CN103275814B - Method for preparing biodiesel without by-product of glycerin by utilization of high acid value waste oil - Google Patents
Method for preparing biodiesel without by-product of glycerin by utilization of high acid value waste oil Download PDFInfo
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- CN103275814B CN103275814B CN201310224904.8A CN201310224904A CN103275814B CN 103275814 B CN103275814 B CN 103275814B CN 201310224904 A CN201310224904 A CN 201310224904A CN 103275814 B CN103275814 B CN 103275814B
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- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention relates to a method for preparing biodiesel without a by-product of glycerin by the utilization of high acid value waste oil, comprising the following steps: carrying out a reaction between waste oil with the acid value of 10-200mgKOH/g and an ester exchanger of carbonic ester according to the mol ratio of 1:2-1:30 in the presence of a composite catalyst at the reaction temperature 20-100 DEG C for 6-48h; filtering to remove the catalyst and distilling to remove excess ester exchanger so as to prepare biodiesel, wherein the addition amount of the composite catalyst accounts for 1%-40% of the weight of the waste oil, and the mass ratio of immobilized enzyme to super absorbent resin in the composite catalyst is 1:1-3:1. According to the preparation method, the composite catalyst is adopted. The catalyst has good reusability and efficient catalytic activity. The color of the obtained biodiesel is light. The preparation method has adnvatages of no by-product of glycerin, no need in washing and no generation of waste liquid. By the adoption of the preparation method, problems, existing in the traditional biodiesel preparation technology, such as high cost of preprocessing a lot of raw oil, environmental burden and the like, are solved.
Description
Technical field
The invention belongs to the preparation field of biofuel, be specifically related to a kind of by the method for high acid value waste oil preparation without the biofuel of glycerin by-product.
Background technology
Because petroleum resources are day by day exhausted, in order to reduce the dependence to oil, scientists strives to find the alternative fuel of oil, facilitates the exploitation paces that research Alternative Diesel Fuel is accelerated in countries in the world widely.Biofuel refers to the organic fatty acid esters class A fuel A carrying out transesterification reaction with Vegetable oil lipoprotein and animal grease etc. for raw material and short chain alcohol and obtain, compared to common fossil fuel, it is high that it has cetane value, not sulfur-bearing and aromatic hydroxy compound, biodegradable, nontoxic renewable, flash-point is petrifaction diesel advantages of higher comparatively, receive various countries (especially American-European countries) to pay close attention to more and more widely, especially the nineties in 20th century is entered, exploitation biofuel substitutes petrifaction diesel one of important channel becoming new energy development, biofuel is expected to become important substitute of diesel fuel.
At present, industrial biofuel mostly adopts the transesterification reaction of homogenous acid or base catalysts catalysis grease and low carbon chain alcohol to prepare.Reaction equation is as follows:
Wherein :-R represents 8 to 22 carbon atoms, straight chain, single or polyunsaturated alkyl or alkenyl;-R ' represent 1 to 5 carbon atom, alkyl, preferable methyl or the ethyl of straight chain or branching.
This technique is catalyst separating difficulty not only, and reaction terminates rear catalyst needs through the process of washing inactivation, a large amount of spent acid, alkali lye is had to discharge, contaminate environment, the more important thing is this technique mainly with refining grease as stock oil, take a large amount of cultivated areas, the edible oil of preciousness is not obviously met the national conditions of China for the production of biofuel.
But annual China all can produce the waste oil of a large amount of high acid value at grease production enterprise and catering industry, as it can be used as the raw material of biofuel; to well cut off the trade root of sewer oil; save resource, protected the health of people, reduce biofuel cost.
And for the biofuel preparation technology of high acid value waste oil, industrial main application first reduces the acid number of grease with homogeneous acid pre-esterification, then the two-step process that homogeneous phase alkali carries out transesterification reaction is added, in order to the harm of homogeneous phase acid base pair environment of forgoing, patent CN1382762A, CN101067091A adopts eco-friendly solid acid, solid alkali replaces homogeneous phase soda acid to achieve the preparation of high-acid value grease biofuel, along with the development of biotechnology, immobilized enzyme catalysis agent is due to its reaction conditions gentleness, reactive behavior advantages of higher obtains in field of biodiesel oil and studies widely, patent CN101020836A, CN101927144A is just with immobilized enzyme Lipozyme TL, 3A molecular sieve composite catalyst, immobilized enzyme Candida sp.99-125 achieves the one-step preparation process of high-acid value grease biofuel.But because most of biodiesel processes is transesterify reagent with methyl alcohol, inevitably will produce by-product glycerin cheap in a large number, and methyl alcohol can make enzyme catalyst poisoning, various reasons, inhibit the development of Biodiesel, therefore the transesterify reagent developing other carries out the derived product of the transesterification reaction coproduction simultaneously glycerine of grease, becomes the very big technology of solution caused by glycerol overstock and the effective ways of economical load.
Exchange in the exploitation of reagent at New Ester, the patent CN101608131A that applicant had previously applied for, CN102199493, short-chain aliphatic ester is developed (as ethyl acetate in CN102199494, methyl acetate, methylcarbonate, diethyl carbonate, dimethyl oxalate, oxalic acid diethyl ester, dimethyl malonate etc.) at solid alkali, under immobilized enzyme catalysis agent effect and refining grease transesterification reaction prepare biofuel without glycerin by-product technique, the by product short-chain fat acid glyceride replacing glycerine to generate just can use as a part for biofuel without the need to removing, applied widely especially with immobilized enzyme catalysis agent in screening of catalyst, application prospect is large, because novel transesterify reagent does not have toxicity to enzyme catalyst, and enzyme catalyst has good reusing, and we also in the urgent need to by these applications of result in high-acid value grease system.
But generate a certain amount of water (by carbonic acid decomposes) because the nonesterified fatty acid meeting in high-acid value grease and carbonates New Ester exchange reagent react, and there is the activity of meeting irreversible suppression immobilized enzyme catalysis agent in water, by filtering out some water-absorbing materials and immobilized enzyme forms composite catalyst, enzyme catalyst is applied to high-acid value grease and New Ester to exchange reagent and prepare biofuel and have a very big significance, in the research that enzyme catalysis methyl alcohol and high-acid value grease react, existing bibliographical information utilizes and adds a certain amount of molecular sieve, the moisture that silica gel generates after removing methyl alcohol and Esterification of Free Fat Acid reaction, these water-retaining agent water-retaining capacities are limited, also need to reclaim molecular sieve after at every turn reacted to carry out high temperature and dewater, otherwise the catalytic activity of next batch can decline greatly, and itself is just more difficult with being separated of molecular sieve to immobilized enzyme, this is industrially very disadvantageous.
Super absorbent resin (SAP, super absorbent resin) be a kind of nontoxic, harmless novel high polymer material, it can absorb sole mass the hundreds of even moisture of several thousand times fast, due to the water-retaining capacity that it is powerful, without the need to being separated the experiment that namely can be applicable to next batch with immobilized enzyme after reacted, and efficient catalytic activity can be kept, which reduce and in a large number the work dewatered is reclaimed to water-retaining agent, for autoclave or fixed bed type reactor, all there is good practicality.
Summary of the invention
The object of the present invention is to provide a kind of by the method for high acid value waste oil preparation without the biofuel of glycerin by-product.
The synthetic technology route that the present invention adopts is:
Wherein ,-R represents 8 to 22 carbon atoms, straight chain, single or polyunsaturated alkyl or alkenyl;-R ' represent 1 to 5 carbon atom, the alkyl of straight chain or branching; By-product acids glyceryl ester is carbonic acid glyceride, can directly use as biofuel.
Goal of the invention of the present invention is achieved through the following technical solutions:
The invention provides and a kind ofly to be prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, comprising:
Be the waste oil of 10 ~ 200mgKOH/g and carbonates transesterify reagent by acid number be 1:2 ~ 1:30 proportioning in molar ratio, add composite catalyst, its addition is 1% ~ 40% of waste oil mass ratio, in composite catalyst, immobilized enzyme and super absorbent resin mass ratio are 1:1 ~ 3:1, at temperature of reaction 20 ~ 100 DEG C, react 6 ~ 48h; Filtration of catalyst also distills the excessive transesterify reagent of removing, obtained biofuel.
Described waste oil is selected from one or several the mixture in the Soybean oil with high acid value squeezing in advance, cook or discard, rapeseed oil, plam oil, Oleum Gossypii semen, Viscotrol C, sunflower seed oil, Semen Maydis oil, sweet oil, walnut oil, Tongzi oil, sesame oil, Rice pollard oil, lard, butter, fish oil, chicken fat.
Preferred waste oil is selected from one or several the mixture in the Semen Maydis oil squeezing in advance, cook or discard, rapeseed oil, soybean oil, plam oil, Oleum Gossypii semen, and its acid number is 60mg ~ 200mgKOH/g.
Described carbonic ether exchanges one or several the mixture trying to be selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, dibutyl carbonate, diamyl carbonate.
Preferred carbonic ether exchanges one or several the mixture trying to be selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, dipropyl carbonate.
The mol ratio that described waste oil and carbonic ether exchange reagent is 1:10 ~ 1:20.
Described composite catalyst addition is 20% ~ 30% of waste oil mass ratio, and in composite catalyst, immobilized enzyme and super absorbent resin mass ratio are 1.5:1 ~ 2.5:1.
Preferred composite catalyst is the mixture of immobilized lipase Novozyme435 and acrylic acid or the like super absorbent resin (hereinafter referred to as acrylic acid or the like SAP, being provided by Yantai Wanhua Polyurethane Co., Ltd, publication number: CN102516578A).
Described temperature of reaction is 40 ~ 80 DEG C; Reaction times 12 ~ 36h.
By research, when the mass ratio of immobilized enzyme and super absorbent resin changes at 1:1 ~ 3:1, the yield of biofuel there will be the Long-term change trend first becoming and diminish greatly, namely there is an optimal proportion, optimize and draw the optimal proportion of immobilized enzyme and super absorbent resin (as shown in Figure 1) between 1.5:1 ~ 2.5:1.
Beneficial effect:
The composite catalyst that the present invention adopts solves first and adds conventional absorbent paper agent as molecular sieve being used alone Novozyme435 lipase or Novozyme435 lipase, after silica gel, catalysis high acid value waste oil and carbonates New Ester exchange the shortcoming that when reagent react prepares biofuel, reusing is very poor, by Novozyme435 lipase and super absorbent resin mixing composition composite catalyst, the catalytic applications scope of Novozyme435 lipase from low acid number, the treated oil of low water content is extended to the waste oil of high acid value, namely the catalyzer filtering gained after reaction can be used for the reaction of next batch without the need to process, catalyzer has good reusing and efficient catalytic activity, the biofuel color obtained is more shallow, no byproduct glycerol, without the need to washing, produce without waste liquid, solve a large amount of stock oil pre-treatment costs occurred in biofuel conventional preparation techniques high, the problems such as environmental pressure.
Accompanying drawing explanation
Fig. 1 is the optimum proportioning research of Novozyme435 lipase and acrylic acid or the like super absorbent resin.
Embodiment
Describe the present invention below in conjunction with embodiment and accompanying drawing.But the following example should not regard limitation of the scope of the invention as.
The present embodiment composite catalyst used is the mixture of immobilized lipase Novozyme435 and acrylic acid or the like super absorbent resin; Wherein, acrylic acid or the like super absorbent resin is provided by Yantai Wanhua Polyurethane Co., Ltd; Immobilized lipase Novozyme435 is provided (Beijing Gao Ruisen Science and Technology Ltd. agency) by Novozymes Company of Denmark.
Embodiment 1
The methylcarbonate of 5g corn high acid value waste oil (acid number is 67mgKOH/g), 8.2g, 1.5gNovozym435/ acrylic acid or the like super absorbent resin composite catalyst (mass ratio 2:1) are added in tool plug Erlenmeyer flask, react 24h in the water bath with thermostatic control shaking table of 60 DEG C after, filtering separation reclaims catalyzer, filtrate steams the excessive methylcarbonate of removing through revolving, leave standstill the appearance without glycerine layering, free glycerol do not detected by gas chromatographic analysis, the yield of biofuel reaches 90.1%.
Embodiment 2
The composite catalyst reclaimed in the methylcarbonate of 5g corn high acid value waste oil (acid number is 67mgKOH/g), 8.2g, example 1 is added in tool plug Erlenmeyer flask, react 24h in the water bath with thermostatic control shaking table of 60 DEG C after, filtering separation reclaims catalyzer, filtrate steams the excessive methylcarbonate of removing through revolving, leave standstill the appearance without glycerine layering, free glycerol do not detected by gas chromatographic analysis, the yield of biofuel reaches 90.3%.
According to the method for example 1 and 2, composite catalyst uses more than 20 times, and the yield of biofuel remains on about 90%, has satisfactory stability and reusing.
Comparative example 1
Comparative example 1 is the same with embodiment 1 process, is used alone 1gNovozym435 as catalyzer, reaches 89.5% by the yield of gas chromatographic analysis biofuel, illustrates that the catalytic activity difference of reacting two kinds of catalyzer is first little.
Comparative example 2
Comparative example 2 is the same with embodiment 2 process, and the Novozym435 reclaimed in comparative example 1 is carried out the reaction of second batch, the yield through gas chromatographic analysis biofuel is 50.1%.
According to the method for example 1 and 2, Novozym435 uses more than 5 times, the yield of biofuel just residue 5% less than, illustrate Novozym435 very poor as its reusing of catalyzer separately, embody the superiority of composite catalyst.
Embodiment 3
The methylcarbonate of 5g corn high acid value Extractive crudeoil (acid number is 160mgKOH/g), 8.2g, the Novozym435/ acrylic acid or the like super absorbent resin composite catalyst (mass ratio 2:1) of 1.5g are added in tool plug Erlenmeyer flask, react 12h in the water bath with thermostatic control shaking table of 60 DEG C after, filtering separation reclaims catalyzer, filtrate steams the excessive methylcarbonate of removing through revolving, leave standstill the appearance without glycerine layering, free glycerol do not detected by gas chromatographic analysis, the yield of biofuel reaches 86.2%.
Embodiment 4
5g restaurant salad oil frying waste oil (acid number is 117mgKOH/g), the methylcarbonate of 8.2g, the Novozym435/ acrylic acid or the like super absorbent resin composite catalyst (mass ratio 2:1) of 1.5g are added in tool plug Erlenmeyer flask, react 24h in the water bath with thermostatic control shaking table of 60 DEG C after, filtering separation reclaims catalyzer, filtrate steams the excessive methylcarbonate of removing through revolving, leave standstill the appearance without glycerine layering, free glycerol do not detected by gas chromatographic analysis, the yield of biofuel reaches 93.5%.
Embodiment 5
In order to investigate the catalytic effect of catalyzer when grease is pure free fatty acids, Novozym435/ acrylic acid or the like super absorbent resin composite catalyst (mass ratio 2:1) composite catalyst of the methylcarbonate of 5g CP level oleic acid (acid number 199mgKOH/g), 15.9g, 1.5g adds in tool plug Erlenmeyer flask by we, react 18h in the water bath with thermostatic control shaking table of 60 DEG C after, filtering separation reclaims catalyzer, filtrate steams the excessive methylcarbonate of removing through revolving, and the yield being obtained biofuel by gas chromatographic analysis reaches 78.5%.
Embodiment 6-12
Embodiment 6-12 is the same with embodiment 1 process, raw material and the results are shown in Table 1.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (9)
1. prepare the method without the biofuel of glycerin by-product by high acid value waste oil, comprising:
Be the waste oil of 10 ~ 200mgKOH/g and carbonates transesterify reagent by acid number be 1:2 ~ 1:30 proportioning in molar ratio, add composite catalyst, its addition is 1% ~ 40% of waste oil mass ratio, in composite catalyst, immobilized lipase and super absorbent resin mass ratio are 1:1 ~ 3:1, at temperature of reaction 20 ~ 100 DEG C, react 6 ~ 48h; Filtration of catalyst also distills the excessive transesterify reagent of removing, obtained biofuel.
2. according to claim 1ly a kind ofly to be prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, it is characterized in that: described waste oil is selected from one or several the mixture in the Soybean oil with high acid value squeezing in advance, cook or discard, rapeseed oil, plam oil, Oleum Gossypii semen, Viscotrol C, sunflower seed oil, Semen Maydis oil, sweet oil, walnut oil, Tongzi oil, sesame oil, Rice pollard oil, lard, butter, fish oil, chicken fat.
3. according to claim 2 a kind of by the method for high acid value waste oil preparation without the biofuel of glycerin by-product, it is characterized in that: described waste oil is selected from one or several the mixture in the Semen Maydis oil squeezing in advance, cook or discard, rapeseed oil, soybean oil, plam oil, Oleum Gossypii semen, and its acid number is 60mg ~ 200mgKOH/g.
4. according to claim 1ly a kind ofly to be prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, it is characterized in that: described carbonic ether exchanges one or several the mixture that examination is selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, dipropyl carbonate, methyl propyl carbonate, dibutyl carbonate, diamyl carbonate.
5. according to claim 4ly a kind ofly to be prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, it is characterized in that: described carbonic ether exchanges one or several the mixture that examination is selected from methylcarbonate, diethyl carbonate, Methyl ethyl carbonate, dipropyl carbonate.
6. according to claim 1ly a kind ofly to be prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, it is characterized in that: the mol ratio that described waste oil and carbonic ether exchange reagent is 1:10 ~ 1:20.
7. according to claim 1 a kind of by the method for high acid value waste oil preparation without the biofuel of glycerin by-product, it is characterized in that: described composite catalyst addition is 20% ~ 30% of waste oil mass ratio, in composite catalyst, immobilized enzyme and super absorbent resin mass ratio are 1.5:1 ~ 2.5:1.
8. a kind of according to claim 1 or 7 is prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, it is characterized in that: described composite catalyst is the mixture of immobilized lipase Novozyme435 and acrylic acid or the like super absorbent resin.
9. according to claim 1ly a kind ofly to be prepared without the method for the biofuel of glycerin by-product by high acid value waste oil, it is characterized in that: described temperature of reaction is 40 ~ 80 DEG C; Reaction times 12 ~ 36h.
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| CN103666773A (en) * | 2013-09-23 | 2014-03-26 | 北京石油化工学院 | Method for producing biodiesel in micro-structure reactor |
| CN111440665A (en) * | 2020-04-07 | 2020-07-24 | 西南林业大学 | Method for weak-base esterification of fatty acid and one-step ester exchange of high-acid-value oil |
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