CN103333720B - Bio-based methanol gasoline emulsification melt water agent and preparation method thereof - Google Patents
Bio-based methanol gasoline emulsification melt water agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of bio-based methanol gasoline emulsification melt water agent and preparation method thereof, it is made up of emulsifying activity component 40 ~ 50%, melt water water resistant component 50 ~ 60%.Two kinds of function ingredients stir at normal temperatures and are bio-based methanol gasoline emulsification melt water agent finished product.The present invention have selected can clean, the oil yeast fat of environmental protection acid soap as the additive of cheapness, not only energy-conservation but also reduce discharging, compared with prior art, cost is low, addition is few, emulsification water resistant Be very effective, can not bring secondary pollution to environment.The material such as yeast fat acid soap and ester class, alcohols etc. used in the present invention, carries out organic synthesis modification, the emulsification melt water agent that synthesizing methanol gasoline is special.Emulsification melt water of the present invention agent generally can dissolve in the water of 5.88 ~ 7.78%, the highest dissolve in 10% water, water solubilization is large, reaches 180 days stationary phase, can meet the requirement in production, accumulating and use completely, the application for moisture biological methanol brings unlimited dawn.
Description
Technical field
The present invention relates to a kind of alcohols fuel substitute field, particularly a kind of based on biomass energy, the emulsification melt water agent that biological alcohols can be admixed at high proportion and preparation method thereof.
Background technology
For a long time, the fuel of all kinds of motor vehicle is always based on gasoline, diesel oil, and this using forestland is more and more subject to the restriction that environmental pollution is serious and resource is day by day in short supply.In order to improve this predicament, have employed various energy resources alternative both at home and abroad, but these alternative, to large-scale promotion, all also exist serious defect.In recent years, because international oil price continues to spiral in a high position, accelerate speed of applying and the flow of research of domestic and international substituting alcohol-ether fuel.Can replace the enforcement of Strategic Policy according to the energy of National Development and Reform Committee's promulgation, people start the various additives testing alcohol gasoline.But just at present, methanol gasoline stores, most distinct issues are oleyl alcohol problem of phase separation in transport and use procedure, thus affects the normal use of methanol gasoline.The biological process particularly limited containing a small amount of moisture content produces the utilization of methyl alcohol, when there was dampness in the air, just there will be muddy layering when meeting a small amount of moisture content, causes most of methyl alcohol to sink to tank bottoms, cause automobile runs malfunctioning.The destruction of visible moisture to methyl alcohol and gasoline intermiscibility is very large.
For solving water to the problem of phase separation of methanol gasoline, there is the patent achievement of a lot of melt water solubility promoter aspect.Its main composition of CN101619247A that has belonging to environmental protection class realizes with partly-hydrolysed ammonium soaps, melt water rate 3 ~ 5%; CN101985569A completes water repelling property with oleic acid, but oleic acid is a kind of acid macromole, and oleic acid too much in methanol gasoline is unfavorable to engine combustion; Melt water rate 3%; Its water resistant composition of CN101302449A is Virahol, primary isoamyl alcohol, melt water rate 3.5%; Emulsifying agent made by CN102329665A, CN101285011B alcohols and tensio-active agent, although these commercial emulsifying agents are effective, market value is high, water resistant rate 2 ~ 6%; CN101747955A uses oil mixing with water agent, separating agent, but does not announce composition, water resistant 5 ~ 10%; What SHE company of CN101203585A Holland was too much highlights water-fast principle, does not announce composition, water resistant 1 ~ 10%; The water repelling property that CN101918518A American South University of California describes fuel flexible mixture reaches 10%, but does not also announce its composition; The water resistant rate of CN102021053A and CN101445752A only has 1.5 ~ 2%.
This invention is in our province emphasis support items EAM (low-temp anaerobic fermentation microorganism species) research, from the oil reservoir of Changqing oilfields deep, be separated facultative oil yeast EAM-AC16-trichosporon viscosity trichosporon (Trichosporonmucoidessp.CGMCC7429) of the plant height Lipid-producing obtained, by lipid acid extractive technique, obtain with C
16~ C
18unsaturated fatty acids is main yeast fat acid, and its lipid acid major ingredient is: Palmiticacid (C16: 0) 30%, palmitinic acid (C16: 1) 5%, stearic acid (C18: 0) 5%, oleic acid (C18: 1) 50%, linolic acid (C18: 2) 10%.The yeast fat acid soap that this additive uses is obtained by saponification yeast unsaturated fatty acids, and its lipid acid extractive technique, saponification process technology are disclosed known technology, and the present invention no longer repeats.Yeast fat acid soap class (saponification amine soap) has good emulsifying dispersion, solublization, studies carefully its mechanism, and its surfactivity is all by molecule oriented adsorption and be agglomerated into the extensions of micella two kinds of fundamental propertys in the liquid phase on interface.The oriented adsorption of molecule makes the surface tension of system sharply decline, thus makes oil product be provided with the abilities such as wetting, de-sludging; The formation of micella makes oil product be provided with the effects such as solubilising.After reaching micelle-forming concentration, solubilising still can strengthen with the increase of concentration, and this is the exclusive character of tensio-active agent.Its tolerance moisture content degree 5.88 ~ 7.78%, reaches as high as about 10%.
Summary of the invention
The object of this invention is to provide the agent of a kind of methanol gasoline emulsification melt water.Another goal of the invention of the present invention is to provide the agent of a kind of bio-based methanol gasoline emulsification melt water.
The purposes of bio-based methanol gasoline emulsification melt water agent and effect: emulsification moisture, melt water water resistant, solve low temperature oleyl alcohol problem of phase separation.And the emulsification melt water additive meeting GB (GB/T23799-2009) M85 Vehicular methanol petrol standard and prepare.
In order to solve the problem and overcome the deficiencies in the prior art, the technical solution adopted in the present invention is, its emulsification melt water agent is made up of two kinds of function ingredients: emulsifying activity component (yeast fat acid soap) and melt water water resistant component (fatty acid ester, fatty alcohol).
The present invention is in our province emphasis support items EAM (low-temp anaerobic fermentation microorganism species) research, from the oil reservoir of Changqing oilfields deep, be separated the facultative oil yeast EAM-AC16 of the plant height Lipid-producing obtained, China Committee for Culture Collection of Microorganisms's common micro-organisms center is preserved on April 7th, 2013, No. 3, Yard 1, BeiChen xi Road, Chaoyang District, Beijing City, address, deposit number CGMCCNO.7429, Classification And Nomenclature is viscosity trichosporon (Trichosporonmucoides).
Lipid acid extractive technique: get quantitative yeast fermentation broth (employing common fermentation processes), the centrifugal 30min of 3000r/min, removes supernatant liquor, adds isopyknic 20%NaOH aqueous solution, 120 DEG C of saponification 30min, are cooled to 60 ~ 70 DEG C and add isopyknic 95% alcohol and shake up.The above-mentioned saponified paraffin of reinforcing body while hot adding alcohol is considered to be worth doing a little, cooling.Now, together with the residual hydrocarbon in saponification liquor is set in solid paraffin, can filter together with yeast slag.With 50% alcohol washes filter residue.Washing lotion and filtrate are merged, evaporation alcohol.Be acidified to pH3.0 with HCl, use ether extraction secondary.Wash ether layer with water, with anhydrous sodium sulfate drying, evaporation ether, weighs and obtains yeast C
16~ C
18unsaturated fatty acids.
By lipid acid extractive technique, obtain with C
16~ C
18unsaturated fatty acids is main yeast fat acid, and its lipid acid major ingredient is: Palmiticacid (C16: 0) 30%, palmitinic acid (C16: 1) 5%, stearic acid (C18: 0) 5%, oleic acid (C18: 1) 50%, linolic acid (C18: 2) 10%.Based on the yeast fat of Palmiticacid, oleic acid acid with trolamine through the partly-hydrolysed C obtained
16~ C
18unsaturated mono fatty acid soap can significantly improve the combustion heat value of oil product, makes up the defect that methyl alcohol calorific value is not enough, power is not strong.
Saponification process process: first yeast C
16~ C
18unsaturated fatty acids dissolves in base oil, dewatering tank by heating, is then added by trolamine with volume ratio 2: 1 ratio, reacts 15 ~ 30min at normal temperatures.All dissolve in oil to fatty acid triethanol amine soap, all dissolve in evenly and get product.
The agent of a kind of bio-based methanol gasoline emulsification melt water is be made up of following volume percent function ingredients: emulsifying activity component 40 ~ 50%: emulsifying activity component is yeast fat acid soap; The fatty acid ester of melt water water resistant component 50 ~ 60%:30 ~ 40% and the fatty alcohol of 18% ~ 20%, described fatty acid ester is made up of with volume ratio 1: 1 ratio tween 80, sorbester p17, and fatty alcohol is with the mixture of volume ratio equal proportion by Virahol, propyl carbinol wherein one or both; Described yeast fat acid soap is C
16~ C
18the acid of oil yeast fat with trolamine with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps RCONHR that saponification is formed
1; Described C
16~ C
18the acid of oil yeast fat is obtained through fermented extracted by the facultative oil yeast EAM-ACl6 of a plant height Lipid-producing, its deposit number CGMCCNO.7429.
The preparation method of described bio-based methanol gasoline emulsification melt water agent, the emulsifying activity component of 40 ~ 50% and 50 ~ 60% melt water water resistant components are joined in stirring tank, stir at normal temperatures and namely obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.51 ~ 7.81.
The present invention adopts above technical scheme major advantage to be:
(1) the present invention have selected can clean, environmental protection, renewable, degradable oil yeast fat acid as cheapness additive, not only energy-conservation but also reduce discharging, for developing Industry Waste grease further and trench swill wet goods opens new approach, have turn waste into wealth, profit give up into can active effect.
(2) emulsification melt water of the present invention agent compared with prior art, and cost is low, nontoxic, pollution-free, addition is few, emulsification water resistant Be very effective, can not bring secondary pollution to environment.
(3) material such as yeast fat acid soap and ester class, alcohols etc. used in the present invention, carries out organic synthesis modification, introduces certain hydrophilic, lipophilic group, synthesized the emulsification melt water agent that methanol gasoline is special, substitute traditional molten aqua.
(4) melt water amount is large, and stationary phase is long.Generally add the methanol gasoline of traditional hydrotropy stablizer, the moisture dissolving in 0.1 ~ 0.5% at normal temperatures will produce and be separated, and emulsification melt water of the present invention agent generally can dissolve in the water of 5.88 ~ 7.78%, the highest dissolve in 10.53% water, reach 180 days stationary phase, if can preserve in closed system more than 2 years not stratified, there is long-time feature of preserving, can meet the requirement of production, accumulating and use completely, the application for moisture biological methanol brings unlimited dawn.
(5) the present invention prepares simple, easy to use, and cost is low, effective, as long as add in methanol gasoline by the present invention, just can produce positive melt water water resistant effect, for biological methanol gasoline open one new by way of, there is promotional value widely.
Embodiment
Below in conjunction with case study on implementation, the present invention is described in further detail, but is not limited to limitation of the invention (seeing the following form).
Emulsification melt water agent (M8503) case study on implementation
Embodiment 1
The agent of a kind of bio-based methanol gasoline emulsification melt water is made up of following volume percent function ingredients:
Emulsifying activity component: C
16~ C
18fatty acid soaps 40.0%;
Melt water water resistant component: C
nfatty acid ester 40.0%; C
3~ C
4fatty alcohol 20.0%;
Wherein: the C of emulsifying activity component
16~ C
18fatty acid soaps is oil yeast fat acid (RCOOH) with organic amine (trolamine) with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps (RCONHR that saponification is formed
1); The C of melt water water resistant component
nfatty acid ester be tween 80, sorbester p17 with the mixture of volume ratio 1: 1 ratio, C
3~ C
4fatty alcohol is carbon alcohol in positive isomery, can be Virahol, propyl carbinol wherein one or both with the mixture of volume ratio equal proportion.Emulsifying activity component and melt water water resistant component are joined in stirring tank, stirs at normal temperatures and can obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.81.
Embodiment 2
The agent of a kind of bio-based methanol gasoline emulsification melt water is made up of following volume percent function ingredients:
Emulsifying activity component: C
16~ C
18fatty acid soaps 44.0%;
Melt water water resistant component: C
nfatty acid ester 38.0%; C
3~ C
4fatty alcohol 18.0%;
Wherein: the C of emulsifying activity component
16~ C
18fatty acid soaps is oil yeast fat acid (RCOOH) with organic amine (trolamine) with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps (RCONHR that saponification is formed
1); The C of melt water water resistant component
nfatty acid ester be tween 80, sorbester p17 with the mixture of volume ratio 1: 1 ratio, C
3~ C
4fatty alcohol is carbon alcohol in positive isomery, be Virahol, propyl carbinol wherein one or both with the mixture of volume ratio equal proportion.Emulsifying activity component and melt water water resistant component are joined in stirring tank, stirs at normal temperatures and can obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.60.
Embodiment 3
The agent of a kind of bio-based methanol gasoline emulsification melt water is made up of following volume percent function ingredients:
Emulsifying activity component: C
16~ C
18fatty acid soaps 46.0%;
Melt water water resistant component: C
nfatty acid ester 36.0%; C
3~ C
4fatty alcohol 18.0%;
Wherein: the C of emulsifying activity component
16~ C
18fatty acid soaps is oil yeast fat acid (RCOOH) with organic amine (trolamine) with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps (RCONHR that saponification is formed
1); The C of melt water water resistant component
nfatty acid ester be tween 80, sorbester p17 with the mixture of volume ratio 1: 1 ratio, C
3~ C
4fatty alcohol is carbon alcohol in positive isomery, be Virahol, propyl carbinol wherein one or both with volume ratio equal proportion mixture.Emulsifying activity component and melt water water resistant component are joined in stirring tank, stirs at normal temperatures and can obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.57.
Embodiment 4
The agent of a kind of bio-based methanol gasoline emulsification melt water is made up of following volume percent function ingredients:
Emulsifying activity component: C
16~ C
18fatty acid soaps 48.0%;
Melt water water resistant component: C
nfatty acid ester 34.0%; C
3~ C
4fatty alcohol 18.0%;
Wherein: the C of emulsifying activity component
16~ C
18fatty acid soaps is oil yeast fat acid (RCOOH) with organic amine (trolamine) with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps (RCONHR that saponification is formed
1); The C of melt water water resistant component
nfatty acid ester be tween 80, sorbester p17 with the mixture of volume ratio 1: 1 ratio, C
3~ C
4fatty alcohol is carbon alcohol in positive isomery, be Virahol, propyl carbinol wherein one or both with volume ratio equal proportion mixture.Emulsifying activity component and melt water water resistant component are joined in stirring tank, stirs at normal temperatures and can obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.53.
Embodiment 5
The agent of a kind of bio-based methanol gasoline emulsification melt water is made up of following volume percent function ingredients:
Emulsifying activity component: C
16~ C
18fatty acid soaps 50.0%;
Melt water water resistant component: C
nfatty acid ester 30.0%; C
3~ C
4fatty alcohol 20.0%;
Wherein: the C of emulsifying activity component
16~ C
18fatty acid soaps is oil yeast fat acid (RCOOH) with organic amine (trolamine) with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps (RCONHR that saponification is formed
1); The C of melt water water resistant component
nfatty acid ester be tween 80, sorbester p17 with the mixture of volume ratio 1: 1 ratio, C
3~ C
4fatty alcohol is carbon alcohol in positive isomery, be Virahol, propyl carbinol wherein one or both with volume ratio equal proportion mixture.Emulsifying activity component and melt water water resistant component are joined in stirring tank, stirs at normal temperatures and can obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.51.
The effect of each reagent raw material in example of the present invention:
(1) yeast fat acid soap (RCONHR
1): be by C
16~ C
18oil yeast fat acid (RCOOH) and organic amine (trolamine) with 2: 1 ratios at normal temperatures through fatty acid soaps that saponification is formed; Emulsion dispersion, solublization is played in additive.
(2) tween 80 (Tween-80): formal name used at school polyoxyethylene sorbitan carboxylic ester, boiling point 93.0 DEG C, flash-point 110.0 DEG C, proportion 1.064; Hydrophilic surfactant active, plays emulsifying effect in additive.
(3) sorbester p17 (Span-80): the anhydrous Span of formal name used at school, boiling point 90.0 DEG C, flash-point 110.0 DEG C, proportion 0.994; Lipophilic emulsifier, plays emulsifying effect in additive.
(4) Virahol (C
3h
8o): boiling point 82.4 DEG C, flash-point 22.0 DEG C, combustion heat value 1984.7kJ/mol, proportion 0.786; Best low temperature solubility promoter, plays the effect such as stable, water resistant, improvement viscosity, inhibition in additive.
(5) propyl carbinol (C
4h
10o): boiling point 117.7 DEG C, flash-point 40.0 DEG C, combustion heat value 2673.2kJ/mol, proportion 0.810; Belong to high boiling point reagent, in additive, play dissolution, stable effect.
Through mutually mating between the above function ingredients of verification experimental verification and raw material, mutually promoting, mutually synergy, to learn from other's strong points to offset one's weaknesses, jointly play emulsification moisture, melt water water resistant, solve the ideal effect that low temperature oleyl alcohol is separated.
[experimental test]
In order to verify that the present invention is to the melt water water resistant of methanol gasoline and phase stabilising effect, in 100ml colorimetric bottle, with M85, M90, M95 tri-kinds of oil products are the A factor, tap water 5.88% is dripped in methanol gasoline oil product, 7.78%, 10.53% is Factor B (volume percent), emulsification melt water agent (embodiment 5) addition in oil product is C factor (volume percent), orthogonal test L9 (34) is adopted to carry out melt water water resistant and phase stability test, its orthogonal test test factor, the design of horizontal gauge outfit and orthogonal test testing program and the results are shown in Table 1, table 2.
Table 1 emulsification melt water agent orthogonal test test factor and the design of horizontal gauge outfit
| Level | A oil product | B alcohol water content (%) | C melt water agent (%) |
| 1 | M85 | 5.88 | 0.00 |
| 2 | M90 | 7.78 | 0.05 |
| 3 | M95 | 10.53 | 0.10 |
Emulsification melt water agent orthogonal test testing program and result
Table 2 bio-based methanol gasoline emulsification melt water agent orthogonal test [L
9(3
4)] testing program and result
Result shows: along with the increase of water content, muddiness in various degree and layering is there is in MM-3, MM-6, MM-9 oil sample, namely it is comparatively serious when moisture content amount reaches 10.53%, and after adding the agent of emulsification melt water, at-20 DEG C, place one week, moisture content is 5.88 ~ 7.78% time, oil product is limpid not stratified, only has in MM-3, MM-6 sample of moisture content 10.53% time and still has some layerings; At room temperature place after 180 days, only have MM-3 sample to occur slight layering, but not muddy.Show emulsification melt water agent of the present invention tolerance moisture content Du Keda 5.88 ~ 7.78%, be up to 10%, and the stability of more than 6 months can be kept.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (2)
1. the agent of bio-based methanol gasoline emulsification melt water, is characterized in that, is to be made up of following volume percent function ingredients: emulsifying activity component 40 ~ 50%: emulsifying activity component is yeast fat acid soap; The fatty acid ester of melt water water resistant component 50 ~ 60%:30 ~ 40% and the fatty alcohol of 18% ~ 20%, described fatty acid ester is made up of with volume ratio 1: 1 ratio tween 80, sorbester p17, and fatty alcohol is with the mixture of volume ratio equal proportion by Virahol, propyl carbinol wherein one or both; Described yeast fat acid soap is C
16~ C
18the acid of oil yeast fat with trolamine with volume ratio 2: 1 ratio at normal temperatures through fatty acid soaps RCONHR that saponification is formed
1; Described C
16~ C
18the acid of oil yeast fat is obtained through fermented extracted by the facultative oil yeast EAM-AC16 of a plant height Lipid-producing, its deposit number CGMCCNO.7429;
Described yeast fat acid soap is obtained by saponification yeast unsaturated fatty acids, is specially:
Lipid acid extractive technique: get quantitative yeast fermentation broth, the centrifugal 30min of 3000r/min, removes supernatant liquor, adds the NaOH aqueous solution of isopyknic 20%, 120 DEG C of saponification 30min, is cooled to 60-70 DEG C and adds isopyknic 95% alcohol and shake up; By the above-mentioned saponified paraffin of the reinforcing body while hot bits adding alcohol, cooling; With 50% alcohol washes filter residue; Washing lotion and filtrate are merged, evaporation alcohol; Be acidified to pH3.0 with HCl, use ether extraction secondary; Wash ether layer with water, with anhydrous sodium sulfate drying, evaporation ether, weighs and obtains yeast C
16~ C
18unsaturated fatty acids;
Saponification process process: first yeast C
16-C
18unsaturated fatty acids dissolves in base oil, dewatering tank by heating, is then added by trolamine with volume ratio 2: 1 ratio, reacts 15-30min at normal temperatures; All dissolve in oil to fatty acid triethanol amine soap, all dissolve in evenly and get product;
Wherein, yeast fermentation broth is that the facultative oil yeast EAM-AC16 of high Lipid-producing is formed by normal fermentation.
2. the preparation method of bio-based methanol gasoline emulsification melt water according to claim 1 agent, it is characterized in that: the emulsifying activity component of 40 ~ 50% and 50 ~ 60% melt water water resistant components are joined in stirring tank, stir at normal temperatures and namely obtain the bio-based methanol gasoline emulsification melt water agent finished product of transparent, limpid aobvious oil red look, pH7.51 ~ 7.81.
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| CN107099345B (en) * | 2017-03-31 | 2020-08-14 | 兰州燚能生物科技有限责任公司 | Biological alcohol-based fuel oil solubilizing aid solubilizer |
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| CN102816616A (en) * | 2012-08-15 | 2012-12-12 | 贵州龙和能源有限责任公司 | Low carbon methanol gasoline composite additive and preparation method thereof |
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