CN101314719B - Method for preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst - Google Patents
Method for preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst Download PDFInfo
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- CN101314719B CN101314719B CN2008100223235A CN200810022323A CN101314719B CN 101314719 B CN101314719 B CN 101314719B CN 2008100223235 A CN2008100223235 A CN 2008100223235A CN 200810022323 A CN200810022323 A CN 200810022323A CN 101314719 B CN101314719 B CN 101314719B
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
A method for catalytically preparing bio-diesel by using tandem double fixed beds and solid catalyst comprises the following steps: selecting animal or vegetable oil exceeding acid value, fatty acid or neutral oil as the raw material, pre-reacting in a bed filled with solid acid to rapidly lower the acid value of the raw material oil, and adding into a bed filled with solid base catalyst to achieve high-efficiency transesterification reaction. Accordingly, high-purity bio-diesel can be obtained by double-bed catalysis adopting the pre-reaction, double-bed catalysis and once transesterification processes and adopting parallel-flow feeding and bed pressure manner to improve mass transfer. Meanwhile, the glycerol phase in the product can be easily separated and can be purified by vacuum rectification to obtain fine glycerol with purity above 98.5 percent, thus improving the use value of the product. The method has the advantages of wide materials, environment-friendly process, efficient product utilization, low investment cost, bright industrial future, etc.
Description
Technical field
The invention of this reality relates to the biochemical industry technical field of new energies, relates to a kind of processing method of utilizing series double-fixed bed solid acid, alkaline catalysts catalysis lipid acid, super acid value animal-plant oil and neutral grease to prepare biofuel specifically.
Background technology
Biofuel (biodiesel) is a kind of liquid fuel that is obtained through transesterification reaction by vegetables oil, animal grease and fatty single methanol, its performance is similar to petrifaction diesel, be better than petrifaction diesel at aspects such as sulphur content, flash-point, biological degradability, aromatic hydrocarbon content, cetane value, biofuel can be mixed with arbitrary proportion with petrifaction diesel simultaneously, makes the biofuel propellant combination.On the other hand, biofuel is mainly elementary composition by C, H, three kinds of O, and product is H in the time of the burning release of heat
2O and CO
2, environmental protection.
The preparation method of biofuel has a lot, divides physics method and chemical method substantially, and the main stream approach of industrial production biofuel is the ester-interchange method in the chemical method at present, and it comprises: homogeneous catalysis method, heterogeneous catalysis method, biological enzyme and supercritical methanol technology.Report adopts sulfuric acid or Phenylsulfonic acid to make biodiesel in CN 132762A and the CN 1412278A patent, though this type of catalyzer does not have particular requirement to the free acid content in the stock oil, but liquid acid corrosive equipment, the postprocessing working procedures complexity, produce a large amount of waste water, contaminate environment and increase processing cost.Prepare biofuel at the document vegetables oil. Wu Guoying etc. Jiangsu Petrochemical Engineering College journal .2002,14 (13): report in 8～11, use liquid alkali catalyst (as KOH, NaOH etc.) preparation biofuel, but the easy saponification of product that obtains of method thus, catalyzer be difficult reclaims, washing produces a large amount of contaminated wastewater environment, and it is neutral grease that the homogeneous phase base-catalyzed method requires raw material, has so also limited raw material sources.Report utilizes lipase to make the catalyzer fixed catalytic to prepare biofuel in patent CN1818026, though the reaction conditions gentleness, can produce continuously, it is short that the life-span is easily poisoned, react to biological enzyme, so also very difficult large-scale commercial production of method.In patent CN 1594504A, report, adopt supercritical process to prepare biofuel, also higher relatively to the requirement of conversion unit though the reaction times is short, transformation efficiency is high, increase production cost.
Thereby fixed-bed reactor can be efficiently, all evenly continuous reactant and catalyzer in the fixed bed are fully contacted react; What fill in the fixed bed is solid catalyst, water resisting property strong, active high, easily recycle and reuse, the nonpollution environment close friend, and the stock oil source is in extensive range, the restriction of acid and alkali value; Fixed-bed reactor can be with pressure work among the present invention, have both increased temperature of reaction and pressure, so also are conducive to heterogeneous mass transfer, thereby and mild condition, plant factor height improved continuous production efficiency, reduced cost.
Summary of the invention
Technical problem: the defective that the objective of the invention is to prepare at existing ester exchange method biofuel, a kind of method of preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst is provided, not only enlarged the source range that comes of stock oil, also simplified simultaneously technological process, improved production efficiency, the catalyzer long service life, be easy to reclaiming, pollution-free, environmental friendliness.
Technical scheme: concrete steps of the present invention are as follows:
(1) stock oil is contained in the different containers with low-carbon alcohol (as methyl alcohol), is pumped in the preheater by weldless steel tube in the certain flow ratio by two volume pumps, the stock oil that pumps into and low-carbon alcohol mole ratio are 1: 3～16.
(2) after reactant mixes by the preheater preheating, enter the fixed bed of loading solid acid catalyst and contact with solid acid after the moulding, heterogeneous reaction takes place, thereby make the acid number of the free fatty acids esterification reduction stock oil in the stock oil.Temperature of reaction control exists: 50 ℃～180 ℃, i.e. the corresponding control of reaction pressure exists:
0.1Mp～2Mp。
(3) enter the fixed bed of loading solid base catalyst through pretreated raw material, contact with solid base catalyst after the moulding, transesterification reaction takes place, thereby obtain biofuel (as fatty acid methyl ester) and glycerol mixture.Temperature of reaction control exists: 50 ℃～180 ℃, i.e. the corresponding control of reaction pressure exists: 0.1Mp～2Mp.
(4) final product is flowed out by the throttle control of alkaline fixed bed lower end.Thereby can utilize the not mutual solubility of biofuel and glycerine and density different in another container standing demix tell glycerine, after directly upper strata material (biofuel and methyl alcohol) is pumped in the rectifying tower by volume pump, boiling-point difference by its material is pressed separation unusually, can get following material behind condenser: the cat head discharging is reaction back remaining low-carbon alcohol (as methyl alcohol), purer biofuel (content is higher than 99%) is flowed out by the tower middle part collects, and is the finished product.
The excessive low-carbon alcohol of (5) fractionation recovered overhead directly passes back into cycling and reutilization in the raw material storage container, and separation column bottom is collected unreacted grease or high boiling other impurity and carried out recycling after the removal of impurities.
Above-mentioned 5 steps are that raw material constantly is pumped to fixed-bed reactor, the continuous production technology process of discharging in the continuous slave unit of product.
In step (1), described stock oil is lipid acid, super acid value oil (catering industry waste oil, oil alkali refining soap stock), neutral grease (various animal grease such as tung oil, Viscotrol C, sweet oil, rapeseed oil, soybean oil, oleum lini, peanut oil, Semen Maydis oil, plam oil, Oleum Gossypii semen, tea-seed oil, engineering algae grease, fish oil, lard, butter), and low-carbon alcohol is methyl alcohol or ethanol.
Beneficial effect: the method for utilization of the present invention " series double-fixed bed and catalysis of solid catalyst " prepares biofuel, can be suitable for various neutrality and super acid value oil, has enlarged the source range that comes of stock oil; Series connection double bed catalysis of solid catalyst is when having improved production efficiency, can simplify original production technique, namely reduced cost, eliminated pollution section again, prolong catalyzer work-ing life, be easy to reclaiming, surplus stock again can recycle, has remarkable economical, society, environmental benefit, has a extensive future.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Have among the figure: methyl alcohol storage tank 1; Glyceride stock storage tank 2; Methyl alcohol volume pump 3; Grease volume pump 4; Pre-mixing well heater 5; Fixed bed 6; Solid acid catalyst 7; Solid base catalyst 8; Pressure regulation throttling valve 9; Standing demix device 10; Volume pump 11; Raw glycerine storage tank 12; Separation column 13; Condenser 14; Biofuel storage tank 15; Column bottoms pump 16; Reclaim methyl alcohol storage tank 17; Volume pump 18;
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments, and embodiment is not limited.
Embodiment 1: the Oleum Gossypii semen that with the acid number is 1.94mgKOH/g is the feedstock production biofuel,
(1) Oleum Gossypii semen and methyl alcohol are contained in methyl alcohol storage tank 1 respectively; In the glyceride stock storage tank 2, with the flow of 9.75mL/min Oleum Gossypii semen is pumped into pre-mixing well heater 5 by weldless steel tube with grease volume pump 4, using another methyl alcohol volume pump 3 simultaneously is that 12: 1 flow velocity together pumps into methyl alcohol in the pre-mixing well heater 5 to react initial material molar ratio of methanol to oil.The preheater temperature is controlled to be 60 ℃.
(2) reactant enters later the fixed bed 6 of loading the self-control solid acid catalyst by preheater preheating and mixing and contacts the generation heterogeneous reaction with solid acid catalyst 7, thereby makes the acid number of the free fatty acids esterification reduction stock oil in the stock oil.Temperature of reaction control is at 95 ℃, i.e. the corresponding control of reaction pressure is at 0.7Mp.
(3) enter the fixed bed 6 of loading solid base catalyst through pretreated raw material, contact with solid base catalyst after the moulding 8, transesterification reaction takes place, obtain biofuel and glycerol mixture.Temperature of reaction control is at 95 ℃, i.e. the corresponding control of reaction pressure is at 0.7Mp.
(4) final product is flowed out by pressure regulation throttling valve 9 controls of alkaline fixed bed lower end.Thereby utilize the not mutual solubility of biofuel and glycerine and density different in another standing demix device 10 standing demix tell glycerine, after directly upper strata material (biofuel and methyl alcohol) is pumped in the separation column 13 by volume pump 11, boiling-point difference by its material is pressed separation unusually, can get following material after condenser 14 condensations: the cat head discharging is the remaining methyl alcohol in reaction back, biofuel is flowed out by the tower middle part and is collected into biofuel storage tank 15, is the finished product.Content through the gas chromatographic detection biofuel is higher than 99%, and the yield that gets biofuel after the calculating of simultaneously product being weighed is 92%.
The direct blowback of excessive low-carbon alcohol of (5) fractionation recovered overhead cycling and reutilization to the glyceride stock storage tank 2, separation column bottom are collected unreacted grease or high boiling other impurity and are carried out recycling after the removal of impurities.Embodiment 2: the discarded edible oil that with the acid number is 38mgKOH/g is the feedstock production biofuel
(1) will discard edible oil and methyl alcohol and be contained in methyl alcohol storage tank 1 respectively; In the glyceride stock storage tank 2, with the flow of 15.3mL/min Oleum Gossypii semen is pumped into pre-mixing well heater 5 by weldless steel tube with grease volume pump 4, using another methyl alcohol volume pump 3 simultaneously is that 15: 1 flow velocity together pumps into methyl alcohol in the pre-mixing well heater 5 to react initial material molar ratio of methanol to oil.The preheater temperature is controlled to be 60 ℃.
(2) reactant enters later the fixed bed 6 of loading the self-control solid acid catalyst by preheater preheating and mixing and contacts the generation heterogeneous reaction with solid acid catalyst 7, thereby makes the acid number of the free fatty acids esterification reduction stock oil in the stock oil.Temperature of reaction control is at 120 ℃, i.e. the corresponding control of reaction pressure is at 1Mp.
(3) enter the fixed bed 6 of loading solid base catalyst through pretreated raw material, contact with solid base catalyst after the moulding 8, transesterification reaction takes place, obtain biofuel and glycerol mixture.Temperature of reaction control is at 120 ℃, i.e. the corresponding control of reaction pressure is at 1Mp.
(4) final product is flowed out by pressure regulation throttling valve 9 controls of alkaline fixed bed lower end.Thereby utilize the not mutual solubility of biofuel and glycerine and density different in another standing demix device 10 standing demix tell glycerine, after directly upper strata material (biofuel and methyl alcohol) is pumped in the separation column 13 by volume pump 11, boiling-point difference by its material is pressed separation unusually, can get following material after condenser 14 condensations: the cat head discharging is the remaining methyl alcohol in reaction back, biofuel flows out collection of biological diesel oil tank 15 by the tower middle part, is the finished product.Content through the gas chromatographic detection biofuel is higher than 99%, and the yield that gets biofuel after the calculating of simultaneously product being weighed is 88%.
The direct blowback of excessive low-carbon alcohol of (5) fractionation recovered overhead cycling and reutilization to the glyceride stock storage tank 2, separation column bottom are collected unreacted grease or high boiling other impurity and are carried out recycling after the removal of impurities.
Embodiment 3: the plam oil that with the acid number is 13mgKOH/g is the feedstock production biofuel
(1) plam oil and methyl alcohol are contained in methyl alcohol storage tank 1 respectively; In the glyceride stock storage tank 2, with the flow of 21.3mL/min Oleum Gossypii semen is pumped into pre-mixing well heater 5 by weldless steel tube with grease volume pump 4, using another methyl alcohol volume pump 3 simultaneously is that 12: 1 flow velocity together pumps into methyl alcohol in the pre-mixing well heater 5 to react initial material molar ratio of methanol to oil.The preheater temperature is controlled to be 60 ℃.
(2) reactant enters later the fixed bed 6 of loading solid acid catalyst by preheater preheating and mixing and contacts the generation heterogeneous reaction with solid acid catalyst 7, thereby the free fatty acids esterification in the stock oil is reduced acid number.Temperature of reaction control is at 100 ℃, i.e. the corresponding control of reaction pressure is at 0.8Mp.
(3) enter the fixed bed 6 of loading solid base catalyst through pretreated raw material, contact with solid base catalyst after the moulding 8, transesterification reaction takes place, obtain biofuel and glycerol mixture.Temperature of reaction control is at 100 ℃, i.e. the corresponding control of reaction pressure is at 0.8Mp.
(4) final product is flowed out by pressure regulation throttling valve 9 controls of alkaline fixed bed lower end.Thereby utilize the not mutual solubility of biofuel, low-carbon alcohol and glycerine and density different in another standing demix device 10 standing demix tell glycerine, after directly upper strata material (biofuel and methyl alcohol) is pumped in the separation column 13 by volume pump 11, boiling-point difference by its material is pressed separation unusually, can get following material after condenser 14 condensations: the cat head discharging is the remaining methyl alcohol in reaction back, biofuel flows out collection of biological diesel oil tank 15 by the tower middle part, is the finished product.Content through the gas chromatographic detection biofuel is higher than 98%, and the yield that gets biofuel after the calculating of simultaneously product being weighed is 90%.
The direct blowback of excessive low-carbon alcohol of (5) fractionation recovered overhead cycling and reutilization to the glyceride stock storage tank 2, separation column bottom are collected unreacted grease or high boiling other impurity and are carried out recycling after the removal of impurities.
Claims (3)
1. the method for a preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst is characterized in that this method may further comprise the steps:
A. stock oil and low-carbon alcohol are contained in the different containers, are pumped into respectively in the preheater in proportion by two volume pumps, the stock oil that pumps into and the mole ratio of low-carbon alcohol are 1:3 ~ 16,
B. stock oil with enter the fixed bed of loading solid acid catalyst after low-carbon alcohol is mixed by the preheater preheating, heterogeneous reaction takes place, thereby makes free fatty acids esterification in the stock oil reduce the acid number of stock oil; Temperature of reaction control exists: 50 ℃ ~ 180 ℃, the corresponding control of reaction pressure exists: 0.1Mp ~ 2Mp,
C. enter the fixed bed of loading solid base catalyst through the pretreated raw material of step b, obtain biofuel and the glycerol mixture that major ingredient is fatty acid methyl ester thereby transesterification reaction takes place; Temperature of reaction control exists: 50 ℃ ~ 180 ℃, the corresponding control of reaction pressure exists: 0.1Mp ~ 2Mp,
D. utilize the different of the not mutual solubility of biofuel and glycerine and density, standing demix is told glycerine in container, then direct biofuel and part methyl alcohol with the upper strata is pumped in the separation column by volume pump, boiling-point difference by its material is pressed separation unusually, can get following material behind condenser: the cat head discharging is the remaining low-carbon alcohol in reaction back, purer product biofuel is flowed out by the tower middle part collects, and tower bottom is collected unreacted grease or high boiling other impurity; The low-carbon alcohol of cat head discharging directly passes back into cycling and reutilization in the raw material storage container, and separation column bottom is collected unreacted grease or high boiling other impurity and carried out recycling after the removal of impurities.
2. according to the method for right 1 described preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst, it is characterized in that: the temperature of preheater exists with the control of bed main body temperature of reaction: 50 ℃ ~ 120 ℃.
3. according to the method for right 1 described preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst, it is characterized in that: described stock oil is lipid acid, super acid value oil or neutral grease.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100223235A CN101314719B (en) | 2008-07-09 | 2008-07-09 | Method for preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst |
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| CN2008100223235A CN101314719B (en) | 2008-07-09 | 2008-07-09 | Method for preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010792B (en) * | 2010-12-15 | 2012-08-22 | 东南大学 | Continuous production method of biodiesel |
| CN102250694A (en) * | 2011-06-20 | 2011-11-23 | 南昌大学 | Method for producing biofuel from high-acid-value Comus wilsoniana fruit oil under co-catalysis of solid acid and solid base |
| CN102250695A (en) * | 2011-06-23 | 2011-11-23 | 南昌大学 | Method for continuously converting oil into fatty acid short chain alcohol ester |
| CN102533309B (en) * | 2012-01-18 | 2014-05-21 | 浙江工业大学 | Biodiesel rectifying tower provided with multiple vaporization layers |
| CN103805343A (en) * | 2012-11-12 | 2014-05-21 | 中国科学院大连化学物理研究所 | Method for continuously producing biodiesel by using two segments of fixed beds |
| CN105462692A (en) * | 2014-08-20 | 2016-04-06 | 丰益(上海)生物技术研发中心有限公司 | Biodiesel preparation method |
| CN104560226A (en) * | 2014-11-04 | 2015-04-29 | 华文蔚 | Preparation method of biodiesel |
| CN104830541B (en) * | 2015-04-28 | 2018-04-17 | 广东河山环保有限公司 | A kind of heterogeneous catalysis esterification prepares the apparatus and method of biodiesel |
| CN109433146A (en) * | 2018-12-06 | 2019-03-08 | 北京航天试验技术研究所 | A kind of continuous catalysis annulation device |
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