CN101402873A - Method for producing light biological diesel oil with seed oil of camphor - Google Patents

Method for producing light biological diesel oil with seed oil of camphor Download PDF

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Publication number
CN101402873A
CN101402873A CNA2008101073786A CN200810107378A CN101402873A CN 101402873 A CN101402873 A CN 101402873A CN A2008101073786 A CNA2008101073786 A CN A2008101073786A CN 200810107378 A CN200810107378 A CN 200810107378A CN 101402873 A CN101402873 A CN 101402873A
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China
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methyl alcohol
carbinol
esterification
under
diesel oil
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CNA2008101073786A
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曾哲灵
万冬满
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Nanchang University
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Nanchang University
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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
    • 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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  • Fats And Perfumes (AREA)

Abstract

The invention relates to a method for preparing light biodiesel from camphor tree seed oil, which includes the pretreatments of impurity removing and degumming. The invention is characterized in that: the pretreated product is added with carbinol under the effect of the molar ratio of 0.5 to 0.7 between the esterification catalyst sulfate propyl sulfonic paramethyl imidazole acidated ion liquid and dissociated fatty acid according to a molar ratio of 5-7 between the carbinol and the dissociated fatty acid for reaction for 90 to 120min at the temperature of 64 to 70 DEG C and then separated through centrifuging; the esterification catalyst and the carbinol return an esterification reaction vessel; the product of esterification and the carbinol enter an ester exchange reaction vessel; under the effect of the molar ratio of 0.15 to 0.2 between the ester exchange catalyst grain-shaped loading type KOH/MgO/Al2O3 and total fatty acid, the carbinol is added according to a molar ratio of 6 to 8 between the carbinol and the total fatty acid for reaction for 180 to 210min at the temperature of 64 to 70 DEG C, then filtered and separated through centrifuging; a glycerin phase recycles the carbinol through film distilling and obtains the glycerin; a formic ester phase recycles the carbinol through film distilling and is decolored for obtaining the light biodiesel which not only can be mixed with light diesel oil or vehicle diesel oil for being used as a diesel oil engine fuel, but also can be directly used as the diesel oil engine fuel.

Description

The method of producing light biological diesel oil with seed oil of camphor
Technical field
The invention belongs to bio-oil materials synthetic field, the particularly preparation of light weight type biofuel.
Background technology
Along with global petroleum resources reserves day by day reduce, weather runs down, the favor that has obtained more and more national is used in the research, development and production of biofuel.Many Europe, America, Asian countries are all paying attention to the development biofuel, research and develop out multiple soybean transformation oil, rapeseed oil, plam oil, little Oleum Verniciae fordii, the isometric chain fatty acid quasi-grease of waste grease (more than the C16) production diesel-fuel blending biofuel-heavy type biodiesel technology in succession, the annual production of heavy type biofuel (more than the C16) has developed into few hundred thousand tonnes of to millions of tons.Be used to produce the raw material major part of heavy type biofuel at present for eating long chain fatty acid quasi-grease (more than the C16), formed situation with food service industry contention raw material, raw material supply wretched insufficiency, cost of material are much higher than diesel-fuel price, and further developing of heavy type biofuel is restricted.
Except the long chain fatty acid quasi-grease (more than the C16) that is suitable for edible and production heavy type biofuel, also there are a variety of non-middle chain fatty acid quasi-greases (C8-C14) that eat, are suitable for producing light weight type biofuel (C8-C14) in nature.Light weight type biofuel good fluidity, distillation recovered temperature are lower, and its physics and performance index and LIGHT DIESEL OIL or derv fuel oil are very approaching, both can with petroleum diesel blending use, also can use separately.Utilize non-edible middle chain fatty acid quasi-grease to produce the light weight type biofuel, have good prospect.But the relevant research, development and production that transform non-edible middle chain fatty acid quasi-grease production light weight type biofuel yet there are no bibliographical information.
Camphor tree seed oil is rich in chain fatty acid (capric acid content 52%, lauric acid content 42%) in capric acid (C10), the lauric acid (C12) etc., and wherein chain fatty acid content reaches more than 94%, is the desirable feedstock of production biofuel.Because by the biofuel product of camphor tree seed oil preparation, its good fluidity, oxidation stability height, distillation recovered temperature are lower, and its physics and performance index and-No. 10 LIGHT DIESEL OIL or-No. 10 derv fuel oils are very approaching, genus light weight type biofuel.
More existing both at home and abroad about camphor tree seed oil extractions, camphor tree seed oil fatty acid compositional analysis, utilize camphor tree seed oil prepare in the bibliographical information of chain fatty acid glyceryl ester (Glycerin, mixed triester with caprylic acid capric acid and laurin) or fatty acid diethanolamine or fatty diglycollic amide research aspect.And the relevant bibliographical information of producing light biological diesel oil with seed oil of camphor aspect that utilizes does not occur so far.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of utilizing producing light biological diesel oil with seed oil of camphor is provided.
Light weight type biofuel of the present invention is meant that carbon chain lengths is C8-C14.The present invention realizes by following preparation process.
1, the removal of impurities pre-treatment of coming unstuck:
Camphor tree seed crude oil is heated with stirring to 65 ± 5 ℃ adds the phosphoric acid (concentration is 85%) of the heavy 0.1-1% of oil and 65 ± 5 ℃ of water of oily heavy 10-15% afterwards while stirring, continue stirring 5-15min, centrifugation, vacuum hydro-extraction.
2, esterification:
With above-mentioned pretreating raw material, be under 0.5～0.7 the esterifying catalyst effect at esterifying catalyst sulfuric acid propyl sulfonic acid base to the mol ratio of Methylimidazole acidifying ionic liquid/free fatty acids, in the mol ratio of methyl alcohol/free fatty acids is that 5～7 ratio adds methyl alcohol, under 64～70 ℃ of temperature, reaction 90～120min, centrifugation.Esterifying catalyst, methyl alcohol return reaction kettle of the esterification mutually, and esterification products, methyl alcohol enter transesterification reactor mutually.
3, transesterification reaction:
With the product in the above-mentioned esterification, at transesterification catalyst particulate supported type KOH/MgO/Al 2O 3The mol ratio of/total fatty acids is under 0.15～0.2 the transesterification catalyst effect, is that 6～8 ratio adds methyl alcohol in the mol ratio of methyl alcohol/total fatty acids, and under 64～70 ℃ of temperature, reaction 180～210min filters, centrifugation.
4, glycerine, methyl alcohol phase (being called for short the glycerine phase) reclaim methyl alcohol and obtain glycerine through thin film distillation, and light weight type biofuel, methyl alcohol phase (being called for short the formicester phase) reclaim methyl alcohol through thin film distillation, and decolouring obtains the lightweight biofuel.
In esterification, the esterifying catalyst after the centrifugation can recycle, every use 7h (4 times), 0.15% catalyzer of make-up catalyst consumption.
In transesterification reaction, when ester exchange rate is lower than 98.0%, transesterification catalyst is regenerated.Regeneration condition is: solvent cleaning, 105 ℃ of oven dry 1h, 1molKOH solution soak damp 2h, 105 ℃ of oven dry 2h, 560 ℃ of calcining 3h.
Esterifying catalyst sulfuric acid propyl sulfonic acid base of the present invention is the prior art for preparing gained to Methylimidazole acidifying ionic liquid, and its preparation method is:
With 1,3-propane sultone is dissolved in the toluene, is placed in the ice-water bath afterwards earlier.Drip equimolar N-Methylimidazole down in magnetic agitation and low temperature (≤5 ℃).After dripping, slowly rise to normal temperature and continue reaction 2h, the throw out that filters out in the reaction solution also respectively washs three times with ether and ethyl acetate, 100 ℃ of oven dry 5h, and the gained white solid is 1-methyl-3-(propyl group-3-sulfonic group) imidazole salts (yield 95.6%).1-methyl-3-(propyl group-3-sulfonic group) imidazole salts is soluble in water, under magnetic agitation and normal temperature, drip equimolar sulfuric acid.After dripping off, slowly be warming up to 90 ℃ of reaction 2h, vaccum dewatering 3h, the light yellow viscous liquid of gained are sulfuric acid propyl sulfonic acid base to Methylimidazole acidifying ionic liquid [HSO 3-pmim] [HSO 4] (yield 99%).
Transesterification catalyst particulate supported type KOH/MgO of the present invention 2/ Al 2O 3Catalyzer is the prior art for preparing gained, and its preparation method is:
With nano level MgO and Al 2O 3The granulation of powder wet-mixed ,-10 ℃ of lyophilize 4h, 105 ℃ of oven dry 1h pulverize and make particulate supported type MgO/Al 2O 3Carrier; In 1molKOH solution, soak damp 2h, 105 ℃ of oven dry 2h, 450 ℃ of calcining 3h get particulate supported type KOH/MgO 2/ Al 2O 3Catalyzer, its specific surface area are 300-350m 2/ g, charge capacity is 3-8mmolKOH/g.
The esterifying catalyst that the present invention has overcome present biofuel Product industrialization production technique can't or be difficult to reuse, esterification with methyl alcohol can't directly recycle, esterification finishes that back methyl alcohol needs that all distillations are recycled, repeated use time weak point (being lower than 500h) after the transesterification catalyst regeneration, glycerine is difficult for separated and collected and purity is lower, product need distill refining, the high deficiency of energy consumption.Esterification yield is 98.22%, and ester exchange rate is 98.85%, and bio-diesel yield (with respect to raw material) is 98.2%, and purity 95.0% glycerine yield (with respect to raw material) is 9.0%.
Esterifying catalyst and most of esterification can directly recycle with methyl alcohol in the esterification process, and remainder methyl alcohol can directly enter the transesterify operation and use, and esterification need not reclaimed through distillation with methyl alcohol; Transesterification catalyst particulate supported type KOH/MgO in the transesterify process 2/ Al 2O 3Catalyzer is renewable more than 8 times, repeated use time accumulative total reaches 672h, and glycerine is easy to separated and collected, purity can reach more than 95%; Product need not distill refining, and energy consumption is low, is equivalent to 0.2 ton of standard coal/ton product.
Light weight type biofuel of the present invention both can be used as diesel motor fuel with LIGHT DIESEL OIL or derv fuel oil blending back, also can directly be used as diesel motor fuel.
Embodiment
The present invention will be described further by following examples.
The described esterifying catalyst of following examples is meant that sulfuric acid propyl sulfonic acid base is to Methylimidazole acidifying ionic liquid; Transesterification catalyst is meant particulate supported type KOH/MgO 2/ Al 2O 3Catalyzer.
Embodiment 1.
Camphor tree seed crude oil is heated with stirring to 65 ℃ adds oily 0.2% phosphoric acid (concentration is 85%) and oily 15% the 65 ℃ of water that weigh of weighing afterwards while stirring, continue stirring 10min, centrifugation, vacuum hydro-extraction;
With above-mentioned pretreating raw material, be under 0.5 the esterifying catalyst effect in the mol ratio of esterifying catalyst/free fatty acids, be that 5 ratio adds methyl alcohol in the mol ratio of methyl alcohol/free fatty acids, under 65 ℃ of temperature, reaction 105min, centrifugation then; Esterifying catalyst, methyl alcohol return reaction kettle of the esterification mutually, and esterification products, methyl alcohol enter transesterification reactor mutually.
With the product in the above-mentioned esterification, being under 0.15 the transesterification catalyst effect in the mol ratio of transesterification catalyst/total fatty acids, is that 7 ratio adds methyl alcohol in the mol ratio of methyl alcohol/total fatty acids, under 65 ℃ of temperature, reaction 210min, filtration, centrifugation.Glycerine, methyl alcohol reclaim methyl alcohol and obtain glycerine through thin film distillation, and light weight type biofuel, methyl alcohol reclaim methyl alcohol through thin film distillation, and decolouring obtains the lightweight biofuel.
Embodiment 2.
Camphor tree seed crude oil is heated with stirring to 68 ℃ adds oily 1% phosphoric acid (concentration is 85%) and oily 12% the 68 ℃ of water that weigh of weighing afterwards while stirring, continue stirring 7min, centrifugation, vacuum hydro-extraction;
With above-mentioned pretreating raw material, be under 0.7 the esterifying catalyst effect in the mol ratio of esterifying catalyst/free fatty acids, be that 7 ratio adds methyl alcohol in the mol ratio of methyl alcohol/free fatty acids, under 70 ℃ of temperature, reaction 90min, centrifugation then; Esterifying catalyst, methyl alcohol return reaction kettle of the esterification mutually, and esterification products, methyl alcohol enter transesterification reactor mutually.
With the product in the above-mentioned esterification, be under 0.2 the transesterification catalyst effect in the mol ratio of transesterification catalyst/total fatty acids, in the mol ratio of methyl alcohol/total fatty acids is that 8 ratio adds methyl alcohol, under 70 ℃ of temperature, reaction 180min, filtration, centrifugation, glycerine, methyl alcohol reclaim methyl alcohol and obtain glycerine through thin film distillation, light weight type biofuel, methyl alcohol reclaim methyl alcohol through thin film distillation, and decolouring obtains the lightweight biofuel.
Embodiment 3.
Camphor tree seed crude oil is heated with stirring to 60 ℃ adds oily 0.1% phosphoric acid (concentration is 85%) and oily 10% the 60 ℃ of water that weigh of weighing afterwards while stirring, continue stirring 5min, centrifugation, vacuum hydro-extraction.
With above-mentioned pretreating raw material, be under 0.6 the esterifying catalyst effect in the mol ratio of esterifying catalyst/free fatty acids, be that 5 ratio adds methyl alcohol in the mol ratio of methyl alcohol/free fatty acids, under 64 ℃ of temperature, reaction 120min, centrifugation then.Esterifying catalyst, methyl alcohol return reaction kettle of the esterification mutually, and esterification products, methyl alcohol enter transesterification reactor mutually.
With the product in the above-mentioned esterification, being under 0.18 the transesterification catalyst effect in the mol ratio of transesterification catalyst/total fatty acids, is that 6 ratio adds methyl alcohol in the mol ratio of methyl alcohol/total fatty acids, under 64 ℃ of temperature, reaction 210min, filtration, centrifugation.Glycerine, methyl alcohol reclaim methyl alcohol and obtain glycerine through thin film distillation, and light weight type biofuel, methyl alcohol reclaim methyl alcohol through thin film distillation, and decolouring obtains the lightweight biofuel.

Claims (1)

1, a kind of method of producing light biological diesel oil with seed oil of camphor, comprise the camphor tree seed crude oil removal of impurities pre-treatment of coming unstuck, it is characterized in that pretreated product, be under 0.5～0.7 the esterifying catalyst effect at esterifying catalyst sulfuric acid propyl sulfonic acid base to the mol ratio of Methylimidazole acidifying ionic liquid/free fatty acids, in the mol ratio of methyl alcohol/free fatty acids is that 5～7 ratio adds methyl alcohol, under 64～70 ℃ of temperature, reaction 90～120min, centrifugation, esterifying catalyst, methyl alcohol returns reaction kettle of the esterification, esterification products mutually, methyl alcohol enters transesterification reactor mutually; At transesterification catalyst particulate supported type KOH/MgO/Al 2O 3The mol ratio of/total fatty acids is under 0.15～0.2 the transesterification catalyst effect, in the mol ratio of methyl alcohol/total fatty acids is that 6～8 ratio adds methyl alcohol, under 64～70 ℃ of temperature, reaction 180～210min, filtration, centrifugation, glycerine, methyl alcohol reclaim methyl alcohol and obtain glycerine through thin film distillation, and light weight type biofuel, methyl alcohol is through thin film distillation recovery methyl alcohol, decolour the lightweight biofuel.
CNA2008101073786A 2008-11-12 2008-11-12 Method for producing light biological diesel oil with seed oil of camphor Pending CN101402873A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101921660A (en) * 2010-08-06 2010-12-22 河南科技大学 Method for intermittently preparing biodiesel from camphor tree seed kernel oil through ultrasonic reaction pot
CN102533308A (en) * 2012-02-14 2012-07-04 华南理工大学 Device for recovering ionic liquid catalyst used for transesterification of vegetable fat
CN102586002A (en) * 2011-01-12 2012-07-18 中国科学院过程工程研究所 Method for extracting oil from microalgae by utilizing ionic liquid
CN103756791A (en) * 2013-12-25 2014-04-30 郑州奇克生物科技有限公司 Synthetic method of biodiesel
CN104911026A (en) * 2015-06-30 2015-09-16 成都易胜科生物科技有限公司 Production system for preparing biodiesel from camphor tree seeds
CN105001972A (en) * 2015-06-30 2015-10-28 成都易胜科生物科技有限公司 Method for preparing liquid fuel from camphor tree seed as raw material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101921660A (en) * 2010-08-06 2010-12-22 河南科技大学 Method for intermittently preparing biodiesel from camphor tree seed kernel oil through ultrasonic reaction pot
CN101921660B (en) * 2010-08-06 2012-09-05 河南科技大学 Method for intermittently preparing biodiesel from camphor tree seed kernel oil through ultrasonic reaction pot
CN102586002A (en) * 2011-01-12 2012-07-18 中国科学院过程工程研究所 Method for extracting oil from microalgae by utilizing ionic liquid
CN102586002B (en) * 2011-01-12 2013-10-16 中国科学院过程工程研究所 Method for extracting oil from microalgae by utilizing ionic liquid
CN102533308A (en) * 2012-02-14 2012-07-04 华南理工大学 Device for recovering ionic liquid catalyst used for transesterification of vegetable fat
CN102533308B (en) * 2012-02-14 2013-12-11 华南理工大学 Device for recovering ionic liquid catalyst used for transesterification of vegetable fat
CN103756791A (en) * 2013-12-25 2014-04-30 郑州奇克生物科技有限公司 Synthetic method of biodiesel
CN103756791B (en) * 2013-12-25 2015-08-19 郑州奇克生物科技有限公司 The synthetic method of biofuel
CN104911026A (en) * 2015-06-30 2015-09-16 成都易胜科生物科技有限公司 Production system for preparing biodiesel from camphor tree seeds
CN105001972A (en) * 2015-06-30 2015-10-28 成都易胜科生物科技有限公司 Method for preparing liquid fuel from camphor tree seed as raw material

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Application publication date: 20090408