CN114349675B - Continuous synthesis method and system of methyl ethyl ketone peroxide - Google Patents
Continuous synthesis method and system of methyl ethyl ketone peroxide Download PDFInfo
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Abstract
The invention relates to a continuous synthesis method and a system of methyl ethyl ketone peroxide, which are based on the characteristics of high-efficiency micro-scale mixing property, good mass transfer and heat transfer performance and intrinsic safety of a microreactor technology, realize continuous production of the methyl ethyl ketone peroxide, introduce an aqueous solution of inorganic salt on the basis of the continuous production to realize high-efficiency and rapid online phase splitting, and greatly improve the production efficiency. The content of active oxygen in the methyl ethyl ketone peroxide obtained by the production process disclosed by the invention reaches 15%, and the water content is lower than 13%.
Description
Technical Field
The invention belongs to the technical field of fine chemical raw material synthesis, and particularly relates to a method for continuously synthesizing methyl ethyl ketone peroxide in a microreactor.
Background
The industry for composite materials, such as unsaturated polyester resins represented by glass fiber reinforced plastic products, is rapidly developing. The yield of unsaturated polyester resin in China is increased from 170 ten thousand tons in 2012 to 297 ten thousand tons in 2017, and the annual composite growth rate reaches 11.8%. However, the matched curing agent (initiator) has single variety and poor quality, and can be applied to the production of small-scale manually-made glass fiber reinforced plastic products, but the imported automatic production line, mechanical continuous operation and high-quality glass fiber reinforced plastic product production seriously depend on imported curing agents.
The organic peroxide is liquid due to its high activity, and is convenient for metering, and is especially suitable for production lines of polyester buttons, polyester plywood, artificial agate, glass fiber reinforced plastic products, artificial marble, etc. In addition, the organic peroxide is used as a high-yield and technically-intensive fine chemical product, is not only suitable for curing agents of unsaturated polyester resins, but also widely used as initiators of unsaturated olefin polymerization, catalysts of a plurality of organic reactions and the like, and has the advantages of high reaction activity and good low-temperature curing performance. With the continuous expansion of the application field, the market prospect is very wide.
Taking a typical organic peroxide methyl ethyl ketone peroxide as an example, the organic peroxide methyl ethyl ketone peroxide is widely applied from 90 s abroad, manufacturers of the organic peroxide methyl ethyl ketone peroxide comprise grease company in Japan, acksu company in the Netherlands, lucidol company in the United states and the like, and the development and production research of the methyl ethyl ketone peroxide only starts from the end of 80 s in China. The manufacturers of the products have been part of the current development, but are limited to small-scale production. In 2020, the domestic market capacity of the main organic peroxide product is about 15 ten thousand tons, and the global market capacity is about 55 ten thousand tons. At present, more than 70 organic peroxides are industrialized abroad, but in China, the development of the organic peroxides is relatively late, so that the organic peroxides are really industrialized by less than 20 kinds. It is not difficult to see that the variety and the productivity of the organic peroxide in China can not meet the requirements of domestic markets.
From the production process, most of the existing synthesis of organic peroxide adopts a batch kettle type reaction process, and the process comprises the steps of reacting hydrogen peroxide and butanone in a certain proportion in the presence of a solvent and under the action of a catalyst, and obtaining a product through the processes of neutralization, water separation, filtration and the like. In the whole production process, the proportion of hydrogen peroxide and butanone, the reaction temperature, the addition amount of the stabilizer, the water content and the active oxygen content of the final product have great influence on the safety and stability of the product. The reaction time of the process is usually 3-5 h, the temperature needs to be strictly controlled in the reaction process, the production efficiency is low, the process controllability is poor, and the safety coefficient is low. The explosion accidents of the organic peroxide occur for many times at home and abroad, and along with the increasing importance of the country and the government on environmental protection and safe production, the development of efficient, safe and continuous synthesis processes and equipment of the organic peroxide is a necessary trend.
Since the proposal of the microchemical technology in 1990, the microchemical technology has become an innovative technology in the chemical and chemical industry due to its high-efficiency and safe characteristics, and is incorporated and selected from "2019 global engineering development front". The technology can enhance the safety of the chemical process, promote the process strengthening and the miniaturization of a chemical system, improve the utilization efficiency of energy and resources, achieve the aim of energy conservation and consumption reduction, and has wider application prospect. The heat transfer coefficient of the microreactor can be increased from 2 kW/(m 2. K) to 20 kW/(m 2. K) compared with a conventional reactor. Therefore, for the rapid reaction with large heat release, such as organic peroxide synthesis, the microreactor can quickly remove the heat generated by the reaction, effectively avoid local temperature overheating, reduce the occurrence of side reactions, further prevent the temperature runaway phenomenon caused by heat accumulation and reduce the risk of reaction runaway.
At present, the production of methyl ethyl ketone peroxide by using a microchemical technology has been reported. For example, patent document 1 discloses a method and a microreactor for continuously producing methyl ethyl ketone peroxide by achieving rapid and uniform mixing of a methyl ethyl ketone solution with a mixture of hydrogen peroxide and sulfuric acid in a micromixer, followed by further reaction in a microreactor to obtain a methyl ethyl ketone peroxide solution.
Cited documents:
patent document 1: CN1800161A.
Disclosure of Invention
Problems to be solved by the invention
In patent document 1, no study is made on the post-treatment of the product obtained in the microreactor, and only brief mention is made of oil-water separation in a plexiglas tube. However, the present inventors have found that the oil-water mixture obtained by the micromixer and the microreactor is almost in a homogeneous state, and the subsequent oil-water phase separation thereof is difficult and requires a long time, which greatly reduces the production efficiency. Therefore, the development of a simple, continuous, short reaction period, high safety and controllability, and high production efficiency production process of methyl ethyl ketone peroxide is urgently needed.
Means for solving the problems
The continuous production method is based on the characteristics of high-efficiency micro-scale mixing characteristic, good mass transfer and heat transfer performance and intrinsic safety of the micro-reactor technology, realizes the continuous production of the methyl ethyl ketone peroxide, introduces the aqueous solution of inorganic salt on the basis of the continuous production method to realize high-efficiency and quick online phase splitting, and greatly improves the production efficiency.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] A continuous synthesis method of methyl ethyl ketone peroxide is characterized by comprising the following steps:
a) Feeding the feed liquid A and the feed liquid B into a No. 1 micro mixer to obtain a mixed liquid D, wherein the feed liquid A is an aqueous solution containing an inorganic acid catalyst and hydrogen peroxide, and the feed liquid B contains methyl ethyl ketone and an optional organic solvent;
b) Reacting the mixed solution D in a microreactor to obtain an oil-water mixed solution E containing methyl ethyl ketone peroxide;
c) Introducing the mixed solution E and the feed liquid C into a No. 2 micro mixer to obtain a mixed solution F, wherein the feed liquid C is an aqueous solution containing inorganic salts; and
d) And separating the mixed solution F.
[2] The method according to [1], wherein the inorganic salt is one or more selected from halides, sulfates, carbonates, bicarbonates, nitrates, phosphates of alkali metals or alkaline earth metals; the inorganic acid catalyst is concentrated sulfuric acid, nitric acid or phosphoric acid.
[3] The method according to [1] or [2], characterized in that the inorganic salt is one or more selected from the group consisting of halides and sulfates of alkali metals, preferably one or more selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.
[4] The method according to [1] or [2], characterized in that the content of the inorganic acid catalyst in the feed liquid A is 0.01 to 30wt%, and the content of the hydrogen peroxide is 20 to 80wt%; the content of the methyl ethyl ketone in the feed liquid B is 20 to 100 weight percent; the content of inorganic salt in the feed liquid C is 5-50 wt%.
5. The method according to claim 1 or 2, wherein in step a), the molar ratio of the hydrogen peroxide in the feed liquid A to the methyl ethyl ketone in the feed liquid B is (1.0-10.0): 1; the volume ratio of the feed liquid A to the feed liquid C is (0.5-10): 1.
[6] the method according to [1] or [2], wherein the No. 1 micromixer and No. 2 micromixer are, independently of each other, a microchannel mixer, a membrane dispersion mixer, or a micromesh mixer; the micro-reactor is a coil micro-reactor or a micro-channel reactor.
[7] The method according to [1] or [2], characterized in that the temperature in the No. 1 micro mixer is 10-70 ℃ and the mixing time is 0.1-10 s; the reaction temperature in the micro-reactor is 5-90 ℃, and the residence time is 0.1-60 min; the temperature in the No. 2 micro mixer is 20-70 ℃; the mixing time is 0.1-10 s.
[8] The method according to [1] or [2], wherein the feed liquid B comprises dimethyl phthalate, diethylene glycol, or a mixture thereof as the organic solvent.
[9] The method according to [1] or [2], characterized in that in the step a), the feed liquid A and the feed liquid B are pumped into a No. 1 micromixer by using a pump; in step C), the feed liquid C is pumped into a No. 2 micro mixer by using a pump.
[10] The utility model provides a system for be used for synthesizing methyl ethyl ketone peroxide in succession, its characterized in that includes No. 1 micromixer, micro-reactor, no. 2 micromixer and knockout, wherein be provided with entry A, entry B and export D on No. 1 micromixer, the entry fluid connection of export D and micro-reactor, be provided with entry C, entry E and export F on No. 2 micromixer, entry E and the outlet fluid connection of micro-reactor, export F with the entry linkage of knockout, the knockout configuration carries out water oil separating to the feed liquid of No. 2 micromixer's export F outflow.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the invention, the inorganic salt water solution is introduced in the phase splitting stage, so that the phase splitting speed is greatly increased, and the full-continuous efficient rapid preparation and online phase splitting of the methyl ethyl ketone peroxide are realized.
The production process solves the problems of large liquid holdup, high danger, low selectivity and low reaction energy efficiency of the existing production process and reaction equipment at home and abroad, improves the intrinsic safety level of the oxidation process, and meets the national important strategic demand of radically eliminating accident potential.
The content of active oxygen in the methyl ethyl ketone peroxide obtained by the production process reaches 15%, and the water content is lower than 13%.
Drawings
FIG. 1 is a process flow diagram of one embodiment of the present invention.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
< terms and definitions >
In the present specification, the numerical range represented by "a value a to B value" means a range including the endpoint value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, the use of "optionally" or "optional" means that certain materials, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and "%" used means weight or mass% unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The invention aims to provide a continuous synthesis method of methyl ethyl ketone peroxide, which comprises the following steps:
a) Feeding the feed liquid A and the feed liquid B into a No. 1 micro mixer to obtain a mixed liquid D, wherein the feed liquid A is an aqueous solution containing an inorganic acid catalyst and hydrogen peroxide, and the feed liquid B contains methyl ethyl ketone and an optional organic solvent;
b) Reacting the mixed solution D in a microreactor to obtain an oil-water mixed solution E containing methyl ethyl ketone peroxide;
c) Introducing the mixed solution E and the feed liquid C into a No. 2 micro mixer to obtain a mixed solution F, wherein the feed liquid C is an aqueous solution containing inorganic salts; and
d) And separating the mixed solution F.
Each step in the synthesis method of the present invention is described in detail below.
Step a)
This step is a step of mixing the raw material for producing methyl ethyl ketone peroxide, i.e., the inorganic acid catalyst and hydrogen peroxide contained in the feed liquid a and the methyl ethyl ketone contained in the feed liquid B in a No. 1 micromixer. By performing the above-described mixing using a micro mixer, the raw materials can be sufficiently mixed with each other.
In one embodiment, the inorganic acid catalyst in feed liquid a is sulfuric acid, nitric acid, or phosphoric acid.
In one embodiment, the content of the inorganic acid catalyst in the feed liquid A is 0.01 to 30wt%, preferably 0.1 to 1wt%, and more preferably 0.3 to 0.7wt%; the hydrogen peroxide content is 20 to 80 wt.%, preferably 30 to 70 wt.%, more preferably 40 to 60 wt.%.
In one embodiment, the content of the methyl ethyl ketone in the feed liquid B is 20 to 100wt%, and the content of the organic solvent is 0 to 80wt%. The organic solvent in the feed liquid B can be dimethyl phthalate, diethylene glycol or a mixed solution thereof. In one embodiment, the content of methyl ethyl ketone in feed liquid B is 95wt% or more, preferably 98wt% or more, and more preferably 99.5wt% (99.5% is an industry standard). In another embodiment, the feed liquid B contains an organic solvent, wherein the content of the organic solvent is less than 80wt%, for example, 40 to 80wt%.
In one embodiment, the dosage ratio of the two inlet feed liquids of the No. 1 micromixer, namely the dosage ratio of the feed liquid A to the feed liquid B, is adjusted so that the molar ratio of the hydrogen peroxide contained in the feed liquid A to the methyl ethyl ketone contained in the feed liquid B (namely the hydrogen peroxide: the methyl ethyl ketone) is (1.0-10.0): 1, preferably (1.5 to 2): 1. by setting the molar ratio of hydrogen oxide to methyl ethyl ketone within the above range, methyl ethyl ketone can be sufficiently oxidized, and the yield of methyl ethyl ketone peroxide can be improved.
For example, the amount ratio of the feed liquid a to the feed liquid B can be adjusted by adjusting the flow rates of the feed liquid a and the feed liquid B to the No. 1 micromixer. In one embodiment, feed liquid a and feed liquid B are passed into a number 1 micromixer using a pump (e.g., advection pump, diaphragm pump, magnetic pump, centrifugal pump, etc.). In one embodiment, the ratio of flow rates of feed liquid a to feed liquid B may be (0.6 to 6): 1.
the number 1 micromixer used in step a) in the present invention is not particularly limited, and may be any micromixer suitable for liquid-liquid mixing known in the art, and examples thereof include a microchannel mixer, a membrane dispersion mixer, and a micromesh mixer.
In one embodiment, the temperature in the number 1 micromixer is 10 to 70 ℃, preferably 20 to 50 ℃, and by controlling the temperature in the number 1 micromixer in the above range, the reaction rate and the yield of methyl ethyl ketone peroxide can be increased, and the heat of reaction can be removed in time.
In one embodiment, the mixing time of the feed liquid A and the feed liquid B in the No. 1 micro mixer is 0.1-10 s, and the mixing time is controlled within the range, so that the full mixing can be ensured and the production efficiency can be considered.
In addition, although the liquid a and the liquid B are mainly mixed in the micro mixer No. 1, a certain amount of methyl ethyl ketone is oxidized at the same time, and thus a certain amount of methyl ethyl ketone peroxide is contained in the mixed liquid D obtained in the micro mixer No. 1.
Step b)
The step is a step of subjecting methyl ethyl ketone to an oxidation reaction with hydrogen peroxide in the presence of an inorganic acid catalyst to produce methyl ethyl ketone peroxide.
This step is carried out in a microreactor, for which the present invention is not particularly limited and may be any microreactor suitable for liquid-liquid phase reactions known in the art, such as the microchannel mixer mentioned above or a coil microreactor and the like, among which a coil microreactor is preferred.
In one embodiment, the reaction temperature in the microreactor is from 5 to 90 ℃, preferably from 10 to 70 ℃. By controlling the temperature of the microreactor within the range, the reaction rate and the yield of the methyl ethyl ketone peroxide can be improved, and the reaction heat can be removed in time.
In one embodiment, the residence time in the microreactor is from 0.1 to 60min, preferably from 0.3 to 40min, more preferably from 0.5 to 30min. By controlling the residence time in the microreactor within the above range, the size and investment of equipment can be reduced while the reaction rate and the yield of methyl ethyl ketone peroxide are ensured.
The oil-water mixed liquid E containing the methyl ethyl ketone peroxide obtained after the reaction in the microreactor is in a state close to homogeneous phase. The phrase "near homogeneous" means that the mixture E has a low degree of turbidity and is substantially clear and transparent when visually observed. At this time, the oil and water do not separate, and the product methyl ethyl ketone peroxide, the raw material methyl ethyl ketone and the hydrogen peroxide are dissolved in the water.
In one embodiment, the microreactor is a coil-type microreactor wherein the length of the coil can be from 0.5 to 50m and the diameter of the coil can be from 0.5 to 5mm.
Step c)
As described above, the mixed solution E obtained in step b) is in a state close to homogeneous phase, and it is difficult to separate the phases. In the step C), the mixed solution E and the feed liquid C containing the inorganic salt water solution are mixed in the No. 2 micro mixer, the inorganic salt is introduced to influence the phase balance, and the solubility of the oil phase methyl ethyl ketone peroxide in water is reduced to separate out the oil phase methyl ethyl ketone peroxide. Meanwhile, as the density of the oil phase methyl ethyl ketone peroxide is close to that of the water phase, the density of the water phase is increased after the inorganic salt is introduced, and the phase splitting is accelerated. Thus, the mixed liquid F can be easily separated into two phases of oil and water.
In one embodiment, the inorganic salt is one or more selected from the group consisting of halides, sulfates, carbonates, bicarbonates, nitrates, phosphates, bicarbonates, dihydrogen phosphates of an alkali metal or an alkaline earth metal. Among them, halides and sulfates of alkali metals are preferable. In a specific embodiment, the inorganic salt is one or more selected from the group consisting of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate. Among them, sodium chloride, potassium chloride, sodium sulfate and potassium sulfate are preferable, and sodium sulfate is more preferable.
In one embodiment, the content of inorganic salts in feed C is 5 to 50 wt.%, preferably 10 to 40 wt.%.
In one embodiment, the volume ratio of feed liquid A to feed liquid C is (0.5 to 10): 1, preferably (0.8 to 2.5): 1. when the amount of the feed liquid C is within the above range, the mixed liquid F can be easily separated into two phases of oil and water.
The micromixer # 2 used in step c) in the present invention is not particularly limited, and may be any microreactor known in the art to be suitable for liquid-liquid mixing, and examples thereof include microchannel mixers, membrane dispersion mixers, micromixers, and the like. Also, the micromixer No. 1 and the micromixer No. 2 may be the same or different.
In one embodiment, the temperature in the number 2 micromixer is 10 to 70 ℃, preferably 20 to 50 ℃, and by controlling the temperature in the number 1 micromixer in the above range, the reaction rate and the yield of methyl ethyl ketone peroxide can be increased, and the heat of reaction can be removed in time.
In one embodiment, the mixing time in the micromixer # 2 is 0.1 to 10 seconds, and by controlling the mixing time within this range, it is possible to achieve the effect of complete phase separation while maintaining the production efficiency.
In one embodiment, feed liquid C is passed into a number 2 micromixer using a pump (e.g., advection pump, diaphragm pump, magnetic pump, centrifugal pump, etc.).
Step d)
In one embodiment, in step d), the oil phase and the aqueous phase of mixture F are separated, the aqueous phase being in the lower layer and the oil phase product in the upper layer. The separation may be carried out by any means known in the art. In one embodiment, the mixture F is passed into a liquid separator for phase separation. For example, the mixed solution F is introduced into an oil-water phase separation tank, wastewater is discharged from the bottom of the phase separation tank, and a product is pumped from the middle upper part of the phase separation tank.
Other steps
In one embodiment, the invention further comprises the step of formulating feed liquid a, feed liquid B and/or feed liquid C.
In one embodiment, feed a is formulated by mixing an aqueous solution of hydrogen peroxide with an aqueous solution of a mineral acid catalyst.
In one embodiment, feed B is formulated by mixing methyl ethyl ketone and an organic solvent.
In one embodiment, feed C is formulated by mixing water and inorganic salts.
The invention also optionally comprises a step of post-treating the oil phase and the aqueous phase obtained in step d). In one embodiment, the work-up includes operations such as separation and purification, including but not limited to washing, extraction, drying, recrystallization, and the like.
In one embodiment, the process of the invention further optionally comprises one or more of the following steps:
e) The organic solvent in the oil phase obtained in step d) is removed, for example by distillation, rectification or the like; the separated organic solvent can be reused for preparing the feed liquid B.
f) A step of removing water from the oil phase obtained in step d), for example, removing water from the oil phase by using a dehydrating agent such as molecular sieve or allochroic silica gel.
g) The inorganic salts in the aqueous phase obtained in step d) can be separated, for example, by recrystallization, evaporation of water, etc., and the separated inorganic salts can be reused for preparing feed liquid C.
h) Separating the inorganic acid catalyst in the water phase obtained in the step d), and recycling the inorganic acid catalyst for preparing the feed liquid A.
The invention also aims to provide a micro-reaction system for continuously synthesizing methyl ethyl ketone peroxide, which comprises a No. 1 micro-mixer, a micro-reactor, a No. 2 micro-mixer and a liquid distributor, wherein the No. 1 micro-mixer is provided with an inlet A, an inlet B and an outlet D, the outlet D is in fluid connection with the inlet of the micro-reactor, the No. 2 micro-mixer is provided with an inlet C, an inlet E and an outlet F, the inlet E is in fluid connection with the outlet of the micro-reactor, the outlet F is connected with the inlet of the liquid distributor, and the liquid distributor is configured to perform oil-water separation on a feed liquid flowing out from the outlet F of the No. 2 micro-mixer.
Micromixers No. 1, microreactors, micromixers No. 2, and dispensers are described above in the synthesis methods section of the present invention, respectively.
In one embodiment, the microreaction system of the present invention is used to perform the continuous methyl ethyl ketone peroxide synthesis process of the present invention. Wherein, the feed liquid A and the feed liquid B are respectively led into a No. 1 micro mixer through an inlet A and an inlet B, and the obtained mixed liquid D is discharged through an outlet D; introducing the mixed solution D into the microreactor from an inlet of the microreactor and reacting in the microreactor to obtain an oil-water mixed solution E containing methyl ethyl ketone peroxide; and (3) leading the mixed liquid E into a No. 2 micro mixer through an inlet E and leading the feed liquid C into the No. 2 micro mixer through an inlet C to obtain a mixed liquid F, discharging the mixed liquid F through an outlet F and leading the mixed liquid F into a liquid distributor for liquid separation.
In one embodiment, the micro-reaction system of the present invention further comprises a pump a, a pump B and/or a pump C in fluid connection with the inlet a, the inlet B and/or the inlet C, respectively, for feeding the feed liquid into the inlet a, the inlet B and the inlet C, respectively. For a specific class of pumps, reference is made to the description above.
In one embodiment, the microreaction system of the present invention further comprises a vessel a, a vessel B, and a vessel C fluidly connected to inlet a, inlet B, and/or inlet C, respectively, for holding feed solution introduced to inlet a, inlet B, and inlet C, respectively.
Examples
The present invention will be further described below by way of specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
The microreactors used in the following examples are as follows:
type 1T microchannel mixer: the material is 316 stainless steel, and the diameter of the channel is 0.25mm.
Type 2T microchannel mixer: the material is 316 stainless steel, and the diameter of the channel is 0.25mm.
A reaction coil: the material is 316 stainless steel, the diameter of the coil pipe is 3mm, and the length is 6m.
The active oxygen content described in the following examples was determined by iodometry, with reference to the national standard GB/T32102-2015.
The water content described in the examples below is determined by the Karl Fischer volumetric method, reference being made to the national standard GB/T6283-2008.
Example 1
497.96g hydrogen peroxide (50 wt% aqueous solution) and 2.04g concentrated sulfuric acid were mixed as feed liquid A. Methyl ethyl ketone to which no solvent was added was used as feed liquid B. 30g of sodium sulfate was weighed and dissolved in 100mL of deionized water as feed solution C. Respectively conveying the material liquid A and the material liquid B into a No. 1T-shaped micro-channel mixer by using a advection pump, wherein the temperature of the mixer is 30 ℃, the mixing time is 2s, the flow rate of the material liquid A is 9.44mL/min, and the flow rate of the material liquid B is 10.56mL/min. The obtained mixed solution enters a reaction coil connected with the outlet of the No. 1T-shaped microchannel mixer, the retention time in the reaction coil is 0.5min, and the temperature of the reaction coil is 70 ℃. The obtained oil-water mixed solution containing methyl ethyl ketone peroxide and close to homogeneous phase is directly introduced into a No. 2T-shaped micro-channel mixer (30 ℃). And (3) conveying the feed liquid C into a No. 2T-shaped micro-channel mixer by using a advection pump, wherein the flow rate is 8mL/min, and the mixing time is 2s, so that the reaction liquid F containing the methyl ethyl ketone peroxide with complete phase separation is obtained at the outlet of a pipeline connected with the No. 2T-shaped micro-channel mixer. And (3) separating the reaction liquid F, and taking an upper-layer organic phase to obtain a methyl ethyl ketone peroxide product, wherein the active oxygen content of the product reaches 15%, and the water content is lower than 13%.
Example 2
496.92g hydrogen peroxide (50 wt% aqueous solution) and 3.08g nitric acid (65 wt% aqueous solution) were mixed as feed A. A20% methyl ethyl ketone solution in dimethyl phthalate was used as feed liquid B. 30g of sodium sulfate is weighed and dissolved in 100mL of deionized water to serve as feed liquid C. Respectively conveying the material liquid A and the material liquid B into a No. 1T-shaped micro-channel mixer by using a advection pump, wherein the temperature of the mixer is 30 ℃, the mixing time is 2s, the flow rate of the material liquid A is 10.12mL/min, and the flow rate of the material liquid B is 9.88mL/min. The obtained mixed solution enters a reaction coil pipe connected with the outlet of the No. 1T-shaped microchannel mixer, the retention time in the reaction coil pipe is 5min, and the temperature of the reaction coil pipe is 30 ℃. The obtained oil-water mixed solution containing methyl ethyl ketone peroxide and close to homogeneous phase is directly introduced into a No. 2T-shaped micro-channel mixer (30 ℃). And (3) conveying the feed liquid C into a No. 2T-shaped micro-channel mixer by using a advection pump, wherein the flow rate is 8mL/min, the mixing time is 2s, and obtaining the reaction liquid F containing the methyl ethyl ketone peroxide with complete phase separation at the outlet of a pipeline connected with the No. 2T-shaped micro-channel mixer. And (3) separating the reaction liquid F, and taking an upper organic phase to obtain a methyl ethyl ketone peroxide product, wherein the active oxygen content of the product reaches 15%, and the water content is lower than 13%.
Example 3
497.65g hydrogen peroxide (50 wt% aqueous solution) and 2.35g phosphoric acid (85 wt% aqueous solution) were mixed as feed A. A methyl ethyl ketone solution to which no solvent was added was used as feed liquid B. 30g of sodium sulfate was weighed and dissolved in 100mL of deionized water as feed solution C. Respectively conveying the material liquid A and the material liquid B into a No. 1T-shaped micro-channel mixer by using a advection pump, wherein the temperature of the mixer is 30 ℃, the mixing time is 2s, the flow rate of the material liquid A is 10.11mL/min, and the flow rate of the material liquid B is 9.89mL/min. The obtained mixed solution enters a reaction coil pipe connected with the outlet of the No. 1T-shaped microchannel mixer, the retention time in the reaction coil pipe is 30min, and the temperature of the reaction coil pipe is 10 ℃. The obtained oil-water mixed solution containing methyl ethyl ketone peroxide and close to homogeneous phase is directly introduced into a No. 2T-shaped micro-channel mixer (30 ℃). And (3) conveying the feed liquid C into a No. 2T-shaped micro-channel mixer by using a advection pump, wherein the flow rate is 8mL/min, the mixing time is 2s, and obtaining the reaction liquid F containing the methyl ethyl ketone peroxide with complete phase separation at the outlet of a pipeline connected with the No. 2T-shaped micro-channel mixer. And (3) separating the reaction liquid F, and taking an upper organic phase to obtain a methyl ethyl ketone peroxide product, wherein the active oxygen content of the product reaches 15%, and the water content is lower than 13%.
Industrial applicability
The continuous synthesis method of methyl ethyl ketone peroxide can be widely used for preparing methyl ethyl ketone peroxide in industry.
Claims (10)
1. A continuous synthesis method of methyl ethyl ketone peroxide is characterized by comprising the following steps:
a) Feeding the feed liquid A and the feed liquid B into a No. 1 micro mixer to obtain a mixed liquid D, wherein the feed liquid A is an aqueous solution containing an inorganic acid catalyst and hydrogen peroxide, and the feed liquid B contains methyl ethyl ketone and an optional organic solvent;
b) Reacting the mixed solution D in a microreactor to obtain an oil-water mixed solution E containing methyl ethyl ketone peroxide;
c) Introducing the mixed solution E and the feed liquid C into a No. 2 micro mixer to obtain a mixed solution F, wherein the feed liquid C is an aqueous solution containing inorganic salts; and
d) Separating the mixed solution F;
wherein the inorganic salt is one or more selected from alkali metal or alkaline earth metal halide, sulfate, carbonate, bicarbonate, nitrate and phosphate.
2. The method of claim 1, wherein the inorganic acid catalyst is concentrated sulfuric acid, nitric acid, or phosphoric acid.
3. The method according to claim 1 or 2, wherein the inorganic salt is one or more selected from a halide and a sulfate of an alkali metal.
4. The method according to claim 3, wherein the inorganic salt is one or more selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, and potassium sulfate.
5. The method according to claim 1 or 2, wherein the content of the inorganic acid catalyst in the feed liquid a is 0.01 to 30wt%, and the content of the hydrogen peroxide is 20 to 80wt%; the content of the methyl ethyl ketone in the feed liquid B is 20 to 100 weight percent; the content of inorganic salt in the feed liquid C is 5-50 wt%.
6. The method according to claim 1 or 2, wherein in step a), the molar ratio of the hydrogen peroxide in the feed liquid A to the methyl ethyl ketone in the feed liquid B is (1.0-10.0): 1; the volume ratio of the feed liquid A to the feed liquid C is (0.5-10): 1.
7. the method of claim 1 or 2, wherein the No. 1 micromixer and No. 2 micromixer are, independently of each other, a microchannel mixer, a membrane dispersion mixer, or a micromesh mixer; the microreactor is a coil-type microreactor or a microchannel reactor.
8. The method according to claim 1 or 2, wherein the temperature in the No. 1 micromixer is 10 to 70 ℃ and the mixing time is 0.1 to 10s; the reaction temperature in the micro-reactor is 5-90 ℃, and the residence time is 0.1-60 min; the temperature in the No. 2 micro mixer is 20-70 ℃, and the mixing time is 0.1-10 s.
9. The method according to claim 1 or 2, wherein the feed liquid B comprises dimethyl phthalate, diethylene glycol or a mixture thereof as the organic solvent.
10. The method according to claim 1 or 2, wherein in step a), the feed liquid A and the feed liquid B are pumped into a No. 1 micromixer; in step C), the feed liquid C is pumped into a No. 2 micro mixer by using a pump.
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