CN106367449A - Method for preparing feed-grade xylooligosaccharide from waste liquid generated in a production process of viscose staple fibers - Google Patents
Method for preparing feed-grade xylooligosaccharide from waste liquid generated in a production process of viscose staple fibers Download PDFInfo
- Publication number
- CN106367449A CN106367449A CN201610737002.8A CN201610737002A CN106367449A CN 106367449 A CN106367449 A CN 106367449A CN 201610737002 A CN201610737002 A CN 201610737002A CN 106367449 A CN106367449 A CN 106367449A
- Authority
- CN
- China
- Prior art keywords
- hemicellulose
- waste liquid
- concentrated solution
- xylooligosaccharide
- production process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/06—Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages
-
- 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
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
-
- 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
- C12P19/12—Disaccharides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Molecular Biology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention relates to a method for preparing feed-grade xylooligosaccharide from waste liquid generated in production process of viscose staple fibers. The method comprises the following steps: extracting hemicellulose, recovering alkali of a concentrated hemicellulose solution, concentrating the hemicellulose, hydrolyzing, neutralizing and enzymatically hydrolyzing the hemicellulose, and concentrating syrup, so that the finished feed-grade xylooligosaccharide product is obtained. According to the method provided by the invention, by preparing the feed-grade xylooligosaccharide from the hemicellulose in the viscose-producing waste liquid, so that the problem that social environment pollution is caused by the emission of a great amount of hemicellulose-containing waste liquid which is generated in the viscose production and is not effectively treated can be solved, and meanwhile, a new way for a xylooligosaccharide raw material source can be offered by taking the hemicellulose in the waste liquid as a raw material for producing the xylooligosaccharide.
Description
Technical field
The present invention relates to a kind of preparation method of xylooligosaccharide, especially relate to a kind of utilization in viscose staple fiber production process
The method that the waste liquid of middle generation prepares feed grade xylooligosaccharide.
Background technology
Xylooligosaccharide, is the feature polymerization sugar being combined into β-Isosorbide-5-Nitrae glycosidic bond by 2-7 xylose molecule.With usual people
Soybean oligo saccharide used, oligofructose, oligomeric isomaltose etc. compare the advantage with uniqueness, it can optionally promote
Enter the proliferation activity of intestinal bifidobacteria, its bifidobacterium factor functional is 10-20 times of other polymerization saccharides.Domestic enterprise at present,
The raw material of processing xylooligosaccharide is mainly derived from the crops such as corn cob, Testa Tritici.
Xylooligosaccharide quantifies, using starting from the initial stage nineties, to be concentrated mainly on the states such as America and Europe and Japan as feed additive
Family.In July, 2003, xylooligosaccharide obtains feedstuff and the feed additive new product certificate that the Ministry of Agriculture of China issues.2009, China
Academy of Agricultural Sciences, national feeding quality Supervision Test Center, Jiangsu Kangwei Bio Co., Ltd., Shandong dragon power biotechnology is limited
The feed additive xylooligosaccharide gb/t23747-2009 that company drafts jointly starts to issue and implement.
Content of the invention
The technical problem to be solved is to provide a kind of preparation method of xylooligosaccharide, and especially a kind of utilization is being glued
The method that the waste liquid producing in glue chopped fiber production process prepares feed grade xylooligosaccharide, half fiber producing in being produced using viscose glue
Element processes feed grade xylooligosaccharide as raw material, solves the problems, such as that in viscose glue production, hemicellulose discharges as production waste,
Prepare for xylooligosaccharide again and provide a kind of new raw material it is achieved that inter-trade Linking Development, promoted China's viscose glue production technology and
The common progress of xylooligosaccharide industry
The technical scheme is that a kind of produce using in viscose staple fiber production process
The method that raw waste liquid prepares feed grade xylooligosaccharide, comprises the following steps:
(1) extraction of hemicellulose: by the waste liquid containing hemicellulose through sheet frame, micropore pretreatment, then pass through nanofiltration
Membrance separation obtains hemicellulose concentrated solution 1 and net liquid 1；
(2) alkali collection of hemicellulose concentrated solution: add soft water in above-mentioned hemicellulose concentrated solution 1, received again
Filter membrane concentrating and separating, obtains hemicellulose concentrated solution 2 and net liquid 2；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half
Cellulose concentrated solution 3 and net liquid 3；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add sulphuric acid or hydrochloric acid to carry out water to above-mentioned hemicellulose concentrated solution 3
Solution, first neutralizes after hydrolysis, adds enzyme, digested, obtain syrup 1；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, by above-mentioned syrup 2 through drying
Dust and obtain feed grade xylooligosaccharide finished product.
The invention has the beneficial effects as follows: it is wooden as raw material preparation feed grade that present invention viscose glue produces hemicellulose in waste liquid
Oligosaccharide, not only solves the substantial amounts of waste liquid containing hemicellulose during viscose glue produces and is unable to effective process and discharges and cause social ring
The problem of border pollution, and using hemicellulose in waste liquid as the raw material producing xylooligosaccharide, the raw material sources for xylooligosaccharide provide
One new approach.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in step (1), described waste liquid is the waste liquid in viscose glue production process (squeezing process), in described waste liquid
The concentration of sodium hydroxide is 180-280 g/l, and hemicellulose level is 30-60 g/l.
Further, in step (1), described plate-and-frame filtration precision is 20 μ, and described microporous filter precision is 5 μ, described nanofiltration
Film is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 200-500 molecular weight, hydroxide in described hemicellulose concentrated solution 1
Sodium content is 180-280 g/l, and hemicellulose level is 50-70 g/l.
It is between 300-500 using the molecular weight that the beneficial effect of above-mentioned further technical scheme is because hemicellulose,
Finally adopt the NF membrane of 200 molecular weight after classified filtering, can by hemicellulose rejection bring up to more than 95% it is ensured that
Thickening efficiency and the degree of purity of net liquid.
Further, in step (2), the soft water of addition is industrial soft water, and addition is hemicellulose concentrated solution 1 volume
1.3-1.5 times, in described hemicellulose concentrated solution 2, sodium hydrate content is 10-50 g/l, and hemicellulose level is 50-70
G/l.
Using above-mentioned further technical scheme beneficial effect be step (2) purpose be exactly add soft water dialyse, enter one
Step reclaims sodium hydroxide so that the response rate of sodium hydroxide reaches more than 85%, does not have inspissation to hemicellulose, and adds
The purpose of soft water is to reclaim the sodium hydroxide in hemicellulose concentrated solution 1, finally makes the hydrogen in hemicellulose concentrated solution 1
Sodium oxide content is reduced to 10-50 g/l.The addition manner of concrete soft water is to add water in concentration, so reduces adding of soft water
Enter amount, save run time.
In waste liquid, the extraction of hemicellulose adopts tandem nanofiltration membrane process, simultaneously enters membrane component using soft water and waste liquid
Process operation, than conventional dilution amount of water reduce 70%；Up to 70 g/l of hemicellulose level simultaneously.
Further, in step (3), described ceramic membrane filter precision is 1000 molecular weight, in described hemicellulose concentrated solution 3
10-50 containing sodium hydroxide g/l, hemicellulose level is 80-150 g/l.
It is because the compact structure of NF membrane using the beneficial effect of above-mentioned further technical scheme, hemicellulose level is
High concentration is 80 g/l, reaches more than 80 g/l and causes pressure reduction too high, exceedes operation pressure it is impossible to normal run, and ceramic
The structure of film is porous type, is not affected by hemicellulose concentration level, hemicellulose concentration can be brought up to 150 g/l.
The reason processed using above-mentioned multi-stage PCE: because ceramic membrane filter precision is 1000 molecular weight, filtering accuracy is lower than NF membrane,
The rejection that result in hemicellulose is 75%.Half fiber in net liquid can be led to ceramic membrane if in low concentration hemicellulose
Element loss is many, uneconomical, so being first to carry out NF membrane retention hemicellulose, reduces sodium hydrate content adding soft water, finally
Using ceramic membrane, improve hemicellulose concentration.
Further, in step (1), step (2) and step (3), described net liquid 1 and net liquid 2 are back to use viscose glue production process
In dipping process, for allotment dipping alkali, described net liquid 3 is back to use the yellow operation in viscose glue production process, for allocating
Dissolving alkali.
Beneficial effect using above-mentioned further technical scheme is resource circulation utilization, does not waste available data, can drop
Low cost, economizes on resources it is adaptable to large scale industry produces, also reduces the generation of garbage and processing cost simultaneously, and concrete because
Different for alkali concn, it is back to different operations in viscose glue production process.
Further, in step (4), the addition of described sulphuric acid or hydrochloric acid is the 0.5%- of hemicellulose concentrated solution 3 mass
2%, hydrolysis temperature is 100-130 degree Celsius, and hydrolysis time is 30-120 minute, and described neutralization adopts sodium hydroxide to neutralize, in
With rear ph value controls between 4.5-6.
Beneficial effect using above-mentioned further technical scheme is that the determination of addition of acid of hydrolysis is to ensure that hydrolyzed solution
Ph value is 1.5-2.5, and 100 degrees Celsius of hydrolysis temperature just has hydrolysis, just can generate xylooligosaccharide, but if it exceeds
130 degrees Celsius can produce xylose or furfural, and hydrolysis temperature therefore to be controlled is between 100-130 degree Celsius.And the time hydrolyzing,
It is to be determined according to composite factors such as hemicellulose concentration, temperature, acid-base value, will ensure that whole hemicelluloses all carry out water as far as possible
Solution.Specifically, it is neutralized to the faintly acid of 4.5-6 it is ensured that neutralization is not excessive with alkali, and ensure that in syrup, there are not basic species
Matter.And adopt sodium hydroxide neutralize, be because in sodium hydroxide and after can produce sodium chloride, sodium chloride is present in feedstuff not shadow
Ring edible, meet the requirement of feed grade.
Further, in step (4), described enzyme is the compound enzyme of xylanase and hemicellulase, and described compound enzyme includes
The component of following mass fraction: 20%-30% xylanase f/10 family, 50%-60% xylanase g/11 family, 10%-
30% hemicellulase；The addition of described compound enzyme is the 0.005%-0.01% of hemicellulose concentrated solution 3 mass, described enzyme
Solution temperature is 45-75 degree Celsius, and enzymolysis time is 120-240 minute.
Using above-mentioned further technical scheme beneficial effect be the proportioning parameter of above-mentioned compound enzyme be according to repeatedly a large amount of
Contrast test and determine, after hydrolysis result, enzyme digestion reaction is gentle, and controllability is strong.
The detailed process of enzymolysis process is: hydrolysis of hemicellulose is first converted into xylooligosaccharide, if reaction temperature higher or
Ph value is too low, overlong time will be converted into xylose, and xylooligosaccharide conversion ratio is low.Control inversion point using mild hydrolysis, recycle
Enzymolysis is slow to be hydrolyzed, and improves xylooligosaccharide conversion ratio further.
Further, in step (4), in described syrup 1, the mass fraction of xylooligosaccharide is 3%-5%；In step (5), described
In syrup 2, the mass fraction of xylooligosaccharide is 20%-30%.
Further, in step (5), in the feed grade xylooligosaccharide finished product obtaining, xylooligosaccharide main component is wooden 2- wood 5 sugar,
Account for more than the 80% of finished product gross mass.
Beneficial effect using above-mentioned further technical scheme is wooden 2- wood 5 sugar, and stability is very good, even if in acid bar
Under part, (ph=2.5-7) is heated to 100 DEG C and does not also substantially decompose, and can effectively facilitate bacillus bifiduss proliferation activity and improve, and improves dynamic
Thing function of intestinal canal, particularly becomes apparent to animal germling effect, therefore the higher the better for content, and the method for the present invention, Ke Yizhan
More than the 80% of finished product gross mass, best results.
Specific embodiment
Hereinafter the principle and feature of the present invention is described, example is served only for explaining the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
A kind of using in viscose staple fiber production process produce waste liquid prepare feed grade xylooligosaccharide method, including with
Lower step:
(1) extraction of hemicellulose: with the waste liquid in viscose glue production process (squeezing process) as raw material, wherein sodium hydroxide
Concentration be 180 g/l, hemicellulose level be 30 g/l, by the above-mentioned waste liquid containing hemicellulose through sheet frame, micropore
Pretreatment, then hemicellulose concentrated solution 1 and net liquid 1 are obtained by nanofiltration membrane separation；Wherein, described plate-and-frame filtration precision is 20 μ,
Described microporous filter precision is 5 μ, and described NF membrane is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 500 molecular weight；Institute
State sodium hydrate content in hemicellulose concentrated solution 1 and be 180 g/l, hemicellulose level is 50 g/l；
(2) alkali collection of hemicellulose concentrated solution: add 1.3 times of volume of work in above-mentioned hemicellulose concentrated solution 1
Industry software water, carries out NF membrane concentrating and separating again, obtains hemicellulose concentrated solution 2 and net liquid 2；Described NF membrane is that 8040 types are resistance to
Alkali film filtering element, filtering accuracy is 500 molecular weight；In described hemicellulose concentrated solution 2, sodium hydrate content is 10 g/l,
Hemicellulose level is 50 g/l；
Collect net liquid 1 and net liquid 2, be back to use the dipping process in viscose glue production process, for allotment dipping alkali；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half
Cellulose concentrated solution 3 and net liquid 3；Described ceramic membrane filter precision is 1000 molecular weight, hydrogeneous in described hemicellulose concentrated solution 3
10 g/l of sodium oxide, hemicellulose level is 80 g/l；
Collect net liquid 3, be back to use the yellow operation in viscose glue production process, for allotment dissolving alkali；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add hemicellulose concentrated solution 3 to above-mentioned hemicellulose concentrated solution 3
The sulphuric acid of quality 0.5% or hydrochloric acid are hydrolyzed, and hydrolysis temperature is 130 degrees Celsius, and hydrolysis time is 30 minutes, in elder generation after hydrolysis
With specifically using sodium hydroxide neutralization, ph value controls between 4.5-5.5, adds hemicellulose concentrated solution 3 mass 0.01%
Xylanase and hemicellulase compound enzyme, digested, described compound enzyme includes the component of following mass fraction: 30%
Xylanase f/10 family, 60% xylanase g/11 family, 10% hemicellulase；Described hydrolysis temperature is 75 degrees Celsius,
Enzymolysis time is 120 minutes, obtains syrup 1；In described syrup 1, the mass fraction of xylooligosaccharide is 3%；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, xylooligosaccharide in described syrup 2
Mass fraction is 20%, above-mentioned syrup 2 is dusted through drying and obtains feed grade xylooligosaccharide finished product, wherein xylooligosaccharide main component
For wooden 2- wood 5 sugar, account for more than the 80% of finished product gross mass.
Embodiment 2
A kind of using in viscose staple fiber production process produce waste liquid prepare feed grade xylooligosaccharide method, including with
Lower step:
(1) extraction of hemicellulose: with the waste liquid in viscose glue production process (squeezing process) as raw material, wherein sodium hydroxide
Concentration be 280 g/l, hemicellulose level be 60 g/l, by the above-mentioned waste liquid containing hemicellulose through sheet frame, micropore
Pretreatment, then hemicellulose concentrated solution 1 and net liquid 1 are obtained by nanofiltration membrane separation；Wherein, described plate-and-frame filtration precision is 20 μ,
Described microporous filter precision is 5 μ, and described NF membrane is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 200 molecular weight；Institute
State sodium hydrate content in hemicellulose concentrated solution 1 and be 280 g/l, hemicellulose level is 70 g/l；
(2) alkali collection of hemicellulose concentrated solution: add 1.5 times of volume of work in above-mentioned hemicellulose concentrated solution 1
Industry software water, carries out NF membrane concentrating and separating again, obtains hemicellulose concentrated solution 2 and net liquid 2；Described NF membrane is that 8040 types are resistance to
Alkali film filtering element, filtering accuracy is 200 molecular weight；In described hemicellulose concentrated solution 2, sodium hydrate content is 50 g/l,
Hemicellulose level is 70 g/l；
Collect net liquid 1 and net liquid 2, be back to use the dipping process in viscose glue production process, for allotment dipping alkali；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half
Cellulose concentrated solution 3 and net liquid 3；Described ceramic membrane filter precision is 1000 molecular weight, hydrogeneous in described hemicellulose concentrated solution 3
50 g/l of sodium oxide, hemicellulose level is 150 g/l；
Collect net liquid 3, be back to use the yellow operation in viscose glue production process, for allotment dissolving alkali；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add hemicellulose concentrated solution 3 to above-mentioned hemicellulose concentrated solution 3
The sulphuric acid of quality 2% or hydrochloric acid are hydrolyzed, and hydrolysis temperature is 100 degrees Celsius, and hydrolysis time is 120 minutes, in elder generation after hydrolysis
With specifically using sodium hydroxide neutralization, ph value controls between 5-6, adds hemicellulose concentrated solution 3 mass 0.005%
Xylanase and the compound enzyme of hemicellulase, are digested, and described compound enzyme includes the component of following mass fraction: 20% wood
Dextranase f/10 family, 50% xylanase g/11 family, 30% hemicellulase；Described hydrolysis temperature is 45 degrees Celsius, enzyme
The solution time is 240 minutes, obtains syrup 1；In described syrup 1, the mass fraction of xylooligosaccharide is 5%；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, xylooligosaccharide in described syrup 2
Mass fraction is 30%, above-mentioned syrup 2 is dusted through drying and obtains feed grade xylooligosaccharide finished product, wherein xylooligosaccharide main component
For wooden 2- wood 5 sugar, account for more than the 80% of finished product gross mass.
Embodiment 3
A kind of using in viscose staple fiber production process produce waste liquid prepare feed grade xylooligosaccharide method, including with
Lower step:
(1) extraction of hemicellulose: with the waste liquid in viscose glue production process (squeezing process) as raw material, wherein sodium hydroxide
Concentration be 220 g/l, hemicellulose level be 40 g/l, by the above-mentioned waste liquid containing hemicellulose through sheet frame, micropore
Pretreatment, then hemicellulose concentrated solution 1 and net liquid 1 are obtained by nanofiltration membrane separation；Wherein, described plate-and-frame filtration precision is 20 μ,
Described microporous filter precision is 5 μ, and described NF membrane is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 300 molecular weight；Institute
State sodium hydrate content in hemicellulose concentrated solution 1 and be 220 g/l, hemicellulose level is 55 g/l；
(2) alkali collection of hemicellulose concentrated solution: add 1.3 times of volume of work in above-mentioned hemicellulose concentrated solution 1
Industry software water, carries out NF membrane concentrating and separating again, obtains hemicellulose concentrated solution 2 and net liquid 2；Described NF membrane is that 8040 types are resistance to
Alkali film filtering element, filtering accuracy is 300 molecular weight；In described hemicellulose concentrated solution 2, sodium hydrate content is 20 g/l,
Hemicellulose level is 55 g/l；
Collect net liquid 1 and net liquid 2, be back to use the dipping process in viscose glue production process, for allotment dipping alkali；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half
Cellulose concentrated solution 3 and net liquid 3；Described ceramic membrane filter precision is 1000 molecular weight, hydrogeneous in described hemicellulose concentrated solution 3
20 g/l of sodium oxide, hemicellulose level is 100 g/l；
Collect net liquid 3, be back to use the yellow operation in viscose glue production process, for allotment dissolving alkali；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add hemicellulose concentrated solution 3 to above-mentioned hemicellulose concentrated solution 3
The sulphuric acid of quality 1% or hydrochloric acid are hydrolyzed, and hydrolysis temperature is 110 degrees Celsius, and hydrolysis time is 100 minutes, in elder generation after hydrolysis
With specifically using sodium hydroxide neutralization, ph value controls between 4.5-5, adds hemicellulose concentrated solution 3 mass 0.007%
Xylanase and hemicellulase compound enzyme, digested, described compound enzyme includes the component of following mass fraction: 25%
Xylanase f/10 family, 55% xylanase g/11 family, 20% hemicellulase；Described hydrolysis temperature is 55 degrees Celsius,
Enzymolysis time is 180 minutes, obtains syrup 1；In described syrup 1, the mass fraction of xylooligosaccharide is 4%；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, xylooligosaccharide in described syrup 2
Mass fraction is 25%, above-mentioned syrup 2 is dusted through drying and obtains feed grade xylooligosaccharide finished product, wherein xylooligosaccharide main component
For wooden 2- wood 5 sugar, account for more than the 80% of finished product gross mass.
Embodiment 4
A kind of using in viscose staple fiber production process produce waste liquid prepare feed grade xylooligosaccharide method, including with
Lower step:
(1) extraction of hemicellulose: with the waste liquid in viscose glue production process (squeezing process) as raw material, wherein sodium hydroxide
Concentration be 240 g/l, hemicellulose level be 50 g/l, by the above-mentioned waste liquid containing hemicellulose through sheet frame, micropore
Pretreatment, then hemicellulose concentrated solution 1 and net liquid 1 are obtained by nanofiltration membrane separation；Wherein, described plate-and-frame filtration precision is 20 μ,
Described microporous filter precision is 5 μ, and described NF membrane is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 400 molecular weight；Institute
State sodium hydrate content in hemicellulose concentrated solution 1 and be 240 g/l, hemicellulose level is 60 g/l；
(2) alkali collection of hemicellulose concentrated solution: add 1.4 times of volume of work in above-mentioned hemicellulose concentrated solution 1
Industry software water, carries out NF membrane concentrating and separating again, obtains hemicellulose concentrated solution 2 and net liquid 2；Described NF membrane is that 8040 types are resistance to
Alkali film filtering element, filtering accuracy is 400 molecular weight；In described hemicellulose concentrated solution 2, sodium hydrate content is 30 g/l,
Hemicellulose level is 60 g/l；
Collect net liquid 1 and net liquid 2, be back to use the dipping process in viscose glue production process, for allotment dipping alkali；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half
Cellulose concentrated solution 3 and net liquid 3；Described ceramic membrane filter precision is 1000 molecular weight, hydrogeneous in described hemicellulose concentrated solution 3
30 g/l of sodium oxide, hemicellulose level is 120 g/l；
Collect net liquid 3, be back to use the yellow operation in viscose glue production process, for allotment dissolving alkali；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add hemicellulose concentrated solution 3 to above-mentioned hemicellulose concentrated solution 3
The sulphuric acid of quality 1.5% or hydrochloric acid are hydrolyzed, and hydrolysis temperature is 120 degrees Celsius, and hydrolysis time is 80 minutes, in elder generation after hydrolysis
With specifically using sodium hydroxide neutralization, ph value controls between 5.5-6, adds hemicellulose concentrated solution 3 mass 0.008%
Xylanase and hemicellulase compound enzyme, digested, described compound enzyme includes the component of following mass fraction: 22%
Xylanase f/10 family, 58% xylanase g/11 family, 20% hemicellulase；Described hydrolysis temperature is 60 degrees Celsius,
Enzymolysis time is 160 minutes, obtains syrup 1；In described syrup 1, the mass fraction of xylooligosaccharide is 3.5%；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, xylooligosaccharide in described syrup 2
Mass fraction is 24%, above-mentioned syrup 2 is dusted through drying and obtains feed grade xylooligosaccharide finished product, wherein xylooligosaccharide main component
For wooden 2- wood 5 sugar, account for more than the 80% of finished product gross mass.
Embodiment 5
A kind of using in viscose staple fiber production process produce waste liquid prepare feed grade xylooligosaccharide method, including with
Lower step:
(1) extraction of hemicellulose: with the waste liquid in viscose glue production process (squeezing process) as raw material, wherein sodium hydroxide
Concentration be 210 g/l, hemicellulose level be 45 g/l, by the above-mentioned waste liquid containing hemicellulose through sheet frame, micropore
Pretreatment, then hemicellulose concentrated solution 1 and net liquid 1 are obtained by nanofiltration membrane separation；Wherein, described plate-and-frame filtration precision is 20 μ,
Described microporous filter precision is 5 μ, and described NF membrane is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 250 molecular weight；Institute
State sodium hydrate content in hemicellulose concentrated solution 1 and be 210 g/l, hemicellulose level is 65 g/l；
(2) alkali collection of hemicellulose concentrated solution: add 1.4 times of volume of work in above-mentioned hemicellulose concentrated solution 1
Industry software water, carries out NF membrane concentrating and separating again, obtains hemicellulose concentrated solution 2 and net liquid 2；Described NF membrane is that 8040 types are resistance to
Alkali film filtering element, filtering accuracy is 250 molecular weight；In described hemicellulose concentrated solution 2, sodium hydrate content is 40 g/l,
Hemicellulose level is 65 g/l；
Collect net liquid 1 and net liquid 2, be back to use the dipping process in viscose glue production process, for allotment dipping alkali；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half
Cellulose concentrated solution 3 and net liquid 3；Described ceramic membrane filter precision is 1000 molecular weight, hydrogeneous in described hemicellulose concentrated solution 3
40 g/l of sodium oxide, hemicellulose level is 130 g/l；
Collect net liquid 3, be back to use the yellow operation in viscose glue production process, for allotment dissolving alkali；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add hemicellulose concentrated solution 3 to above-mentioned hemicellulose concentrated solution 3
The sulphuric acid of quality 1.8% or hydrochloric acid are hydrolyzed, and hydrolysis temperature is 130 degrees Celsius, and hydrolysis time is 50 minutes, in elder generation after hydrolysis
With specifically using sodium hydroxide neutralization, ph value controls between 5-6, adds the wood of hemicellulose concentrated solution 3 mass 0.01%
Dextranase and the compound enzyme of hemicellulase, are digested, and described compound enzyme includes the component of following mass fraction: 28% wood is poly-
Carbohydrase f/10 family, 54% xylanase g/11 family, 28% hemicellulase；Described hydrolysis temperature is 50 degrees Celsius, enzymolysis
Time is 200 minutes, obtains syrup 1；In described syrup 1, the mass fraction of xylooligosaccharide is 4.5%；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, xylooligosaccharide in described syrup 2
Mass fraction is 28%, above-mentioned syrup 2 is dusted through drying and obtains feed grade xylooligosaccharide finished product, wherein xylooligosaccharide main component
For wooden 2- wood 5 sugar, account for more than the 80% of finished product gross mass.
Comparative example
The feed grade xylooligosaccharide of certain famous brand name commercially available.
Interpretation of result:
Respectively the feed grade xylooligosaccharide finished product and comparative example obtaining in above-described embodiment 1-5 is chemically examined, analysis data
As shown in the table:
Embodiment 1-5 analysis data
| Oligomeric xylose content % >= | 40 |
| Moisture %≤ | 5 |
| Ph value | 3-6 |
| Burn residue %≤ | 13 |
| Arsenic (mg/kg, in terms of as)≤ | 0.5 |
| Lead (mg/kg, in terms of as)≤ | 2 |
| Total number of bacteria (cfu/g)≤ | 5000 |
| Total number of molds (cfu/g)≤ | 200 |
| Salmonella | No |
Comparative example analysis data
| Oligomeric xylose content % >= | 36 |
| Moisture %≤ | 8 |
| Ph value | 3-6 |
| Burn residue %≤ | 14 |
| Arsenic (mg/kg, in terms of as)≤ | 0.7 |
| Lead (mg/kg, in terms of as)≤ | 3 |
| Total number of bacteria (cfu/g)≤ | 5000 |
| Total number of molds (cfu/g)≤ | 300 |
| Salmonella | No |
And it is directed to feed grade xylooligosaccharide, its GB is as follows:
Feed additive oligomeric xylose GB gb/t23747-2009
| Oligomeric xylose content % >= | 35 |
| Moisture %≤ | 8 |
| Ph value | 3-6 |
| Burn residue %≤ | 15 |
| Arsenic (mg/kg, in terms of as)≤ | 1 |
| Lead (mg/kg, in terms of as)≤ | 5 |
| Total number of bacteria (cfu/g)≤ | 10000 |
| Total number of molds (cfu/g)≤ | 500 |
| Salmonella | No |
From above-mentioned analysis data, the effect of comparative example is better than GB, and the effect of embodiment 1-5 and comparative example class
Seemingly, also superior to GB, and relative, and the effect of embodiment 1-5 is also slightly more preferable than comparative example.As can be seen here, the present invention is real
Apply a feed grade xylooligosaccharide for 1-5 preparation and comply fully with GB, can carry out producing and sell.
And in embodiment 1-5, the waste that the waste liquid containing hemicellulose produces as viscose glue does not have economic worth in itself,
And subsequent treatment also needs to expend substantial amounts of water and high processing cost, and adopt the technique of the present invention, remove after processing
Reagent among in processing procedure, heating, allotment, outside cost of labor, can also obtain profit is per ton can to reach 5000
Unit, has purified production system, and not only low cost, moreover it is possible to bring benefits, turns waste into wealth, and how has both solved the waste liquid of viscose glue production
The problem processing, also add raw material prepared by feed grade xylooligosaccharide carrys out source problem, achieves many things at one stroke.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement made etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of method preparing feed grade xylooligosaccharide using the waste liquid producing in viscose staple fiber production process, its feature exists
In comprising the following steps:
(1) extraction of hemicellulose: by the waste liquid containing hemicellulose through sheet frame, micropore pretreatment, then divided by NF membrane
From obtaining hemicellulose concentrated solution 1 and net liquid 1；
(2) alkali collection of hemicellulose concentrated solution: add soft water in above-mentioned hemicellulose concentrated solution 1, carry out NF membrane again
Concentrating and separating, obtains hemicellulose concentrated solution 2 and net liquid 2；
(3) concentration of hemicellulose: above-mentioned hemicellulose concentrated solution 2 is carried out concentration by ceramic membrane, obtains half fiber
Plain concentrated solution 3 and net liquid 3；
(4) hydrolysis of hemicellulose, neutralization, enzymolysis: add sulphuric acid or hydrochloric acid to be hydrolyzed to above-mentioned hemicellulose concentrated solution 3,
First neutralize after hydrolysis, add enzyme, digested, obtain syrup 1；
(5) syrup concentrates: above-mentioned syrup 1 is concentrated to give syrup 2 through multiple-effect evaporation, above-mentioned syrup 2 is dusted through drying
Obtain feed grade xylooligosaccharide finished product.
2. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
The method of sugar is it is characterised in that in step (1), described waste liquid is the waste liquid in viscose glue production process, hydroxide in described waste liquid
The concentration of sodium is 180-280 g/l, and hemicellulose level is 30-60 g/l.
3. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
It is characterised in that in step (1), described plate-and-frame filtration precision is 20 μ, described microporous filter precision is 5 μ to the method for sugar, described
NF membrane is the alkaline-resisting film filtering element of 8040 types, and filtering accuracy is 200-500 molecular weight, hydrogen in described hemicellulose concentrated solution 1
Sodium oxide content is 180-280 g/l, and hemicellulose level is 50-70 g/l.
4. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
The method of sugar is it is characterised in that in step (2), the soft water of addition is industrial soft water, and addition is hemicellulose concentrated solution 1 body
Long-pending 1.3-1.5 times, in described hemicellulose concentrated solution 2, sodium hydrate content is 10-50 g/l, and hemicellulose level is 50-
70 g/l.
5. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
It is characterised in that in step (3), described ceramic membrane filter precision is 1000 molecular weight, described hemicellulose concentrates the method for sugar
10-50 containing sodium hydroxide g/l in liquid 3, hemicellulose level is 80-150 g/l.
6. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
The method of sugar is it is characterised in that in step (1), step (2) and step (3), described net liquid 1 and net liquid 2 are back to use viscose glue and produce
During dipping process, for allotment dipping alkali, described net liquid 3 is back to use the yellow operation in viscose glue production process, is used for
Allotment dissolving alkali.
7. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
The method of sugar is it is characterised in that in step (4), the addition of described sulphuric acid or hydrochloric acid is hemicellulose concentrated solution 3 mass
0.5%-2%, hydrolysis temperature is 100-130 degree Celsius, and hydrolysis time is 30-120 minute, and described neutralization adopts in sodium hydroxide
With after neutralization, ph value controls between 4.5-6.
8. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
The method of sugar is it is characterised in that in step (4), described enzyme is the compound enzyme of xylanase and hemicellulase, described compound enzyme
Component including following mass fraction: 20%-30% xylanase f/10 family, 50%-60% xylanase g/11 family,
10%-30% hemicellulase；The addition of described compound enzyme is the 0.005%-0.01% of hemicellulose concentrated solution 3 mass,
Described hydrolysis temperature is 45-75 degree Celsius, and enzymolysis time is 120-240 minute.
9. a kind of few using the waste liquid producing in viscose staple fiber production process preparation feed grade wood according to claim 1
The method of sugar is it is characterised in that in step (4), in described syrup 1, the mass fraction of xylooligosaccharide is 3%-5%；In step (5),
In described syrup 2, the mass fraction of xylooligosaccharide is 20%-30%.
10. a kind of waste liquid preparation using generation in viscose staple fiber production process according to any one of claim 1 to 9
The method of feed grade xylooligosaccharide is it is characterised in that in step (5), in the feed grade xylooligosaccharide finished product obtaining, xylooligosaccharide mainly becomes
It is divided into wooden 2- wood 5 sugar, account for more than the 80% of finished product gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610737002.8A CN106367449A (en) | 2016-08-26 | 2016-08-26 | Method for preparing feed-grade xylooligosaccharide from waste liquid generated in a production process of viscose staple fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610737002.8A CN106367449A (en) | 2016-08-26 | 2016-08-26 | Method for preparing feed-grade xylooligosaccharide from waste liquid generated in a production process of viscose staple fibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106367449A true CN106367449A (en) | 2017-02-01 |
Family
ID=57902598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610737002.8A Pending CN106367449A (en) | 2016-08-26 | 2016-08-26 | Method for preparing feed-grade xylooligosaccharide from waste liquid generated in a production process of viscose staple fibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106367449A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11006658B2 (en) | 2018-08-15 | 2021-05-18 | Cambridge Glycoscience Ltd | Compositions, their use, and methods for their formation |
| US11248247B2 (en) | 2018-02-21 | 2022-02-15 | Cambridge Glycoscience Ltd | Methods and systems of producing oligosaccharides |
| US11297865B2 (en) | 2019-08-16 | 2022-04-12 | Cambridge Glycoscience Ltd | Methods of treating biomass to produce oligosaccharides and related compositions |
| US11871763B2 (en) | 2019-12-12 | 2024-01-16 | Cambridge Glycoscience Ltd | Low sugar multiphase foodstuffs |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099431A (en) * | 2014-08-01 | 2014-10-15 | 沈阳新华环境工程有限公司 | Method for extracting xylose from viscoce chemical fiber squeezed alkali liquor |
| CN104357591A (en) * | 2014-11-07 | 2015-02-18 | 宜宾雅泰生物科技有限公司 | Process for producing feed-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor |
| CN105483184A (en) * | 2016-01-07 | 2016-04-13 | 中国科学院过程工程研究所 | Production method of high-yield xylooligosaccharide |
-
2016
- 2016-08-26 CN CN201610737002.8A patent/CN106367449A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104099431A (en) * | 2014-08-01 | 2014-10-15 | 沈阳新华环境工程有限公司 | Method for extracting xylose from viscoce chemical fiber squeezed alkali liquor |
| CN104357591A (en) * | 2014-11-07 | 2015-02-18 | 宜宾雅泰生物科技有限公司 | Process for producing feed-grade xylo-oligosaccharide from viscose fiber squeezed alkali liquor |
| CN105483184A (en) * | 2016-01-07 | 2016-04-13 | 中国科学院过程工程研究所 | Production method of high-yield xylooligosaccharide |
Non-Patent Citations (2)
| Title |
|---|
| 刘亮伟等: "F/10木聚糖酶研究进展", 《食品与生物技术学报》 * |
| 王立东等: "利用木聚糖酶酶解小麦麸皮制备低聚木糖工艺参数的研究", 《黑龙江八一农垦大学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11248247B2 (en) | 2018-02-21 | 2022-02-15 | Cambridge Glycoscience Ltd | Methods and systems of producing oligosaccharides |
| US11006658B2 (en) | 2018-08-15 | 2021-05-18 | Cambridge Glycoscience Ltd | Compositions, their use, and methods for their formation |
| US11596165B2 (en) | 2018-08-15 | 2023-03-07 | Cambridge Glycoscience Ltd | Compositions, their use, and methods for their formation |
| US11903399B2 (en) | 2018-08-15 | 2024-02-20 | Cambridge Glycoscience Ltd | Compositions, their use, and methods for their formation |
| US11297865B2 (en) | 2019-08-16 | 2022-04-12 | Cambridge Glycoscience Ltd | Methods of treating biomass to produce oligosaccharides and related compositions |
| US11771123B2 (en) | 2019-08-16 | 2023-10-03 | Cambridge Glycoscience Ltd | Methods for treating biomass to produce oligosaccharides and related compositions |
| US11871763B2 (en) | 2019-12-12 | 2024-01-16 | Cambridge Glycoscience Ltd | Low sugar multiphase foodstuffs |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101855368B (en) | Process for preparing a sugar product | |
| CN106367449A (en) | Method for preparing feed-grade xylooligosaccharide from waste liquid generated in a production process of viscose staple fibers | |
| CN104593446B (en) | A kind of preparation method of pure xylo-oligosaccharide powder | |
| CN1107117C (en) | Process for producing L-arabinose by acid hydrolysis method | |
| CN106715704A (en) | Method of preparing sugar solution | |
| JP5431499B2 (en) | Monosaccharide production method | |
| JPS6052800B2 (en) | Manufacturing method of glucose from vegetable raw materials | |
| CN102154876B (en) | Method for extracting and separating components in ramulus mori skin | |
| CN103131802B (en) | Process for producing xylose by lignocellulose biomass | |
| CN103468834A (en) | Method for preparing xylooligosaccharide by treating plant fibers via neutral sulfite | |
| JP7141774B2 (en) | Method for preparing purified solution of poplar xylooligosaccharide, purified solution of poplar xylooligosaccharide prepared by the method, solid xylooligosaccharide and use thereof | |
| CN106222313A (en) | A kind of method utilizing the waste liquid produced in viscose staple fiber production process to prepare food stage xylose | |
| CN103082393A (en) | Preparation method of tobacco flakes through tobacco stems using biochemical machinery method | |
| CN101575369B (en) | Technique for separating and preparing rapeseed protein cogenerating rapeseed polyoses from the low-temperature cold pressing rapeseed dregs film | |
| CN104231116A (en) | Method for preparing hemicellulose, humate and feed additive by utilizing straws | |
| CN108410923B (en) | Method for preparing microcrystalline cellulose from sorghum straws | |
| CN101565468B (en) | Method for producing xylo-oligosaccharide by utilizing cotton seed hulls | |
| CN103981235B (en) | A kind of method improving hydrolyzing ligno-cellulose with cellulosic enzyme efficiency | |
| CN115011651B (en) | Method for efficiently preparing sugar by reed | |
| CN1032322C (en) | Method for making artificial fibre pulp and xylitol using corn stalk as material | |
| CN1217041C (en) | Protein synthetic fiber and its production method | |
| RU2750146C2 (en) | Methods for obtaining bioplastics and bioproducts from manure | |
| CN101429535B (en) | Method for improving utilization ratio of starch in corn hull | |
| CN104846032A (en) | Method for preparing cellulose hydrolyzed sugar by using cellulase | |
| CN1410451A (en) | Method of producing carboxy methyl cellulose and xylose using straw |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170201 |
|
| RJ01 | Rejection of invention patent application after publication |