CN102093572A - Method for preparing lignin amide for preparing modified lignosulfonate - Google Patents
Method for preparing lignin amide for preparing modified lignosulfonate Download PDFInfo
- Publication number
- CN102093572A CN102093572A CN2009102167094A CN200910216709A CN102093572A CN 102093572 A CN102093572 A CN 102093572A CN 2009102167094 A CN2009102167094 A CN 2009102167094A CN 200910216709 A CN200910216709 A CN 200910216709A CN 102093572 A CN102093572 A CN 102093572A
- Authority
- CN
- China
- Prior art keywords
- lignin
- preparation
- acid amides
- prepare
- 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.)
- Pending
Links
Landscapes
- Compounds Of Unknown Constitution (AREA)
Abstract
The invention discloses a method for preparing lignin amide for preparing modified lignosulfonate, which is characterized by comprising the following steps of: (a) adding 20 to 60 grams of sodium lignosulfonate into a round bottomed flask into which a thermometer is inserted, adding 80 to 120 milliliters of water, and stirring uniformly by magnetic force; and (b) dripping 0.9 to 1.5 milliliters of diethylenetriamine into the round bottomed flask, dripping formaldehyde solution slowly, heating to the temperature of between 70 and 90 DEG C, keeping the temperature for 6 to 7 hours and the like. Compared with the prior art, the preparation method is extremely simple and quick in preparation process, and does not have hazardous operation in the preparation process, so the safety of operators can be ensured. Simultaneously, the prepared lignin amide has stable performance, and meets various performance requirements of the modified lignosulfonate prepared by a method of fatty amine completely.
Description
Technical field
The present invention relates to a kind of synthetic optimization method, specifically be meant a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate.
Background technology
Xylogen claims lignin again, is the complicated macromolecular compound of forming with phenylpropyl alcohol alkanes structural unit, contains various active functional groups such as methoxyl group, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbonyl.Xylogen extensively exists in higher plant, is the main component that constitutes the plant skeleton, estimates that the annual whole world can produce 1,500 hundred million tons of xylogen by plant-growth.At present, industrial lignin is mainly derived from papermaking wastewater, and wherein China produces 5,000,000 tons every year approximately, and industrial lignin utilization ratio less than 10% is most of as discharging of waste liquid.Because country is to the requirement of environmental protection increasingly stringent, the increasing mass-producing of paper pulp enterprise for reclaiming xylogen as the Industrial products condition of providing convenience, also provides cheap widely source for xylogen as industrial chemicals.Though chemistry of lignin has the history in 150 years nearly, its major cause that is not widely used is the chemical structure complexity, and chemical property is general.In recent decades, lignin modification is obtained remarkable achievement.Xylogen has enlarged the range of application of xylogen by reaction modifyings such as sulfonation, oxidation, graft copolymerization, condensation reaction, Mannich reaction, alkylated reactions.
Sulfonated lignin contain sulfonic group, and polarity is bigger, and hydrophilicity is better, have only the lipophilicity that improves xylogen could obtain highly active lignin modification product.This just need be incorporated into fatty clan elder's carbochain in the molecular structure of xylogen.The normal at present method of modifying that adopts mainly contains following three kinds: first kind is and the alkylphenol condensation; Second kind is by phenolic hydroxyl group and alkylating reagent condensation; The third is for using the aliphatic amide modification.
But for first method, the adjustable range and the handiness of modification are little, still can not be used the modified lignin mahogany sulfonate that can reach ultralow oil-water interfacial tension separately.For second method, the alkyl chain of introducing in alkylated reaction then generates the water soluble surfactant active if contain 6～18 carbon atoms; If contain 18～24 carbon atoms, then generate oil soluble surfactant.With modified sulphur hydrochlorate xylogen 3% solution that this method is made, interfacial tension can be reduced to 0.1mN/m.With sulfonated organic solvent xylogen and the reaction of halo dodecane, be catalyzer with the pyridine, the mol ratio of add-on and bromoalkane 1: 1, at 60 ℃ of reaction 6h, product is through the dialysis postlyophilization.Product is identical with Reax-85A character as dye dispersant.Its surface tension can be lower than 40mN/m in strength of solution during for 1g/L, and critical micelle concentration cmc value has extraordinary dispersing property simultaneously for 0.084g/L is an exemplary surfactants character.Though after with preceding two kinds of methods xylogen being carried out modification, the activity of gained lignin product has had and significantly improves, the ability that reduces oil-water interfacial tension is still limited.For the third method, according to the constructional feature of xylogen, the hydrogen on its phenolic hydroxyl group ortho position is very active, fully can with fatty amine and aldehyde generation Mannich reaction, but rare both at home and abroad at present relevant report.So, want to prepare modified lignin mahogany sulfonate by the method for aliphatic amide modification, wherein the preparation of lignin acid amides is just particularly crucial, but adopts present method to prepare the lignin acid amides, and its performance does not reach requirement far away.
Summary of the invention
The performance that the objective of the invention is to overcome at present prepared oleoyl chloride does not reach the defective that the preparation modified lignin mahogany sulfonate requires, and a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate is provided.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate mainly may further comprise the steps:
(a) sodium lignosulfonate that takes by weighing 20～60g joins in the round-bottomed flask that is inserted with thermometer, and to add volume be the water of 80～120mL, and magnetic agitation is even.
(b) in round-bottomed flask, drip 0.9～1.5ml diethylenetriamine, be warming up to 70～90 ℃ after slowly dripping formaldehyde solution then, be incubated 6～7 hours.
(c) dripping concentration in round-bottomed flask is 8～12% NaOH solution, and the pH value of whole solution is transferred to is 7～8.
(d) in 2～3 hours, drip long carbochain fat acyl chloride, and the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.
(e) treat reinforced the end after, continue to stir 0.5～1.5 hour, drip concentration simultaneously and be 3～7% NaOH solution and keep pH value of reactants between 7～8, and generate acyl chlorides.
(f) treat after the irritating smell completely dissolve of acyl chlorides, stop to stir, reactant is placed on drying, porphyrize get final product infrared lamp under.
Further, the quality of the sodium lignosulfonate that is taken by weighing in the step (a) is 30～60g, and its best in quality is 50g.
The concentration of the diethylenetriamine that is dripped in the step (b) is 1～1.3%, and its optimum concentration value is 1.1%.
The concentration of the NaOH solution that is dripped in the step (c) is 9～11%, and its optimum concentration value is 10%.
After step (e) is treated reinforced the end, continue to stir 1 hour.
Preparation method of the present invention compares very simple than prior art, and preparation process is very fast, and the operation of not dangerous property in preparation process it is hereby ensured operator's safety.Simultaneously, the lignin acid amides performance quite stable that the present invention is prepared satisfies the various performance requriementss that the method that adopts aliphatic amide prepares modified lignin mahogany sulfonate fully.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation process of present embodiment is as follows: add the 20g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 80mL, magnetic agitation is even, drip the 0.9ml diethylenetriamine, be warming up to 70 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 8% NaOH solution is adjusted this pH value of reactants to 7 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 2 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 0.5 hour, drip concentration simultaneously and be 3% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
Embodiment 2
The preparation process of present embodiment is as follows: add the 30g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 100mL, magnetic agitation is even, drip the 1.0ml diethylenetriamine, be warming up to 75 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 7 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 9.5% NaOH solution is adjusted this pH value of reactants to 7.5 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 2.5 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1 hour, drip concentration simultaneously and be 5% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
Embodiment 3
The preparation process of present embodiment is as follows: add the 50g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 110mL, magnetic agitation is even, drip the 1.1ml diethylenetriamine, be warming up to 80 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6.5 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 10% NaOH solution is adjusted this pH value of reactants to 8 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 3 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1.5 hours, drip concentration simultaneously and be 6% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
Embodiment 4
The preparation process of present embodiment is as follows: add the 55g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 120mL, magnetic agitation is even, drip the 1.3ml diethylenetriamine, be warming up to 90 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6.5 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 12% NaOH solution is adjusted this pH value of reactants to 8 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 3 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1.5 hours, drip concentration simultaneously and be 6.5% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
Embodiment 5
The preparation process of present embodiment is as follows: add the 60g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 120mL, magnetic agitation is even, drip the 1.5ml diethylenetriamine, be warming up to 90 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 7 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 12% NaOH solution is adjusted this pH value of reactants to 8 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 3 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 3 hours, drip concentration simultaneously and be 7% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
Embodiment 6
The preparation process of present embodiment is as follows: add the 60g sodium lignosulfonate in being inserted with the 150ml round-bottomed flask of thermometer, adding volume is the water of 120mL, magnetic agitation is even, drip the 1.1ml diethylenetriamine, be warming up to 80 ℃ after slowly dripping the formaldehyde solution of predetermined amount then, be incubated 6.5 hours, with synthetic lignin amine.
After treating that lignin amine is synthetic, be that 11% NaOH solution is adjusted this pH value of reactants to 8 with concentration.Dripped the long carbochain fat acyl chloride of predetermined amount in 3 hours, the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent.Behind reinforced the end, continue to stir 1 hour, drip concentration simultaneously and be 6% NaOH solution and keep pH value of reactants between 7～8.Treat after the irritating smell completely dissolve of acyl chlorides, stop to stir.Reactant is placed on dry, porphyrize under the infrared lamp, can obtains the lignin acid amides of brown ceramic powder.
As mentioned above, just can well realize the present invention.
Claims (8)
1. a preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate is characterized in that, mainly may further comprise the steps:
(a) sodium lignosulfonate that takes by weighing 20～60g joins in the round-bottomed flask that is inserted with thermometer, and to add volume be the water of 80～120mL, and magnetic agitation is even;
(b) in round-bottomed flask, drip 0.9～1.5ml diethylenetriamine, be warming up to 70～90 ℃ after slowly dripping formaldehyde solution then, be incubated 6～7 hours;
(c) dripping concentration in round-bottomed flask is 8～12% NaOH solution, and the pH value of whole solution is transferred to is 7～8;
(d) in 2～3 hours, drip long carbochain fat acyl chloride, and the dilute solution that drips sodium bicarbonate simultaneously is as acid binding agent;
(e) treat reinforced the end after, continue to stir 0.5～1.5 hour, drip concentration simultaneously and be 3～7% NaOH solution and keep pH value of reactants between 7～8, and generate acyl chlorides;
(f) treat after the irritating smell completely dissolve of acyl chlorides, stop to stir, reactant is placed on drying, porphyrize get final product infrared lamp under.
2. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the quality of the sodium lignosulfonate that is taken by weighing in the step (a) is 30～60g.
3. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 2, it is characterized in that: the quality of described sodium lignosulfonate is 50g.
4. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the concentration of the diethylenetriamine that is dripped in the step (b) is 1～1.3%.
5. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 4, it is characterized in that: the concentration of the diethylenetriamine that is dripped in the step (b) is 1.1%.
6. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 1, it is characterized in that: the concentration of the NaOH solution that is dripped in the step (c) is 9～11%.
7. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 6, it is characterized in that: the concentration of the NaOH solution that is dripped is 10%.
8. a kind of preparation method who is used to prepare the lignin acid amides of modified lignin mahogany sulfonate according to claim 1 is characterized in that: after step (e) is treated reinforced the end, continue to stir 1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102167094A CN102093572A (en) | 2009-12-11 | 2009-12-11 | Method for preparing lignin amide for preparing modified lignosulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102167094A CN102093572A (en) | 2009-12-11 | 2009-12-11 | Method for preparing lignin amide for preparing modified lignosulfonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102093572A true CN102093572A (en) | 2011-06-15 |
Family
ID=44126854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102167094A Pending CN102093572A (en) | 2009-12-11 | 2009-12-11 | Method for preparing lignin amide for preparing modified lignosulfonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102093572A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113019334A (en) * | 2021-03-11 | 2021-06-25 | 东北林业大学 | Preparation of modified lignin magnetic composite material and method for removing dye in wastewater by using modified lignin magnetic composite material |
| CN114672292A (en) * | 2020-12-24 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature-resistant composite plugging and blending agent as well as preparation method and application thereof |
| CN114763468A (en) * | 2021-01-14 | 2022-07-19 | 中国石油化工股份有限公司 | Hydrolyzed lignin amide, water shutoff profile control agent, and preparation method and application thereof |
-
2009
- 2009-12-11 CN CN2009102167094A patent/CN102093572A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672292A (en) * | 2020-12-24 | 2022-06-28 | 中国石油化工股份有限公司 | High-temperature-resistant composite plugging and blending agent as well as preparation method and application thereof |
| CN114672292B (en) * | 2020-12-24 | 2023-05-30 | 中国石油化工股份有限公司 | High-temperature-resistant composite plugging agent and preparation method and application thereof |
| CN114763468A (en) * | 2021-01-14 | 2022-07-19 | 中国石油化工股份有限公司 | Hydrolyzed lignin amide, water shutoff profile control agent, and preparation method and application thereof |
| CN113019334A (en) * | 2021-03-11 | 2021-06-25 | 东北林业大学 | Preparation of modified lignin magnetic composite material and method for removing dye in wastewater by using modified lignin magnetic composite material |
| CN113019334B (en) * | 2021-03-11 | 2022-09-23 | 东北林业大学 | Preparation of modified lignin magnetic composite material and method for removing dye in wastewater by using modified lignin magnetic composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102093573A (en) | Method for preparing modified lignosulfonate | |
| CN101186459A (en) | Method for preparing aliphatic high efficiency water reducing agent by using industrial by-product and application thereof | |
| CN101386587A (en) | Production technology of methyl naphthalenesulfonic acid-methyl aldehyde condensation compound | |
| CN102093572A (en) | Method for preparing lignin amide for preparing modified lignosulfonate | |
| CN103601657B (en) | CLT acid factory effluent stoste prepares method and the compound product of high efficiency water reducing agent monomer | |
| CN104190314B (en) | Aliphatic amine polyoxyethylene ether diethyl disulfonate surfactant and preparation method thereof | |
| CN104194002A (en) | High-sulfonation-degree lignosulfonate containing alkyl sulfonic acid, and preparation method and application thereof | |
| CN100540557C (en) | A kind of method of utilizing sulphonation waste gas to prepare sodium lignosulfonate | |
| CN102114396A (en) | Non-quinoline dispersant MF and production process | |
| Wang et al. | Lignin to dispersants, adsorbents, flocculants and adhesives: A critical review on industrial applications of lignin | |
| CN102580610A (en) | Lignosulfonate alkylation modified surfactant and preparation method and application thereof | |
| CN102372456B (en) | Method for preparing naphthalene series additive from low-acidity process waste water | |
| CN106145236A (en) | Extractant and the method using waste water in the process H acid production of this extractant | |
| CN106810412B (en) | Method for improving sulfonation reaction efficiency and production method of dispersing agent MF | |
| CN103011362B (en) | Preparation method for high-efficiency dye decolorizing agent | |
| CN108751370A (en) | A kind of lignin-base polyquaternium cationic water treatment agent and preparation method thereof | |
| CN102614809B (en) | Method for preparing dispersing-stabilizing agent by using papermaking sludge | |
| CN104987303B (en) | A kind of complexometric extraction technique extracts 5-sodium sulfo isophthalate method from three monomer waste water | |
| CN102690516B (en) | Biodegradable cross-linked chitosan chelating resin and preparation method thereof | |
| CN102093201A (en) | Preparation method of lauroyl chloride for preparing modified lignosulfonate | |
| CN105419766A (en) | Technology method of synthesizing heavy oil sulfonate surfactant with sulfonation promoter | |
| CN107840969A (en) | A kind of method of modifying of lignosulfonates | |
| CN102093205A (en) | Method for preparing oleoylchloride for preparing modified lignosulfonate | |
| CN102173636A (en) | Device and method for preparing concrete water-reducing agent using phenolic resin wastewater | |
| CN105838828A (en) | Leather working treating agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110615 |