Background technology
Biofuel is to utilize the produced New-type fuels that can substitute the clean and safe of petrifaction diesel of renewable resources such as Vegetable oil lipoprotein or animal grease.Main component is that the saturated unsaturated fatty acidss of long-chain such as Palmiticacid, stearic acid, oleic acid, linolic acid are with methyl alcohol or the formed ester compound of ethanol.Characteristics such as that biofuel has is renewable, be easy to biological degradation, the discharging of Air thing is low, greenhouse gas emission is low.Biofuel and petrifaction diesel have close performance.And its impayable superiority is arranged: (1) has good environmental protection characteristic.(2) has good low-temperature engine starting performance.(3) has lubricity preferably.(4) has good safety performance.(5) has good combustionproperty.(6) has renewable performance.(7) need not to change diesel engine, can directly add use, need not to add in addition bunkering facilities, storage facilities and personnel's special technique training simultaneously.(8) biofuel is in harmonious proportion with certain proportion and petrifaction diesel and uses, and can reduce oil consumption, improve dynamic property, and reduce tail gas pollution.The production biofuel has great importance to solving ecocrisis and energy dilemma.
Technical in production of biodiesel, formed that chemical catalyst catalyzed oil lipidol is separated biodiesel technology, biological enzyme agent catalyzed oil lipidol is separated biodiesel technology and supercritical methanol grease alcoholysis biodiesel technology.
But the chemical method biodiesel synthesis has following shortcoming: complex process, and alcohol must be excessive, and subsequent technique must have corresponding pure retrieving arrangement, the energy consumption height, color and luster is dark, and unsaturated fatty acids is at high temperature apt to deteriorate in the fat; Esterification products is difficult to reclaim the cost height; Production process has the waste lye discharging.For addressing the above problem, people begin one's study and use the biological enzyme biodiesel synthesis.The enzyme process biodiesel synthesis has that mild condition, pure consumption are little, the advantage of non-pollution discharge, but one of subject matter is at present: low to methyl alcohol and ethanol conversion, the easy inactivation of lipase, lipase costs an arm and a leg, and is unfavorable for shortcomings such as large-scale industrial production.Overcritical preparation method reacts under High Temperature High Pressure and need not catalyzer.The reaction times of traditional method is 1~8h, and overcritical preparation method only needs 20~40min, has shortened the reaction times greatly, can carry out operate continuously.Have saponification resultant to generate in the produced in conventional processes process, and overcritical preparation rule does not have saponification resultant, thereby simplified the subsequent processes of product, reduced production cost.Compared with traditional method, overcritical preparation method technical process is simple, the product yield height.As seen, overcritical preparation method is compared with traditional method and is had very big advantage.But because the method for preparing biodiesel under supercritical condition need be carried out under high-temperature and high-pressure conditions, cause higher productive expense and energy expenditure, making the industrialization difficulty needs further research and development.
Summary of the invention
The objective of the invention is to disclose a kind of novel method of biodiesel manufacture, utilize ultrasonic wave radiation Assisted Preparation of Biodiesel Oil, help accelerating the transesterification reaction time, improve the yield of biofuel, reduce catalyst levels, the purity of glycerine improves greatly simultaneously, has reduced production cost and pollution on the environment.
The present invention adopts following technical scheme: a kind of method of utilizing ultrasonic wave radiation Assisted Preparation of Biodiesel Oil is characterized in that its transesterification reaction carries out under the ultrasonic wave radiation.
More satisfactory is that its concrete production process comprises the steps:
(1), be under the condition of 30-200W and at ultrasonic power with carrying out transesterification reaction under the catalyst action with various stock oils and methanol mixed;
(2) with step (1) gained reactant standing demix;
(3) supernatant liquid is reclaimed methyl alcohol through methanol distillation column, to clarification of water, upper oil phase is removed moisture obtain the biofuel product with the water washing that is higher than 5 ℃-10 ℃ of oil temperature.
The novel method that a kind of production of biodiesel is provided of the present invention utilizes the ultrasonic wave radiation to produce partial High Temperature High Pressure, can promote the biofuel for preparing of transesterification reaction simultaneously.By accelerated the production rate of biofuel with ultrasonic wave, obviously shorten the reaction times, and improved the yield of biofuel, reduced the consumption of catalysts, reduced environmental pollution, improved the benefit of enterprise.
Embodiment
The invention will be further described below in conjunction with specific embodiment, to help understanding content of the present invention.
Embodiment 1,
Take by weighing the 100g sewer oil and put into Erlenmeyer flask, add the 25g methyl alcohol and the 2 gram vitriol oils, above-mentioned various materials are mixed in Erlenmeyer flask, bottle stopper beyond the Great Wall, place KQ5200DB type numerical control supersonic cleanser to react 10min, temperature of reaction is 58-63 ℃, and ultrasonic power is 100W.Reaction finishes back standing demix 90min, and the upper strata is mainly fatty acid methyl ester and small amount of methanol, and lower floor is mainly glycerine, the vitriol oil, small amount of methanol.After the upper strata product reclaimed methyl alcohol by methyl alcohol distillation tower vacuum,, to get upper oil phase and remove moisture by thin-film evaporator through vacuum distilling and obtain biofuel elaboration 97.6 grams with 15ml65 ℃ hot wash, centrifugal layering. the reaction total yield is 97.6%.
Embodiment 2,
Take by weighing the 100g sewer oil and put into Erlenmeyer flask, add the 25g methyl alcohol and the 2 gram vitriol oils, above-mentioned various materials are mixed in Erlenmeyer flask, bottle stopper is heated to 60 ℃ of reaction 60min on magnetic stirring apparatus beyond the Great Wall.Reaction finishes back standing demix 90min, and the upper strata is mainly fatty acid methyl ester and small amount of methanol, and lower floor is mainly glycerine, the vitriol oil, small amount of methanol.After the upper strata product reclaimed methyl alcohol by methyl alcohol distillation tower vacuum,, get upper oil phase and remove moisture through vacuum distilling and obtain biofuel elaboration 85.5 grams with 15ml65 ℃ hot wash, centrifugal layering.The reaction total yield is 85.5%.
Utilize overcritical radiation Assisted Preparation of Biodiesel Oil more as can be seen from example 1 and example 2, the reaction times shortens to 10min from 60min, and bio-diesel yield but brings up to 97.6% from 85.5%.
Embodiment 3,
The biofuel that obtains from example 1 detects through Shandong Supervision and Inspection Institute for Product Quality, and it the results are shown in Table 1. every indexs and is better than the existing biofuel standard GB/T20828-2007 of country, reaches German biofuel standard.
Table 1 biofuel specific targets
Index and unit of measurement are described |
Biofuel |
Germany |
China |
Petroleum diesel |
DIN V 51606 |
GB/T 20828 |
EN 590: 1999 |
Be applicable to |
|
FAME |
S500 |
S50 |
Diesel |
Density in the time of 15 ℃ |
g/cm
3 |
0.89 |
0.875~0.90 |
0.82~0.9 |
0.82~0.84 5 |
Kinetic viscosity in the time of 40 ℃ |
mm
2/s
|
4.0 |
3.5~5.0 |
1.9~6.0 |
2.0~4.5 |
Flash-point |
℃ |
140min |
110min |
130min |
55min |
Cold filter clogging temperature (CFPP) |
℃ |
-10 |
Spring: 0 autumn in summer :-10 winters :-20 |
Report |
The country variant different standards |
Sulphur content |
mg/kg |
0.005 |
0.01max |
0.05 max |
0.005 max |
350max |
Carbon residue (10%dist.resi due) |
The % massfraction |
0.2 |
0.3max |
0.3max |
0.3max |
Moisture |
mg/kg |
Vestige |
300max |
500max |
200max |
Total impurities |
mg/kg |
Do not have |
20max |
Do not have |
24max |
Corrosion usefulness to copper |
3h/50℃ |
1 |
1 |
1 |
1 |
Cetane value |
|
53 |
49min |
49min |
51min |
Acidity value |
mgKOH/g |
0.3 |
0.5max |
0.80max |
|
Embodiment 4,
Take by weighing 100g lard and put into Erlenmeyer flask, add 25g methyl alcohol and 0.4gKOH above-mentioned various materials are mixed in Erlenmeyer flask, bottle stopper places KQ5200DB type numerical control supersonic cleanser to react 10min beyond the Great Wall, temperature of reaction is 58-63 ℃, and ultrasonic power is 100W.Reaction finishes back standing demix 90min, and the upper strata is mainly fatty acid methyl ester and small amount of methanol, and lower floor is mainly glycerine, KOH, small amount of methanol and soap.After the upper strata product reclaimed methyl alcohol by methyl alcohol distillation tower vacuum,, to get upper oil phase and remove moisture through vacuum distilling and obtain biofuel elaboration 99.5 grams with 15ml65 ℃ hot wash, centrifugal layering. the reaction total yield is 99.5%.
Embodiment 5,
Take by weighing 100g lard and put into Erlenmeyer flask, add 25g methyl alcohol and 0.8 gram KOH, above-mentioned various materials are mixed in Erlenmeyer flask, bottle stopper is heated to 60 ℃ of reaction 60min on magnetic stirring apparatus beyond the Great Wall.Reaction finishes back standing demix 90min, and the upper strata is mainly fatty acid methyl ester and small amount of methanol, and lower floor is mainly glycerine, KOH, small amount of methanol and soap.After the upper strata product reclaimed methyl alcohol by methyl alcohol distillation tower vacuum,, get upper oil phase and remove moisture through vacuum distilling and obtain biofuel elaboration 93.7 grams with the hot wash of 65 ℃ of 15ml, centrifugal layering.The reaction total yield is 93.7%.
Utilize overcritical radiation Assisted Preparation of Biodiesel Oil more as can be seen from example 4 and example 5, the reaction times shortens to 10min from 60min, and bio-diesel yield but brings up to 99.5% from 93.7%, and the consumption of catalyzer KOH has lacked 50%.
Embodiment 6,
Take by weighing 100g lard and put into Erlenmeyer flask, add 25g methyl alcohol and 0.4gKOH above-mentioned various materials are mixed in Erlenmeyer flask, bottle stopper places KQ5200DB type numerical control supersonic cleanser to react 10min beyond the Great Wall, temperature of reaction is 58-63 ℃, and ultrasonic power is 50W.Reaction finishes back standing demix 90min, and the upper strata is mainly fatty acid methyl ester and small amount of methanol, and lower floor is mainly glycerine, KOH, small amount of methanol and soap.After the upper strata product reclaimed methyl alcohol by methyl alcohol distillation tower vacuum,, to get upper oil phase and remove moisture through vacuum distilling and obtain biofuel elaboration 90.7 grams with the hot wash of 65 ℃ of 15ml, centrifugal layering. the reaction total yield is 90.7%.
Embodiment 7,
Take by weighing 100g lard and put into Erlenmeyer flask, add 25g methyl alcohol and 0.4gKOH above-mentioned various materials are mixed in Erlenmeyer flask, bottle stopper places KQ5200DB type numerical control supersonic cleanser to react 10min beyond the Great Wall, temperature of reaction is 58-63 ℃, and ultrasonic power is 150W.Reaction finishes back standing demix 90min, and the upper strata is mainly fatty acid methyl ester and small amount of methanol, and lower floor is mainly glycerine, KOH, small amount of methanol and soap.After the upper strata product reclaimed methyl alcohol by methyl alcohol distillation tower vacuum,, to get upper oil phase and remove moisture through vacuum distilling and obtain biofuel elaboration 99.8 grams with the hot wash of 65 ℃ of 15ml, centrifugal layering. the reaction total yield is 99.8%.