CN102504891B - Preparation method of glyceryl biological fuel additives - Google Patents
Preparation method of glyceryl biological fuel additives Download PDFInfo
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- CN102504891B CN102504891B CN201110340800.4A CN201110340800A CN102504891B CN 102504891 B CN102504891 B CN 102504891B CN 201110340800 A CN201110340800 A CN 201110340800A CN 102504891 B CN102504891 B CN 102504891B
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Abstract
The invention provides a preparation method for converting glycerol into a glycerol derivative system simultaneously containing glycerin ether and glyceride to be used as a fuel additive. Low-carbon alcohol and glycerol are used as starting materials, the mol ratio of the low-carbon alcohol to the glycerol is 2:1 to 8:1, the dosage of acid catalysts accounts for 0.5 percent to 10 percent of the total mass of reactants, water absorbents account for 1.5 percent to 10 percent of the total mass of the reactants, nitrogen gas is used for replacing air in a kettle, the initial pressure in the kettle is 0 to 4 MPa, the reaction temperature is 30 to 130 DEG C, and the reaction time is 4 to 10 hours; and the reduced pressure distillation is carried out after cooling, then, the acylation reaction is carried out, the reaction temperature is 60 to 150 DEG C, the reaction time is 1 to 4 hours, and glyceryl biological fuel additives are obtained. The fuel combustion performance can be improved through glycerin ether, and simultaneously, the fuel viscocity can be improved through the contained glyceride. The acidylation is carried out after the etherification, and the problem of low glycerol hydroxyl etherification rate is solved, so the additives and the fuel are mixed more uniformly. The catalyst and the water absorbents recovered through filtering and the low-carbon alcohol can be repeatedly utilized.
Description
Technical field
The present invention relates to fuel technology field, especially relate to the preparation method who improves fuel combustion performance and reduce the fuel dope of Air–pollution From Combustion, be specifically related to utilize acid catalysis by the first etherificate of glycerine, rear acidylate is prepared the method for glyceryl biological fuel additives.
Background technology
Along with day by day reducing of world's Nonrenewable energy resources and day by day increasing the weight of of environmental pollution, environmentally friendly and reproducible biofuel has obtained various countries scientific research personnel's extensive concern, and global yield of biodiesel in 2011 is estimated to reach 2,600 ten thousand tons.Glycerine is prepared the by product of biofuel as transesterification reaction, its price constantly declines along with the increase year by year of yield of biodiesel, how efficiently to utilize glycerine, and preparing high value-added product becomes one of important research direction in recent years.Transformation of glycerol, for improving the additive of fuel characteristic, is had broad prospects, become the focus of research.
The hydroxyl that glycerol molecule contains 3 polarity, causes glycerine to mix with biofuel poor, and insufficient meeting of burning produces the obnoxious flavoures such as carbon monoxide, and glycerine viscosity greatly easily causes motor fault simultaneously.Glycerine is developed to glyceryl fuel dope through approach such as etherificate, esterification or oxidations and makes an addition in fuel gasoline diesel oil, can reduce the quantity discharged of obnoxious flavour, improve flash-point, cetane value, reduce cold filter clogging temperature, reduce viscosity and strengthen oxidisability etc.Solve the superfluous problem of glycerine simultaneously, increase the economic benefit of biofuel.
For example, in prior art: CN101970390A is by being used solid acid catalyst, use primary alconol as etherifying agent by glycerine etherificate, change into boiling point lower and be soluble in the glyceryl ether fuel dope of diesel oil, 60～300 ℃ of temperature of reaction, reaction times 5～8h.
US5476971 and US6174501 are under the existence of strong acid catalyst, glycerine is reacted with gas-liquid two-phase form with iso-butylene or isopentene, obtain reducing the glyceryl ether of biofuel viscosity, although the transformation efficiency of glycerine is high, but gas-liquid two-phase reacting phase is to homogeneous reaction complex process, energy consumption is high, will increase production cost, and the easy polymerization reaction take place of alkene obtains nonflammable throw out simultaneously.
US5308365, US1968033 and US5578090 have explored under acid catalyst exists, glycerine reacts with alkene or short chain alcohol the method for preparing glyceryl ether, although the glyceryl ether boiling point obtaining is lower than glycerine, but often with one or two hydroxyl, be not suitable for the application of fuel dope on molecule.
US20100016641 is 150～300 ℃ of temperature of reaction, reaction pressure 0.1～2.2psia, under the condition of solid acid catalysis, glycerine reacts and has obtained the ether of boiling point lower than glycerine with low-carbon (LC) straight chain alcohol (C1～C4), and the additive that can be used as fuel improves the combustionproperty of biofuel.
Above glyceryl ether is mixed into the cetane value that all can improve fuel in biofuel, but because steric effect makes the glycerine diether and the glycerine three ether yields that make low, still have certain hydroxy radical content, cause additive and biofuel miscible not exclusively, and insufficient may the causing of burning contained CO in products of combustion.
In addition, in prior art: US7637969B2 has described under Catalyzed by p-Toluenesulfonic Acid, 90 ℃ of temperature of reaction, reaction times 10～36h, vegetables oil reacts the mixture fuel that obtains fatty acid methyl ester (biofuel) and glycerol mono acetate bulk with ritalin, the existence of glycerol mono acetate bulk makes mixture fuel reduced viscosity, and condensation point declines 1～10 ℃.Therefore, glycerine direct esterification is prepared to glycerol mono acetate bulk, can be used as a kind of approach of exploitation fuel dope.
But glycerol mono acetate bulk is not obvious as fuel dope effect in other respects, such as its relative ethers of cetane value is low, the relative ethers of density is larger etc.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency existing for overcoming above-mentioned prior art, and providing transformation of glycerol is the glycerol derivative system that simultaneously contains glyceryl ether and the glyceryl ester preparation method as fuel dope.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: the preparation method of glyceryl biological fuel additives, comprise the following steps: 1) low-carbon alcohol is mixed in autoclave pressure with glycerine, low-carbon alcohol and glycerine mol ratio 2:1 are to 8:1, acid catalyst consumption is 0.5%～10% of reactant total mass, and water-retaining agent or azeotropy dehydrant consumption are 1.5%～10% of reactant total mass; 2) before reaction starts, utilize the interior air of nitrogen replacement still, in still, first pressing is 0～4MPa, and 30～130 ℃ of temperature of reaction are boosted after reaction in still certainly, reaction times 4～10h; 3) reaction finish cooling after, emptying gas reactor, by product underpressure distillation, collects low-carbon alcohol, if use azeotropy dehydrant to reclaim; 4) by steaming the ether (mixtures of glycerine one ether, glycerine diether and glycerine three ethers) and a small amount of unreacted glycerine that obtain after alcohol in step 3, join in acylation reaction device, drip diacetyl oxide and carry out acylation reaction, diacetyl oxide consumption is by not determined by the hydroxyl molar weight of etherificate, 60～150 ℃ of temperature of reaction, reaction times 1～4h; 5) after acylation reaction finishes, add solid alkali neutralization, filter, if use water-retaining agent to reclaim, underpressure distillation liquid mixture, 140～160 ℃ of distillation temperatures, vacuum tightness 0.01～0.09Mpa, residuum is target product.
Step 1) low-carbon alcohol described in can be selected as propyl alcohol, Virahol, isopropylcarbinol, the trimethyl carbinol, primary isoamyl alcohol or their mixture.
Step 1) acid catalyst described in can be selected acidic ion liquid, organic acid, mineral acid, acidic ion exchange resin, hydrochlorate zeolite molecular sieve, solid-carrying heteropolyacid, solid super-strong acid, and various immobilized an acidic catalysts, or their mixture.
Step 1) water-retaining agent described in can be selected discolour silica gel, gac, water-absorbing resin, activated alumina, magnesium sulfate, copper sulfate, dicyclohexylcarbodiimide (DCC) or their mixture.Wherein said azeotropy dehydrant is industrial conventional benzene, toluene, normal hexane, hexanaphthene etc.
Step 2) rare gas element described in is generally selected nitrogen.
The glyceryl biological fuel additives obtaining according to above-mentioned preparation method, is the derivative class material of glycerine, contains glyceryl ether, other is without hydroxyl glycerol derivative or glyceryl ether and other mixture without hydroxyl glycerol derivative.Wherein glyceryl ether is glycerine three ethers and the isomers being obtained after low-carbon alcohol etherificate.Wherein other is the glycerine ether-ether that obtains after acidylate again of etherificate and isomers, glycerine triacetate without hydroxyl glycerol derivative, or the mixture of glycerine ether-ether and isomers and glycerine triacetate.
Compared with prior art, adopt technical scheme tool of the present invention to have the following advantages.
1, the glyceryl ether in the additive that this preparation method obtains can improve the combustionproperty of fuel, and the glyceryl ester simultaneously containing also has contribution for improving fuel viscosity and condensation point.
2, etherificate again acidylate solved the low problem of glycerine hydroxy ethers rate, make additive and fuel mix more even, burning and exhausting is more clean.
3, adopt low-carbon alcohol and non-pneumatic as the raw material of etherification reaction, technological operation safety, although the water that reaction generates is unfavorable for transformation of glycerol, after water-retaining agent absorption, remaining a small amount of water effective has been controlled the polymerization of intermediate product alkene.
4, the low-carbon alcohol of Distillation recovery and the solid catalyst of filtered and recycled and water-retaining agent can reuse, cost-saving.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is etherification procedure reaction formula of the present invention.
Fig. 3 is acylation process reaction formula of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, and embodiment is not subject to the restriction of embodiment.
embodiment 1:fig. 1 is the preparation method's of glyceryl biological fuel additives technical process, and concrete steps are as follows: step 1 is mixed the 39.5g trimethyl carbinol, 12.6g glycerine, 1.5gD002 ion exchange resin and 1.5g discolour silica gel in autoclave pressure.Step 2 seal-off pressure still, before reaction starts, passes into air in nitrogen replacement still, and strengthening nitrogen pressure is 1MPa to first pressing in still, and etherification reaction temperature is controlled at 90 ℃, keeps from boosting reaction times 8h in reaction process in still.
Fig. 2 is etherification procedure reaction formula, and wherein ROH represents low-carbon alcohol, and A, B, C represent the derivative glycerine of glycerine one ether, glycerine diether and glycerine three ethers and isomers.
Step 3 reaction finishes rear cooling, with ice-water bath cooling pressure still, then emptying gas reactor, by product underpressure distillation, obtains glyceryl ether after collecting the lower boiling trimethyl carbinol.The alcohol of Distillation recovery can reuse.
Liquid after gas chromatographic analysis distillation, hydroxyl transformation efficiency is 51%.
Step 4 will steam the liquid obtaining after alcohol in step 3, join in acylation reaction device, drips diacetyl oxide 20.5g and carries out acylation reaction, 140 ℃ of acylation reaction temperature, acylation reaction time 2h.
Fig. 3 is acylation process reaction formula, and wherein D, E represent glycerine ether-ether and isomers, and F is glycerine triacetate.
After step 5 acylation reaction finishes, add anhydrous sodium carbonate to be neutralized to after neutrality, filtering recovering catalyst and water-retaining agent, underpressure distillation liquid mixture obtains target product, 140 ℃ of distillation temperatures, vacuum tightness 0.09MPa.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 98.9%.
Fuel dope of the present invention is the mixing liquid of C, D, E, F, with mix, represents.Wherein, in etherification reaction, the transformation efficiency of glycerine can reach 99%, so glycerol conversion yield can be estimated as 100% in computation process.So can not calculated with following formula by etherified hydroxy groups molar weight described in the present invention's technical scheme: hydroxyl molar weight=2 * n(A)+n(B), n represents amount of substance, the amount of substance of A, B can be calculated by gas chromatographic analysis.
The fuel dope that table 1 makes by embodiment 1 and the mixed indices of biofuel B100.
embodiment 2:step 1 is mixed 32.9g propyl alcohol, 12.6g glycerine, the agent of 1.4g Phosphotungstic Acid Supported by Activated Carbon and 1.5g water-absorbing resin in autoclave pressure.
Step 2 seal-off pressure still, passes into air in methane displacement still, and strengthening pressure of methane is 3MPa to first pressing in still, and temperature of reaction is controlled at 95 ℃, reaction times 9h.
Step 3 is with embodiment 1 step 3.
Step 4 will steam the liquid obtaining after alcohol in step 3, join in acylation reaction device, drips diacetyl oxide 21.8g and carries out acylation reaction, 140 ℃ of acidylate temperature, acidylate time 2h.
Step 5 adds anhydrous sodium carbonate to be neutralized to after neutrality, filtering recovering catalyst and water-retaining agent, and underpressure distillation liquid mixture obtains target product, 160 ℃ of distillation temperatures, vacuum tightness 0.05MPa.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 97.2%.
embodiment 3:step 1 is mixed 12.0g Virahol, 9.2g glycerine, 1.1g macroporous network type resin GD001 and 1.4g activated alumina in autoclave pressure.
Step 2 seal-off pressure still, passes into air in nitrogen replacement still, and strengthening nitrogen pressure is 4MPa to first pressing in still, and temperature of reaction is controlled at 80 ℃, after reaction times 10h.
Step 3 is with embodiment 1 step 3.
Step 4, by the liquid that steams alcohol in step 3 and obtain, joins in acylation reaction device, drips diacetyl oxide 20.1g and carries out acylation reaction, 120 ℃ of acidylate temperature, acidylate time 2h.
Step 5 is with embodiment 2 steps 5.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 98.9%.
embodiment 4:step 1 is by 40.6g isopropylcarbinol, 12.6g glycerine, 1.5gSO
4 2-/ TiO
2solid super-strong acid and 0.5g discolour silica gel mix in autoclave pressure.
Step 2 is with embodiment 6 steps 2.
Step 3 is with embodiment 1 step 3.
Step 4 will steam the liquid obtaining after alcohol in step 3, join in acylation reaction device, drips diacetyl oxide 19.7g and carries out acylation reaction, 110 ℃ of acidylate temperature, acidylate time 2h.
Step 5 is with embodiment 4 steps 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 99.0%.
embodiment 5:step 1 is by 48.3g primary isoamyl alcohol, 12.6g glycerine, 1.2g solid-carrying heteropolyacid salt TiSiW
12o
40/ TiO
2catalyzer and 1.5g normal hexane azeotropy dehydrant mix in autoclave pressure.
Step 2 is with embodiment 6 steps 2.
Ice-water bath cooling pressure still for step 3, emptying gas reactor reclaims product primary isoamyl alcohol and normal hexane under underpressure distillation.
Step 4 will steam the liquid obtaining after alcohol in step 3, join in acylation reaction device, drips diacetyl oxide 21.4g and carries out acylation reaction, 150 ℃ of acidylate temperature, acidylate time 2h.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 98.9%.
embodiment 6:step 1 is by 30.2g primary isoamyl alcohol, 8.7g propyl alcohol, 12.6g glycerine, 1.4g acid-treated clay load ZnCl
2catalyzer and 1.5g benzene azeotropic dewatering agent mix in autoclave pressure.
Step 2 is with embodiment 2 steps 2.
Ice-water bath cooling pressure still for step 3, emptying gas reactor reclaims product butanols and isopropylcarbinol and benzene under underpressure distillation.
Step 4 will steam the liquid obtaining after alcohol in step 3, join in acylation reaction device, drips diacetyl oxide 22.2g and carries out acylation reaction, 100 ℃ of acidylate temperature, acidylate time 3h.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 97.8%.
Claims (6)
1. the preparation method of glyceryl biological fuel additives, comprises the following steps:
1) low-carbon alcohol is mixed in autoclave pressure with glycerine, low-carbon alcohol and glycerine mol ratio be 2:1 to 8:1, acid catalyst consumption is 0.5%～10% of reactant total mass, water-retaining agent or azeotropy dehydrant consumption are 1.5%～10% of reactant total mass; Described low-carbon alcohol is wherein a kind of of propyl alcohol, Virahol, isopropylcarbinol, the trimethyl carbinol, primary isoamyl alcohol or their mixture;
2) before reaction starts, utilize the interior air of inert gas replacement still, in still, first pressing is 0～4MPa, and 30～130 ℃ of temperature of reaction are boosted after reaction in still certainly, reaction times 4～10h;
3) reaction finish cooling after, emptying gas reactor, by product underpressure distillation, collects low-carbon alcohol;
4) mixture and a small amount of unreacted glycerine that in step 3, steam glycerine one ether, glycerine diether and glycerine three ethers that after alcohol, obtain are joined in acylation reaction device, drip diacetyl oxide and carry out acylation reaction, diacetyl oxide consumption is by not determined by the hydroxyl molar weight of etherificate, 60～150 ℃ of temperature of reaction, reaction times 1～4h;
5) after acylation reaction finishes, add solid alkali neutralization, filter, underpressure distillation, obtains target product, 140～160 ℃ of distillation temperatures, vacuum tightness 0.01～0.09MPa.
2. according to preparation method claimed in claim 1, it is characterized in that, described acid catalyst is acidic ionic liquid catalysts, organic acid catalyst, inorganic acid catalyst, acidic ion exchange resin catalyst, hydrochlorate zeolite [molecular sieve, solid super acid catalyst, and various immobilized an acidic catalyst.
3. according to preparation method claimed in claim 1, it is characterized in that, described water-retaining agent is discolour silica gel, gac, water-absorbing resin, activated alumina, dicyclohexylcarbodiimide.
4. according to the glyceryl biological fuel additives of claim 1 preparation, it is characterized in that, described additive is the derivative class material of glycerine, contains glyceryl ether, other is without hydroxyl glycerol derivative, or glyceryl ether and other mixture without hydroxyl glycerol derivative.
5. according to glyceryl biological fuel additives claimed in claim 4, it is characterized in that glycerine three ethers and the isomers (C) of described glyceryl ether for being obtained after described low-carbon alcohol etherificate.
6. according to glyceryl biological fuel additives claimed in claim 5; it is characterized in that; described other without hydroxyl glycerol derivative, be the glycerine ether-ether that obtains after acidylate again of etherificate and isomers (D, E), glycerine triacetate (F), or their mixture.
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| CN103611568A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Preparation method of dual-core acidic ionic liquid immobilized SBA-15 molecular sieve catalyst used for synthesizing tert butyl glycidyl ether |
| CN103964988A (en) * | 2014-05-23 | 2014-08-06 | 天津科林泰克科技有限公司 | Application method of compound catalyst in dehydration and condensation reaction |
| CN103990492A (en) * | 2014-05-23 | 2014-08-20 | 天津科林泰克科技有限公司 | Composite catalyst for dehydration condensation reaction and preparation method thereof |
| CN104017617A (en) * | 2014-06-20 | 2014-09-03 | 长沙理工大学 | Research on biomass glyceryl-based blended fuel |
| CN107841366A (en) * | 2017-11-23 | 2018-03-27 | 广西银英生物质能源科技开发股份有限公司 | A kind of biomass fuel feed additives |
| CN111057594B (en) * | 2019-12-30 | 2021-10-29 | 李旭 | Preparation method of alcohol-based fuel additive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1331260A2 (en) * | 2002-01-18 | 2003-07-30 | Industrial Management S.A. | Procedure to obtain biodiesel fuel with improved properties at low temperature |
| CN101970390A (en) * | 2008-03-13 | 2011-02-09 | 科学与工业研究委员会 | A process for the preparation of primary alkyl glycerol ethers useful as biofuel additive from glycerol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6174501B1 (en) * | 1997-10-31 | 2001-01-16 | The Board Of Regents Of The University Of Nebraska | System and process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
| US6015440A (en) * | 1997-10-31 | 2000-01-18 | Board Of Regents Of The University Of Nebraska | Process for producing biodiesel fuel with reduced viscosity and a cloud point below thirty-two (32) degrees fahrenheit |
| CN101092353B (en) * | 2007-07-12 | 2010-12-01 | 上海交通大学 | Preparation method for transforming animal and vegetable oil and fat to mono ester fatty acid |
| CN102226134A (en) * | 2011-05-12 | 2011-10-26 | 福建漳州鼎能生物科技有限公司 | Method for producing biodiesel by using waste oil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1331260A2 (en) * | 2002-01-18 | 2003-07-30 | Industrial Management S.A. | Procedure to obtain biodiesel fuel with improved properties at low temperature |
| CN101970390A (en) * | 2008-03-13 | 2011-02-09 | 科学与工业研究委员会 | A process for the preparation of primary alkyl glycerol ethers useful as biofuel additive from glycerol |
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