CN103184064A - Method for preparing biodiesel based on crude sulphate soap as material - Google Patents
Method for preparing biodiesel based on crude sulphate soap as material Download PDFInfo
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Abstract
本发明提供了一种以粗硫酸盐皂为原料制备生物柴油的方法，具体为：在催化剂存在下，以粗硫酸盐皂与C1至C6链烷醇为原料反应制备生物柴油，所述催化剂为酸性催化剂或乙酰氯。本发明提供的生物柴油制备方法工艺简单、能耗低，采用成本低廉的粗硫酸盐皂作为原料制备具有高附加值的生物柴油产品，大大降低了生物柴油的成本。The invention provides a method for preparing biodiesel with crude sulfate soap as a raw material, specifically: in the presence of a catalyst, reacting crude sulfate soap with C1 to C6 alkanols as a raw material to prepare biodiesel, the catalyst is Acid catalyst or acetyl chloride. The biodiesel preparation method provided by the invention has simple process and low energy consumption, and uses low-cost crude sulfate soap as a raw material to prepare biodiesel products with high added value, thereby greatly reducing the cost of biodiesel.
Description
Technical field
The invention belongs to the bioenergy technical field, be specifically related to a kind of preparation method of biofuel.
Background technology
Biofuel is a kind of lipid acid ethers, particularly methyl, ethyl ether lipid acid that is comprising low alkyl group because its cleaning, renewable, have a Biodegradable, replacing traditional petroleum-type diesel oil to cause many concerns.
The characteristic of biofuel has been illustrated in existing research, and has the research report to use biofuel to do the engine driven experiment, and the result shows that biofuel is a kind of good substitute of petroleum-type diesel oil.Really, biofuel has been used in the Application Areas of some diesel oil, and has been found with oil character similar or that be superior to traditional oil is arranged.Biofuel can be used separately or thereby part is mixed use replacement petroleum-type diesel oil with conventional diesel.Using biofuel to do raw material compares with traditional petroleum-type diesel oil, the hydrocarbon polymer that has significantly reduced carbonic acid gas, smoke particle and fully do not burnt output, thereby can effectively improve Air quality, improvement global greenhouse effect, so biofuel will become a very potential neutral carbon fuel.
Document [Ma et al., Bioresource Tech., 70,1 (1999)] reported that carrying out the fat exchange student with pure glyceride to vegetable oil and useless vegetable oil produces the mol ratio that thing diesel oil is subjected to glyceride and alcohol, reaction times and temperature of reaction, the influence of the content of free fatty acid and water in the vegetables oil ﹠ fat in addition.Adopt this method to prepare biofuel and can produce this by product of glycerine usually, glycerine is at a commercial very important product.
Yet, adopt aforesaid method production biofuel, owing to need to use vegetable oil or animal oil, therefore not only cost is higher, output is very low simultaneously is difficult to replace effectively petroleum-type diesel oil.
Reduce generating the most important thing that the diesel production cost becomes the application of expansion biofuel, yet up to the present, seldom relevant for the report that how to reduce the production of biodiesel cost.
It is the raw material production method of bio-diesel oil that patent [US7695532B2] discloses with thick tall oil, its transformation efficiency can reach about 55% of thick tall oil raw material, yet go relatively to calculate with thick tall oil (current market value 3000-3500RMB/ ton) and the market value of biofuel, in this way make the cost value of biofuel also a little more than existing biodiesel market price, so industrialization is difficult to also be achieved.
A kind of shortening method is disclosed in the document [Coll et al., Energy﹠Fuels, 15,1166 (2001)] with the method for the sylvic acid composition conversion biodiesel additive in the thick tall oil.Yet this catalytic hydrogenation method requires the high pressure of 100 to 150 bar and 350 to 400 ℃ high temperature, and severe reaction conditions, cost are very high, and this method only is fit to the refining of high precision oil.Though this technology is not used the fat method, its sylvic acid composition that has disclosed thick tall oil can be by the possibility of fatization.
Mentioned the technology of producing biofuel and fuel dope with thick tall oil hydrogenation catalyst on the website at Canada sustainable use fuel center.Yet this method is a hydrogen regenerative process, more than the hydrocarbon polymer biofuel amount of generation.
The method of producing biodiesel additive from pine tar is disclosed in the document [Liu et al., Petrol Sci.﹠Tech., 16 (5-6)], rather than biofuel.The petroleum-type diesel oil on the biofuel that this technology produces and basis mixes, and is generally used in road and the combustion test.
This shows that the preparation of existing biofuel has two kinds of methods usually:
The one, employing changes into lipid acid with the triglyceride level in vegetable oil or the animal oil and changes into alkane ether with methyl alcohol or ethanol acidifying catalyzed reaction again under the effect of basic catalyst (KOH or NaOH), an acidic catalyst (sulfuric acid) or enzyme (for example lipase).Yet, adopt this method production biofuel need use vegetable oil or animal oil, therefore not only cost is higher, and output is very low simultaneously is difficult to replace effectively petroleum-type diesel oil.
The 2nd, adopting the deep processed product tall oil of crude sulfate soap is the feedstock production biofuel.Yet, adopt this method production biofuel from crude sulfate soap, to process to separate earlier and obtain thick tall oil.Crude sulfate soap is the byproduct of effective high economic worth that the alkali recycle section produces in the pulp and paper industry, its complicated component, comprise thick tall oil soap, rosin oil slick and xylogen, paper pulp fiber fines and fatty acid components such as oleic acid, linolenic acid and sylvic acid, it can be used as drilling mud additives, dressing agent, tensio-active agent; It can further be processed into thick tall oil, refining tall oil, extract rosin, lignin and lipid acid.In the global range, the annual production of tall oil is 1,600 ten thousand tons, and in the U.S., tall oil is produced 2/3rds raw materials that provide for industrial fat acid, and is one of main raw material of producing rosin and varnish; Simultaneously, because it is limited and extraction yield is lower to extract the product category of thick tall oil, the cost that therefore extracts thick tall oil soars, and causes the source of goods deficiency of thick tall oil in recent years, and its price increases year by year.The price of crude sulfate soap has only the 600-800RMB/ ton in paper industry, with the price of thick tall oil 3000-3500RMB/ ton than low 4-5 doubly.Compare characteristics such as crude sulfate soap has separate easier from pulping back liquor, cost is lower, and component is more complicated with thick tall oil.Calculate according to input-output ratio, also simply acid goes out, and is that raw material (bio-diesel yield 33%) ratio is the high 2-3 of raw material (bio-diesel yield 55%) economic benefit times with thick tall oil with the crude sulfate soap.This be because, in the technological process of thick tall oil conversion, need a large amount of strong acid and anti-strongly-acid etching apparatus by crude sulfate soap, in transforming the process of thick tall oil, crude sulfate soap needs by multiplex's segment process [forestry institute, northeast chemistry of forest product teaching and research groups such as desalination, removal of impurity fibers simultaneously, the papermaking mechanics of communication, 1,39-49(1976)], and productive rate is more or less the same, and these have brought huge industrial cost.How under the situation of not removing impurity and directly the vegetable fatty acid composition in the crude sulfate soap can be effectively utilized, become one to make biofuel be able to the new problem that the industrialization angle is considered saving cost.
As mentioned above, reduce the production of biodiesel cost and become the most important thing that enlarges the biofuel application, yet up to the present, almost not about how reducing the report of production of biodiesel cost.
Summary of the invention
Goal of the invention: the purpose of this invention is to provide a kind of with low cost be the feedstock production method of bio-diesel oil with the crude sulfate soap, to reduce the production cost of biofuel.
Technical scheme: provided by the invention a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, be specially: in the presence of catalyzer, be that raw material reaction prepares biofuel with crude sulfate soap and C1 to C6 alkanol, described catalyzer is an acidic catalyst or Acetyl Chloride 98Min..
As preferably, described C1 to C6 alkanol is methyl alcohol, ethanol or butanols, particular methanol.
When catalyzer was an acidic catalyst, described an acidic catalyst was the vitriol oil, and the mass percent concentration of the described vitriol oil is 72～98%, and preferred concentration is 96%;
As preferably, the amount ratio of described an acidic catalyst, C1 to C6 alkanol and crude sulfate soap is (10～30) mL:(200～500) mL:150g, be preferably 20mL:(200～500) mL:150g; Adopt an acidic catalyst of above-mentioned amount can improve the productive rate of biofuel greatly.
Preferred as another kind, carry out in this reaction enclosed space; Temperature of reaction is 55～120 ℃, is preferably 60～110 ℃, more preferably 65～100 ℃; Reaction times is 15 minutes～2 hours, is preferably 1/2 hour～1 hour, more preferably 1/2 hour.
When catalyzer was the Acetyl Chloride 98Min. catalyzer, the amount ratio of described Acetyl Chloride 98Min., C1 to C6 alkanol and crude sulfate soap was (10～100mL): (300～600mL): 150g; Adopt the catalyst acetyl chloride of above-mentioned amount can improve the productive rate of biofuel greatly.
As preferably, carry out in this reaction enclosed space; Temperature of reaction is 20～65 ℃, is preferably 30～65 ℃, most preferably is 55 ℃; Reaction times is 30 minutes～6 hours, is preferably 30 minutes～1.5 hours, most preferably is 1h.
Preferred as another kind, to carry out in this reaction open system, temperature of reaction is 10-35 ℃, preferred 20 ℃, the reaction times is 6-24 hour, is preferably 24hrs.
Wherein, before the reaction, should slowly add Acetyl Chloride 98Min. under-10～10 ℃ of conditions in the mixing solutions of crude sulfate soap and C1 to C6 alkanol, preferably dropping temperature is 0～10 ℃.
Above-mentioned purification process comprises the steps:
(1) the biofuel reaction solution is removed C1 to C6 alkanol through underpressure distillation;
(2) residual mixed liquor after the distillation is mixed the formation suspension liquid with polar liquid;
(3) suspension liquid that generates with organic solvent and step (2) mixes, and obtains organic phase and polar liquid behind the standing demix mutually; Wherein be rich in biofuel in the organic phase;
(4) get organic phase, organic solvent is reclaimed in evaporation, and remaining material obtains biofuel through underpressure distillation.
In the step (2), described polar liquid is water; Residual mixed liquor after the distillation and the volume ratio of polar liquid are (1～3): (1～3), preferred volume ratio are 1:2.
In the step (3), the volume ratio of organic solvent and suspension liquid is (1～3): (1～3), described organic solvent are ethyl acetate, methylene dichloride, ethylene dichloride, chloroform, hexane or sherwood oil, ethyl acetate.Preferably, but repeating step (3), and with the washing of organic phase through twice above polar liquid, layering after leaving standstill keeps organic phase.
In the step (4), the underpressure distillation condition for decompression to 2mmHg, the cut between collecting 160～200 ℃, thus obtain biofuel, the organic solvent of recovery can be recycled.
Beneficial effect: biodiesel oil preparing process technology provided by the invention is simple, energy consumption is low, adopts crude sulfate soap with low cost as the biofuel product that feedstock production has high added value, greatly reduces the cost of biofuel.
This method is compared owing to adopting crude sulfate soap to prepare method of bio-diesel oil as raw material with the employing foodstuff raw material, the ester of having avoided vegetable oil, dull vegetable oil, fat and analogue being transformed other lipid acid of earning reacts, not only need not to adopt foodstuff raw material, and operating process is simple.
This method is owing to adopt crude sulfate soap to compare with the method that adopts thick preparing biodiesel from tall oil as raw material, it has avoided the technical process of the separation and purification of thick tall oil, realize still obtaining with the start material of complicated component the biofuel product of high purity high conversion, greatly reduced the production cost of biofuel.
Description of drawings
The gas chromatogram of the biofuel that Fig. 1 prepares for the inventive method.
Fig. 2 is the standard model gas chromatogram of four kinds of esters; Wherein, MP is methyl palmitate; ML is methyl linoleate; MO is Witconol 2301; MS is methyl stearate.
Embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand that the described concrete material proportion of embodiment, processing condition and result thereof only are used for explanation the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1: being catalyzer by the vitriol oil prepares biofuel from crude sulfate soap in capping system.
(water ratio 33% pH9.5-10) is dissolved in 400 ml methanol, mixes to be placed in the 1L round-bottomed flask, adds the 30mL96% vitriol oil then in mixing solutions, round-bottomed flask is added a cover cover tightly, at 65 ℃ of heating mixed system 1hr with 150 gram crude sulfate soaps.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 1.0, this shows that the conversion reaction of biofuel need be carried out under enough strong acidic conditions; With organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 50.25 grams, accounts for 33.5% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 40.2MJ/kg.
Record mineral diesel 0# oil calorific value 44.95MJ/kg in [Cai Yingying et al., Yunnan Chemical Technology, 35 (1), 74 (2008)]; The biofuel calorific value that other vegetables oil obtains through the ester conversion: 37～40MJ/kg.
The gas chromatographic analysis result shows, see Fig. 1 and Fig. 2, the biofuel main component that the present invention prepares is linolic acid (first, second or fourth) ester and oleic acid ester, also have a small amount of Palmitate and stearate, it is consistent with the basic composition of the biofuel that extract with vegetable oil.
Embodiment 2: being catalyzer by the vitriol oil prepares biofuel from crude sulfate soap in capping system.
With 150 gram crude sulfate soap (water ratio 33%, pH9.5-10) be dissolved in 300 ml methanol, mix being placed in the 1L round-bottomed flask, add the 20mL96% vitriol oil then in mixing solutions, round-bottomed flask added a cover cover tightly, at 60 ℃ of heating mixed system 0.5hr.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 2.0, this shows that the conversion reaction of biofuel need be carried out under enough strong acidic conditions; With organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 52.8 grams, accounts for 35.2% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 41.3MJ/kg.
Embodiment 3: being catalyzer by the vitriol oil prepares biofuel from crude sulfate soap in capping system.
With 150 gram crude sulfate soap (water ratio 33%, pH9.5-10) be dissolved in 200 milliliters of ethanol, mix being placed in the 1L round-bottomed flask, add the 10mL98% vitriol oil then in mixing solutions, round-bottomed flask added a cover cover tightly, at 120 ℃ of heating mixed system 15min.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:1, adding methylene dichloride more fully mixes, the volume ratio of methylene dichloride and suspension liquid is 1:1, and standing demix is removed water layer, water pH is 1.5, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 53.6 grams, accounts for 35.7% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 42.7MJ/kg.
Embodiment 4: being catalyzer by the vitriol oil prepares biofuel from crude sulfate soap in capping system.
(water ratio 33% pH9.5-10) is dissolved in 500 milliliters of butanols, mixes to be placed in the 1L round-bottomed flask, adds the 30mL72% vitriol oil then in mixing solutions, round-bottomed flask is added a cover cover tightly, at 55 ℃ of heating mixed system 2hr with 150 gram crude sulfate soaps.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 2:1, adding ethylene dichloride more fully mixes, the volume ratio of ethylene dichloride and suspension liquid is 2:1, and standing demix is removed water layer, water pH is 1.7, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 51.7 grams, accounts for 34.5% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 40.9MJ/kg.
Embodiment 5: being catalyzer by the vitriol oil prepares biofuel from crude sulfate soap in capping system.
With 150 gram crude sulfate soap (water ratio 33%, pH9.5-10) be dissolved in 300 milliliters of ethanol, mix being placed in the 1L round-bottomed flask, add the 15mL85% vitriol oil then in mixing solutions, round-bottomed flask added a cover cover tightly, at 110 ℃ of heating mixed system 0.5hr.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 3:1, adding chloroform more fully mixes, the volume ratio of chloroform and suspension liquid is 3:1, and standing demix is removed water layer, water pH is 1.3, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 50.9 grams, accounts for 33.9% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 41.8MJ/kg.
Embodiment 6: being catalyzer by the vitriol oil prepares biofuel from crude sulfate soap in capping system.
(water ratio 33% pH9.5-10) is dissolved in 300 ml methanol, mixes to be placed in the 1L round-bottomed flask, adds the 20mL96% vitriol oil then in mixing solutions, round-bottomed flask is added a cover cover tightly, at 65 ℃ of heating mixed system 6hrs with 150 gram crude sulfate soaps.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, standing demix is removed water layer, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 45.15 grams, accounts for 30.1% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 39.5MJ/kg.
Embodiment 7: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in capping system.
With 150 gram crude sulfate soap (water ratio 33%, pH9.5-10) be dissolved in 600 ml methanol, mix being placed in the 1L round-bottomed flask, dropwise add then in 100mL Acetyl Chloride 98Min. and the mixing solutions, round-bottomed flask added a cover cover tightly, at 55 ℃ of heating mixed system 1hr.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 1.1, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 56.55 grams, accounts for 37.7% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 38.5MJ/kg.
Embodiment 8: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in capping system.
(water ratio 33% pH9.5-10) is dissolved in 400 ml methanol, mixes to be placed in the 1L round-bottomed flask, dropwise adds then in 30mL Acetyl Chloride 98Min. and the mixing solutions, round-bottomed flask is added a cover cover tightly, at 55 ℃ of heating mixed system 1hr with 150 gram crude sulfate soaps.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 1.9, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 51.75 grams, accounts for 34.5% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 37.5MJ/kg.
Embodiment 9: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in capping system.
(water ratio 33% pH9.5-10) is dissolved in 300 ml methanol, mixes to be placed in the 1L round-bottomed flask, dropwise adds then in 10mL Acetyl Chloride 98Min. and the mixing solutions, round-bottomed flask is added a cover cover tightly, at 20 ℃ of heating mixed system 6hr with 150 gram crude sulfate soaps.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:3, adding hexane more fully mixes, the volume ratio of hexane and suspension liquid is 1:3, and standing demix is removed water layer, water pH is 1.5, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 55.8 grams, accounts for 37.2% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 39.1MJ/kg.
Embodiment 10: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in capping system.
With 150 gram crude sulfate soap (water ratio 33%, pH9.5-10) be dissolved in 400 milliliters of ethanol, mix being placed in the 1L round-bottomed flask, dropwise add then in 50mL Acetyl Chloride 98Min. and the mixing solutions, round-bottomed flask added a cover cover tightly, at 30 ℃ of heating mixed system 1.5hr.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:3, adding sherwood oil more fully mixes, the volume ratio of sherwood oil and suspension liquid is 1:3, and standing demix is removed water layer, water pH is 1.4, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 54.6 grams, accounts for 36.4% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 38.2MJ/kg.
Embodiment 11: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in capping system.
With 150 gram crude sulfate soap (water ratio 33%, pH9.5-10) be dissolved in 500 milliliters of butanols, mix being placed in the 1L round-bottomed flask, dropwise add then in 70mL Acetyl Chloride 98Min. and the mixing solutions, round-bottomed flask added a cover cover tightly, at 65 ℃ of heating mixed system 30min.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:1, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 1.5, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The output of biofuel is 58.8 grams, accounts for 39.2% of the thick tall oil weight of reaction beginning, and the method for pressing the GB384-81 regulation detects, and calorific value is 37.9MJ/kg.
Embodiment 12: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in open reaction system.
150 gram crude sulfate soaps (water ratio 33%, pH9.5-10)) are dissolved in 600 ml methanol, mix being placed in the 1L round-bottomed flask, dropwise add in 100mL Acetyl Chloride 98Min. and the mixing solutions then.Mixing solutions was stirred 24 hours in 20 ℃ of open systems.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 1.8, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The quality of the biofuel that obtains is 62.3 grams, and yield is 41.5% of reaction beginning crude sulfate soap weight, and the method for pressing the GB384-81 regulation detects, and calorific value is 37.5MJ/kg.
Embodiment 13: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in open reaction system.
150 gram crude sulfate soaps (water ratio 33%, pH9.5-10)) are dissolved in 600 ml methanol, mix being placed in the 1L round-bottomed flask, dropwise add in 100mL Acetyl Chloride 98Min. and the mixing solutions then.Mixing solutions was stirred 24 hours in 10 ℃ of open systems.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:3, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:3, and standing demix is removed water layer, water pH is 1.4, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The quality of the biofuel that obtains is 60.8 grams, and yield is 40.5% of reaction beginning crude sulfate soap weight, and the method for pressing the GB384-81 regulation detects, and calorific value is 38.0MJ/kg.
Embodiment 14: being catalyzer by Acetyl Chloride 98Min. prepares biofuel from crude sulfate soap in open reaction system.
150 gram crude sulfate soaps (water ratio 33%, pH9.5-10)) are dissolved in 300 milliliters of ethanol, mix being placed in the 1L round-bottomed flask, dropwise add in 30mL Acetyl Chloride 98Min. and the mixing solutions then.Mixing solutions was stirred 6 hours in 35 ℃ of open systems.
With above-mentioned reacted biofuel reaction solution behind vacuum distillation recovered solvent, with surplus materials add water fully mix suspension liquid, the volume ratio that surplus materials adds water is 1:2, adding ethyl acetate more fully mixes, the volume ratio of ethyl acetate and suspension liquid is 1:2, and standing demix is removed water layer, water pH is 1.0, with organic layer again water give a baby a bath on the third day after its birth time; Merge organic layer, wherein ethyl acetate reduction vaporization is being fallen; Distill under (2mmHg) condition in decompression then, the cut between collecting 160 ℃ to 200 ℃ is biofuel.
The quality of the biofuel that obtains is 61.5 grams, and yield is 41.0% of reaction beginning crude sulfate soap weight, and the method for pressing the GB384-81 regulation detects, and calorific value is 37.9MJ/kg.
Claims (9)
1. one kind is the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: in the presence of catalyzer, be that raw material reaction prepares biofuel with crude sulfate soap and C1 to C6 alkanol, described catalyzer is an acidic catalyst or Acetyl Chloride 98Min..
According to claim 1 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: described C1 to C6 alkanol is methyl alcohol, ethanol or butanols.
According to claim 1 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: when catalyzer was an acidic catalyst, described an acidic catalyst was the vitriol oil, and the mass percent concentration of the described vitriol oil is 72～98%.
According to claim 3 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: the amount ratio of described an acidic catalyst, C1 to C6 alkanol and crude sulfate soap is for (10～30) mL:(200～500) mL:150g.
According to claim 3 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: temperature of reaction is 55～120 ℃; Reaction times is 15 minutes～2 hours.
According to claim 1 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: when catalyzer was Acetyl Chloride 98Min., the amount ratio of described Acetyl Chloride 98Min., C1 to C6 alkanol and crude sulfate soap was (10～100mL): (300～600mL): 150g.
According to claim 6 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: carry out in this reaction enclosed space; Temperature of reaction is 20～65 ℃, and the reaction times is 30 minutes～6 hours.
According to claim 6 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: carry out in this reaction open system, temperature of reaction is 10-35 ℃, and the reaction times is 6-24 hour.
According to claim 1 a kind of be the feedstock production method of bio-diesel oil with the crude sulfate soap, it is characterized in that: described purification process comprises the steps:
(1) the biofuel reaction solution is removed C1 to C6 alkanol through underpressure distillation;
(2) residual mixed liquor after the distillation is mixed the formation suspension liquid with polar liquid;
(3) suspension liquid that generates with organic solvent and step (2) mixes, and obtains organic phase and polar liquid behind the standing demix mutually;
(4) get organic phase, organic solvent is reclaimed in evaporation, and remaining material obtains biofuel through underpressure distillation.
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| US20070130820A1 (en) * | 2005-11-16 | 2007-06-14 | Chatterjee Siddharth G | Process for making biodiesel from crude tall oil |
| CN101880602A (en) * | 2010-06-17 | 2010-11-10 | 暨南大学 | A method for preparing biodiesel from oil with high acid value |
| CN102181323A (en) * | 2011-03-29 | 2011-09-14 | 南京林业大学 | Method for preparing biodiesel |
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| US20070130820A1 (en) * | 2005-11-16 | 2007-06-14 | Chatterjee Siddharth G | Process for making biodiesel from crude tall oil |
| CN101880602A (en) * | 2010-06-17 | 2010-11-10 | 暨南大学 | A method for preparing biodiesel from oil with high acid value |
| CN102181323A (en) * | 2011-03-29 | 2011-09-14 | 南京林业大学 | Method for preparing biodiesel |
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| WO2021260275A1 (en) * | 2020-06-26 | 2021-12-30 | Molcycle Oy | Method for processing black liquor soap |
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