CN1304950A - Process for preparing surfactant from lignosulfonates - Google Patents
Process for preparing surfactant from lignosulfonates Download PDFInfo
- Publication number
- CN1304950A CN1304950A CN00130812.2A CN00130812A CN1304950A CN 1304950 A CN1304950 A CN 1304950A CN 00130812 A CN00130812 A CN 00130812A CN 1304950 A CN1304950 A CN 1304950A
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- CN
- China
- Prior art keywords
- sulfonated lignin
- lignin
- straight
- chain
- sulfonated
- 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.)
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- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 27
- 239000004094 surface-active agent Substances 0.000 title abstract description 9
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 235000019357 lignosulphonate Nutrition 0.000 claims description 23
- 239000013543 active substance Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000002152 alkylating effect Effects 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 4
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920005610 lignin Polymers 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- -1 alkylbenzene sulfonate Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
A process for preparing surfactant, alkylated lignosulfonate, from lignosulfonate includes regulating the pH valve of lignosulfonate solution to 10-12, adding C8-C16 straight-chain haloalkane, sealing, heating to 130-170 deg.C and reaction for 1-3 hr. Said surfactant features better amphipathy, and high surface activity.
Description
The present invention relates to a kind of method for preparing tensio-active agent with sulfonated lignin.
Xylogen is one of main component in the plant fiber material.In pulp and paper industry, the lignin dissolution in the plant fiber material forms sulfonated lignin or alkali lignin in cooking liquor.These two kinds of important by-products that industrial lignin is a pulp and paper industry, at present also very insufficient to their utilization.Industrial lignin has many-sided character such as dispersion, bonding and surfactivity, now as dispersion agent, cement water reducing agent, tackiness agent, also can be used for sacrifice agent that tensio-active agent recovers the oil etc.But the xylogen surfactivity is relatively poor, still can not be used alone as tensio-active agent.If wish they are made tensio-active agent efficiently, also need pass through a series of chemical modification.For example, be that raw material carries out sulfomethylation with the alkali lignin, introduce hydrophilic sulfonic group and lipophilic methyl, increase hydrophilic and oleophilic functional group, can make alkali lignin have certain surfactivity, but such modification is quite limited to improving the surfactivity role.Contain hydrophilic sulfonic group, lipophilic phenyl ring and alkyl group side chain on the lignosulfonic acid molecules of salt, therefore surfactivity is higher than alkali lignin, but because intramolecularly lacks the more regular lipophilic group of structure, so surfactivity is still relatively poor, can only become complexed surfactant with other surfactant compound usually.For example, Kalfoglou etc. mix use with sulfonated lignin with alkylbenzene sulfonate etc., can reduce the consumption of alkylbenzene in the surfactant system.But in complexed surfactant, sulfonated lignin can only play the effect of cosurfactant, reduce surface tension and interfacial tension effect significantly and play, and mainly are still synthetic surfactants such as sulfonated petro-leum.
Sulfonated lignin are carried out alkylation, can strengthen and improve its surfactivity.Early the useful methyl-sulfate of alkylation that uses methylates, or methylates with diazomethane.The alkyl carbon chain that but this method is introduced is very short, and can't play increases the oil loving effect of sulfonated lignin, and the agents useful for same costliness, and severe reaction conditions does not possess practical value.People such as Meister introduce alkyl chain with sulfonated lignin and vinyl monomer copolymerization to lignin molecule, can increase the lipophilicity (the 3457th page of J.Appl.Polym.Sci.1984 the 29th volume) of sulfonated lignin.But other for example makes sulfonated lignin and propylene oxide copolymerization to the method for xylogen introducing side chain, then can not increase the surfactivity of xylogen, but xylogen is made the prepolymer (J.Appl.Polym.Sci. of engineering plastics, 1984,29 volumes, 1113 pages).
The purpose of this invention is to provide and a kind ofly prepare the method for tensio-active agent,, increase substantially its surfactivity by sulfonated lignin are carried out chemical modification with sulfonated lignin.
The present invention is alkylating reagent with the halogenated alkane, introduces long alkyl chain on the lignosulfonic acid molecules of salt.The alkylating method of sulfonated lignin is: sulfonated lignin are dissolved in the water, regulate pH value to 10～12 with alkali, add the halo straight-chain paraffin that contains 8～16 carbon atoms that accounts for sulfonated lignin weight 20%～40%, the sealing post-heating, be warming up to 130～170 ℃, naturally cooling discharging behind reaction 1～3h.
Used sulfonated lignin are generally sodium lignosulfonate or calcium lignosulfonate, and the former is better than the latter at performance.
Halohydrocarbon is the halo straight-chain paraffin that contains 8～16 carbon atoms, wherein preferably contains the bromo straight-chain paraffin of 12～16 carbon atoms.Though the alkane iodide reactive behavior is higher, higher because of cost, directly do not use.Though branched paraffin can react with sulfonated lignin, the surface tension of product water solution is higher, therefore is not suitable for preparing tensio-active agent.
The alkylation sulfonated lignin made from the present invention have amphipathic preferably, very high solubleness is all arranged in water and oil, and surfactivity strengthen greatly.At room temperature, the surface tension of the alkylation surfactant soln of 1% weight percentage can be reduced to 36mN/m, and the interfacial tension between this solution and the oil can reduce to 10
-3MN/m.
Can directly use through the sulfonated lignin behind the alkylation modification, also can use, to obtain better to reduce the effect of oil water interfacial tension with other tensio-active agents are collaborative as the major surfaces promoting agent.This tensio-active agent is used for tertiary oil recovery, can use separately, also can be used with alkali, polymkeric substance etc., plays the effect of the recovery ratio that improves crude oil.
Embodiment 1
The 10g sodium lignosulfonate is dissolved in the 50mL water, add sodium hydroxide, regulate pH value to 10, add the 4g bromohexadecane, above-mentioned reaction mixture is added in the autoclave, and logical nitrogen is driven away oxygen in the reactor, then sealed reactor and be warming up to 150 ℃, behind reaction 3h under this temperature, be cooled to the room temperature discharging.Product is a dark-brown liquid.
Embodiment 2
The 10g calcium lignin sulphonate is dissolved in the 50mL water, add sodium hydroxide, regulate pH value to 10, add the 4g bromododecane, above-mentioned reaction mixture is added in the autoclave, logical nitrogen is driven away oxygen in the reactor, after the sealing, be warming up to 130 ℃, behind reaction 3h under this temperature, be cooled to the room temperature discharging.Product is a dark-brown liquid.
Embodiment 3
The 10g sodium lignosulfonate is dissolved in the 50mL water, add sodium hydroxide, regulate pH to 10, add the 2.5g bromohexadecane then, said mixture is added in the autoclave, logical nitrogen is driven away the oxygen in the reactor, after the sealing, be warming up to 150 ℃, under this temperature, react 2.5h, be cooled to the room temperature discharging.Product is a dark-brown liquid.
Embodiment 4
The 10g calcium lignin sulphonate is dissolved in the 50mL water, adds sodium hydroxide, regulate pH to 10, add 2.5g bromo nonane then, said mixture is added in the autoclave, and logical nitrogen is driven away the oxygen in the reactor, after the sealing, be warming up to 150 ℃, under this temperature, react 2h, be cooled to the room temperature discharging.Product is a dark-brown liquid.
Claims (3)
1, a kind of method for preparing tensio-active agent with sulfonated lignin, it is characterized in that with the halogenated alkane being alkylating reagent, on the lignosulfonic acid molecules of salt, introduce alkyl chain, its alkylating method is: sulfonated lignin are dissolved in the water, regulate pH value to 10～12, add the halo straight-chain paraffin that contains 8～16 carbon atoms that accounts for sulfonated lignin weight 20%～40%, the sealing post-heating, be warming up to 130～170 ℃, naturally cooling discharging behind reaction 1～3h.
2,, it is characterized in that described sulfonated lignin are sodium lignosulfonate according to the method described in the claim 1.
3,, it is characterized in that described halo straight-chain paraffin is the bromo straight-chain paraffin that contains 12～16 carbon atoms according to the method described in the claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130812.2A CN1100080C (en) | 2000-11-22 | 2000-11-22 | Process for preparing surfactant from lignosulfonates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130812.2A CN1100080C (en) | 2000-11-22 | 2000-11-22 | Process for preparing surfactant from lignosulfonates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1304950A true CN1304950A (en) | 2001-07-25 |
| CN1100080C CN1100080C (en) | 2003-01-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00130812.2A Expired - Fee Related CN1100080C (en) | 2000-11-22 | 2000-11-22 | Process for preparing surfactant from lignosulfonates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1100080C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503990A (en) * | 2011-09-22 | 2012-06-20 | 华南理工大学 | Method for preparing surfactant by taking lignin thermo-chemically degraded phenol product as raw material |
| CN102580610A (en) * | 2012-01-09 | 2012-07-18 | 中科院广州化学有限公司 | Lignosulfonate alkylation modified surfactant and preparation method and application thereof |
| CN105085933A (en) * | 2015-08-11 | 2015-11-25 | 湖州长盛化工有限公司 | Method for synthesizing surfactant by alkylating sodium lignin sulfonate |
| CN105441055A (en) * | 2015-11-14 | 2016-03-30 | 山东宝莫生物化工股份有限公司 | Modified lignosulfonate compound and application thereof in thermal/chemical flooding of oil field |
| CN105461916A (en) * | 2015-10-29 | 2016-04-06 | 清华大学 | Preparation method of lignin-based polyether sulfonate surfactant |
| US20170166749A1 (en) * | 2014-03-14 | 2017-06-15 | Regents Of The University Of Minnesota | Compositions including lignin |
| CN107778922A (en) * | 2016-08-30 | 2018-03-09 | 江苏吉华化工有限公司 | A kind of preparation method of Lignins nano-dispersed dyestuff |
| CN108341971A (en) * | 2018-03-21 | 2018-07-31 | 中国林业科学研究院林产化学工业研究所 | New-type emulsifier is prepared by alkali lignin and undecenoic acid grafting |
| TWI780075B (en) * | 2016-12-28 | 2022-10-11 | 大陸商安集微電子科技(上海)股份有限公司 | Chemical mechanical polishing slurry and applications thereof |
-
2000
- 2000-11-22 CN CN00130812.2A patent/CN1100080C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503990B (en) * | 2011-09-22 | 2014-07-30 | 华南理工大学 | Method for preparing surfactant by taking lignin thermo-chemically degraded phenol product as raw material |
| CN102503990A (en) * | 2011-09-22 | 2012-06-20 | 华南理工大学 | Method for preparing surfactant by taking lignin thermo-chemically degraded phenol product as raw material |
| CN102580610A (en) * | 2012-01-09 | 2012-07-18 | 中科院广州化学有限公司 | Lignosulfonate alkylation modified surfactant and preparation method and application thereof |
| US20170166749A1 (en) * | 2014-03-14 | 2017-06-15 | Regents Of The University Of Minnesota | Compositions including lignin |
| US10119027B2 (en) * | 2014-03-14 | 2018-11-06 | Regents Of The University Of Minnesota | Compositions including lignin |
| CN105085933A (en) * | 2015-08-11 | 2015-11-25 | 湖州长盛化工有限公司 | Method for synthesizing surfactant by alkylating sodium lignin sulfonate |
| CN105085933B (en) * | 2015-08-11 | 2017-11-24 | 湖州长盛化工有限公司 | A kind of method of sodium lignin sulfonate alkylation synthetic surfactant |
| CN105461916A (en) * | 2015-10-29 | 2016-04-06 | 清华大学 | Preparation method of lignin-based polyether sulfonate surfactant |
| CN105441055B (en) * | 2015-11-14 | 2018-08-21 | 山东宝莫生物化工股份有限公司 | Modified lignin mahogany sulfonate compound and its application in oil field heat/chemical flooding |
| CN105441055A (en) * | 2015-11-14 | 2016-03-30 | 山东宝莫生物化工股份有限公司 | Modified lignosulfonate compound and application thereof in thermal/chemical flooding of oil field |
| CN107778922A (en) * | 2016-08-30 | 2018-03-09 | 江苏吉华化工有限公司 | A kind of preparation method of Lignins nano-dispersed dyestuff |
| TWI780075B (en) * | 2016-12-28 | 2022-10-11 | 大陸商安集微電子科技(上海)股份有限公司 | Chemical mechanical polishing slurry and applications thereof |
| CN108341971A (en) * | 2018-03-21 | 2018-07-31 | 中国林业科学研究院林产化学工业研究所 | New-type emulsifier is prepared by alkali lignin and undecenoic acid grafting |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1100080C (en) | 2003-01-29 |
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