CN104672113B - A kind of preparation method of fatty acid ester sulfonate - Google Patents
A kind of preparation method of fatty acid ester sulfonate Download PDFInfo
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Abstract
The preparation method that the invention discloses a kind of fatty acid ester sulfonate, utilize microbial grease for raw material, anion surfactant fatty acid ester sulfonate is obtained by series reaction such as ester exchange, epoxidation, open loop, sulfonating reactions, the microbial grease that the present invention adopts, it is with straw for raw material, adopts yeast, algae fermentation to obtain; This grease production cost is low, and its product is easily achieved large-scale industrial and produces, and present invention achieves and straw is changed into soap, detergent. Anion surfactant fatty acid ester sulfonate prepared by the present invention, there is greater activity content of material, the problem that its preparation method is absent from " striving grain with people ", and it is long to overcome the current animal and plant fat production cycle, being limited by season and weather, raw material sources are narrow, the problem taking extra cultivated land resource, solve the yield of animal and plant fat especially far from the problem meeting commercial production MES demand, possess good economic benefit and wide application prospect.
Description
Technical field:
The present invention relates to technical field of biochemical industry, the preparation method being specifically related to a kind of fatty acid ester sulfonate.
Background technology:
Surfactant can be substantially reduced the surface tension of solvent when addition is little, changes interface state, thus producing the series of properties such as moistening, emulsifying or breakdown of emulsion, foaming or froth breaking. Surfactant, as commercial auxiliaries, " industry monosodium glutamate ", functional additional materials, plays increasing effect in Chinese national economy every field, defence and military and people's lives various aspects. By the research that deepens continuously of Surfactant, economic growth and social progress certainly will will be produced important meaning.
Main active component in current detergent mostly is the surfactants such as alkylbenzenesulfonate (LAS), lauryl sulfate (AS), �� olefin sulfonate (��-AOS), and they are all petrochemicals. Along with quickly consuming and people's raising day by day to environmental protection consciousness of petroleum resources, utilize Renewable resource to produce the surfactant being compatible with the environment, be one of feature of surfactant technology development over nearly 20 years. Methyl sodiosul foaliphatate (MES) is a kind of just is the environmental friendliness surfactant that raw material is made by natural animal-plant oils and fats, owing to MES has excellent soil release performance, hard water resistance property, low irritant and toxicity, and surface activity is better than LAS, biological degradability is similar to soap, therefore MES can be widely applied to substitute the LAS in detergent, improve formula composition, reduce the consumption of sodium tripolyphosphate (STPP); In addition its performance is gentle, to the zest of human body lower than LAS, suitable with AS, polyoxyethylenated alcohol sodium sulfate (AES);Washing performance is good, can keep good scourability in cold water and hard water, even if the MES detergency of C16��18 is also above LAS and AS in soft water, in hard water, gap becomes apparent from, the main weakness of this LAS just; Meanwhile, its without phosphorus characteristic is better than LAS, is not having alkali, and when lacking STTP, LAS dirt-removing power is had a greatly reduced quality, and MES but subtracts effect seldom, so being particularly suitable for producing without phosphorus/phosphorus environment-friendly type detergent.
The preparation method that Chinese patent 102618398A, 103320236A propose a kind of detergent containing methyl sodiosul foaliphatate, the preparation method that Chinese patent 101921678A proposes a kind of fancy soap containing fatty-acid ethyl ester sulfonate, what above patent was solely focused on is the performance of cleaning product, but ignores the research to middle raw fatty acid methyl ester sulfonate. MES obtains with natural plant grease for raw material, but, the Vegetable oil lipoprotein production cycle is long, is limited by season and weather, and raw material sources are narrow, take extra cultivated land resource, the problem that there is " striving grain with people " especially. And along with the development of science and technology, according to scholarly forecast, world population will be doubled from 2000 to the year two thousand fifty, detergent total amount will increase to 120,000,000 tons from 50,000,000 tons, have a net increase of 1.4 times, the demand growth amplitude of fatty acid ester sulfonate, the yield of Vegetable oil lipoprotein is far from meeting industrial demand.
Microbial grease, it is utilized carbohydrate, Hydrocarbon and common oils and fats to be carbon source, nitrogenous source under certain condition by microorganisms such as yeast, mycete, antibacterial and algae, be aided with the oils and fats of production of inorganic, synthesizing under certain condition and be stored in endobacillary glyceride, its constituent includes: myristic acid, 15 carbonic acid, Palmic acid, palmitoleic acid, trans palmitoleic acid, 17 carbonic acid, stearic acid, linoleic acid, oleic acid. Wherein Palmic acid, oleic acid, linoleic content are of a relatively high, similar to commercial animal and plant fat.
Chinese patent 102634549A, 103131529A, 103642858A and 103013834A etc. individually disclose the extracting method of a kind of microbial grease and the cultural method of a kind of oleaginous microorganism; Chinese patent 101307342A and 101974371A etc. discloses a kind of preparation method that microbial grease is used for biodiesel. The extraction of the more concern oleaginous microorganism of all circles' researcheres and microbial grease, for the application aspect of microbial grease, is also only limitted in biodiesel, and about in chemical products, especially the applied research of MES aspect rarely has report.
Summary of the invention:
The preparation method that it is an object of the invention to provide a kind of fatty acid ester sulfonate, utilize microbial grease for raw material, obtain anion surfactant fatty acid ester sulfonate by ester exchange, epoxidation, open loop, sulfonating reaction, owing to microbial grease is with short production cycle, do not limited by season and weather, raw material sources are wide, solve with animal and plant fat for raw material, and the production cycle is long, limited by season and weather, raw material sources are narrow, take extra cultivated land resource, the problem that there is " striving grain with people ".
The present invention is achieved by the following technical programs:
The preparation method of a kind of fatty acid ester sulfonate, comprises the following steps:
A, ester exchange reaction: in microbial grease, add alcohol, normal hexane, acid or base catalyst, stir, 50-80 DEG C of isothermal reaction 1-3 hour, post-treated obtain microbial grease Ester; The quality of described alcohol is the 25%��50% of microbial grease quality, and the quality of catalyst is the 0.1%��5% of microbial grease quality;
B, epoxidation reaction: with reference to CN104356097A, the step a microbial grease Ester obtained adds organic acid, acidic catalyst, 40-80 DEG C of stirring reaction, then peroxide it is slowly added dropwise, after adding, isothermal reaction 4-8 hour, post-treated obtain epoxidation microbial grease esters product; Described organic acid quality is the 5%��50% of microbial grease esters quality, and the quality of acidic catalyst is the 1%��4% of microbial oil aliphatic radical esters quality, and the quality of peroxide is the 80%��150% of microbial grease esters quality;
C, ring-opening reaction: in the step b epoxidation microbial grease esters product obtained, add alcohol as ring opening agent, any one in concentrated sulphuric acid, concentrated hydrochloric acid, phosphoric acid or fluoboric acid is as catalyst, 50-105 DEG C of constant temperature stirring reaction 1-4 hour, after reaction terminates, remove solvent, with ethyl acetate with hot water, the crude product obtained is extracted, wash make solution becomes neutrality; Microbial grease esters polyhydric alcohol is obtained after the product at reduced pressure distillation dehydration after washing; The quality of described alcohol is the 60%��120% of epoxidation microbial grease esters quality, and the quality of catalyst is the 0.1%��1% of epoxidation microbial grease esters quality;
D, sulfonating reaction: be slowly added dropwise into sulfonating agent in the step c microbial grease esters polyhydric alcohol obtained, after 70-90 DEG C of sulfonation 0.5��2h, it is cooled to 80 DEG C of aging 0.5h��1h, after solution to be mixed cooling, first adjusting pH value is 5��6, then being 7��9, rotary evaporation removes water, and vacuum drying obtains target product; The quality of sulfonating agent is the 150%��300% of microbial grease esters polyol quality.
In step a, any one in methanol, ethanol, butanol of described alcohol; Any one in concentrated sulphuric acid, phosphoric acid, concentrated hydrochloric acid of described acid catalyst, any one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate of base catalyst.
In step b, any one in formic acid, acetic acid, propanoic acid of described organic acid; Any one in concentrated sulphuric acid, concentrated hydrochloric acid, phosphoric acid or solid acid catalyst of described acidic catalyst; Any one in sodium peroxide, potassium peroxide, hydrogen peroxide, peracetic acid of described peroxide.
Described solid acid catalyst is selected from the zeolite molecular sieve such as ZMS-5 zeolite, X, B zeolite; H3PW12O40Deng cation exchange resiies such as heteropoly acids; Any one in the natural clay ore deposit load peracid metallic salts such as galapectite, attapulgite, montmorillonite.
In step c, any one in methanol, ethanol or butanol of described ring opening agent.
In step d, any one in concentrated sulphuric acid, gaseous sulfur trioxide, oleum, chlorosulfonic acid of sulfonating agent.
Described anion surfactant fatty acid ester sulfonate, in the chemical products field use such as surfactant, biodiesel.
Relative to prior art, there is advantages that
The microbial grease that the present invention adopts, is with straw for raw material, adopts yeast, algae fermentation to obtain; This grease production cost is low; its product is easily achieved large-scale industrial and produces; the present invention utilizes microbial grease for raw material; anion surfactant fatty acid ester sulfonate is obtained by series reaction such as ester exchange, epoxidation, open loop, sulfonating reactions; achieve and straw is changed into soap, detergent; solve the problem of environmental pollution that crop straw burning brings, meet national green, environmental protection, the principles and policies of sustainable development.
Anion surfactant fatty acid ester sulfonate prepared by the present invention, there is greater activity content of material, the problem that its preparation method is absent from " striving grain with people ", and it is long to overcome the current animal and plant fat production cycle, being limited by season and weather, raw material sources are narrow, the problem taking extra cultivated land resource, solve the yield of animal and plant fat especially far from the problem meeting commercial production MES demand, possess good economic benefit and wide application prospect.
Detailed description of the invention:
The following is further illustrating the present invention rather than limitation of the present invention.
Unless stated otherwise, the commercial reagent of the present invention adopts reagent, equipment and routine that method is the art, equipment and conventional use of method.
The active matter content of the present invention, uses following evaluation methodology to be evaluated.
According to GB/T5173-1995 method, for each embodiment, often the active matter content averaged as each embodiment tested 3 times by group sample.
Embodiment 1: the preparation method of a kind of fatty acid ester sulfonate
First ester exchange reaction is carried out: first take 10g microbial grease (iodine number is 60), normal hexane 10g, methanol 2.5g, catalyst sodium hydroxide 0.01g, add heating in water bath in reactor, it is warming up to 50 DEG C, react 1 hour, after reaction terminates, carry out washing with the hot water crude product to obtaining and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain target crude product, the crude product obtained uses vacuum distillation range instrument be purified and refining obtains microbial grease methyl ester; Then epoxidation reaction is carried out: take microbial grease methyl ester 10g, formic acid 0.5g, catalyst concentrated sulphuric acid 0.1g, stirring, is slowly added dropwise 8g sodium peroxide, after completion of dropwise addition, 60 DEG C are reacted 4 hours, after reaction terminates, with hot water, crude product is carried out washing and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain epoxidation microbial grease methyl ester; Carry out ring-opening reaction again: take epoxidation microbial grease methyl ester 10g, ring opening agent methanol 6g, catalyst concentrated sulphuric acid 0.01g, stirring, 50 DEG C are reacted 1 hour, after reaction terminates, remove solvent, with hot water, the crude product obtained is extracted by ethyl acetate, wash and make solution become neutral, after the product at reduced pressure distillation dehydration after washing, obtain microbial grease methyl ester polyhydric alcohol; Finally carry out sulfonating reaction: take 10g microbial grease methyl ester polyhydric alcohol, it is slowly added dropwise sulfonating agent concentrated sulphuric acid 15g, stirring, after 70 DEG C of sulfonation 0.5 hour, be cooled to 80 DEG C aging 0.5 hour, after solution to be mixed cooling, first being neutralized to pH value with sodium hydroxide dilute alkaline soln is 5��6, being neutralized to pH value with sodium hydrate methanol solution again is 7��9, and a small amount of water of rotary evaporation, vacuum drying obtains product.
Embodiment 2: the preparation method of a kind of fatty acid ester sulfonate
Reference example 1, is distinguished by: ethanol 4g in ester exchange reaction, and catalyst is potassium hydroxide 0.04g, and 60 DEG C are reacted 2 hours; Epoxidation reaction takes microbial grease ethyl ester 10g, acetic acid 1.3g, catalyst concentrated hydrochloric acid 0.2g, stirring, it is slowly added dropwise 10g potassium peroxide, 65 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent ethanol 10g, catalyst fluoboric acid 0.05g in ring-opening reaction, 75 DEG C are reacted 2 hours; Sulfonating agent 20g in sulfonating reaction, after 80 DEG C of sulfonation 1 hour, aging 0.7 hour.
Embodiment 3: the preparation method of a kind of fatty acid ester sulfonate
Reference example 1, is distinguished by: butanol 5g in ester exchange reaction, and catalyst is potassium bicarbonate 0.1g, and 80 DEG C are reacted 2 hours; Epoxidation reaction takes microbial grease ethyl ester 10g, propanoic acid 5g, catalyst concentrated hydrochloric acid 0.4g, stirring, it is slowly added dropwise 15g potassium peroxide, 90 DEG C are reacted 8 hours; Taking epoxidation microbial grease butyl ester 10g, ring opening agent butanol 12g, catalyst concentrated hydrochloric acid 0.1g in ring-opening reaction, 105 DEG C are reacted 4 hours, sulfonating agent 30g in sulfonating reaction, after 90 DEG C of sulfonation 2 hours, and aging 1 hour.
Embodiment 4: the preparation method of a kind of fatty acid ester sulfonate
First ester exchange reaction is carried out: first take 10g microbial grease (iodine number is 80), normal hexane 10g, methanol 2.5g, catalyst sodium carbonate 0.05g, add heating in water bath in reactor, it is warming up to 50 DEG C, react 1 hour, after reaction terminates, carry out washing with the hot water crude product to obtaining and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain target crude product, the crude product obtained uses vacuum distillation range instrument be purified and refining obtains microbial grease methyl ester; Then epoxidation reaction is carried out: take microbial grease methyl ester 10g, formic acid 0.5g, catalyst phosphoric acid 0.2g, stirring, is slowly added dropwise 8g hydrogen peroxide, after completion of dropwise addition, 60 DEG C are reacted 4 hours, after reaction terminates, with hot water, crude product is carried out washing and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain epoxidation microbial grease methyl ester; Carry out ring-opening reaction again: take epoxidation microbial grease methyl ester 10g, ring opening agent methanol 6g, catalyst concentrated sulphuric acid 0.01g, stirring, 50 DEG C are reacted 1 hour, after reaction terminates, remove solvent, with ethyl acetate with hot water, the crude product obtained is extracted, wash make solution becomes neutrality; Microbial oil aliphatic radical esters polyhydric alcohol is obtained after the product at reduced pressure distillation dehydration after washing; Finally carry out sulfonating reaction: take 10g microbial grease methyl ester polyhydric alcohol, it is slowly added dropwise sulfonating agent gaseous sulfur trioxide 15g, stirring, after 70 DEG C of sulfonation 0.5 hour, be cooled to 80 DEG C aging 0.5 hour, after solution to be mixed cooling, first being neutralized to pH value with sodium hydroxide dilute alkaline soln is 5��6, being neutralized to pH value with sodium hydrate methanol solution again is 7��9, and a small amount of water of rotary evaporation, vacuum drying obtains product.
Embodiment 5: the preparation method of a kind of fatty acid ester sulfonate
Reference example 4, is distinguished by: ethanol 4g in ester exchange reaction, and catalyst is concentrated sulphuric acid 0.4g, and 60 DEG C are reacted 2 hours; Taking microbial grease ethyl ester 10g, acetic acid 2g in epoxidation reaction, catalyst is ZMS-5 zeolite 0.1g, stirring, is slowly added dropwise 10g peracetic acid, and 65 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent ethanol 10g, catalyst fluoboric acid 0.05g in ring-opening reaction, 75 DEG C are reacted 3 hours; Sulfonating agent 20g in sulfonating reaction, after 80 DEG C of sulfonation 1 hour, aging 0.7 hour.
Embodiment 6: the preparation method of a kind of fatty acid ester sulfonate
Reference example 4, is distinguished by: butanol 5g in ester exchange reaction, and catalyst is concentrated hydrochloric acid 0.5g, and 80 DEG C are reacted 3 hours; Epoxidation reaction takes microbial grease ethyl ester 10g, acetic acid 0.5g, catalyst X zeolite 0.2g, stirring, it is slowly added dropwise 8g potassium peroxide, 90 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent butanol 12g, catalyst phosphoric acid 0.1g in ring-opening reaction, 105 DEG C are reacted 4 hours; Sulfonating agent 30g in sulfonating reaction, after 90 DEG C of sulfonation 2 hours, aging 1 hour.
Embodiment 7: the preparation method of a kind of fatty acid ester sulfonate
First ester exchange reaction is carried out: first take 10g microbial grease (iodine number is 105), normal hexane 10g, methanol 2.5g, catalyst sodium bicarbonate 0.05g, add heating in water bath in reactor, it is warming up to 50 DEG C, react 1 hour, after reaction terminates, carry out washing with the hot water crude product to obtaining and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain target crude product, the crude product obtained uses vacuum distillation range instrument be purified and refining obtains microbial grease methyl ester;Then epoxidation reaction is carried out: take microbial grease methyl ester 10g, formic acid 0.5g, catalyst H3PW12O400.4g, stirring, it is slowly added dropwise 8g hydrogen peroxide, after completion of dropwise addition, 60 DEG C are reacted 4 hours, after reaction terminates, with hot water, crude product are carried out washing and make solution become neutrality, obtain epoxidation microbial grease methyl ester after the product at reduced pressure distillation dehydration after washing; Finally carry out ring-opening reaction: take epoxidation microbial grease methyl ester 10g, ring opening agent methanol 6g, catalyst concentrated sulphuric acid 0.01g, stirring, 50 DEG C react 1 hour, reaction terminate after, remove solvent, with ethyl acetate with hot water, the crude product obtained is extracted, wash make solution becomes neutrality; Microbial oil aliphatic radical esters polyhydric alcohol is obtained after the product at reduced pressure distillation dehydration after washing. Finally carry out sulfonating reaction: take 10g microbial grease methyl ester polyhydric alcohol, it is slowly added dropwise sulfonating agent chlorosulfonic acid 15g, stirring, after 70 DEG C of sulfonation 0.5 hour, be cooled to 80 DEG C aging 0.5 hour, after solution to be mixed cooling, first being neutralized to pH value with sodium hydroxide dilute alkaline soln is 5��6, being neutralized to pH value with sodium hydrate methanol solution again is 7��9, and a small amount of water of rotary evaporation, vacuum drying obtains product.
Embodiment 8: the preparation method of a kind of fatty acid ester sulfonate
Reference example 7, is distinguished by: ethanol 4g in ester exchange reaction, and catalyst is concentrated sulphuric acid 0.35g, and 60 DEG C are reacted 2 hours; Taking microbial grease ethyl ester 10g, acetic acid 2g in epoxidation reaction, catalyst is B zeolite 0.1g, stirring, is slowly added dropwise 10g sodium peroxide, and 65 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent ethanol 10g, catalyst fluoboric acid 0.05g in ring-opening reaction, 75 DEG C are reacted 3 hours; Sulfonating agent 20g in sulfonating reaction, after 80 DEG C of sulfonation 1 hour, aging 0.8 hour.
Embodiment 9: the preparation method of a kind of fatty acid ester sulfonate
Reference example 7, is distinguished by: butanol 5g in ester exchange reaction, and catalyst is concentrated hydrochloric acid 0.4g, and 80 DEG C are reacted 3 hours; Epoxidation reaction takes microbial grease ethyl ester 10g, acetic acid 0.5g, catalyst X zeolite 0.2g, stirring, it is slowly added dropwise 8g potassium peroxide, 90 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent butanol 12g, catalyst phosphoric acid 0.1g in ring-opening reaction, 105 DEG C are reacted 4 hours; Sulfonating agent 30g in sulfonating reaction, after 90 DEG C of sulfonation 2 hours, aging 1 hour.
Embodiment 10: the preparation method of a kind of fatty acid ester sulfonate
First ester exchange reaction is carried out: first take 10g microbial grease (iodine number is 120), normal hexane 10g, methanol 2.5g, catalyst sodium carbonate 0.05g, add heating in water bath in reactor, it is warming up to 50 DEG C, react 1 hour, after reaction terminates, carry out washing with the hot water crude product to obtaining and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain target crude product, the crude product obtained uses vacuum distillation range instrument be purified and refining obtains microbial grease methyl ester; Then epoxidation reaction is carried out: take microbial grease methyl ester 10g, formic acid 0.5g, catalyst is montmorillonite-loaded crosses acid metal salt 0.1g, stirring, is slowly added dropwise 8g hydrogen peroxide, after completion of dropwise addition, 60 DEG C are reacted 4 hours, after reaction terminates, with hot water, crude product is carried out washing and make solution become neutrality, after the product at reduced pressure distillation dehydration after washing, obtain epoxidation microbial grease methyl ester; Carry out ring-opening reaction again: take epoxidation microbial grease methyl ester 10g, ring opening agent methanol 6g, catalyst concentrated sulphuric acid 0.01g, stirring, 50 DEG C react 1 hour, reaction terminate after, remove solvent, with ethyl acetate with hot water, the crude product obtained is extracted, wash make solution becomes neutrality;Microbial oil aliphatic radical esters polyhydric alcohol is obtained after the product at reduced pressure distillation dehydration after washing; Finally carry out sulfonating reaction: take 10g microbial grease methyl ester polyhydric alcohol, it is slowly added dropwise sulfonating agent oleum 15g, stirring, after 70 DEG C of sulfonation 0.5 hour, be cooled to 80 DEG C aging 0.5 hour, after solution to be mixed cooling, first being neutralized to pH value with sodium hydroxide dilute alkaline soln is 5��6, being neutralized to pH value with sodium hydrate methanol solution again is 7��9, and a small amount of water of rotary evaporation, vacuum drying obtains product.
Embodiment 11: the preparation method of a kind of fatty acid ester sulfonate
Reference example 10, is distinguished by: ethanol 4g in ester exchange reaction, and catalyst is concentrated sulphuric acid 0.4g, and 60 DEG C are reacted 2 hours; Taking microbial grease ethyl ester 10g, acetic acid 2g in epoxidation reaction, catalyst is that attapulgite load crosses acid metal salt 0.1g, stirring, is slowly added dropwise 10g peracetic acid, and 65 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent ethanol 10g, catalyst fluoboric acid 0.05g in ring-opening reaction, 75 DEG C are reacted 3 hours; Sulfonating agent 20g in sulfonating reaction, after 80 DEG C of sulfonation 1 hour, aging 0.7 hour.
Embodiment 12: the preparation method of a kind of fatty acid ester sulfonate
Reference example 10, is distinguished by: butanol 5g in ester exchange reaction, and catalyst is concentrated hydrochloric acid 0.5g, and 80 DEG C are reacted 3 hours; Taking microbial grease ethyl ester 10g, acetic acid 0.5g in epoxidation reaction, catalyst galapectite load crosses acid metal salt 0.4g, stirring, is slowly added dropwise 8g potassium peroxide, and 90 DEG C are reacted 6 hours; Taking epoxidation microbial grease ethyl ester 10g, ring opening agent butanol 12g, catalyst phosphoric acid 0.1g in ring-opening reaction, 105 DEG C are reacted 4 hours; Sulfonating agent 30g in sulfonating reaction, after 90 DEG C of sulfonation 2 hours, aging 1 hour.
Embodiment 13: the performance of anion surfactant fatty acid ester sulfonate
Anion surfactant fatty acid ester sulfonate prepared by embodiment 1-12 has carried out 3 groups of experiments respectively, after measured, and its performance data (active matter content, unit %) as shown in the table:
The Product Activity thing content of a kind of anion surfactant fatty acid ester sulfonate prepared by the known present invention of above-mentioned experimental data is between 20-70%; With microbial grease for main production raw material, it is achieved that straw to be changed into soap, detergent, solve the problem of environmental pollution that crop straw burning brings; meet national green, environmental protection; the principles and policies of sustainable development, and its production cost is low, it is easy to accomplish large-scale industrial produces. The problem that this product is absent from " striving grain with people ", and it is long to overcome the current animal and plant fat production cycle, limited by season and weather, raw material sources are narrow, the problem taking extra cultivated land resource, solve the yield of animal and plant fat especially far from the problem meeting commercial production MES demand, possess good economic benefit and wide application prospect.
Claims (5)
1. the preparation method of a fatty acid ester sulfonate, it is characterised in that comprise the following steps:
A, in microbial grease, add alcohol, normal hexane, acid or base catalyst, stir, 50-80 DEG C of isothermal reaction 1-3 hour, post-treated obtain microbial grease Ester; The quality of described alcohol is the 25%��50% of microbial grease quality, and the quality of catalyst is the 0.1%��5% of microbial grease quality;
B, in the step a microbial grease Ester obtained, add organic acid, acidic catalyst, 40-80 DEG C of stirring reaction, be then slowly added dropwise peroxide, after adding, isothermal reaction 4-8 hour, post-treated obtain epoxidation microbial grease esters product;Described organic acid quality is the 5%��50% of microbial grease esters quality, and the quality of acidic catalyst is the 1%��4% of microbial oil aliphatic radical esters quality, and the quality of peroxide is the 80%��150% of microbial grease esters quality; Any one in formic acid, acetic acid, propanoic acid of described organic acid;
C, in the step b epoxidation microbial grease esters product obtained add alcohol as ring opening agent, any one in concentrated sulphuric acid, concentrated hydrochloric acid, phosphoric acid or fluoboric acid is as catalyst, 50-105 DEG C of constant temperature stirring reaction 1-4 hour, after reaction terminates, remove solvent, with ethyl acetate with hot water, the crude product obtained is extracted, wash make solution becomes neutrality; Microbial grease esters polyhydric alcohol is obtained after the product at reduced pressure distillation dehydration after washing; The quality of described alcohol is the 60%��120% of epoxidation microbial grease esters quality, and the quality of catalyst is the 0.1%��1% of epoxidation microbial grease esters quality; Any one in methanol, ethanol or butanol of described alcohol;
D, it is slowly added dropwise into sulfonating agent in the step c microbial grease esters polyhydric alcohol obtained, after 70-90 DEG C of sulfonation 0.5��2h, is cooled to 80 DEG C of aging 0.5h��1h, after solution to be mixed cooling, first adjusting pH value is 5��6, is then 7��9, rotary evaporation removes water, and vacuum drying obtains target product; The quality of sulfonating agent is the 150%��300% of microbial grease esters polyol quality.
2. the preparation method of fatty acid ester sulfonate according to claim 1, it is characterised in that in step a, any one in methanol, ethanol, butanol of described alcohol; Any one in concentrated sulphuric acid, phosphoric acid, concentrated hydrochloric acid of described acid catalyst, any one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate of base catalyst.
3. the preparation method of fatty acid ester sulfonate according to claim 1, it is characterised in that in step b, any one in concentrated sulphuric acid, concentrated hydrochloric acid, phosphoric acid or solid acid catalyst of described acidic catalyst; Any one in sodium peroxide, potassium peroxide, hydrogen peroxide, peracetic acid of described peroxide.
4. the preparation method of fatty acid ester sulfonate according to claim 3, it is characterised in that described solid acid catalyst is selected from ZMS-5 zeolite, X, B zeolite molecular sieve; H3PW12O40Heteropoly acid cation exchange resin; Any one in galapectite, attapulgite, montmorillonite ore deposit load peracid metallic salt.
5. the preparation method of fatty acid ester sulfonate according to claim 1, it is characterised in that in step d, any one in concentrated sulphuric acid, gaseous sulfur trioxide, oleum, chlorosulfonic acid of sulfonating agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19741911C1 (en) * | 1997-09-25 | 1999-01-14 | Henkel Kgaa | Fatty acid polyglycol ester sulphate as foam booster for surfactants |
| CN101760328A (en) * | 2009-12-31 | 2010-06-30 | 大连理工大学 | Method for producing branched biodiesel |
| CN104356097A (en) * | 2014-10-20 | 2015-02-18 | 中国科学院广州能源研究所 | Preparation method of microbial oil-based epoxide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19741911C1 (en) * | 1997-09-25 | 1999-01-14 | Henkel Kgaa | Fatty acid polyglycol ester sulphate as foam booster for surfactants |
| CN101760328A (en) * | 2009-12-31 | 2010-06-30 | 大连理工大学 | Method for producing branched biodiesel |
| CN104356097A (en) * | 2014-10-20 | 2015-02-18 | 中国科学院广州能源研究所 | Preparation method of microbial oil-based epoxide |
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