CN100560692C - Utilize waste cooking oil to produce biodiesel processes - Google Patents

Utilize waste cooking oil to produce biodiesel processes Download PDF

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Publication number
CN100560692C
CN100560692C CNB2005100455690A CN200510045569A CN100560692C CN 100560692 C CN100560692 C CN 100560692C CN B2005100455690 A CNB2005100455690 A CN B2005100455690A CN 200510045569 A CN200510045569 A CN 200510045569A CN 100560692 C CN100560692 C CN 100560692C
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cooking oil
waste cooking
biofuel
lower alcohol
technology
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CN1986737A (en
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丁以钿
陈登龙
刘五连
张雄枝
陈孔院
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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 present invention relates to a kind of technology of utilizing waste cooking oil production biofuel, comprise the steps: 1) with waste cooking oil, lower alcohol and multicomponent SO 4 2-/ M xO yThe type super acidic catalyst mixes stirring, is incubated 75～85 ℃ and reacts 8～12 hours down; 2) after intensification steams the residue lower alcohol, leave standstill and tell lower floor's catalyzer and rare glycerol liquor, get coarse biodiesel; 3) heat and add the hydrogen peroxide oxidation decolouring, regulate pH value 6.5～7, leave standstill and filter the back and separate water outlet and foreign material, get biofuel to back more than 70 ℃.This technology need not normal pressure or underpressure distillation, and simple, safe and reliable, cost is low, and is pollution-free, and the marketing prospect is good.

Description

Utilize waste cooking oil to produce biodiesel processes
Technical field
The present invention relates to a kind of technology of production biofuel, especially utilize the technology of waste cooking oil production biofuel.
Background technology
Later each state of the oil crisis seventies in 20th century all pays close attention to the problem of the energy.With China is example, nineteen ninety to 2002 a year China's oil consumption annually increase by 1,103 ten thousand tons, and the same period crude oil growth only be 2,420,000 tons, impel the annual imported crude oil 7000 of China～80,000,000 tons.Estimate crude oil in China output 1.7～1.9 hundred million in 2010 ton, the year two thousand twenty is 1.8～200,000,000 tons, and forecast demand amount 2010 is up to 3.5～3.8 hundred million tons, and the year two thousand twenty is 4.8～5.2 hundred million tons.Till that time, the China's oil breach is up to 51.4～62.5%.
In the rural area, with the development of mechanization of agriculture and rural economy, the industrial diesel oil of the amount ratio of agricultural diesel oil is more in short supply.Regard as the state key product innovation by the Ministry of Science and Technology, the Ministry of Commerce, State Administration of Taxation, quality supervision and test general bureau, national environmental protection portion in April, 2003 according to the biofuel that the invention of number of patent application 02115477.5 " utilizes waste animal vegetable oil to produce biodiesel processes " to produce, item number 2003ED72005, and this process quilt is classified 2005 annual State Torch Program as.Therefore, making biofuel with waste oil, is a vital task of contemporary scientific research with renewable energy source substituting disposable performance source.
Summary of the invention
The purpose of this invention is to provide a kind of technology of utilizing waste cooking oil production biofuel, this method has solved urban catering waste oil and has processed a production technology difficult problem that changes into biofuel on the spot, need not normal pressure or underpressure distillation, not only production technique is simple, and it is safe and reliable, cost is low, and is pollution-free.
The present invention utilizes the technology of waste cooking oil production biofuel to comprise the steps:
(1) with waste cooking oil, lower alcohol with organize SO more 4 2-/ M xO yThe type super acidic catalyst is by following mass ratio
Waste cooking oil 100
Lower alcohol 16～18
Multicomponent SO 4 2-/ M xO yType super acidic catalyst 2～3
Mix and stir, be incubated 75～85 ℃ and reacted 8～12 hours down;
(2) after intensification steams the residue lower alcohol, leave standstill and tell lower floor's catalyzer and rare glycerol liquor, get coarse biodiesel;
(3) heat and add the hydrogen peroxide oxidation decolouring, regulate pH value 6.5～7, leave standstill and filter the back and separate water outlet and foreign material, get biofuel to back more than 70 ℃.
Waste cooking oil in this specification sheets comprises frying oil, hogwash fat or sewer oil.Wherein, frying oil is meant the waste oil that repetition fry, fried use peroxide value exceed standard; Hogwash fat is meant that restaurant, city and dining room leftovers are poured on the oil slick on upper strata, back together; Sewer oil is meant the oil slick that effusive ground ditch-water skims through the post precipitation upper strata in restaurant or the dining room trench.Mainly contain free lipid acid triglyceride and lipid acid in the waste cooking oil.
Lower alcohol in this specification sheets comprises methyl alcohol or ethanol, multicomponent SO 4 2-/ M xO yType super acidic catalyst (M is a metal) is preferably SO 4 2-/ ZrO 2-TiO 2-SnO 2, hydrogen peroxide concentration is preferably 30%～40%.Hydrogen peroxide add-on weight ratio is 2%～3% of a gained coarse biodiesel.
Reaction mechanism of the present invention be under the katalysis of catalyzer, to utilize lower alcohol to waste cooking oil in free lipid acid triglyceride carry out alcoholysis and to waste cooking oil in free lipid acid carry out esterification.
The present invention adopts the esterification of urban catering waste oil and lower alcohol and alcoholysis reaction to carry out simultaneously, 1.05 tons of waste cooking oils, and 0.14 ton of industrial methanol can be produced 1 ton of biofuel, reclaims the 60kg industry glycerol, and its transformation efficiency can be up to more than 96%.The biofuel that is generated is verified through pilot scale, can substitute solar oil fully.
Advantage of the present invention is:
1. technical process is short, and cost is low, does not have " three wastes " and pollutes, and catalyzer can be recycled through after leaching, clean, activating, and does not have the pollution of other chemical method spent acid, alkali, soap and helps the recovery of by-product glycerin.
2. product need not normal pressure or underpressure distillation, and the residual acid number of oil product is low, and neutral oil is few, is applicable to that farm machinery and boats and ships are with oily.
Embodiment
The following examples can make the professional and technical personnel more fully understand the present invention, but do not limit the present invention in any way.
Specific embodiment 1
In the glass-lined reactor of the tool reflux condensate device of 5000L, drop into sewer oil 3000kg, multicomponent SO 4 2-/ ZrO 2-TiO 2-SnO 2Superpower solid acid catalyst 60kg, content are greater than 98% industrial methanol 540kg.Stirring heats up down reacts, the boiling of bubbling in the jar when material reaches 70 ℃ of left and right sides.Uprise with the esterification degree, quantity of methyl alcohol reduces in the retort, and temperature of charge rises to 80～85 ℃ automatically in jar, continues insulation reaction 10 hours.Sampling and measuring acid number≤5mgKOH/g, lipid acid triglyceride content≤3%, then the explanation reaction is finished, otherwise the proper extension reaction times is qualified up to middle control.
Intensification is advanced canister closure valve with backflow methyl alcohol, methyl alcohol is steamed until the jar temperature reach 90 ℃.After reclaiming residual methanol, thick ester is pumped to the seasoning of standing demix jar more than 4 hours, tells the rare glycerol liquor of lower floor, catalyzer, obtain coarse biodiesel.Reclaiming dilute methanol (concentration 50～56%) send the distillation of ripple distillation tower to carry to remake the raw material reuse after dense; Rare glycerol liquor is sold and is extracted the glycerine raw material;
For further economizing on the use of funds, catalyzer is cleaned through 20% dilute sulphuric acid, filters, dry back reuse behind 500 ℃ of calcination activations.
In the 5000L glass-lined reactor, drop into coarse biodiesel 3000kg, be warmed up to 60 ℃, stir the hydrogen peroxide 60kg that slowly adds concentration 30% down.After adding, material can autoxidation be warmed up to 80～90 ℃, continues insulated and stirred 30 minutes.With the pH6.5 that neutralizes under the saturated aqueous common salt stirring that contains soda ash 10%, this moment, the coarse biodiesel color became extremely shallow transparent orange from light brown, got finished product after disk centrifugal separator elimination water is assorted.
Reaction mechanism is:
Free lipid acid triglyceride alcoholysis in the waste cooking oil:
Free fatty acid esterification in the waste cooking oil:
Figure C20051004556900042

Claims (6)

1, a kind of waste cooking oil that utilizes is produced biodiesel processes, it is characterized in that this technology comprises the steps:
(1) with waste cooking oil, lower alcohol and multicomponent SO 4 2-/ M xO yThe type super acidic catalyst is by following weight ratio
Waste cooking oil 100
Lower alcohol 16～18
Multicomponent SO 4 2-/ M xO yType super acidic catalyst 2～3
Mix and stir, be incubated 75～85 ℃ and reacted 8～12 hours down; Described multicomponent SO 4 2-/ M xO yThe type super acidic catalyst is SO 4 2-/ ZrO 2-TiO 2-SnO 2
(2) after intensification steams the residue lower alcohol, leave standstill and tell lower floor's catalyzer and rare glycerol liquor, get coarse biodiesel;
(3) heat and add the hydrogen peroxide oxidation decolouring, regulate pH value 6.5～7, leave standstill and filter the back and separate water outlet and foreign material, get biofuel to back more than 70 ℃.
2,, it is characterized in that described waste cooking oil comprises frying oil, hogwash fat or sewer oil according to the described technology of utilizing waste cooking oil production biofuel of claim 1.
3,, it is characterized in that described lower alcohol comprises methyl alcohol or ethanol according to the described technology of utilizing waste cooking oil production biofuel of claim 1.
4,, it is characterized in that described hydrogen peroxide concentration is 30%～40% according to the described technology of utilizing waste cooking oil production biofuel of claim 1.
5, according to the described technology of utilizing waste cooking oil production biofuel of claim 1, the weight ratio that it is characterized in that described hydrogen peroxide add-on is 2%～3% of a coarse biodiesel.
6, according to claim 1,2,3, the 4 or 5 described technologies of utilizing waste cooking oil production biofuel is characterized in that described lower floor's catalyzer of telling is clean through 20% dilute sulphuric acid, filter dry back reuse behind 500 ℃ of calcination activations.
CNB2005100455690A 2005-12-19 2005-12-19 Utilize waste cooking oil to produce biodiesel processes Expired - Fee Related CN100560692C (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101798520A (en) * 2010-04-02 2010-08-11 王国庆 Black diesel decoloration and deodorization method
CN101993784A (en) * 2010-12-01 2011-03-30 沈阳工业大学 Method for preparing biodiesel from hogwash oil catalyzed by solid super acid
CN102154058B (en) * 2011-03-11 2012-10-10 江苏恒顺达生物能源有限公司 Process for carrying out pretreatment on waste oil
CN102876465A (en) * 2012-09-07 2013-01-16 宝林 Method for preparing biodiesel by using kitchen waste oil
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
固体超强酸催化剂的研究进展. 刘桂荣，王洪章.江西化工，第NO.3 　期. 2005
固体超强酸催化剂的研究进展. 刘桂荣，王洪章.江西化工，第NO.3 期. 2005 *

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