CN1900223A - Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor - Google Patents
Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor Download PDFInfo
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- CN1900223A CN1900223A CNA2006100364198A CN200610036419A CN1900223A CN 1900223 A CN1900223 A CN 1900223A CN A2006100364198 A CNA2006100364198 A CN A2006100364198A CN 200610036419 A CN200610036419 A CN 200610036419A CN 1900223 A CN1900223 A CN 1900223A
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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
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Abstract
The present invention is process of continuously producing biological diesel oil with solid acid catalyst and plug flow reactor. The process includes the following steps: 1. pre-esterification of well mixed material oil and methanol in a solid packed bed reactor filled with solid acid catalyst; 2. ester interchange reaction of the pre-esterified materials inside a tubular plug flow reactor to produce biological diesel oil and by product glycerin; and 3. separation. The present invention has wide applicable material oil range, waste utilization, environment friendship and other advantages.
Description
Technical field
The invention belongs to chemical technology field, especially a kind of employing solid acid catalyst and plug flow reactor continuous production method of bio-diesel oil.
Technical background
Biofuel is typical green, renewable energy source, has safety, anti-knocking property are good, premium propertiess such as sufficient combustion.Begun the suitability for industrialized production of biofuel both at home and abroad, adopt the homogeneous catalysis ester-interchange method mostly, promptly liquid catalyst is (as the vitriol oil or NaOH, KOH), make glycerin fatty acid ester and methyl alcohol generation transesterification reaction generate fatty acid methyl ester (biofuel) and glycerine, but all have a lot of shortcomings.And, the activity of the free acid infringement basic catalyst in the stock oil.Though liquid acid catalyst does not have particular requirement to the moisture and the free acid content of stock oil, it has corrodibility, and is very high to equipment requirements, and methyl alcohol is difficult to separate with by-product glycerin after the reaction end, and cost is risen.In addition, adopt liquid acid, in last handling process, can discharge large amount of sewage, cause environmental pollution as catalyzer.
With the solid acid resin catalyst free acid in the raw material is carried out pre-esterification,, can avoid acid solution to reclaim, separate, and simplify technology as transesterification catalyst production biofuel with alkaline catalysts, help the recovery, multiplexing of catalyzer, become the focus that people pay close attention to.Solid acid catalyst is formed difference by it and is broadly divided into five big classes: heteropoly acid type, inorganic acid salt, metal oxide and mixture thereof, zeolite molecular sieve and Zeo-karb.Can be divided into four grades according to its strength of acid difference: weak acid, middle strong acid, strong acid and super acids.Traditional an acidic catalyst is mineral acid and Lewis acid mostly, these catalyzer not only use up aftertreatment get up cumbersome, equipment is had corrosive nature, and the discharging of spent acid causes severe contamination to environment.Amberlyst 15 belongs to bronsted acid, and its acid sites combines with skeleton structure as a substituting group, and its strength of acid is that the acid matter of acidic-group is (as-SO
3H＞-COOH) and the decision of the characteristic electron of skeleton, the increase of acidic-group can make the intensity of preferential H migration increase.The contrast experiment shows that Nation-H is equivalent to 85% sulfuric acid, the strength of acid of Amberlyst 15 is equivalent to 60% sulfuric acid, far below the strength of acid of 80% trimethylammonium sulfonic acid, this be because the solid rockiness hindered acid sites with the H migration in cooperate.That polymer catalyst has is easy to use, environmental friendliness, be advantage such as zero to equipment corrosion, caused domestic and international chemical industry and catalyzer expert's special concern.
Simultaneously, prior art overwhelming majority biofuel chemical production processes is all carried out the conversion of biofuel with tank reactor, be unfavorable for the serialization production of biofuel.Though have pair continuous production method of bio-diesel oil to conduct a research at present, adopt solid acid catalyst continuous production method of bio-diesel oil not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of employing solid acid catalyst and plug flow reactor combination producing method of bio-diesel oil,, realize the continuous production of biofuel to overcome the defective of prior art.
The inventive method comprises the steps:
(1) pre-esterification reactor process
After stock oil and methyl alcohol thorough mixing in mixing tank is even, enter the pre-esterification reactor device by volume pump.The pre-esterification reactor device is a fixing packed bed reactor, is filled with solid acid catalyst in the reactor.Finish pre-esterification reactor through pretreated stock oil at fixed-bed reactor, remove free fatty acids (Free Fatty Acid), for ester-exchange reaction is prepared.
The inventive method to stock oil without limits, vegetables oil or all can be used as stock oil and use through coming unstuck, take off sewer oil, frying oil, oil leftover that soap, glue look handle.
Described reaction conditions is: methyl alcohol is 4-6% to the weight ratio of raw material, the fixed bed interior reaction temperature is 50-62 ℃, catalyst system therefor is a solid acid catalyst, loaded catalyst fixed bed volumetrical 1/3 to 2/3, and the reaction times of stock oil in the pre-esterification reactor device is 0.5-1 hour;
Described solid acid catalyst is preferably Amberlyst-15, and all the other solid acid catalysts commonly used also can use, for example Nation H type resin, Amberlite IR 120, zirconium sulfate (Zr (SO
4)
24H
2O) etc.
(2) ester-exchange reaction
Stock oil anhydrous methanol is back with the basic catalyst mixing and the process pre-esterification reactor pumps into and enters the tubular type plug flow reactor in the mixing tank behind the thorough mixing.Transesterification generation biofuel and by-product glycerin are taking place between tri-glyceride and the methyl alcohol under the basic catalyst katalysis.
The feature of this step is that transesterification reactor is a plug flow reactor, and reaction conditions is: temperature of reaction 50-62 ℃, methyl alcohol was to the mol ratio of raw material 4: 1 to 6: 1, reaction times 20-40 minute.
Described basic catalyst can be sodium methylate or other basic catalysts commonly used.
(3) sepn process
Reaction product makes the biofuel product through glycerine, water, methyl alcohol after separating.
Sepn process can be: reaction product is earlier through a biodiesel/glycerin phase splitter separation of glycerin, again through a washing phase splitter, and residual methyl alcohol in the separating bio diesel oil, impurity such as KOH.And then enter rectifying tower and obtain purified biofuel product.
Stock oil of the present invention is applied widely, can realize utilization of waste material, and has solved environmental issue.Can realize the continuous production of biofuel, owing to adopt solid acid catalyst and plug flow reactor to unite the method for use, the speed of response of having avoided using single acid catalyst to cause is slow, and the problems such as adaptability to raw material difference of using single alkaline catalysts to bring.Thereby combine the advantage of acid system and alkaline process effectively, avoided shortcoming separately.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
The raw material that present embodiment adopts is a vegetables oil or through coming unstuck, take off the sewer oil that soap, glue look are handled, and describedly comes unstuck, takes off soap and the decoloration process process is:
Come unstuck: (1) is heated to 70 ℃ with waste grease, and adding oil, to weigh 3% concentration be 50% citric acid, and uniform mixing 5 minutes is cooled to 25 ℃.(2) add oil and weigh 50 ℃ of hot water of 3%, the 90rpm rotating speed stirred 1 hour down, changed 30rpm rotating speed slow-speed 1 hour, 65 ℃ leave standstill 12 hours after, get supernatant fluid.
Take off soap: (1) joins the heavy water of 20% oil in the oil, and 85 ℃, 60rpm stirred 0.5 hour, leaves standstill, and separatory is removed the water of lower part and saponified.(2) with the oil of alkali refining under strong mixing 90-95rpm, the concentration that adds the heavy 3%-5% of oil is that 10% citric acid solution mixed 5 minutes.
Decolouring: add oil and weigh 12% carclazyte, at 105 ℃, 90rpm stirs decompression decolouring in 30 minutes fast under the 0.02MPa condition.The solids removed by filtration residue can repeat repeatedly.
As shown in Figure 1: the stock oil in the material tank 1 enters strainer 4 through pump 2 and under meter 3, enters mixing tank 7 again.Temperature in the mixing tank 7 is 50 ℃.Methyl alcohol in the methyl alcohol storage tank 5 enters mixing tank 7 through electromagnetic dosing pump 6 simultaneously.Stock oil in the mixing tank 7 and methanol mixture enter stirred reactor 8 again, and in whipping process, the methyl alcohol that may overflow is back in 8 through vertical (type) condenser 9.Raw material that comes out from stirred reactor and carbinol mixture are through oil pump 10, and under meter 11 and preheater 12 enter in the fixed-bed reactor 13, carry out the pre-esterification of free acid in the raw material.Reaction conditions in the fixed bed is: methyl alcohol is 4-6% to the weight ratio of raw material.The fixed bed interior reaction temperature is 50-62 ℃, and catalyst system therefor is Amberlyst 15 resins or other solid acid catalyst, and loaded catalyst is a Solid Bed volumetrical 1/3 to 2/3.The reaction times of stock oil in reactor 13 is 0.5-1 hour.The oil of the pre-esterification of warp of coming out from reactor 13 enters mixing tank 16 again.Simultaneously, the KOH/ methanol solution in the KOH/ methanol tank 14 enters mixing tank 16 through volume pump 15.The add-on of KOH is by 1% calculating of handling oil mass in the KOH/ methanol tank 14, and the methyl alcohol flow is by 6: 1 to calculate at 4: 1 by the mol ratio with stock oil.The pre-esterification feed oil, the methyl alcohol/KOH solution that come out from mixing tank 16 enter plug flow reactor 17.Reaction conditions in plug flow reactor is: temperature of reaction 50-62 ℃, methyl alcohol was to the mol ratio of raw material 4: 1 to 6: 1, reaction times 20-40 minute.Biofuel that generates in plug flow reactor and glycerine enter glycerin separator 18, and isolated glycerine enters glycerine holding tank 19, and coarse biodiesel enters holding tank 20.Coarse biodiesel comes out from holding tank 20, enters washed reaction device 27 through oil pump 21 and under meter 22.Be used for neutral phosphoric acid simultaneously and enter heating tank 26 through water pump 24 through storage tank 25 and the water that is used to wash, after heating tank is heated to 50 ℃, enter stirred pot 27, mix with the coarse biodiesel after the separation of glycerin, after washing 5 minutes therein, enter water/biofuel phase splitter 28, isolated water enters water lotion holding tank 29, and the thick methyl esters of isolated biofuel enters thick methyl esters holding tank 30.The washing water yield generally is controlled at about 30% of oil mass; The KOH that uses in the complete neutralization reaction of acetic acid add-on need energy.Methyl esters in the thick methyl esters holding tank 30 enters rectifying tower through oil pump again and carries out the refining of product, makes standard compliant biofuel.
Be used to realize that the device of method of the present invention comprises:
A material tank 1 is used to hold stock oil;
A strainer 4 is used for the raw material oil filtration;
A methyl alcohol storage tank 5 is used for holding the methyl alcohol that reaction process is used;
A mixing tank 7 is used for the well blend of stock oil and methyl alcohol;
A stirred reactor 8 is used for the first of stock oil and methyl alcohol and mixes;
A vertical methanol condensed return channel 9 is used for the condensing reflux of methyl alcohol;
A pre-heaters 12 is used for preheating of stock oil/methyl alcohol;
3 fixed-bed reactor 13 are used for the pre-esterification of stock oil free acid;
A KOH/ methanol tank 14 is used to hold the methanol solution of KOH;
A plug flow reactor 17 is used for the transesterification reaction under the alkaline catalysts effect;
A continuous phase splitter 18 is used for biofuel and the continuous of glycerine separates;
A glycerine storage tank 19 is used for the storage of isolated glycerine;
A coarse biodiesel storage tank 20 is used for the storage of the coarse biodiesel after glycerine separates;
A phosphoric acid storage tank 25 is used for providing the neutralized crude biofuel a spot of alkali;
A water heating tank 26, the heating that is used to wash water;
A water washing tank 27 is used for the washing of the biofuel after glycerine separates;
A water phase splitter 28 is used for separating biofuel after the washing and water;
A water lotion storage tank 29 is used for the storage of biofuel water lotion;
A thick methyl esters storage tank 30 is used for separating and washing through glycerine the storage of artifact diesel oil;
Claims (4)
1, a kind of employing solid acid catalyst and plug flow reactor continuous production method of bio-diesel oil comprise the steps:
(1) pre-esterification reactor process
After stock oil and methyl alcohol thorough mixing are even, enter the pre-esterification reactor device by volume pump, the pre-esterification reactor device is a fixing packed bed reactor, reaction conditions is: methyl alcohol is 4-6% to the weight ratio of raw material, the fixed bed interior reaction temperature is 50-62 ℃, catalyst system therefor is a solid acid catalyst, loaded catalyst fixed bed volumetrical 1/3 to 2/3, and the reaction times of stock oil in the pre-esterification reactor device is 0.5-1 hour;
(2) ester-exchange reaction
Anhydrous methanol is mixed the back with basic catalyst pump into stock oil and enter the tubular type plug flow reactor in the mixing tank behind the thorough mixing, generate biofuel and by-product glycerin in that transesterification takes place between tri-glyceride and the methyl alcohol under the basic catalyst katalysis through pre-esterification reactor; Reaction conditions is: temperature of reaction 50-62 ℃, methyl alcohol was to the mol ratio of raw material 4: 1 to 6: 1, reaction times 20-40 minute.
(3) sepn process
Reaction product makes the biofuel product through glycerine, water, methyl alcohol after separating.
2, employing solid acid catalyst as claimed in claim 1 and plug flow reactor continuous production method of bio-diesel oil, it is characterized in that: described stock oil is vegetables oil.
3, employing solid acid catalyst as claimed in claim 1 and plug flow reactor continuous production method of bio-diesel oil is characterized in that: described stock oil comes unstuck, takes off sewer oil or the frying oil or the oil leftover of soap, the processing of glue look for process.
4, employing solid acid catalyst as claimed in claim 1 and plug flow reactor continuous production method of bio-diesel oil, it is characterized in that: described solid acid catalyst is Amberlyst-15.
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| CNB2006100364198A CN100448946C (en) | 2006-07-10 | 2006-07-10 | Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor |
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| CNB2006100364198A CN100448946C (en) | 2006-07-10 | 2006-07-10 | Method for conitinuously producing biological diesel oil using solid acid catalyst and piston flow reactor |
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| CN1900223A true CN1900223A (en) | 2007-01-24 |
| CN100448946C CN100448946C (en) | 2009-01-07 |
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Cited By (15)
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| CN100545240C (en) * | 2007-03-09 | 2009-09-30 | 厦门大学 | A kind of solid acid and solid alkali two-step catalysis method production method of bio-diesel oil utilized |
| CN101921659A (en) * | 2009-06-15 | 2010-12-22 | 高资明 | Method for preparing fatty acid methyl ester from high fatty-acid grease by using recycled methanol |
| CN101935592A (en) * | 2010-09-27 | 2011-01-05 | 温州中科新能源科技有限公司 | Process for preparing biodiesel by using low-acid-value waste oil |
| CN101955848A (en) * | 2010-09-27 | 2011-01-26 | 温州中科新能源科技有限公司 | Process for preparing biodiesel from waste oil with high acid value |
| CN101245252B (en) * | 2007-02-14 | 2011-10-26 | 南京工业大学 | Method for producing biological diesel oil by using waste oil |
| US20120167648A1 (en) * | 2012-03-09 | 2012-07-05 | Antonio Cantizani | Processes And Apparatus For Small-Scale In Situ Biodiesel Production |
| CN101397504B (en) * | 2008-11-04 | 2013-01-23 | 中国科学院广州能源研究所 | Production process of biological diesel oil and apparatus |
| CN103242968A (en) * | 2013-05-21 | 2013-08-14 | 山东大学 | Method for preparing biodiesel by virtue of two-step catalytic conversion of microalgae with high acid value |
| CN104120038A (en) * | 2013-04-25 | 2014-10-29 | 中国石油化工股份有限公司 | Method for reducing oil acid value |
| CN104403805A (en) * | 2014-09-29 | 2015-03-11 | 成都新柯力化工科技有限公司 | Biodiesel preparation method |
| CN104651060A (en) * | 2015-02-03 | 2015-05-27 | 江苏西方环保科技有限公司 | Biodiesel continuous ester interchange technology |
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| CN107236597A (en) * | 2017-07-03 | 2017-10-10 | 中国科学院广州能源研究所 | A kind of transesterification real-time Dynamic Separation continuous reaction system of biodiesel and its application |
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| CN101397504B (en) * | 2008-11-04 | 2013-01-23 | 中国科学院广州能源研究所 | Production process of biological diesel oil and apparatus |
| CN101921659B (en) * | 2009-06-15 | 2012-10-17 | 高资明 | Method for preparing fatty acid methyl ester from high fatty-acid grease by using recycled methanol |
| CN101921659A (en) * | 2009-06-15 | 2010-12-22 | 高资明 | Method for preparing fatty acid methyl ester from high fatty-acid grease by using recycled methanol |
| CN101955848A (en) * | 2010-09-27 | 2011-01-26 | 温州中科新能源科技有限公司 | Process for preparing biodiesel from waste oil with high acid value |
| CN101935592A (en) * | 2010-09-27 | 2011-01-05 | 温州中科新能源科技有限公司 | Process for preparing biodiesel by using low-acid-value waste oil |
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| CN104651060A (en) * | 2015-02-03 | 2015-05-27 | 江苏西方环保科技有限公司 | Biodiesel continuous ester interchange technology |
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| CN104830543A (en) * | 2015-04-28 | 2015-08-12 | 广东河山环保有限公司 | Device and method for preparing biodiesel through continuous gas-phase catalytic esterification |
| CN107236597A (en) * | 2017-07-03 | 2017-10-10 | 中国科学院广州能源研究所 | A kind of transesterification real-time Dynamic Separation continuous reaction system of biodiesel and its application |
| CN107236597B (en) * | 2017-07-03 | 2023-11-24 | 中国科学院广州能源研究所 | Biodiesel transesterification real-time dynamic separation continuous reaction system and application thereof |
| CN109675502A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | A kind of pre-esterification method preparing biodiesel |
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