CN105061779B - A kind of preparation of modified sodium lignosulfonate - Google Patents
A kind of preparation of modified sodium lignosulfonate Download PDFInfo
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- CN105061779B CN105061779B CN201510503203.7A CN201510503203A CN105061779B CN 105061779 B CN105061779 B CN 105061779B CN 201510503203 A CN201510503203 A CN 201510503203A CN 105061779 B CN105061779 B CN 105061779B
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- lignin
- sodium lignin
- laccase
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Abstract
The invention discloses a kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant：Choose lignin sulfonic acid sodium raw materials of the molecular weight 5,000 9000；With sodium lignin sulfonates of the pH for 45 80 95g/L of acetic acid sodium acetate buffer preparation, add the laccase of 2 2.8U/g sodium lignin sulfonates, the carbohydrase of 23 U/g sodium lignin sulfonates is reacted at 50 56 DEG C after 6 9h, and boiling inactivates laccase and carbohydrase；By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.Obtained sodium lignin sulfonate, of light color, staining is few, and molecular weight ranges are small and temperature, resistance to more than 150 DEG C of high temperature.
Description
Technical field
The invention belongs to macromolecule chemical industry technical field, and in particular to a kind of preparation of modified sodium lignosulfonate.
Background technology
Lignin is the abundant natural high polymer with aromatic structure of nature content second, be it is extremely important can be again
Raw living resources, nature can about produce 6 × 10 every year14T.The exhaustion of traditional ore resource and the enhancing of mankind's environmental consciousness are given
The basic research and industrialization of lignin utilize and bring strong impetus.Lignosulfonates are the derivatives of lignin, and it changes
Property prepare surfactant and flourish in recent years and achieve serial impressive progress, modified product is widely used for industrial or agricultural life
Production.
Lignin be by guaiacyl, three phenylpropyl alcohol alkyl structure units of lilac base and p-hydroxyphenyl by C-C keys and
C-O keys are connected with each other, baroque natural polymer formed by random coupling.But for sulfomethylated lignin
The molecular structure of hydrochlorate, has scholar to be considered tridimensional network, also has and is considered three-dimensional spherical structure, there is no uniformly recognize at present
Know.Also there is the structure that-CH CH-,-OH and phenyl ring are conjugated in lignosulfonates, industrial lignin sulfonate
Phenolic hydroxyl group is also possible to and heavy metal ion formation complex compound.These special molecular structures make lignosulfonates with special
Color, its chromogenic mechanism not yet studies clear completely so far, constrains the lignin sulfonate modified work for preparing surfactant
Make.Color is to prepare the problem that Novel wooden quality sulfosalt surfactant must pull against, and is relied primarily on：（1）The method of physics
It is separated off foreign pigment；（2）The chromogenic mechanism of lignosulfonate molecules in itself is studied, is entered from the angle of electromagnetic energy absorption
Row MOLECULE DESIGN, structurally-modified process is removed or closing chromophore, lignosulfonates is not produced between visible region
Or only produce weak absorption.
The present invention is intended to provide a kind of preparation of modified sodium lignosulfonate, its technique is simply operated well, face can be prepared
Color is very shallow, and heat-resistant stability is good, is suitable as the sodium lignin sulfonate of dyestuff dispersant.
The content of the invention
The technical problem existed based on background technology, the problem of present invention exists for background technology, the present invention provides one
The preparation of modified sodium lignosulfonate is planted, its technique is simply operated well, can prepare very slight color, heat-resistant stability is good, fitted
The sodium lignin sulfonate of cooperation dyestuff dispersant.
Heat-resistant stability refers to that the ground dye dispersion system of dispersant is carried out in spray-drying process in different dryings
At a temperature of situation of change, generally, heat resisting temperature reaches that 130 DEG C can meet requirement, to be on the safe side, it is desirable to
The heat resisting temperature of dye dispersion system after dispersant processing reaches 140 DEG C or 150 DEG C.Influence the factor of Heat-resistant stable a lot,
For example:Unreacted intermediate, inorganic salts of former dyestuff water-washing process residual of synthesis etc., put down in Lignin Dispersants production
It is excessive wetting agent in the impurity, and formula such as average molecular weight very low lignin, reduced sugar, calcium ion, inorganic salts, dust-proof
Agent, defoamer etc..
Natural lignin is almost colourless, and industrial lignin is obtained by chemical method, makes in preparation process wooden
Element carries different colors.The major defect of Lignin Dispersants is exactly to have contamination to fiber, that is, described " fiber is stained with
Color ".The degree of fiber staining depends on several factors:The color of Lignin Dispersants, the type of fiber, Lignin Dispersants
Solubility, the molecular weight of Lignin Dispersants, the structure of Lignin Dispersants.The color of Lignin Dispersants is on lignin
Double bond, quinoid structure determine, dissolubility be sulfonation degree determine.Lignin and the principle of fiber staining are " hydrogen bond reasons
By ".The staining of lignin is aggravated if group (such as amino, carboxyl and hydroxyl) strong containing polarized in fruit fiber.Therefore,
And chemical modification can be carried out to reduce the staining to fiber from the color of reduction sodium lignin sulfonate.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose lignin sulfonic acid sodium raw materials of the molecular weight in 5000-9000；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 80-95g/L sodium lignin sulfonate, adds 2-
The laccase of 2.8U/g sodium lignin sulfonates, the carbohydrase of 2-3 U/g sodium lignin sulfonates is reacted after 6-9h at 50-56 DEG C, is boiled
Boiling inactivates laccase and carbohydrase；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
Preferably, the concrete scheme of the present invention is：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 5000 sodium lignin sulfonate；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 80g/L sodium lignin sulfonate, adds 2U/g wooden
The laccase of plain sodium sulfonate, the carbohydrase of 2 U/g sodium lignin sulfonates is reacted after 6h at 50 DEG C, and boiling makes laccase and carbohydrase
Inactivation；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
The present invention is advantageous in that：
Technique is simply operated well, can prepare very slight color, and heat-resistant stability is good, is suitable as the wood of dyestuff dispersant
Quality sodium sulfonate.Obtained sodium lignin sulfonate, of light color, staining is few, and molecular weight ranges are small and temperature, resistance to more than 150 DEG C
High temperature.
Embodiment
Embodiment 1：
The plain sodium sulfonate of raw material wood of the present invention is all from sulfurous method pulping waste liquor, and sodium lignin sulfonate mass fraction is about
70%。
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 5000 sodium lignin sulfonate；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 80g/L sodium lignin sulfonate, adds 2U/g wooden
The laccase of plain sodium sulfonate, the carbohydrase of 2 U/g sodium lignin sulfonates is reacted after 6h at 50 DEG C, and boiling makes laccase and carbohydrase
Inactivation；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
As a result：
The molecular weight distribution of obtained sodium lignin sulfonate is between 2-2.2 ten thousand, and mean molecule quantity 2.05 ten thousand, color is pole
Shallow brown.
As sodium lignin sulfonate dye dispersant, kept for 10 minutes at 150 DEG C, its diffusion reaches 5 grades,
Kept for 10 minutes at 160 DEG C, its diffusion reaches 5 grades.
Under pH7, the whiteness value influence on pure cotton fiber is less than 0.5%, and the whiteness value influence on wool fiber is less than
0.8%。
Embodiment 2：
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 9000 sodium lignin sulfonate；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 95g/L sodium lignin sulfonate, adds 2.8U/g wood
The laccase of quality sodium sulfonate, the carbohydrase of 3 U/g sodium lignin sulfonates is reacted after 9h at 56 DEG C, and boiling makes laccase and saccharification
Enzyme is inactivated；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
As a result：
The molecular weight distribution of obtained sodium lignin sulfonate is between 2.2-2.5 ten thousand, mean molecule quantity 2.32 ten thousand, and color is
Extremely shallow brown.
As sodium lignin sulfonate dye dispersant, kept for 10 minutes at 150 DEG C, its diffusion reaches 5 grades,
Kept for 10 minutes at 160 DEG C, its diffusion reaches 4 grades.
Under pH7, the whiteness value influence on pure cotton fiber is less than 0.6%, and the whiteness value influence on wool fiber is less than
0.9%。
Embodiment 3：
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 8000 sodium lignin sulfonate；
（2）With sodium lignin sulfonates of the pH for 5 NaAc_HAc buffer solution preparation 80g/L, 2.5U/g is added wooden
The laccase of plain sodium sulfonate, the carbohydrase of 2.5 U/g sodium lignin sulfonates is reacted after 6-9h at 55 DEG C, and boiling makes laccase and sugar
Change enzyme inactivation；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
As a result：
The molecular weight distribution of obtained sodium lignin sulfonate is between 2-2.4 ten thousand, and mean molecule quantity 2.15 ten thousand, color is pole
Shallow brown.
As sodium lignin sulfonate dye dispersant, kept for 10 minutes at 150 DEG C, its diffusion reaches 5 grades,
Kept for 10 minutes at 160 DEG C, its diffusion reaches 4 grades.
Under pH7, the whiteness value influence on pure cotton fiber is less than 0.6%, and the whiteness value influence on wool fiber is less than
0.8%。
Embodiment 4：
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 7500 sodium lignin sulfonate；
（2）With sodium lignin sulfonates of the pH for 5 NaAc_HAc buffer solution preparation 92g/L, 2.3U/g is added wooden
The laccase of plain sodium sulfonate, the carbohydrase of 2.5 U/g sodium lignin sulfonates is reacted after 8h at 52 DEG C, and boiling makes laccase and saccharification
Enzyme is inactivated；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
As a result：
The molecular weight distribution of obtained sodium lignin sulfonate is between 2.1-2.6 ten thousand, mean molecule quantity 2.29 ten thousand, and color is
Extremely shallow brown.
As sodium lignin sulfonate dye dispersant, kept for 10 minutes at 150 DEG C, its diffusion reaches 5 grades,
Kept for 10 minutes at 160 DEG C, its diffusion reaches 4 grades.
Under pH7, the whiteness value influence on pure cotton fiber is less than 0.5%, and the whiteness value influence on wool fiber is less than
0.9%。
Embodiment 5：
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 7000 sodium lignin sulfonate；
（2）With sodium lignin sulfonates of the pH for 4 80 g/L of NaAc_HAc buffer solution preparation, 2U/g is added wooden
The laccase of plain sodium sulfonate, the carbohydrase of 3 U/g sodium lignin sulfonates is reacted after 6-9h at 56 DEG C, and boiling makes laccase and saccharification
Enzyme is inactivated；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
As a result：
The molecular weight distribution of obtained sodium lignin sulfonate is between 2.1-2.3 ten thousand, mean molecule quantity 2.15 ten thousand, and color is
Extremely shallow brown.
As sodium lignin sulfonate dye dispersant, kept for 10 minutes at 150 DEG C, its diffusion reaches 5 grades,
Kept for 10 minutes at 160 DEG C, its diffusion reaches 5 grades.
Under pH7, the whiteness value influence on pure cotton fiber is less than 0.6%, and the whiteness value influence on wool fiber is less than
0.9%。
The contrast test of embodiment 6：
A kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 5000 sodium lignin sulfonate；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 80g/L sodium lignin sulfonate, adds 2U/g wooden
The laccase of plain sodium sulfonate is reacted after 6h at 50 DEG C, and boiling inactivates laccase and carbohydrase；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
As a result：
The molecular weight distribution of obtained sodium lignin sulfonate is between 1.2-1.8 ten thousand, mean molecule quantity 1.36 ten thousand, and color is
Shallow brown.
As sodium lignin sulfonate dye dispersant, kept for 10 minutes at 150 DEG C, its diffusion reaches 4 grades,
Kept for 10 minutes at 160 DEG C, its diffusion reaches 3 grades.
Under pH7, the whiteness value influence on pure cotton fiber is more than 1%, and the whiteness value influence on wool fiber is more than 1.6%.
As can be seen here, carbohydrase and laccase serve joint synergy, compared to being only modified with laccase, obtained lignin
The molecular weight distribution of sodium sulfonate is small, and mean molecule quantity is high, and color is substantially shallow, and staining is few.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (4)
1. a kind of preparation method of the sodium lignin sulfonate of dyestuff dispersant, step is as follows：
（1）Choose lignin sulfonic acid sodium raw materials：Choose the plain sulfonic acid sodium raw materials of the rugose wood from sulfurous method pulping waste liquor；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 80-95g/L sodium lignin sulfonate, adds sulfomethylated lignin
The laccase of sour sodium, the carbohydrase of sodium lignin sulfonate is reacted after 6-9h at 50-56 DEG C, and boiling inactivates laccase and carbohydrase；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained；
The step（1）Choose lignin sulfonic acid sodium raw materials of the molecular weight in 5000-9000；
The step（2）Add the laccase of 2-2.8U/g sodium lignin sulfonates, the carbohydrase of 2-3 U/g sodium lignin sulfonates.
2. the preparation method of the sodium lignin sulfonate of the dyestuff dispersant described in claim 1, it is characterised in that：
（1）Choose lignin sulfonic acid sodium raw materials：Choose molecular weight and be used as raw material in 5000 sodium lignin sulfonate；
（2）The NaAc_HAc buffer solution for being 4-5 with pH prepares 80g/L sodium lignin sulfonate, adds 2U/g sulfomethylated lignins
The laccase of sour sodium, the carbohydrase of 2 U/g sodium lignin sulfonates is reacted after 6h at 50 DEG C, and boiling inactivates laccase and carbohydrase；
（3）By the product prepared filtering, after filtrate is freeze-dried, modified sodium lignosulfonate is obtained.
3. the innovation wood that the dyestuff described in claim 1 or 2 is prepared with the preparation method of the sodium lignin sulfonate of dispersant
Quality sodium sulfonate.
4. the modified sodium lignosulfonate described in claim 3, it is characterised in that：Its resistance to more than 150 DEG C high temperature.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101743257A (en) * | 2007-04-19 | 2010-06-16 | 马斯科马公司 | The combined thermochemical pre-treatment of lignocellulose biomass and refining |
| CN102585247A (en) * | 2012-01-12 | 2012-07-18 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose |
| CN104774876A (en) * | 2015-04-10 | 2015-07-15 | 山东龙力生物科技股份有限公司 | Method for comprehensive utilization of lignocellulosic biomasses |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1995023232A1 (en) * | 1994-02-25 | 1995-08-31 | Novo Nordisk A/S | Laccase/peroxidase treatment of lignosulphonates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101743257A (en) * | 2007-04-19 | 2010-06-16 | 马斯科马公司 | The combined thermochemical pre-treatment of lignocellulose biomass and refining |
| CN102585247A (en) * | 2012-01-12 | 2012-07-18 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose |
| CN104774876A (en) * | 2015-04-10 | 2015-07-15 | 山东龙力生物科技股份有限公司 | Method for comprehensive utilization of lignocellulosic biomasses |
Non-Patent Citations (2)
| Title |
|---|
| "木质素降解酶预处理玉米秸秆试验研究";陈伟;《河南农业大学硕士论文》;20090415(第4期);摘要 * |
| "漆酶改性木质素磺酸钠的结构表征及吸附特征";周海峰等;《高等学校化学学报》;20130131;第34卷(第1期);第218-224页 * |
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Effective date of registration: 20210129 Address after: 333000 Leping Industrial Park, Jingdezhen City, Jiangxi Province Patentee after: Jiangxi Shilong New Material Co.,Ltd. Address before: 313000 shapukou, Changchao Town, Nanxun District, Huzhou City, Zhejiang Province Patentee before: HUZHOU CHANGSHENG CHEMICAL Co.,Ltd. |
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