CN115894224A - Method for preparing raw film bulk ester by adopting micro-channel continuous flow reactor - Google Patents
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- 150000002148 esters Chemical class 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000011552 falling film Substances 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- LDRWAWZXDDBHTG-UHFFFAOYSA-N 3,5,5-trimethylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CC(C)(C)C1 LDRWAWZXDDBHTG-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000010408 film Substances 0.000 claims abstract description 25
- 229960001860 salicylate Drugs 0.000 claims abstract description 15
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 41
- 229960001047 methyl salicylate Drugs 0.000 claims description 37
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- -1 salicylate ester Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 claims description 4
- RQTVIKMRXYJTDX-UHFFFAOYSA-N 1-(4-methylphenyl)sulfonyl-4-phenylpiperidine-4-carbonitrile Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1CCC(C=2C=CC=CC=2)(C#N)CC1 RQTVIKMRXYJTDX-UHFFFAOYSA-N 0.000 claims description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 claims description 2
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 claims description 2
- PMGCQNGBLMMXEW-UHFFFAOYSA-N Isoamyl salicylate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1O PMGCQNGBLMMXEW-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KJLDTYUGZVCMRD-UHFFFAOYSA-L [dodecanoyloxy(diphenyl)stannyl] dodecanoate Chemical compound C=1C=CC=CC=1[Sn+2]C1=CC=CC=C1.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O KJLDTYUGZVCMRD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 230000000739 chaotic effect Effects 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 229940005667 ethyl salicylate Drugs 0.000 claims description 2
- ZMCZWKGAWRLZNP-UHFFFAOYSA-N methyl-oxo-phenyltin Chemical compound C[Sn](=O)C1=CC=CC=C1 ZMCZWKGAWRLZNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- XHXUANMFYXWVNG-ADEWGFFLSA-N (-)-Menthyl acetate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(C)=O XHXUANMFYXWVNG-ADEWGFFLSA-N 0.000 claims 2
- 239000001605 (5-methyl-2-propan-2-ylcyclohexyl) acetate Substances 0.000 claims 1
- XHXUANMFYXWVNG-UHFFFAOYSA-N D-menthyl acetate Natural products CC(C)C1CCC(C)CC1OC(C)=O XHXUANMFYXWVNG-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 34
- 238000010924 continuous production Methods 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 93
- 239000002994 raw material Substances 0.000 description 46
- 239000000047 product Substances 0.000 description 42
- PFYHAAAQPNMZHO-UHFFFAOYSA-N Methyl 2-methoxybenzoate Chemical compound COC(=O)C1=CC=CC=C1OC PFYHAAAQPNMZHO-UHFFFAOYSA-N 0.000 description 22
- 238000007086 side reaction Methods 0.000 description 16
- 239000002918 waste heat Substances 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 14
- 238000012546 transfer Methods 0.000 description 12
- 239000000376 reactant Substances 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-methoxybenzoate Natural products COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 8
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000005794 Hymexazol Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KGVPNLBXJKTABS-UHFFFAOYSA-N hymexazol Chemical compound CC1=CC(O)=NO1 KGVPNLBXJKTABS-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 150000003902 salicylic acid esters Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
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- 229920001220 nitrocellulos Polymers 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 239000011541 reaction mixture Substances 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing raw film bulk ester by adopting a micro-channel continuous flow reactor, which comprises the following steps: mixing and preheating salicylate and isophorol, then introducing the mixture and an ester exchange catalyst into a micro-channel continuous flow reactor for reaction, and performing post-treatment after the reaction is finished to obtain the ortho-membranaceous bulk ester; the micro-channel continuous flow reactor comprises one or N reaction units connected in series, and each reaction unit is formed by connecting a micro-channel reactor and a falling-film evaporator in series. The method has the advantages of mild reaction conditions, less by-products generated by the reaction, high reaction selectivity and capability of realizing continuous production.
Description
Technical Field
The invention relates to the technical field of raw film bulk ester preparation, in particular to a method for preparing raw film bulk ester by adopting a micro-channel continuous flow reactor.
Background
The proto-menthane, chemical name 3, 5-trimethylcyclohexanol salicylate, molecular formula C 16 H 22 O 3 The ultraviolet absorbent is an efficient ultraviolet absorbent and can efficiently absorb ultraviolet with the wavelength of 295-315 nm. The protopanaxate has higher fat solubility, and can be used as a light stabilizer when being added into polyvinyl chloride plastics, cellulose nitrate, acrylic resin and polyurethane coating; the protopanaxate has good biocompatibility and safety, and can be used as a chemical sunscreen agent to be added into high-grade cosmetics to protect skin from being damaged by ultraviolet irradiation.
The patent US2369084A of Fries corporation of 1944 discloses the structure of raw hymexazol for the first time, and at present, the raw hymexazol is mostly produced industrially by transesterification. U.S. Pat. No. 4,46, 2802A discloses a process for the synthesis of raw filmatic esters by transesterification using sodium methoxide as a catalyst, which is expensive and not recyclable, and the large amount of waste salts generated from the treatment of alkaline waste water is difficult to handle.
Patent JP2006104192A discloses a method for preparing raw hymexazol ester, which adopts methyl salicylate and isophorol to produce in a reaction kettle, uses organic tin as a catalyst, the reaction temperature is 140-170 ℃, and after 2-20 h, the raw hymexazol ester is prepared by ester exchange method, the yield in the embodiment is about 75-92%, and the reaction formula is as follows:
the existing preparation method mainly adopts intermittent operation, has long reaction time, higher reaction temperature and high back mixing degree, and the long-time high-temperature heating of a large amount of materials aggravates the occurrence of side reaction to generate more byproducts, which not only have great influence on the conversion rate of raw materials and the yield of products, but also have difficult separation of the products generated by the side reaction, and can continuously accumulate along with the indiscriminate use of the raw materials, thereby finally having adverse effect on the industrial production.
Disclosure of Invention
During a series of ester exchange processes for synthesizing the raw menthane, researchers find that the following two side reactions cause lower product selectivity and lower product yield:
side reaction 1:
side reaction 2:
the side reaction 1 is that the phenolic hydroxyl group of methyl salicylate breaks a bond with the byproduct methanol under the condition of long-time high-temperature heating to generate methyl o-methoxybenzoate (the byproduct is presumed to be generated by GC graphs of figures 2 and 3 and a mass spectrum of figure 4), and water is generated, the generation of the side reaction causes the reduction of the conversion rate of the methyl salicylate, the generation of the water causes the hydrolysis of the methyl salicylate to generate salicylic acid and methanol, the generation of the salicylic acid can deteriorate and deactivate an alkaline catalyst in a reaction system, the generation of the methanol can not only inhibit the main reaction, but also continuously participate in other side reactions, and the content of the methyl o-methoxybenzoate in the reaction process is 1% -3%, so the inhibition of the generation of the methyl o-methoxybenzoate is a problem which needs to be solved urgently in the production process.
The side reaction 2 is a process of producing (3, 5-trimethylcyclohexyl) -2-methoxybenzoate (which is presumed to be a by-product from the GC diagrams of fig. 2 and 3 and the mass spectrum diagram of fig. 5) from raw menthane and methanol at a high temperature, and the reaction is caused to occur in a large amount due to the high operation temperature in the reaction process and the subsequent separation process, and is also a key factor for reducing the final yield of raw menthane, and the product reaches 2% -5% in a later period, and the boiling point of the product is close to that of the raw menthane, so that the separation is difficult, and therefore, the production of the product is inhibited, which is beneficial for improving the yield and the purity of the raw menthane.
The technical problem to be solved by the invention is to provide a method for preparing raw film bulk ester by adopting a micro-channel continuous flow reactor, which has the advantages of mild reaction conditions, less by-products generated by the reaction, high reaction selectivity and capability of realizing continuous production.
The technical scheme of the invention is as follows:
a method for preparing raw film bulk ester by using a micro-channel continuous flow reactor, comprising the following steps:
mixing and preheating salicylate and isophorol, then introducing the mixture and an ester exchange catalyst into a micro-channel continuous flow reactor for reaction, and performing post-treatment after the reaction is finished to obtain the ortho-membranaceous bulk ester;
the micro-channel continuous flow reactor comprises one or N reaction units connected in series, and each reaction unit is formed by connecting a micro-channel reactor and a falling-film evaporator in series;
wherein N is more than or equal to 2 and less than or equal to 10.
Compared with the batch kettle type reaction mode in the prior art, the invention utilizes the microchannel reactor to reduce the reaction temperature and improve the reaction rate, and simultaneously, the invention unexpectedly discovers and solves the problem which can not be solved by the traditional reaction mode and inhibits the generation of byproducts (methyl o-methoxybenzoate, (3, 5-trimethylcyclohexyl) -2-methoxybenzoate); the device is combined with a falling-film evaporator, by the characteristics that the falling-film evaporator has short residence time and is suitable for processing heat-sensitive materials, and the like, by-products such as methanol and the like can be rapidly removed, the reaction is pushed to be carried out rightwards, and simultaneously, due to the characteristics that the microchannel reactor has small liquid holdup and the like, the device has higher safety coefficient, can be continuously operated, the materials in the microchannel continuously move forwards, and has low back-mixing degree, thereby realizing continuous generation and having industrial application value.
Preferably, the number of the reaction units connected in series is 3 to 6.
Preferably, the preheating temperature is 80-100 ℃, and the reaction temperature in the microchannel reactor is 80-100 ℃. The reaction liquid is subjected to high-efficiency heat exchange on the wall surface of the micro-channel, so that the reaction temperature is effectively reduced, the problems of local overheating, uneven heat transfer and the like are avoided, the generation of byproducts is reduced, the synthesis of the target product, namely the raw membrana-lose ester is facilitated, and the difficulty of post-treatment is reduced.
The micro-negative pressure state is adopted in the micro-channel reactor, and preferably, the reaction pressure is-0.01 MPa to-0.05 MPa.
Because the size of the internal channel is miniaturized, the heat transfer coefficient and the mass transfer coefficient are 1 to 3 orders of magnitude higher than those of the conventional reaction, the mass transfer and the heat transfer of reactants are enhanced, the reaction liquid is mixed in a very short time, the reaction time is reduced from 6 to 10 hours to 0.3 to 30 minutes, the reaction efficiency is greatly improved, and preferably, the residence time of the reaction materials in the microchannel reactor is 0.5 to 20 minutes (when a plurality of reaction units are arranged, the residence time is the total residence time); more preferably, the retention time is 1.5min to 10min.
Preferably, the flow rate of the isophorol is 5g/min to 200g/min, and the flow rate of the salicylate is 5g/min to 300g/min; more preferably, the flow rate of the isophorol is 5g/min to 50g/min, and the flow rate of the salicylate is 5g/min to 75g/min; more preferably, the flow rate of the isophorol is 14g/min to 30g/min, and the flow rate of the salicylate is 18g/min to 38g/min.
Preferably, the salicylate is one or more of methyl salicylate, ethyl salicylate, isopropyl salicylate, isobutyl salicylate and isoamyl salicylate.
Preferably, the transesterification catalyst is an acidic catalyst or a basic catalyst, organic titanium, organic tin (dibutyl tin oxide, methyl phenyl tin oxide, tetraethyl tin, dibutyl tin diacetate, diphenyl tin dilaurate) or a combination of more thereof.
Preferably, the acid catalyst is sulfuric acid or p-benzenesulfonic acid;
the alkaline catalyst is sodium methoxide.
Preferably, the mole ratio of the isophorol to the salicylate is 1;
the molar ratio of the catalyst to the salicylate is 0.01-10%.
Preferably, the hydraulic radius of the micro-channel in the micro-channel reactor is 0.1 mm-1.0 mm, the length of the micro-channel is 100 m-200 m, and the micro-channel structure of the micro-channel reactor is a reinforced mixed type heart-shaped structure, a Z-shaped structure, a T-shaped ribbon wave structure or a convex ridge chaotic structure.
Preferably, the post-treatment is distillation under reduced pressure.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention firstly mixes the salicylate and the isophorol, then the mixture and the ester exchange catalyst are introduced into the microchannel reactor, and the reactant and the catalyst are mixed in a very short time, so that the reaction time is greatly reduced, and the occurrence of side reaction 1 is effectively reduced;
(2) The invention adopts the microchannel reactor for reaction, effectively reduces the reaction temperature, and the reduction of the temperature can be beneficial to the generation of the side reaction 1 and the side reaction 2, thereby reducing the generation of byproducts;
(3) The microchannel reactor and the falling film evaporator are connected in series, reaction liquid continuously runs forwards, the back mixing degree is reduced, the generation of byproducts is reduced, meanwhile, the byproduct methanol in each reaction unit is removed in the falling film evaporator, the phenomenon that the methanol byproducts are mixed in a system to inhibit the forward reaction is avoided, the probability that the methanol, methyl salicylate and ortho-film bulk ester generate side reaction 1 and side reaction 2 is reduced, and continuous production can be realized;
(4) The microchannel reactor disclosed by the invention is small in liquid holdup and higher in safety factor.
Drawings
FIG. 1 is a flow diagram of a process for preparing orthomenthyl esters according to the invention;
FIG. 2 is a GC graph of the product obtained when preparing raw menthyl ester according to the method of comparative example 1;
FIG. 3 is an enlarged view of a portion of FIG. 2;
FIG. 4 is a mass spectrum of a by-product obtained by the side reaction 1 occurring when preparing raw menthane according to the method of comparative example 1;
FIG. 5 is a mass spectrum of a by-product obtained by the side reaction 2 occurring when preparing raw menthane according to the method of comparative example 1.
Detailed Description
FIG. 1 is a flow chart of the process for preparing orthomenthyl esters of the present invention, which comprises the following steps:
firstly, salicylic acid ester and isophorol are introduced into a preheater to be mixed, and then the mixture is introduced into a micro-channel continuous flow reactor, wherein the micro-channel continuous flow reactor comprises N reaction units which are connected in series, N is more than or equal to 1 and less than or equal to 10, each reaction unit contains a micro-channel reactor and a falling-film evaporator, the micro-channel reactors are connected in series with the falling-film evaporator, the first set of micro-channel reactor is provided with two raw material inlets, one raw material inlet is a feeding port for a mixture of isophorol and salicylic acid ester, the other raw material inlet is a feeding port for an ester exchange catalyst, the catalyst is a liquid catalyst, and the inlet of the falling-film evaporator is connected with a material outlet of the micro-channel reactor; the raw material inlet of the 2 nd set of falling film evaporator is connected with the material outlet of the 2 nd set of micro-channel reactor; and analogizing in turn, in the Nth set of the microchannel reactor and the falling-film evaporator, two raw material inlets of the microchannel reactor are respectively a catalyst feeding port and an outlet material feeding port of the (N-1) th set of the falling-film evaporator, the raw material inlet of the Nth set of the falling-film evaporator is connected with the material outlet of the Nth set of the microchannel mixer, the material outlet of the Nth set of the falling-film evaporator is connected with a final buffer kettle, and the material collected from the buffer kettle is subjected to reduced pressure distillation to obtain a raw film bulk ester product, and meanwhile, the catalyst can be recovered and reused.
Example 1
The reaction equation is:
this example illustrates the invention in detail using as an example 1 set of a microchannel reactor and a falling film evaporator connected in series:
adding raw materials and a catalyst by using a metering pump according to a certain flow rate, wherein 18.24g/min (0.12 mol/min) of methyl salicylate and 14.2g/min (purity is 99 percent and 0.1 mol/min) of isophorol are firstly preheated in a preheater, the temperature is set to be 90 ℃, then the preheated raw materials and the catalyst are respectively added into a microchannel reactor together with 0.21g/min (0.0006 mol and 0.5mol percent) of dibutyltin diacetate, the temperature is set to be 90 ℃, the pressure is-0.02 MPa, the isophorol, the methyl salicylate and the dibutyltin diacetate fully carry out mass and heat transfer in the microchannel reactor, the hydraulic radius of a microchannel in a microchannel module is 0.6mm, the length of the microchannel is 150m, reaction materials stay in the microchannel for 90s and then enter a falling film evaporator to remove a by-product methanol, a buffer kettle is used for obtaining a liquid-phase product containing a product of raw film bulk ester, and the liquid-phase product is collected for 10min; sampling and measuring GC, wherein the content of the protoplasmid is 75.53 percent, the content of methyl salicylate is 17.31 percent, the content of isophorol is 7.11 percent, the content of methanol is 0.01 percent, the content of methyl o-methoxybenzoate is less than 0.01 percent, the content of (3, 5-trimethylcyclohexyl) -2-methoxybenzoate is less than 0.01 percent, and the reaction selectivity is more than 99.9 percent; the reaction liquid is subjected to reduced pressure rectification separation to finally obtain 208.55g of raw pad-film ester product, the weight of rectification residue is 14.61g, the raw pad-film ester product mainly contains organic tin catalyst (liquid state), the yield of the raw pad-film ester is 85.21%, the total content (GC) is 99.7%, and the content of (3, 5-trimethyl cyclohexyl) -2-methoxybenzoate is less than 0.01%.
Example 2
This example was continued with the rectification residue (containing the catalyst) obtained in example 1 being fed back into the reactor of the same type as in example 1:
adding raw materials and a catalyst by using a metering pump according to a certain flow rate, wherein 18.24g/min (0.12 mol/min) of methyl salicylate and 14.2g/min (purity 99%,0.1 mol/min) of isophorol are firstly preheated in a preheater, the temperature is set to 90 ℃, then the preheated raw materials and the catalyst and 1.46g/min of dibutyltin diacetate (concentration: omega (cat) =14.1% of recycled catalyst) are respectively added into a microchannel mixer, the temperature is set to 90 ℃, the pressure is-0.02 MPa, the isophorol, methyl salicylate and dibutyltin diacetate fully carry out mass and heat transfer in a microchannel reactor, the hydraulic radius of a microchannel in a microchannel module is 0.6mm, the length of the microchannel is 150m, reaction materials stay in the microchannel for 90s and enter a falling film evaporator, methanol is removed by using waste heat, a liquid-phase product containing a product raw film bulk ester is obtained in a buffer kettle, and the liquid-phase product is collected for 10min; sampling and measuring GC, wherein the content of the protoplasmid is 73.25 percent, the content of methyl salicylate is 18.88 percent, the content of isophorol is 7.97 percent, the content of methanol is 0.03 percent, the content of methyl o-anisate is less than 0.01 percent, and the other content is 0.01 percent; the reaction selectivity is more than 99.9 percent, the reaction liquid is rectified and separated under reduced pressure, 215.2g of raw mentha-acrylate product is finally obtained, 13.28g of rectification residue is obtained, the yield of the raw mentha-acrylate is 82.67 percent, the total content (GC) is 99.6 percent, and the content of (3, 5-trimethyl cyclohexyl) -2-methoxybenzoate is less than 0.01 percent.
Example 3
This example illustrates 2 sets of microchannel reactor and falling film evaporator connected in series to explain the invention in detail:
a combined device of a microchannel reactor and a falling film evaporator for preparing raw filmatic ester comprises 2 sets of microchannel reactors and falling film evaporators which are connected in sequence, wherein in the 1 st set of microchannel reactor and falling film evaporator, two inlets of the microchannel reactor are respectively a feeding port for a mixture of isophorol and methyl salicylate and a catalyst feeding port, and a raw material inlet of the falling film evaporator is connected with a material outlet of the 1 st set of microchannel reactor; in the 2 nd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is a 1 st set of falling-film evaporator outlet, a raw material inlet of the falling-film evaporator is connected with a material outlet of the 2 nd set of micro-channel reactor, a material outlet of the 2 nd set of falling-film evaporator enters a buffer kettle, and a product is obtained through subsequent reduced pressure rectification.
Adding raw materials and a catalyst, namely 27.35g/min (0.18 mol/min) of methyl salicylate and 21.5g/min (purity is 99 percent and 0.15 mol/min) of isophorol into a metering pump at a certain flow rate, firstly preheating the mixture in a preheater at the temperature of 90 ℃, and then respectively adding the preheated mixture and 0.325g/min of dibutyltin diacetate into a microchannel mixer, wherein the temperature of a first set of microchannel reactor is set to be 90 ℃, the pressure is-0.02 MPa, the isophorol, the methyl salicylate and the dibutyltin diacetate fully carry out mass and heat transfer in the microchannel reactor, the radius of a microchannel of a module at the section is 0.6mm, the length of the microchannel is 120m, reactants stay in the module for 72s and enter a falling film evaporator, and removing a byproduct methanol by using waste heat; the temperature of the second set of micro-channel reactor is set to be 110 ℃, and the pressure is-0.02 MPa. The hydraulic radius of a micro-channel in the micro-channel module is 0.6mm, the length of the micro-channel is 30m, a reaction material stays in the micro-channel for 18s, enters a falling film evaporator, a byproduct methanol is removed by using waste heat, a liquid-phase product containing a product raw film bulk ester is obtained by a buffer kettle, and the liquid-phase product is collected for 10min; sampling and measuring GC, wherein the content of the protopanaxate is 80.92 percent, the content of the methyl salicylate is 14.58 percent, the content of the isophorol is 4.48 percent, the content of the methanol is 0.02 percent, the content of the methyl o-anisate is less than 0.01 percent, and the other content is 0.01 percent; the reaction selectivity is more than 99.9 percent, the reaction liquid is subjected to rectification separation under reduced pressure, and 355.46g of raw mentha-13-yl benzoate is finally obtained, the rectification residue is 4.35g, the yield of the raw mentha-butyl ester is 90.74 percent, the total content (GC) is 99.6 percent, and the content of (3, 5-trimethylcyclohexyl) -2-methoxybenzoate is less than 0.01 percent.
Example 4
This example illustrates 3 sets of microchannel reactor and falling film evaporator connected in series to explain the invention in detail:
a combined device of a microchannel reactor and a falling film evaporator for preparing raw filmatic ester comprises 3 sets of microchannel reactors and falling film evaporators which are connected in sequence, wherein in the 1 st set of microchannel reactor and falling film evaporator, two raw material inlets of the microchannel reactor are respectively a feeding port for a mixture of isophorol and methyl salicylate and a catalyst feeding port, and a raw material inlet of the falling film evaporator is connected with a material outlet of the 1 st set of microchannel reactor; in the 2 nd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is an outlet of the 1 st set of falling-film evaporator, and a raw material inlet of the falling-film evaporator is connected with a material outlet of the 2 nd set of micro-channel reactor; in the 3 rd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is a 2 nd set of falling-film evaporator outlet, a raw material inlet of the 3 rd set of falling-film evaporator is connected with a material outlet of the 3 rd set of micro-channel reactor, and a material outlet of the 3 rd set of falling-film evaporator enters a buffer kettle and is subjected to subsequent reduced pressure rectification to obtain a product.
Adding raw materials and a catalyst by using a metering pump according to a certain flow rate, wherein 36.5g/min (0.24 mol/min) of methyl salicylate and 28.4g/min (purity is 99 percent and 0.2 mol/min) of isophorol enter a preheater for preheating, the temperature is set to be 90 ℃, and then the methyl salicylate and the isophorol and 0.42g/min (0.0012mol and 0.5mol percent) of dibutyltin diacetate respectively enter a microchannel mixer, wherein the temperature of a first set of microchannel reactor is set to be 90 ℃, the pressure is-0.02 MPa, the isophorol, methyl salicylate and dibutyltin diacetate fully carry out mass and heat transfer in the microchannel reactor, the radius of a microchannel of a module at the section is 0.6mm, the length of the microchannel is 90m, reactants stay in the module for 54s and enter a falling film evaporator, and a byproduct is removed by using waste heat; the temperature of the second set of micro-channel reactor is set to be 110 ℃, the pressure is-0.02 MPa, the length of the module is 45m, reactants stay in the module for 27s and enter a falling film evaporator, and a byproduct methanol is further removed by utilizing waste heat; setting the temperature of a third set of microchannel reactor at 120 ℃, setting the pressure at-0.02 MPa, setting the length of the microchannel at 15m, allowing the reaction materials to stay in the microchannel for 9s, allowing the reaction materials to enter a falling film evaporator, removing a byproduct methanol by using waste heat, obtaining a liquid-phase product containing the product raw film bulk ester by using a buffer kettle, and collecting the liquid-phase product for 10min; sampling and measuring GC, wherein the content of the protopanaxate is 84.61 percent, the content of the methyl salicylate is 12.95 percent, the content of the isophorol is 2.41 percent, the content of the methanol is 0.01 percent, the content of the methyl o-anisate is less than 0.01 percent, and the other content is 0.01 percent; the reaction selectivity is more than 99.9 percent, the reaction liquid is rectified and separated under reduced pressure, 482.30g of raw mentha-olum product and 15.46g of rectification residue are finally obtained, the yield of the raw mentha-olum is 95.03 percent, the total content (GC) is 99.8 percent, and the content of (3, 5-trimethyl cyclohexyl) -2-methoxybenzoate is less than 0.01 percent.
Example 5
This example illustrates 3 sets of microchannel reactor and falling film evaporator connected in series to explain the invention in detail:
a combined device of a microchannel reactor and a falling film evaporator for preparing raw filmatic ester comprises 3 sets of microchannel reactors and falling film evaporators which are connected in sequence, wherein in the 1 st set of microchannel reactor and falling film evaporator, two raw material inlets of the microchannel reactor are respectively a feeding port for a mixture of isophorol and methyl salicylate and a catalyst feeding port, and a raw material inlet of the falling film evaporator is connected with a material outlet of the 1 st set of microchannel reactor; in the 2 nd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is an outlet of the 1 st set of falling-film evaporator, and a raw material inlet of the falling-film evaporator is connected with a material outlet of the 2 nd set of micro-channel reactor; in the 3 rd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is an outlet of the 2 nd set of falling-film evaporator, a raw material inlet of the 3 rd set of falling-film evaporator is connected with a material outlet of the 3 rd set of micro-channel reactor, and a material outlet of the 3 rd set of falling-film evaporator enters a buffer kettle to obtain a product through subsequent reduced pressure rectification.
Adding raw materials and a catalyst by using a metering pump according to a certain flow rate, wherein 9.2g/min (0.06 mol/min) of methyl salicylate and 7.1g/min (purity 99%,0.05 mol/min) of isophorol enter a preheater for preheating, the temperature is set to 80 ℃, and then the methyl salicylate and the isophorol and 0.1g/min (0.5 mol%) of dibutyltin diacetate respectively enter a microchannel mixer, wherein the temperature of a first set of microchannel reactor is set to 90 ℃, the pressure is-0.02 MPa, the isophorol, the methyl salicylate and the dibutyltin diacetate fully carry out mass and heat transfer in the microchannel reactor, the radius of a microchannel of a module at the section is 0.6mm, the length of the microchannel is 90m, reactants stay in the module for 54s and enter a falling film evaporator, and a byproduct methanol is removed by using waste heat; the temperature of the second set of micro-channel reactor is set to be 110 ℃, the pressure is-0.02 MPa, the length of the section of the module is 45m, reactants stay in the module for 27s and enter the falling-film evaporator, and the byproduct methanol is further removed by utilizing the waste heat; setting the temperature of a third set of micro-channel reactor at 120 ℃, the pressure at-0.02 MPa, the length of the micro-channel at 15m, allowing the reaction materials to stay in the micro-channel for 9s, allowing the reaction materials to enter a falling film evaporator, removing a byproduct methanol by using waste heat, obtaining a liquid-phase product containing the product raw film bulk ester in a buffer kettle, and collecting the liquid-phase product for 10min; sampling and measuring GC, wherein the content of the protoplasmid is 82.14 percent, the content of the methyl salicylate is 13.75 percent, the content of the isophorol is 3.24 percent, the content of the methanol is 0.02 percent, the content of the methyl o-anisate is less than 0.01 percent, and the other content is 0.01 percent; the reaction selectivity is more than 99.8 percent, the reaction liquid is jected to vacuum rectification separation to finally obtain 123.20g of the raw filmatic ester product, the weight of the rectification residue is 1.2g, the yield of the raw filmatic ester is 94.56 percent, the total content (GC) is 99.5 percent, and the content of the (3, 5-trimethyl cyclohexyl) -2-methoxybenzoate is less than 0.01 percent.
Example 6
This example illustrates 3 sets of microchannel reactor and falling film evaporator connected in series to explain the invention in detail:
a combined device of a microchannel reactor and a falling film evaporator for preparing raw filmatic ester comprises 3 sets of microchannel reactors and falling film evaporators which are connected in sequence, wherein in the 1 st set of microchannel reactor and falling film evaporator, two raw material inlets of the microchannel reactor are respectively a feeding port for a mixture of isophorol and methyl salicylate and a catalyst feeding port, and a raw material inlet of the falling film evaporator is connected with a material outlet of the 1 st set of microchannel reactor; in the 2 nd set of micro-channel reactor and the falling film evaporator, a raw material inlet of the micro-channel reactor is an outlet of the 1 st set of falling film evaporator, and a raw material inlet of the falling film evaporator is connected with a material outlet of the 2 nd set of micro-channel reactor; in the 3 rd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is an outlet of the 2 nd set of falling-film evaporator, a raw material inlet of the 3 rd set of falling-film evaporator is connected with a material outlet of the 3 rd set of micro-channel reactor, and a material outlet of the 3 rd set of falling-film evaporator enters a buffer kettle to obtain a product through subsequent reduced pressure rectification.
Adding raw materials and a catalyst by using a metering pump according to a certain flow rate, wherein 36.5g/min (0.24 mol/min) of methyl salicylate and 28.4g/min (purity 99%,0.2 mol/min) of isophorol enter a preheater for preheating, the temperature is set to 90 ℃, and then the raw materials and the catalyst respectively enter a microchannel mixer together with 0.42g/min (0.0012mol, 0.5 mol%) of dibutyltin diacetate, wherein the temperature of a first set of microchannel reactor is set to 90 ℃, the pressure is-0.02 MPa, the isophorol, the methyl salicylate and the dibutyltin diacetate fully carry out mass and heat transfer in the microchannel reactor, the radius of a microchannel of a module at the section is 0.6mm, the length of the microchannel is 90m, reactants stay in the module for 54s and enter a falling film evaporator, and a by-product methanol is removed by using waste heat; the temperature of the second set of micro-channel reactor is set to be 110 ℃, the pressure is-0.02 MPa, the length of the section of the module is 45m, reactants stay in the module for 27s and enter the falling-film evaporator, and the byproduct methanol is further removed by utilizing the waste heat; setting the temperature of a third set of micro-channel reactor at 120 ℃, the pressure at-0.02 MPa, the length of the micro-channel at 15m, allowing the reaction materials to stay in the micro-channel for 9s, allowing the reaction materials to enter a falling film evaporator, removing a byproduct methanol by using waste heat, obtaining a liquid-phase product containing the product raw film bulk ester in a buffer kettle, and collecting the liquid-phase product for 10min; sampling and measuring GC, wherein the content of the protopanaxate is 78.93 percent, the content of the methyl salicylate is 15.27 percent, the content of the isophorol is 4.70 percent, the content of the methanol is 0.01 percent, the content of the methyl o-anisate is less than 0.01 percent, and the other content is 0.01 percent; the reaction selectivity is more than 99.9 percent, the reaction liquid is rectified and separated under reduced pressure, 465.44g of raw mentha-acrylate product and 6.5g of rectification residue are finally obtained, the yield of the raw mentha-acrylate is 89.60 percent, the total content (GC) is 99.8 percent, and the content of (3, 5-trimethyl cyclohexyl) -2-methoxybenzoate is less than 0.01 percent.
Example 7
This example illustrates 3 sets of microchannel reactor and falling film evaporator connected in series to explain the invention in detail:
a combined device of a microchannel reactor and a falling film evaporator for preparing raw filmogen is provided with 3 sets of microchannel reactors and falling film evaporators which are connected in sequence, in the 1 st set of microchannel reactor and falling film evaporator, two raw material inlets of the microchannel reactor are respectively a feeding port of a mixture of isophorol and methyl salicylate and a catalyst feeding port, and a raw material inlet of the falling film evaporator is connected with a material outlet of the 1 st set of microchannel reactor; in the 2 nd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is an outlet of the 1 st set of falling-film evaporator, and a raw material inlet of the falling-film evaporator is connected with a material outlet of the 2 nd set of micro-channel reactor; in the 3 rd set of micro-channel reactor and the falling-film evaporator, a raw material inlet of the micro-channel reactor is a 2 nd set of falling-film evaporator outlet, a raw material inlet of the 3 rd set of falling-film evaporator is connected with a material outlet of the 3 rd set of micro-channel reactor, and a material outlet of the 3 rd set of falling-film evaporator enters a buffer kettle and is subjected to subsequent reduced pressure rectification to obtain a product.
Adding raw materials and a catalyst by using a metering pump according to a certain flow rate, wherein 36.5g/min (0.24 mol/min) of methyl salicylate and 28.4g/min (purity 99%,0.2 mol/min) of isophorol enter a preheater for preheating, the temperature is set to 90 ℃, and then the raw materials and the catalyst respectively enter a microchannel mixer together with 0.23g/min (0.001mol, 0.5 mol%) of tetraethyl tin, wherein the temperature of a first set of microchannel reactor is set to 90 ℃, the pressure is-0.02 MPa, the isophorol, the methyl salicylate and the tetraethyl tin fully carry out mass and heat transfer in the microchannel reactor, the radius of a microchannel of a module in the section is 0.6mm, the length of the microchannel is 90m, reactants stay in the module for 54s, enter a falling film evaporator, and a by-product methanol is removed by using waste heat; the temperature of the second set of micro-channel reactor is set to be 110 ℃, the pressure is-0.02 MPa, the length of the module is 45m, reactants stay in the module for 27s and enter a falling film evaporator, and a byproduct methanol is further removed by utilizing waste heat; setting the temperature of a third set of microchannel reactor at 120 ℃, setting the pressure at-0.02 MPa, setting the length of the microchannel at 15m, allowing the reaction materials to stay in the microchannel for 9s, allowing the reaction materials to enter a falling film evaporator, removing a byproduct methanol by using waste heat, obtaining a liquid-phase product containing the product raw film bulk ester by using a buffer kettle, and collecting the liquid-phase product for 10min; sampling and measuring GC, wherein the content of the protoplasmid is 72.66 percent, the content of methyl salicylate is 18.80 percent, the content of isophorol is 8.51 percent, the content of methanol is 0.01 percent, the content of methyl o-anisate is less than 0.01 percent, and the other content is 0.02 percent; the reaction selectivity is more than 99.9 percent, the reaction liquid is rectified and separated under reduced pressure, 428.55g of raw mentha-13, 7.3g of rectification residue are finally obtained, the yield of the raw mentha-13 is 82.23 percent, the total content (GC) is 99.5 percent, and the content of (3, 5-trimethyl cyclohexyl) -2-methoxybenzoate is less than 0.01 percent.
Comparative example 1
This example illustrates the present invention in detail by taking a batch reactor of the prior art as an example:
putting 245.96g of isophorol, 315.52g of methyl salicylate and 12.3g of sodium methoxide into a 1000mL flask, building a whole set of reflux device, checking air tightness, starting a stirring device, and rotating at 400rpm; and starting an electric heating sleeve to control the temperature, raising the temperature to 100 ℃, setting the reflux ratio to be 1. When the temperature of the top end is lower than 50 ℃, the temperature of the electric heating sleeve is adjusted, so that the stable and smooth extraction of fractions is ensured; when the temperature of the kettle reaches 120 ℃, preserving heat for 2 hours, gradually raising the temperature to 150 ℃ and keeping the total reaction time for 10 hours. After the reaction, cooled to 50 ℃, and sampled for GC-MS analysis, wherein the GC plot is shown in fig. 2, fig. 3 is an enlarged view of fig. 2, fig. 4 is an MS plot at 10min, which is a by-product methyl o-anisate, fig. 5 is an MS plot at 21min, which is a by-product (3, 5-trimethylcyclohexyl) -2-methoxybenzoate, in combination with an internal standard method, the results of quantitative analysis: 19.84% of methyl salicylate, 10.46% of isophorol, 57.12% of HMS, 0.5% of methanol, 2.3% of methyl o-methoxybenzoate, 3.1% of (3, 5-trimethylcyclohexyl) -2-methoxybenzoate, the catalyst was removed by acid washing and alkali washing, and the reaction mixture was rectified to obtain 328.45g of raw film bulk ester, 73.58% of HMS, 95.3% of total content (GC), 0.2% of methyl o-methoxybenzoate and 4.6% of (3, 5-trimethylcyclohexyl) -2-methoxybenzoate.
When the traditional batch kettle type reaction is adopted, in order to achieve a certain conversion rate, the reaction temperature requirement is higher, the reaction time is longer, more byproducts of methyl o-anisate and (3, 5-trimethylcyclohexyl) -2-methoxybenzoate are generated in the reaction, and especially the (3, 5-trimethylcyclohexyl) -2-methoxybenzoate is not easy to remove by a rectification means; with the microchannel continuous flow process of the present invention, however, essentially no two by-products are produced.
Claims (11)
1. A method for preparing raw film bulk ester by using a micro-channel continuous flow reactor, which is characterized by comprising the following steps:
mixing and preheating salicylate and isophorol, then introducing the mixture and an ester exchange catalyst into a micro-channel continuous flow reactor for reaction, and performing post-treatment after the reaction is finished to obtain the raw membranogen ester;
the micro-channel continuous flow reactor comprises one or N reaction units connected in series, and each reaction unit is formed by connecting a micro-channel reactor and a falling-film evaporator in series;
wherein N is more than or equal to 2 and less than or equal to 10.
2. The method for preparing raw hymenium ester by using the micro-channel continuous flow reactor as claimed in claim 1, wherein the number of the reaction units connected in series is 3 to 6.
3. The method for preparing raw film bulk ester by using the micro-channel continuous flow reactor as claimed in claim 1, wherein the temperature for mixing and preheating is 80 ℃ to 100 ℃;
the reaction temperature in the microchannel reactor is also 80-100 ℃.
4. The method for preparing raw hymenium ester by using the micro-channel continuous flow reactor as claimed in claim 1, wherein the reaction pressure is-0.01 MPa to-0.05 MPa.
5. The method for preparing raw film bulk ester by using the micro-channel continuous flow reactor as claimed in claim 1, wherein the residence time of the reaction materials in the micro-channel reactor is 0.5 min-20 min.
6. The method for preparing orthomembrane bulk ester by using a micro-channel continuous flow reactor as claimed in claim 1, wherein the flow rate of the isophorol is 5g/min to 200g/min, and the flow rate of the salicylate is 5g/min to 300g/min.
7. The method for preparing raw menthyl acetate by using the micro-channel continuous flow reactor as claimed in claim 1, wherein the salicylate ester is one or more of methyl salicylate, ethyl salicylate, isopropyl salicylate, isobutyl salicylate and isoamyl salicylate.
8. The method for preparing raw pipe film ester by using micro-channel continuous flow reactor as claimed in claim 1, wherein the ester exchange catalyst is one or more of acid catalyst, alkaline catalyst, organic titanium and organic tin.
9. The method for preparing raw film bulk ester by using micro-channel continuous flow reactor as claimed in claim 8, wherein the acidic catalyst is sulfuric acid or p-benzenesulfonic acid;
the alkaline catalyst is sodium methoxide;
the organic tin is one or more of dibutyltin oxide, methyl phenyl tin oxide, tetraethyl tin, dibutyltin diacetate or diphenyltin dilaurate.
10. The method for preparing orthomembrance bulk ester by using micro-channel continuous flow reactor as claimed in claim 1, wherein the molar ratio of the isophorol to the salicylate is 1;
the molar ratio of the catalyst to the salicylate is 0.01-10%: 1.
11. the method for preparing raw film bulk ester by using the micro-channel continuous flow reactor as claimed in claim 1, wherein: the hydraulic radius of the micro-channel in the micro-channel reactor is 0.1 mm-1.0 mm, the length of the micro-channel is 100 m-200 m, and the micro-channel structure of the micro-channel reactor is a reinforced mixed type heart-shaped structure, a Z-shaped structure, a T-shaped ribbon wave structure or a convex ridge chaotic structure.
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| JP2006104192A (en) * | 2004-09-07 | 2006-04-20 | Kao Corp | Preparation method of salicylic ester |
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| CN112321434A (en) * | 2020-10-10 | 2021-02-05 | 马鞍山科思化学有限公司 | Preparation method of salicylate green synthesis process |
| CN112457163A (en) * | 2021-01-22 | 2021-03-09 | 黄冈美丰化工科技有限公司 | Micro-channel mixed catalytic hydrogenation device and method for preparing isophorol |
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| JP2006104192A (en) * | 2004-09-07 | 2006-04-20 | Kao Corp | Preparation method of salicylic ester |
| CN105541634A (en) * | 2014-11-04 | 2016-05-04 | 南京秾康生物科技有限公司 | Synthetic method of homosalate |
| CN104962397A (en) * | 2015-03-20 | 2015-10-07 | 南京工业大学 | Method for producing biodiesel through ester exchange in continuous flow microchannel reactor |
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