CN101985580B - Method for preparing biodiesel from low-boiling-point substance through continuous rectification of oleic acid - Google Patents
Method for preparing biodiesel from low-boiling-point substance through continuous rectification of oleic acid Download PDFInfo
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- CN101985580B CN101985580B CN201010542669A CN201010542669A CN101985580B CN 101985580 B CN101985580 B CN 101985580B CN 201010542669 A CN201010542669 A CN 201010542669A CN 201010542669 A CN201010542669 A CN 201010542669A CN 101985580 B CN101985580 B CN 101985580B
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Abstract
The invention relates to a method for preparing biodiesel from a low-boiling-point substance through continuous rectification of oleic acid. The method comprises the following steps of: mixing the low-boiling-point substance and methanol according to a quantitative ratio; 2, continuously esterifying at high temperature under high pressure; 3, performing scraped film distillation; 4, performing short-range molecular distillation to remove residues; and 5, continuously performing alkali refining for deacidification. The method is a new way to comprehensively utilize the low-boiling-point substance through continuous rectification of the oleic acid. The produced biodiesel is renewable and green novel energy, and the method creates good conditions for the development of low carbon economy and recycling economy.
Description
Technical field
The present invention relates to a kind of oleic acid continuous rectification low-boiling-point substance and prepare method of bio-diesel oil.Belong to the oil chemistry industrial circle.
Background technology
There is the low-boiling-point substance about 2% to produce in the vegetable oil and fat refining leftover bits and pieces acidifying oil continuous rectification oleic acid process; The whole nation has 500,000 tons of left and right sides acidifying oil to be used for the production of continuous rectification oleic acid at present; There is every year the low-boiling-point substance about 10,000 tons to produce; Low-boiling-point substance can not get utilizing well for a long time, usually with cheap sell at competitive.In recent years, countries in the world all tap a new source of energy in quickening, particularly the exploitation paces of renewable energy source.Vegetable oil lipoprotein and by product thereof prepare fatty acid methyl ester-biofuel, have caused people's attention especially, because its combustionproperty can also directly be used for petroleum diesel fields such as oil motor at all no less than petroleum diesel.It is believed that fatty acid methyl ester-biofuel will be the substitute of future petroleum diesel oil.Fatty acid methyl ester-biofuel has the following advantages, poisonless biological degradable, and cetane value is high; Sulfide carbon monoxide discharge capacity is few; And its discharging carbon from atmosphere, compare with petroleum diesel, can reduce emission of carbon-dioxide significantly; Meet national low-carbon economy, the recycling economy STRATEGIES OF SUSTAINABLE DEVELOPMENT.Fatty acid-esterified industrialization technology route generally adopts the acid catalyzed esterification processing technology routine both at home and abroad.Adopt HTHP catalyst-free continuous esterification industrial production device that report had not been arranged.We have invented a kind of oleic acid continuous rectification low-boiling-point substance finally and have prepared method of bio-diesel oil through scientific experiment and the research of long period for this reason, and this method has not only solved the problem of environmental pollution that acid catalysis is brought; And processing ease; Cost is low, and the product yield is high, constant product quality.
Summary of the invention
The technical problem that the present invention will solve is the new way of oleic acid continuous rectification low-boiling-point substance comprehensive utilization.Adopt advanced HTHP continuous esterification production technique, not only solved the problem of environmental pollution that acid catalysis is brought, and processing ease, cost is low, and the product yield is high, constant product quality.In order to solve the problems of the technologies described above, the present invention adopts following technical scheme, and this method may further comprise the steps:
1, low-boiling-point substance mixes through quantitative proportioning with methyl alcohol.
1.1 the low-boiling-point substance temperature generally is controlled at 40～90 ℃, preferentially is controlled at 50～80 ℃, especially 60～70 ℃;
1.2 the weight ratio of low-boiling-point substance and methyl alcohol generally is controlled at 1: 0.6～1.2, preferentially is controlled at 1: 0.8～1.1, especially 1: 0.9～1;
1.3 mixed traffic generally is controlled at 0.1～20T/h, preferentially is controlled at 0.5～15T/h, especially 1～10T/h.
2, HTHP continuous esterification.
2.1 preheating temperature generally is controlled at 200～230 ℃, preferentially is controlled at 210～230 ℃, especially 220～225 ℃;
2.2 the continuous esterification temperature generally is controlled at 210～250 ℃, preferentially is controlled at 215～235 ℃, especially 220～225 ℃;
2.3 continuous esterification pressure generally is controlled at 3～5MPa, preferentially is controlled at 3.5～4.5MPa, especially 3.8～4.2MPa;
2.4 the continuous esterification residence time generally was controlled at 2～12 hours, preferentially was controlled at especially 4～8 hours 3～10 hours.
3, scraper plate thin film distillation.
3.1 scraper plate thin film distillation vacuum tightness generally is controlled at 50～500Pa, preferentially is controlled at 100～350Pa, especially 150～200Pa;
3.2 scraper plate thin film distillation thermal oil temperature generally is controlled at 200～260 ℃, preferentially is controlled at 210～250 ℃, especially 220～240 ℃;
3.3 the scraper plate thin film distillation adopts speed control by frequency variation short-path distillation pump to input of raw material current stabilization and the output of product current stabilization.Flow generally is controlled at 0.1～10T/h, preferentially is controlled at 0.5～8T/h, especially 1～5T/h.
4, short-range molecular distillation takes off residue.
Generally be controlled at 1～100Pa 4.1 short-range molecular distillation takes off residue vacuum tightness, preferentially be controlled at 5～50Pa, especially 10～20Pa;
Generally be controlled at 200～250 ℃ 4.2 short-range molecular distillation takes off residue thermal oil temperature, preferentially be controlled at 210～240 ℃, especially 220～230 ℃;
Generally be controlled at 20～70 ℃ 4.3 short-range molecular distillation takes off residue recirculated cooling water temperature, preferentially be controlled at 30～60 ℃, especially 35～55 ℃;
Adopt the charging of speed control by frequency variation mug(unit of measure) pump current stabilization 4.4 short-range molecular distillation takes off residue, flow generally is controlled at 0.1～10T/h, preferentially is controlled at 0.5～8T/h, especially 1～5T/h;
4.5 taking off the discharging of residue pitch, short-range molecular distillation adopts gravity fluid-tight continuous blow-down.
5, continuous alkali-refining deacidification.
5.1 continuous alkali-refining liquid caustic soda concentration general range preferentially is controlled at 16～24 degree Beaume, especially 18～22 degree Beaume at 12～26 degree Beaume;
5.2 the continuous alkali-refining temperature generally is controlled at 50～95 ℃, preferentially is controlled at 60～90 ℃, especially 80～90 ℃;
Mix with the precisely quantitative proportioning of liquid caustic soda 5.3 continuous alkali-refining carries out fatty acid methyl ester by dynamic mixer, wear out by postponing jar, the retarding ageing time generally is controlled at 10～60min, preferentially is controlled at 15～45min, especially 20～30min.Get into the butterfly centrifugal machine then and take off soap stock;
5.4 continuous alkali-refining carries out fatty acid methyl ester and the quantitative proportioning mixing, washing of technology soft water by dynamic mixer, wash temperature generally is controlled at 80～95 ℃, preferentially is controlled at 85～93 ℃, especially 88～92 ℃.Get into the dehydration of butterfly centrifugal machine then;
5.5 the further vacuum hydro-extraction of continuous alkali-refining fatty acid methyl ester.Dehydration vacuum tightness generally is controlled at 720～760mmHg, preferentially is controlled at 730～750mmHg, especially 735～745mmHg.Dehydration temperaturre generally is controlled at 120～160 ℃, preferentially is controlled at 130～150 ℃, especially 135～145 ℃.
Embodiment
Oleic acid continuous rectification low-boiling-point substance is heated to 60 ℃, is sent to mixing tank with the frequency conversion surge pump with 2 tons flow per hour, the methyl alcohol of 99.5% above concentration simultaneously, and also another frequency conversion surge pump of usefulness is sent to mixing tank with 2 tons flow per hour.Mixing solutions is preheating to 220 ℃ through tubulation, gets into the continuous esterification tower bottom, and this moment, esterification column was preheating to 225 ℃ with methanol steam; 4.0Mpa pressure; Mixing solutions progressively is full of esterification column, remains 225 ℃ of temperature of esterification column and 4.0Mpa pressure, and esterification stopped after 6 hours; Through cat head integration variable valve, the balance of control input flow rate and output flow.The esterification mixed solution gets into flash distillation dealcoholysis jar; The thick methyl esters that removes methyl alcohol gets into the scrapper thin film evaporator continuous still battery after through the tubulation preheating; About 230 ℃ of control chuck thermal oil temperature, the vacuum residual voltage keeps 150Pa, and flow control is per hour about 2 tons; The recirculated cooling water inflow temperature is less than 40 ℃, and distilled fatty acid methyl esters drop temperature is lower than 60 ℃.The acid value that obtains the distilled fatty acid methyl esters is less than 5, and the liquid concentrator of scrapper thin film evaporator gets into short-range molecular distillation and arranges residue continuously, steams fatty acid methyl ester as far as possible to the greatest extent.About 230 ℃ of control chuck thermal oil temperature,, the vacuum residual voltage keeps 15Pa, 60 ℃ of built-in condensation inflow temperature controls, the distillation residue exhaust temperature is less than 220 ℃.Volatilizable methyl esters residual quantity is less than 5% in the distillation residue.The distilled fatty acid methyl esters is through getting into the continuous alkali-refining system behind the plate-type heat-exchange; The distilled fatty acid methyl esters is preheating to about 90 ℃ and gets into dynamic mixer and mix with the alkali lye of accurate measurement 18 degree Beaume; Again through the aging 30min that stops of retarding ageing jar; Get into the separation of butterfly centrifugal machine and take off soap, the alkali refining ester dehydrates system at the dynamic mixer mixing, washing after the butterfly centrifugal machine separates the entering continous vacuum with 20% soft water again.Dehydration temperaturre keeps 140 ℃, and dehydration vacuum tightness keeps 740mmHg.The final acid value that obtains meets national biofuel standard less than the biofuel (fatty acid methyl ester) of 0.8 moisture content less than 0.05% oleic acid continuous rectification low-boiling-point substance.
Claims (6)
1. an oleic acid continuous rectification low-boiling-point substance prepares method of bio-diesel oil, and this method comprises the steps:
(1) low-boiling-point substance mixes through quantitative proportioning with methyl alcohol,
Said step (1) is specially: the low-boiling-point substance temperature is controlled at 40～90 ℃, and the weight ratio of low-boiling-point substance and methyl alcohol is controlled at 1: 0.6～1.2, and mixed traffic is controlled at 0.1～20T/h;
(2) HTHP continuous esterification,
Said step (2) is specially: preheating temperature is controlled at 200～230 ℃, and the continuous esterification temperature is controlled at 210～250 ℃, and the continuous esterification pressure-controlling is at 3～5MPa, and the continuous esterification residence time was controlled at 2～12 hours;
(3) scraper plate thin film distillation,
Said step (3) is specially: scraper plate thin film distillation vacuum degree control is at 50～500Pa; Scraper plate thin film distillation thermal oil temperature is controlled at 200～260 ℃; The scraper plate thin film distillation adopts speed control by frequency variation short-path distillation pump to input of raw material current stabilization and the output of product current stabilization, and flow control is at 0.1～10T/h;
(4) short-range molecular distillation takes off residue,
Said step (4) is specially: short-range molecular distillation takes off the residue vacuum degree control at 1～100Pa; Short-range molecular distillation takes off residue thermal oil temperature and is controlled at 200～250 ℃; Short-range molecular distillation takes off residue recirculated cooling water temperature and is controlled at 20～70 ℃; Short-range molecular distillation takes off residue and adopts the charging of speed control by frequency variation mug(unit of measure) pump current stabilization, and flow control is at 0.1～10T/h, and short-range molecular distillation takes off the discharging of residue pitch and adopts gravity fluid-tight continuous blow-down;
(5) continuous alkali-refining deacidification,
Said step (5) is specially: continuous alkali-refining liquid caustic soda concentration range is at 12～26 degree Beaume; The continuous alkali-refining temperature is controlled at 50～95 ℃, and continuous alkali-refining carries out fatty acid methyl ester by dynamic mixer to be mixed with the precisely quantitative proportioning of liquid caustic soda, aging by postponing jar again; The retarding ageing time is controlled at 10～60min; Get into the butterfly centrifugal machine then and take off soap stock, continuous alkali-refining carries out fatty acid methyl ester and the quantitative proportioning mixing, washing of technology soft water by dynamic mixer, and wash temperature is controlled at 80～95 ℃; Get into the dehydration of butterfly centrifugal machine then; The further vacuum hydro-extraction of continuous alkali-refining fatty acid methyl ester, the dehydration vacuum degree control is at 720～760mmHg, and dehydration temperaturre is controlled at 120～160 ℃.
2. a kind of oleic acid continuous rectification low-boiling-point substance according to claim 1 prepares method of bio-diesel oil, it is characterized in that:
Said step (1) is specially: the low-boiling-point substance temperature is controlled at 50～80 ℃, and the weight ratio of low-boiling-point substance and methyl alcohol is controlled at 1: 0.8～1.1, and mixed traffic is controlled at 0.5～5T/h.
3. a kind of oleic acid continuous rectification low-boiling-point substance according to claim 1 prepares method of bio-diesel oil, it is characterized in that:
Said step (2) is specially: preheating temperature is controlled at 210～230 ℃, and the continuous esterification temperature is controlled at 215～235 ℃, and the continuous esterification pressure-controlling is at 3.5～4.5MPa, and the continuous esterification residence time was controlled at 3～10 hours.
4. a kind of oleic acid continuous rectification low-boiling-point substance according to claim 1 prepares method of bio-diesel oil, it is characterized in that:
Said step (3) is specially: scraper plate thin film distillation vacuum degree control is at 100～350Pa, and scraper plate thin film distillation thermal oil temperature is controlled at 210～250 ℃, and flow control is at 0.5～8T/h.
5. a kind of oleic acid continuous rectification low-boiling-point substance according to claim 1 prepares method of bio-diesel oil, it is characterized in that:
Said step (4) is specially: short-range molecular distillation takes off the residue vacuum degree control at 5～50Pa; Short-range molecular distillation takes off residue thermal oil temperature and is controlled at 210～240 ℃; Short-range molecular distillation takes off residue recirculated cooling water temperature and is controlled at 30～60 ℃, and flow control is at 0.5～8T/h.
6. a kind of oleic acid continuous rectification low-boiling-point substance according to claim 1 prepares method of bio-diesel oil, it is characterized in that:
Said step (5) is specially: continuous alkali-refining liquid caustic soda concentration is controlled at 16～24 degree Beaume; The continuous alkali-refining temperature is controlled at 60～90 ℃; The retarding ageing time is controlled at 15～45min; Wash temperature is controlled at 85～93 ℃, and the dehydration vacuum degree control is at 730～750mmHg, and dehydration temperaturre is controlled at 130～150 ℃.
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| CN102618388A (en) * | 2012-03-13 | 2012-08-01 | 江苏永林油脂化工有限公司 | Method for separating oleic acid by continuous rectification of nigre acidification oil black fatty acid |
| CN103421614B (en) * | 2012-05-14 | 2016-02-03 | 陕西德融新能源股份有限公司 | The preparation technology of a kind of polished fat production biofuel |
| CN104419456A (en) * | 2013-08-27 | 2015-03-18 | 丹阳市助剂化工厂有限公司 | Refining method and refining apparatus of high-quality biodiesel |
| CN103756790B (en) * | 2014-01-23 | 2015-07-15 | 湖南未名创林生物能源有限公司 | Production method of biodiesel |
| CN103756793B (en) * | 2014-01-23 | 2015-07-15 | 湖南未名创林生物能源有限公司 | Production method of biodiesel |
| CN103725424B (en) * | 2014-01-23 | 2016-01-13 | 湖南未名创林生物能源有限公司 | A kind of production method of biofuel |
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| CN100526426C (en) * | 2006-06-29 | 2009-08-12 | 华南理工大学 | Method of producing biological diesel oil directly using molecular distillation technology |
| CN101338212B (en) * | 2007-07-05 | 2012-02-15 | 中国石油化工股份有限公司 | Method for preparing biodesel |
| CN101760299A (en) * | 2010-01-26 | 2010-06-30 | 江苏永林油脂化工有限公司 | Continuous alkali-refining deacidification method for biodiesel |
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