consumption and glucose and xylose yield, 9:The volume ratio of 1 (V/V) dioxane and water is preferable condition.
Embodiment 3
Except step 1) in addition to the acid concentration of the acid dioxane, remaining condition and step are consistent with embodiment 1,
The acid concentration of acid dioxane takes 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2% respectively in the present embodiment,
1.5%, after measured, the yield of glucose is respectively 67.5%, 75.1%, 79.3%, 85.0%, 91.7%, 94.1%,
94.9%, the yield of xylose is 80.7%, 78.9%, 76.7%, 74.8%, 71.8%, 69.4%, 67.1%, it is considered to pair set
Standby requirement, environmental pollution and glucose and xylose yield, the preferable acidity conditions of 1.0wt%.
Embodiment 4
Except step 1) in addition to the acid dioxane reaction temperature, remaining condition and step are consistent with embodiment 1,
Reaction temperature takes 70 DEG C respectively in the present embodiment, and 80 DEG C, 90 DEG C are after measured, and the yield of glucose is respectively 76.0%, 76.8%,
91.2%, the yield of xylose is：76.8%, 71.5%, 71.8%, it is considered to equipment requirement, energy consumption cost and glucose and wood
Sugared yield, 90 DEG C are preferably reaction temperatures.
Embodiment 5
Except step 1) in addition to the acid dioxane reaction time, remaining condition and step are consistent with embodiment 1,
The reaction time takes 10min, 20min, 30min, 40min respectively in the present embodiment, and 50min after measured, distinguish by the yield of glucose
For 87.0%, 91.7%, 92.7%, 93.3%, 94.1%, the yield of xylose is 73.7%, 71.8%, 70.1%, 63.4%,
62.8%, it is considered to equipment requirement, energy consumption cost and glucose and xylose yield, 20min are preferably reaction temperatures.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. a kind of preprocess method of agriculture and forestry organic waste material, comprises the following steps：
A), by agriculture and forestry organic waste material, acid catalyst, water and organic solvent hybrid reaction, reaction solution and residue are obtained；
B), by step A) obtained residue and acid liquid reaction, obtain reaction solution and residue；
C), by step B) obtained residue digested, and obtains glucose.
2. preprocess method according to claim 1, it is characterised in that the acid catalyst is selected from sulfuric acid, hydrochloric acid, phosphorus
One or more in acid, acetic acid, formic acid, acetic acid and adipic acid.
3. preprocess method according to claim 1, it is characterised in that the organic solvent is selected from gamma-valerolactone, dioxy
Six rings, dimethyl sulfoxide (DMSO), tetrahydrofuran, methyl iso-butyl ketone (MIBK), methylcellulose, dimethylformamide and 2- methyltetrahydrofurans
In one or more.
4. preprocess method according to claim 1, it is characterised in that the volume ratio of the water and organic solvent is 1：(1
~12).
5. preprocess method according to claim 1, it is characterised in that the agriculture and forestry organic waste material, acid catalyst, water and
In the system that organic solvent is mixed to get, liquid-solid ratio is (5~20) mg：1mg, the concentration of acid catalyst for 0.2wt%~
1.5wt%.
6. preprocess method according to claim 1, it is characterised in that the organic solvent is dioxane, the acid
Catalyst is hydrochloric acid.
7. preprocess method according to claim 1, it is characterised in that step A) in, time of the reaction for 10~
50min, temperature is 60~100 DEG C.
8. preprocess method according to claim 1, it is characterised in that step B) in, the concentration of the acid solution for 0.4~
1.0wt%, the temperature of the reaction is 100~130 DEG C, and the time of the reaction is 20~50min.
9. preprocess method according to claim 1, it is characterised in that step C) in, the enzymolysis is by enzyme and nitrine
Change in the system of sodium composition and carry out.
10. preprocess method according to claim 1, it is characterised in that the agriculture and forestry organic waste material is selected from maize straw, jade
One or more in meter Xin, rice straw, broomcorn straw, bagasse, wheat stalk and microalgae.
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Cited By (5)
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| CN108660171A (en) * | 2018-06-11 | 2018-10-16 | 中国科学技术大学 | A kind of method of efficient green pretreatment agriculture and forestry organic waste material |
| CN112575045A (en) * | 2020-12-14 | 2021-03-30 | 中国科学技术大学 | Method for efficiently removing lignin based on acidic ethylene glycol solution |
| CN113736831A (en) * | 2021-09-28 | 2021-12-03 | 西华大学 | Method for processing edible fungus dregs and application thereof |
| CN114426330A (en) * | 2020-10-29 | 2022-05-03 | 中国环境科学研究院 | Method for preparing steady-state enhanced denitrification slow-release carbon source filler by water-methanol-alkali system |
| CN115010537A (en) * | 2022-05-06 | 2022-09-06 | 广州大丘有机农产有限公司 | Fermentation treatment process of agricultural and forestry waste |
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