CN102533453A - Biodiesel production method - Google Patents
Biodiesel production method Download PDFInfo
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- CN102533453A CN102533453A CN2011104414040A CN201110441404A CN102533453A CN 102533453 A CN102533453 A CN 102533453A CN 2011104414040 A CN2011104414040 A CN 2011104414040A CN 201110441404 A CN201110441404 A CN 201110441404A CN 102533453 A CN102533453 A CN 102533453A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention relates to a biofuel production method, and especially relates to a biodiesel production method with mild reaction conditions, a high conversion rate, high yield, and no waste water discharge. The biodiesel production method comprises the following steps: S1, mixing raw materials of grease and medium and short-chain alcohol, completing a transesterification reaction under the action of a homogeneous base catalyst; S2, separating the reaction solution completing the transesterification reaction to obtain crude biodiesel; S3, adding a solid neutralizer into the crude biodiesel, reacting for 10-60 minutes; S4, separating the solid neutralizer to obtain the biodiesel.
Description
Technical field
The present invention relates to a kind of method for producing bio-fuel, particularly a kind of have a reaction conditions gentleness, and transformation efficiency is high, and yield is high, and the method for producing biodiesel of non-wastewater discharge.
Background technology
Along with the exhaustion day by day and the Ecological environment worsening of fossil oil, countries in the world are developing biomass energy as its following energy strategy, to break away from the serious dependence to fossil energy.And biofuel receives various countries investigator's favor deeply as a kind of novel energy of reproducible, environmental sound.Biofuel is to be raw material with animal oil and fat, woody oil crop, draft oil crop, seaweeds and industry, catering trade waste grease, carries out the longer chain fatty acid mono alkyl ester that transesterification reaction obtains with low-carbon alcohol such as methyl alcohol, ethanol.It four kinds of different production methods successively occurred: direct mixing method, microemulsion method, pyrolysis method and ester-interchange method, but the production of biofuel at present mainly is to adopt ester-interchange method.In the ester-interchange method production process, use different catalyst according to the different mining of its raw material.The kind of catalyzer mainly contains acid, alkali and lypase.Traditional acid base catalysator has developed into alkaline process from the sulphuric acid catalysis method and has made catalyzer, because the price of sodium hydroxide is low, catalytic activity is high and reaction conditions is gentle existing by employing widely.Enzyme process then because of long reaction time, control poor stability and be limited to promote the use of.Therefore, alkaline process catalysis is practical at present operational path! Yet also there is a significantly deficiency at present in this technology, i.e. transesterification reaction completion rear catalyst can remain in the product, needs neutralization and washing, produces a large amount of waste water thus.For this reason, also there are many investigators to propose to adopt the catalyzer of solid acid-base as production of biodiesel.Wherein, patent CN101045878, a kind of utilization in solid acid and the solid alkali two-step catalysis method production method of bio-diesel oil utilizes solid super-strong acid as catalyzer, but temperature of reaction is higher and the catalyzer price is also expensive; Patent CN101884931, the solid acid SO of preparation in a kind of preparation method of solid super acid catalyst and the application
4 2-/ ZrO
2-CeO
2Prepare the catalyzer of biofuel as Jatropha curcas oil, but this catalyzer not only prepare loaded down with trivial details and require the transesterification reaction time long, temperature is higher; Patent CN101474571, a kind of solid base catalyst that is used for preparing biofuel has prepared the catalyzer of houghite compound as biodiesel manufacture, and has obtained gratifying yield, but require the reaction times long, temperature of reaction is higher.To sum up; Though the preparation of adopting the solid acid alkali catalytic agent to replace traditional acid base catalysator to carry out biofuel has the advantage of non-wastewater discharge; But because reaction is an inhomogeneous reaction; With homogeneous catalytic reaction (as make catalyzer etc. with sodium hydroxide) Comparatively speaking, all have the cumbersome and problem such as cost an arm and a leg of the reaction times is longer, temperature of reaction is higher, needs are higher alcohol oil rate, Preparation of catalysts, be difficult to realize suitability for industrialized production truly in the short period of time.
Summary of the invention
The present invention is directed to the above-mentioned technical problem that exists in the existing production technique, provide a kind of based on the solid neutralizing agent and there is not the method for producing biodiesel that waste water produces.Wherein the action principle of solid neutralizing agent is: utilize the ion exchange of solid neutralizing agent to discharge hydrogen ion, neutralize with residual alkaline catalysts, and in N-process, do not have the generation of salt.
This method for producing biodiesel comprises the steps:
S1 mixes raw oil material with middle short chain alcohol, and under the effect of homogeneous phase alkaline catalysts, accomplishes transesterification reaction;
S2 separates the reaction solution of accomplishing transesterification reaction, gets coarse biodiesel;
S3 adds the solid neutralizing agent in coarse biodiesel, stir itself and homogeneous phase alkaline catalysts are reacted;
S4 promptly obtains biofuel behind the separate solid neutralizing agent.
Preferably, when said raw oil material is the higher grease of acid number, before the said step S1, also comprises raw oil material carried out preparatory esterif iotacation step:
S0 mixes raw oil material, and under the sulphuric acid catalysis effect, carries out pre-esterification reactor with middle short chain alcohol.
Preferably, the molar ratio of short chain alcohol and raw oil material is 3.5:1 ~ 30:1 among the said S1.
Preferably, the molar ratio of short chain alcohol and raw oil material is 3.5:1 ~ 30:1 among the said S0.
Preferably, the consumption of said homogeneous phase alkali is 0.1% ~ 3% of a raw oil material quality.
Preferably, short chain alcohol is a kind of in methyl alcohol, ethanol or the propyl alcohol in said.
Preferably, said homogeneous phase alkaline catalysts is a kind of in sodium hydroxide, Pottasium Hydroxide or the sodium methylate.
Preferably, said solid neutralizing agent is one or more mixtures in acidic white earth, resin, zeolite molecular sieve, the modified zeolite molecular sieve.
Further, said modified zeolite molecular sieve is through placing 0.3 ~ 1.5molL with zeolite molecular sieve
-1Hydrochloric acid or sulphuric acid soln in soak 1 ~ 24h, more successively through separation, washing, oven dry and make.
Preferably, said raw oil material is Jatropha curcas oil, rapeseed oil, Semen Maydis oil, VT 18, Viscotrol C, Oleum Cocois, peanut oil, sewer oil, lard and algae grease.
Preferably, solid neutralizing agent and homogeneous phase alkaline catalysts reaction times are 10 ~ 60 minutes among the said step S3.
This technical scheme compared with prior art has following beneficial effect:
Present method combines the advantage of homogeneous phase base catalysis and heterogeneous catalysis, has the reaction conditions gentleness, and transformation efficiency is high, and yield is high, and the characteristics of non-wastewater discharge, can effectively solve the drawback that present production of biodiesel exists.
Description of drawings
Fig. 1 is a production of biodiesel process flow sheet provided by the present invention.
Specific embodiment
The embodiments described below only are the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
Embodiment 1
In the there-necked flask of 2000ml, be that 6:1 adds Semen Maydis oil 800g and mixes with methyl alcohol 132.27g by molar ratio of methanol to oil, add concentration again and be 15% methanol-hydrogen sodium hydroxide solution 53.33g; Stirring reaction 40min afterreaction finishes under 60 ℃ condition; Pour standing demix in the separating funnel then into, the upper strata is a coarse biodiesel, and lower floor is the by product raw glycerine; Steam behind the crude glycerine and remove unnecessary methyl alcohol, obtain coarse biodiesel like this.In coarse biodiesel, add 38.4g solid neutralizing agent---acidic white earth again, isolate solid neutralizing agent---acidic white earth behind the stirring reaction 30min, can obtain the product biofuel.Productive rate 96.7%.
Embodiment 2
In the there-necked flask of 2000ml; By molar ratio of methanol to oil is that 6:1 adds rapeseed oil 1200g and mixes with methyl alcohol 198.4g, is 15% methanol-hydrogen sodium hydroxide solution 80g adding concentration that standing demix in the separating funnel is poured in the end of stirring reaction 40min afterreaction then under 60 ℃ condition; The upper strata is a coarse biodiesel; Lower floor is the by product raw glycerine, steams behind the crude glycerine and removes unnecessary methyl alcohol, obtains coarse biodiesel.In coarse biodiesel, add 45.7g solid neutralizing agent---the mixture of modified zeolite molecular sieve and acidic white earth 1:3 (mass ratio) again, isolate modified zeolite molecular sieve and acidic white earth behind the stirring reaction 30min, can obtain the product biofuel.Productive rate 95.3%.
In the there-necked flask of 1000ml; Be that 6:1 adds Oleum Gossypii semen 610g and methyl alcohol 100.87g mixes, be 15% methanol-hydrogen potassium oxide solution 40.67g in adding concentration by molar ratio of methanol to oil; Stirring reaction 45min afterreaction finishes under 60 ℃ condition, pours standing demix in the separating funnel then into, and the upper strata is a coarse biodiesel; Lower floor is the by product raw glycerine, distills out unnecessary methyl alcohol behind the crude glycerine.In coarse biodiesel, add 23.1g solid neutralizing agent---the mixture of modified zeolite molecular sieve and strong acid type resin 1:1 (mass ratio) again, isolate modified zeolite molecular sieve and strong acid type resin behind the stirring reaction 30min, can obtain the product biofuel.Productive rate 94.6%.
In the there-necked flask of 3000ml; By molar ratio of methanol to oil is that 6:1 adds peanut oil 2012g and methyl alcohol 332.65g to mix, add then concentration be 15% methanol-hydrogen potassium oxide solution 134.13g; Stirring reaction 45min afterreaction finishes under 60 ℃ condition, pours standing demix in the separating funnel then into, and the upper strata is a coarse biodiesel; Lower floor is the by product raw glycerine, distills out unnecessary methyl alcohol behind the crude glycerine.In coarse biodiesel, add 73.5g solid neutralizing agent---acidic white earth again, isolate the solid acid carclazyte behind the stirring reaction 30min, can obtain the product biofuel.Productive rate 94.8%.
Embodiment 5
In the there-necked flask of 3000ml; By molar ratio of methanol to oil is that 6:1 adds Jatropha curcas oil 1825g, methyl alcohol 405.15g; Stirring also slowly adds the 18.25g vitriol oil as catalyzer under 60 ℃ condition, treats that the 50min afterreaction finishes, and pours standing demix in the separating funnel then into.Lower floor is for removing the Jatropha curcas oil of free fatty acids; Adding concentration is 15% methanol-hydrogen sodium hydroxide solution 121.67g and methyl alcohol 301.73g; Stirring reaction 40min afterreaction finishes under 60 ℃ condition, pours standing demix in the separating funnel then into, and the upper strata is a coarse biodiesel; Lower floor is the by product raw glycerine, distills out unnecessary methyl alcohol behind the crude glycerine.In coarse biodiesel, add 62.5g solid neutralizing agent---acidic white earth again, isolate acidic white earth behind the stirring reaction 25min, can obtain the product biofuel.Productive rate 87.8%.
Embodiment 6
In the there-necked flask of 3000ml; By molar ratio of methanol to oil is that 6:1 adds Jatropha curcas oil 1500g, methyl alcohol 333g; Stirring also slowly adds the 15g vitriol oil as catalyzer under 60 ℃ condition, treats that the 50min afterreaction finishes, and pours standing demix in the separating funnel then into.Lower floor is for removing the Jatropha curcas oil of free fatty acids; Adding concentration is 15% methanol-hydrogen potassium oxide solution 100g and methyl alcohol 248g; Stirring reaction 40min afterreaction finishes under 60 ℃ condition; Pour standing demix in the separating funnel then into, the upper strata is a coarse biodiesel, and lower floor is the by product raw glycerine.Distill out unnecessary methyl alcohol behind the crude glycerine, in coarse biodiesel, add 49g solid neutralizing agent---modified zeolite molecular sieve again, isolate modified zeolite molecular sieve behind the stirring reaction 25min, can obtain the product biofuel.Productive rate 88.4%.
Embodiment 7
In the there-necked flask of 3000ml; By molar ratio of methanol to oil is that 6:1 adds peanut oil 2012g and methyl alcohol 332.65g to mix, add then concentration be 15% methanol-hydrogen potassium oxide solution 134.13g; Stirring reaction 45min afterreaction finishes under 60 ℃ condition, pours standing demix in the separating funnel then into, and the upper strata is a coarse biodiesel; Lower floor is the by product raw glycerine, distills out unnecessary methyl alcohol behind the crude glycerine.Add 73.5g solid neutralizing agent---the zeolite molecular sieve after the regeneration again in the coarse biodiesel, isolate the zeolite molecular sieve after the regeneration behind the stirring reaction 30min, can obtain the product biofuel.Productive rate 93.9%.
Above disclosedly be merely some preferred embodiments of the present invention, can not limit the present invention's interest field certainly with this, the equivalent variations of therefore doing according to claim of the present invention still belongs to the scope that the present invention is contained.
Claims (9)
1. a method for producing biodiesel comprises the steps:
S1 mixes raw oil material with middle short chain alcohol, and under the effect of homogeneous phase alkaline catalysts, accomplishes transesterification reaction;
S2 separates the reaction solution of accomplishing transesterification reaction, gets coarse biodiesel;
S3 adds the solid neutralizing agent in coarse biodiesel, stir itself and homogeneous phase alkaline catalysts are reacted;
S4 promptly obtains biofuel behind the separate solid neutralizing agent.
2. method for producing biodiesel as claimed in claim 1; It is characterized in that; Said raw oil material is an acid number during greater than 1.0mgKOH/g, before the said step S1, also comprises raw oil material is carried out preparatory esterif iotacation step: S0; Raw oil material is mixed with middle short chain alcohol, and under the sulphuric acid catalysis effect, carry out pre-esterification reactor.
3. according to claim 1 or claim 2 method for producing biodiesel is characterized in that, said in the molar ratio of short chain alcohol and raw oil material be 3.5:1 ~ 30:1.
4. method for producing biodiesel as claimed in claim 1 is characterized in that, the consumption of said homogeneous phase alkali is 0.1% ~ 3% of a raw oil material quality.
5. method for producing biodiesel as claimed in claim 1 is characterized in that, said in short chain alcohol be a kind of in methyl alcohol, ethanol or the propyl alcohol.
6. method for producing biodiesel as claimed in claim 1 is characterized in that, said homogeneous phase alkaline catalysts is a kind of in sodium hydroxide, Pottasium Hydroxide or the sodium methylate.
7. method for producing biodiesel as claimed in claim 1 is characterized in that, said solid neutralizing agent is one or more mixtures in acidic white earth, strong acid type resin, the modified zeolite molecular sieve.
8. method for producing biodiesel as claimed in claim 7 is characterized in that, said modified zeolite molecular sieve is through zeolite molecular sieve is placed 0.3 ~ 1.5molL
-1Hydrochloric acid or sulphuric acid soln in soak 1 ~ 24h, more successively through separation, washing, oven dry and make.
9. method for producing biodiesel as claimed in claim 1 is characterized in that, said raw oil material is Jatropha curcas oil, rapeseed oil, Semen Maydis oil, VT 18, Viscotrol C, Oleum Cocois, peanut oil, sewer oil, lard and algae grease.
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| CN2011104414040A CN102533453B (en) | 2011-12-26 | 2011-12-26 | Biodiesel production method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642535A (en) * | 2013-12-24 | 2014-03-19 | 济南开发区星火科学技术研究院 | Bio-compound diesel oil and preparation method thereof |
| CN104178360A (en) * | 2014-09-04 | 2014-12-03 | 四川大学 | Method for preparing biodiesel from sarson seed oil |
Citations (3)
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|---|---|---|---|---|
| CN1826403A (en) * | 2003-07-21 | 2006-08-30 | 巴西石油公司 | Process for producing biodiesel |
| CN101104810A (en) * | 2006-07-14 | 2008-01-16 | 上海桑迪精细化工研究所有限公司 | Preparation method for biological diesel oil |
| CN101358141A (en) * | 2008-09-28 | 2009-02-04 | 四川省国政生物质能源科技发展股份有限公司 | Method for preparing bio diesel oil by idesia polycarpa maxim. var. vestita diels oil catalysis using solid base as catalyst |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826403A (en) * | 2003-07-21 | 2006-08-30 | 巴西石油公司 | Process for producing biodiesel |
| CN101104810A (en) * | 2006-07-14 | 2008-01-16 | 上海桑迪精细化工研究所有限公司 | Preparation method for biological diesel oil |
| CN101358141A (en) * | 2008-09-28 | 2009-02-04 | 四川省国政生物质能源科技发展股份有限公司 | Method for preparing bio diesel oil by idesia polycarpa maxim. var. vestita diels oil catalysis using solid base as catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 李为民 等: "地沟油制备生物柴油", 《粮食与食品工业》 * |
| 舒陈华: "地沟油制备生物柴油研究进展", 《广东化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642535A (en) * | 2013-12-24 | 2014-03-19 | 济南开发区星火科学技术研究院 | Bio-compound diesel oil and preparation method thereof |
| CN104178360A (en) * | 2014-09-04 | 2014-12-03 | 四川大学 | Method for preparing biodiesel from sarson seed oil |
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| CN102533453B (en) | 2013-08-14 |
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