CN103361186B - Method for producing plasticizer by using biodiesel - Google Patents
Method for producing plasticizer by using biodiesel Download PDFInfo
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- CN103361186B CN103361186B CN201210088921.9A CN201210088921A CN103361186B CN 103361186 B CN103361186 B CN 103361186B CN 201210088921 A CN201210088921 A CN 201210088921A CN 103361186 B CN103361186 B CN 103361186B
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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; agitating and reacting; after acting, applying two-dimensional separation between oil and water, and washing and drying the oil phase to obtain 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 production of biodiesel softening agent.
Background technology
Biofuel is the new industry emerged mankind's 21 century, receives the most attention of countries in the world.First biofuel is produce as the substitute of petroleum diesel, be subject to the impact of petroleum diesel price at present, 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, biofuel deep process technology must be developed, producing high value added product.
Biofuel is that raw material after chemical reaction is produced by grease and short chain alcohol, and its chemical composition is lipid acid short-chain alcohol ester (hereinafter referred to as fatty acid ester) mainly.The epoxy aliphatic ester utilizing fatty acid ester epoxidation to produce is the plastic plasticizer of environmental protection, nontoxic, tasteless, easily degrade, of many uses, not only can replace traditional, harmful DOP softening agent, also be used as celluosic resin and elastomeric additive.
CN101108982A discloses a kind of method of biodiesel preparation plastics environment protecting workability agent, first obtains biofuel with vegetables oil, then carries out epoxidation to biofuel.Its epoxidizing method is in biofuel, add a certain amount of 98% vitriol oil, glacial acetic acid, is heated to 50 ~ 60 DEG C, stirs the hydrogen peroxide dripping 35%, reacts 10 hours.Finished product can be obtained through alkali neutralization, dehydration and filtration to the epoxidation product obtained.But the defect of the method is obvious: use the vitriol oil of 98% to induce some side reactions on the one hand, product colour is dark, 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 reactor by 1: 0.005 ~ 0.035: 0.05 ~ 0.15, when being heated to 55 ~ 65 DEG C, slow dropping quality is 30% hydrogen peroxide of biofuel 0.3 ~ 0.7 times, reacts 8 ~ 10 hours.Reacted rear and carried out layering to product, removing water layer, wash until neutral to ester layer with hydrothermal reaction, underpressure distillation, removes low-boiling point material, finally filters to obtain product.But the method long reaction time, production efficiency is low, emulsifying agent separation difficulty, and poor quality, application is restricted.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method utilizing production of biodiesel softening agent, and the method can obtain the softening agent had compared with 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 forming biofuel, small carboxylic acid molecules and titanium-silicon molecular sieve catalyst, in obtained mixture, under agitation slowly add hydrogen peroxide reaction, to add after hydrogen peroxide stirring reaction again, then recovered plasticizer, wherein, the temperature of reaction of described reaction is 40 DEG C ~ 80 DEG C, and total reaction time is 3h ~ 6h; Described small carboxylic acid molecules is 1 % by weight ~ 20 % by weight of biofuel, be biofuel in the titanium-silicon molecular sieve catalyst that HTS is described 1 % by weight ~ 10 % by weight; Be biofuel in the described hydrogen peroxide of hydrogen peroxide 10 % by weight ~ 30 % by weight.
The method of production of biodiesel softening agent provided by the invention, by the mixing of biofuel, small carboxylic acid molecules and titanium-silicon molecular sieve catalyst, form the mixture comprising biofuel, small carboxylic acid molecules and HTS reaching temperature of reaction, then under temperature of reaction and stirring, in this mixture, add hydrogen peroxide to react, stirring reaction for some time is continued at the reaction temperatures after adding hydrogen peroxide, then recovered plasticizer, total reaction time is 3h ~ 6h, is preferably 4h ~ 5h.Described total reaction time is from starting to add calculating hydrogen peroxide, comprises time of adding hydrogen peroxide and time of stirring reaction after adding hydrogen peroxide.Described slowly adds hydrogen peroxide, and the joining day preferably controlling hydrogen peroxide is 1h ~ 2h, after adding hydrogen peroxide, preferably, and insulation reaction 3h ~ 4h under stirring and temperature of reaction.Described temperature of reaction is 40 DEG C ~ 80 DEG C, preferably 50 DEG C ~ 70 DEG C.
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 ~ 10 % by weight of biofuel consumption, 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 lattice framework, this kind of material is well known in the prior art, such as, have titanium-containing zeolite TS-1, Ti-ZSM-48 of MFI topological framework and have the Ti-MCM-41 with mesostructured material isomorphous skeleton structure.
The method of production of biodiesel softening agent provided by the invention
in, described small carboxylic acid molecules's consumption is equivalent to 1 % by weight ~ 20 % by weight of biofuel consumption, and preferably 3 % by weight ~ 15 % by weight.Described small carboxylic acid molecules refers to formic acid and/or acetic acid, preferable formic acid.When described molecular sieve carboxylic acid comprises formic acid, formic acid consumption is 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, preferably 30 % by weight ~ 50 % by weight, and hydrogen peroxide consumption, in hydrogen peroxide wherein, is equivalent to 10 % by weight ~ 30 % by weight of biofuel, and preferably 15 % by weight ~ 25 % by weight.
Described recovered plasticizer, the reaction mixture sat layering that can will obtain, isolates lower aqueous layer and catalyzer, and by water layer and catalyst filtration, the catalyzer obtained can reuse; Or first filter out catalyzer, then stratification, be separated the water except sub-cloud; Oil reservoir is washed, underpressure distillation extracts remaining moisture and low-boiling products out, namely obtain softening agent product, existing method can be adopted.
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, is preferably not less than 80 I
2/ 100g.Described biofuel can be produced by the waste grease produced in animal-plant oil, micro-algae oil or their productive consumptions and short chain alcohol after chemical reaction such as transesterification reaction, one or more in animal-plant oil such as soybean oil, rapeseed oil, Oleum Gossypii semen, sunflower seed oil, plam oil and Chinese vegetable tallow, tea oil, 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 take biofuel as raw material, and using titanium-silicon molecular sieve catalyst, take small carboxylic acid molecules as reaction promoter, take hydrogen peroxide as the environment-friendly plasticizer of oxidant production high-quality, compared with prior art, production of biodiesel softening agent method of the present invention, the time of reaction is short, 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 production process cleans, can be recycled after catalyst separating, without the need to adding sulfuric acid, emulsifying agent or solvent etc., there is not the environmental pollution problem of sulfuric acid, also there is not the problem of emulsifying agent or separated from solvent difficulty, three waste discharge is few.
Embodiment
According to the method for production of biodiesel softening agent provided by the invention, preferably, the temperature of reaction of described reaction is 50 DEG C ~ 70 DEG C, and total reaction time is 4h ~ 5h, and the feed time of hydrogen peroxide is 1 hour ~ 2 hours; Described small carboxylic acid molecules is 3 % by weight ~ 15 % by weight of biofuel, be biofuel in the titanium-silicon molecular sieve catalyst that HTS is described 3 % by weight ~ 8 % by weight; Be biofuel in the described hydrogen peroxide of hydrogen peroxide 15 % by weight ~ 25 % by weight, the iodine number of described biofuel is 80 I
2/ 100g ~ 200g I
2/ 100g.This is conducive to the oxirane value of the softening agent prepared by raising, and can obtain the softening agent that oxirane value is more than 5%, the oxirane value of described softening agent can be 5% ~ 7%.
The following examples are further described method of the present invention, therefore do not limit the present invention.
In embodiment, TS-1 used presses the method preparation of CN 101428814A embodiment 3; Ti-MCM-41 is prepared according to the method for CN 102344150A embodiment 8.Described biofuel is that grease and methyl alcohol are obtained by reacting.
Embodiment 1
20g soybean oil biofuel (iodine number 128 I
2/ 100g) and the titanium-silicon molecular sieve TS-1 being equivalent to biofuel 5 % by weight, the formic acid that is equivalent to biofuel 3 % by weight join in reactor, stir and heat to 60 DEG C, constant temperature, the hydrogen peroxide 19.6g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 20 % by weight of biofuel) is slowly added drop-wise in reactor, the feed time of hydrogen peroxide is 1 hour, under stirring, continue insulation reaction again after dropwising, total reaction time is 5h.Stratification, point water outlet and catalyzer, oil reservoir washes with water to neutral (pH value 6.5 ~ 7.5), and drying under reduced pressure, the product obtained carries out oxirane value mensuration, and recording oxirane value is 6.4%.
Embodiment 2
20g Rapeseed Biodiesel (iodine number 97 I
2/ 100g) and the titanium-silicon molecular sieve TS-1 being equivalent to biofuel 8 % by weight, the formic acid that is equivalent to biofuel 10 % by weight join together in reactor, stir and heat to 70 DEG C, constant temperature, under stirring, the hydrogen peroxide 5.8g of concentration 48.7 % by weight (hydrogen peroxide is equivalent to 14 % by weight of biofuel) is slowly added drop-wise in reactor, the feed time of hydrogen peroxide is 1 hour, continues insulation reaction again after dropwising, and total reaction time is 4h.Stratification, point water-yielding stratum, is washed to neutrality, drying under reduced pressure, and extract low-boiling products out, the product obtained carries out oxirane value mensuration, and recording oxirane value is 5.5%.
Embodiment 3
20g sunflower seed oil biofuel (iodine number 137 I
2/ 100g biofuel) and the HTS Ti-MCM-41 being equivalent to biofuel 3 % by weight, the formic acid that is equivalent to biofuel 15 % by weight join together in reactor, stir and heat to 50 DEG C, constant temperature, in the hydrogen peroxide 24.5g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 25 % by weight of biofuel) slowly dropwise reaction device, the feed time of hydrogen peroxide is 1 hour, at stirring and 50 DEG C, continue insulation reaction again after dropwising, total reaction time is 4h.Stratification, point water-yielding stratum, is washed to neutrality, drying under reduced pressure, and extract low-boiling products out, the product obtained carries out oxirane value mensuration, and recording oxirane value is 6.7%.
Embodiment 4
Biofuel (iodine number 90 I prepared by 20g 24 degree of plam oils and 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 reactor together, stir and heat to 60 DEG C, constant temperature, in the hydrogen peroxide 8.3g of concentration 48.7 % by weight (hydrogen peroxide is equivalent to 20 % by weight of biofuel) slowly dropwise reaction device, the feed time of hydrogen peroxide is 1.5 hours, again in stirring and 60 DEG C of insulation reaction after dropwising, total reaction time is 4.5h.Stratification, point water-yielding stratum, is washed to neutrality, drying under reduced pressure, and extract low-boiling products out, the product obtained carries out oxirane value mensuration, and recording oxirane value is 5.1%.
Embodiment 5
Biofuel (iodine number 90I prepared by 20g 24 degree of plam oils and 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 reactor together, stir and heat to 60 DEG C, constant temperature, in the hydrogen peroxide 8.3g of concentration 48.7% (hydrogen peroxide is equivalent to 20 % by weight of biofuel) slowly dropwise reaction device, the feed time of hydrogen peroxide is 1 hour, continue at 60 DEG C of insulation reaction after dropwising again, total reaction time is 4.5h.Stratification, point water-yielding stratum, is washed to neutrality, drying under reduced pressure, and extract low-boiling products out, the product obtained carries out oxirane value mensuration, and recording oxirane value is 5.1%.
Embodiment 6
Biofuel (iodine number 101 I prepared by 20g waste cooking oil
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 reactor together, stir and heat to 60 DEG C, constant temperature, in the hydrogen peroxide 16.3g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 25 % by weight of biofuel) slowly dropwise reaction device, the feed time of hydrogen peroxide is 1 hour, continue insulation reaction again after dropwising, total reaction time is 4.5h.Stratification, point water-yielding stratum, is washed to neutrality, drying under reduced pressure, and extract low-boiling products out, the product obtained carries out oxirane value mensuration, and recording oxirane value is 6.0%.
Embodiment 7
Biofuel (iodine number 124g/100g) prepared by 20g soybean acidified oil (a kind of soybean oil foot processing waste grease) and be equivalent to the HTS Ti-MCM-41 of biofuel 5 % by weight, the formic acid of 15 % by weight joins in reactor together, stir and heat to 60 DEG C, constant temperature, in the hydrogen peroxide 13.1g of concentration 30.6 % by weight (hydrogen peroxide is equivalent to 20 % by weight of biofuel) slowly dropwise reaction device, the joining day of hydrogen peroxide is 1 hour, continue insulation reaction again after dropwising, total reaction time is 4.5h.Stratification, point water-yielding stratum, is washed to neutrality, drying under reduced pressure, and extract low-boiling products out, the product obtained carries out oxirane value mensuration, and recording oxirane value is 6.3%.
Embodiment 8
According to the method for embodiment 1, unlike, 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, unlike, the add-on of HTS is 1 % by weight of biofuel, and 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 the softening agent product had compared with high epoxy value in the short period of time, and the product colour that color obtains compared with sulfuric acid process is shallow, visible product selectivity is high, and side reaction is few, and reaction efficiency is high, product color is good, and quality is good.
Claims (9)
1. the method for a production of biodiesel softening agent, step is: under agitation, slowly hydrogen peroxide is added in the mixture that biofuel, small carboxylic acid molecules and titanium-silicon molecular sieve catalyst form, stirring reaction, after reaction terminates, carry out water-oil phase separation, oil phase obtains softening agent after washing and drying, and the catalyst separating Posterior circle in aqueous phase uses; The temperature of reaction of described reaction is 40 DEG C ~ 80 DEG C, and total reaction time is 3h ~ 6h; Described small carboxylic acid molecules is 1 % by weight ~ 20 % by weight of biofuel, be biofuel in the titanium-silicon molecular sieve catalyst that HTS is described 1 % by weight ~ 10 % by weight; Be biofuel in the described hydrogen peroxide of hydrogen peroxide 10 % by weight ~ 30 % by weight.
2. according to the method for production of biodiesel softening agent according to claim 1, it is characterized in that, described temperature of reaction is 50 DEG C ~ 70 DEG C, and described small carboxylic acid molecules accounts for 3 % by weight ~ 15 % by weight of biofuel, and described HTS accounts for 3 % by weight ~ 8 % by weight of biofuel.
3. according to the method for production of biodiesel softening agent according to claim 1, it is characterized in that, described total reaction time is 4h ~ 5h.
4. according to the method for the production of biodiesel softening agent described in claim 1,2 or 3, it is characterized in that, the joining day of described hydrogen peroxide is 1 hour ~ 2 hours, to add after hydrogen peroxide under agitation insulation reaction 3 hours ~ 4 hours.
5. according to the method for production of biodiesel softening agent according to claim 1, it is characterized in that, described hydrogen peroxide consumption, count 15 % by weight ~ 25 % by weight of biofuel with hydrogen peroxide wherein.
6. in accordance with the method for claim 1, it is characterized in that, described HTS is one or more in TS-1, Ti-MCM-41 and Ti-ZSM-48 molecular sieve.
7. according to the method for production of biodiesel softening agent according to claim 1, it is characterized in that, described small carboxylic acid molecules comprises formic acid.
8. according to the method for production of biodiesel softening agent according to 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 production of biodiesel softening agent according to claim 1, it is characterized in that, described biofuel is fatty acid methyl ester and/or fatty-acid ethyl ester.
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2012
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| CN101029177A (en) * | 2007-02-27 | 2007-09-05 | 张伟明 | Method for producing epoxy plasticizer dirty oil and vegetable and animal waste oil |
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