CN102190606B - Preparation method of novel sulfonated grease - Google Patents
Preparation method of novel sulfonated grease Download PDFInfo
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- CN102190606B CN102190606B CN201010129724.8A CN201010129724A CN102190606B CN 102190606 B CN102190606 B CN 102190606B CN 201010129724 A CN201010129724 A CN 201010129724A CN 102190606 B CN102190606 B CN 102190606B
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- grease
- sulfonated
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- lanolin
- methyl esters
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Abstract
The invention discloses a preparation method of novel sulfonated grease. The preparation method comprises the following steps that: methyl esters of plant oil and lanolin are mixed in nitrogen atmosphere to obtain mixing grease; the mixing grease and an SO3 gas are subjected to falling-film sulfonation reaction; and then a series of steps including aging processing, neutralizing processing, and discoloring processing are carried out to obtain novel sulfonated grease. The sulfonated grease is paste-shape cream yellow sulfonated lanolin, which has good fluidity, good emulsifying ability, green environmental protection quality and remarkable fatliquoring performance. Moreover, the novel sulfonated grease enables leather to have good fullness, flexibility, oiliness, and waxy feeling and can be used as a main material of a fatliquoring agent of high quality leather.
Description
Technical field
The invention belongs to leather chemical industry technical field, be specifically related to a kind of compound lard of take vegetables oil methyl esters and lanolin and prepare the method for novel sulfonated grease as raw material.
Background technology
Lanolin, as a kind of special biological raw material, has a wide range of applications in daily chemical industry, medicine and other fields.Lanolin self structure is very easily combined with leather fiber, be easy to be absorbed by leather, remarkable for leather greasing effect, can give fullness, flexibility, moisture feeling and wax sense that leather is good, so the application of wool lipid leather fat in leather processing procedure also progressively increasing.
Lanolin fatting agent is substantially all through modification, composite forming both at home and abroad at present; the groups such as hydroxyl, ester group, α hydrogen and carbon-carbon double bond of technical thought based in lanolin molecule, its main method has maleic anhydride esterification, esterification, phosphorylation, the acetylize of oxyethane ether, sulphiting, acetylize etc.Lanolin and diacetyl oxide are carried out to modification, then make Modulan, modified vegetable oil, the mixture of fish oil and synthetic neat's foot oil is under the effect of load type metal soap catalyzer, 80～85 ℃ of oxidation 5～6h, then oxidation products and S-WAT are carried out to sulfited reaction, 80～90 ℃ of reaction 2～3h, obtain a kind of novel sulphiting class lanolin fatting agent (preparation > > of < < sulfited lanolin leather fat, < < daily chemical industry > >, 2003, 33 6 phase of volume 363-365 pages).In Chinese patent CN1546690, first by lanolin and ethanamide under basic catalyst condition, 90～150 ℃ of reaction 2～6h, make amidation lanolin, again amidation lanolin is mixed with P2O5 mineral oil and derivative thereof with MALEIC ANHYDRIDE, at 60～110 ℃, react 2～6h, be cooled to 40～60 ℃, NaOH is neutralized to pH6.0～8.0, obtains a kind of wool grease leather fatliquoring agent.The shortcomings such as the lanolin fatting agent that these modification mode make exists color darker, has peculiar smell, and technique is loaded down with trivial details, the time is long.
At present, Yi You producer take natural fats and oils or Synthetic Oil as raw material, adopt sulphur trioxide gas phase falling film sulfonation technology to prepare sulfonation class leather fat, the fatting agent product obtaining due to this technology has excellent stuffing performance, and three-waste free discharge in production process, fundamentally solved the problem of environmental pollution in leather fat production process, reached the environmental protection of production process, so this technology is comparatively advanced at present leather fat production technology.Yet lanolin constituent is complicated, ester content is about 94%, and in ester, various lanoceric acids and Wool wax alcohol approximately respectively account for 50%, non-hydroxyl ester (R
1cH
2cOOR
2) account for 60%, hydroxy ester
account for 40% (being mainly Alpha-hydroxy).The typical triglyceride structure that the monoesters structure of the mixture of this complexity of lanolin and other natural animal-plant greases have
difference is larger, so lanolin is at normal temperatures and is difficult to mobile paste, and fusing point is 36～42 ℃.Because lanolin has this kind of structural performance, while adopting existing sulphur trioxide gas phase falling film sulfonation technology sulfonation lanolin, there is many difficult points: SO
3gas phase xanthation is a consecutive production, must guarantee that higher temperature could keep the mobility of raw material and sulfonation acid esters, neutralized reaction product; And 40% the alpha-hydroxy esters of having an appointment in the structure of lanolin has higher reactive behavior than general grease structure, make reaction be undertaken to reaction conditions, as temperature, reactant ratio, reaction depth etc. are strict, controlling by expection.Excess Temperature easily makes the even coking carbonization of lanolin oversulfonate, and reaction depth not easily produces various by products affects product performance, and overreact meeting makes product dehydrate charing.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art part, provide a kind of compound lard of take vegetables oil methyl esters and lanolin to prepare the method for novel sulfonated grease as raw material, the sulfonation lanolin obtaining through the method, there is good biological degradability and usability, meet the development trend of current environment-friendly and green.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for novel sulfonated grease, is comprised of following steps:
A, prepare compound lard: in temperature, be, under the nitrogen atmosphere of 40～70 ℃, vegetables oil methyl esters and lanolin fully to be mixed 30～150 minutes, obtain compound lard;
B, sulfonation reaction: by compound lard and SO
3gas carries out continuous sulfonation in multi-tube film sulfonation reactor, obtains sulfonated products, and wherein to enter the temperature of sulfonation reactor be 30～60 ℃ to compound lard, and the chuck water temperature of sulfonation reactor is 25～75 ℃;
C, burin-in process: sulfonated products is carried out to burin-in process, and aging temperature is 50～70 ℃, and digestion time is 20～60 minutes;
D, neutralizing treatment: adopting neutralizing agent to be neutralized to pH value to the sulfonated products after aging is 5～9, and neutral temperature is 40～70 ℃;
E, decolouring are processed: the sulfonated products after adopting discoloring agent to neutralization is carried out neutralizing treatment, obtains novel sulfonated grease, and wherein, bleaching time is 0.5～2 hour, and bleaching temperature is 25～60 ℃.
As preferably, described vegetables oil methyl esters is selected from soybean oil methyl ester, rape oil methyl esters, plam oil methyl esters and Oleum Gossypii semen methyl esters.
As preferably, in A step, the weight ratio of vegetables oil methyl esters and lanolin is 0.6～1.5: 1.
As preferably, in B step, compound lard and SO
3mass ratio be 10～15: 1.
As preferably, in B step, SO
3gas adopts dry air dilution, SO
3the volume percent of gas in dry air is 2%～4%.
As preferably, described neutralizing agent is selected from sodium hydroxide, potassium hydroxide, trolamine and ammoniacal liquor.
As preferably, in E step, 1～20w% of the sulfonated products of the consumption of discoloring agent after for neutralization.
As preferably, described discoloring agent is selected from hydrogen peroxide, clorox and sodium borohydride.
The sulfonation lanolin obtaining by the present invention, overcome the color that lanolin modified technique existed in the past dark, have peculiar smell and the shortcoming such as the loaded down with trivial details time of technique is long, have that good fluidity, emulsifying power are good, environmental protection and the feature such as stuffing performance is outstanding, can give pliability and glossy sense that leather is good, can be as the main raw of high leather fatting agent; And production unit is advanced, easy and simple to handle, has shortened the production time, is continuous production, and turndown ratio is large, and the three wastes are few, and environmental pollution is little.
Embodiment
Embodiment 1
1, prepare compound lard:
1000g soybean oil methyl ester is mixed in reactor with 600g lanolin and pass into nitrogen, temperature is controlled 50 ℃, and fully mix and blend 60min, obtains compound lard.
2, sulphur trioxide gas phase falling film sulfonation compound lard:
By compound lard and SO
3gas carries out continuous sulfonation in multi-tube film sulfonation reactor, obtains sulfonated products.Wherein, reactor jacket water temperature is controlled 28 ℃; Compound lard and SO
3mass ratio be 12.5: 1; SO
3gas adopts dry air dilution, SO
3the volume percent of gas in dry air is 4%.
3, burin-in process:
Sulfonated products enters digestion tank, 60 ℃ of aging 30min.
4, neutralizing treatment:
Sulfonated products after aging is neutralized to pH7～9 with trolamine in 50 ℃.
5, decolouring is processed:
In the sulfonated products after neutralization, add 50g hydrogen peroxide, 35 ℃ are stirred decolouring 0.5h, obtain the paste product of milk yellow good fluidity.This product is for after leather greasing, and leather softness is good.
Embodiment 2
1, prepare compound lard:
1000g rape oil methyl esters and 1500g lanolin are mixed in and in reactor, mix and pass into nitrogen, and temperature is controlled 40 ℃, and fully mix and blend 90min, obtains compound lard.
2, sulphur trioxide gas phase falling film sulfonation compound lard:
By compound lard and SO
3gas carries out continuous sulfonation in multi-tube film sulfonation reactor, obtains sulfonated products.Wherein, reactor jacket water temperature is controlled 32 ℃; Compound lard and SO
3mass ratio be 15: 1; SO
3gas adopts dry air dilution, SO
3the volume percent of gas in dry air is 2%.
3, burin-in process:
Sulfonated products enters digestion tank, 50 ℃ of aging 20min.
4, neutralizing treatment:
Sulfonated products after aging is neutralized to pH7～9 with ammoniacal liquor in 60 ℃.
5, decolouring is processed:
In the sulfonated products after neutralization, add 100g clorox, 40 ℃ are stirred decolouring 1h, obtain the paste product of yellow good fluidity.This product is for after leather greasing, and leather fullness ratio is good.
Embodiment 3
1, prepare compound lard:
1000g plam oil methyl esters is mixed in reactor with 800g lanolin and pass into nitrogen, temperature is controlled 70 ℃, and fully mix and blend 90min, obtains compound lard.
2, sulphur trioxide gas phase falling film sulfonation compound lard:
Compound lard temperature is reduced to 60 ℃, with SO
3gas carries out continuous sulfonation in multi-tube film sulfonation reactor, obtains sulfonated products.Wherein, reactor jacket water temperature is controlled 40 ℃; The mass ratio of compound lard and SO3 is 14: 1; SO
3gas adopts dry air dilution, SO
3the volume percent of gas in dry air is 3%.
3, burin-in process:
Sulfonated products enters digestion tank, 70 ℃ of aging 20min.
4, neutralizing treatment:
Sulfonated products after aging is neutralized to pH7～9 with potassium hydroxide in 40 ℃.
5, decolouring is processed:
In the sulfonated products after neutralization, add 60g sodium borohydride, 55 ℃ are stirred decolouring 1h, obtain the paste product of milk yellow good fluidity.This product is for after leather greasing, and leather oil moisture feeling is outstanding.
Embodiment 4
1, prepare compound lard:
1000g Oleum Gossypii semen methyl esters is mixed in reactor with 1000g lanolin and pass into nitrogen, temperature is controlled 60 ℃, and fully mix and blend 120min, obtains compound lard.
2, sulphur trioxide gas phase falling film sulfonation compound lard:
Compound lard and SO
3gas carries out continuous sulfonation in multi-tube film sulfonation reactor, obtains sulfonated products.Wherein, reactor jacket water temperature is controlled 36 ℃; Compound lard and SO
3mass ratio be 10: 1; SO
3gas adopts dry air dilution, SO
3the volume percent of gas in dry air is 3.5%.
3, burin-in process:
Sulfonated products enters digestion tank, 55 ℃ of aging 30min.
4, neutralizing treatment:
Sulfonated products after aging is neutralized to pH7～9 with sodium hydroxide in 70 ℃.
5, decolouring is processed:
In the sulfonated products after neutralization, add 175g hydrogen peroxide, 60 ℃ are stirred decolouring 1.5h, obtain the paste product of brown color good fluidity.This product is for after leather greasing, and leather has wax sense.
Claims (6)
1. a preparation method for novel sulfonated grease, is characterized in that, following steps, consists of:
A, prepare compound lard: in temperature, be, under the nitrogen atmosphere of 40～70 ℃, vegetables oil methyl esters and lanolin fully to be mixed 30～150 minutes, obtain compound lard; Wherein, the weight ratio of described vegetables oil methyl esters and lanolin is 0.6～1.5:1; Described vegetables oil methyl esters is selected from soybean oil methyl ester, rape oil methyl esters, plam oil methyl esters and Oleum Gossypii semen methyl esters;
B, sulfonation reaction: by compound lard and SO
3gas carries out continuous sulfonation in multi-tube film sulfonation reactor, obtains sulfonated products, and wherein to enter the temperature of sulfonation reactor be 30～60 ℃ to compound lard, and the chuck water temperature of sulfonation reactor is 25～75 ℃;
C, burin-in process: sulfonated products is carried out to burin-in process, and aging temperature is 50～70 ℃, and digestion time is 20～60 minutes;
D, neutralizing treatment: adopting neutralizing agent to be neutralized to pH value to the sulfonated products after aging is 5～9, and neutral temperature is 40～70 ℃;
E, decolouring are processed: the processing of decolouring of the sulfonated products after adopting discoloring agent to neutralization, obtain novel sulfonated grease, and wherein, bleaching time is 0.5～2 hour, bleaching temperature is 25～60 ℃.
2. preparation method according to claim 1, is characterized in that, in B step, and compound lard and SO
3mass ratio be 10～15:1.
3. preparation method according to claim 1, is characterized in that, in B step, and SO
3gas adopts dry air dilution, SO
3the volume percent of gas in dry air is 2%～4%.
4. preparation method according to claim 1, is characterized in that, described neutralizing agent is selected from sodium hydroxide, potassium hydroxide, trolamine and ammoniacal liquor.
5. preparation method according to claim 1, is characterized in that, in E step, the consumption of discoloring agent is 1～20w% of the sulfonated products after neutralizing.
6. preparation method according to claim 1, is characterized in that, described discoloring agent is selected from hydrogen peroxide, clorox and sodium borohydride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010129724.8A CN102190606B (en) | 2010-03-19 | 2010-03-19 | Preparation method of novel sulfonated grease |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010129724.8A CN102190606B (en) | 2010-03-19 | 2010-03-19 | Preparation method of novel sulfonated grease |
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| CN102190606A CN102190606A (en) | 2011-09-21 |
| CN102190606B true CN102190606B (en) | 2014-03-12 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561400B (en) * | 2014-12-18 | 2017-02-22 | 广州市日用化学工业研究所有限公司 | Sulfonated leather greasing agent containing fatty acid low-carbon ester and preparation method thereof |
| CN105950797A (en) * | 2016-07-13 | 2016-09-21 | 嘉兴赞宇科技有限公司 | Novel preparation process of synthetic fatting agent and device |
| CN106148591A (en) * | 2016-08-30 | 2016-11-23 | 四川达威科技股份有限公司 | A kind of waterproof currying agent and preparation method thereof |
| CN114605293A (en) * | 2022-03-17 | 2022-06-10 | 广州市浪奇实业股份有限公司 | Preparation process of fatty acid methyl ester sulfonate |
| CN114682185B (en) * | 2022-03-23 | 2024-04-09 | 中国日用化学研究院有限公司 | Continuous sulfonation device and process for flexible material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4285688A (en) * | 1979-03-28 | 1981-08-25 | Leather Life, Inc. | Saddle oil |
| SU981361A1 (en) * | 1980-11-12 | 1982-12-15 | Восточно-Сибирский технологический институт | Composition for fat-liquoring skins |
| CN1472344A (en) * | 2002-07-31 | 2004-02-04 | 浙江赞成科技有限公司 | Production of leather chemicals from natural oil and fat by SO3 gas phase sulfonation |
| ATE388246T1 (en) * | 2003-08-04 | 2008-03-15 | Dystar Textilfarben Gmbh & Co | COMPOSITION FOR TREATING LEATHER |
| CN1580288A (en) * | 2003-08-11 | 2005-02-16 | 阮文娟 | Method for manufacturing leather fattening agent |
| CN100475977C (en) * | 2005-07-08 | 2009-04-08 | 浙江赞宇科技股份有限公司 | Method of preparing new type sulfonation leather fattening agent by gaseous phase method |
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Address after: 510660 East Whampoa Road, Guangdong, Guangzhou, No. 128 Co-patentee after: GUANGZHOU DAILY CHEMICAL INDUSTRY RESEARCH INSTITUTE CO.,LTD. Patentee after: GUANGZHOU LONKEY INDUSTRIAL Co.,Ltd. Address before: 510660 East Whampoa Road, Guangdong, Guangzhou, No. 128 Co-patentee before: GUANGZHOU Research Institute OF DAILY CHEMICAL INDUSTRY Patentee before: GUANGZHOU LONKEY INDUSTRIAL Co.,Ltd. |
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Effective date of registration: 20230710 Address after: 511455 No. 8 Xiaohu South Third Road, Xiaohu Island, Huangge Town, Nansha District, Guangzhou City, Guangdong Province Patentee after: GUANGZHOU LANGQI DAILY NECESSITIES CO.,LTD. Patentee after: GUANGZHOU DAILY CHEMICAL INDUSTRY RESEARCH INSTITUTE CO.,LTD. Address before: 510660 No. 128, Whampoa Avenue, Guangzhou, Guangdong Patentee before: GUANGZHOU LONKEY INDUSTRIAL Co.,Ltd. Patentee before: GUANGZHOU DAILY CHEMICAL INDUSTRY RESEARCH INSTITUTE CO.,LTD. |