CN101642716B - Preparation method and application of alkaline earth metal glyceride catalyst - Google Patents
Preparation method and application of alkaline earth metal glyceride catalyst Download PDFInfo
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- CN101642716B CN101642716B CN2009101958163A CN200910195816A CN101642716B CN 101642716 B CN101642716 B CN 101642716B CN 2009101958163 A CN2009101958163 A CN 2009101958163A CN 200910195816 A CN200910195816 A CN 200910195816A CN 101642716 B CN101642716 B CN 101642716B
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- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention belongs to the technical field of environmental catalyst and new energy and particularly relates to a preparation method and an application of an alkaline earth metal glyceride catalyst. The solid base catalyst is prepared through method of precipitation by using glycerol, alkali metal hydroxide, alkaline earth metal chloride and methanol or alcohol as raw materials and the main component is alkaline earth metal glyceride which is not soluble in alcohol. The catalyst can promote the ester exchange reaction between lower alcohol and fat and oil, the reaction time is short, the conversion rate is high, the catalyst can be recycled though simple centrifugal separation or suction filtration and the catalyst can be used repeatedly. The invention provides a preparation method of alkaline earth metal glyceride solid base catalyst, alkaline earth metal glyceride is used as catalyst to catalyze the production of biodiesel and the production is characterized by high catalytic activity, mild reaction conditions, simple technological process, environmental friend and the like.
Description
Technical field
The invention belongs to environmental catalysis and technical field of new energies, be specifically related to a kind of preparation method and application thereof of alkaline earth metal glyceride catalyst.
Background technology
Biodiesel is a kind of reproducible, eco-friendly biomass energy.The raw material sources that can be used for preparing biodiesel very extensively can be used for the production biodiesel as palm oil, Jatropha curcas oil, soybean oil, olive oil, trench wet goods.The mixture of pure biodiesel or biodiesel and traditional petrifaction diesel can be used as the alternative fuel of diesel engine.And along with the raising of worldwide energy crisis and people's environmental consciousness, biodiesel more and more receives the attention of national governments with its superior environmental-protecting performance and recyclability.Biodiesel has high cetane number, and sulfur-bearing and arene compound are not biodegradable, and environmental friendliness, and flash-point is that diesel oil is high than oil is more conducive to transport safely and good characteristic such as storage.
The production method of biodiesel is varied.What use the earliest is a kind of method that is called Pintsch process.The diesel oil that is obtained by this method and traditional petrifaction diesel are similar, but Pintsch process needs 300-500 ℃ high temperature, and the composition of product is very complicated, and the characteristic of product receives the influence of raw material very big.
The research for preparing biodiesel through postcritical method also has report, though fewer.The common way of supercritical process is at 250-300 ℃; Under the condition of 30-65MPa with overcriticalization of methyl alcohol; Can let grease and methyl alcohol react (molar ratio of methanol to oil of this kind method usually at 40: 1, higher about 3 times) than traditional ester-interchange method with KOH catalysis.This method need not used catalyst, thereby the separation of product is simple, and reaction receives in the raw material influence of free aliphatic acid and moisture little, generally within several minutes, just can reach very high conversion ratio.But supercritical process exists energy consumption that it is obvious that is high, to the high shortcoming that requires of equipment.
Enzyme catalysis method can be facilitated ester exchange reaction under the condition of gentleness.And the immobilized enzyme catalysis agent can be repeated to use after regeneration.But enzyme catalysis method exists catalytic efficiency low, and the low-carbon alcohols of high concentration and glycerine all can produce toxic action to enzyme, and the shortcoming such as cost an arm and a leg of enzyme, and these have all limited its application in industry.
Homogeneous acid or heterogeneous acid catalysts method prepare biodiesel also has many research.Acid catalyzed process does not have strict especially requirement to the acid number and the moisture of raw material yet.Usually the material as homogeneous acid catalyst comprises the concentrated sulfuric acid, benzene sulfonic acid, phosphoric acid etc.Though the existence of free fatty and low amounts of water is little to the catalytic capability influence of acid catalyst; But the homogeneous acid catalysis method exists, and reaction temperature is high, reaction rate is too slow, etching apparatus, the higher alcohol oil rate of needs, and can the generation acid-bearing wastewater in the separation and purification process of product etc. problem.Solid acid catalyst catalyzed transesterification (or being referred to as the heterogeneous acid catalysts agent) also becomes the research focus in recent years.Equally, come catalyzed transesterification that the quality of raw material is not had strict especially requirement with solid acid catalyst, and with solid acid as the catalyst of heterogeneous reaction have catalyst be easy to separate with product, to advantages such as corrosion on Equipment property are less.But use solid acid catalyst still exist reaction temperature height, reaction time oversize, need higher shortcomings such as alcohol oil rate.
Under comparing, coming the catalytic transesterification method through the base catalysis method is more reasonable method of a kind of more economy.The catalyst that uses in the base catalysis method can be divided into two types of homogeneous phase base catalyst and solid base catalysts (or heterogeneous base catalyst) equally.Potassium hydroxide and NaOH are modal homogeneous catalysts, also are the catalyst that is adopted in the traditional ester exchange process.Use this type catalyst, it is heavy by about 1% that its consumption is about oil, and reaction temperature generally is the boiling point of methyl alcohol, and reaction speed is fast, and conversion ratio is high.If but contain more free fatty and moisture in the raw material, will make reactant and catalyst generation saponification (this can reduce ester conversion rate undoubtedly).But be to use the maximum shortcoming of homogeneous phase base catalyst also to be: the product washing that need neutralize, and a large amount of industrial wastewaters that thereupon bring can cause environmental pollution, the subsequent treatment complicacy.
Solid base catalyst is expected to solve the problem that the homogeneous phase base catalyst is brought.The solid base catalyst that Recent study gets often comprises: alkali alcoholate, and the oxide of alkaline-earth metal, carbonate, and various load type solid body base catalysts etc.Use solid base catalyst, it is simply many that the separation of product and purifying will become, and catalyst can be repeated to use and regenerate.Aspect the catalyzed by solid base ester exchange, it is maximum that CaO is studied.(M.Kouzu such as Masato Kouzu; M.Tsunomori, S.Yamanaka and J.Hidaka, Heterogeneous catalysis of calcium oxide used for transesterification ofsoybean oil with refluxing methanol; Appl Catal A:Gen; 2009, the XRD figure of CaO when 355:94-99.) having compared with CaO in detail, and the variation between the XRD figure of CaO after using repeatedly as catalyst.They find that CaO has become glycerine calcium (Ca (C after using
3H
7O
3)
2), and after repeatedly using except XRD figure does not have significant change, catalyst also maintains good catalytic activity.During as catalyst, CaO and glycerine have generated Ca (C in reaction system with CaO in this explanation
3H
7O
3)
2, Ca (C
3H
7O
3)
2In reaction system can stable existence, and the carrying out of catalyzed transesterification well.Masato Kouzu etc. has also confirmed Ca (C
3H
7O
3)
2To CO
2With moisture certain anti-toxic is arranged all, even the moisture of trace can also improve ester conversion rate.Masato Kouzu etc. has described them and has obtained Ca (C
3H
7O
3)
2Method be: through CaCO
3Calcine 1.5h down for 900 ℃ and obtain CaO, let newly-generated CaO and glycerine directly react then and obtain Ca (C
3H
7O
3)
2The invention provides the more easy and effective method that another kind obtains alkaline earth metal glyceride, the ester exchange reaction that this catalyst is used for catalysis grease and alcohol has obtained excellent catalytic effect.This catalytic process need not use separating of cosolvent and catalyst and product simple.Catalyst is reusable after reclaiming, and catalyst receives in air a little less than the toxic action of moisture and carbon dioxide, and stability is stronger.
Summary of the invention
The objective of the invention is to propose a kind of novel solid body base catalyst---the preparation method of alkaline earth metal glyceride; This compound process is simple, and with the catalyst for preparing be used for the catalysis grease with alcohol ester exchange reaction obtained excellent catalytic effect.This catalytic process need not used cosolvent, and catalyst is simple with separating of product, and catalyst is reusable after reclaiming, and catalyst all has anti-preferably toxic to moisture and carbon dioxide.
Another object of the present invention is to propose a kind ofly to utilize above-mentioned alkaline earth metal glyceride as the production process of catalyst applications in catalysis biological diesel oil.
The preparation method of the alkaline earth metal glyceride catalyst that the present invention proposes, its step is following:
At first configuration concentration is low-carbon alcohols (methyl alcohol or the ethanol) solution of the alkaline earth metal chloride of 0.1-0.4g/ml, preserves subsequent use.Getting a certain amount of alkali metal hydroxide and glycerine then is added in the reaction vessel together; The dosage of alkali-metal hydroxide adds 10-40g by every 100mL glycerine and is advisable; Then under stirring, reaction vessel is heated between 110-160 ℃, reaction continues 2-6h.When no longer including steam in the question response container and being steamed, the clear solution that generates is transferred in the tool plug ground conical flask (or container of other band sealing device).Treat that solution is cooled to about 40-60 ℃, be added in the aforementioned clear solution low-carbon alcohols (methyl alcohol or the ethanol) solution of the alkaline earth metal chloride of front preparation and mixing, can see having a large amount of white precipitates to generate in the solution this moment, and be attended by violent exothermic phenomenon.Wait to no longer include deposition and generate, with its cool to room temperature, through Buchner funnel suction filtration collecting precipitation, in the suction filtration process with low-carbon alcohols (methyl alcohol or ethanol) wash solids 2-3 time, to remove excessive glycerine.Suction filtration after accomplishing is preserved sealed solid.The white precipitate for preparing of method is the alkaline earth metal glyceride with catalytic activity thus.
Alkaline earth metal glyceride proposed by the invention is used for the production of catalysis biological diesel oil as catalyst, and its step is following:
The grease and the low-carbon alcohols (methyl alcohol or ethanol) of low acid number are mixed, and wherein, the mol ratio of low-carbon alcohols and grease is 3～45: 1; Add alkaline earth metal glyceride again as catalyst; Mix stirring down at 50-70 ℃, react after 1-4h hour, product standing demix or centrifugation.After standing demix or centrifugation, reaction system is divided three-phase: the upper strata is a biodiesel, and bottom one is catalyst mutually, and middle one is glycerine mutually.With lower floor's glycerine phase and catalyst separation, can obtain the bullion biodiesel.Coarse biodiesel can be collected and obtain refined biometric diesel oil after washing of NaCl saturated solution and decompression distillation (under vacuum＜5mmHg condition, collecting 130-190 ℃ of cut).It is reusable to separate the catalyst that obtains.
Alkali-metal hydroxide of the present invention comprises NaOH, potassium hydroxide or their mixture.
The chloride of alkaline-earth metal of the present invention comprises material or their mixtures such as magnesium chloride, calcium chloride, barium chloride.
Grease of the present invention comprises Jatropha curcas oil, cottonseed oil, rapeseed oil, transgenosis rapeseed oil, castor oil, soybean oil, genetically engineered soybean oil, coptis wood oil, literary composition hat oil, litsea citrate oil, palm oil, sunflower oil, peanut wet goods.
The acid number of the grease of low acid number according to the invention is below 1mg KOH/g; Because what can envision be free fatty to the catalyst of solid base type is toxic effect; Too high acid number can cause the carrying out of side reactions such as saponification, and will have influence on the repeat performance of catalyst.If on 1mg KOH/g, needing that grease is carried out depickling, handles acid number.Depickling processing procedure commonly used has: alkali refining method, steam distillation, esterification process, liquid-liquid extraction method etc.Existing mature technique and supporting equipment in alkali refining method and the steam distillation industry; Esterification process be through the concentrated sulfuric acid or other solid acids etc. as catalyst by the free fatty in the grease and methyl alcohol (or ethanol) in advance ester be converted into fatty acid methyl ester (or ethyl ester) and reach the purpose that reduces acid number; Liquid-liquid extraction method; Promptly through the characteristics of the solubility of free fatty in methyl alcohol (or ethanol) greater than the solubility in grease; With grease and 1: 2 by volume consumption of methyl alcohol (or ethanol); Extract 3-5 time, reach with the aliphatic acid in the grease be extracted into methyl alcohol mutually in the purpose of the acid number that reduces the grease phase.Be used to extract the methyl alcohol after the depickling, through decompression distillation reuse once again.
The decompression distillation of coarse biodiesel of the present invention after the washing of NaCl saturated solution is under the condition of vacuum＜5mmHg, to carry out, and collects 130-190 ℃ of cut, can obtain refined biometric diesel oil.
The specific embodiment
Following embodiment is used to further specify the present invention, is not to qualification of the present invention.
Embodiment 1
At first get 18g CaCl
2, being added in the 100mL methyl alcohol, vibration makes CaCl
2Dissolving can be prepared the methanol solution that obtains calcium chloride, preserves subsequent use.Taking by weighing the KOH of 20g and the glycerine of 100mL then is added in the there-necked flask of 250mL together.Under magnetic agitation, reaction vessel is heated to 120 ℃, reaction continues 3h.When no longer including steam in the question response container and being steamed, the clear solution that generates is transferred in the ground conical flask of a tool plug.When solution is cooled to about 40-60 ℃, be added in the transparent solution methanol solution of the calcium chloride of front preparation and mixing, can see having a large amount of white precipitates to generate in the solution this moment, and be attended by violent exothermic phenomenon.Wait to no longer include deposition and generate, under its cool to room temperature, through Buchner funnel suction filtration collecting precipitation, in the suction filtration process with methanol wash solid 2 times, to remove excessive glycerine.Suction filtration after accomplishing is preserved sealed solid.The white precipitate for preparing of method is the glycerine calcium Ca (C with catalytic activity thus
3H
7O
3)
2
Get the soybean oil of 50mL and the methyl alcohol of 25mL, add the Ca (C of 1.5g
3H
7O
3)
2As catalyst, mix stirring down at 60 ℃, react after 2h hour, product is centrifugalized under 8000r/min.After centrifugation, reaction system is divided three-phase: the upper strata is a biodiesel, and bottom one is catalyst mutually, and middle one is glycerine mutually.Isolate the glycerine phase and the catalyst of lower floor, can obtain the bullion biodiesel.Coarse biodiesel can be collected and obtain refined biometric diesel oil after washing of NaCl saturated solution and decompression distillation (under vacuum＜5mmHg condition, collecting 130-190 ℃ of cut).The catalyst that separation obtains still can obtain desirable conversion ratio after reusing three times.
Embodiment 2
At first get 20gMgCl
2, being added in the 100mL ethanol, vibration makes MgCl
2Dissolving can be prepared the ethanolic solution that obtains magnesium chloride, preserves subsequent use.Taking by weighing the NaOH of 20g and the glycerine of 80mL then is added in the there-necked flask of 250mL together.Under magnetic agitation, reaction vessel is heated to 120 ℃, reaction continues 3h.When no longer including steam in the question response container and being steamed, the clear solution that generates is transferred in the ground conical flask of a tool plug.When solution is cooled to about 40-60 ℃, be added in the clear solution ethanolic solution of the magnesium chloride of front preparation and mixing, can see having a large amount of white precipitates to generate in the solution this moment, and be attended by violent exothermic phenomenon.Wait to no longer include deposition and generate, under its cool to room temperature, through Buchner funnel suction filtration collecting precipitation, in the suction filtration process with washing with alcohol solid 2 times, to remove excessive glycerine.Suction filtration after accomplishing is preserved sealed solid.The white precipitate for preparing of method is the glycerine magnesium Mg (C that can have catalytic activity thus
3H
7O
3)
2
Get the Jatropha curcas oil (acid number is less than 1mg KOH/g) after the methanol extraction depickling of 50mL and the methyl alcohol of 25mL, add the Mg (C of 2g
3H
7O
3)
2As catalyst, mix stirring down at 60 ℃, react after 2h hour, product is centrifugalized under 8000r/min.After centrifugation, reaction system is divided three-phase: the upper strata is a biodiesel, and bottom one is catalyst mutually, and middle one is glycerine mutually.Isolate the glycerine phase and the catalyst of lower floor, can obtain the bullion biodiesel.Coarse biodiesel can be collected and obtain refined biometric diesel oil after washing of NaCl saturated solution and decompression distillation (under vacuum＜5mmHg condition, collecting 130-190 ℃ of cut).
Embodiment 3
At first get 12gBaCl
2, being added in the 100mL methyl alcohol, vibration makes BaCl
2Dissolving can be prepared the methanol solution that obtains barium chloride, preserves subsequent use.Taking by weighing the KOH of 20g and the glycerine of 100mL then is added in the there-necked flask of 250mL together.Under magnetic agitation, reaction vessel is heated to 140 ℃, reaction continues 2h.When no longer including steam in the question response container and being steamed, the clear solution that generates is transferred in the ground conical flask of a tool plug.When solution is cooled to about 40-60 ℃, be added in the clear solution methanol solution of the barium chloride of front preparation and mixing, can see having a large amount of white precipitates to generate in the solution this moment, and be attended by violent exothermic phenomenon.Wait to no longer include deposition and generate, under its cool to room temperature, through Buchner funnel suction filtration collecting precipitation, in the suction filtration process with methanol wash solid 2 times, to remove excessive glycerine.Suction filtration after accomplishing is preserved sealed solid.The white precipitate for preparing of method is the glycerine barium Ba (C that can have catalytic activity thus
3H
7O
3)
2
The acid number of getting 50mL adds the Ba (C of 2g less than the Jatropha curcas oil of 1mgKOH/g and the methyl alcohol of 100mL
3H
7O
3)
2As catalyst, mix stirring down at 60 ℃, react after 2h hour, product is centrifugalized under 8000r/min.After centrifugation, reaction system is divided three-phase: the upper strata is a biodiesel, and bottom one is catalyst mutually, and middle one is glycerine mutually.Isolate the glycerine phase and the catalyst of lower floor, can obtain the bullion biodiesel.Coarse biodiesel can be collected and obtain refined biometric diesel oil after washing of NaCl saturated solution and decompression distillation (under vacuum＜5mmHg condition, collecting 130-190 ℃ of cut).
Embodiment 4
At first get 18gCaCl
2, being added in the 100mL methyl alcohol, vibration makes CaCl
2Dissolving can be prepared the methanol solution that obtains calcium chloride, preserves subsequent use.Taking by weighing the NaOH of 20g and the glycerine of 100mL then is added in the there-necked flask of 250mL together.Under magnetic agitation, reaction vessel is heated to 130 ℃, reaction continues 3h.When no longer including steam in the question response container and being steamed, the clear solution that generates is transferred in the ground conical flask of a tool plug.When solution is cooled to about 40-60 ℃, be added in the clear solution methanol solution of the calcium chloride of front preparation and mixing, can see having a large amount of white precipitates to generate in the solution this moment, and be attended by violent exothermic phenomenon.Wait to no longer include deposition and generate, under its cool to room temperature, through Buchner funnel suction filtration collecting precipitation, in the suction filtration process with methanol wash solid 2 times, to remove excessive glycerine.Suction filtration after accomplishing is preserved sealed solid.The white precipitate for preparing of method is the glycerine calcium Ca (C that can have catalytic activity thus
3H
7O
3)
2
Get the sunflower oil of acid number below 1mgKOH/g and the methyl alcohol of 50mL of 100mL, add 4g Ca (C
3H
7O
3)
2As catalyst, mix stirring down at 65 ℃, react after 2h hour, product is centrifugalized under 8000r/min.After centrifugation, reaction system is divided three-phase: the upper strata is a biodiesel, and bottom one is catalyst mutually, and middle one is glycerine mutually.Isolate the glycerine phase and the catalyst of lower floor, can obtain the bullion biodiesel.Coarse biodiesel can be collected and obtain refined biometric diesel oil after washing of NaCl saturated solution and decompression distillation (under vacuum＜5mmHg condition, collecting 130-190 ℃ of cut).
Claims (7)
1. the preparation method of an alkaline earth metal glyceride catalyst, its step is following:
At first configuration concentration is the low-carbon alcohol solution of the alkaline earth metal chloride of 0.1-0.4g/ml, preserves subsequent use; The amount that adds the 10-40g alkali metal hydroxide by every 100mL glycerine then is added to alkali metal hydroxide and glycerine in the reaction vessel together, then under stirring, reaction vessel is heated between 110-160 ℃, and reaction continues 2-6h; When no longer including steam in the question response container and being steamed, the clear solution that generates is transferred in the container of tool plug ground conical flask or other band sealing device, treated that solution is cooled to 40-60 ℃; Be added in the aforementioned clear solution low-carbon alcohol solution of the alkaline earth metal chloride of front preparation and mixing, can see having a large amount of white precipitates to generate in the solution this moment, and be attended by violent exothermic phenomenon; Waiting to no longer include deposition generates; With its cool to room temperature, through Buchner funnel suction filtration collecting precipitation, in the suction filtration process with low-carbon alcohols wash solids 2-3 time; To remove excessive glycerine; After suction filtration is accomplished, sealed solid is preserved, promptly made alkaline earth metal glyceride with catalytic activity; Wherein, described low-carbon alcohols is methyl alcohol or ethanol.
2. the preparation method of alkaline earth metal glyceride catalyst according to claim 1 is characterized in that alkali metal hydroxide is NaOH, potassium hydroxide or their mixture.
3. the preparation method of alkaline earth metal glyceride catalyst according to claim 1 is characterized in that alkaline earth metal chloride is magnesium chloride, calcium chloride, barium chloride material or their mixture.
4. an alkaline earth metal glyceride as claimed in claim 1 is as the application of catalyst in the production process of catalysis biological diesel oil; Its step is following: grease and the low-carbon alcohols that at first will hang down acid number are mixed; Wherein, The mol ratio of low-carbon alcohols and grease is 3～45: 1; Add alkaline earth metal glyceride again as catalyst; Mix stirring down at 50-70 ℃, react after 1-4h hour, product standing demix or centrifugation; After standing demix or centrifugation, reaction system is divided three-phase: the upper strata is a biodiesel, and bottom one is catalyst mutually, and middle one is glycerine mutually; With lower floor's glycerine phase and catalyst separation, can obtain the crude product biodiesel; Coarse biodiesel can be collected and obtain refined biometric diesel oil after washing of NaCl saturated solution and decompression distillation.
5. alkaline earth metal glyceride according to claim 4 is characterized in that as the application of catalyst in the production process of catalysis biological diesel oil: said grease is Jatropha curcas oil, cottonseed oil, rapeseed oil, castor oil, soybean oil, coptis wood oil, literary composition hat oil, litsea citrate oil, palm oil, sunflower oil or peanut oil.
6. alkaline earth metal glyceride according to claim 4 is as the application of catalyst in the production process of catalysis biological diesel oil; It is characterized in that: the acid number of said low acid number grease is less than 1mg KOH/g; If on 1mg KOH/g, needing that grease is carried out depickling, handles acid number.
7. alkaline earth metal glyceride according to claim 4 is as the application of catalyst in the production process of catalysis biological diesel oil; It is characterized in that: the decompression distillation of coarse biodiesel after the washing of NaCl saturated solution; Be under the condition of vacuum＜5mmHg, to carry out; Collect 130-190 ℃ of cut, promptly make refined biometric diesel oil.
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| CN2009101958163A CN101642716B (en) | 2009-09-17 | 2009-09-17 | Preparation method and application of alkaline earth metal glyceride catalyst |
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|---|---|---|---|
| CN2009101958163A CN101642716B (en) | 2009-09-17 | 2009-09-17 | Preparation method and application of alkaline earth metal glyceride catalyst |
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| CN101642716B true CN101642716B (en) | 2012-08-22 |
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| CN104911034A (en) * | 2015-05-08 | 2015-09-16 | 湖北天基生物能源科技发展有限公司 | Method for continuously recycling depickling crude glycerine in biodiesel |
| TWI637052B (en) * | 2016-09-02 | 2018-10-01 | 崑山科技大學 | Preparation method of biodiesel using microwave heater and diglycerin calcium |
| TWI613290B (en) * | 2016-09-02 | 2018-02-01 | Preparation method of biodiesel using ultrasonic oscillator and microwave heater | |
| TWI621706B (en) * | 2016-09-02 | 2018-04-21 | Preparation method of biodiesel using homogenizer and diglycerin calcium |
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