CN115536765B - Catalytic polymerization method of fatty acid methyl ester - Google Patents
Catalytic polymerization method of fatty acid methyl ester Download PDFInfo
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- 235000019387 fatty acid methyl ester Nutrition 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 52
- 239000011630 iodine Substances 0.000 claims abstract description 52
- 239000003225 biodiesel Substances 0.000 claims abstract description 36
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims abstract description 36
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 72
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000011261 inert gas Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000000199 molecular distillation Methods 0.000 description 17
- 238000010907 mechanical stirring Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 238000007664 blowing Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- -1 trimer acid methyl ester Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/12—Esters of phenols or saturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present disclosure relates to a method for the catalytic polymerization of fatty acid methyl esters, the method comprising: s01, contacting the mixed fatty acid methyl ester with an iodine catalyst under a closed condition and carrying out polymerization reaction to obtain a first product; s02, recovering the iodine catalyst from the first product to obtain a second product; s03, separating biodiesel from the second product to obtain the polymeric methyl ester. In the catalytic polymerization method of fatty acid methyl ester, the polyunsaturated fatty acid methyl ester in the mixed fatty acid methyl ester is catalyzed by the iodine simple substance catalyst under the closed condition to carry out polymerization reaction, so that the polymerized methyl ester and the biodiesel with good oxidation stability can be prepared, and the polymerization reaction has the advantages of high catalytic efficiency, short reaction time, easy separation of products, small material loss and the like.
Description
Technical Field
The disclosure relates to the technical field of chemical synthesis, in particular to a catalytic polymerization method of fatty acid methyl ester.
Background
The method for producing the polymerized methyl ester with better economic benefit is realized by taking the cheap mixed fatty acid methyl ester as the raw material and carrying out catalytic polymerization reaction. However, common heterogeneous catalysts such as clay, montmorillonite and clay have the problems of low catalytic efficiency, large catalyst consumption, high reaction temperature, long reaction time, serious side reaction and the like in catalytic polymerization, and have the problems of material loss, difficult catalyst post-treatment and the like caused by the phenomena of adsorption and entrainment of products after the reaction. In addition, the polymerization reaction is catalyzed by a homogeneous catalyst such as sulfuric acid and anhydrous aluminum chloride, and the catalytic efficiency is improved, but the catalyst is easy to deactivate and the catalyst cost is high.
Biodiesel refers to fatty acid methyl ester or ethyl ester formed by esterification of natural grease, but the biodiesel has the common problem of poor oxidation stability because the natural grease contains more polyunsaturated fatty acids.
How to efficiently and rapidly produce the polymeric methyl ester and the biodiesel with good oxidation stability in the same reaction process is a problem to be solved at present.
Disclosure of Invention
The object of the present disclosure is to provide a catalytic polymerization method of fatty acid methyl esters, which is capable of efficiently and rapidly producing polymerized methyl esters and biodiesel having good oxidation stability.
In order to achieve the above object, the present disclosure provides a catalytic polymerization method of fatty acid methyl esters, the method comprising:
s01, contacting the mixed fatty acid methyl ester with an iodine catalyst under a closed condition and carrying out polymerization reaction to obtain a first product;
s02, recovering the iodine catalyst from the first product to obtain a second product;
s03, separating biodiesel from the second product to obtain the polymeric methyl ester.
Optionally, the iodine catalyst is used in an amount of 0.1wt% to 10wt% of the mixed fatty acid methyl ester.
Preferably, the iodine catalyst is used in an amount of 0.2wt% to 5wt% of the amount of the mixed fatty acid methyl ester.
Optionally, the mixed fatty acid methyl ester comprises fatty acid methyl ester with a carbon chain length of 16-18 carbon atoms, and the mixed fatty acid methyl ester contains polyunsaturated fatty acid methyl ester.
Alternatively, the polyunsaturated fatty acid methyl ester is present in an amount of 5 wt.% or more, preferably 10 wt.% or more, more preferably 15 wt.% or more, based on the weight of the mixed fatty acid methyl esters.
Alternatively, the polymerization reaction is carried out under stirring and heating conditions including: the reaction pressure is 0.1 MPa-10 MPa, the reaction temperature is 140-350 ℃ and the reaction time is 10-480 min.
Preferably, the reaction pressure of the polymerization reaction is 0.1 MPa-5 MPa, the reaction temperature is 190-300 ℃ and the reaction time is 10-100 min.
Optionally, the polymerization is carried out under oxygen-barrier conditions.
Optionally, in step S02, the recovering the iodine catalyst from the first product to obtain a second product includes:
the first product is purged with an inert gas to recover the iodine catalyst, with the remainder being the second product.
According to the technical scheme, in the catalytic polymerization method of fatty acid methyl ester, the polyunsaturated fatty acid methyl ester in the mixed fatty acid methyl ester is catalyzed by the iodine simple substance catalyst under the airtight condition to carry out polymerization reaction, so that the polymerized methyl ester and biodiesel with good oxidation stability can be prepared, and the polymerization reaction has the advantages of high catalytic efficiency, short reaction time, easiness in product separation, small material loss and the like.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a graph of the results of high resolution mass spectrometry analysis of polymeric methyl esters in an embodiment of the present disclosure.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The present disclosure provides a method for the catalytic polymerization of fatty acid methyl esters, the method comprising: s01, contacting the mixed fatty acid methyl ester with an iodine catalyst under a closed condition and carrying out polymerization reaction to obtain a first product; s02, recovering the iodine catalyst from the first product to obtain a second product; s03, separating biodiesel from the second product to obtain the polymeric methyl ester.
In the method, iodine simple substance is used as a catalyst, polyunsaturated fatty acid methyl esters in mixed fatty acid methyl esters are catalyzed to carry out polymerization reaction under a closed condition, and the polymerized methyl esters and biodiesel with good oxidation stability can be prepared simultaneously in the same reaction process. The iodine catalyst exists in a gaseous or liquid state under the reaction condition, so that the reaction raw materials are not adsorbed and entrained in the reaction process, solid waste is not generated after the reaction, and the separation is easy, and the method disclosed by the invention has the advantages of small material loss and easy separation of products; moreover, in the catalytic polymerization reaction of the present disclosure, the iodine catalyst in a gaseous or liquid state can be sufficiently contacted with the reaction raw material, which makes it have a higher catalytic efficiency; in addition, the catalytic polymerization reaction is carried out under the airtight condition, and the contents of the iodine catalyst, the reaction raw materials and the reaction products are not reduced due to leakage, so that the catalytic polymerization reaction can always maintain higher reaction efficiency, and has higher raw material conversion rate and product recovery rate.
The relative amounts of the iodine catalyst and the mixed fatty acid methyl esters may vary within a range, for example, the catalyst may be used in an amount of 0.1wt% to 10wt%, preferably 0.2wt% to 5wt%, of the mixed fatty acid methyl esters according to the present disclosure.
According to the present disclosure, the mixed fatty acid methyl esters may be selected within a range, for example, the mixed fatty acid methyl esters may include fatty acid methyl esters having a carbon chain length of 16 to 18 carbon atoms. The fatty acid methyl ester may contain polyunsaturated fatty acid methyl esters, and the content of the polyunsaturated fatty acid methyl esters may be 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight or more, based on the weight of the mixed fatty acid methyl esters. Under the above preferred conditions, the polyunsaturated fatty acid methyl ester content in the mixed fatty acid methyl esters is relatively high, which can effectively improve the yield of the polymerized methyl ester.
According to the present disclosure, the polymerization reaction may be performed under stirring and heating, and the reaction is performed under a preset stabilization and pressure for a preset time. Specifically, the reaction conditions include: the reaction pressure is 0.1MPa to 10MPa, the reaction temperature is 140 ℃ to 350 ℃ and the reaction time is 10min to 480min; preferably, the reaction pressure is 0.1 MPa-5 MPa, the reaction temperature is 190-300 ℃ and the reaction time is 10-100 min. The reaction pressure to which the present disclosure relates may specifically be gauge pressure. Under the reaction conditions provided by the disclosure, the generation speed of the polymerized methyl ester is high, and side reactions such as cracking are less, so that the preparation efficiency of the polymerized methyl ester and the purity of the prepared polymerized methyl ester can be effectively improved.
According to the present disclosure, the polymerization reaction may be performed under an oxygen-free condition in order to avoid side reactions such as oxidation of the polyunsaturated fatty acid methyl esters under high temperature conditions. Specifically, the operation of isolating oxygen can be realized by introducing inert gases such as nitrogen into the closed reaction system, and the operation of isolating oxygen can also be realized by vacuumizing the closed reaction system.
According to the present disclosure, in step S02, when recovering the iodine catalyst from the first product to obtain a second product, the first product may be purged with an inert gas to recover the iodine catalyst, and the remaining portion is used as the second product.
In the present disclosure, the biodiesel may specifically refer to the single fatty acid methyl ester moiety in the second product. In step S03, when separating biodiesel from the second product to obtain polymerized methyl ester, a distillation method may be used to separate methyl monofatty acid from the second product as the biodiesel, and the remainder may be the polymerized methyl ester, wherein the distillation method may be selected from reduced pressure distillation, molecular distillation, thin film evaporation, rectification, and the like. The fatty acid methyl ester may be the original component contained in the mixed fatty acid methyl ester, or may be a side reaction product of polyunsaturated fatty acid methyl ester in the mixed fatty acid methyl ester.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
The materials, reagents, instruments and equipment involved in the embodiments of the present disclosure, unless otherwise specified, are all available commercially.
Example 1
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 20.9 wt%) and 1.8g of iodine catalyst (the content of iodine catalyst is 0.6 wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be at about 0.4MPa, the reaction temperature is kept at 260 ℃ after the reaction temperature is kept for 40min, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 200 ℃, then discharging is carried out, single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the conditions of 120 ℃ and 3Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
The content of the polyunsaturated fatty acid methyl ester was reduced from 20.9% to 0.7% before and after the reaction, which revealed that the polymerization conversion rate of the polyunsaturated fatty acid methyl ester was 96.7% in this example. The oxidation stability index of the separated biodiesel is 7.2h by an accelerated oxidation method. The polymerized methyl ester obtained by the reaction was analyzed by high-resolution mass spectrometry, and as a result, in fig. 1, a peak having a mass-to-charge ratio of 613.5142 was a dimer acid methyl ester peak, a peak having a mass-to-charge ratio of 907.7680 was a trimer acid methyl ester peak, and a peak having a mass-to-charge ratio of 1202.0226 was a tetrameric acid methyl ester peak, as shown in fig. 1.
Example 2
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 20.9 wt%) and 2.4g of iodine catalyst (the content of iodine catalyst is 0.8 wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be about 0.6MPa, the reaction temperature is kept at 240 ℃ after the reaction temperature is kept for 30min, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 200 ℃, then discharging is carried out, single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the condition of 160 ℃ and 30Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 97.1%, and the oxidation stability index of the separated biodiesel is 7.5 hours.
Example 3
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 20.9 wt%) and 3.0g of iodine catalyst (the content of iodine catalyst is 1.0 wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be about 0.5MPa, the reaction temperature is kept for 50min after 230 ℃, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 200 ℃, then discharging is carried out, and single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the condition of 110 ℃ and 1Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 97.3%, and the oxidation stability index of the separated biodiesel is 7.9 hours.
Example 4
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 20.9 wt%) and 6.0g of iodine catalyst (the content of iodine catalyst is 2.0 wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, air suction is carried out for 2min by a rotary vane vacuum pump, then heating is started, the reaction pressure is controlled to be not more than 0.2MPa in the heating process, the reaction temperature is kept at 210 ℃ for 80min, then heating is stopped, the temperature is reduced to about 200 ℃, the iodine catalyst is blown out by nitrogen, then discharging is carried out, single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the conditions of 180 ℃ and 30Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 97.7%, and the oxidation stability index of the separated biodiesel is 7.7 hours.
Example 5
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 20.9 wt%) and 12.0g of iodine catalyst (the content of iodine catalyst is 4.0 wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be about 0.1MPa, the reaction temperature is kept for 100min after the reaction temperature reaches 190 ℃, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 200 ℃, then discharging is carried out, and single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the conditions of 190 ℃ and 10Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
According to measurement and calculation, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 95.9%, and the oxidation stability index of the separated biodiesel is 8.4 hours.
Example 6
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 33.7wt%) and 1.2g of iodine catalyst (the content of iodine catalyst is 0.4wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be at about 1.0MPa, the reaction temperature is kept at 260 ℃ for 60min, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 200 ℃, then discharging is carried out, single fatty acid methyl ester (namely biodiesel) is separated by reduced pressure distillation under the vacuum degree of 500Pa, heating is stopped after the temperature of the tower kettle reaches 260 ℃, and the rest part in the tower kettle is polymerized methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 95.9%, and the oxidation stability index of the separated biodiesel is 7.0h.
Example 7
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 33.7wt%) and 0.6g of iodine catalyst (the content of iodine catalyst is 0.2wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, heating is started, the whole process is controlled to be at about 3.0MPa in the heating process, the reaction temperature is kept at 300 ℃ for 80min, heating is stopped, the temperature is reduced to about 200 ℃, the iodine catalyst is blown out by nitrogen, then the material is discharged, the single fatty acid methyl ester (namely biodiesel) is separated by reduced pressure distillation under the vacuum degree of 500Pa, heating is stopped after the temperature of the tower kettle reaches 270 ℃, and the rest of the tower kettle is polymeric methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 95.2%, and the oxidation stability index of the separated biodiesel is 6.3 hours.
Example 8
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 33.7wt%) and 1.5g of iodine catalyst (the content of iodine catalyst is 0.5wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be at about 0.4MPa, the reaction temperature is kept for 20min after 270 ℃, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 180 ℃, then discharging is carried out, and single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the conditions of 120 ℃ and 1Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 96.3%, and the oxidation stability index of the separated biodiesel is 7.4 hours.
Example 9
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
300g of mixed fatty acid methyl ester (the content of polyunsaturated fatty acid methyl ester is 33.7wt%) and 2.4g of iodine catalyst (the content of iodine catalyst is 0.8wt%) are added into a 500mL stainless steel reaction kettle, mechanical stirring is started after sealing, nitrogen is used for blowing for 2min, then heating is started, the whole process is controlled to be at about 4.0MPa, the reaction temperature is kept at 250 ℃ for 30min after the reaction temperature is kept at about 250 ℃, then heating is stopped, the iodine catalyst is blown out by nitrogen when the temperature is reduced to about 200 ℃, then discharging is carried out, single fatty acid methyl ester (namely biodiesel) is separated by molecular distillation under the conditions of 120 ℃ and 2Pa, and the molecular distillation heavy phase is the polymeric methyl ester.
According to measurement, the polymerization conversion rate of the polyunsaturated fatty acid methyl ester in the embodiment is 96.6%, and the oxidation stability index of the separated biodiesel is 6.8 hours.
Comparative example 1
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
Adding 300g of mixed fatty acid methyl ester with the polyunsaturated fatty acid methyl ester content of 20.9wt% into a 500mL stainless steel reaction kettle, starting mechanical stirring after sealing, purging with nitrogen for 2min, then starting heating, controlling the reaction pressure to be about 1.0MPa in the whole process in the heating process, keeping the reaction temperature at 260 ℃ for 30min after the reaction temperature is up, stopping heating, and performing molecular distillation at 120 ℃ and 3Pa to obtain only the fatty acid methyl ester (biodiesel) without obtaining polymerized methyl ester, and measuring the oxidation stability index of the separated biodiesel by using an accelerated oxidation method to be 5.4h.
Comparative example 2
The mixed fatty acid methyl esters were catalytically polymerized by the following method.
Adding 300g of mixed fatty acid methyl ester with polyunsaturated fatty acid methyl ester content of 33.7wt% into a 500mL stainless steel reaction kettle, sealing, starting mechanical stirring, pumping air for 2min by a rotary vane vacuum pump, then starting heating, controlling the reaction pressure not to exceed about 0.3MPa in the heating process, keeping the reaction temperature for 60min after the reaction temperature reaches 240 ℃, stopping heating, and carrying out molecular distillation at 110 ℃ and 1Pa to obtain only the polymerized methyl ester of fatty acid methyl ester (biodiesel), wherein the oxidation stability index of the separated biodiesel is 3.9h by an accelerated oxidation method.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (11)
1. A method for the catalytic polymerization of fatty acid methyl esters, comprising:
s01, contacting the mixed fatty acid methyl ester with an iodine catalyst under a closed condition and carrying out polymerization reaction to obtain a first product;
s02, recovering the iodine catalyst from the first product to obtain a second product;
s03, separating biodiesel from the second product to obtain polymeric methyl ester; the polymerization reaction is carried out under stirring and heating conditions including: the reaction pressure is 0.1MPa to 10MPa, and the reaction temperature is 140 ℃ to 350 ℃; the pressure is gauge pressure.
2. The method according to claim 1, wherein the amount of the iodine catalyst is 0.1 to 10wt% of the amount of the mixed fatty acid methyl esters.
3. The method according to claim 2, wherein the amount of the iodine catalyst is 0.2 to 5wt% of the amount of the mixed fatty acid methyl esters.
4. The method of claim 1, wherein the mixed fatty acid methyl esters comprise fatty acid methyl esters having a carbon chain length of 16 to 18 carbon atoms, and wherein the mixed fatty acid methyl esters comprise polyunsaturated fatty acid methyl esters.
5. The method according to claim 4, wherein the polyunsaturated fatty acid methyl ester is present in an amount of 5% by weight or more based on the weight of the mixed fatty acid methyl esters.
6. The method according to claim 5, wherein the polyunsaturated fatty acid methyl ester is present in an amount of 10% by weight or more based on the weight of the mixed fatty acid methyl esters.
7. The method according to claim 6, wherein the polyunsaturated fatty acid methyl ester is present in an amount of 15% by weight or more based on the weight of the mixed fatty acid methyl esters.
8. The method according to any one of claims 1 to 7, wherein the reaction time is from 10min to 480min.
9. The method according to claim 8, wherein the reaction pressure of the polymerization reaction is 0.1MPa to 5MPa, the reaction temperature is 190 ℃ to 300 ℃ and the reaction time is 10min to 100min.
10. The process according to any one of claims 1 to 7, wherein the polymerization is carried out under oxygen-barrier conditions.
11. The method according to any one of claims 1 to 7, wherein in step S02, the recovering the iodine catalyst from the first product yields a second product comprising:
the first product is purged with an inert gas to recover the iodine catalyst, with the remainder being the second product.
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