CN104152274B - A kind of method utilizing gasified methanol esterification high-acid value grease - Google Patents
A kind of method utilizing gasified methanol esterification high-acid value grease Download PDFInfo
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- CN104152274B CN104152274B CN201410417599.9A CN201410417599A CN104152274B CN 104152274 B CN104152274 B CN 104152274B CN 201410417599 A CN201410417599 A CN 201410417599A CN 104152274 B CN104152274 B CN 104152274B
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Abstract
The present invention discloses a kind of method utilizing gasified methanol esterification high-acid value grease, is the grease of high acid value to be added bottom with in the reactor of circulation line, and is heated to default temperature of reaction; Again grease is constantly circulated in circulation line, and with the gasified methanol constantly passed in circulation line reverse contact mix after send into reactor again, until the material acid number≤1mgKOH/g in reactor; Acid catalyst is added with catalytic esterification in reactor.The present invention contacts inverse in circulation line to gasified methanol and grease, both can be made fully to mix and esterification be advanceed to carry out fast in circulation line, reaction times is shortened, only once need heat grease before reaction, reaction process is without the need to controlling the temperature in reactor, more do not need to use outside well heater constantly to heat reaction mass, have that easy manipulation, speed are fast, less cost of power.
Description
Technical field
The invention belongs to production of biodiesel technical field, be specifically related to a kind of method utilizing gasified methanol esterification high-acid value grease.
Background technology
Biofuel is a kind of reproducible clean energy, and grease, catalyzer and Liquid Phase Methanol mainly add in reactor by existing biofuel acid-catalyzed esterification reaction technique, keep constant temperature to carry out esterification after being heated to certain temperature.When temperature of reaction is more than 65 DEG C, methyl alcohol does not also carry out esterification is just made still internal pressure increase by evaporation, simultaneously, undergo phase transition owing to constantly there being Liquid Phase Methanol in temperature-rise period and reaction process and absorb amount of heat, cause temperature-rise period comparatively slow, temperature of reaction is difficult to control, the reaction times of reaction workshop section is 6 hours, consuming time longer, and in esterification reaction process, produce more moisture, stop reaction forward to be carried out.When adopting external heater to heat grease, because grease all needs by well heater in whole reaction process, easily cause the blocking of well heater.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method utilizing gasified methanol esterification high-acid value grease, have consuming time less, the advantage such as easy temperature control system and save energy.
For solving the problem, the present invention will by the following technical solutions:
Utilize a method for gasified methanol esterification high-acid value grease, be the grease of high acid value is added bottom with in the reactor of circulation line, and be heated to default temperature of reaction; Again grease is constantly circulated in circulation line, and with the gasified methanol constantly passed in circulation line reverse contact mix after send into reactor again, until the material acid number≤1mgKOH/g in reactor; Acid catalyst is added with catalytic esterification in reactor.
In technique scheme:
Described acid catalyst preferably adds at twice, and first time adds after grease is heated to default temperature of reaction, and add-on is 1.5 ‰ ~ 2.5 ‰ of the oil quality added; Add after the material acid number≤50mgKOH/g of second time in reactor, add-on is 0.5 ‰ ~ 1.5 ‰ of the oil quality added.
Described acid catalyst generally refers to industrial concentrated sulfuric acid solution, and generally >=70%, preferably, first can be diluted to sulfuric acid massfraction with methyl alcohol before adding is 30% ~ 45% to its sulfuric acid massfraction.
Described default temperature of reaction is 130 ~ 145 DEG C; Pressure in described reactor should control at 0.04 ~ 0.06MPa.
The temperature of described gasified methanol is preferably 110 ~ 130 DEG C; Described gasified methanol intake hourly is 8% ~ 15% of the oil quality added.
The acidity of the grease of described high acid value is 100 ~ 200mgKOH/g; The stock oil used by preparation biofuel that grease can select acidification oil, plam oil, trench wet goods common; Grease also preferably after purification, foreign material sedimentation, then will dewater to weight content≤0.5% of water before adding reactor.
Compared to the prior art, the present invention has the following advantages:
1, the present invention contact inverse in circulation line to gasified methanol and grease, and both can be made fully to mix and esterification be advanceed to and carry out fast in circulation line, make the reaction times foreshorten to 3 ~ 4 hours, speed of response promotes greatly; Only once need heat grease before reaction, can esterification be completed, without the need to controlling the temperature in reactor, more not need to use outside well heater constantly to heat reaction mass, there is the advantage of easy manipulation, less energy consumption;
2, because the in line methanol vapor of esterification reaction process one, while taking moisture out of, also the acid catalyst of part can be taken out of, the present invention adopts secondary to add the mode of acid catalyst, the catalyzer of replenish loss when acid number is lower, catalyzer can be made in reactor to keep concentration stabilize, be beneficial to the carrying out of catalytic esterification.
Embodiment
Be described with specific embodiment below, but the present invention is not limited to these embodiments.
Embodiment 1
The soybean acidified oil by acid number being 138mgKOH/g, through purification, after foreign material sedimentation, dewaters to water-content and is less than 0.5%, then squeeze into soybean acidified oil 5m toward bottom with in the reactor of circulation line
3.Soybean acidified oil is heated to 140 DEG C, then in reactor, adding the acid catalyst of soybean acidified oil quality 1.5 ‰, (acid catalyst is the sulphuric acid soln of sulfuric acid massfraction 98%, first being diluted to sulfuric acid massfraction with methyl alcohol before adding is 35%), mix reverse contact of circulation line and the soybean acidified oil of circulation with the gasified methanols of 120 DEG C, enter in reactor after a segment pipe and carry out esterification, gasified methanol intake hourly is 10% of the soybean acidified oil quality added.Pressure-controlling in reactor is 0.05MPa, reacts after 1.5 hours, and measure material acid number, as AV≤50mgKOH/g, the acid catalyst adding soybean acidified oil quality 0.5 ‰ carries out second step catalytic esterification; Logical gasified methanol carries out reaction after 1.5 hours again, measures material acid number, as AV≤1mgKOH/g, stops passing into gasified methanol, terminates reaction.
Embodiment 2
The plam oil by acid number being 160mgKOH/g, through purification, after foreign material sedimentation, dewaters to water-content and is less than 0.5%, then squeeze into plam oil 5m toward bottom with in the reactor of circulation line
3.Plam oil is heated to 130 DEG C, then in reactor, adding the acid catalyst of plam oil quality 2.0 ‰, (acid catalyst is the sulphuric acid soln of sulfuric acid massfraction 70%, first being diluted to sulfuric acid massfraction with methyl alcohol before adding is 45%), mix reverse contact of circulation line and the plam oil of circulation with the gasified methanols of 110 DEG C, enter in reactor after a segment pipe and start to carry out esterification, gasified methanol intake hourly is 12% of the oil quality added.Pressure-controlling in reactor is 0.04MPa, reacts after 1.5 hours, and measure material acid number, as AV≤50mgKOH/g, the acid catalyst adding plam oil quality 0.5 ‰ carries out second step catalytic esterification; Logical gasified methanol carries out reaction after 1.5 hours again, measures material acid number, as AV≤1mgKOH/g, stops passing into gasified methanol, terminates reaction.
Embodiment 3
The sewer oil by acid number being 120mgKOH/g, through purification, after foreign material sedimentation, dewaters to water-content and is less than 0.5%, then squeeze into sewer oil 5m toward bottom with in the reactor of circulation line
3.Sewer oil is heated to 145 DEG C, then in reactor, adding the acid catalyst of sewer oil quality 2 ‰, (acid catalyst is the sulphuric acid soln of sulfuric acid massfraction 98%, first being diluted to sulfuric acid massfraction with methyl alcohol before adding is 45%), mix reverse contact of circulation line and the sewer oil of circulation with the gasified methanols of 130 DEG C, enter in reactor after a segment pipe and carry out esterification, gasified methanol intake hourly is 8% of the sewer oil quality added.Pressure-controlling in reactor is 0.06MPa, reacts after 1.5 hours, and measure material acid number, as AV≤50mgKOH/g, the acid catalyst adding sewer oil quality 1.5 ‰ carries out second step catalytic esterification; Logical gasified methanol carries out reaction after 1.5 hours again, measures material acid number, as AV≤1mgKOH/g, stops passing into gasified methanol, terminates reaction.
Claims (6)
1. utilize a method for gasified methanol esterification high-acid value grease, it is characterized in that: the grease of high acid value is added bottom with in the reactor of circulation line, and be heated to default temperature of reaction; Again grease is constantly circulated in circulation line, and with the gasified methanol constantly passed in circulation line reverse contact mix after send into reactor again, until the material acid number≤1mgKOH/g in reactor; Acid catalyst is added with catalytic esterification in reactor; Described default temperature of reaction is 130 ~ 145 DEG C, and the temperature of gasified methanol is 110 ~ 130 DEG C, and the pressure-controlling in reactor is at 0.04 ~ 0.06MPa.
2. method according to claim 1, is characterized in that: described acid catalyst adds at twice, and first time adds after grease is heated to default temperature of reaction, and add-on is 1.5 ‰ ~ 2.5 ‰ of the oil quality added; Add after the material acid number≤50mgKOH/g of second time in reactor, add-on is 0.5 ‰ ~ 1.5 ‰ of the oil quality added.
3. method according to claim 1 and 2, is characterized in that: described acid catalyst is the sulphuric acid soln of sulfuric acid massfraction >=70%, and being first diluted to sulfuric acid massfraction with methyl alcohol before adding is 30% ~ 45%.
4. method according to claim 1, is characterized in that: described gasified methanol intake hourly is 8% ~ 15% of the oil quality added.
5. method according to claim 1, is characterized in that: the acidity of the grease of described high acid value is 100 ~ 200mgKOH/g.
6. method according to claim 1 or 5, is characterized in that: also after purification, foreign material sedimentation, will dewater to weight content≤0.5% of water before the grease of described high acid value adds reactor.
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| CN201410417599.9A CN104152274B (en) | 2014-08-22 | 2014-08-22 | A kind of method utilizing gasified methanol esterification high-acid value grease |
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| CN201410417599.9A CN104152274B (en) | 2014-08-22 | 2014-08-22 | A kind of method utilizing gasified methanol esterification high-acid value grease |
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| CN104152274B true CN104152274B (en) | 2016-02-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105132190A (en) * | 2015-08-21 | 2015-12-09 | 中国林业科学研究院林产化学工业研究所 | Cyclic esterification method for preparing biodiesel from high-acid-value grease |
| CN106350232A (en) * | 2016-08-31 | 2017-01-25 | 防城港市中能生物能源投资有限公司 | Production method of biodiesel |
| CN113563977B (en) * | 2021-07-21 | 2022-08-16 | 湖北天基生物能源科技发展有限公司 | Treatment system and treatment method for waste grease |
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| CN101195572B (en) * | 2006-12-08 | 2010-06-09 | 四川古杉油脂化学有限公司 | Method for synthesizing fatty acid methyl ester |
| CN102191133A (en) * | 2011-04-13 | 2011-09-21 | 云南师范大学 | Process for preparing bio-diesel through fatty acid two-step esterifying method |
| CN102703223B (en) * | 2012-05-31 | 2013-08-21 | 源华能源科技（福建）有限公司 | Process for preparing biodiesel by catalytic esterification and alcoholysis of gas-phase methanol |
| CN103031216A (en) * | 2013-01-09 | 2013-04-10 | 杨玉峰 | Pre-esterification process for producing biodiesel from illegal cooking oil |
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