CN109022160A - A kind of continuous pre-esterification method and device of gutter oil superelevation - Google Patents
A kind of continuous pre-esterification method and device of gutter oil superelevation Download PDFInfo
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- CN109022160A CN109022160A CN201811072031.2A CN201811072031A CN109022160A CN 109022160 A CN109022160 A CN 109022160A CN 201811072031 A CN201811072031 A CN 201811072031A CN 109022160 A CN109022160 A CN 109022160A
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- superelevation
- gutter oil
- oil
- esterification
- continuous pre
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
Abstract
The invention belongs to field of renewable energy, the continuous pre-esterification method of specifically a kind of gutter oil superelevation and equipment.By the gutter oil through pre-treatment, the superelevation continuity under no catalyst, oxygen free condition is reacted with glycerol, so that gutter oil is able to the continuous pre-esterification of superelevation.Processing method of the present invention is not only used without catalyst, saves the lock out operation of catalyst, and high temperature water removal improves reaction efficiency, and the continuity of superelevation, and production capacity is high, is easier to realize industrialization；This invention simplifies operating processes, avoid the single control for being easy to subsequent reactions of equipment burn into product, environmentally protective, have significant economic and social benefit.
Description
Technical field sheet
The invention belongs to field of renewable energy, the continuous pre-esterification method of specifically a kind of gutter oil superelevation and dress
It sets.
Background technique
Gutter oil is the general designation of various waste oils, and quality is very poor, and poisonous and harmful element severely exceeds, and direct emission causes
Environmental pollution；Long-term intake causes to poison by food, induces an illness, is even carcinogenic.If being recycled as resource reclaim, gutter oil warp
Transesterification can biodiesel synthesis.However a large amount of free fatty acid contained in gutter oil is (usually using acid value as weighing apparatus
Amount standard) and content range fluctuation is greatly (20~180mgKOH/g), meeting and catalyzing glycerol ester occur transesterification and prepare first
The basic catalysts such as ester NaOH, KOH generate saponification, therefore directly directly can not prepare biological bavin using a step base catalysis method
Soyate, this, which is also why the low-grade glyceride stock such as gutter oil prepares biodiesel process, will much be more complex than plant
The main reason of the high-grades such as crude oil glyceride stock (acid value≤4mgKOH/g).Therefore, useless using gutter oil, acidification oil etc.
It abandons grease principle to prepare in biodiesel process, how to remove the free fatty acid in glyceride stock is the difficult point in preparation process
With the key point of technology.
Esterification deacidification technology traditional at present is that esterification occurs using sulfuric acid catalysis free fatty acid and methanol
And then the acid value of raw material is reduced, reach the technique requirement of base catalysis transesterification.But acid-catalyzed esterification reaction there is
Following main problem: alcohol dosage is big, and the reaction time is long；The concentrated sulfuric acid can generate carbonization to grease, so that biodiesel oil product
Color is deteriorated, and influences product quality；To equipment, there are corrosivenesses, cannot use conventional stainless steel reaction container；Catalysis is anti-
The specificity answered is poor, while the esterification of catalysis methanol and fatty acid, goes back the reaction of catalyzing glycerol ester hydrolysis, so that the
Technological parameter determines difficult during two step base catalysis transesterifications；Generate a large amount of acid waste water；It is needed after reaction using quiet
It sets separation sulfuric acid and massive laundering to neutrality is needed just to can be carried out next step base catalysis transesterification.The most key, acid is urged
Change the water for being difficult to remove that esterification generates in reaction system in esterification reaction process, reaction balance caused to be difficult to move right,
The side reactions such as hydrolysis also occur simultaneously.Therefore being badly in need of one kind can synthesising biological using the continuous transesterification of gutter oil progress
The method of diesel oil.
Summary of the invention
It is an object of that present invention to provide a kind of continuous pre-esterification method and devices of gutter oil superelevation.
To achieve the above object, the invention adopts a technical scheme as:
A kind of continuous pre-esterification device of gutter oil superelevation, device are integrated dynamic response device, and reactor head is equipped with charging
Mouth (1) is exported with water gas import (3) and with water gas, and bottom is equipped with discharge port (2), and two sides are respectively equipped with heat conductive oil inlet
(5) and conduction oil outlet (6)；The band water gas outlet is connected with one end of collection device (10), the other end and cooling device
(9) one end is connected, and the condensing unit other end is to vacuumize outlet.
The heat conductive oil inlet (5) and conduction oil outlet (6) are set to reactor two sides, and import is set to bottom.
Reactor (7) top is inserted with thermocouple (8).
A method of using device to the continuous pre-esterification of gutter oil superelevation, by through pre-treatment gutter oil and glycerol in nothing
Superelevation continuity is reacted under catalyst, oxygen free condition, so that gutter oil is able to the continuous pre-esterification of superelevation.
The purpose of pre-esterification reactor is to keep free fatty acid glyceride corresponding with glycerine reaction generation in glyceride stock mixed
Object is closed, to reach requirement of the transesterification to feedstock oil acid value.Pre-esterification reactor equation is as follows:
(note: R, R1,R2,R3=C15H31,C17H35,C17H33,C17H31..., wherein R1,R2,R3Three may be identical or not
Together.)
Further, pretreated gutter oil (gutter oil form in terms of oleic acid) and glycerol will be cleaned in mixing in device
Uniformly, it is then passed through nitrogen, and is reacted under heat medium and nitrogen atmosphere in 210-230 DEG C；Wherein, removal of impurities is pre-
The gutter oil (gutter oil form in terms of oleic acid) and glycerol of processing 1:0.8-1 in molar ratio.
In the clean pretreated gutter oil and glycerol mixture injection described device, charge velocity 0.1-1L/
Min, time residence time 150-240min, is reacted under heat medium and nitrogen atmosphere in 210-230 DEG C, by-product
Water is detached from from reaction system rapidly, and then realizes that gutter oil is able to the continuous pre-esterification of superelevation.
The gutter oil is dining room gutter oil, hogwash fat or dining room remaining meal oil, 20~180mgKOH/g of acid value of oil and fat, glycerol
It is not less than the industry glycerol of 95wt.% for content.
Advantage for present invention:
China's grease pre-esterification efficiency is general at present, and alcohol dosage is big, and the reaction time is long, and at high cost, product quality is poor, to setting
Standby corrosion is big, and product unicity is poor；Waste oil pre-esterifying process method of the present invention, it is suitable for gutter oil such as hogwash fats, frying
Old oil, dining room remaining meal oil etc.；The present invention uses glycerine esterification reaction under superelevation continuity reaction unit high temperature to make in glyceride stock
Free fatty acid glyceride mixture corresponding with glycerine reaction generation, no catalyst are used, are urged after eliminating esterification
The operation of agent separation, can directly carry out base catalysis transesterification operation, simplify process；Ester by-products under hot conditions
Water is detached from from reaction system rapidly, is promoted the right phase shift of balance, raw material acid value can be made to be reduced to extremely low level, favorably
In the progress of subsequent base catalysis transesterification；Esterification products are single, be glyceride mixture (traditional handicraft be glyceride and
Mixtures of methyl esters), the subsequent easily controllable selection of base catalysis transesterification parameter；Superelevation successive reaction, high production efficiency are easier to
Realize industrialization.The method of the present invention reduces acid value effect, improves reaction efficiency, simplify superelevation continuity operating process, avoid setting
Standby burn into is easy to the control of subsequent reactions.
Detailed description of the invention
Fig. 1 is the continuous pre-esterification equipment figure of gutter oil superelevation provided in an embodiment of the present invention；Wherein 1, feed inlet, 2, discharging
Mouthful, 3, N2Import, 4, vacuumize outlet, 5, heat conductive oil inlet, 6, conduction oil outlet, 7, dynamic response device, 8, thermocouple, 9, cold
But device, 10, collection device.
Specific embodiment
A kind of continuous pre-esterification method and device of gutter oil superelevation of the present invention is made further below with reference to embodiment
It is bright.
Embodiment 1:
The continuous pre-esterification device of gutter oil superelevation is shown in Figure 1, and device is integrated dynamic response device, and reactor head is set
There are feed inlet 1, band water gas import 3 and exported with water gas, bottom is equipped with discharge port 2, and two sides are respectively equipped with heat conductive oil inlet 5
With conduction oil outlet 6；Described export with water gas is connected with one end of collection device 10, one end of the other end and cooling device 9
It is connected, the condensing unit other end is to vacuumize outlet.
Screw rod is equipped with inside the dynamic response device (7), there is the power source of coupled driving screw rod rotation in outside (such as
Motor), and then can reach the purpose of spiral charging.
The heat conductive oil inlet 5 and conduction oil outlet 6 are set to reactor two sides, and import is set to bottom.
7 top of reactor is inserted with thermocouple 8.
Heat-conducting oil heating is entered by import 3 before the reaction, and outlet 6 enters heating device, to reach circulating-heating；Trench
Oil and glycerol enter dynamic response device by injection port 1, are discharged by certain time by outlet 2；N2As band water gas by into
Mouth 3 enters dynamic response device, takes the water that reaction generates out of dynamic response device, through the condensation of condensing unit 9 by 10 collection devices time
It receives, N2It is extracted under vacuum conditions by outlet 4.
Continuous pre-esterification method:
(1) by dining room gutter oil through pre-treatments such as the removal of impurities of grease treatment plant, dehydration, deodorizations；
(2) before starting reaction, heat-conducting oil heating to 250 DEG C of dynamic response device temperature is 220 DEG C, and simultaneous reactions device persistently leads to
Enter nitrogen, for replacing the air in discharge system；
(3) to be that 150mgKOH/g gutter oil and 95% glycerol of content pass through centrifugal pump respectively for acid value after step 1) processing defeated
It mixes after the metering of warp let-off flowmeter and is injected in dynamic response device with 0.2L/min rate into dynamic response device, glycerol and ground
Ditch molar equivalent is 1:0.8, gutter oil and glycerol in the residence time 240min of dynamic response device, is excluded by discharge port.
(4) water that simultaneous reactions generate enters in water distributing can through condenser pipe is cooling, and part water is by N2It takes out of and is discharged into air
In, and then realize the glyceride product that production is obtained to the continuous pre-esterification of gutter oil superelevation.
Embodiment 2:
Continuous pre-esterification method:
(1) by hogwash fat through pre-treatments such as the removal of impurities of grease treatment plant, dehydration, deodorizations；
(2) before starting reaction, heat-conducting oil heating to 250 DEG C of dynamic response device temperature is 230 DEG C, and simultaneous reactions device persistently leads to
Enter nitrogen, for replacing the air in discharge system；
(3) to be that 80mgKOH/g gutter oil and 95% glycerol of content pass through centrifugal pump respectively for acid value after step 1) processing defeated
It mixes after the metering of warp let-off flowmeter and is injected in dynamic response device with 0.4L/min rate into dynamic response device, glycerol and ground
Ditch molar equivalent is 1:0.9, gutter oil and glycerol in the residence time 210min of dynamic response device, is excluded by discharge port.
(4) water that simultaneous reactions generate enters in water distributing can through condenser pipe is cooling, and part water is by N2It takes out of and is discharged into air
In, and then realize the glyceride product that production is obtained to the continuous pre-esterification of gutter oil superelevation.
Embodiment 3:
Continuous pre-esterification method:
(1) by dining room remaining meal oil through pre-treatments such as the removal of impurities of grease treatment plant, dehydration, deodorizations；
(2) before starting reaction, heat-conducting oil heating to 250 DEG C of dynamic response device temperature is 210 DEG C, and simultaneous reactions device persistently leads to
Enter nitrogen, for replacing the air in discharge system；
(3) to be that 30mgKOH/g gutter oil and 95% glycerol of content pass through centrifugal pump respectively for acid value after step 1) processing defeated
It mixes after the metering of warp let-off flowmeter and is injected in dynamic response device with 0.8L/min rate into dynamic response device, glycerol and ground
Ditch molar equivalent is 1:1, gutter oil and glycerol in the residence time 160min of dynamic response device, is excluded by discharge port.
(4) water that simultaneous reactions generate enters in water distributing can through condenser pipe is cooling, and part water is by N2It takes out of and is discharged into air
In, and then realize the glyceride product that production is obtained to the continuous pre-esterification of gutter oil superelevation.
Quality testing is carried out to the glyceride product produced in above-described embodiment, testing result such as table 1 meets national mark
It is quasi-.
Product quality testing result in 1 embodiment of table
Claims (8)
1. a kind of continuous pre-esterification device of gutter oil superelevation, it is characterised in that: device is integrated dynamic response device, reactor (7)
Top is equipped with feed inlet (1), band water gas import (3) and exports with water gas, and bottom is equipped with discharge port (2), and two sides are set respectively
There are heat conductive oil inlet (5) and conduction oil outlet (6)；The band water gas outlet is connected with one end of collection device (10), another
End is connected with one end of cooling device (9), and the condensing unit other end is to vacuumize outlet.
2. the continuous pre-esterification device of gutter oil superelevation according to claim 1, it is characterised in that: the heat conductive oil inlet (5)
Reactor two sides are set to conduction oil outlet (6), import is set to bottom.
3. the continuous pre-esterification device of gutter oil superelevation according to claim 1, it is characterised in that: the dynamic response device (7)
Inside is equipped with screw rod, and there is the power source of coupled driving screw rod rotation in outside.
4. the continuous pre-esterification device of gutter oil superelevation according to claim 1, it is characterised in that: reactor (7) top
It is inserted with thermocouple (8).
5. it is a kind of using claim 1 described device to the method for the continuous pre-esterification of gutter oil superelevation, it is characterised in that: will be premenstrual
The gutter oil of processing with glycerol react by the superelevation continuity under no catalyst, oxygen free condition, so that gutter oil is able to superelevation
Continuous pre-esterification.
6. the method as described in claim 5 to the continuous pre-esterification of gutter oil superelevation, it is characterised in that: will clean pretreated
Gutter oil (gutter oil forms in terms of oleic acid) and glycerol are then passed through nitrogen, and in heat medium in being uniformly mixed in device
And it is reacted under nitrogen atmosphere in 210-230 DEG C；Wherein, clean pretreated gutter oil (gutter oil forms in terms of oleic acid)
With glycerol 1:0.8-1 in molar ratio.
7. the method as described in claim 5 to the continuous pre-esterification of gutter oil superelevation, it is characterised in that: the removal of impurities pretreatment
Gutter oil and glycerol mixture injection described device in, charge velocity 0.1-1L/min, time residence time 150-
240min is reacted under heat medium and nitrogen atmosphere in 210-230 DEG C, and by-product water takes off from reaction system rapidly
From, and then realize that gutter oil is able to the continuous pre-esterification of superelevation.
8. by described in claim 5-7 to the method for the continuous pre-esterification of gutter oil superelevation, it is characterised in that: the gutter oil is
Dining room gutter oil, hogwash fat or dining room remaining meal oil, 20~180mgKOH/g of acid value of oil and fat, glycerol are that content is not less than 95wt.%
Industry glycerol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811072031.2A CN109022160A (en) | 2018-09-14 | 2018-09-14 | A kind of continuous pre-esterification method and device of gutter oil superelevation |
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| CN201811072031.2A CN109022160A (en) | 2018-09-14 | 2018-09-14 | A kind of continuous pre-esterification method and device of gutter oil superelevation |
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Citations (8)
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|---|---|---|---|---|
| US20050006290A1 (en) * | 2003-06-05 | 2005-01-13 | Patten J. P. | Mobile biodiesel refinery |
| CN101451071A (en) * | 2007-12-05 | 2009-06-10 | 青岛生物能源与过程研究所 | Biodiesel preparation method and removable production apparatus thereof |
| CN202322732U (en) * | 2011-11-23 | 2012-07-11 | 福建漳州鼎能生物科技有限公司 | Efficient biological oil reaction furnace |
| US20120240452A1 (en) * | 2011-03-23 | 2012-09-27 | Endicott Biofuels ll, LLC | Production of biodiesel fuels |
| CN103013681A (en) * | 2012-12-28 | 2013-04-03 | 北京石油化工学院 | Method for preparing fatty acid methyl ester by using waste edible oil |
| CN203890322U (en) * | 2014-03-14 | 2014-10-22 | 河南久大实业有限公司 | Glycerolysis and esterification reaction device |
| CN105038995A (en) * | 2015-08-21 | 2015-11-11 | 中国林业科学研究院林产化学工业研究所 | Non-catalytic esterification deacidification method for high-acid-value grease |
| CN105623861A (en) * | 2016-01-26 | 2016-06-01 | 浙江工业大学 | Glycerol esterification reactor |
-
2018
- 2018-09-14 CN CN201811072031.2A patent/CN109022160A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050006290A1 (en) * | 2003-06-05 | 2005-01-13 | Patten J. P. | Mobile biodiesel refinery |
| CN101451071A (en) * | 2007-12-05 | 2009-06-10 | 青岛生物能源与过程研究所 | Biodiesel preparation method and removable production apparatus thereof |
| US20120240452A1 (en) * | 2011-03-23 | 2012-09-27 | Endicott Biofuels ll, LLC | Production of biodiesel fuels |
| CN202322732U (en) * | 2011-11-23 | 2012-07-11 | 福建漳州鼎能生物科技有限公司 | Efficient biological oil reaction furnace |
| CN103013681A (en) * | 2012-12-28 | 2013-04-03 | 北京石油化工学院 | Method for preparing fatty acid methyl ester by using waste edible oil |
| CN203890322U (en) * | 2014-03-14 | 2014-10-22 | 河南久大实业有限公司 | Glycerolysis and esterification reaction device |
| CN105038995A (en) * | 2015-08-21 | 2015-11-11 | 中国林业科学研究院林产化学工业研究所 | Non-catalytic esterification deacidification method for high-acid-value grease |
| CN105623861A (en) * | 2016-01-26 | 2016-06-01 | 浙江工业大学 | Glycerol esterification reactor |
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Application publication date: 20181218 |