CN102690726A - Method for preparing biodiesel by fixed bed catalytic membrane reactor - Google Patents
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- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention relates to a method for preparing biodiesel by a fixed bed catalytic membrane reactor. The method comprises the following steps: oil and methyl alcohol are preheated at a specific ratio and then directly filled into a membrane reactor for transesterification; the reaction products ( namely biodiesel and glycerin) and unreacted methyl alcohol pass through a separation membrane to be collected from the outlet of the reactor shell; unreacted oil circularly enters the inlet of the reactor from the outlet of the shell; and the material from the shell is subjected to vacuum flashing and stands for layering to obtain the biodiesel product on the upper layer and crude glycerine on the lower layer. According to the method, the transesterification of the oil and the separation process of the oil, biodiesel and other products are coupled in the membrane reactor filled with solid alkali or acid catalysts, so that the production process and a reaction device are simplified, the equipment cost is reduced, and the production process has low energy consumption and high efficiency; the yield of the biodiesel can reach more than 98%; and furthermore, the method can be operated continuously, is environment-friendly and is easy to be spread.
Description
Technical field
The present invention relates to a kind of process method of utilizing the fixed-bed catalytic membrane reactor to prepare biofuel.
Background technology
Biofuel is as a kind of reproducible biomass energy, with its superior feature of environmental protection, good safety performance, and advantage such as especially its combustionproperty and fossil fuel be close and receive the extensive concern of countries in the world.
At present, intermittently or in the successive tank reactor adopting liquid acid/alkali as the Catalyst Production biofuel mostly in the industry, product obtains meeting the biofuel product of purity requirement through steps such as pickling, alkali cleaning, neutralization, rectifying.Because methyl alcohol and the not mutual solubility of raw oil and the reversibility of transesterification reaction, the transformation efficiency of biofuel is not high in the still reaction, and its follow-up separation purification step is complicated, and facility investment and energy consumption are bigger.In order to overcome above drawback, further reduce the biofuel cost improving its competitive power, people are incorporated into membrane separation technique in the production, purifying technique of biofuel.Under the prerequisite that the biofuel manufacturing cost still remains high and under the requirement of global low-carbon economy Development patterns; The low cost of membrane separation technique, less energy-consumption and high efficiency advantage seem outstanding especially, for green, safety, the economic preparation technology of biofuel provides technical foundation.
The patent No. is that the patent of CN 101265413A discloses a kind of immobilized lipase-porous membrane bio-reactor and prepares method of bio-diesel oil; The tubular fibre porous-film membrane module of immobilized lipase is assembled into the enzyme membrane bio-reactor; The mixture of grease and low-carbon alcohol is walked the shell side of membrane module, and water is walked the tube side of membrane module, under catalytic action of immobilized lipase; Grease and low-carbon alcohol circulating reaction certain hour, the biofuel yield can reach more than 90%.The patent No. is CN 101255347; The patent SEPARATE APPLICATION of CN101255348 be the immobilized lipase membrane bioreactor of separation assembly with water permeable membrane, alcohol permselective membrane; These methods have all reduced the separation in the production of biodiesel, purification step to a certain extent, and have obtained the higher biofuel product of purity.But reason such as higher owing to the cost of enzyme, that the catalysis object is single and the life-span is short, the industrial value of enzyme mebrane reactor reduces greatly.
The patent No. is that the USP of US 20100307051 discloses a kind of use membrane reactor production method of bio-diesel oil; Use the transesterification reaction of lower concentration NaOH as catalyst grease and methyl alcohol; The grease transformation efficiency reaches more than 95% under optimum conditions, separates the middle mutually FAME content of the rich oil that obtains and reaches 85%.Aforesaid method uses homogeneous catalyst, and its technological process is higher to the requirement for anticorrosion of a whole set of conversion unit, and aftertreatment is complicated, can produce great amount of wastewater simultaneously, greatly reduces the feature of environmental protection of membrane separation technique.The patent No. is that the USP of US 20110150713 discloses a kind of catalytic film that is applied to production of biodiesel; At tubulose single passage or hyperchannel separation membrane surface load one deck heterogeneous catalyst; This catalytic film is applied to membrane reactor prepares in the biofuel, under suitable condition, can obtain the higher biofuel product of purity.But this method catalytic film prepares the process complicacy, and cost is corresponding higher, and the scope of application is narrower.
Summary of the invention
Technical problem: to long reaction time in the conventional production of biodiesel technology, shortcoming such as yield is low, energy consumption is high, technical process is long, the present invention provide a kind of membrane reactor that heterogeneous catalysis and membrane separation technique are coupled to prepare method of bio-diesel oil.Adopt this method production biofuel not only to improve the raw oil transformation efficiency, it is simple also to have a technical process, advantages such as production efficiency height, process environment close friend.
Technical scheme: the present invention is that a kind of employing fixed-bed catalytic membrane reactor prepares method of bio-diesel oil, and this method may further comprise the steps:
A. raw oil and low-carbon alcohol get in the preheater respectively in proportion; The mol ratio of said raw oil and low-carbon alcohol is 1:3～1:16, and said preheater temperature is 50～70 ℃;
B. raw oil after the preheating and low-carbon alcohol get in the membrane reactor that is filled with catalyzer through mixing tank and react; The service temperature of said membrane reactor is 50～200 ℃; The total working pressure of reactor drum is 0.1～20MPa, and the outlet of reactor drum tube side remains on 50～500kPa with the pressure reduction of shell side outlet;
C. tube side discharging circulation gets into membrane reactor;
D. the shell side material continuously flows into vacuum flasher, and vacuum flashing cat head material obtains low-carbon alcohol after condensation, and sends into the low-carbon alcohol storage tank; Bottoms material standing demix after the interchanger cooling is told lower coarse glycerine and is conveyed into storage tank, and upper materials is the biofuel product.
The membrane element of said membrane reactor is made up of tubular separation membrane and the solid acid or the alkaline catalysts that are filled in the separatory membrane pipe.
Said tubular separation membrane is that the aperture is organic membrane or the mineral membrane of 0.05 μ m～3 μ m.
Described raw oil is lipid acid, acid grease or neutral grease, and low-carbon alcohol is methyl alcohol or ethanol.
Described catalyzer is solid acid, solid base catalyst.
Beneficial effect: fixed bed membrane reactor provided by the present invention prepares method of bio-diesel oil can make raw oil reach higher transformation efficiency in the short period of time, has reduced subsequent separation process simultaneously, has reduced separating energy consumption.The reactor drum assembling is simple and convenient, and flexibility of operation is high, is easy to large-scale production; Highly active solid catalyst directly fills in the tubular membrane main aperture road, and is to the membrane material no requirement (NR), applied widely; Be applicable to the production process of acid catalysis and base catalysis simultaneously, raw material is applied widely.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.Wherein: 1-methyl alcohol storage tank, 2-methyl alcohol volume pump, 3-methanol preheater, 4-grease volume pump, 5-grease preheater; The 6-blow-off valve, 7-grease storage tank, 8-membrane reactor, 9-recycle pump, 10-back pressure valve; The 11-interchanger, 12-intermediates storage tank, 13-flashing tower fresh feed pump, 14-flashing tower, 15-interchanger; The 16-interchanger, 17-quantizer, 18-raw glycerine storage tank, 19-biofuel storage tank.
Fig. 2 is a membrane reactor tubular membrane component synoptic diagram.20-sealring wherein, 21-film pipe grid distributor, 22-separatory membrane pipe, 22-solid catalyst.
Embodiment
Membrane reactor in the inventive method is that solid acid, alkaline catalysts are loaded in tubular separation membrane, reaches the coupled purpose of membrane sepn and heterogeneous catalysis process with this.
Concrete steps of the present invention are following:
(1) raw oil and low-carbon alcohol are conveyed in the preheater in proportion, the raw oil of charging and the mol ratio of low-carbon alcohol are 1:3～1:16,50～70 ℃ of preheater temperature.
(2) raw oil and low-carbon alcohol get into the catalytic film assembly be filled with solid acid or solid alkali through static mixer after through the preheater preheating.Temperature of reactor is controlled at 50～200 ℃, and pressure-controlling is at 0.1～20MPa.
(3) outlet of reactor drum tube side remains on 50～500kPa with the pressure reduction of shell side outlet.
(4) tube side discharging circulation gets into membrane reactor;
(5) mixture of biofuel and methyl alcohol, glycerine is flowed out by the reactor drum shell side, gets into vacuum flasher continuously, and the storage tank that the low-carbon alcohol that the cat head material obtains after condensation gets into low-carbon alcohol recycles; The bottoms material is after the interchanger cooling, and standing demix, supernatant liquid are the biofuel product, and lower floor is a raw glycerine.
Described raw oil is lipid acid, acid grease (catering industry waste oil, oil alkali refining soap stock), neutral grease (various animal-plant oil such as Viscotrol C, sweet oil, VT 18, tung oil, Oleum Gossypii semen, peanut oil, plam oil, engineering algae grease, fish oil, lard, butter), and low-carbon alcohol is methyl alcohol or ethanol.
Described catalyzer is solid acid, solid base catalyst.
Described separatory membrane is organic membrane or the mineral membrane of aperture 0.05 μ m～3 μ m.
1 couple of the present invention is described further below in conjunction with Figure of description, 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, and catalyzer is homemade KF/Ca-Al hydrotalcite solid base catalyst, and separatory membrane is that the aperture is the 7 passage ceramic membranes of 0.2 μ m, and concrete steps are following:
(1) homemade KF/Ca-Al hydrotalcite solid base catalyst is loaded in the ceramic separation film main channel.Total reactor length is 60cm, film length of tube 58cm.Oleum Gossypii semen and methyl alcohol are contained in respectively in grease storage tank 7, the methyl alcohol storage tank 1, close back pressure valve 10.Methanol preheater 3, grease preheater 5 temperature are controlled at 60 ℃; Temperature of reactor is controlled to be 65 ℃.
(2) methanol feeding speed is 5.0mL/min, and Oleum Gossypii semen pumps into reactor drum through preheater 3,5 respectively with the 9.6mL/min flow velocity simultaneously, regulates back pressure valve 10, recycle pump 9 simultaneously, makes that the outlet of reactor drum tube side and the pressure reduction of shell side outlet are 210kPa.
(3) penetrating fluid cools off after relay tank 12 pumps into flashing tower 14 by flashing tower fresh feed pump 13 through interchanger 11; The cat head material is carried back the methyl alcohol storage tank after the interchanger cooling; The bottoms material gets into standing demix in the quantizer 17 after the interchanger cooling, the upper strata product is a biofuel.
Through detecting, the Oleum Gossypii semen transformation efficiency reaches 99.6%, and the biofuel yield is 99.1%.
Embodiment 2: the discarded food and drink that with the acid number is 58mgKOH/g uses oil to be the feedstock production biofuel, uses homemade PTMA/MCM-41 solid acid catalyst, and separatory membrane is that the aperture is the single passage ceramic separation film of 0.1 μ m, and concrete steps are following:
(1) homemade PTMA/MCM-41 solid acid catalyst is filled in the main channel of ceramic separation film.Total reactor length is 100cm, film length of tube 95cm.To discard food and drink and be contained in respectively in grease storage tank 7, the methyl alcohol storage tank 1, close back pressure valve 10 with oil and methyl alcohol, methanol preheater 3, grease preheater 5 temperature are controlled at 60 ℃; Temperature of reactor is controlled to be 65 ℃.
(2) methyl alcohol with the input speed of 5.0mL/min through methanol preheater 3; Discarded food and drink pumps into reactor drum with the 6.4mL/min flow velocity through grease preheater 5 with oil; Regulate back pressure valve 10, recycle pump 9, make that the outlet of reactor drum tube side and the pressure reduction of shell side outlet are 130kPa.
(3) penetrating fluid cools off after relay tank 12 pumps into flashing tower 14 by flashing tower fresh feed pump 13 through interchanger 11; The cat head material is carried back the methyl alcohol storage tank after the interchanger cooling; The bottoms material gets into standing demix in the quantizer 17 after the interchanger cooling, the upper strata product is a biofuel.
Through detecting, discarded food and drink reaches 99.2% with oily transformation efficiency, and the biofuel yield is 98.4%.
Embodiment 3: the plam oil that with the acid number is 12mgKOH/g is the feedstock production biofuel, uses the homemade KF/Ca-Al HT of catalyzer solid base catalyst, and separatory membrane is that the aperture is 0.05 μ m single passage pvdf membrane, and its concrete steps are following:
(1) homemade KF/Ca-Al HT solid base catalyst is filled in the main channel of pvdf membrane.Total reactor length is 100cm, film length of tube 95cm.Plam oil and methyl alcohol are contained in respectively in grease storage tank 7, the methyl alcohol storage tank 1, close back pressure valve 10.Methanol preheater 3, grease preheater 5 temperature are controlled at 60 ℃; Temperature of reactor is controlled to be 65 ℃.
(2) methyl alcohol is with the input speed of 8.0mL/min; Plam oil pumps into reactor drum through methanol preheater 3 and grease preheater 5 respectively with the 15.7mL/min flow velocity; Regulate back pressure valve 10, recycle pump 9, the outlet of controlling reactor tube side is 370kPa with the pressure reduction of shell side outlet.
(3) penetrating fluid cools off after relay tank 12 pumps into flashing tower 14 by flashing tower fresh feed pump 13 through interchanger 11; The cat head material is carried back the methyl alcohol storage tank after the interchanger cooling; The bottoms material gets into standing demix in the quantizer 17 after the interchanger cooling, the upper strata product is a biofuel.
Through detecting, the plam oil transformation efficiency reaches 99.4%, and the biofuel yield is 99.0%.
Claims (5)
1. one kind is adopted the fixed-bed catalytic membrane reactor to prepare method of bio-diesel oil, it is characterized in that this method may further comprise the steps:
A. raw oil and low-carbon alcohol get in the preheater respectively in proportion; The mol ratio of said raw oil and low-carbon alcohol is 1:3～1:16, and said preheater temperature is 50～70 ℃;
B. raw oil after the preheating and low-carbon alcohol get in the membrane reactor that is filled with catalyzer through mixing tank and react; The service temperature of said membrane reactor is 50～200 ℃; The total working pressure of reactor drum is 0.1～20MPa, and the outlet of reactor drum tube side remains on 50～500kPa with the pressure reduction of shell side outlet;
C. tube side discharging circulation gets into membrane reactor;
D. the shell side material continuously flows into vacuum flasher, and vacuum flashing cat head material obtains low-carbon alcohol after condensation, and sends into the low-carbon alcohol storage tank; Bottoms material standing demix after the interchanger cooling is told lower coarse glycerine and is conveyed into storage tank, and upper materials is the biofuel product.
2. employing fixed-bed catalytic membrane reactor according to claim 1 prepares method of bio-diesel oil, it is characterized in that, the membrane element of said membrane reactor is made up of tubular separation membrane and the solid acid or the alkaline catalysts that are filled in the separatory membrane pipe.
3. employing fixed-bed catalytic membrane reactor according to claim 2 prepares method of bio-diesel oil, it is characterized in that, said tubular separation membrane is that the aperture is organic membrane or the mineral membrane of 0.05 μ m～3 μ m.
4. employing fixed-bed catalytic membrane reactor according to claim 2 prepares method of bio-diesel oil, it is characterized in that, described raw oil is lipid acid, acid grease or neutral grease, and low-carbon alcohol is methyl alcohol or ethanol.
5. employing fixed-bed catalytic membrane reactor according to claim 1 prepares method of bio-diesel oil, it is characterized in that, described catalyzer is solid acid, solid base catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013673A (en) * | 2012-12-10 | 2013-04-03 | 中国科学院广州能源研究所 | Continuous separation method and device for producing glycerin from biodiesel |
| 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 |
| CN103981033A (en) * | 2014-05-13 | 2014-08-13 | 沈阳化工大学 | Method utilizing supercritical catalysis process to continuously prepare biodiesel |
| CN104877763A (en) * | 2015-04-30 | 2015-09-02 | 宁波诺哈斯化工科技有限公司 | Hybrid catalytic membrane reactor and method for preparing biodiesel by using same |
| CN109574779A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of 2- alkyl anthracene |
| CN109569469A (en) * | 2019-01-30 | 2019-04-05 | 北京今大禹环境技术股份有限公司 | A kind of chemistry micro-reaction device and its application method |
| CN113150877A (en) * | 2021-03-26 | 2021-07-23 | 东南大学 | Continuous modularized biodiesel preparation process |
| CN113583724A (en) * | 2020-04-30 | 2021-11-02 | 河南工程学院 | Efficient green continuous preparation method of biodiesel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338212A (en) * | 2007-07-05 | 2009-01-07 | 中国石油化工股份有限公司 | Method for preparing biodesel |
| CN101423770A (en) * | 2008-12-08 | 2009-05-06 | 中国科学院广州能源研究所 | Method for preparing biodiesel by using high acid number feed lipid |
| US20110150713A1 (en) * | 2009-12-17 | 2011-06-23 | Bin Wen | Catalytic membrane for biodiesel production |
-
2012
- 2012-05-29 CN CN2012101734249A patent/CN102690726A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338212A (en) * | 2007-07-05 | 2009-01-07 | 中国石油化工股份有限公司 | Method for preparing biodesel |
| CN101423770A (en) * | 2008-12-08 | 2009-05-06 | 中国科学院广州能源研究所 | Method for preparing biodiesel by using high acid number feed lipid |
| US20110150713A1 (en) * | 2009-12-17 | 2011-06-23 | Bin Wen | Catalytic membrane for biodiesel production |
Non-Patent Citations (7)
| Title |
|---|
| GUANGYUAN TENG ET AL.: "Transesterification of Soybean Oil to Biodiesel over Heterogeneous Solid Base Catalyst", 《ENERGY FUELS》, vol. 23, 20 July 2009 (2009-07-20), pages 4630 - 4634 * |
| LIJING GAO,ET AL.: "Biodiesel from palmoil via loading KF/Ca-Al hydrotalcite catalyst", 《BIOMASS AND BIOENERGY》, vol. 34, 28 April 2010 (2010-04-28), pages 1283 - 1288, XP027087533, DOI: doi:10.1016/j.biombioe.2010.03.023 * |
| YANG XIAO ET AL.: "Experimental and Modeling Study of Continuous Catalytic Transesterification to Biodiesel in a Bench-Scale Fixed-Bed Reactor", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, vol. 51, 5 March 2012 (2012-03-05), pages 11860 - 11865 * |
| 冯耀辉 等: "阳离子交换树脂填充固定床连续催化酯化制备生物柴油", 《化工进展》, vol. 29, 31 December 2010 (2010-12-31), pages 712 - 713 * |
| 吕洁，等: "固定床反应器的最新研究进展", 《石油化工》, vol. 37, 31 December 2008 (2008-12-31), pages 698 - 701 * |
| 王乐夫 等: "固定床催化膜反应器对甲醇脱氢制甲酸甲酯反应性能的影响", 《天然气化工》, vol. 25, no. 4, 31 December 2000 (2000-12-31), pages 5 - 8 * |
| 费德君 主编: "《化学实验研究方法及技术》", 31 March 2008, article "反应-膜分离耦合实验技术", pages: 171-174 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103013673A (en) * | 2012-12-10 | 2013-04-03 | 中国科学院广州能源研究所 | Continuous separation method and device for producing glycerin from biodiesel |
| CN103981033A (en) * | 2014-05-13 | 2014-08-13 | 沈阳化工大学 | Method utilizing supercritical catalysis process to continuously prepare biodiesel |
| CN104877763A (en) * | 2015-04-30 | 2015-09-02 | 宁波诺哈斯化工科技有限公司 | Hybrid catalytic membrane reactor and method for preparing biodiesel by using same |
| CN109574779A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of 2- alkyl anthracene |
| CN109574779B (en) * | 2017-09-28 | 2021-03-12 | 中国石油化工股份有限公司 | Method for producing 2-alkyl anthracene |
| CN109569469A (en) * | 2019-01-30 | 2019-04-05 | 北京今大禹环境技术股份有限公司 | A kind of chemistry micro-reaction device and its application method |
| CN113583724A (en) * | 2020-04-30 | 2021-11-02 | 河南工程学院 | Efficient green continuous preparation method of biodiesel |
| CN113150877A (en) * | 2021-03-26 | 2021-07-23 | 东南大学 | Continuous modularized biodiesel preparation process |
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Application publication date: 20120926 |