CN106433996A - Biodiesel esterification method - Google Patents
Biodiesel esterification method Download PDFInfo
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- CN106433996A CN106433996A CN201610904585.9A CN201610904585A CN106433996A CN 106433996 A CN106433996 A CN 106433996A CN 201610904585 A CN201610904585 A CN 201610904585A CN 106433996 A CN106433996 A CN 106433996A
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- Prior art keywords
- biodiesel
- esterification process
- liquid
- storage tank
- methanol
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention relates to the field of biodiesel, in particular to a biodiesel esterification method. The method comprises the steps of gas treating and cyclic mixing. Gas which is originally acidic in an esterification reaction is treated with alkaline liquor, proceeding of the esterification reaction is effectively promoted through multiple mixing effects, therefore, the esterification reaction time can be effectively shortened, and then the biodiesel preparation cycle can be shortened; in addition, pollution can be reduced, the cost can be reduced, and the methanol recycling rate can be increased.
Description
Technical field
The present invention relates to field of biodiesel oil, in particular to the esterification process of biodiesel.
Background technology
Biodiesel is the regenerative resource of cleaning, it using biomass resource as raw material based on one kind for processing
Diesel oil（Liquid fuel）, main chemical compositions are fatty acid methyl esters.Specifically, vegetable and animals oils, such as Oleum Brassicae campestriss, soybean oil, flower
Oil generation, Semen Maydis oil, Testa oryzae oil, Oleum Gossypii semen；And animal and vegetable oil leftover acidification oil, fatty acid；Animal oil：Adeps Sus domestica, chicken oil, duck
Oil, animal bone scalp pomade etc. are through a series of chemical conversions, and the liquid fuel for refining, is the petroleum diesel succedaneum of high-quality.Raw
Thing diesel oil is typical " green energy resource ", greatly develops biodiesel to sustainable economic development, advances energy substitution, mitigates ring
Border pressure, control urban atmospheric pollution has great strategic importance.
Existing biodiesel mainly has base catalysiss method, acid catalyzed process, lipase or biological enzyme, supercritical extraction,
It is contemplated that the factor of each side, commercially produces most employing base catalysiss method and acid catalyzed process, and in current state of China
Under feelings and current oil price, use food stage oils and fatss also unrealistic as raw material next life generation diesel oil, waste cooking oil and portion
Comparatively cost is relatively low to divide industrial oils and fatss.But, these waste greases usually contain higher free fatty, so right
First to be esterified with acid catalyzed process in these waste greases, then ester exchange reaction be carried out by base catalyst.Base catalysiss
Method and acid catalyzed process are otherwise known as chemical method.
It is accompanied by stirring in esterification reaction process to be fully contacted, accelerate response speed, guarantee to ensure methanol and oils and fatss
Reaction is complete, and under the stirring of routine, esterification needs longer time, causes to prepare the biodiesel cycle using chemical method
Longer, under convention stir, reaction time of esterification is 12 hours or so.
Mostly using phosphoric acid or sulphuric acid as catalyst in esterification process, sulphuric acid or phosphoric acid are with vapor and methanol mixed
Combination gas is formed, methanol loop system is entered, through condensing, obtaining the useless methanol acid solution that pH is 4 or so, enter back into methanol essence
Evaporate tank to separate methanol with waste liquid, the methanol after separating is continuing with, and waste liquid is discharged after treatment.But due to containing big in waste liquid
Measure sulphuric acid or phosphoric acid, belong to dangerization waste water, intractability is big, it is high to consume；While the presence of sulphuric acid causes equipment in whole process
Have high demands, each storage tank needs to use stainless steel, pump needs, with magnetic drive pump etc., to cause investment needed for engineering high；Rectification gained first
The aobvious acidity of alcohol, is not suitable for ester exchange reaction, and during rectification, methanol concentration is relatively low, and rectification is consumed greatly and methanol loss is larger, typically
For methanol in wastewater of rectification containing 5～7%.
Content of the invention
For the problems referred to above, the present invention proposes a kind of esterification process of biodiesel, can with effective process by acid, water,
The gas based on methanol, consumes and cost of investment so as to reduce production.
To achieve these goals, the technical solution adopted in the present invention is, a kind of esterification process of biodiesel includes
Circulation mixing and gas treatment.
Described gas treatment is comprised the following steps：
1. gas alkalization：The gas for discharging in reactor is sprayed using original alkali liquor, makes gas pH >=9；
2. condense：Gas after alkalization enters storage tank after being condensed；
3. dispensing：Liquid in storage tank is entered in material-compound tank and carries out mix with alkali, obtains circulation alkali liquor；
4. circulate：Original alkali liquor repeat step in replacing step 1. using circulation alkali liquor 1. 3. 1 time or repeatedly；
5. methanol rectification：After 1 time or repeatedly circulation, in liquid in storage tank during methanol content >=65wt%, liquid in storage tank is entered
Row methanol rectification, obtains methanol with waste water.
Described circulation mixing is comprised the following steps：
A Hydrodynamic cavitation：Using the reactant mixture in pump abstraction reaction kettle, it is -0.085～-0.095MPa's to enter vacuum
In vacuum environment；
B venturi reacts：The pipeline for then gradually expanding will first be shunk by one section by the reactant mixture of vacuum environment；
C penetrates oil：It is mapped in the solid target in positioned at reactor by the reactant mixture of step b.
Described reactant mixture is the material in Biodiesel esterification course of reaction in reactor.
Further, the step 1. in alkali liquor be one kind or mixing in sodium hydroxide solution or potassium hydroxide.
Further, the alkali that 3. step plants is sodium hydroxide or the one kind in potassium hydroxide or mixing.
Preferably, the step 1. the solute of middle alkali liquor and the step 3. in alkali be material of the same race, be hydroxide
One kind in sodium or potassium hydroxide.
Further, the step 3. in circulation alkali liquor pH >=10.
Preferably, the step is 5. in liquid in storage tank during methanol content >=75wt%, methanol essence is carried out to liquid in storage tank
Evaporate.
Further, in step a, the lift of pump is 40～50m.
Further, in step a, the vacuum of vacuum environment is -0.09～-0.092MPa.
Further, in step c, solid target is cone, and reactant mixture shooting centre is located at conical top.
Preferably, described vacuum environment, first shrinking the pipeline for then gradually expanding and being respectively positioned on directly over solid target.
Further, described solid target is fixed on ullage in reactor
Preferably, the solid target at institute family is located at reactor center.
The mixed gas for adopting method of the present invention to process in esterification can be with effectively solving subsequent processes
Etching problem of the middle acid as catalyst to equipment, makes the stainless steel storage tank of script be replaced by ordinary carbon steel material, incite somebody to action originally
Magnetic drive pump be replaced by conventional pumps, cost of investment is not enough the 1/5 of original cost of investment；Rectification gained methanol shows alkalescence and can be used for subsequently
Ester exchange reaction is used, and methanol tank；In rectification gained waste water for sodium sulfate with less than 1wt% methanol, be Conventional waste water,
Process convenient, cost for wastewater treatment low；After repeatedly circulating, methanol content height, rectification loss is little, and power consumption is less, while this
Invention is reacted by Hydrodynamic cavitation, venturi reacts, looped cycle is reacted and is equipped with effect of impact, can effectively accelerate reaction
Thing mixes and contacts, and its mixing benefit is significantly larger than stirring action, so as to effectively accelerate the response speed of esterification, so as to
Effectively shorten the production cycle of biodiesel, the esterification of 12 hours or so can be needed to foreshorten to 3.5 script little
When.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1：A kind of esterification process of biodiesel includes circulation mixing and gas treatment.
Described gas treatment is comprised the following steps：
1. gas alkalization：Gas is sprayed using potassium hydroxide solution, makes gas pH >=9；
2. condense：Gas after alkalization enters storage tank after being condensed；
3. dispensing：Liquid in storage tank is entered in material-compound tank and carries out mix with sodium hydroxide and potassium hydroxide, is circulated
Alkali liquor, circulation alkali liquor pH >=10；
4. circulate：Original alkali liquor repeat step in replacing step 1. using circulation alkali liquor 1. 3. 1 time；
5. methanol rectification：After 1 circulation, in liquid in storage tank during methanol content >=65wt%, methanol is carried out to liquid in storage tank
Rectification, obtains methanol with waste water.
Described circulation mixing is comprised the following steps：
A Hydrodynamic cavitation：Reactant mixture in reaction kettle of the esterification is taken using pumping of the lift for 45m, it is -0.09 to enter vacuum
In the vacuum environment of～-0.092MPa；
B venturi reacts：The pipeline for then gradually expanding will first be shunk by one section by the reactant mixture of vacuum environment；
C penetrates oil：It is mapped to by the reactant mixture of step b and ullage in reaction kettle of the esterification is fixed on, positioned at reaction kettle of the esterification
In the conical solid target at center, reactant mixture shooting centre is located at conical top.
Described vacuum environment, first shrink the pipeline for then gradually expanding and be respectively positioned on directly over solid target.
The aobvious alkalescence of methanol to be obtained through checking, in waste water, main component is sodium sulfate, methanol content is 1wt%.Ester after 3.5h
Change reaction fully reaction complete.
Embodiment 2:A kind of esterification process of biodiesel includes circulation mixing and gas treatment.
Described gas treatment is comprised the following steps：
1. gas alkalization：Mixed liquor to gas using potassium hydroxide solution with potassium hydroxide solution is sprayed, and makes gas pH
≥9；
2. condense：Gas after alkalization enters storage tank after being condensed；
3. dispensing：Liquid in storage tank is entered in material-compound tank and carries out mix with sodium hydroxide, obtains circulation alkali liquor, circulation alkali
Liquid pH >=10；
4. circulate：Original alkali liquor repeat step in replacing step 1. using circulation alkali liquor 1. 3. 3 times；
5. methanol rectification：After 3 circulations, in liquid in storage tank during methanol content >=75wt%, methanol is carried out to liquid in storage tank
Rectification, obtains methanol with waste water.
Described circulation mixing is comprised the following steps：
A Hydrodynamic cavitation：Reactant mixture in reaction kettle of the esterification is taken using pumping of the lift for 50m, enter vacuum for-
In the vacuum environment of 0.085～-0.09MPa；
B venturi reacts：The pipeline for then gradually expanding will first be shunk by one section by the reactant mixture of vacuum environment；
C penetrates oil：It is mapped in the solid target in positioned at reaction kettle of the esterification by the reactant mixture of step b.
In step c, solid target is cone, and reactant mixture shooting centre is located at conical top, described vacuum ring
Border, first shrink the pipeline for then gradually expanding and be respectively positioned on directly over reaction kettle of the esterification, described solid target is fixed in reactor
Ullage, be located at reaction kettle of the esterification center.
The aobvious alkalescence of methanol to be obtained through checking, in waste water, main component is sodium sulfate, methanol content is 0.8wt%.3.6h after
Esterification reaction is complete.
Embodiment 3：A kind of esterification process of biodiesel includes circulation mixing and gas treatment.
Described gas treatment is comprised the following steps：
1. gas alkalization：Gas is sprayed using sodium hydroxide solution, makes gas pH >=9；
2. condense：Gas after alkalization enters storage tank after being condensed；
3. dispensing：Liquid in storage tank is entered in material-compound tank and carries out mix with sodium hydroxide, obtains circulation alkali liquor, circulation alkali
Liquid pH >=10；
4. circulate：Original alkali liquor repeat step in replacing step 1. using circulation alkali liquor is 1. 3. multiple；
5. methanol rectification：After repeatedly circulating, in liquid in storage tank during methanol content >=75wt%, first is carried out to liquid in storage tank
Alcohol rectification, obtains methanol with waste water.
Described circulation mixing is comprised the following steps：
A Hydrodynamic cavitation：Reactant mixture in esterification process reactor is taken using pumping of the lift for 40m, enter vacuum for-
In the vacuum environment of 0.085～-0.09MPa；
B venturi reacts：The pipeline for then gradually expanding will first be shunk by one section by the reactant mixture of vacuum environment；
C penetrates oil：It is mapped in the solid target in positioned at esterification process reactor by the reactant mixture of step b.
In step c, solid target is cone, and reactant mixture shooting centre is located at conical top, described vacuum ring
Border, first shrink the pipeline for then gradually expanding and be respectively positioned on directly over esterification process reactor, described solid target is fixed on reaction
Ullage in kettle, it is located at esterification process reactor center.
The aobvious alkalescence of methanol to be obtained through checking, in waste water, main component is sodium sulfate, methanol content is 0.5wt%.3.3h
Afterwards, esterification is completed.
Embodiment 4：With 3 basic simlarity of embodiment, its difference is：Sodium hydroxide is replaced using potassium hydroxide.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for the skill of this area
For art personnel, can there are various modifications and variations in the spirit and principles in the present invention, the modification of these equivalents or replacement etc.,
It is all contained within protection scope of the present invention.
Claims (10)
1. a kind of esterification process of biodiesel, mixes including circulation and gas treatment, it is characterised in that：
Described gas treatment is comprised the following steps：
1. gas alkalization：The gas for discharging in reactor is sprayed using original alkali liquor, makes gas pH >=9；
2. condense：Gas after alkalization enters storage tank after being condensed；
3. dispensing：Liquid in storage tank is entered in material-compound tank and carries out mix with alkali, obtains circulation alkali liquor；
4. circulate：Original alkali liquor repeat step in replacing step 1. using circulation alkali liquor 1. 3. 1 time or repeatedly；
5. methanol rectification：After 1 time or repeatedly circulation, in liquid in storage tank during methanol content >=65wt%, liquid in storage tank is entered
Row methanol rectification, obtains methanol with waste water；
Described circulation mixing is comprised the following steps：
A Hydrodynamic cavitation：Using the reactant mixture in pump abstraction reaction kettle, it is -0.085～-0.095MPa's to enter vacuum
In vacuum environment；
B venturi reacts：The pipeline for then gradually expanding will first be shunk by one section by the reactant mixture of vacuum environment；
C penetrates oil：It is mapped in the solid target in positioned at reactor by the reactant mixture of step b；
Described reactant mixture is the material in Biodiesel esterification course of reaction in reactor.
2. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：The step 1. in alkali liquor
For the one kind in sodium hydroxide solution or potassium hydroxide or mixing.
3. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：The alkali that 3. step plants is
One kind or mixing in sodium hydroxide or potassium hydroxide.
4. the esterification process of a kind of biodiesel according to Claims 2 or 3, it is characterised in that：The step 1. middle alkali
The solute of liquid and the step 3. in alkali be material of the same race, be sodium hydroxide or the one kind in potassium hydroxide.
5. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：The step 3. in circulation
Alkali liquor pH >=10.
6. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：The step is 5. in storage tank liquid
In body during methanol content >=75wt%, methanol rectification is carried out to liquid in storage tank.
7. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：In step a, pump raises
Journey is 40～50m.
8. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：Vacuum ring in step a
The vacuum in border is -0.09～-0.092MPa.
9. the esterification process of a kind of biodiesel according to claim 1, it is characterised in that：Solid target in step c
For cone, reactant mixture shooting centre is positioned at conical top.
10. the esterification process of a kind of biodiesel according to claim 1 or 8 or 9, it is characterised in that：Described vacuum
Environment, first shrink the pipeline for then gradually expanding and be respectively positioned on directly over solid target, described solid target is fixed on liquid in reactor
Above face.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610904585.9A CN106433996A (en) | 2016-10-18 | 2016-10-18 | Biodiesel esterification method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610904585.9A CN106433996A (en) | 2016-10-18 | 2016-10-18 | Biodiesel esterification method |
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| CN106433996A true CN106433996A (en) | 2017-02-22 |
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| CN201610904585.9A Pending CN106433996A (en) | 2016-10-18 | 2016-10-18 | Biodiesel esterification method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995288A (en) * | 2006-12-25 | 2007-07-11 | 昆明理工大学 | Process for preparing biodiesel oil |
| CN101376818A (en) * | 2008-10-09 | 2009-03-04 | 济南大学 | Method for preparing biodiesel by synergic ion liquid catalysis under cavitation effect |
-
2016
- 2016-10-18 CN CN201610904585.9A patent/CN106433996A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995288A (en) * | 2006-12-25 | 2007-07-11 | 昆明理工大学 | Process for preparing biodiesel oil |
| CN101376818A (en) * | 2008-10-09 | 2009-03-04 | 济南大学 | Method for preparing biodiesel by synergic ion liquid catalysis under cavitation effect |
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Application publication date: 20170222 |