CN102190606A - Preparation method of novel sulfonated grease - Google Patents
Preparation method of novel sulfonated grease Download PDFInfo
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- CN102190606A CN102190606A CN2010101297248A CN201010129724A CN102190606A CN 102190606 A CN102190606 A CN 102190606A CN 2010101297248 A CN2010101297248 A CN 2010101297248A CN 201010129724 A CN201010129724 A CN 201010129724A CN 102190606 A CN102190606 A CN 102190606A
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- grease
- lanolin
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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 the leather chemical industry technical field, being specifically related to a kind of compound lard with vegetables oil methyl esters and lanolin is the novel sulfonated greasy method of feedstock production.
Background technology
Lanolin has application widely as a kind of special biological raw material in daily chemical industry, medicine and other fields.The lanolin self structure very easily combines with leather fiber, be easy to be absorbed by leather, it is remarkable to be used for the leather greasing effect, can give the good fullness of leather, flexibility, moisture feeling and wax sense, so the application of wool lipid leather fat in leather processing procedure also progressively increasing.
The lanolin fatting agent substantially all is through modification, composite forming both at home and abroad at present; technical thought is based on groups such as the hydroxyl in the lanolin molecule, ester group, α hydrogen and carbon-carbon double bonds, and its main method has maleic anhydride esterification, esterification, phosphorylation, the acetylize of oxyethane ether, sulphiting, acetylize etc.Lanolin and diacetyl oxide are carried out modification; the mixture that makes Modulan, modified vegetable oil, fish oil and synthetic neat's foot oil then 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 sulfited reaction; 80～90 ℃ of reaction 2～3h get a kind of novel sulphiting class lanolin fatting agent (" preparation of sulfited lanolin leather fat ", " daily chemical industry "; 2003,33 volumes, 6 phase 363-365 pages or leaves).Among the Chinese patent CN1546690, at first with lanolin and ethanamide under the 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, react 2～6h down, be cooled to 40～60 ℃ at 60～110 ℃, NaOH is neutralized to pH6.0～8.0, gets a kind of wool grease leather fatliquoring agent.Shortcomings such as the lanolin fatting agent that these modification mode make exists color darker, and peculiar smell is arranged, and technology is loaded down with trivial details, the time is long.
At present, also there is producer to be raw material, to adopt sulphur trioxide gas phase falling film type sulfonation technology to prepare sulfonation class leather fat with natural fats and oils or Synthetic Oil, because the fatting agent product that this technology obtains has excellent stuffing performance, and three-waste free discharge in the production process, fundamentally solved the problem of environmental pollution in the 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 complexity, ester content is about 94%, and various lanoceric acids and Wool wax alcohol respectively account for 50%, non-hydroxyl ester (R approximately in the ester
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 are had
Difference is bigger, so lanolin is at normal temperatures and is difficult to the mobile paste, and fusing point is 36～42 ℃.Because lanolin has this kind structural performance, there is many difficult points: SO when adopting existing sulphur trioxide gas phase falling film type sulfonation technology sulfonation lanolin
3Gas phase xanthation is a continuity production, must guarantee that higher temperature could keep the flowability 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, and reaction is needed reaction conditions by expection, as strict control such as temperature, reactant ratio, reaction depth.Temperature is too high easily to make lanolin oversulfonate even coking carbonization, and reaction depth easily produces various by products inadequately influences product performance, and the overreact meeting makes the product dehydration carbonization.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art part, it is the novel sulfonated greasy method of feedstock production that a kind of compound lard with vegetables oil methyl esters and lanolin is provided, the sulfonation lanolin that obtains through this method, have excellent biodegradability 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 kind of novel sulfonated greasy preparation method, be made up of following steps:
A, preparation compound lard: be under 40～70 ℃ the nitrogen atmosphere in temperature, with vegetables oil methyl esters and lanolin thorough mixing 30～150 minutes, must compound lard;
B, sulfonation reaction: with compound lard and SO
3Gas carries out continuous sulfonation in multi-tube film sulfonation reactor, sulfonated products, wherein to enter the temperature of sulfonation reactor be 30～60 ℃ to compound lard, the chuck water temperature of sulfonation reactor is 25～75 ℃;
C, burin-in process: sulfonated products is carried out burin-in process, and aging temperature is 50～70 ℃, and digestion time is 20～60 minutes;
D, neutralizing treatment: adopting neutralizing agent that the sulfonated products after aging is neutralized to the pH value is 5～9, and neutral temperature is 40～70 ℃;
E, decolouring are handled: the sulfonated products after adopting discoloring agent to neutralization is carried out neutralizing treatment, gets 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 the A step, the weight ratio of vegetables oil methyl esters and lanolin is 0.6～1.5: 1.
As preferably, in the B step, compound lard and SO
3Mass ratio be 10～15: 1.
As preferably, in the 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 the 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 that obtains by the present invention, overcome the color that lanolin modified technique in the past exists dark, shortcomings such as peculiar smell and loaded down with trivial details time of technology is long are arranged, characteristics such as have that good fluidity, emulsifying power are good, environmental protection and stuffing performance are outstanding, can give good pliability of leather and glossy sense, can be as the main raw of high leather fatting agent; And the production unit advanced person, easy and simple to handle, shortened the production time, be continuous production, turndown ratio is big, and the three wastes are few, and environmental pollution is little.
Embodiment
Embodiment 1
1, preparation compound lard:
The 1000g soybean oil methyl ester mixed in reactor with 600g lanolin and feed nitrogen, 50 ℃ of temperature controls, thorough mixing stirs 60min, compound lard.
2, sulphur trioxide gas phase falling film type sulfonation compound lard:
With compound lard and SO
3Gas carries out continuous sulfonation in multi-tube film sulfonation reactor, get sulfonated products.Wherein, the control of reactor jacket water temperature is 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 handled:
Add the 50g hydrogen peroxide in the sulfonated products after the neutralization, 35 ℃ are stirred decolouring 0.5h, the paste product of milk yellow good fluidity.After this product was used for leather greasing, leather softness was good.
Embodiment 2
1, preparation compound lard:
1000g rape oil methyl esters and 1500g lanolin is mixed in mixes in the reactor and feed nitrogen, 40 ℃ of temperature controls, thorough mixing stirs 90min, compound lard.
2, sulphur trioxide gas phase falling film type sulfonation compound lard:
With compound lard and SO
3Gas carries out continuous sulfonation in multi-tube film sulfonation reactor, get sulfonated products.Wherein, the control of reactor jacket water temperature is 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 handled:
Add the 100g clorox in the sulfonated products after the neutralization, 40 ℃ are stirred decolouring 1h, the paste product of yellow good fluidity.After this product was used for leather greasing, the leather fullness ratio was good.
Embodiment 3
1, preparation compound lard:
1000g plam oil methyl esters mixed in reactor with 800g lanolin and feed nitrogen, 70 ℃ of temperature controls, thorough mixing stirs 90min, compound lard.
2, sulphur trioxide gas phase falling film type sulfonation compound lard:
The compound lard temperature is reduced to 60 ℃, with SO
3Gas carries out continuous sulfonation in multi-tube film sulfonation reactor, get sulfonated products.Wherein, the control of reactor jacket water temperature is 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 handled:
Add the 60g sodium borohydride in the sulfonated products after the neutralization, 55 ℃ are stirred decolouring 1h, the paste product of milk yellow good fluidity.After this product was used for leather greasing, the leather oil moisture feeling was outstanding.
Embodiment 4
1, preparation compound lard:
1000g Oleum Gossypii semen methyl esters mixed in reactor with 1000g lanolin and feed nitrogen, 60 ℃ of temperature controls, thorough mixing stirs 120min, compound lard.
2, sulphur trioxide gas phase falling film type sulfonation compound lard:
Compound lard and SO
3Gas carries out continuous sulfonation in multi-tube film sulfonation reactor, get sulfonated products.Wherein, the control of reactor jacket water temperature is 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 handled:
Add the 175g hydrogen peroxide in the sulfonated products after the neutralization, 60 ℃ are stirred decolouring 1.5h, the paste product of pale brown look good fluidity.After this product was used for leather greasing, leather had the wax sense.
Claims (8)
1. a novel sulfonated greasy preparation method is characterized in that, is made up of following steps:
A, preparation compound lard: be under 40～70 ℃ the nitrogen atmosphere in temperature, with vegetables oil methyl esters and lanolin thorough mixing 30～150 minutes, must compound lard;
B, sulfonation reaction: with compound lard and SO
3Gas carries out continuous sulfonation in multi-tube film sulfonation reactor, sulfonated products, wherein to enter the temperature of sulfonation reactor be 30～60 ℃ to compound lard, the chuck water temperature of sulfonation reactor is 25～75 ℃;
C, burin-in process: sulfonated products is carried out burin-in process, and aging temperature is 50～70 ℃, and digestion time is 20～60 minutes;
D, neutralizing treatment: adopting neutralizing agent that the sulfonated products after aging is neutralized to the pH value is 5～9, and neutral temperature is 40～70 ℃;
E, decolouring are handled: processings of decolouring of the sulfonated products after adopting discoloring agent to neutralization, get 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, 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.
3. preparation method according to claim 1 is characterized in that, in the A step, the weight ratio of vegetables oil methyl esters and lanolin is 0.6～1.5: 1.
4. preparation method according to claim 1 is characterized in that, in the B step, and compound lard and SO
3Mass ratio be 10～15: 1.
5. preparation method according to claim 1 is characterized in that, in the B step, and SO
3Gas adopts dry air dilution, SO
3The volume percent of gas in dry air is 2%～4%.
6. preparation method according to claim 1 is characterized in that described neutralizing agent is selected from sodium hydroxide, potassium hydroxide, trolamine and ammoniacal liquor.
7. preparation method according to claim 1 is characterized in that, in the E step, the consumption of discoloring agent is 1～20w% of the sulfonated products after neutralizing.
8. preparation method according to claim 1 is characterized in that described discoloring agent is selected from hydrogen peroxide, clorox and sodium borohydride.
Priority Applications (1)
| 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 true CN102190606A (en) | 2011-09-21 |
| CN102190606B CN102190606B (en) | 2014-03-12 |
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| CN201010129724.8A Active CN102190606B (en) | 2010-03-19 | 2010-03-19 | Preparation method of novel sulfonated grease |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561400A (en) * | 2014-12-18 | 2015-04-29 | 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 |
| CN114682185A (en) * | 2022-03-23 | 2022-07-01 | 中国日用化学研究院有限公司 | Continuous sulfonation device and process for flexible material |
Citations (6)
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|---|---|---|---|---|
| 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 |
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| CN1580288A (en) * | 2003-08-11 | 2005-02-16 | 阮文娟 | Method for manufacturing leather fattening agent |
| EP1512759A1 (en) * | 2003-08-04 | 2005-03-09 | Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. | Composition for the treatment of leather |
| CN1718744A (en) * | 2005-07-08 | 2006-01-11 | 浙江赞成科技有限公司 | Method of preparing new type sulfonation leather fattening agent by gaseous phase method |
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2010
- 2010-03-19 CN CN201010129724.8A patent/CN102190606B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| 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 |
| EP1512759A1 (en) * | 2003-08-04 | 2005-03-09 | Dr. Th. Böhme KG Chem. Fabrik GmbH & Co. | Composition for the treatment of leather |
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Non-Patent Citations (1)
| Title |
|---|
| 磺化技术在生产皮革加脂剂中的应用: "兰云军等", 《中国皮革》, vol. 30, no. 11, 30 June 2001 (2001-06-30) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104561400A (en) * | 2014-12-18 | 2015-04-29 | 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 |
| CN114682185A (en) * | 2022-03-23 | 2022-07-01 | 中国日用化学研究院有限公司 | Continuous sulfonation device and process for flexible material |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN102190606B (en) | 2014-03-12 |
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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. |