CN105602736A - Method for preparing biodiesel by aid of avocados - Google Patents
Method for preparing biodiesel by aid of avocados Download PDFInfo
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- CN105602736A CN105602736A CN201610027054.6A CN201610027054A CN105602736A CN 105602736 A CN105602736 A CN 105602736A CN 201610027054 A CN201610027054 A CN 201610027054A CN 105602736 A CN105602736 A CN 105602736A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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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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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- Catalysts (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a method for preparing biodiesel by the aid of avocados. The method includes steps of adding zeolite molecular sieve adsorbents into the avocado oil and pre-treating the avocado oil to obtain pure avocado oil; adding the pure avocado oil, methanol and magnetic nano-catalysts into a reaction kettle according to a weight ratio of 100:25-50:0.5-2.0 and carrying out esterification reaction; separating crude products of the biodiesel from one another and purifying the crude products to obtain the biodiesel. The magnetic nano-catalysts are introduced into esterification reaction, the method is high in catalytic efficiency, obvious catalytic effects can be realized, accordingly, the reaction time can be shortened, and the biodiesel yield can be increased; the magnetic nano-catalysts can be conveniently and quickly separated from one another and recycled according to external magnetic fields and can be reused. Besides, the method has the advantages of simple preparation processes, energy conservation, environmental protection, short reaction time, high yield and product purity and the like. In addition, the method is excellent in social efficiency and has excellent ecological and economical benefits, and the biodiesel is easy to industrially produce on a large scale.
Description
Technical field
The present invention relates to biomass energy technology field, especially a kind of method of utilizing butter fruit to prepare biodiesel.
Background technology
Present Global oil demand constantly increases and the gradually contradiction of exhaustion of fossil energy order; energy resource supply situation is more and more nervous; international market crude oil price continues to sharp rise; diversification, renewableization of the energy and clean the inevitable choice that becomes human social development; exploitation biomass energy is one of direction solving global energy crisis, rapid in countries in the world development as the biodiesel of novel alternative energy source. Biodiesel refers to oil crops as soybean, rape, cotton, palm etc., and the water plant greases such as Wild oil plant and engineering microalgae and animal fat, food garbage wet goods are the reproducibility diesel fuel of the replaced petrifaction diesel made by ester exchange or thermochemical processes of feedstock oil.
Biodiesel has the performance advantage of following uniqueness: (1) bioenergy is renewable performance: as regenerative resource, different from petroleum reserves, it obtains by agricultural and living resources, can supply can be exhausted, and the biological degradability of biodiesel is higher than conventional diesel oil, can under natural situation, realize biodegradation, reduce the pollution to environment for human survival. (2) there is good environmental protection characteristic: be mainly manifested in because sulfur content in biodiesel is low, make the discharge of sulfur dioxide and sulfide low; In biodiesel, do not contain the aromatic series alkane that can pollute environment, thereby waste gas damages lower than diesel oil to human body. (3) good greasy property, reduces the wearing and tearing of injection pump, engine cylinder-body and connecting rod, long service life. (4) good fuel performance: biodiesel Cetane number is high, makes its flammability be better than diesel oil, and combustion residue is subacidity extends the service life of catalyst and engine motor oil. (5) prepare the raw material sources of biodiesel more extensive: comprise that oil crops, Wild oil plant and alga plant grease and animal fat can serve as raw material, even can utilize waste oil in catering trade, waste oil as raw material, can accomplish to reclaim the advantages such as the object that rubbish turns waste into wealth.
China is the relatively poor countries of petroleum resources; but woody oleiferous plants resource and abundant; along with deepening continuously to the research of woody oleiferous plants crop for the energy, development and utilization; biomass energy is huge in China's development potentiality; development woody oleiferous plants Biodiesel is not only conducive to solve oil replacement, ecological environmental protection and agriculture, rural areas and farmers problem, also can be and brings new development opportunity for China's forestry industry. Butter fruit (Perseaamericana) Lauraceae Persea aiphyllium, has another name called avocado, avocado. Perenniporia martius plant, and extensively plantation, originate in Mexico and Central America, and through introducing, also there is cultivation in existing Guangdong, Guangxi, Hainan, Fujian, Taiwan, Yunnan etc. Avocado pulp is nutritious; fatty 23.49 grams of every 100 grams of pulp; 5.6 grams of sugars, 1.25 grams, protein, 1.8 grams of fibers; 0.7 gram of ash content; 8 milligrams of vitamin Cs, are a kind of high heat energy fruit, and nutritive value and cream are suitable; having the effects such as antioxygen is anti-ageing, chest enlarge, protection liver, beauty treatment, solution diabetes, protection uterus health, is one of a kind of fruit and woody oil tree species. Therefore, very big as the development potentiality of biodiesel raw material. Utilizing at present the main method of butter fruits biodiesel is ester-interchange method, but traditional ester-interchange method mostly exist catalytic efficiency low, yield poorly, color and luster is dark, apt to deteriorate, reaction time length, etching apparatus, complex process, reaction temperature are high, energy consumption more greatly, easily causes the shortcomings such as secondary pollution and accessory substance lose, cost is higher.
Summary of the invention
The present invention is directed to the problem that traditional Production of Biodiesel Via Transesterification Method exists, a kind of method of utilizing butter fruit to prepare biodiesel is provided. The present invention is taking magnetic nano solid acid as catalyst, and not only etching apparatus not, can also improve catalytic efficiency significantly, can Reaction time shorten and reduce energy consumption etc.
For realizing above object, the present invention is achieved through the following technical solutions:
Utilize butter fruit to prepare a method for biodiesel, comprise the following steps:
1. pretreatment of raw material: adding weight ratio in galam butter is the zeolite adsorbent of 1.0%-2.0%, is to stir 10-20min under 120-180r/min at rotating speed, can obtain pure galam butter;
2. esterification: pure galam butter, methyl alcohol and magnetic nano-catalyst are added in reactor taking weight ratio as 100:25-50:0.5-2.0, be that 60-65 DEG C, mixing speed are under 180-250r/min in temperature, carry out esterification 18-25min, obtain esterification products;
3. separating bio diesel oil crude product: be centrifugal 5-15min under 300-1000r/min by esterification products at rotating speed, after staticly settling, upper strata liquid separated with subnatant, upper strata liquid is biodiesel crude product, and lower floor is glycerine;
4. purification biodiesel: biodiesel crude product obtained above is added to agitator, add again the mixed adsorbent with magnesium silicate and polyvinyl lactam composition, its addition is the 1.5-3.5% of biodiesel crude product weight, under rotating speed 100-150r/min, stir 8-15min, can obtain biodiesel product.
The above magnetic nano-catalyst comprises B2O3-Fe3O4、ZrO2-Fe3O4And Al2O3-Fe3O4。
The mixed adsorbent of the above magnesium silicate and polyvinyl lactam composition is made up of 30-40% magnesium silicate and 60-70% polyvinyl lactam.
Compared with prior art, advantage of the present invention and beneficial effect:
1, the present invention utilizes renewable resource galam butter to prepare biodiesel, can effectively solve Present Global energy crisis and problem of environmental pollution, and the biodiesel of production not only quality obtains larger raising, and productive rate can be promoted to 90% left and right.
2, the present invention is incorporated into magnetic nano-catalyst in the production of biodiesel, wherein magnetic nano-catalyst has the features such as reaction interface is large, surface area is large, resistance to mass tranfer is little, reaction condition is gentle, activity is high, activity stability is good, make that its catalytic efficiency in esterification is high, catalytic effect is remarkable, thus Reaction time shorten and improve the productive rate of biodiesel. Magnetic nano-catalyst can facilitate according to exterior magnetic field on the other hand, be isolated rapidly, reclaim, can recycled for multiple times, overcome the shortcoming that non magnetic nanocatalyst difficultly reclaims, cost is high, to alleviating environmental pollution, improve enterprise's productivity effect, realize resources circulation and efficiently utilize significant.
3, the present invention adopts absorption method purification biodiesel, simple to operate, cost is low, can effectively solve large and " three wastes " emission problem of power consumption; Select the mixture of magnesium silicate and polyvinyl lactam composition as adsorbent, the impurity such as free acid that not only can fine absorption biodiesel, methyl alcohol, glycerine, glyceride, also there is good dehydrating effect simultaneously, can overcome dark, the perishable and conventional way of distillation of biodiesel color and luster and have the problems such as complex process, power consumption is large, the reaction time is long.
4, the present invention first carried out pretreatment with zeolite molecular sieve to galam butter before esterification, can adsorb impurity and the part free acid of galam butter, and the soap that esterification reaction process is produced is few, had alleviated the difficulty of follow-up refining coarse biodiesel.
5, the inventive method has that preparation technology is simple, energy-conserving and environment-protective, catalytic efficiency is high, the reaction time is short, productive rate is high, product purity advantages of higher, has good social efficiency, ecological benefits and economic benefit, easily realizes scale, industrialization is produced.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but be not limited to protection scope of the present invention.
Embodiment 1
The present embodiment magnetic nano-catalyst used is ZrO2-Fe3O4. Its preparation method comprises the following steps:
A. magnetic Fe3O4The preparation of Nano microsphere: the FeCl that is 1:3 by mass ratio2And FeCl3Be dissolved in distilled water water, pass into nitrogen, under 550r/min rotating speed, stir, dropwise adding ammoniacal liquor to pH value is 12; Controlling temperature again and be 70 DEG C, rotating speed is 2000r/min, stirs 3h, is cooled to room temperature after reaction, utilizes magnetite suction-operated to collect Fe3O4Particulate, to neutral, is 70 DEG C at vacuum drying 2h in temperature with distilled water cleaning, obtains magnetic Fe3O4Nano microsphere, the particle diameter of microballoon is 79nm.
b.ZrO2-Fe3O4The preparation of magnetic nano-catalyst: the magnetic Fe_3O_4 Nano microsphere and the zirconium nitrate solution that are 1:12 by mass ratio add to ultrasonic stirrer, then add and magnetic Fe3O4Nano microsphere mass ratio is the ethanol of 1:35; be that 250r/min, temperature are at 50 DEG C at rotating speed; dropwise add ammoniacal liquor to pH be 11; after ultrasonic agitation 4h; the product of gained separates through magnetic, then with distilled water clean 6 times, with microwave be 65 DEG C of dry 10h; finally roasting 3h under 4500 DEG C and nitrogen protection, can make .ZrO2-Fe3O4Magnetic nano-catalyst.
Utilize butter fruit to prepare a method for biodiesel, comprise the following steps:
1. pretreatment of raw material: adding the zeolite adsorbent of 1.0g in 100g galam butter, is to stir 20min under 120r/min at rotating speed, can obtain pure galam butter;
2. esterification: pure galam butter, methyl alcohol and magnetic nano-catalyst are added in reactor taking weight ratio as 100:25:2.0, are that 60 DEG C, mixing speed are under 180r/min in temperature, carry out esterification 25min, obtain esterification products;
3. separating bio diesel oil crude product: be centrifugal 5min under 1000r/min by esterification products at rotating speed, after staticly settling, upper strata liquid separated with subnatant, upper strata liquid is biodiesel crude product, and lower floor is glycerine;
4. purification biodiesel: 97.74g biodiesel crude product obtained above is added to agitator, add again the mixed adsorbent of 1.5g with 60% magnesium silicate and 40% polyvinyl lactam composition, under rotating speed 150r/min, stir 8min, can obtain biodiesel product 91.13g.
Embodiment 2
The present embodiment magnetic nano-catalyst used is Al2O3-Fe3O4. Its preparation method comprises the following steps:
A. magnetic Fe3O4The preparation of Nano microsphere: the FeCl that is 1:2.5 by mass ratio2And FeCl3Be dissolved in distilled water water, pass into nitrogen, under 400r/min rotating speed, stir, dropwise adding ammoniacal liquor to pH value is 12; Controlling temperature again and be 55 DEG C, rotating speed is 200r/min, stirs 2h, is cooled to room temperature after reaction, utilizes magnetite suction-operated to collect Fe3O4Particulate, to neutral, is 75 DEG C at vacuum drying 3h in temperature with distilled water cleaning, obtains magnetic Fe3O4Nano microsphere, the particle diameter of microballoon is 67nm.
b.Al2O3-Fe3O4The preparation of magnetic nano-catalyst: the magnetic Fe that is 1:11 by mass ratio3O4Nano microsphere and aluminum sulfate solution add to ultrasonic stirrer, then add and magnetic Fe3O4Nano microsphere mass ratio is the ethanol of 1:30; be that 300r/min, temperature are at 60 DEG C at rotating speed; dropwise add ammoniacal liquor to pH be 12; after ultrasonic agitation 4h; the product of gained separates through magnetic, then with distilled water clean 7 times, with microwave be 70 DEG C of dry 5.5h; finally roasting 3h under 450 DEG C and nitrogen protection, can make Al2O3-Fe3O4Magnetic nano-catalyst.
Utilize butter fruit to prepare a method for biodiesel, comprise the following steps:
1. pretreatment of raw material: adding the zeolite adsorbent of 1.5g in 100g galam butter, is to stir 15min under 150r/min at rotating speed, can obtain pure galam butter;
2. esterification: pure galam butter, methyl alcohol and magnetic nano-catalyst are added in reactor taking weight ratio as 100:35:1.5, are that 62 DEG C, mixing speed are under 200r/min in temperature, carry out esterification 20min, obtain esterification products;
3. separating bio diesel oil crude product: be centrifugal 10min under 700r/min by esterification products at rotating speed, after staticly settling, upper strata liquid separated with subnatant, upper strata liquid is biodiesel crude product, and lower floor is glycerine;
4. purification biodiesel: 98.12g biodiesel crude product obtained above is added to agitator, add again the mixed adsorbent of 2.5g with 50% magnesium silicate and 50% polyvinyl lactam composition, under rotating speed 120r/min, stir 10min, can obtain biodiesel product 90.69g.
Embodiment 3
The present embodiment magnetic nano-catalyst used is B2O3-Fe3O4. Its preparation method comprises the following steps:
A. magnetic Fe3O4The preparation of Nano microsphere: the FeCl that is 1:2.5 by mass ratio2And FeCl3Be dissolved in distilled water water, pass into nitrogen, under 300r/min rotating speed, stir, dropwise adding ammoniacal liquor to pH value is 12; Controlling temperature again and be 68 DEG C, rotating speed is 100r/min, stirs 2.5h, is cooled to room temperature after reaction, utilizes magnetite suction-operated to collect Fe3O4Particulate, to neutral, is 65 DEG C at vacuum drying 3h in temperature with distilled water cleaning, obtains magnetic Fe3O4Nano microsphere, the particle diameter of microballoon is 52nm.
b.B2O3-Fe3O4The preparation of magnetic nano-catalyst: the magnetic Fe_3O_4 Nano microsphere that is 1:9 by mass ratio and Boron Nitride solution add to ultrasonic stirrer; the ethanol that to add with magnetic Fe_3O_4 Nano microsphere mass ratio be 1:20 again; be that 300r/min, temperature are at 56 DEG C at rotating speed; dropwise adding ammoniacal liquor is 12 to pH, and after ultrasonic agitation 3h, the product of gained separates through magnetic; clean 6 times with distilled water again; with microwave be 70 DEG C of dry 8h, finally roasting 2h under 460 DEG C and nitrogen protection, can make B2O3-Fe3O4Magnetic nano-catalyst.
Utilize butter fruit to prepare a method for biodiesel, comprise the following steps:
1. pretreatment of raw material: adding the zeolite adsorbent of 2.0g in 100g galam butter, is to stir 10min under 180r/min at rotating speed, can obtain pure galam butter;
2. esterification: pure galam butter, methyl alcohol and magnetic nano-catalyst are added in reactor taking weight ratio as 100:45:0.5, are that 65 DEG C, mixing speed are under 250r/min in temperature, carry out esterification 18min, obtain esterification products;
3. separating bio diesel oil crude product: be centrifugal 15min under 300r/min by esterification products at rotating speed, after staticly settling, upper strata liquid separated with subnatant, upper strata liquid is biodiesel crude product, and lower floor is glycerine;
4. purification biodiesel: 97.34g biodiesel crude product obtained above is added to agitator, add again the mixed adsorbent of 2.5g with 40% magnesium silicate and 60% polyvinyl lactam composition, under rotating speed 100r/min, stir 15min, can obtain biodiesel product 89.93g.
Claims (3)
1. utilize butter fruit to prepare a method for biodiesel, it is characterized in that, comprise the following steps:
(1) pretreatment of raw material
In galam butter, adding weight ratio is the zeolite adsorbent of 1.0%-2.0%, is 120-180r/min at rotating speedLower stirring 10-20min, can obtain pure galam butter;
(2) esterification
Pure galam butter, methyl alcohol and magnetic nano-catalyst are added to reactor taking weight ratio as 100:25-50:0.5-2.0In, be that 60-65 DEG C, mixing speed are under 180-250r/min in temperature, carry out esterification 18-25min, obtain esterificationProduct;
(3) separating bio diesel oil crude product
Be centrifugal 5-15min under 300-1000r/min by esterification products at rotating speed, after staticly settling, by upper strata liquid and lower floorLiquid separates, and upper strata liquid is biodiesel crude product, and lower floor is glycerine;
(4) purification biodiesel
Biodiesel crude product obtained above is added to agitator, then add the mixing suction with magnesium silicate and polyvinyl lactam compositionAttached dose, its addition is the 1.5-3.5% of biodiesel crude product weight, under rotating speed 100-150r/min, stirs 8-15min,Can obtain biodiesel product.
2. a kind of method of utilizing butter fruits to prepare biodiesel according to claim 1, is characterized in that: described magneticNanocatalyst comprises B2O3-Fe3O4、ZrO2-Fe3O4And Al2O3-Fe3O4。
3. according to a kind of method of utilizing butter fruit to prepare biodiesel described in claim 1 or 2, it is characterized in that: described inThe mixed adsorbent of magnesium silicate and polyvinyl lactam composition is made up of 40-60% magnesium silicate and 40-60% polyvinyl lactam.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891787A (en) * | 2005-07-07 | 2007-01-10 | 南昌大学 | Production technology for preparing biodiesel by solid magnetic catalyst |
| CN101812378A (en) * | 2010-03-08 | 2010-08-25 | 中山大学 | Biodiesel and preparation method thereof |
-
2016
- 2016-01-15 CN CN201610027054.6A patent/CN105602736A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891787A (en) * | 2005-07-07 | 2007-01-10 | 南昌大学 | Production technology for preparing biodiesel by solid magnetic catalyst |
| CN101812378A (en) * | 2010-03-08 | 2010-08-25 | 中山大学 | Biodiesel and preparation method thereof |
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| 周建伟 等: "《新能源化学》", 31 August 2009, 郑州大学出版社 * |
| 尾崎 萃 等: "《催化剂手册（按元素分类）》", 30 April 1982, 化学工业出版社 * |
| 李培经: "《科苑撷英—东莞理工学院科研项目（成果、平台）汇编》", 30 April 2012, 广州市人杰彩印厂 * |
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| 王九 等: "《生物柴油生产及应用技术》", 30 June 2013, 中国石化出版社 * |
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