CN103361186A - Method for producing plasticizer by using biodiesel - Google Patents
Method for producing plasticizer by using biodiesel Download PDFInfo
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- CN103361186A CN103361186A CN2012100889219A CN201210088921A CN103361186A CN 103361186 A CN103361186 A CN 103361186A CN 2012100889219 A CN2012100889219 A CN 2012100889219A CN 201210088921 A CN201210088921 A CN 201210088921A CN 103361186 A CN103361186 A CN 103361186A
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- biofuel
- biodiesel
- hydrogen peroxide
- softening agent
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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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Abstract
The invention discloses a method for producing a plasticizer by using biodiesel. The method comprises the steps of: forming a mixture containing the biodiesel, small molecular carboxylic acid and a titanium silicalite molecular sieve catalyst; slowly adding hydrogen peroxide to the mixture under agitation; and agitating, reacting and recovering the plasticizer. The method for producing the plasticizer by using the biodiesel provided by the invention is short in reaction time, high in product epoxide number, good in product color, clean in production process, and less in emission of three wastes; the catalyst can be used in cycle after being separated; and the problem of environmental pollution of sulfuric acid is not generated.
Description
Technical field
The present invention relates to the method by the production of biodiesel softening agent.
Background technology
Biofuel is the new industry that emerges human 21 century, has been subject to the generally attention of countries in the world.Biofuel at first is to produce as the substitute of petroleum diesel, be subject at present the impact of petroleum diesel price, biofuel price and income are not reciprocity, and enterprise's productivity effect is limited, often need government subsidy to produce, this has fettered the developing steps of Biodiesel.In order to change this passive situation of Biodiesel, must develop the biofuel deep process technology, produce high value added product.
Biofuel is that the raw material after chemical reaction is produced by grease and short chain alcohol, and its chemical composition mainly is lipid acid short chain alcohol ester (hereinafter to be referred as fatty acid ester).The epoxy aliphatic ester that utilizes the production of fatty acid ester epoxidation is the plastic plasticizer of environmental protection, nontoxic, tasteless, easy degraded, of many uses, not only can replace traditional, harmful DOP softening agent, also as celluosic resin and elastomeric additive.
CN101108982A discloses a kind of method with the biodiesel preparation plastics environment protecting workability agent, makes biofuel with vegetables oil first, again biofuel is carried out epoxidation.Its epoxidizing method is to add a certain amount of 98% vitriol oil, glacial acetic acid in biofuel, is heated to 50～60 ℃, drips 35% hydrogen peroxide while stir, and reacts 10 hours.Can obtain finished product to the epoxidation product that obtains through alkali neutralization, dehydration and filtration.But the defective of the method is obvious: use on the one hand 98% the vitriol oil to bring out some side reactions, product colour is dark, and is of poor quality; Reaction times reaches 10 hours on the other hand, and production efficiency is low.
CN101921248A discloses a kind of preparation method of epoxidation biodiesel plasticizer, biofuel, emulsifying agent, formic acid (88%) are blended in the reactor by 1: 0.005～0.035: 0.05～0.15, when being heated to 55～65 ℃, slowly dripping quality is 30% hydrogen peroxide of 0.3～0.7 times of biofuel, reacts 8～10 hours.After reaction is finished product is carried out layering, remove water layer, the ester layer is washed with hydrothermal reaction until neutral, low-boiling point material is removed in underpressure distillation, filters at last to get product.But the method long reaction time, production efficiency is low, the emulsifying agent separation difficulty, poor quality, application is restricted.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method of utilizing the production of biodiesel softening agent, and the method can obtain to have the softening agent than high epoxy value within the shorter reaction times.The present invention also provides a kind of high epoxy value biodiesel plasticizer.
The invention provides a kind of method of production of biodiesel softening agent, the method comprises: the mixture that forms biofuel, small molecules carboxylic acid and titanium-silicon molecular sieve catalyst, under agitation in resulting mixture, slowly add the hydrogen peroxide reaction, restir reacts after adding hydrogen peroxide, then recovered plasticizer, wherein, the temperature of reaction of described reaction is 40 ℃～80 ℃, and total reaction time is 3h～6h; Described small molecules carboxylic acid is 1 % by weight～20 % by weight of biofuel, 1 % by weight take the described titanium-silicon molecular sieve catalyst of HTS as biofuel～10 % by weight; 10 % by weight take the described hydrogen peroxide of hydrogen peroxide as biofuel～30 % by weight.
The method of production of biodiesel softening agent provided by the invention, mixing with biofuel, small molecules carboxylic acid and titanium-silicon molecular sieve catalyst, formation reaches the mixture that comprises biofuel, small molecules carboxylic acid and HTS of temperature of reaction, then adding hydrogen peroxide in this mixture in temperature of reaction and under stirring reacts, under temperature of reaction, continue stirring reaction for some time after adding hydrogen peroxide, then recovered plasticizer, total reaction time is 3h～6h, is preferably 4h～5h.Described total reaction time is calculating from beginning to add hydrogen peroxide, the time of stirring reaction after comprising the time that adds hydrogen peroxide and adding hydrogen peroxide.Described slow adding hydrogen peroxide, the joining day of preferably controlling hydrogen peroxide is 1h～2h, add hydrogen peroxide after, preferred, stir and temperature of reaction under insulation reaction 3h～4h.Described temperature of reaction is 40 ℃～80 ℃, preferred 50 ℃～70 ℃.
The method of production of biodiesel softening agent provided by the invention
In, described titanium-silicon molecular sieve catalyst contains HTS, can also contain carrier.In HTS, the consumption of described titanium-silicon molecular sieve catalyst is equivalent to 1 % by weight of biofuel consumption～10 % by weight, is preferably 3 % by weight～8 % by weight.Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in the lattice framework, this class material is well known in the prior art, for example has titanium-containing zeolite TS-1, the Ti-ZSM-48 of MFI topological framework and has Ti-MCM-41 with mesopore molecular sieve MCM-41 isomorphous skeleton structure.
The method of production of biodiesel softening agent provided by the invention
In, described small molecules carboxylic acid consumption is equivalent to 1 % by weight of biofuel consumption～20 % by weight, preferred 3 % by weight～15 % by weight.Described small molecules carboxylic acid refers to formic acid and/or acetic acid, preferable formic acid.When described small molecules sieve carboxylic acid comprised formic acid, the formic acid consumption was 1 % by weight～20 % by weight of biofuel consumption, is preferably 3 % by weight～15 % by weight.
The method of production of biodiesel softening agent provided by the invention
In, described hydrogen peroxide concentration is 25 % by weight～60 % by weight, preferred 30 % by weight～50 % by weight, and the hydrogen peroxide consumption is in wherein hydrogen peroxide, is equivalent to 10 % by weight of biofuel～30 % by weight, preferred 15 % by weight～25 % by weight.
Described recovered plasticizer can be isolated lower aqueous layer and catalyzer with the reaction mixture sat layering that obtains, water layer and catalyzer filtered, but the catalyzer reuse that obtains; Perhaps filter out first catalyzer, then standing demix separates the water except sub-cloud; Moisture and low-boiling products to oil reservoir washs, the underpressure distillation extraction is remaining namely obtain the softening agent product, can adopt existing method.
In the method for production of biodiesel softening agent provided by the invention, the iodine number of described biofuel is not less than 60g I
2/ 100g is generally 60g I
2/ 100g～200 I
2/ 100g preferably is not less than 80 I
2/ 100g.Described biofuel can be by the waste grease that produces in animal-plant oil, little algae oil or their productive consumptions and for example transesterification reaction production of short chain alcohol after chemical reaction, animal-plant oil is one or more in soybean oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil, plam oil and Chinese vegetable tallow, the tea oil for example, and described short chain alcohol is preferably methyl alcohol and/or ethanol.Described biofuel can be fatty acid methyl ester and/or fatty-acid ethyl ester.
The present invention uses titanium-silicon molecular sieve catalyst, take the small molecules carboxylic acid as reaction promoter take biofuel as raw material, the high-quality environment-friendly plasticizer take hydrogen peroxide as oxidant production, compared with prior art, production of biodiesel softening agent method of the present invention, the time of reaction is short, the product oxirane value is high, product selectivity is high, and side reaction is few, and reaction efficiency is high, product color is good, and quality is good; And the production process cleaning, can be recycled after the catalyst separating, need not to add sulfuric acid, emulsifying agent or solvent etc., there is not the environmental pollution problem of sulfuric acid, there are not emulsifying agent or separated from solvent hard problem yet, three waste discharge is few.
Embodiment
According to the method for production of biodiesel softening agent provided by the invention, preferred, the temperature of reaction of described reaction is 50 ℃～70 ℃, and total reaction time is 4h～5h, and the feed time of hydrogen peroxide is 1 hour～2 hours; Described small molecules carboxylic acid is 3 % by weight～15 % by weight of biofuel, 3 % by weight take the described titanium-silicon molecular sieve catalyst of HTS as biofuel～8 % by weight; 15 % by weight take the described hydrogen peroxide of hydrogen peroxide as biofuel～25 % by weight, the iodine number of described biofuel are 80 I
2/ 100g～200g I
2/ 100g.This is conducive to improve the oxirane value of prepared softening agent, can obtain oxirane value and be the softening agent more than 5%, and the oxirane value of described softening agent can be 5%～7%.
The following examples further specify method of the present invention, therefore do not limit the present invention.
Used TS-1 presses the method preparation of CN 101428814A embodiment 3 among the embodiment; Ti-MCM-41 is according to the method preparation of CN 102344150A embodiment 8.Described biofuel is that grease and methyl alcohol reaction obtain.
Embodiment 1
20g soybean oil biofuel (iodine number 128 I
2/ 100g) and be equivalent to the titanium-silicon molecular sieve TS-1 of biofuel 5 % by weight, the formic acid that is equivalent to biofuel 3 % by weight joins in the reactor, stirring also heats to 60 ℃, constant temperature, slowly be added drop-wise to the hydrogen peroxide 19.6g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 20 % by weight of biofuel) in the reactor, the feed time of hydrogen peroxide is 1 hour, again in stirring lower continuation insulation reaction, total reaction time is 5h after dropwising.Standing demix, minute water outlet and catalyzer, oil reservoir wash with water to neutral (pH value 6.5～7.5 gets final product), and drying under reduced pressure, the product that obtains carry out oxirane value to be measured, and recording oxirane value is 6.4%.
Embodiment 2
20g Rapeseed Biodiesel (iodine number 97 I
2/ 100g) and be equivalent to the titanium-silicon molecular sieve TS-1 of biofuel 8 % by weight, the formic acid that is equivalent to biofuel 10 % by weight joins in the reactor together, stirring also heats to 70 ℃, constant temperature, stir lower, slowly be added drop-wise to the hydrogen peroxide 5.8g of concentration 48.7 % by weight (hydrogen peroxide is equivalent to 14 % by weight of biofuel) in the reactor, the feed time of hydrogen peroxide is 1 hour, continues insulation reaction after dropwising again, and total reaction time is 4h.Standing demix, minute water-yielding stratum is washed to neutrality, and drying under reduced pressure is extracted low-boiling products out, and the product that obtains carries out oxirane value to be measured, and recording oxirane value is 5.5%.
Embodiment 3
20g sunflower seed oil biofuel (iodine number 137 I
2/ 100g biofuel) and be equivalent to the HTS Ti-MCM-41 of biofuel 3 % by weight, the formic acid that is equivalent to biofuel 15 % by weight joins in the reactor together, stirring also heats to 50 ℃, constant temperature, in the slow dropwise reaction device of the hydrogen peroxide 24.5g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 25 % by weight of biofuel), the feed time of hydrogen peroxide is 1 hour, again in stirring and 50 ℃ of lower continuation insulation reaction, total reaction time is 4h after dropwising.Standing demix, minute water-yielding stratum is washed to neutrality, and drying under reduced pressure is extracted low-boiling products out, and the product that obtains carries out oxirane value to be measured, and recording oxirane value is 6.7%.
Embodiment 4
Biofuel (iodine number 90 I of 20g 24 degree plam oils and the preparation of soybean oil mixing oil
2/ 100g) and be equivalent to the titanium-silicon molecular sieve TS-1 of biofuel 5 % by weight, the formic acid of 15 % by weight joins in the reactor together, stirring also heats to 60 ℃, constant temperature, in the slow dropwise reaction device of the hydrogen peroxide 8.3g of concentration 48.7 % by weight (hydrogen peroxide is equivalent to 20 % by weight of biofuel), the feed time of hydrogen peroxide is 1.5 hours, again in stirring and 60 ℃ of insulation reaction, total reaction time is 4.5h after dropwising.Standing demix, minute water-yielding stratum is washed to neutrality, and drying under reduced pressure is extracted low-boiling products out, and the product that obtains carries out oxirane value to be measured, and recording oxirane value is 5.1%.
Embodiment 5
Biofuel (the iodine number 90I of 20g 24 degree plam oils and the preparation of soybean oil mixing oil
2/ 100g) and be equivalent to the HTS Ti-MCM-41 of biofuel 5 % by weight, the formic acid of 15 % by weight joins in the reactor together, stirring also heats to 60 ℃, constant temperature, in the slow dropwise reaction device of the hydrogen peroxide 8.3g of concentration 48.7% (hydrogen peroxide is equivalent to 20 % by weight of biofuel), the feed time of hydrogen peroxide is 1 hour, continue at 60 ℃ of insulation reaction after dropwising, total reaction time is 4.5h again.Standing demix, minute water-yielding stratum is washed to neutrality, and drying under reduced pressure is extracted low-boiling products out, and the product that obtains carries out oxirane value to be measured, and recording oxirane value is 5.1%.
Embodiment 6
Biofuel (iodine number 101 I of 20g waste cooking oil preparation
2/ 100g) and be equivalent to the HTS Ti-MCM-41 of biofuel 5 % by weight, the formic acid of 9 % by weight joins in the reactor together, stirring also heats to 60 ℃, constant temperature, in the slow dropwise reaction device of the hydrogen peroxide 16.3g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 25 % by weight of biofuel), the feed time of hydrogen peroxide is 1 hour, continue insulation reaction after dropwising, total reaction time is 4.5h again.Standing demix, minute water-yielding stratum is washed to neutrality, and drying under reduced pressure is extracted low-boiling products out, and the product that obtains carries out oxirane value to be measured, and recording oxirane value is 6.0%.
Embodiment 7
The biofuel (iodine number 124g/100g) of 20g soybean acidified oil (a kind of soybean oil foot processing waste grease) preparation and be equivalent to the HTS Ti-MCM-41 of biofuel 5 % by weight, the formic acid of 15 % by weight joins in the reactor together, stirring also heats to 60 ℃, constant temperature, in the slow dropwise reaction device of the hydrogen peroxide 13.1g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 20 % by weight of biofuel), the joining day of hydrogen peroxide is 1 hour, continue insulation reaction after dropwising, total reaction time is 4.5h again.Standing demix, minute water-yielding stratum is washed to neutrality, and drying under reduced pressure is extracted low-boiling products out, and the product that obtains carries out oxirane value to be measured, and recording oxirane value is 6.3%.
Embodiment 8
According to the method for embodiment 1, different is that the add-on of HTS is 10 % by weight of biofuel, formic acid accounts for biofuel weight 10 % by weight, hydrogen peroxide feed time 1.5 hours, and total reaction times is 6 hours, other condition is constant, and recording oxirane value is 3.9%.
Embodiment 9
According to the method for embodiment 1, different is, the add-on of HTS is 1 % by weight of biofuel, and the formic acid add-on accounts for the acetic acid of biofuel weight 9 % by weight, and other condition is constant, and recording oxirane value is 3.2%
As can be seen from the above embodiments, the inventive method can obtain to have the softening agent product than high epoxy value in the short period of time, and color is shallow than the product colour that sulfuric acid process obtains, as seen this product selectivity is high, and side reaction is few, and reaction efficiency is high, product color is good, and quality is good.
Claims (10)
1. the method for a production of biodiesel softening agent comprises: form the mixture that comprises biofuel, small molecules carboxylic acid and titanium-silicon molecular sieve catalyst, under agitation slowly add hydrogen peroxide, stirring reaction, and recovered plasticizer in described mixture; The temperature of reaction of described reaction is 40 ℃～80 ℃, and total reaction time is 3h～6h; Described small molecules carboxylic acid is 1 % by weight～20 % by weight of biofuel, 1 % by weight take the described titanium-silicon molecular sieve catalyst of HTS as biofuel～10 % by weight; 10 % by weight take the described hydrogen peroxide of hydrogen peroxide as biofuel～30 % by weight.
2. according to the method for production of biodiesel softening agent claimed in claim 1, it is characterized in that, described temperature of reaction is 50 ℃～70 ℃, and described small molecules carboxylic acid accounts for 3 % by weight of biofuel～15 % by weight, and described HTS accounts for 3 % by weight of biofuel～8 % by weight.
3. according to the method for production of biodiesel softening agent claimed in claim 1, it is characterized in that, described total reaction time is 4h～5h.
4. according to the method for claim 1,2 or 3 described production of biodiesel softening agent, it is characterized in that, the joining day of described hydrogen peroxide is 1 hour～2 hours, adds behind the hydrogen peroxide under agitation insulation reaction 3 hours～4 hours.
5. according to the method for production of biodiesel softening agent claimed in claim 1, it is characterized in that described hydrogen peroxide consumption is counted 15 % by weight of biofuel～25 % by weight with hydrogen peroxide wherein.
6. in accordance with the method for claim 1, its characteristic quantity is, described HTS is one or more in TS-1, Ti-MCM-41 and the Ti-ZSM-48 molecular sieve.
7. according to the method for production of biodiesel softening agent claimed in claim 1, its characteristic quantity is, described small molecules sieve carboxylic acid comprises formic acid.
8. according to the method for production of biodiesel softening agent claimed in claim 1, it is characterized in that, the iodine number of described biofuel is 80g I
2/ 100g～200g I
2/ 100g.
9. according to the method for the arbitrary described production of biodiesel softening agent of claim 1～8, it is characterized in that, described biofuel is fatty acid methyl ester and/or fatty-acid ethyl ester.
10. the softening agent by production of biodiesel is characterized in that, the oxirane value of described softening agent is 5.0%～7.0%.
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| CN201210088921.9A CN103361186B (en) | 2012-03-30 | 2012-03-30 | Method for producing plasticizer by using biodiesel |
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Citations (7)
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| CN102391210A (en) * | 2011-09-14 | 2012-03-28 | 江苏恒顺达生物能源有限公司 | Method for preparing epoxy fatty acid methyl ester |
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2012
- 2012-03-30 CN CN201210088921.9A patent/CN103361186B/en active Active
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| US5684170A (en) * | 1993-12-23 | 1997-11-04 | Arco Chemical Technology, L.P. | Epoxidation process |
| CN101029177A (en) * | 2007-02-27 | 2007-09-05 | 张伟明 | Method for producing epoxy plasticizer dirty oil and vegetable and animal waste oil |
| CN101139328A (en) * | 2007-10-15 | 2008-03-12 | 源华卓越能源科技（福建）有限公司 | Novel process for synthesizing epoxy aliphatic acid methyl ester |
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