CN105733804A - Decoloration method in process for preparing biodiesel from waste cooking oil - Google Patents

Decoloration method in process for preparing biodiesel from waste cooking oil Download PDF

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Publication number
CN105733804A
CN105733804A CN201610185908.3A CN201610185908A CN105733804A CN 105733804 A CN105733804 A CN 105733804A CN 201610185908 A CN201610185908 A CN 201610185908A CN 105733804 A CN105733804 A CN 105733804A
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cooking oil
waste cooking
activated carbon
waste
biodiesel
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胡献国
李川
汪向阳
陈金思
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Hefei University of Technology
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Hefei University of Technology
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    • 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
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)

Abstract

The invention discloses a decoloration method in a process for preparing biodiesel from waste cooking oil. The decoloration method comprises the following steps: forming a compound decoloration agent by using hydrogen peroxide, kaolin and activated carbon, and decoloring the waste cooking oil; and carrying out a pre-esterification reaction and an ester exchange reaction to the decolored waste cooking oil, thereby obtaining yellow clarified transparent biodiesel. The product color is improved, and main physicochemical indexes are kept stable; and moreover, the decoloration method disclosed by the invention is simple, reliable and low in cost and has important application value in the field of preparation of biodiesel from the waste cooking oil.

Description

A kind of discoloration method in preparing biodiesel by food and beverage waste oil technique
One, technical field
The invention discloses a kind of discoloration method, especially relate to the discoloration method in preparing biodiesel by food and beverage waste oil technique.
Two, background technology
Waste cooking oil (wastecookingoil, WCO) generally comprise: the waste grease [Yao Yaguang that waste oil, hogwash fat, frying waste oil, lampblack absorber condensation recovered oil, food enterprise and relevant enterprise produce, Ji Wei, Zhang Chuanlong etc. the regeneration of waste edible oil from catering trade and retrieval management [J]. regenerative resource, 2006, (2): 62-64.].WCO is of poor quality, and the severe overweight such as peroxide value, acid number, moisture, containing substantial amounts of deteriorative factor, and the prolonged and repeated use under the condition of high temperature of some oil, contact with the oxygen in air, be hydrolyzed, aoxidize, the complex reaction such as polymerization, causing oil viscosity to increase, color and luster is deepened.WCO is mainly composed of triglyceride, if not recycling, not only wastes resource, and mishandling will cause environmental pollution.Therefore, the comprehensive utilization to WCO, it is possible to fundamentally solve WCO and return to dining table and environmental pollution problem.
At present, WCO mainly has following 4 kinds of comprehensive utilization modes: (1) utilizes fatty acid in WCO to produce soap；(2) oleic acid is produced；(3) hydrogenation Hydrolyze method coproduction glycerol, stearic acid are utilized；(4) preparation biodiesel is reacted with short chain alcohol.Wherein, method (1)～(3) are backward in technique, deficiency in economic performance；And method (4) utilizes WCO to prepare biodiesel can not only realize the recycling of WCO, and the problem [P.Felizardo of biodiesel raw material shortage can be alleviated, M.JoanaNeivaCorreia, I.Raposo, etal, Productionofbiodieselfromwastefryingoils [J] .WasteManagement.2006,26:487 494.].
Oils and fats at high temperature aoxidizes or is subject to the coloring matters such as the oxidation product of xanthine oxidase effect generation, chromatoplast, these materials not only can affect color and luster and the stability of WCO, also the stability of later product can be affected, therefore waste cooking oil must be carried out desolventing technology, can as the raw material of biodiesel.The decolouring of WCO is generally adopted absorption method, and the adsorbent of employing is generally activated carbon and active hargil, but these absorption have certain defect.Zhang Jun etc. compare the decolorizing effect of several activated carbon, after parameters optimization, the percent of decolourization of waste oil is 50-65% [Zhang Jun, Cen Xinguang, Xie Qiang. the research [J] of waste edible oil activated carbon decolorizing technique. environmental project journal .2008,2 (5): 716-720.]；Deng Qi etc. explore the active hargil decoloration process to WCO, waste oil percent of decolourization reaches about 90%, but temperature required higher [Deng Qi, Yin Pinghe, Zhao Ling etc. the active hargil exploration [J] to waste edible oil from catering trade decoloration process. Environmental Pollution and Control .2004,26 (2): 126-128.].
Therefore, it is necessary to develop a kind of new waste cooking oil discoloration method, in order to provide a kind of comparatively ideal raw material for producing biodiesel, form composite decolorising agent with hydrogen peroxide, Kaolin and activated carbon both at home and abroad at present and waste cooking oil decolouring is had no report.
Three, summary of the invention
The present invention is for avoiding the weak point existing for above-mentioned prior art, discoloration method in a kind of preparing biodiesel by food and beverage waste oil technique is provided, it is intended to form composite decolorising agent with hydrogen peroxide, Kaolin and activated carbon, it is achieved the purpose that bleaching temperature is low, decolorization rate is fast.
This invention address that technical problem, adopt the following technical scheme that
Discoloration method in preparing biodiesel by food and beverage waste oil technique of the present invention, it is characterized in that: be form composite decolorising agent with hydrogen peroxide, Kaolin and activated carbon, waste cooking oil is decoloured.Specifically include following steps:
(1) waste cooking oil is filtered, to remove solid impurity；
(2) waste cooking oil adds hydrogen peroxide after filtration, decolour under heated and stirred, stratification, take supernatant liquid；
(3) in supernatant liquid, add Kaolin and activated carbon, decolour further under heated and stirred, be finally filtered again.
Wherein: the consumption of described hydrogen peroxide accounts for after filtration the 0.1～5% of waste cooking oil quality；Kaolinic consumption accounts for after filtration the 1～10% of waste cooking oil quality；The consumption of activated carbon accounts for after filtration the 1～5% of waste cooking oil quality；Described Kaolin and activated carbon pore size are distributed between 0.5～100nm.In step (2) bleaching temperature of hydrogen peroxide be 30～70 DEG C, bleaching time be 5～30min；In step (3) bleaching temperature of Kaolin and activated carbon be 40～80 DEG C, bleaching time be 10～50min.Mixing speed in step (2) and step (3) is 10～150rpm.
After decolouring, waste cooking oil is by pre-esterification reactor and ester exchange reaction, can obtain the biodiesel of yellow clear.
The dominant mechanism of discoloration method of the present invention is:
The strong oxidation that hydrogen peroxide has, it is possible to will in liquid phase adsorption pigment macromole oxidation Decomposition, thus reach decolouring effect.In liquid phase adsorption, the absorption of macromole is played an important role by mesopore, and mesopore is the path of adsorbate and controls adsorption rate, to can not also play absorption positioning action by the macromole in access aperture.Kaolin and activated carbon pore structure mesopore are all more flourishing, and in mesopore range, pore-size distribution is different, can be well composite thus adsorbing coloring matter in waste cooking oil.
Compared with the prior art, the advantage of the present invention is embodied in:
1, the present invention is by waste cooking oil desolventing technology, not only making waste cooking oil color and luster improve, and the acid number of the front and back waste cooking oil that decolours and saponification number are almost constant, and this illustrates that waste cooking oil main component and triglyceride are not affected by decolorization.
2, the present invention is high to waste cooking oil decolorizing efficiency, and required bleaching temperature is low, bleaching time is shorter, and does not result in secondary pollution.
3, the present invention is by waste cooking oil desolventing technology, biodiesel color and luster prepared by waste cooking oil is not only made to improve, and other physical and chemical indexs of biodiesel remain stable for, this illustrates that biodiesel main component and fatty acid methyl ester are not affected by decolorization.
Four, detailed description of the invention
Used by following example, waste cooking oil is collected in restaurant, standby after elimination is except solid impurity.
Hydrogen peroxide, Kaolin and activated carbon used by following example are purchased from market, standby after the pretreatment such as Kaolin and activated carbon drying, high-temperature activation.
Instrument used by following example mainly has electric-heated thermostatic water bath, 722E visible spectrophotometer, stirring and defecator.
Following example color and luster of Spectrophotometric Determination waste cooking oil and decoloration process effect:
Make reference with distilled water, measure absorbance with the maximum absorption wavelength 480nm place of 1cm cuvette, be then calculated as follows the percent of decolourization of waste cooking oil:
St=(A0-A1)/A0
S in formulatRepresent the percent of decolourization of t, A0And A1Represent the absorbance of initial time and t waste cooking oil respectively.
Embodiment 1
100mL conical flask adds the waste cooking oil (absorbance A after 40g filters0It is 1.257), it is heated to 70 DEG C, is firstly added 1.2g hydrogen peroxide, under 20rpm, stir 10min, then separatory is stood with separatory funnel, take supernatant liquid, sequentially add Kaolin that 4g aperture is 2～50nm and 2g aperture is the activated carbon of 0.5～40nm, at 80 DEG C, stirring 30min under 20rpm, take out waste cooking oil after decolouring, using low speed filter paper filtering immediately, filtrate is tested with 722E visible spectrophotometer, records the absorbance A of waste cooking oil after decolouring1Being 0.136, percent of decolourization reaches 89.2%.
Decolouring before and after each performance indications of waste cooking oil relatively in Table 1.
Table 1 waste cooking oil decolouring fore/aft properties compares
Performance indications Before decolouring After decolouring
20 DEG C of density (kg/m3) 901 905
40 DEG C of viscosity (mm2/s) 32.51 31.14
Acid number (mgKOH/g) 19.10 18.26
Saponification number (mgKOH/g) 215.6 217.2
Visible by waste cooking oil desolventing technology, not only making waste cooking oil color and luster improve, and the acid number of the front and back waste cooking oil that decolours and saponification number are almost constant, and this illustrates that waste cooking oil main component and triglyceride are not affected by decolorization.
Sulphuric acid (after accounting for decolouring the 1% of waste cooking oil quality) that waste cooking oil and mass concentration after decolouring are 98%, methanol (oleyl alcohol mol ratio is 1:12) are placed in equipped with thermometer, reflux condensing tube three mouthfuls of round-bottomed flasks in, under 70 DEG C of water-baths, stirring carries out pre-esterification reactor 4h；After having reacted, stratification, washing are also distilled, it is thus achieved that the waste cooking oil after pre-esterification.
Then the waste cooking oil after pre-esterification and methanol (oleyl alcohol mol ratio is 1:6), sodium hydroxide (accounting for 1% of the waste cooking oil quality after pre-esterification) are placed in equipped with thermometer, reflux condensing tube three mouthfuls of round-bottomed flasks in, under 60 DEG C of water-baths stirring carry out ester exchange reaction 1h；After having reacted, it is layered, neutralizes, washes and distills, namely obtain biodiesel.Biodiesel conversion rate is 85.9%.
For contrasting, no bleaching waste cooking oil is prepared into biodiesel in the same fashion.The performance indications of two kinds of biodiesel are in Table 1.
The performance indications of table 2 biodiesel
Can be seen that, by waste cooking oil is carried out desolventing technology, not only making biodiesel color and luster prepared by waste cooking oil improve, and other physical and chemical indexs of biodiesel remain stable for, this illustrates that biodiesel main component and fatty acid methyl ester are not affected by decolorization.
Embodiment 2
Waste cooking oil after identical filtration is decoloured by the present embodiment by the mode that embodiment 1 is identical, differs only in hydrogen peroxide for decoloration temperature and changes 65 DEG C into.
After tested, the absorbance A of waste cooking oil after decolouring1Being 0.155, percent of decolourization is 87.7%.
Embodiment 3
Waste cooking oil after identical filtration is decoloured by the present embodiment by the mode that embodiment 1 is identical, differs only in the hydrogen peroxide for decoloration time and changes 8min into.
After tested, the absorbance A of waste cooking oil after decolouring1Being followed successively by 0.150, percent of decolourization is followed successively by 88.1%.
Embodiment 4
Waste cooking oil after identical filtration is decoloured by the present embodiment by the mode that embodiment 1 is identical, differs only in Kaolin and activated carbon decolorizing temperature changes 60 DEG C into.
After tested, the absorbance A of waste cooking oil after decolouring1Being followed successively by 0.195, percent of decolourization is followed successively by 84.5%.
Embodiment 5
Waste cooking oil after identical filtration is decoloured by the present embodiment by the mode that embodiment 1 is identical, differs only in Kaolin and the activated carbon decolorizing time changes 25min into.
After tested, the absorbance A of waste cooking oil after decolouring1Being followed successively by 0.167, percent of decolourization is followed successively by 86.7%.

Claims (6)

1. the discoloration method in a preparing biodiesel by food and beverage waste oil technique, it is characterised in that: it is form composite decolorising agent with hydrogen peroxide, Kaolin and activated carbon, waste cooking oil is decoloured.
2. discoloration method according to claim 1, it is characterised in that comprise the following steps:
(1) waste cooking oil is filtered, to remove solid impurity；
(2) waste cooking oil adds hydrogen peroxide after filtration, decolour under heated and stirred, stratification, take supernatant liquid；
(3) in supernatant liquid, add Kaolin and activated carbon, decolour further under heated and stirred, be finally filtered again.
3. discoloration method according to claim 2, it is characterized in that: the consumption of described hydrogen peroxide accounts for after filtration the 0.1～5% of waste cooking oil quality, kaolinic consumption accounts for after filtration the 1～10% of waste cooking oil quality, and the consumption of activated carbon accounts for after filtration the 1～5% of waste cooking oil quality.
4. discoloration method according to claim 2, it is characterised in that: described Kaolin and activated carbon pore size are distributed between 0.5～100nm.
5. discoloration method according to claim 2, it is characterised in that: in step (2) bleaching temperature of hydrogen peroxide be 30～70 DEG C, bleaching time be 5～30min；In step (3) bleaching temperature of Kaolin and activated carbon be 40～80 DEG C, bleaching time be 10～50min.
6. discoloration method according to claim 2, it is characterised in that: step (2) and the mixing speed in step (3) they are 10～150rpm.
CN201610185908.3A 2016-03-25 2016-03-25 Decoloration method in process for preparing biodiesel from waste cooking oil Pending CN105733804A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106720950A (en) * 2016-12-13 2017-05-31 广州市通合塑料制品有限公司 A kind of processing method of remaining meal rubbish
CN111073779A (en) * 2019-12-11 2020-04-28 江西省金泰茶脂开发有限公司 Soap powder prepared from kitchen waste grease and preparation method thereof
CN112725079A (en) * 2020-11-11 2021-04-30 广东电网有限责任公司 Decoloring process for producing kitchen waste grease-based natural ester insulating oil

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106720950A (en) * 2016-12-13 2017-05-31 广州市通合塑料制品有限公司 A kind of processing method of remaining meal rubbish
CN111073779A (en) * 2019-12-11 2020-04-28 江西省金泰茶脂开发有限公司 Soap powder prepared from kitchen waste grease and preparation method thereof
CN112725079A (en) * 2020-11-11 2021-04-30 广东电网有限责任公司 Decoloring process for producing kitchen waste grease-based natural ester insulating oil

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Application publication date: 20160706