CN101130163B - Load type flyash solid base catalyst for producing biological diesel oil and method of producing the same - Google Patents
Load type flyash solid base catalyst for producing biological diesel oil and method of producing the same Download PDFInfo
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- CN101130163B CN101130163B CN200710018464A CN200710018464A CN101130163B CN 101130163 B CN101130163 B CN 101130163B CN 200710018464 A CN200710018464 A CN 200710018464A CN 200710018464 A CN200710018464 A CN 200710018464A CN 101130163 B CN101130163 B CN 101130163B
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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 invention discloses a solid alkaline catalyst of loaded coal ash to make biological diesel, which comprises the following parts: coal ash + alkaline metal hydroxide, coal ash + alkaline earth metal hydroxide, coal ash + alkaline metal salt, coal ash + alkaline earth metal salt, coal ash + alkaline metal hydroxide + alkaline metal salt, coal ash + alkaline metal hydroxide + alkaline metal salt and alkaline metal in the composite system, wherein the total weight of alkaline metal hydroxide, alkaline earth metal hydroxide, alkaline metal salt, alkaline metal salt and alkaline metal is 10-40%; the total weight of coal ash is 60-90%; the catalyst can accelerate the ester exchange reaction effectively under mild reacting condition. The invention has simple technique, low cost to immerse the activated coal ash carrier in the alkaline or salt solution or suspension, which is sintered after aging and adding drying solvent in the mafu stove to generate polymer powder to be grinded and sieved to prepare.
Description
Technical field
The present invention relates to a kind of catalyst, especially relate to a kind of under the methyl alcohol boiling point catalysis fatty glyceride and methyl alcohol carry out load type flyash solid base catalyst and the preparation method that ester exchange reaction prepares biodiesel.
Background technology
Biodiesel causes people's extensive concern and research with the advantage of its abundant raw material sources, good recyclability and environmental protection aspect, its aspect combustibility at all no less than petrifaction diesel, and can be directly used in diesel engine, be considered to the substitute of petrifaction diesel.Biodiesel is a fatty acid methyl ester, is obtained through ester exchange reaction by reproducible grease and short chain alcohol (generally with methyl alcohol or ethanol), is a kind of regenerative resource that can substitute the cleaning of petrifaction diesel use.Its raw material sources are abundant, can be any natural oil (or fat), as vegetable fat (soybean oil, corn oil, rapeseed oil, palm wet goods), animal fat (animal tallow) and waste edible oil and industrial oil foot etc.
The main method of production biodiesel has chemical method production and enzyme process synthetic method at present, and the former adopts animal and plant fat and low-carbon alcohols such as methyl alcohol or ethanol to carry out the ester exchange reaction under acidity or base catalyst, generates corresponding fatty acid methyl ester or ethyl ester.With respect to the acid catalysis system, base catalysis has short, advantage such as temperature is low and molar ratio of methanol to oil is little of reaction time, but preparing with the liquid base catalyzed transesterification in the traditional handicraft of biodiesel, to produce a large amount of spent lyes in the last handling process, cause secondary pollution, increased running cost and Environmental costs.Utilize the biological enzyme biodiesel synthesis to have advantages such as mild condition, pure consumption are few, non-pollutant discharge.But, cause enzymatic conversion method rate low (being lower than 90%), and the high industrialization that limits this method of enzyme cost because low-carbon alcohols is toxic to enzyme.By liquid base is carried out the immobilization transformation, can keep under the prerequisite of high activity of catalyst, simplify process procedure, (Min Enze, Chinese engineering science, 2005,7 (4): 1-4) reduce production costs.
In existing solid base type ester exchange catalyst design; the general base strength of all emphasizing load alkali center; and ignored the polar activation of metal ion to carbonyl; make and descend through the acyl acceptor of alkali center activation formation and the reaction efficiency of carbonyl; under same transesterification conditions, the formation speed of fatty acid methyl ester will be subjected to restriction (Li Weimin, the chemical industry journal of this step; 2005,56 (4): 711-716).Because the restriction of acidylate speed, reaction needed is by improving the yield that temperature or time expand guarantee the biodiesel product, and this can make production efficiency reduce.In order to overcome this technical problem, Chinese scholars has been carried out the exploration of positive effort, has obtained a series of achievement, and Hak-Joo Kim etc. utilizes Na/NaOH/ γ-Al
2O
3The biodiesel that is converted into catalysis rape oil has obtained the effect same with homogeneous phase NaOH catalysis (hak-Joo Kimet al, Catalysis Today 93-95 (2004) 315-320); Naomi Shibasaki-Kitakawa etc. utilizes anion exchange resin catalyzed triglyceride of PA306s type and ethanol ester exchange reaction also to obtain comparatively desirable effect (Naomi Shibasaki-Kitakawa et al, BioresourceTechnology 98 (2007) 416-421).Chinese patent (CN200510037862.2) utilizes MgO-NaOH respectively, MgO-Na, K/KOH/ γ-Al in reaching (CN200610034182.X)
2O
3And the catalyzed oil lipidols such as catalyst that form of alkali metal salt and alkaline earth oxide or alkali metal hydroxide and alkaline earth oxide are separated reaction and have also been obtained the result who comparatively is satisfied with.But above-mentioned Preparation of catalysts requires harsh, the process complexity, and the Catalyst Production cost is very high, has limited its industrial application value.
Flyash is grey or linen powder, contains a large amount of activating oxide (Al
2O
3, SiO
2Deng), have the loose structure of inner ratio surface area greatly.When it is used as catalyst carrier, except the effect that can play dispersion and stabilizing active component, itself can also provide acid, basic active center, act synergistically with catalytic component.The material that is used as catalyst carrier at present mostly is: γ-Al
2O
3, active carbon etc., the main feature of this class catalyst is inner porous, has bigger inner ratio surface area, can play peptizaiton preferably, and relevant flyash is done the correlative study of catalyst carrier and also do not aroused attention.
Summary of the invention
Purpose of the present invention is intended at above-mentioned problems of the prior art, provide a kind of can be under the reaction condition of gentleness, promote ester exchange reaction efficiently to carry out, technology is simple, the load type flyash solid base catalyst and the preparation method of the preparation biodiesel that cost is low.
According to studies have shown that of applicant, relevant flyash is made catalyst and has been overcome solid base catalyst with its particular performances and be subject to H
2O and CO
2The shortcoming of poisoning is not also as the phenomenon of solid strong acid catalyst because of the coking inactivation.Therefore, the flyash catalyst is that a class is with low cost, the green new bio diesel catalytic converter of stable performance, environment-friendly high-efficiency.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of load type flyash solid base catalyst that is used to prepare biodiesel, it is characterized in that this load type flyash solid base catalyst is made up of flyash and alkali metal or alkaline-earth metal material, wherein, flyash content is 60%～90% of total catalyst weight by mass percentage, and alkali metal or alkaline-earth metal material content are 10%～40% of total catalyst weight by mass percentage;
Described alkali metal material comprises alkali metal, alkali metal hydroxide, alkali metal salt a kind of, two or three mixture wherein.
Described alkaline-earth metal material comprises alkaline earth metal hydroxide, alkali salt one or both mixtures wherein.
The mass ratio of described mixture is: alkali metal: alkali metal hydroxide or alkaline earth metal hydroxide: alkali metal salt or alkali salt :=0～20%: 0～100%: 0～100%, and the consumption sum of its each raw material is 100%.
The preparation method of the above-mentioned load type flyash solid base catalyst that is used to prepare biodiesel is as follows:
Compositing formula by catalyst will be immersed in the aqueous solution or suspension of alkali metal hydroxide, alkali metal salt or alkaline-earth metal material through the flyash of 550 ℃ of activation processing 2h, through stirring after ageing floods at least 1h, solvent is dried in heating, the poly-powder of gained is calcined 2h～5h in muffle furnace under 200 ℃～350 ℃, grind after the cooling less than 100 purpose powder, preparation is finished.
Perhaps will be immersed in the aqueous solution of alkali metal hydroxide, alkali metal salt or alkaline-earth metal material through the flyash of 550 ℃ of activation processing 2h by catalyst proportion, through stirring after ageing floods at least 1h, solvent is dried in heating, add a certain amount of alkali metal then and under 50 ℃～200 ℃, add thermal agitation, treat the alkali metal fusing and mix in the back immigration muffle furnace under 200 ℃～350 ℃ conditions, to calcine 2h～4h, grind after the cooling less than 100 purpose powder, preparation is finished.
The present invention introduces the flyash carrier surface with charge density higher alkali metal or alkaline-earth metal ions, promotes two consecutive steps in the catalytic reaction simultaneously, realizes quickening the purpose of ester exchange reaction, improves the activity of solid base catalyst.This solid base catalyst can be under the reaction condition of gentleness (pressure＜0.5MPa, temperature＜70 ℃, acid value＜3mg KOH/g) promote ester exchange reaction efficiently to carry out, catalytic efficiency is near homogeneous liquid base catalysts such as sodium methoxides, the fatty acid methyl ester conversion rate reaches more than 95%, and product can satisfy 0 after separation and purification
#The main performance index of diesel oil, and with the solid base particle of heterogeneous form participation reaction, simple and easy to do with separating of biodiesel product, postprocessing working procedures obtains simplifying, catalyst can reclaim repeated use repeatedly, greatly reduces the job costs and the Environmental costs of production of biodiesel.
The specific embodiment
According to technical scheme of the present invention, the load type flyash solid base catalyst of preparation biodiesel is made up of flyash and alkali metal or alkaline-earth metal material, wherein, flyash content is 60%～90% of total catalyst weight by mass percentage, and alkali metal or alkaline-earth metal material content are 10%～40% of total catalyst weight by mass percentage; This load type flyash solid base catalyst that makes can promote ester exchange reaction efficiently to carry out under the reaction condition of gentleness, and its technology is simple, and cost is low.
The active testing of catalyst ester exchange reaction has adopted methyl alcohol/material system of 6: 1～15: 1 of vegetable oil mol ratio, in weight be 2%～6% catalyst of reactant in the mode that suspends at 101.325kPa, under 62 ± 3 ℃ the condition, reaction 30min～100min, obtain product, form through the gas chromatographic analysis mixture, calculate the productive rate of fatty acid methyl ester.For preventing solid base catalyst because of surperficial saponification inactivation, require the acid number of feedstock oil to be controlled at below the 3mg/g, if use the higher grease of acid number, must before reaction, carry out depickling and handle raw material as raw material.
China is a coal-fired big country, and nearly 200,000,000 tons of the annual flyash that produces because of burning coal can produce a series of negative effect if these flyash can not get rational disposal, as occupy cultivated land, polluted river and air etc.How to recycle flyash, allow it turn waste into wealth, have very important economy and Significance for Environment.Flyash is grey or linen powder, contains a large amount of activating oxide (Al
2O
3, SiO
2Deng), have the loose structure of inner ratio surface area greatly, be glassy more.When flyash is used as catalyst carrier, except the effect that can play dispersion and stabilizing active component, can also provide acid, basic active center, play synergy with catalytic component.
The above-mentioned load type flyash solid base catalyst that is used to prepare biodiesel, wherein the concrete prescription of flyash and alkali metal or alkaline-earth metal material composition comprises following several:
First kind of prescription: be made up of flyash and alkali metal hydroxide, wherein, flyash content is 60%～90% of total catalyst weight by mass percentage, and alkali metal hydroxide content is 10%～40% of total catalyst weight by mass percentage;
Second kind of prescription: form by flyash and alkali metal hydroxide and alkali metal, flyash content is 60%～90% of total catalyst weight by mass percentage, and alkali metal hydroxide and alkali metal content are 10%～40% of total catalyst weight by mass percentage; Wherein, alkali metal hydroxide and alkali-metal mass ratio are: alkali metal hydroxide: alkali metal=80%～100%: 0～20%, and the consumption sum of its each raw material is 100%;
The third prescription: be made up of flyash and alkali metal salt, wherein, flyash content is 60%～90% of total catalyst weight by mass percentage, and alkali metal salt content is 10%～40% of a total catalyst weight;
The 4th kind of prescription: form by flyash and alkali metal salt and alkali-metal mixture, flyash content is 60%～90% of total catalyst weight by mass percentage, alkali metal salt and alkali metal content are 10%～40% of total catalyst weight, wherein, the mass ratio of alkali metal salt and alkali-metal mixture is: 80%～100%: 0～20%, and the consumption sum of its each raw material is 100%;
The 5th kind of prescription: the mixture by flyash and alkali metal hydroxide and alkali metal salt is formed, flyash content is 60%～90% of total catalyst weight by mass percentage, and the mixture content of alkali metal hydroxide and alkali metal salt is 10%～40% of a total catalyst weight; Wherein, the mass ratio of the mixture of alkali metal hydroxide and alkali metal salt is: alkali metal hydroxide: alkali metal salt=0～100%: 0～100%, and the consumption sum of its each raw material is 100%;
The 6th kind of prescription: form by flyash and alkali metal hydroxide, alkali metal salt and alkali-metal mixture, flyash content is 60%～90% of total catalyst weight by mass percentage, and alkali metal hydroxide, alkali metal salt and alkali-metal mixture content are 10%～40% of total catalyst weight; Wherein, the mass ratio of alkali metal hydroxide, alkali metal salt and alkali-metal mixture is: 0～100%: 0～100%: 0～20%, and the consumption sum of its each raw material is 100%;
The 7th kind of prescription: be made up of flyash and alkaline earth metal hydroxide, wherein, flyash is 60%～90% of total catalyst weight, and alkaline earth metal hydroxide content is 10%～40% of total catalyst weight by mass percentage;
The 8th kind of prescription: form by flyash and alkaline earth metal hydroxide and alkali-metal mixture, flyash is 60%～90% of total catalyst weight, alkaline earth metal hydroxide and alkali-metal mixture content are 10%～40% of total catalyst weight by mass percentage, wherein, the mass ratio of alkaline earth metal hydroxide and alkali-metal mixture is: 80～100%: 0～20%, and the consumption sum of its each raw material is 100%;
The 9th kind of prescription: be made up of flyash and alkali salt, wherein, flyash content is 60%～90% of total catalyst weight by mass percentage, and the alkaline-earth metal salt content is 10%～40% of total catalyst weight by mass percentage;
The tenth kind of prescription: form by flyash and alkali salt and alkali-metal mixture, wherein, flyash content is 60%～90% of total catalyst weight by mass percentage, alkali salt and alkali-metal mixture content are 10%～40% of total catalyst weight by mass percentage, wherein, the mass ratio of alkali salt and alkali-metal mixture is: 80～100%: 0～20%, and the consumption sum of its each raw material is 100%;
The 11 kind of prescription: the mixture by flyash and alkaline earth metal hydroxide and alkali salt is formed, flyash content is 60%～90% of total catalyst weight by mass percentage, the mixture content of alkaline earth metal hydroxide and alkali salt is 10%～40% of total catalyst weight by mass percentage, wherein, the mass ratio of the mixture of alkaline earth metal hydroxide and alkali salt is: 0～100%: 0～100%, and the consumption sum of its each raw material is 100%;
The 12 kind of prescription: form by flyash and alkaline earth metal hydroxide, alkali salt and alkali-metal mixture, flyash content is 60%～90% of total catalyst weight by mass percentage, alkaline earth metal hydroxide, alkali salt and alkali-metal mixture content are 10%～40% of total catalyst weight by mass percentage, wherein, alkaline earth metal hydroxide, alkali salt and alkali-metal mass ratio are: 0～100%: 0～100%: 0～20%, and the consumption sum of its each raw material is 100%;
Described alkali metal is at least a among Li, Na, K, the Rb; Described alkali metal hydroxide is at least a among LiOH, NaOH, KOH, the RbOH; Alkali metal salt is LiNO
3, NaNO
3, KNO
3, RbNO
3In at least a; Described alkaline earth metal hydroxide is Be (OH)
2, Mg (OH)
2, Ca (OH)
2, Sr (OH)
2, Ba (OH)
2In at least a, described alkali salt is Be (NO
3)
2, Mg (NO
3)
2, Ca (NO
3)
2, Sr (NO
3)
2, Ba (NO
3)
2In at least a.
The following examples can make the professional and technical personnel further understand the present invention, and these embodiment are some more excellent examples, and the present invention is not limited to these embodiment.
Embodiment 1:
Weighing sodium hydroxide 2.00g pours in the beaker, is dissolved in the 100mL deionized water, gets sodium hydroxide solution.The flyash carrier 8.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in the aqueous solution of NaOH, after stirring ageing dipping 2.0h, solvent is dried in heating, the poly-powder of gained is calcined 3.0h in muffle furnace under 230 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into rapeseed oil 1mol, the methyl alcohol 10mol that handles through depickling, dehydration etc., add above-mentioned catalyst 5.0%, at 65 ℃ of following stirring and refluxing reaction 80min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 98.6%, and the purity of lower floor's glycerine reaches 95.4%.
Embodiment 2:
Take by weighing potassium hydroxide 1.50g and pour in the beaker, be dissolved in the 100mL deionized water, get potassium hydroxide solution.The flyash carrier 8.50g that takes by weighing through 550 ℃ of activation processing 2h is immersed in the aqueous solution of potassium hydroxide, after stirring ageing dipping 2.0h, solvent is dried in heating, the poly-powder of gained is calcined 3h in muffle furnace under 258 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into water white gourd oil 1mol, the methyl alcohol 10mol that handles through depickling, dehydration etc., add above-mentioned catalyst 3.5%, at 62 ℃ of following stirring and refluxing reaction 90min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 98.4%, and the purity of lower floor's glycerine reaches 96.0%.
Embodiment 3:
Take by weighing lithium hydroxide 4.00g and pour in the beaker, be dissolved in the 100mL deionized water, get lithium hydroxide solution.The flyash carrier 6.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in the aqueous solution of lithium hydroxide, after stirring ageing dipping 2.0h, solvent is dried in heating, the poly-powder of gained is calcined 3h in muffle furnace under 270 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into camellia seed oil 1mol, the methyl alcohol 15mol that handles through depickling, dehydration etc., add above-mentioned catalyst 3.2%, at 63 ℃ of following stirring and refluxing reaction 100min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 97.6%, and the purity of lower floor's glycerine reaches 95.7%.
Embodiment 4:
Each 2.00g of weighing sodium hydroxide and potassium nitrate pours in the beaker, is dissolved in the 100mL deionized water, gets the mixed solution of NaOH and potassium nitrate.The flyash carrier 6.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixed aqueous solution, after stirring ageing dipping 4.2h, solvent is dried in heating, and the poly-powder of gained is calcined 4.0h in muffle furnace under 280 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into oily certain herbaceous plants with big flowers oil 1mol, the methyl alcohol 10mol that handle through depickling, dehydration etc., add above-mentioned catalyst 4%, at 65 ℃ of following stirring and refluxing reaction 100min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 98.6%, and the purity of lower floor's glycerine reaches 93.5%.
Embodiment 5:
Take by weighing each 1.50g of calcium hydroxide and calcium nitrate and pour in the beaker, adding 100mL deionized water also stirs, and gets the blend mixture suspension of calcium hydroxide and calcium nitrate.The flyash carrier 7.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixture, after stirring ageing dipping 2.3h, solvent is dried in heating, and the poly-powder of gained is calcined 3.2h in muffle furnace under 300 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into the samara oil 1mol, the methyl alcohol 12mol that handle through depickling, dehydration etc., add above-mentioned catalyst 4.5%, at 62 ℃ of following stirring and refluxing reaction 55min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 96.4%, and the purity of lower floor's glycerine reaches 96.7%.
Embodiment 6:
Take by weighing magnesium hydroxide 2.00g and calcium nitrate 1.00g pours in the beaker, add the 100mL deionized water and also stir, the mixture suspension of magnesium hydroxide and calcium nitrate.The flyash carrier 7.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixture suspension, after stirring ageing dipping 3.5h, solvent is dried in heating, the poly-powder of gained is calcined 3.3h in muffle furnace under 300 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into apricot kernel oil 1mol, the methyl alcohol 13mol that handles through depickling, dehydration etc., add above-mentioned catalyst 6.0%, at 61 ℃ of following stirring and refluxing reaction 76min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 97.8%, and the purity of lower floor's glycerine reaches 94.6%.
Embodiment 7:
Take by weighing beryllium hydroxide 1.50g and barium nitrate 0.50g pours in the beaker, add the 100mL deionized water and also stir, the mixture suspension of beryllium hydroxide and barium nitrate.The flyash carrier 8.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixture suspension, after stirring ageing dipping 3.5h, solvent is dried in heating, the poly-powder of gained is calcined 3.5h in muffle furnace under 285 ℃, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into castor oil 1mol, the methyl alcohol 15mol that handles through depickling, dehydration etc., add above-mentioned catalyst 5.2%, at 63 ℃ of following stirring and refluxing reaction 90min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 96.4%, and the purity of lower floor's glycerine reaches 95.6%.
Embodiment 8:
Weighing sodium hydroxide 2.50g pours in the beaker, is dissolved in the 100mL deionized water, gets sodium hydroxide solution.The flyash carrier 7.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixed aqueous solution, after stirring ageing dipping 2.5h, solvent is dried in heating, add the sodium metal of 0.50g then and under 120 ℃, add thermal agitation, Deng sodium metal fusing and mix the back and move in the muffle furnace in 245 ℃ of calcining 2.5h down, to grind less than 100 purpose powder after the poly-powder cooling of gained, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into siritch 1mol, the methyl alcohol 12mol that handles through depickling, dehydration etc., add above-mentioned catalyst 4.8%, at 62 ℃ of following stirring and refluxing reaction 85min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 97.5%, and the purity of lower floor's glycerine reaches 94.7%.
Embodiment 9:
Take by weighing magnesium hydroxide 1.80g and pour in the beaker, adding 100mL deionized water also stirs, and gets magnesium magma.The flyash carrier 8.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this suspension, after stirring ageing dipping 3.5h, solvent is dried in heating, add the lithium metal of 0.20g then and under 200 ℃, add thermal agitation, Deng sodium metal fusing and mix the back and move in the muffle furnace in 325 ℃ of calcining 3.0h down, to grind less than 100 purpose powder after the poly-powder cooling of gained, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into Fructus Zanthoxyli oil 1mol, the methyl alcohol 14mol that handles through depickling, dehydration etc., add above-mentioned catalyst 5.0%, at 65 ℃ of following stirring and refluxing reaction 95min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 96.8%, and the purity of lower floor's glycerine reaches 93.0%.
Embodiment 10:
Take by weighing barium hydroxide 2.50g and pour in the beaker, be dissolved in the 100mL deionized water, get barium hydroxide solution.The flyash carrier 7.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixed aqueous solution, after stirring ageing dipping 2.4h, solvent is dried in heating, add the lithium metal of 0.50g then and under 200 ℃, add thermal agitation, Deng lithium metal fusing and mix the back and move in the muffle furnace in 350 ℃ of calcining 3.5h down, to grind less than 100 purpose powder after the poly-powder cooling of gained, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into sesame oil 1mol, the methyl alcohol 10mol that handles through depickling, dehydration etc., catalyst 5.2%, at 64 ℃ of following stirring and refluxing reaction 96min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 98.4%, and the purity of lower floor's glycerine reaches 96.7%.
Embodiment 11:
Take by weighing potassium hydroxide 1.50g and sodium nitrate 1.00g pours in the beaker, add 100mL deionized water and stirring and dissolving, the mixed solution of potassium hydroxide and sodium nitrate.The flyash carrier 7.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixture suspension, after stirring ageing dipping 3.5h, solvent is dried in heating, add the metallic potassium of 0.50g then and under 95 ℃, add thermal agitation, Deng metallic potassium fusing and mix the back and move in the muffle furnace in 235 ℃ of calcining 3.5h down, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into soybean oil 1mol, the methyl alcohol 12mol that handles through depickling, dehydration etc., add above-mentioned catalyst 4.5%, at 65 ℃ of following stirring and refluxing reaction 46min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 98.8%, and the purity of lower floor's glycerine reaches 92.6%.
Embodiment 12:
Take by weighing calcium hydroxide 1.00g and barium nitrate 1.50g pours in the beaker, add the 100mL deionized water and also mix, the mixture suspension of calcium hydroxide and barium nitrate.The flyash carrier 7.00g that takes by weighing through 550 ℃ of activation processing 2h is immersed in this mixture suspension, after stirring ageing dipping 4.5h, solvent is dried in heating, add the sodium metal of 0.50g then and under 120 ℃, add thermal agitation, Deng sodium metal fusing and mix the back and move in the muffle furnace in 265 ℃ of calcining 3.5h down, grind after the cooling less than 100 purpose powder, get solid base catalyst.
In the reactor of 1.5 liters tool reflux condensation modes and mechanical stirring device, drop into waste cooking oil 1mol, the methyl alcohol 15mol that handles through depickling, dehydration etc., add above-mentioned catalyst 3.5%, at 65 ℃ of following stirring and refluxing reaction 65min, reaction steams unnecessary methyl alcohol after finishing, reacting liquor while hot is filtered, isolate catalyst, then with the centrifugal layering of filtrate, the upper strata is a biodiesel, lower floor is a byproduct glycerine, detect through chromatogram, the fatty acid methyl ester of upper strata biodiesel is 97.8%, and the purity of lower floor's glycerine reaches 93.6%.
Claims (5)
1. load type flyash solid base catalyst that is used to prepare biodiesel, it is characterized in that, this load type flyash solid base catalyst is by flyash, form with alkali metal or alkaline-earth metal material, wherein, flyash is 60%～90% of total catalyst weight by mass percentage, and alkali metal or alkaline-earth metal material are 10%～40% of total catalyst weight by mass percentage;
Described alkali metal or alkaline-earth metal material comprise wherein a kind of of alkali metal, alkali metal hydroxide, alkali metal salt or alkaline earth metal hydroxide, alkali salt, or two or three mixture.
2. the load type flyash solid base catalyst that is used to prepare biodiesel as claimed in claim 1, it is characterized in that, the mass ratio of described alkali metal or alkaline-earth metal material is: alkali metal: alkali metal hydroxide or alkaline earth metal hydroxide: alkali metal salt or alkali salt :=0～20%: 0～100%: 0～100%, and the consumption sum of its each raw material is 100%.
3. the load type flyash solid base catalyst that is used to prepare biodiesel as claimed in claim 1 is characterized in that, described alkali metal is at least a among Li, Na, K, the Rb; Described alkali metal hydroxide is at least a among LiOH, NaOH, KOH, the RbOH; Alkali metal salt is LiNO
3, NaNO
3, KNO
3, RbNO
3In at least a; Described alkaline earth metal hydroxide is Be (OH)
2, Mg (OH)
2, Ca (OH)
2, Sr (OH)
2, Ba (OH)
2In at least a; Described alkali salt is Be (NO
3)
2, Mg (NO
3)
2, Ca (NO
3)
2, Sr (NO
3)
2, Ba (NO
3)
2In at least a.
4. claim 1 or the 2 described preparation methods that are used to prepare the load type flyash solid base catalyst of biodiesel, it is characterized in that, compositing formula by catalyst will be immersed in the aqueous solution or suspension of alkali metal hydroxide, alkali metal salt or alkaline-earth metal material through the flyash of 550 ℃ of activation processing 2h, through stirring after ageing floods at least 1h, solvent is dried in heating, the poly-powder of gained is calcined 2h～5h in muffle furnace under 200 ℃～350 ℃, grind after the cooling less than 100 purpose powder, preparation is finished.
5. claim 1 or the 2 described preparation methods that are used to prepare the load type flyash solid base catalyst of biodiesel, it is characterized in that, to be immersed in alkali metal hydroxide through the flyash of 550 ℃ of activation processing 2h by catalyst proportion, in the aqueous solution of alkali metal salt or alkaline-earth metal material, through stirring after ageing floods at least 1h, solvent is dried in heating, add a certain amount of alkali metal then and under 50 ℃～200 ℃, add thermal agitation, treat the alkali metal fusing and mix in the back immigration muffle furnace under 200 ℃～350 ℃ conditions, to calcine 2h～4h, grind after the cooling less than 100 purpose powder, preparation is finished.
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| WO2010082210A2 (en) * | 2008-06-04 | 2010-07-22 | Tata Chemicals Ltd. | A process for production of biodiesel |
| CN101811038A (en) * | 2010-04-30 | 2010-08-25 | 太原理工大学 | Method for synthesizing biodiesel solid base catalyst and application |
| CN102335632A (en) * | 2011-07-20 | 2012-02-01 | 北京工业大学 | Method for preparing solid base catalyst with porous SiO2 material as carrier and application of solid base catalyst |
| CN102965204B (en) * | 2012-10-31 | 2014-06-25 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel with catalysis of fly ash solid acid catalyst |
| CN105344344B (en) * | 2015-09-30 | 2018-01-05 | 榆林学院 | Modified eggshell biodiesel catalyst and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580190A (en) * | 2004-05-21 | 2005-02-16 | 北京化工大学 | Method for preparing biodiesel by solid acid-base catalyst |
| CN1680514A (en) * | 2005-01-27 | 2005-10-12 | 清华大学 | Solid alkali catalyst, preparation and use thereof |
| CN1861749A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Production process of biological diesel |
| CN1990825A (en) * | 2006-03-14 | 2007-07-04 | 黄晓琳 | Low energy consumption production method of biological diesel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580190A (en) * | 2004-05-21 | 2005-02-16 | 北京化工大学 | Method for preparing biodiesel by solid acid-base catalyst |
| CN1680514A (en) * | 2005-01-27 | 2005-10-12 | 清华大学 | Solid alkali catalyst, preparation and use thereof |
| CN1861749A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Production process of biological diesel |
| CN1990825A (en) * | 2006-03-14 | 2007-07-04 | 黄晓琳 | Low energy consumption production method of biological diesel oil |
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