CN101058743A - Process of preparing biological diesel oil - Google Patents

Process of preparing biological diesel oil Download PDF

Info

Publication number
CN101058743A
CN101058743A CNA2007100410769A CN200710041076A CN101058743A CN 101058743 A CN101058743 A CN 101058743A CN A2007100410769 A CNA2007100410769 A CN A2007100410769A CN 200710041076 A CN200710041076 A CN 200710041076A CN 101058743 A CN101058743 A CN 101058743A
Authority
CN
China
Prior art keywords
methyl alcohol
magnesium
oil
reaction
mixing solutions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2007100410769A
Other languages
Chinese (zh)
Inventor
陈晴
颜涌捷
任铮伟
黄慨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CNA2007100410769A priority Critical patent/CN101058743A/en
Publication of CN101058743A publication Critical patent/CN101058743A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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

Landscapes

  • Fats And Perfumes (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention discloses a making method of biological diesel coproducted glycerine and magnesium oxide through catalyzing plant oil by magnesium carbinol, which is characterized by the following: adopting non-refined plant oil as raw material; using magnesium carbinol as non-even phase catalyst; reacting through ester exchange to obtain the product and glycerine and magnesium oxide as by-product without neutralizing and processing; improving the receiving rate of magnesium oxide without discharging waste liquid.

Description

A kind of technology for preparing biofuel
Technical field
The present invention relates to the production technical field of biofuel, specifically adopting magnesium methylate is heterogeneous catalyst, and adopts this biodiesel and coproduction glycerine and magnesian technology.
Background technology
Biofuel is to be the renewable energy source of raw material production with the animal-plant oil, has good fuel performance and good environmental protection characteristic, is fine petrifaction diesel surrogate.Along with the exhaustion day by day of petroleum resources and the raising of people's environmental consciousness, biofuel is subjected to extensive concern as a kind of clean energy.The common method of industrial production biofuel is chemical ester-interchange method, and promptly main component triglyceride level in the animal-plant oil and low-carbon alcohol (methyl alcohol, ethanol etc.) are carried out transesterification reaction, generates fatty acid methyl ester (biofuel), simultaneously by-product glycerol.
The homogeneous acid alkaline catalysts is the traditional catalyst that is used for transesterification reaction, is generally dense H 2SO 4Or NaOH, KOH, sodium methylate etc.Homogeneous acid base-catalyzed transesterification technical maturity is suitable for large-scale industrial application.The shortcoming that exists is: acid base catalysator (especially liquid acid) has corrodibility to equipment; The homogeneous acid alkaline catalysts flows out with product, is difficult for separating with product, can not reuse, and brings higher catalyzer cost; The acid base catalysator that exists in the product must neutralize, wash after reaction finish, and produces a large amount of trade effluents, causes environmental pollution.
Overcritical transesterify, enzyme catalysis, solid catalyst are the important directions of Recent study.
When supercritical methanol technology is carried out transesterification reaction, can not add catalyzer, the reaction times is short, the transformation efficiency height, and aftertreatment is simple.But react temperature required, pressure is higher, production technique is to the equipment requirements height, and the molar ratio of methanol to oil height, the Methanol Recovery internal circulating load is big.
When lipase is used for transesterification reaction, the reaction conditions gentleness, product is easy to collect, non-pollution discharge, but transformation efficiency is on the low side, and enzyme is short work-ing life.
Solid catalyst, especially solid base catalyst are the focuses of Recent study.Mainly contain alkaline earth metal oxide, alkaline earth metal hydroxides, carbonate, composite oxides and alkaline molecular sieve etc.Solid alkali has the reactive behavior height, selectivity is good, reaction conditions is gentle, easily separated, can be recycled, to advantages such as conversion unit corrodibility are little.But solid base catalyst preparation process more complicated, the cost costliness; Easily by CO in the atmosphere 2With contaminating impurity such as water, make actively significantly to descend; Its life problems also has to be solved.Deactivated catalyst residue mostly is mixture, if deal with improperly, also can cause noxious waste pollution.Therefore, realizing the comprehensive utilization of (comprising catalyzer) of whole raw materials, is the fundamental way of avoiding environmental pollution.
At present, metal alkoxide is the custom catalysts of transesterification reaction, as CH because have very high catalytic activity 3ONa is exactly the homogeneous phase alkaline catalysts of using always.The classical theory of alkoxide catalyzed transesterification is: the hydridization carbon atom of alkoxide ion attack ester group makes it to transform into positive four sides intermediate.
Figure A20071004107600051
Metal alkoxide can be produced by metal, metal oxide or metal hydroxides and alcohol reaction.Can make by following reaction as sodium methylate, calcium methylate
Na+CH 3OHCH 3ONa+H 2↑
NaOH+CH 3OHCH 3ONa+H 2O
Ca+2CH 3OHCa(CH 3O) 2+H 2↑
CaO+2CH 3OHCa(CH 3O) 2+H 2O。
Summary of the invention
The objective of the invention is to propose a kind of technology for preparing biofuel, solve traditional technology and require harshness, catalyzer and product separation difficulty, product scavenging process to produce the problem of a large amount of waste water the stock oil moisture content.
Design of the present invention:
The contriver thinks that in transesterification reaction, suitable metal alkoxide is real catalyzer, can pass through metal, metal oxide or metal hydroxides and alcohol reaction generation.When for example being catalyzer with NaOH, the sodium methylate of generation has very high catalytic activity.But this reaction is a reversing process, and the existence of water and free alkali can cause saponification reaction to take place, and reduces target product yield, brings difficulty to separation.
Adopting magnesium methylate is that catalyzer has following characteristics: (1) has very high catalytic activity; (2) magnesium methylate is slightly soluble in methyl alcohol, is insoluble to vegetables oil, is suspension in reaction system, belongs to heterogeneous catalyst, by filtering or centrifugal can the separation with product; (3) reaction of magnesium methylate and less water generates methyl alcohol and MgO, and the removal of water can avoid saponification reaction to take place; The MgO that generates can separate with product, and product need not neutralize; (4) magnesium compound can be converted into magnesium oxide.The principal reaction formula is as follows:
Mg+2CH 3OH→Mg(CH 3O) 2+H 2↑
Mg(CH 3O) 2+H 2O→MgO+2CH 3OH
Method of the present invention comprises the steps:
(2) vegetables oil is added the mixing solutions of magnesium methylate and methyl alcohol, in confined conditions, back flow reaction, carry out transesterify, the reaction times is 2～6 hours, and temperature of reaction is 50～70 ℃, filter or centrifugation the thick product of collection of biological diesel oil from liquid phase mixture then;
Vegetables oil and methyl alcohol mol ratio are: 1: 9～18, and magnesium methylate and methyl alcohol mol ratio are: 1: 6～48.
With 80～90 ℃ the thick product of hot wash diesel oil, the underpressure distillation dehydration is refining then, obtains biofuel of the present invention;
The volumetric usage of hot water is V Water: V Give birth to bavin=1: 1～2;
Said vegetables oil is selected from green soy bean oil, rape seed oil, Oleum Gossypii semen or palm wet goods;
The mixing solutions of said magnesium methylate and methyl alcohol is preparation like this:
Do MAGNESIUM METAL and methyl alcohol react under 40～60 ℃, stirring, reflux conditions?～? hour, the mixing solutions of acquisition magnesium methylate and methyl alcohol, this process by-product hydrogen should be handled and recycle;
The mol ratio of MAGNESIUM METAL and methyl alcohol is: MAGNESIUM METAL: methyl alcohol=1: 8～50;
According to preferable methods of the present invention, also comprise the steps:
(2) recovery of glycerine
To the separating obtained solid-phase mixture of step (1), the hot water that adds 80～90 ℃ extracts, and filters, and obtains filter cake, and the mixing solutions of G ﹠ W, collects glycerine then from the mixing solutions of G ﹠ W;
According to preferable methods of the present invention, also comprise the steps:
(3) preparation magnesium oxide
Step (2) is separated the filter cake that obtains,, through 800～900 ℃ of calcining 4～10h, obtain magnesium oxide again in 100～120 ℃ of oven dry;
Useful technique effect of the present invention is fairly obvious: 1. the heterogeneous catalyst magnesium methylate catalytic activity height of Cai Yonging; Preparation process is simple, only needs a step chemical reaction; Can separate with product by centrifugal or filtration; 2. this catalyzer can be avoided saponification reaction, helps improving target product yield, and requires lower to the stock oil moisture content; 3. the treated higher magnesium oxide of economic worth that is converted into behind the catalyst deactivation avoids causing catalyst solid to pollute; 4. the recovery technology of the aftertreatment of the purification of biofuel, catalyzer, byproduct glycerine runs through mutually, and non-pollutant discharge is reused in water in the process and the circulation of methyl alcohol totality; 5. byproduct glycerine, magnesian recovery have increased value-added content of product, have reduced the technology cost.
Embodiment
Embodiment 1
Preparation of catalysts:
Take by weighing the 4g MAGNESIUM METAL, 98.4g methyl alcohol places agitator is housed, thermometer is in the there-necked flask of prolong, heating in water bath for reaction, control reaction temperature slowly rises to 65 ℃ by 40 ℃, all disappears until MAGNESIUM METAL, generate milky magnesium methylate and methanol solution, timing 1.5 hours.
The preparation of biofuel:
Slowly add 160g green soy bean oil (water-content about 0.7%) in above-mentioned solution, continued stirring reaction 3 hours, control reaction temperature is 65 ℃, after reaction finishes, mixture is filtered, collect filtrate and filter cake, the filtrate air distillation, about 120 ℃ of temperature reclaim unreacted methanol.The hot wash that adds 80 ℃ of 100ml again, the coarse biodiesel decompression dehydration is refining, and vacuum tightness is 0.07～0.1MPa, and about 100 ℃ of temperature finally obtain biofuel 157g, through gas chromatographic analysis, fatty acid methyl ester 95.46%.
The aftertreatment of catalyzer:
The filter cake of the gained water with 80 ℃ of 100ml is extracted, stir 1 hour after-filtration, filtrate is mainly glycerine---the aqueous solution, carry out underpressure distillation and dewater, vacuum tightness is 0.07MPa, about 120 ℃ of temperature, finally obtain glycerine 15g, yield 94%, purity is 97%;
Solid 80ml methanol wash, the filtration rear filtrate is fatty acid methyl ester a---methanol solution, the solid after the washing in 850 ℃ of calcinings 6 hours, obtains magnesium oxide 6.58g, the magnesium rate of recovery 98.7% again prior to 110 ℃ of oven dry 3 hours.
Embodiment 2
With rape seed oil is the feedstock production biofuel, and the reaction times is 6 hours, and temperature of reaction is 50 ℃, and other processing condition are with embodiment 1.Rape seed oil 200g, magnesium 6g, methyl alcohol 128g gets biofuel 192g, fatty acid methyl ester 97.9%.Catalyzer aftertreatment water 120ml, methyl alcohol 100ml gets glycerine 19.2g, yield 96%, purity 96.4%.Make magnesium oxide 9.93g, the magnesium rate of recovery 99.3%.

Claims (8)

1. a technology for preparing biofuel is characterized in that, comprises the steps:
(1) vegetables oil is added the mixing solutions of magnesium methylate and methyl alcohol, in confined conditions, back flow reaction is carried out transesterify, filters or centrifugation the thick product of collection of biological diesel oil from liquid phase mixture then; With the thick product of hot wash diesel oil, the underpressure distillation dehydration is refining then, obtains biofuel.
2. technology according to claim 1 is characterized in that, vegetables oil and methyl alcohol mol ratio are 1: 9～18, and magnesium methylate and methyl alcohol mol ratio are 1: 6～48.
3. technology according to claim 1 is characterized in that, the reaction times is 2～6 hours, and temperature of reaction is 50～70 ℃.
4. technology according to claim 1 is characterized in that, the volumetric usage of hot water is V Water: V Give birth to bavin=1: 1～2.
5. technology according to claim 1 is characterized in that, also comprises the steps:
(2) recovery of glycerine
To the separating obtained solid-phase mixture of step (1), the hot water that adds 80～90 ℃ extracts, and filters, and obtains filter cake, and the mixing solutions of G ﹠ W, collects glycerine then from the mixing solutions of G ﹠ W.
6. technology according to claim 5 is characterized in that, also comprises the steps:
(3) preparation magnesium oxide:
Step (2) is separated the filter cake that obtains,, through 800～900 ℃ of calcining 4～10h, obtain magnesium oxide again in 100～120 ℃ of oven dry.
7. according to each described technology of claim 1～6, it is characterized in that said vegetables oil is selected from green soy bean oil, rape seed oil, Oleum Gossypii semen or palm wet goods.
8. technology according to claim 1, it is characterized in that, the mixing solutions of said magnesium methylate and methyl alcohol is like this preparation: MAGNESIUM METAL and methyl alcohol reacted 1～2 hour under 40～60 ℃, stirring, reflux conditions, obtain the mixing solutions of magnesium methylate and methyl alcohol, this process by-product hydrogen should be handled and recycle; The mol ratio of MAGNESIUM METAL and methyl alcohol is: MAGNESIUM METAL: methyl alcohol=1: 8～50.
CNA2007100410769A 2007-05-23 2007-05-23 Process of preparing biological diesel oil Pending CN101058743A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2007100410769A CN101058743A (en) 2007-05-23 2007-05-23 Process of preparing biological diesel oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2007100410769A CN101058743A (en) 2007-05-23 2007-05-23 Process of preparing biological diesel oil

Publications (1)

Publication Number Publication Date
CN101058743A true CN101058743A (en) 2007-10-24

Family

ID=38865050

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2007100410769A Pending CN101058743A (en) 2007-05-23 2007-05-23 Process of preparing biological diesel oil

Country Status (1)

Country Link
CN (1) CN101058743A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103146488A (en) * 2013-03-07 2013-06-12 姬大菊 Method for producing -5 DEG C biodiesel by using drainage oil or waste cooking oil
CN108299163A (en) * 2018-03-09 2018-07-20 兰州大学 A kind of method that aromatic ester hydrolyzes in a mild condition
CN113755250A (en) * 2021-10-09 2021-12-07 浙江工业大学 Treatment process of biodiesel byproduct crude glycerol containing solid base catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103146488A (en) * 2013-03-07 2013-06-12 姬大菊 Method for producing -5 DEG C biodiesel by using drainage oil or waste cooking oil
CN103146488B (en) * 2013-03-07 2015-02-18 姬大菊 Method for producing -5 DEG C biodiesel by using drainage oil or waste cooking oil
CN108299163A (en) * 2018-03-09 2018-07-20 兰州大学 A kind of method that aromatic ester hydrolyzes in a mild condition
CN108299163B (en) * 2018-03-09 2021-10-12 兰州大学 Method for hydrolyzing aromatic ester under mild condition
CN113755250A (en) * 2021-10-09 2021-12-07 浙江工业大学 Treatment process of biodiesel byproduct crude glycerol containing solid base catalyst
CN113755250B (en) * 2021-10-09 2024-03-12 浙江工业大学 Treatment process of biodiesel by-product crude glycerin containing solid base catalyst

Similar Documents

Publication Publication Date Title
CN101892127B (en) Biodiesel preparation method
CN101319169B (en) Quick and clean process for preparing biological diesel oil with esterification/ester exchange reaction
CN102465058A (en) Production process for preparing biodiesel
CN1928016A (en) Preparation method of biological diesel oil
EP2675879A1 (en) Improved process for the preparation of fatty acid alkyl esters (biodiesel) from triglyceride oils using eco-friendly solid base catalysts
CN101696372A (en) Method for preparing biodiesel by solid acid-base two-step method
CN111205931A (en) Method for catalytically synthesizing biodiesel by using roasted Ca-Al hydrotalcite
CN101074389A (en) Production of biological diesel oil
CN100475333C (en) Catalyst for synthesizing bio diesel oil and preparation method thereof
CN101130700A (en) Novel method for producing biological diesel oil with solid alkali catalysis
CN101058743A (en) Process of preparing biological diesel oil
CN1743417A (en) Method for synthesizing biodiesel utilizing swill water oil
CN101045878A (en) Two-step solid acid and solid alkali catalyzing process for producing biodiesel oil
CN100375780C (en) Production of biological diesel oil with solid alkali
CN101429441A (en) Production process for biodiesel for automobile
CN108893135B (en) Method for preparing biodiesel by using waste oil
CN101642716B (en) Preparation method and application of alkaline earth metal glyceride catalyst
CN100523130C (en) Method of preparing biological diesel oil catalyzed by silicate
US20160102041A1 (en) Heterogeneous catalyst for transesterification and method of preparing same
CN101225324B (en) One-step method for preparing biodiesel by low-acid catalytic fatty or fatty acid
KR101107719B1 (en) Solid-phase basic catalyst for bio-diesel and method for manufacturing the same, and method for manufacturing bio-diesel
US20180178202A1 (en) Heterogeneous catalyst for transesterification and method of preparing same
CN1827743A (en) Method for synthesizing preparing bio-diesel oil by using crude fatty acid
CN103614244A (en) Method for preparing biodiesel by using carbon-based sulfonic acid functionalized solid acid as catalyst
CN107760445B (en) Method for catalyzing ester exchange reaction by using boehmite composite basic ionic liquid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Open date: 20071024