CN111675615A - Preparation method and device of methyl myristate - Google Patents
Preparation method and device of methyl myristate Download PDFInfo
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- CN111675615A CN111675615A CN202010527836.2A CN202010527836A CN111675615A CN 111675615 A CN111675615 A CN 111675615A CN 202010527836 A CN202010527836 A CN 202010527836A CN 111675615 A CN111675615 A CN 111675615A
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- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- 239000000047 product Substances 0.000 claims abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011973 solid acid Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000605 extraction Methods 0.000 claims description 28
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000004445 quantitative analysis Methods 0.000 claims description 5
- 239000012264 purified product Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000002309 gasification Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003930 superacid Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- 239000003377 acid catalyst Substances 0.000 abstract description 6
- 239000012467 final product Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 4
- 235000021360 Myristic acid Nutrition 0.000 description 4
- 239000003225 biodiesel Substances 0.000 description 3
- 239000000686 essence Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
Abstract
The invention provides a method and a device for preparing methyl myristate. The preparation method comprises the following steps: mixing and stirring the tetradecanoic acid and the methanol according to the molar ratio of 1 (2-6) to form a mixture, heating to 50-60 ℃, and adding a solid acid catalyst accounting for 10-30 wt% of the mixture for esterification reaction. The preparation method uses the solid acid catalyst to replace the liquid acid catalyst, the specific surface area and the pore volume of the solid acid catalyst are large, good selectivity and reaction activity are ensured, the product is easy to separate and purify, the product can be repeatedly used, the equipment corrosion and the environmental pollution are avoided, and the enterprise can continuously produce the product; under the specific condition of the catalyst dosage of 10-30 wt% of the mixture, the reaction efficiency is improved, the occurrence of side reaction is inhibited, the conversion rate of the product reaches 97.8% -99.7%, and the yield of the final product, namely methyl myristate, is improved.
Description
Technical Field
The invention relates to the field of preparation of methyl myristate, and particularly relates to a preparation method and a device of methyl myristate.
Background
Due to exhaustion of conventional non-renewable diesel and increase of artificial emission of greenhouse gases, biodiesel is regarded as a promising alternative energy source and has received wide attention in recent years. Methyl myristate, as one of the main components of biodiesel, has the advantages of high cetane number, high flash point, good emission characteristics, reproducibility and excellent biodegradability, and is considered as a diesel additive and a fuel substitute with great potential. Besides being used for biodiesel, the methyl myristate can also be used for edible essences such as honey, coconut and the like, daily essences and can also be used for preparing organic chemicals. Therefore, the methyl myristate serving as an important fatty acid methyl ester has great application value, and the development of a green and economic methyl myristate process route is of great practical significance.
At present, myristic acid and methanol are generally adopted in industrial production of methyl myristate, and concentrated sulfuric acid is used as a catalyst to perform esterification reaction, has quite high activity, but has the defects of serious equipment corrosion, difficulty in continuous production, strict acidity requirement, serious environmental pollution and the like, is difficult to separate and purify a product, has a plurality of byproducts, and greatly reduces the yield.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of methyl myristate, which uses a solid acid catalyst to replace a liquid acid catalyst, has larger specific surface area and pore volume, ensures good selectivity and reaction activity, is easy for product separation and purification, can be repeatedly used for many times, avoids equipment corrosion and environmental pollution, and enables enterprises to continuously produce; under the specific condition of the specific solid acid catalyst dosage, the reaction efficiency is greatly improved, the occurrence of side reactions is inhibited, the conversion rate of the product can reach 97.8-99.7%, and the yield of the final product, namely methyl myristate, is improved.
The second purpose of the invention is to provide a device adopting the preparation method, which has low cost and convenient operation and can obtain the methyl myristate with high yield by utilizing the device.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of methyl myristate, which comprises the following steps:
mixing and stirring the tetradecanoic acid and the methanol according to the molar ratio of 1 (2-6) to form a mixture, heating to 50-60 ℃, and adding a solid acid catalyst accounting for 10-30 wt% of the mixture for esterification reaction.
In the prior art, the industrial production of methyl myristate generally adopts myristic acid and methanol as raw materials, concentrated sulfuric acid as a catalyst to carry out esterification reaction, the concentrated sulfuric acid has quite high activity, but has the defects of serious equipment corrosion, difficult continuous production, strict acidity requirement, serious environmental pollution and the like, and the product is difficult to separate and purify, has a plurality of byproducts and greatly reduces the yield.
According to the preparation method, the solid acid catalyst is used for replacing the liquid acid catalyst, the specific surface area and the pore volume of the solid acid catalyst are large, good selectivity and reaction activity are ensured, the product is easy to separate and purify, the solid acid catalyst can be repeatedly used for many times, equipment corrosion and environmental pollution are avoided, and an enterprise can continuously produce the solid acid catalyst; under the specific condition of the catalyst dosage of 10-30 wt% of the mixture, the reaction efficiency is greatly improved, the occurrence of side reactions is inhibited, the conversion rate of the product can reach 97.8% -99.7%, and the yield and the quality of the final product, namely, the methyl myristate, are greatly improved.
In the scheme of the invention, the solid acid catalyst is adopted to replace the traditional liquid acid catalyst, and the dosage of the adopted solid acid catalyst is optimized, because when the dosage of the catalyst is too large, the burden of subsequent treatment is increased, the conversion rate of the reaction cannot be further increased, and if the dosage of the catalyst is too small, the due catalytic effect cannot be achieved, so that the proper dosage of the catalyst is necessary.
Preferably, the amount of the solid acid catalyst is 15-25 wt% of the mass of the mixture; preferably, the solid acid catalyst is used in an amount of 20 wt%. The inventor finds out through a great deal of practice that the specific surface area of the solid acid catalyst is large, so that the catalyst generated by loading metal ions can obtain good dispersion degree, reactant can be adsorbed on the outer surface structure of a cavity, the concentration of the catalyst at the position of a reaction center is greatly improved due to the reaction between reactant molecules and the metal ions, the reaction activity is greatly improved, and when the optimal using amount of the catalyst is 20 wt%, the conversion rate of a product reaches 99.7%.
Preferably, the solid acid catalyst is at least one of cation exchange resin and solid super acid; compared with other solid acid catalysts, the solid acid catalyst is cation exchange resin, and the cation exchange resin and the solid super acid have the characteristics of good stability, easy separation from reactants and repeated use, and particularly the cation exchange resin not only has excellent catalytic performance, but also has higher mechanical strength.
Preferably, the cation exchange resin is Amberlyst39wet, Amberlyst36wet or Amberlyst35 wet. Preferably, the cation exchange resin is Amberlyst39 wet. Amberlyst39wet, Amberlyst36wet or Amberlyst35wet are ion exchange resin series produced by the Dow chemical method, especially Amberlyst39wet is a macroporous strong acid low crosslinking degree catalyst, and the open pore structure is especially suitable for esterification reaction.
Preferably, the stirring speed is 400rpm-600rpm, the raw material conversion rate can be improved by controlling the proper stirring speed, and the produced methyl myristate has more excellent performance.
Preferably, after the esterification reaction, the method further comprises the step of performing quantitative analysis on a reaction product after the esterification reaction, wherein the quantitative analysis adopts a gas chromatograph;
preferably, the operating condition of the gas chromatograph is that the carrier gas is N2And column front pressure: 45.2 kPa; the tail blow (N2) flow rate was: 30 mL/min; h2: 40 mL/min; air: 400 mL/min; the temperature of the gasification chamber is 270-280 ℃, the temperature of the detector is 280-290 ℃, and the sample injection amount is 0.5 mu L. The gas chromatograph is adopted to carry out qualitative and quantitative analysis on the sample, and the esterification reaction process, the product quality and the yield can be quickly and accurately controlled and analyzed.
The invention also provides a preparation device adopting the preparation method, which comprises a premixing tank for premixing the raw materials, wherein the premixing tank is connected with a full mixing kettle, the full mixing kettle is provided with a catalyst inlet for introducing the solid acid catalyst and a raw material inlet for introducing the raw materials, and the full mixing kettle is provided with a temperature control device.
Preferably, the side wall of the full mixing kettle is provided with a product outlet, and a reaction product enters the catalyst separator from the product outlet to separate and recover the catalyst;
preferably, a liquid phase outlet is arranged at the top of the catalyst separator, and a membrane filter is connected to the liquid phase outlet for separating the catalyst in the liquid phase material;
preferably, the bottom of the membrane filter is provided with a catalyst recovery port, the side wall of the membrane filter is provided with a product outlet for discharging purified products, and the catalyst recovery port is connected with the side wall of the catalyst separator for returning part of materials to the catalyst separator to continue purification and separation.
Preferably, the bottom of the full mixing kettle is provided with a first catalyst outlet; and a second catalyst outlet is arranged at the bottom of the catalyst separator, and the second catalyst outlet is communicated with the first catalyst outlet for common recovery.
Preferably, the preparation device further comprises a catalyst regenerator, and the side wall of the catalyst regenerator is respectively connected with the first catalyst outlet and the second catalyst outlet; preferably, the side wall of the catalyst regenerator is connected to the catalyst inlet for the regenerated catalyst to be returned to the complete mixing tank.
Preferably, the product outlet is connected to a first rectification column for separating the product from methanol; and a tower top condenser is arranged at the tower top of the first rectifying tower, part of condensate coming out of the tower top condenser returns to the first rectifying tower, and part of condensate goes to the premixing tank.
Preferably, a heavy component outlet is formed in the bottom of the first rectifying tower, and the heavy component outlet is connected with an extraction tower for product extraction and purification.
Preferably, the top of the extraction tower is provided with an extraction solvent spray nozzle, the bottom of the extraction tower is provided with an extraction liquid outlet, and the extraction liquid outlet is connected with the second rectification tower to remove the extraction solvent.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method uses the solid acid catalyst to replace the liquid acid catalyst, the specific surface area and the pore volume of the solid acid catalyst are large, good selectivity and reaction activity are ensured, the product is easy to separate and purify, the product can be repeatedly used, the equipment corrosion and the environmental pollution are avoided, and the enterprise can continuously produce the product; under the specific condition of the catalyst dosage of 10-30 wt% of the mixture, the reaction efficiency is greatly improved, the occurrence of side reactions is inhibited, the conversion rate of the product can reach 97.8% -99.7%, and the yield of the final product, namely methyl myristate, is improved.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic structural diagram of a preparation apparatus for methyl myristate according to an embodiment of the present invention;
FIG. 2 is a graph showing the influence of the amount of the catalyst used in examples 1 to 5 on the esterification reaction of tetradecanoic acid;
FIG. 3 is a graph showing the relationship between the effects of different catalysts on the esterification reaction of tetradecanoic acid in examples 6 to 9;
FIG. 4 is a gas chromatogram of the reaction product obtained in example 3 of the present invention;
FIG. 5 is a gas chromatogram of the product obtained in example 10 of the present invention.
Description of the drawings:
1-a premixing tank; 2-a full mixing kettle;
21-raw material inlet; 22-catalyst inlet;
23-a product outlet; 24-a first catalyst outlet;
201-temperature control device;
3-a catalyst separator; 31-a liquid phase outlet;
301-a membrane filter; 3010-product outlet;
32-a second catalyst outlet; 4-a first rectification column;
401-overhead condenser; 42-heavy ends outlet;
5-an extraction column; 51-an extract outlet;
501-an extraction solvent spray head; 6-a second rectification column;
7-catalyst regenerator.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Example 1
Adopting the device shown in FIG. 1, introducing the myristic acid and methanol into a premixing tank 1 according to the molar ratio of 1:5, stirring at the speed of 400rpm-600rpm until the myristic acid is completely dissolved to form a mixture, and then feeding the mixture into a full mixing kettle 2 from a raw material inlet 21;
simultaneously, a catalyst Amberlyst39wet accounting for 10 wt% of the mixture is added into the full mixing kettle 2 through a catalyst inlet 22 for esterification reaction, a temperature control device 201 is arranged on the full mixing kettle 2 and used for controlling the temperature in the esterification reaction process to be kept at 50-60 ℃, samples are taken at certain time intervals for gas chromatography analysis, and the operating condition of a gas chromatograph is that the carrier gas is N2And column front pressure: 452 kPa; tail blowing (N)2) The flow rate is as follows: 30 mL/min; h2: 40 mL/min; air: 400 mL/min; the temperature of the gasification chamber is 270-280 ℃, the temperature of the detector is 280-290 ℃, and the sample injection amount is 0.5 mu L.
The reaction product enters a catalyst separator 3 for catalyst separation after coming out from a product outlet 23, a liquid phase outlet 31 is arranged at the top of the catalyst separator 3, the liquid phase outlet 31 is connected with a membrane filter 301 for separating the catalyst in the liquid phase material, a product outlet 3010 is arranged on the side wall of the membrane filter 301 for discharging the purified product, the purified product coming out from the product outlet 3010 enters a first rectifying tower 4 for rectification to separate the product from the methanol, a tower top condenser 401 is arranged at the tower top of the first rectifying tower 4, a part of condensate coming out from the tower top condenser 401 returns to the first rectifying tower 4, a part of condensate is premixed to a tank 1, a heavy component outlet 42 is arranged at the tower bottom of the first rectifying tower 4, the product after the methanol is separated enters an extraction tower 50 from the heavy component outlet 42 for product extraction, an extraction solvent spray nozzle 501 is arranged at the top of the extraction tower 5, organic solvent enters from the top of the extraction tower 5 and is extracted by a spraying mode, an extraction liquid outlet 51 is formed in the bottom of the extraction tower 50, extraction liquid enters the second rectifying tower 6 after coming out from the extraction liquid outlet 51 to remove the extraction solvent, and a final product methyl myristate after the organic solvent is removed is extracted from the bottom of the second rectifying tower 6.
In addition, the bottom of the complete mixing kettle 2 is provided with a first catalyst outlet 24, the bottom of the catalyst separator 3 is provided with a second catalyst outlet 32, and the outlets of the first catalyst outlet 24 and the second catalyst outlet 32 are communicated and recovered together, in this embodiment, the preparation device further comprises a catalyst regenerator 7, and the side wall of the catalyst regenerator 7 is respectively connected with the first catalyst outlet 24 and the second catalyst outlet 32; the side wall of the catalyst regenerator 7 is connected with the catalyst inlet 22 for the regenerated catalyst to return to the full mixing kettle 2 for utilization.
Example 2
The procedure of this example is identical to that of example 1, except that Amberlyst39wet, a catalyst of 15% by weight of the mass of the mixture, is used.
Example 3
The procedure of this example is identical to that of example 1, except that 20% by weight of the mixture mass of catalyst Amberlyst39wet is added. The gas chromatogram of the specific product is shown in FIG. 3.
Example 4
The procedure of this example was identical to that of example 1, except that Amberlyst39wet, a catalyst amount of 25 wt% of the mixture mass, was used.
Example 5
The procedure of this example was identical to that of example 1, except that 30% by weight of the mixture mass of the catalyst Amberlyst39wet was added.
As can be seen from FIG. 2, by comparing the amounts of the catalysts used in examples 1 to 5 of the present invention, the solid acid catalyst content of the present invention, under the specific conditions of the amount of the mixture of 10 to 30 wt%, achieves a product conversion of 97.8% to 99.7%, and particularly, at the amount of the mixture of 30 wt%, the product conversion reaches a maximum of 99.7%, which means that the optimum amount of the catalyst is 30 wt%.
Example 6
The procedure of this example is identical to that of example 1, except that Amberlyst 15wet, a catalyst in an amount of 10% by weight of the mixture mass, is added to the complete mixing tank 2.
Example 7
The procedure of this example is identical to that of example 1, except that Amberlyst35wet, a catalyst amount of 10% by weight of the mixture mass, is added to the complete mixing tank 2.
Example 8
The procedure of this example is identical to that of example 1, except that Amberlyst36wet, a catalyst in an amount of 10% by weight of the mixture mass, is added to the complete mixing tank 2.
Example 9
The procedure of this example is identical to that of example 1, except that Lewatit K2620 catalyst, 10% by weight of the mixture mass, is added to the full-mixing tank 2.
As can be seen from fig. 3, by changing the kind of the catalyst, the solid acid catalyst Amberlyst39wet had the best activity and the highest yield of methyl myristate was obtained, compared with examples 6 to 9 and 1.
Example 10
The procedure of this example is identical to that of example 3, except that tetradecanoic acid and methanol are introduced into premix tank 1 at a molar ratio of 1:3, and the gas chromatogram of the specific product is shown in FIG. 4.
As can be seen from the gas chromatograms in FIGS. 4 and 5, the methyl myristate obtained by the scheme of the present invention was obtained in a desired yield.
In a word, the preparation method uses the solid acid catalyst to replace the liquid acid catalyst, the specific surface area and the pore volume of the solid acid catalyst are both large, good selectivity and reaction activity are ensured, the product is easy to separate and purify, the product can be repeatedly used for many times, the corrosion of equipment and the environmental pollution are avoided, and enterprises can continuously produce the product; under the specific condition of the catalyst dosage of 10-30 wt% of the mixture, the reaction efficiency is greatly improved, the occurrence of side reaction is inhibited, the conversion rate of the product can reach 97.8% -99.7%, and the yield and the quality of the final product, namely, the methyl myristate, are improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of methyl myristate is characterized by comprising the following steps:
mixing and stirring the tetradecanoic acid and the methanol according to the molar ratio of 1 (2-6) to form a mixture, heating to 50-60 ℃, and adding a solid acid catalyst accounting for 10-30 wt% of the mixture for esterification reaction.
2. The method according to claim 1, wherein the solid acid catalyst is used in an amount of 15 to 25 wt% based on the mass of the mixture;
preferably, the solid acid catalyst is used in an amount of 20 wt% of the mass of the mixture.
3. The method according to claim 1, wherein the solid acid catalyst is at least one of a cation exchange resin and a solid super acid;
preferably, the solid acid catalyst is a cation exchange resin;
preferably the type of cation exchange resin is at least one of Amberlyst39wet, Amberlyst36wet, Amberlyst35 wet;
preferably, the cation exchange resin is of the type Amberlyst39 wet.
4. The method of claim 1, wherein the mixing and stirring rate is 400rpm to 600 rpm.
5. The method according to claim 1, further comprising a step of performing quantitative analysis of the reaction product after the esterification reaction, wherein the quantitative analysis is performed by using a gas chromatograph;
preferably, the gasification temperature of the gas chromatograph is 270-280 ℃, and the detection temperature is 280-290 ℃.
6. A preparation device adopting the preparation method of methyl myristate according to any one of claims 1-5, characterized by comprising a premixing tank for premixing raw materials, wherein the premixing tank is connected with a full mixing kettle, the full mixing kettle is provided with a catalyst inlet for introducing a solid acid catalyst and a raw material inlet for introducing raw materials, and the full mixing kettle is provided with a temperature control device.
7. The preparation device of claim 6, wherein the side wall of the complete mixing kettle is provided with a product outlet, and reaction products enter the catalyst separator from the product outlet for separation and recovery of the catalyst;
preferably, a liquid phase outlet is arranged at the top of the catalyst separator, and a membrane filter is connected to the liquid phase outlet for separating the catalyst in the liquid phase material;
preferably, the bottom of the membrane filter is provided with a catalyst recovery port, the side wall of the membrane filter is provided with a product outlet for discharging purified products, and the catalyst recovery port is connected with the side wall of the catalyst separator for returning part of materials to the catalyst separator to continue purification and separation.
8. The preparation device of claim 7, wherein the bottom of the complete mixing kettle is provided with a first catalyst outlet; a second catalyst outlet is formed in the bottom of the catalyst separator, and the second catalyst outlet is communicated with the first catalyst outlet for common recovery;
preferably, the preparation device further comprises a catalyst regenerator, and the side wall of the catalyst regenerator is respectively connected with the first catalyst outlet and the second catalyst outlet;
preferably, the side wall of the catalyst regenerator is connected to the catalyst inlet for the regenerated catalyst to be returned to the complete mixing tank.
9. The production apparatus according to claim 7, wherein the product outlet is connected to a first rectification column for separating a product from methanol; and a tower top condenser is arranged at the tower top of the first rectifying tower, part of condensate coming out of the tower top condenser returns to the first rectifying tower, and part of condensate goes to the premixing tank.
10. The device as claimed in claim 7, wherein a heavy component outlet is arranged at the bottom of the first rectifying tower, and an extraction tower is connected to the heavy component outlet for product extraction and purification;
preferably, the top of the extraction tower is provided with an extraction solvent spray nozzle, the bottom of the extraction tower is provided with an extraction liquid outlet, and the extraction liquid outlet is connected with the second rectification tower to remove the extraction solvent.
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