CN102212414A - Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and waste oil under alkali catalysis and preparation method thereof - Google Patents

Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and waste oil under alkali catalysis and preparation method thereof Download PDF

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CN102212414A
CN102212414A CN2011101040549A CN201110104054A CN102212414A CN 102212414 A CN102212414 A CN 102212414A CN 2011101040549 A CN2011101040549 A CN 2011101040549A CN 201110104054 A CN201110104054 A CN 201110104054A CN 102212414 A CN102212414 A CN 102212414A
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oil
idesia polycarpa
mixing
biofuel
waste
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CN102212414B (en
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刘长根
秦丹
冯义高
简华杰
陈建文
刘剑
刘怡
冯磊
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Guangdong Dingfeng Ecological Agriculture Development Co ltd
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刘长根
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

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Abstract

The invention discloses biodiesel prepared by performing ester exchange reaction on mixed oil prepared by mixing Idesia polycarpa var.vestita Diels oil and waste animal and vegetable oil in a certain ratio and low-carbon alcohol under catalysis of solid alkali serving as a catalyst. A preparation method of the biodiesel comprises the following process steps of: preparing the mixed oil; hydrating to degum; performing alkali refining to deacidify; decoloring; performing reaction under the catalysis of the solid alkali; and separating. The Idesia polycarpa var.vestita Diels with high yield in the high yield period and good oil quality is developed and utilized, so that the raw material cost is effectively reduced. However, the best method to solve the problem of low yield of the Idesia polycarpa var.vestita Diels in the initial period is that: the Idesia polycarpa var.vestita Diels oil is utilized unremittingly, so that planting area is enlarged by farmers, the effects of half the work with double results such as increasing farmer income and the like are achieved, and the waste oil is used for producing the biodiesel. The biodiesel prepared by the method has high recovery rate and low cost, improves the environment and products, and can reach the national standard.

Description

Base catalysis Idesia polycarpa oil and waste oil are produced biofuel and method
Technical field
The present invention relates to the preparation of Regeneratable biological diesel oil, particularly Idesia polycarpa oil and depleted vegetable and animals oils (be called for short: the uniform mixing oil of preparing by a certain percentage waste oil), produce biofuel itself and preparation method through catalyzed by solid base.
Technical background
The diesel oil that uses in a large number belongs to non-renewable resource as the diesel oil of refining of petroleum at present, and its resource is more and more exhausted.In production, processing and the use of this class diesel oil, the eubiosis of physical environment is being deposited immeasurable recessiveness and directly threat, become one of outstanding problem in the current global warming Greenhouse effect.It is extremely low that biofuel has sulphur content, and aromatic hydrocarbon content is few, oxygen level height, the characteristics that the waste gas effusion is few.The development biofuel is of value to preserves the ecological environment.The development and use biofuel meets the requirement of developing a circular economy with Sustainable development.Developing wild oilseed plant is one of important topic of following sustainable development of China.Because China is populous, should not use the edible fat production biofuel.So domestic universities and colleges, R﹠D institution, company and enterprise etc. have carried out one after another curcas oil, Zanthoxylum simulans oil, rubber seed oil, Oleum Gossypii semen, wilson dogwood oil, coptis root wood oil, seeds of a tung oil tree wet goods have been developed research.Find in the practice that also there is such or such problem in these species, as: yield poorly; Stock number is limited; Plantation is subjected to region restriction etc.Through relevant expert's estimation, China's its raw materials cost of development biofuel accounts for 70% of biofuel total cost, makes it to become a big bottleneck of biofuel industry development.Qin Dan, Liu Changgen in 2008 etc. are through the research and development of more than ten years to Idesia polycarpa, in " the international renewable energy resources in Guangzhou scientific seminar ", delivered " new way---the Idesia polycarpa of development biomass energy ", introduced the research and development prospect and the plantation situation of Idesia polycarpa.This project obtains national spark program (certificate number: meter is sent out [2004] No. 140 by state section).Successfully solve wild Idesia polycarpa difficulty and bred problem, big area breeding.The long root of Liu in 2004, Qin Dan etc. have declared national inventing patent (ZL200410081444.9).These provide solid foundation for developing Idesia polycarpa and then production biofuel.
In December, 2010, National Ministry of Finance, the State Tax Administration dispatch a joint document " about to utilizing the depleted vegetable and animals oils to produce the notice of pure thing diesel oil exempt from consumption tax ".Its purpose for effectively preventing depleted vegetable and animals oils " backflow " dining table, helps food safety exactly.Simultaneously also for promoting the biofuel industry development to seek available breeding resource.
The production method of biofuel.Mainly being chemical catalysis at present, secondly is catalyzed by biological enzyme and supercutical fluid method.Chemical catalysis production biofuel be with chemical substance as catalyzer, as strong acid-sulfuric acid, highly basic-sodium hydroxide, potassium hydroxide, sodium methylate etc., the transesterification reaction of catalysis animals and plants fat and short chain alcohol.Chemical method production biofuel method is simple, and the grease transformation efficiency is higher, can reach about 90%, and the reaction times is shorter, can finish reaction in 4~6 hours, realizes suitability for industrialized production easily.At present, the suitability for industrialized production method of bio-diesel oil adopts chemical method more, but there is very big drawback in chemical method production biofuel, requires further improvement, perfect.
In order to improve the deficiency in the chemical catalysis, produced the method for solid catalyst.The investigator mainly concentrates on the development of solid catalyst and using.The use of solid catalyst can reduce the product separating difficulty greatly, and can reuse, and reduces the pollution to environment of spent acid or waste lye, and catalyzer is separated with product than being easier to, and reaction conversion ratio is higher, and the process of producing of biofuel is comparatively simple.
With Idesia polycarpa oil preparation biofuel, declare three families that have of patent: " a kind of water white gourd oil prepares method of bio-diesel oil " of Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology, (ZL20061015380.0) its method was equipped with biofuel for the base-catalyzed transesterification legal system at present; Chu great " preparation method of bio-diesel oil by the water white gourd oil ", (ZL200610042737.5) its method was under the base catalysis condition, stirred and carried out esterification in 30~60 minutes; (application number: 200810046195.8), its method is a catalyzed by solid base to " with catalyzed by solid base Idesia polycarpa oil preparation method of bio-diesel oil " of Song Hang etc.More than the common ground of three patents all be the simple natural wild Idesia polycarpa oil of base catalysis.The actual state of China's Idesia polycarpa development: fundamentally, one or two tame enterprise few in number effort through more than ten years is arranged, implemented than the establishing in large scale Idesia polycarpa, the Idesia polycarpa of also just having accomplished the part artificial culture tries flower, bears fruit, and also needs certain time but will reach mass-producing; Have, do raw material by wild Idesia polycarpa oil fully, neither reality is also unrealistic.
Summary of the invention
The objective of the invention is to produce the defective of biofuel for overcoming above-mentioned dependence Idesia polycarpa oil wild at present or a little artificial culture, take to utilize waste oils and fats and the mixed mixing oil of existing crude vegetal to produce biofuel, not only can solve insufficient raw material, also reduce raw materials cost.Also improve environmental quality simultaneously.It promptly is the mixing oil production biofuel of preparing by a certain percentage with catalyzed by solid base Idesia polycarpa oil and waste oils and fats.This is according to the DEVELOPMENT PROSPECT amount of Idesia polycarpa oil and depleted vegetable and animals oils generation, and a kind of method that bottleneck problem appears in current development biofuel that helps promoting to solve is provided.Because generally be that the enterprise development rule of raw material is mostly with the kind of plant: raw material output does not increase, and just can not use; Can not use, the peasant just can not be sold; The peasant is no longer plantation just, and output does not just increase forever yet.Unique method is exactly: have only the product that under any circumstance can purchase the peasant, could transfer peasant's enthusiasm.Production biofuel of the present invention uses waste oils and fats to come compensating hair leaf idesia oil deficiency, also effectively prevents its backflow dining table simultaneously, helps food safety and promotes the Idesia polycarpa industry development.Also solved underproduce problem of the Idesia polycarpa early stage of development.Like this, more can transfer the plantation enthusiasm of vast farmers, impel the peasant to satisfy the demand by establishing in large scale woody oleiferous plants plant Idesia polycarpa, make it obtain high economic benefit and do not occupy cultivated land again, help solving well the agriculture, rural areas and farmers problem.Reduce the production cost of biofuel especially from the source, promote the Sustainable development of biofuel industry.
Technical scheme of the present invention be with Idesia polycarpa oil and waste oils and fats in proportion uniform mixing make mixing oil and produce biofuel with catalyzed by solid base.Described Idesia polycarpa oil and waste oils and fats ratio are 1: 0.01--1: 4.
Described Idesia polycarpa oil and the moving mixing oil of planting oil of depleted, hereinafter to be referred as: mixing oil or oil; Idesia polycarpa oil is called for short: crude oil; The moving oil of planting of depleted is called for short: waste oil.
With crude oil and the waste oil mixing oil behind the uniform mixing in proportion, through the processing step and the condition of preparing biological diesel oil catalyzed by solid base:
(1) preparation mixing oil: with crude oil. waste oil in proportion: 1: 0.01--1: 4 uniform mixing;
(2) hydration degum; Mixing oil is heated to 65-80 ℃, add the heavy 6-8% of mixing oil with the synthermal water of oil phase, carry out hydration degum 40-50mim;
(3) alkali-refining deacidification: the mixing oil after will coming unstuck carries out after drying dewaters, heat and also control oily temperature at 60-80 ℃, the 6-8% concentration that the adding mixing oil weighs under stirring is that sodium hydroxide (or potassium hydroxide or yellow soda ash) solution of 18-20% carries out alkali-refining deacidification 45-60min;
(4) decolouring: the oil behind the alkali refining adds the also pre-atlapulgites prior to 160 ℃ of activation 1.5-2.5h of oily heavy 6-7%, decolouring 40-55min under 70-85 ℃;
(5) catalyzed by solid base reaction: (alcohol, molar equivalent are 5.5: 1--10: 1) to add low-carbon alcohol in the bleached oil, catalyzer (Mg-Al composite oxides) weight is that the heavy 1.5-3% of oil adds in oil, the pure mixed solution, and temperature is controlled under the 70-80 ℃ of condition and stirs 3-5h.(low-carbon alcohol can be a methyl alcohol. ethanol or Virahol);
(6) separate: reclaim low-carbon alcohol, Mg-Al composite oxides, glycerine and biofuel.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail; but it must be noted that following examples can not understand limiting the scope of the invention, some nonessential improvement that the person skilled in the art of this area makes according to content of the present invention or adjust and then still belong to protection domain of the present invention.
Embodiment one
(1) mixing oil: with crude oil. waste oil in proportion: 1: 3.5 preparation mixing oil 60.2g;
(2) hydration degum: the heavy 60.2g of mixing oil is heated to 75 ℃, add mixing oil weight 6% and the synthermal water of oil phase, carry out hydration degum 45mim;
(3) alkali-refining deacidification: the oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 75 ℃, stir add down oil heavy 6%, concentration is that 20% sodium hydroxide solution carries out alkali-refining deacidification 50min;
(4) decolouring: the oil behind the alkali refining 70 ℃ add down mixing oil heavy 6% and in advance prior to 160 ℃ of atlapulgites of activation 1.5h down, decolouring 40min;
(5) catalyzed by solid base reaction: after bleached oil and the 9.12g methyl alcohol (molar ratio of methanol to oil: 6: 1) of 37.28g mixed, add solid alkali (Mg-Al composite oxides) again by the mixing oil weight 2% after the decolouring, be controlled at 70 ℃ of temperature condition lower magnetic forces in temperature and stir, reaction 3h;
(6) separate: after reaction finished, unreacted methanol was reclaimed in distillation, isolates the renewable repeated use of catalyzer, then filtrate is poured into standing demix in the separating funnel.The upper strata is a biofuel, and lower floor is a glycerin layer.This example biofuel yield 83.3%.
Embodiment two
(1) mixing oil: with crude oil. waste oil in proportion: 1: 0.01 preparation mixing oil 104.25g;
(2) hydration degum: the mixing oil of 104.25g under 70 ℃ of conditions, is added oil and weighs 7% equal temperature water, carry out hydration degum 40min;
(3) alkali-refining deacidification: the mixing oil drying after will coming unstuck dewaters, and heats and controls to 75 ℃, under agitation adds 7% of mixing oil, and concentration is that 18% potassium hydroxide solution carries out alkali-refining deacidification 45min;
(4) decolouring: the mixing oil behind the alkali refining adds the activated decoloration 50min that mixing oil weighs 7% (and activating 1.5h down prior to 160 ℃ in advance) under 75 ℃;
(5) catalyzed by solid base reaction: with the mixing oil after the 52.55g decolouring and 12.35g methyl alcohol (alcohol. molar equivalent: 6: 1) mix after, the solid alkali (Mg-Al composite oxides) that adds weight of oil 3.0% again, temperature is controlled at 70 ℃ of temperature condition lower magnetic forces and stirs, reaction 4h.
(6) separate: after reaction finished, unreacted methanol was reclaimed in distillation, isolates the renewable repeated use of catalyzer, then filtrate is poured into standing demix in the separating funnel.The upper strata is a biofuel, and lower floor is a glycerine.This example biofuel yield 84.3%.
Embodiment three
(1) mixing oil: with crude oil. waste oil in proportion: 1: 0.1 preparation mixing oil 81.55g.
(2) hydration degum; Mixing oil 81.55g is heated to 70 ℃, add 6% and the synthermal water of oil phase of mixing oil weight, carry out hydration degum 45mim.
(3) alkali-refining deacidification; Oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 75 ℃, stir add down oil heavy 6%, concentration is that 18% sodium carbonate solution carries out alkali-refining deacidification 45min.
(4) decolouring; Mixing oil behind the alkali refining adds mixing oil heavy 6% and pre-activated decoloration 40min prior to 160 ℃ of following activation 1.5h under 75 ℃.
(5) catalyzed by solid base reaction: with the 51.28g bleached oil with after 12.05g methyl alcohol (molar ratio of methanol to oil: 5.5: 1) mixes, add the solid alkali (Mg-Al composite oxides) of pressing weight of oil 2% again, be controlled under 75 ℃ of temperature condition magnetic agitation reaction 2h in temperature.
(6) separate: after reaction finished, unreacted methanol was reclaimed in distillation, isolated catalyst regeneration and reused, and then filtrate was poured into standing demix in the separating funnel.The upper strata is a biofuel, and lower floor is a glycerine.This example biofuel yield 84.1%.
Embodiment four
(1) preparation mixing oil: with crude oil. waste oil in proportion: 1: 1.5 preparation mixing oil 86.88g;
(2) hydration degum: the heavy 86.88g of mixing oil is heated to 70 ℃, add mixing oil weigh 6% with the synthermal water of oil phase, carry out hydration degum 45mim;
(3) alkali-refining deacidification: the oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature at 65 ℃, stir add down oil heavy 6%, concentration is that 20% sodium carbonate solution carries out alkali-refining deacidification 40min;
(4) decolouring: the oil behind the alkali refining 70 ℃ add down mixing oil weigh 6% and in advance prior to 160 ℃ of atlapulgites of activation 1.5h down, decolouring 40min;
(5) catalyzed by solid base reaction: after bleached oil and the 31.76g ethanol (molar ratio of methanol to oil: 9: 1) of 61.63g mixed, add by the mixing oil after the decolouring again and weigh 2.5% solid alkali (Mg-Al composite oxides), be controlled at 80 ℃ of temperature condition lower magnetic forces in temperature and stir, reaction 3h;
(6) separate: after reaction finished, unreacted ethanol was reclaimed in distillation, isolates the renewable repeated use of catalyzer, then filtrate is poured into standing demix in the separating funnel.The upper strata is a biofuel, and lower floor is a glycerin layer.This example biofuel yield 84.3%.

Claims (2)

1. biofuel of producing with catalyzed by solid base, it is characterized in that mixing oil with Idesia polycarpa oil and waste oil in proportion uniform mixing make, described waste oil is the depleted vegetable and animals oils, the ratio 1 of the oily and waste oil of described Idesia polycarpa: 0.01-1: 4.
2. be mixed in proportion through catalyzed by solid base the processing step and the condition of preparation biofuel with waste oil with Idesia polycarpa oil:
(1) preparation mixing oil: with Idesia polycarpa oil and waste oil in 1: 0.01--1: 4 ratio uniform mixing;
(2) hydration degum; Mixing oil is heated to 65-80 ℃, add the heavy 6-8% of mixing oil with the synthermal water of oil phase, carry out hydration degum 40-50mim;
(3) alkali-refining deacidification: the mixing oil after will coming unstuck carries out after drying dewaters, heating also control oil temperature stirs at 60-80 ℃ that any solution carries out alkali-refining deacidification 45-60min in sodium hydroxide that the concentration that adds the heavy 6-8% of mixing oil down is 18-20% or potassium hydroxide or the yellow soda ash;
(4) decolouring: the oil behind the alkali refining adds the also pre-prior to 160 ℃ of atlapulgites that activate 1.5-2.5h down of oily heavy 6-7%, decolouring 40-55min under 70-85 ℃;
(5) catalyzed by solid base reaction: add alcohol, molar equivalent 5.5: 1-10 in the bleached oil: 1 low-carbon alcohol, with solid base catalyst Mg-Al composite oxides heavily is that the heavy 1.5-3% of oil adds in oil, the pure mixed solution, and temperature is controlled under the 70-80 ℃ of condition and stirs 3-5h.Described low-carbon alcohol can be a methyl alcohol. any in ethanol or the Virahol;
(6) separate: reclaim low-carbon alcohol, solid base catalyst Mg-Al composite oxides, glycerine and biofuel.
CN2011101040549A 2011-04-26 2011-04-26 Biodiesel prepared from Idesia polycarpa var.vestita Diels oil and waste oil under alkali catalysis and preparation method thereof Expired - Fee Related CN102212414B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106244337A (en) * 2016-08-03 2016-12-21 佛山市盈合电力燃料有限公司 A kind of biodiesel for car use
CN108795578A (en) * 2018-07-06 2018-11-13 扬州工业职业技术学院 A method of utilizing catalyzed by solid base preparing biodiesel by ester exchange
CN109880696A (en) * 2019-03-04 2019-06-14 扬州中天利新材料股份有限公司 A method of biodiesel is prepared using waste grease

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687314A (en) * 2005-04-27 2005-10-26 莫春礼 Technique for producing biologic diesel oil through obsolete animal and vegetable oils in high acid value
CN101358141A (en) * 2008-09-28 2009-02-04 四川省国政生物质能源科技发展股份有限公司 Method for preparing bio diesel oil by idesia polycarpa maxim. var. vestita diels oil catalysis using solid base as catalyst
CN101608131A (en) * 2008-06-20 2009-12-23 华东理工大学 A kind of biodiesel oil preparing process of no byproduct glycerol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1687314A (en) * 2005-04-27 2005-10-26 莫春礼 Technique for producing biologic diesel oil through obsolete animal and vegetable oils in high acid value
CN101608131A (en) * 2008-06-20 2009-12-23 华东理工大学 A kind of biodiesel oil preparing process of no byproduct glycerol
CN101358141A (en) * 2008-09-28 2009-02-04 四川省国政生物质能源科技发展股份有限公司 Method for preparing bio diesel oil by idesia polycarpa maxim. var. vestita diels oil catalysis using solid base as catalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106244337A (en) * 2016-08-03 2016-12-21 佛山市盈合电力燃料有限公司 A kind of biodiesel for car use
CN108795578A (en) * 2018-07-06 2018-11-13 扬州工业职业技术学院 A method of utilizing catalyzed by solid base preparing biodiesel by ester exchange
CN109880696A (en) * 2019-03-04 2019-06-14 扬州中天利新材料股份有限公司 A method of biodiesel is prepared using waste grease

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