CN106397789B - A kind of method of modifying of lignosulfonates - Google Patents
A kind of method of modifying of lignosulfonates Download PDFInfo
- Publication number
- CN106397789B CN106397789B CN201610866262.5A CN201610866262A CN106397789B CN 106397789 B CN106397789 B CN 106397789B CN 201610866262 A CN201610866262 A CN 201610866262A CN 106397789 B CN106397789 B CN 106397789B
- Authority
- CN
- China
- Prior art keywords
- solution
- lignosulfonates
- exchange resin
- resin
- concentration
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paper (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention discloses a kind of method of modifying of lignosulfonates, lignosulfonates are aoxidized using oxidant first, then a certain amount of formaldehyde is added and sodium hydrogensulfite carries out sulfonation, sulfonated products are subjected to separating-purifying by anion and cation exchange resin, introducing Short chain sulfonic acids base in the lignin phenyl ring of modified lignosulfonates is finally obtained, the water solubility, dispersibility and emulsibility of alkali lignin can be effectively improved.
Description
Technical field
The invention belongs to lignosulfonates technical fields, are related to a kind of method of modifying of lignosulfonates.
Background technique
Lignosulfonates improve the content of the sulfonate radical of lignosulfonates itself by sulfonating reaction, improve wooden
The water solubility and reactivity of element, prepare water-reducing agent to later period modified lignin mahogany sulfonate and provide advantage, at present state
There are many inside and outside research to lignin, but since lignin derives from papermaking wastewater, the difference for the treatment of process in paper-making process
And lignin itself is the natural polymer of tridimensional network, there are three types of different monomers, relative molecular masses
Unevenness, thus difficulty is caused to the separating-purifying of lignin.
Patent name is the method for producing sulfonated lignin, the Chinese invention of Publication No. CN1434068
Patent；Patent name is the highly sulfonated lignosulfonates and the preparation method and application thereof containing alkyl sulfonic acid, Publication No.
The Chinese invention patent of CN104194002A.The method of above-mentioned patent disclosure by being with formaldehyde, the second light industry bureau base ketone or oxidant
Initiator catalysis oxidation lignin, process is simple, but grafting efficiency is not high, and the Short chain sulfonic acids group and band introduced
The anchorage effect on positive particles surface is not strong enough, limits the industrial application of lignosulfonates.
Water solubility, molecular weight is low, molecular weight distribution is wide and reactivity worth is poor, and the industry for seriously limiting alkali lignin is answered
With.It is water-soluble that its can be changed using functional group's progress chemical modification such as sulfonation, oxidation, ammonification, alkylation, condensation, graft copolymerization etc.
Property, molecular weight and surface can prepare the lignin-base surfactant product of high added value, and method of modifying common at present is logical
Sulfonation modifying is crossed into lignosulfonates, its main feature is that introducing Short chain sulfonic acids base in lignin benzene ring structure, there is surface energy
Effectively improve the performances such as the water solubility, dispersibility and emulsification danger of alkali lignin.
Summary of the invention
The purpose of the present invention is to provide a kind of method of modifying of lignosulfonates.By taking sulfonation after initial oxidation
Method introduces Short chain sulfonic acids base in the lignin phenyl ring of the lignosulfonates for the modification being prepared, and can effectively improve alkali wood
Water solubility, dispersibility and the emulsibility of quality.
The purpose of the present invention is achieved through the following technical solutions:
The method of modifying of this lignosulfonates, comprising the following steps:
Step 1,5 parts of lignosulfonates are taken by mass fraction, above-mentioned lignosulfonates, which are dissolved in volume parts, is
In 80 parts of distilled water, the oxidant that volume parts are 2 parts is added, reacts 1-2h at 55-60 DEG C, obtains solution a；
Step 2, solution a is warming up to 60-100 DEG C, 4 parts of mass parts numerical digit of formaldehyde and sodium hydrogensulfite is then added,
5-9h is reacted, then cools to room temperature, obtains solution b；
Step 3, by solution b followed by anion exchange resin and cation exchange resin, then using distillation washing
Anion exchange resin and cation exchange resin are washed, the PH of the cleaning solution after cleaning obtains extracting solution until 7；
Step 4, extracting solution is dried at 80-100 DEG C, obtains modified lignosulfonates.
Further, the features of the present invention also characterized in that:
Wherein the preparation process of cation exchange resin is in step 3, soaks in the hydrogen chloride solution that concentration is 2mol/L
The strong acidic ion resin of 12h is steeped, and washing above-mentioned strong acidic ion resin to pH using distilled water is neutrality, is obtained
To cation exchange resin.
Wherein the preparation process of anion exchange resin is in step 3, in the sodium hydroxide solution that concentration is 2mol/L
The strongly basic anionic resin of 12h is impregnated, and washing above-mentioned strongly basic anionic resin to pH using distilled water is neutrality,
Obtain anion exchange resin.
Wherein make to be washed with distilled water anion exchange resin and cation exchange resin, until the pH of washing efflux is
When property, all cleaning solutions are collected, extracting solution is obtained.
Wherein the mass ratio of formaldehyde and sodium hydrogensulfite is 1-2:3 in step 2.
Wherein the oxidant in step 1 is the hydrogenperoxide steam generator that concentration is 30%.
Wherein the pH for having dissolved the aqueous solution of lignosulfonates is adjusted to 2-3 using hydrogen chloride solution in step 1,
The concentration of middle hydrogen chloride is 0.5mol/L.
Wherein in step 1 after oxidant reaction, it is molten that the sodium hydroxide that concentration is 0.5mol/L is added into acquired solution
Liquid adjusts the pH of acquired solution to 8-9, obtains solution a.
The beneficial effects of the present invention are: first being aoxidized using oxidant and lignosulfonates, lignin sulfonic acid is opened
The tridimensional network of salt allows more active sites to be exposed, and formaldehyde is then added and sodium hydrogensulfite carries out sulfonation and changes
Property；To increase the water solubility of lignosulfonates, the sulfonation degree of lignosulfonates is improved, while improving sulfomethylated lignin
The reactivity of hydrochlorate.
Detailed description of the invention
Fig. 1 is lignosulfonates absorbance under the wavelength of 80nm under 10-100mg/l concentration range in the present invention
Standard concentration curve figure；
Fig. 2 is the curve graph that lignosulfonates conductivity in different volumes sodium hydroxide solution is measured in the present invention；
Fig. 3 is the curve of lignosulfonates conductivity in the sodium hydroxide solution of different volumes modified in the present invention
Figure.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawing:
The present invention provides a kind of method of modifying of lignosulfonates, comprising the following steps:
Step 1,5 parts of lignosulfonates are taken by mass fraction, above-mentioned lignosulfonates, which are dissolved in volume parts, is
In 80 parts of distilled water, then acquired solution pH is adjusted to 2-3 using the hydrogen chloride solution of 0.5mol/L；Add parts by volume
The oxidant that number is 2 parts, oxidant is the hydrogenperoxide steam generator that concentration is 30%；1-2h is reacted at 55-60 DEG C, is then used
The sodium hydroxide solution of 0.5mol/L adjusts the pH of acquired solution to 8-9, obtains solution a.
Step 2, solution a is warming up to 60-100 DEG C, 4 parts of mass parts numerical digit of formaldehyde and sodium hydrogensulfite is then added,
Wherein the mass ratio of formaldehyde and sodium hydrogensulfite is 1-2:3, reacts 5-9h, then cools to room temperature, obtain solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 80-100 DEG C, obtains modified lignosulfonates.
The absorbance of the modified lignosulfonates of 10 groups of different quality concentration, and root are determined at wavelength 280nm
Its mass concentration is calculated according to standard concentration curve, obtains curve graph as shown in Figure 1, the concrete meaning of map parameter is:
| Fitting function | GaussAmp |
| Fit equation | Y=y0+ A*exp (- 0.5 ((x-xc)/w :) |
| Coefficient R | 0.97147 |
| Y0 | 3.524 |
| Xc | 95.66239 |
| W | 53.72579 |
| A | 0.60985 |
Using the lignosulfonates for the modification that the sodium hydroxide solution of 0.0025mol/L titrates, sodium hydroxide and
Sulfonate ion occurs neutralization reaction and conductivity is fallen before, and with the increase of the amount of sodium hydroxide, conductivity rises, most
Lower is the amount of sulfonate radical, and result is as shown in Fig. 2, the concrete meaning of map parameter is:
| Fitting function | GaussAmp |
| Fit equation | Y=y0+ A*exp (- 0.5 ((x-xc)/w :) |
| Coefficient R | 0.98912 |
| Y0 | 993.52044 |
| Xc | 26.51782 |
| W | 1275.29814 |
| A | -992.76696 |
Preparation method of the invention is simple, and easy to operate, can see from Fig. 1 and Fig. 2, the modification that the present invention obtains
Lignosulfonates, more sulfonic groups have been introduced on the basis of original lignosulfonates, have improved lignin sulfonic acid
The water solubility and reactivity of salt, convenient for creating favorable conditions in subsequent modification.
It is 0-30ml concentration in volume is 2mol/L's that Fig. 3, which is the modified lignosulfonates of 0.02g, 0.03g and 0.04g,
The curve graph of conductivity in sodium hydroxide solution.With the consumption of sodium hydroxide solution, sodium hydroxide neutralized sulfonate radical from
Son, i.e., so that its conductivity declines；When sulfonate ion is depleted, conductivity touches the bottom；It then proceedes to drip
Adding sodium hydroxide solution, so that conductivity rises.
The embodiment of the present invention are as follows:
Embodiment 1
Step 1,5g lignosulfonates are taken, above-mentioned lignosulfonates are dissolved in the distilled water of 80ml, are then made
The pH of acquired solution is adjusted to 2 with the hydrogen chloride solution of 0.5mol/L；The oxidant of 2ml is added, oxidant is that concentration is
30% hydrogenperoxide steam generator；1h is reacted at 55 DEG C, then uses the sodium hydroxide solution of 0.5mol/L by acquired solution
PH is adjusted to 8, obtains solution a.
Step 2, solution a is warming up to 60 DEG C, the formaldehyde and sodium hydrogensulfite of 4g is then added, wherein formaldehyde is 1g, sub-
Sodium bisulfate is 3g, reacts 5-9h, then cools to room temperature, obtain solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 80-100 DEG C, obtains modified lignosulfonates.
Embodiment 2
Step 1,5g lignosulfonates are taken, above-mentioned lignosulfonates are dissolved in the distilled water of 80ml, are then made
The pH of acquired solution is adjusted to 3 with the hydrogen chloride solution of 0.5mol/L；The oxidant of 2ml is added, oxidant is that concentration is
30% hydrogenperoxide steam generator；2h is reacted at 60 DEG C, then uses the sodium hydroxide solution of 0.5mol/L by acquired solution
PH is adjusted to 9, obtains solution a.
Step 2, solution a is warming up to 100 DEG C, the formaldehyde of 1.6g and the sodium hydrogensulfite of 2.4g is then added, react 9h,
It then cools to room temperature, obtains solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 80-100 DEG C, obtains modified lignosulfonates.
Embodiment 3
Step 1,5g lignosulfonates are taken, above-mentioned lignosulfonates are dissolved in the distilled water of 80ml, are then made
The pH of acquired solution is adjusted to 2.5 with the hydrogen chloride solution of 0.5mol/L；The oxidant of 2ml is added, oxidant is concentration
For 30% hydrogenperoxide steam generator；1.5h is reacted at 58 DEG C, it is then using the sodium hydroxide solution of 0.5mol/L that gained is molten
The pH of liquid is adjusted to 8.5, obtains solution a.
Step 2, solution a is warming up to 70 DEG C, the formaldehyde of 1g and the sodium hydrogensulfite of 3g is then added, react 6h, then
It is cooled to room temperature, obtains solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 85 DEG C, obtains modified lignosulfonates.
Embodiment 4
Step 1,5g lignosulfonates are taken, above-mentioned lignosulfonates are dissolved in the distilled water of 80ml, are then made
The pH of acquired solution is adjusted to 2.7 with the hydrogen chloride solution of 0.5mol/L；The oxidant of 2ml is added, oxidant is concentration
For 30% hydrogenperoxide steam generator；100min is reacted at 59 DEG C, then uses the sodium hydroxide solution of 0.5mol/L by gained
The pH of solution is adjusted to 8.8, obtains solution a.
Step 2, solution a is warming up to 80 DEG C, the formaldehyde and sodium hydrogensulfite of 4g is then added, wherein formaldehyde and sulfurous acid
The mass ratio of hydrogen sodium is 1:2, reacts 7h, then cools to room temperature, obtain solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 95 DEG C, obtains modified lignosulfonates.
Embodiment 5
Step 1,5g lignosulfonates are taken, above-mentioned lignosulfonates are dissolved in the distilled water of 80ml, are then made
The pH of acquired solution is adjusted to 2.3 with the hydrogen chloride solution of 0.5mol/L；The oxidant of 2ml is added, oxidant is concentration
For 30% hydrogenperoxide steam generator；110min is reacted at 56 DEG C, then uses the sodium hydroxide solution of 0.5mol/L by gained
The pH of solution is adjusted to 8.2, obtains solution a.
Step 2, solution a is warming up to 90 DEG C, the formaldehyde and 3g sodium hydrogensulfite of 1g is then added, react 8.5h, then
It is cooled to room temperature, obtains solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 100 DEG C, obtains modified lignosulfonates.
Embodiment 6
Step 1,5g lignosulfonates are taken, above-mentioned lignosulfonates are dissolved in the distilled water of 80ml, are then made
The pH of acquired solution is adjusted to 2 with the hydrogen chloride solution of 0.5mol/L；The oxidant of 2ml is added, oxidant is that concentration is
30% hydrogenperoxide steam generator；70min is reacted at 55 DEG C, then uses the sodium hydroxide solution of 0.5mol/L by acquired solution
PH adjust to 8.4, obtain solution a.
Step 2, solution a is warming up to 65 DEG C, 1.6 formaldehyde and 2.4g sodium hydrogensulfite is then added, reacts 7h, then
It is cooled to room temperature, obtains solution b.
Step 3, the strongly basic anionic resin of 12h is impregnated in the sodium hydroxide solution that concentration is 2mol/L, and is made
Being washed above-mentioned strongly basic anionic resin to pH with distilled water is neutrality, obtains anion exchange resin；It is 2mol/ in concentration
The strong acidic ion resin of 12h is impregnated in the hydrogen chloride solution of L, and uses distilled water by above-mentioned strong acidic ion resin
Washing is neutrality to pH, obtains cation exchange resin；By solution b followed by anion exchange resin and cation exchange tree
Then rouge makes to be washed with distilled water anion exchange resin and cation exchange resin, until will wash when the pH of efflux is neutral
It washs liquid to collect, obtains extracting solution.
Step 4, extracting solution is dried at 100 DEG C, obtains modified lignosulfonates.
Claims (4)
1. a kind of method of modifying of lignosulfonates, which comprises the following steps:
Step 1,5 parts of lignosulfonates are taken by mass fraction, it is 80 parts that above-mentioned lignosulfonates, which are dissolved in volume parts,
Distilled water in, the pH for having dissolved the aqueous solution of lignosulfonates is adjusted to 2-3 using hydrogen chloride solution, adds volume
The oxidant that number is 2 parts, reacts 1-2h at 55-60 DEG C, and the hydroxide that concentration is 0.5mol/L is added into acquired solution
Sodium solution adjusts the pH of acquired solution to 8-9, obtains solution a, and wherein oxidant is that the hydrogen peroxide that concentration is 30% is molten
Liquid；
Step 2, solution a is warming up to 60-100 DEG C, formaldehyde and sodium hydrogensulfite that mass fraction is 4 parts, reaction is then added
5-9h is then cooled to room temperature, and obtains solution b；
Step 3, by solution b followed by anion exchange resin and cation exchange resin, then make to be washed with distilled water yin
Ion exchange resin and cation exchange resin, the PH of the cleaning solution after cleaning obtain extracting solution until 7；
The preparation process of the cation exchange resin is that the strong of 12h is impregnated in the hydrogen chloride solution that concentration is 2mol/L
Acidic cationic resin, and being washed above-mentioned strong acidic ion resin to pH using distilled water is neutrality, obtains cation
Exchanger resin；
The preparation process of the anion exchange resin is to impregnate 12h's in the sodium hydroxide solution that concentration is 2mol/L
Strongly basic anionic resin, and using distilled water by above-mentioned strongly basic anionic resin wash to pH for neutrality, obtain yin from
Sub-exchange resin；
Step 4, extracting solution is dried at 80-100 DEG C to get modified lignosulfonates are arrived.
2. the method for modifying of lignosulfonates according to claim 1, which is characterized in that described to make to be washed with distilled water
Anion exchange resin and cation exchange resin, until collect all cleaning solutions when the pH of washing efflux is neutral,
Obtain extracting solution.
3. the method for modifying of lignosulfonates according to claim 1, which is characterized in that in the step 2 formaldehyde and
The mass ratio of sodium hydrogensulfite is 1-2:3.
4. the method for modifying of lignosulfonates according to claim 1, which is characterized in that hydrogen chloride in the step 1
Concentration be 0.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610866262.5A CN106397789B (en) | 2016-09-29 | 2016-09-29 | A kind of method of modifying of lignosulfonates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610866262.5A CN106397789B (en) | 2016-09-29 | 2016-09-29 | A kind of method of modifying of lignosulfonates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397789A CN106397789A (en) | 2017-02-15 |
| CN106397789B true CN106397789B (en) | 2019-11-08 |
Family
ID=59228564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610866262.5A Active CN106397789B (en) | 2016-09-29 | 2016-09-29 | A kind of method of modifying of lignosulfonates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397789B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189073A (en) * | 2017-06-16 | 2017-09-22 | 陕西科技大学 | A kind of graft copolymer and preparation method thereof |
| CN107840969A (en) * | 2017-12-20 | 2018-03-27 | 陕西科技大学 | A kind of method of modifying of lignosulfonates |
| CN113926592A (en) * | 2021-09-18 | 2022-01-14 | 武汉工程大学 | Modified lignin compound type calcium and magnesium inhibitor for phosphorite flotation and preparation method thereof |
| CN115849644A (en) * | 2022-08-10 | 2023-03-28 | 河南土化石环保建材有限公司 | Sludge solidification modifier and preparation method thereof |
| CN115746330B (en) * | 2022-11-08 | 2024-02-20 | 安徽成弘建新材料有限公司 | Modified alkali lignin, preparation method thereof, semi-coke grinding aid and use method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147480A (en) * | 2007-09-13 | 2008-03-26 | 华南理工大学 | Modified lignosulfonate pesticide dispersing agent and its preparation method |
| CN102627673A (en) * | 2012-03-23 | 2012-08-08 | 辽宁岩砂晶建材有限公司 | Method for sulfomethylation of lignin degradation |
| CN104672467A (en) * | 2013-12-03 | 2015-06-03 | 青岛惠城石化科技有限公司 | Study of taking modified lignosulfonate as dye dispersant modification condition |
| CN104724970A (en) * | 2013-05-02 | 2015-06-24 | 新疆荣能新材料有限公司 | Synthetic process of modified lignin sulfonate water reducer |
| CN104892953A (en) * | 2015-06-24 | 2015-09-09 | 济南圣泉集团股份有限公司 | Modified lignosulphonate and preparing method and application thereof |
-
2016
- 2016-09-29 CN CN201610866262.5A patent/CN106397789B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147480A (en) * | 2007-09-13 | 2008-03-26 | 华南理工大学 | Modified lignosulfonate pesticide dispersing agent and its preparation method |
| CN102627673A (en) * | 2012-03-23 | 2012-08-08 | 辽宁岩砂晶建材有限公司 | Method for sulfomethylation of lignin degradation |
| CN104724970A (en) * | 2013-05-02 | 2015-06-24 | 新疆荣能新材料有限公司 | Synthetic process of modified lignin sulfonate water reducer |
| CN104672467A (en) * | 2013-12-03 | 2015-06-03 | 青岛惠城石化科技有限公司 | Study of taking modified lignosulfonate as dye dispersant modification condition |
| CN104892953A (en) * | 2015-06-24 | 2015-09-09 | 济南圣泉集团股份有限公司 | Modified lignosulphonate and preparing method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 木质素磺酸钠分散剂的制备及其在农药中的应用;李志礼 等;《中国造纸》;20101231;第29卷(第5期);第38-42页 * |
| 高磺化度木质素磺酸钠的工艺条件研究;陈珍喜 等;《化学工程与装备》;20131231(第12期);第36-38页，摘要、引言和第1.2节部分 * |
| 麦草碱木质素的氧化和磺甲基化改性;梁文学 等;《华南理工大学学报（自然科学版）》;20070531;第35卷(第5期);第117-121页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397789A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106397789B (en) | A kind of method of modifying of lignosulfonates | |
| CN102990751B (en) | Manufacturing method of bamboo fiber | |
| CN103358374B (en) | A kind of method for bleaching of furniture yellow poplar timber | |
| CN109280174A (en) | A kind of hyperbranched lignin grafted cation polyacrylamide flocculant and preparation method thereof | |
| CN102796222B (en) | Synthesis method of hydrophobically associated polyacrylamide | |
| CN105800996B (en) | A kind of method that utilization waste wool keratin prepares cement blowing agent | |
| CN105821653A (en) | Method for preparing polyacrylonitrile antibacterial fiber | |
| CN102995137B (en) | Preparation method of bamboo fiber materials for shirts | |
| CN102030905B (en) | Method for preparing solvent-free high hydrogen containing silicone oil | |
| CN102746198A (en) | Method for preparing leather fat-liquoring agent | |
| CN108018386A (en) | A kind of preparation method of poly anhydride modification camellia oil fatting agent | |
| CN105771790B (en) | A kind of preparation method of albumen based surfactants | |
| CN109134843A (en) | The synthetic method of thickening type low-freezing sodium sulfate of polyethenoxy ether of fatty alcohol | |
| CN109627195A (en) | A method of heavy alkylbenzene sulfonate is prepared using microreactor | |
| CN102093573A (en) | Method for preparing modified lignosulfonate | |
| CN110938022A (en) | Preparation method of improved sodium dodecyl benzene sulfonate solution | |
| CN102995140B (en) | Preparation method of bamboo fiber materials for towels | |
| CN103255669B (en) | Paper and preparation method thereof | |
| CN103613509A (en) | Synthetic method of dodecyl dimethyl betaine | |
| CN107840969A (en) | A kind of method of modifying of lignosulfonates | |
| CN104178589A (en) | Sulfonation cup aromatic tanning agent for leather tanning and preparation method thereof | |
| CN103485212A (en) | Stripping agent, preparation method thereof and method for stripping by utilizing stripping agent | |
| CN102989509A (en) | Catalyst of sulfonated polystyrene grafted polytetrafluoroethylene fiber metal complex and preparation method thereof | |
| CN111805668A (en) | Method for treating willow wood by vapor phase method | |
| CN106498708A (en) | A kind of method for removing cotton seed hullss on bafta using ozone in the liquid phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |