Aliphatic epoxy diluent whole-process continuous production system and process thereof

Abstract

The invention provides a whole-process continuous production system for an aliphatic epoxy diluent. The invention further provides a whole-process continuous production process of the aliphatic epoxy diluent. The invention further provides an aliphatic epoxy diluent which is prepared by the production process. According to the full-process continuous production system and process for the aliphatic epoxy diluent, through continuous process design and device optimization, the problems of high labor intensity and large product quality fluctuation in traditional intermittent method epoxy diluent production are effectively solved, the production efficiency and the product quality stability are improved, and the production cost is reduced. And the method has great application value and market competitiveness.

Description

Technical Field

[0001] The invention belongs to the technical field of epoxy diluent preparation, and relates to a full-process continuous production system and process of an aliphatic epoxy diluent. Background Art

[0002] Aliphatic epoxy diluents (also known as fatty alcohol-epoxide ethers) can be prepared by using fatty alcohols and epichlorohydrin to undergo a ring-opening addition reaction to obtain an intermediate, and then allowing the intermediate to undergo a further ring-closing reaction under alkaline conditions. Aliphatic epoxy diluents are low-viscosity compounds containing an epoxy structure, which can be used to reduce the viscosity and toughen epoxy resins, and can be widely used in coatings, adhesives, composite materials, chemical intermediates, and other purposes.

[0003] In the synthesis method of aliphatic epoxy diluent, the reaction of the ring-opening addition of fatty alcohol and epichlorohydrin to generate chlorohydrin ether is a strong exothermic reaction, the heat and mass transfer performance has a great influence on the reaction, and the reaction process is highly dangerous. The ring-opening addition reactor generally used at home and abroad is a kettle reactor. However, in terms of mass transfer, the residence time of the material in the system is inconsistent due to the dropwise addition of the material epichlorohydrin in the kettle reactor, which is easy to cause the occurrence of various side reactions, affecting the yield and product quality of the final product. At the same time, the concentration and reaction time of the materials in the autoclave reactor are different, and there is a certain amount of back mixing between the materials. The back mixing of the materials reduces the reaction driving force, reduces the reaction speed, and is prone to side reactions, which in turn affects the reaction conversion rate and the distribution of the reaction products. In terms of heat transfer, the autoclave reactor generally controls the temperature by means of jacket and coil cooling. Its heat exchange area is small. Once the ring-opening addition reaction is initiated, it will react quickly and release a large amount of heat. If the heat is not removed in time, a local hot spot will form, which will cause epichlorohydrin self-polymerization, which is very likely to explode, posing a great safety hazard. At the same time, due to the limited heat transfer area of ​​the autoclave reaction, the reaction rate is limited, resulting in low etherification reaction efficiency. At the same time, the intermittent process has problems such as low degree of automation, excessive labor intensity, and low production efficiency.

[0004] The cyclization reaction of chlorohydrin ether with alkali is an exothermic reaction. The reaction is liquid-liquid-solid three-phase, and a large amount of solid sodium chloride will be generated at the same time. The heat and mass transfer performance has a great influence on the reaction. The closed-loop cyclization reaction currently used at home and abroad also often uses an intermittent reactor, and the product after the reaction needs to be separated from the solid and liquid. The traditional intermittent process requires frequent feeding and discharge of products, resulting in a low degree of automation, excessive labor intensity, and low production efficiency.

[0005] The post-processing process after the reaction includes filtration, washing and solvent removal. At present, the intermittent process is widely used both at home and abroad. The post-processing process is exposed to toxic and harmful substances such as toluene. The intermittent process causes operators to frequently contact toxic substances such as toluene, which is harmful to health. Intermittent washing will lead to a large amount of washing water, low efficiency of intermittent solvent removal, and high solvent consumption. At the same time, the intermittent desolventizing material is heated for too long, which will lead to adverse effects such as material polymerization and yellowing.

[0006] In order to solve the above problems, technicians in this field have invested a lot of cost and energy, and conducted a lot of research and exploration on reaction process design, catalyst system, and its specific condition parameters, but the research results obtained are still unsatisfactory. So far, people are still eager to develop a new technology that can solve the above technical problems. Summary of the invention

[0007] In view of the characteristics of the prior art described above, the purpose of the present invention is to provide a full-process continuous production system and process for aliphatic epoxy diluents, so as to solve the problems of low degree of automation, excessive labor intensity, low production efficiency, large fluctuation of product quality, etc. in the traditional intermittent epoxy diluent production process, and to develop a new reaction process with the characteristics of sufficient mixing, high heat transfer efficiency, short residence time of reaction products, good repeatability, etc.

[0008] To achieve the above-mentioned and other related purposes, the first aspect of the present invention provides a full-process continuous production system for aliphatic epoxy diluents, comprising an etherification reactor, a cyclization reactor, a phase separation component, an extraction scrubber, and a falling film evaporator. The etherification reactor, the cyclization reactor, the phase separation component, the extraction scrubber, and the falling film evaporator are connected in sequence via pipelines along the production route, and the falling film evaporator is also connected to the phase separation component via a pipeline.

[0009] The second aspect of the present invention provides a full-process continuous production process of an aliphatic epoxy diluent, which uses the above-mentioned full-process continuous production system of an aliphatic epoxy diluent, comprising the following steps:

[0010] 1) subjecting the epoxy material to an etherification reaction with a fatty alcohol to obtain an etherification reaction material;

[0011] 2) subjecting the etherification reaction product to a cyclization reaction with a base, and performing phase separation on the obtained cyclization reaction material to obtain a liquid material and a waste material;

[0012] 3) washing the liquid material in countercurrent to separate the phases to obtain an oil phase material and a water phase material;

[0013] 4) The oil phase material is subjected to falling film evaporation to remove the organic solvent and water to provide the desired reaction product.

[0014] The third aspect of the present invention provides an aliphatic epoxy diluent prepared by the above production process.

[0015] As described above, the present invention provides a full-process continuous production system and process of an aliphatic epoxy diluent, which is a new reaction process with the characteristics of sufficient mixing, high heat transfer efficiency, short residence time of reaction products, good repeatability, etc., and has the following beneficial effects:

[0016] (1) The present invention provides a full-process continuous production system and process for aliphatic epoxy diluents, which solves the problems of high labor intensity, large fluctuations in product batch quality, low liquid-solid separation efficiency of the reaction liquid, large amounts of washing wastewater, high product volatiles, high energy consumption, and large amounts of wastewater and exhaust gas emissions in the conventional intermittent epoxy diluent production process in the prior art.

[0017] (2) The present invention provides a full-process continuous production system and process for aliphatic epoxy diluents, which can realize the full-process continuous production of epoxy diluents, and effectively solve the problems of high labor intensity and large fluctuations in product quality in traditional intermittent processes. At the same time, the process is efficient, stable, and energy-saving, and can improve production efficiency and product quality stability.

[0018] (3) The present invention provides a full-process continuous production system and process for aliphatic epoxy diluents. The continuous production process can effectively reduce labor intensity, reduce manual operations, and improve production efficiency compared to the traditional intermittent process. The etherification reaction time is shortened from 4h to 10-30min; the cyclization reaction time is shortened from 4-6h to 1-2h.

[0019] (4) The present invention provides a full-process continuous production system and process for an aliphatic epoxy diluent, which can realize continuous processing of the reaction liquid and efficient liquid-liquid separation, improve the liquid-liquid separation efficiency and reduce the time that intermittent filtration operators are exposed to toxic and hazardous materials such as toluene, thereby realizing closed operation and reducing harm to workers.

[0020] (5) The present invention provides a full-process continuous production system and process for an aliphatic epoxy diluent, which reduces the amount of washing wastewater. The amount of washing wastewater is reduced to 30% to 80% of that of the intermittent process through efficient washing in a continuous countercurrent washing tower, and the washing and evaporation effects are excellent.

[0021] (6) The present invention provides a full-process continuous production system and process for aliphatic epoxy diluents. Through the continuous falling film evaporation of solvent and water process, the solvent and water in the oil phase are effectively removed, so that the volatile content in the product is reduced to 0.2%, and the material heating time is shortened from 2 to 4 hours to 10 minutes, achieving the application index of wind power epoxy. The continuous falling film desolventization process reduces the volatilization of solvents such as toluene, and the unit consumption of solvents such as toluene is reduced by 80%.

[0022] (7) The present invention provides a full-process continuous production system and process for an aliphatic epoxy diluent. Due to the use of a continuous production process, the reaction time is shortened, the steam consumption is reduced by 70%, and the energy consumption and the emission of wastewater and waste gas can be reduced. The wastewater discharge is reduced by 30%-80%, and the waste gas emission is reduced by 50%-90%, thereby achieving the effect of energy saving and environmental protection.

[0023] (8) The present invention provides a full-process continuous production system and process for an aliphatic epoxy diluent. Due to the use of a continuous production process, the control parameters of each production link fluctuate very little, and the epoxy value, the main technical indicator of the product, is very stable.

[0024] (9) The present invention provides a full-process continuous production system and process for aliphatic epoxy diluents, which have advantages over the prior art in terms of continuous production, stable product quality, excellent washing and evaporation effects, energy saving and environmental protection, etc. Through continuous process design and device optimization, the present invention effectively solves the problems of high labor intensity and large product quality fluctuation in the traditional intermittent production of epoxy diluents, improves production efficiency and product quality stability, and has great application value and market competitiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Shown is a structural schematic diagram of a full-process continuous production system of an aliphatic epoxy diluent in the present invention.

[0026] Reference numerals

[0027] 1 Etherification reactor

[0028] 2 Cyclization Reactor

[0029] 3-phase components

[0030] 4Extraction Scrubber

[0031] 41 Primary extraction washing tower

[0032] 42 Secondary Neutralization Scrubber

[0033] 43 three-stage extraction washing tower

[0034] 5 Falling film evaporator

[0035] 51 One-stage falling film evaporation unit

[0036] 52 two-stage falling film evaporation unit

[0037] 61 Heat transfer oil inlet pipe

[0038] 62 heat transfer oil output pipe

[0039] 71 circulating water inlet pipe

[0040] 72 circulating water output pipe

[0041] 8Reaction material input pipe

[0042] 9 Epoxy material feed pipe

[0043] 10 Fatty alcohol feed tube

[0044] 11. First catalyst feed pipe

[0045] 12 first connecting pipe

[0046] 13 Liquid caustic soda feed pipe

[0047] 14 Second catalyst feed pipe

[0048] 17 Second connecting pipe

[0049] 18 Sodium chloride liquid output tube

[0050] 19Third connecting pipe

[0051] 20 Wastewater discharge pipe

[0052] 21 First oil phase output pipe

[0053] 22 Second oil phase output pipe

[0054] 23 first water phase output pipe

[0055] 24 Second water phase output pipe

[0056] 25 countercurrent washing pipe

[0057] 26 Second washing solvent input pipe

[0058] 27 Third washing solvent input pipe

[0059] 28 Fourth connecting pipe

[0060] 291 first liquid return branch

[0061] 292 Second liquid return branch

[0062] 293 Liquid return pipe

[0063] 30 Fifth connecting pipe

[0064] 31 Product output pipe DETAILED DESCRIPTION

[0065] The first aspect of the present invention provides a full-process continuous production system of an aliphatic epoxy diluent, such as Figure 1As shown, it includes an etherification reactor, a cyclization reactor, a phase separation component, an extraction scrubber, and a falling film evaporator. The etherification reactor, the cyclization reactor, the phase separation component, the extraction scrubber, and the falling film evaporator are connected in sequence through pipelines along the production route, and the falling film evaporator is also connected to the phase separation component through a pipeline.

[0066] In the above system, if Figure 1 As shown, the etherification reactor is a reaction tube. The reaction tube is a conventionally used single reaction tube.

[0067] In one embodiment, the diameter of the reaction tube of the etherification reactor is 1 / 10-1 / 2, preferably 1 / 8-1 / 4.

[0068] In one embodiment, the reaction tube length of the etherification reactor is 15-100 m, preferably 20-30 m.

[0069] In the above system, if Figure 1 As shown, the etherification reactor is provided with a heat transfer oil input pipe and a heat transfer oil output pipe.

[0070] In one embodiment, if Figure 1 As shown, the heat transfer oil output pipe is arranged at the reaction input end of the etherification reactor, and the heat transfer oil input pipe is arranged at the reaction output end of the etherification reactor. The reaction input end is located at an end away from the connection end between the etherification reactor and the cyclization reactor, and the reaction output end is located at an end close to the connection end between the etherification reactor and the cyclization reactor.

[0071] In the above system, if Figure 1 As shown, the etherification reactor is provided with a reaction material input pipe.

[0072] In one embodiment, if Figure 1 As shown, one end of the reaction material input pipe is connected to the reaction input end of the etherification reactor, and the other end of the reaction material input pipe is connected to the epoxy material feed pipe, the fatty alcohol feed pipe, and the first catalyst feed pipe.

[0073] In the above system, if Figure 1 As shown, the etherification reactor is connected to the cyclization reactor via a first connecting pipe.

[0074] In one embodiment, if Figure 1 As shown, the first connecting pipe is connected to a liquid alkali feeding pipe and a second catalyst feeding pipe.

[0075] In a further embodiment, Figure 1 As shown, the connecting ends of the liquid alkali feed pipe, the second catalyst feed pipe and the first connecting pipe are close to the cyclization reactor.

[0076] In one embodiment, if Figure 1 As shown, the first connecting pipe is connected to the material input end of the cyclization reactor. The material input end of the cyclization reactor is located at an end close to the connecting end of the cyclization reactor and the etherification reactor.

[0077] In the above system, if Figure 1 As shown, the cyclization reactor is a reaction tube. The reaction tube is a conventionally used single reaction tube.

[0078] In one embodiment, if Figure 1 As shown, the diameter of the reaction tube of the cyclization reactor is 1 / 10-1 / 2, preferably 1 / 8-1 / 4.

[0079] In one embodiment, if Figure 1 As shown, the reaction tube length of the cyclization reactor is 25-100 m, preferably 30-40 m.

[0080] In one embodiment, if Figure 1 As shown, a circulating water input pipe and a circulating water output pipe are provided on the reaction tube of the cyclization reactor.

[0081] In a further embodiment, Figure 1 As shown, the circulating water output pipe is arranged at the reaction input end of the reaction tube, and the circulating water input pipe is arranged at the reaction output end of the reaction tube. The reaction input end is located at an end away from the end connecting the etherification reactor and the reaction tube, and the reaction output end is located at an end close to the end connecting the etherification reactor and the reaction tube.

[0082] In the above system, if Figure 1 As shown, the phase separation component is a phase separator. The phase separator is a conventional continuous phase separator. It is used to achieve liquid-liquid separation through the phase separator.

[0083] In one embodiment, if Figure 1 As shown, the phase separator is connected to a sodium chloride liquid output pipe.

[0084] In a further embodiment, Figure 1 As shown, the sodium chloride liquid output pipe is arranged at the lower part of the phase separator, which is the output end of the liquid brine produced by liquid-liquid phase separation.

[0085] In the above system, if Figure 1 As shown, the cyclization reactor is connected to the phase separation component via a second connecting pipe.

[0086] In one embodiment, if Figure 1As shown, one end of the second connecting pipe is connected to the material output end of the cyclization reactor, and the other end of the second connecting pipe is connected to the input end of the phase separation component. The material output end of the cyclization reactor is located at an end close to the connection end between the cyclization reactor and the phase separation component. The input end of the phase separation component is located at the top of the phase separation component, which is the input end of the phase separation component before separation.

[0087] In the above system, if Figure 1 As shown, the phase separation component is connected to the extraction scrubber via a third connecting pipe.

[0088] In one embodiment, if Figure 1 As shown, the output end of the phase separation component is connected to the input end of the primary extraction washing tower through the third connecting pipe. The input end of the primary extraction washing tower is located at the lower part of the primary extraction washing tower.

[0089] In the above system, if Figure 1 As shown, the extraction scrubber includes a primary extraction scrubber, a secondary neutralization scrubber, and a tertiary extraction scrubber which are sequentially connected in series.

[0090] The above-mentioned first-stage extraction washing tower, second-stage neutralization washing tower and third-stage extraction washing tower are all conventionally used washing towers, specifically, a rotary disc extraction tower or a turbine rotary disc extraction tower.

[0091] In one embodiment, the number of plates of the primary extraction washing tower, the secondary neutralization washing tower, and the tertiary extraction washing tower are all 30-50.

[0092] In one embodiment, if Figure 1 As shown, the bottom of the first-stage extraction and washing tower is also connected to a wastewater discharge pipe.

[0093] In one embodiment, if Figure 1 As shown, the top of the primary extraction washing tower is connected to the lower part of the secondary neutralization washing tower through the first oil phase output pipe.

[0094] In one embodiment, if Figure 1 As shown, the top of the secondary neutralization washing tower is connected to the lower part of the tertiary extraction washing tower through the second oil phase output pipe.

[0095] In one embodiment, if Figure 1 As shown, the bottom of the secondary neutralization washing tower is connected to a first water phase output pipe, and the bottom of the tertiary extraction washing tower is connected to a second water phase output pipe. The first water phase output pipe and the second water phase output pipe are connected to one end of a countercurrent washing pipe, and the other end of the countercurrent washing pipe is connected to the upper part of the primary extraction washing tower.

[0096] In one embodiment, if Figure 1As shown, the upper portion of the secondary neutralization washing tower is connected to a second washing solvent input pipe.

[0097] In one embodiment, if Figure 1 As shown, the upper part of the three-stage extraction washing tower is connected to a third washing solvent input pipe.

[0098] In the above system, if Figure 1 As shown, the extraction scrubber is connected to the falling film evaporator via a fourth connecting pipe.

[0099] In one embodiment, if Figure 1 As shown, one end of the fourth connecting pipe is connected to the top of the three-stage extraction washing tower, and the other end of the fourth connecting pipe is connected to the falling film evaporator.

[0100] In the above system, if Figure 1 As shown, the falling film evaporator comprises a plurality of falling film evaporation units connected in series.

[0101] In one embodiment, if Figure 1 As shown, the falling film evaporation unit is a conventional falling film evaporator.

[0102] In one embodiment, if Figure 1 As shown, the falling film evaporation units of several stages are connected with the part of the third connecting pipe near the phase separation component through the liquid return pipe.

[0103] In one embodiment, if Figure 1 As shown, the number of series-connected stages of the falling film evaporation unit is not less than 2, preferably 2.

[0104] In a further embodiment, Figure 1 As shown, when the number of series-connected falling film evaporation units is 2, the falling film evaporator comprises a primary falling film evaporation unit and a secondary falling film evaporation unit which are sequentially connected in series.

[0105] In a further embodiment, Figure 1 As shown, the middle portion of the first-stage falling film evaporation unit is connected to one end of the fourth connecting pipe.

[0106] In a further embodiment, Figure 1 As shown, the first-stage falling film evaporation unit is connected to the second-stage falling film evaporation unit via a fifth connecting pipe.

[0107] In the most preferred embodiment, Figure 1 As shown, one end of the fifth connecting pipe is connected to the bottom of the first falling film evaporation unit, and the other end of the fifth connecting pipe is connected to the middle of the second falling film evaporation unit.

[0108] In a further embodiment, Figure 1As shown, the secondary falling film evaporation unit is connected to a product output pipe.

[0109] In the most preferred embodiment, Figure 1 As shown, the product output pipe is connected to the bottom of the secondary falling film evaporation unit.

[0110] In a further embodiment, Figure 1 As shown, the liquid return pipe includes a first liquid return branch pipe, a second liquid return branch pipe, and a liquid return main pipe. One end of the first liquid return branch pipe is connected to the top of the first falling film evaporation unit, one end of the second liquid return branch pipe is connected to the top of the second falling film evaporation unit, the other end of the first liquid return branch pipe and the other end of the second liquid return branch pipe are connected to one end of the liquid return main pipe, and the other end of the liquid return main pipe is connected to the input end of the phase separation component.

[0111] The second aspect of the present invention provides a full-process continuous production process of an aliphatic epoxy diluent, which uses the above-mentioned full-process continuous production system of an aliphatic epoxy diluent, comprising the following steps:

[0112] 1) subjecting the epoxy material to an etherification reaction with a fatty alcohol to obtain an etherification reaction material;

[0113] 2) subjecting the etherification reaction product to a cyclization reaction with a base, and performing phase separation on the obtained cyclization reaction material to obtain a liquid material and a waste material;

[0114] 3) washing the liquid material in countercurrent to separate the phases to obtain an oil phase material and a water phase material;

[0115] 4) The oil phase material is subjected to falling film evaporation to remove the organic solvent and water to provide the desired reaction product.

[0116] In the above production process, the full-process continuous production process of the aliphatic epoxy diluent adopts the above-mentioned full-process continuous production system of the aliphatic epoxy diluent, and comprises the following steps:

[0117] 11) performing an etherification reaction on the epoxy material and the fatty alcohol in an etherification reactor to obtain an etherification reaction material;

[0118] 21) subjecting the etherification reaction product to a cyclization reaction with a base in a cyclization reactor, and separating the obtained cyclization reaction material in a phase separation component to obtain a liquid material and a waste material;

[0119] 31) washing the liquid material in a countercurrent manner in an extraction scrubber to separate the phases, thereby obtaining an oil phase material and an aqueous phase material;

[0120] 41) The oil phase material is subjected to falling film evaporation in a falling film evaporator to remove the organic solvent and water to provide the desired reaction product.

[0121] In the above step 1), the epoxy material is epichlorohydrin.

[0122] In the above step 1), the fatty alcohol is an alcohol containing at least one hydroxyl group, such as a monohydric alcohol or a polyhydric alcohol (each hydration group is n, n>1 and n is a positive integer), preferably 1,4-butanediol, ethylene glycol, 1,6-hexanediol, C 4～14 Monohydric alcohol, C 4～14 of polyols, etc.

[0123] In the above step 1), the molar ratio of the epoxy material to the fatty alcohol added per minute is (1-1.5)n:1. (each 1 yuan is n, n>1 and n is a positive integer).

[0124] In one embodiment, when the fatty alcohol is a monohydric alcohol, the molar ratio of the epoxy material to the fatty alcohol added per minute is 1.1-1.5:1; when the fatty alcohol is a polyhydric alcohol (the number of hydrations is n, n>1 and n is a positive integer), the molar ratio of the epoxy material to the fatty alcohol added per minute is (1-1.5)n:1.

[0125] In a further embodiment, when the polyol is a diol, the molar ratio of the epoxy material to the fatty alcohol added per minute is 2.0 to 2.5:1.

[0126] In the above step 1), a first catalyst is also added into the etherification reaction.

[0127] In one embodiment, the first catalyst is selected from at least one of boron trifluoride etherate, aluminum trichloride, tin tetrachloride, and niobium pentachloride.

[0128] In a further embodiment, the first catalyst is boron trifluoride etherate.

[0129] In one embodiment, the first catalyst is added in an amount of 0.1-1 wt% of the fatty alcohol feed, specifically 0.4-0.6 wt%, preferably 0.5 wt%.

[0130] In the above step 1), the reaction temperature of the etherification reaction is 70-110°C, preferably 80-90°C.

[0131] In the above step 1), the reaction time of the etherification reaction is 20-40 min, specifically 25-35 min, preferably 30 min.

[0132] In the above etherification reaction, the material is continuously fed into the etherification reactor, and the etherification reaction material is continuously discharged after the etherification reaction.

[0133] In the above step 2), the alkali is an aqueous solution of sodium hydroxide.

[0134] In one embodiment, the mass percentage concentration of the sodium hydroxide aqueous solution is 5-25%, preferably 10-20%.

[0135] In the above step 2), the base (calculated as pure ash, specifically as OH - The molar ratio of the amount of epoxy material added per minute is 1 to 2:1.

[0136] In one embodiment, when the fatty alcohol is a monohydric alcohol, the base (calculated as pure ash, specifically as OH - The molar ratio of the amount of epoxy material added per minute is 1.2 to 2:1; when the fatty alcohol is a polyol (the number is n, n>1 and n is a positive integer), the base (calculated as soda ash, specifically as OH - The molar ratio of the amount of epoxy material added per minute is 1 to 1.8:1.

[0137] In a further embodiment, when the polyol is a diol, the base (measured in pure ash, specifically in OH - The molar ratio of the amount of epoxy material added per minute is 1.1-1.8:1; when the polyol is a polyol other than a diol (where n is n, n>1 and n is a positive integer), the base (in terms of soda ash, specifically, OH - The molar ratio of the amount of epoxy material added per minute is 1 to 1.7:1.

[0138] In the above step 2), a phase transfer catalyst is also added into the cyclization reaction.

[0139] In one embodiment, the phase transfer catalyst includes but is not limited to benzyltriethylammonium chloride, benzyltrimethylammonium chloride, crown ether, and the like.

[0140] In a further embodiment, the phase transfer catalyst is selected from at least one of benzyltriethylammonium chloride, benzyltrimethylammonium chloride or a crown ether.

[0141] In a further embodiment, the phase transfer catalyst is in the form of an aqueous solution, and the mass percentage concentration of the phase transfer catalyst in the aqueous solution of the phase transfer catalyst is 4-6%, preferably 5%.

[0142] In one embodiment, the phase transfer catalyst is added in an amount of 1 to 10 wt % of the fatty alcohol feed, preferably 2 to 4 wt %.

[0143] In the above step 2), the reaction time of the cyclization reaction is 30-120 min, preferably 30-60 min.

[0144] In the above step 2), the reaction temperature of the cyclization reaction is 20-60°C, preferably 40-50°C.

[0145] The cyclization reaction material obtained in the above cyclization reaction is continuously discharged to the phase separation component, and liquid-liquid separation is carried out in the phase separator. In the above step 2), when the phase separation is liquid-liquid two-phase, the two-phase material is in the phase separator, and due to the different density difference between the two phases, the residence time in the phase separator is 10min to 60min, preferably 25-45min. The light phase overflows from the baffle in the phase separator, and the heavy phase enters the water collection bag to achieve liquid-liquid two-phase separation. The obtained liquid material is continuously discharged into the extraction scrubber, and the waste is discharged. Liquid waste is obtained by phase separation.

[0146] In the above step 3), the first washing solvent for the countercurrent washing of the liquid material in the primary extraction washing tower is the bottom aqueous phase in the secondary neutralization washing tower and the tertiary extraction washing tower. The first washing solvent is the aqueous phase discharged from the bottom of the secondary neutralization washing tower and the tertiary extraction washing tower, and the aqueous phase after the countercurrent washing is discharged from the bottom of the primary extraction washing tower as waste water.

[0147] In the above step 3), the second washing solvent for countercurrent washing of the liquid material in the secondary neutralization washing tower is a weak acid aqueous solution, which can be used as a neutralizing agent.

[0148] In one embodiment, the second washing solvent is selected from at least one of a citric acid aqueous solution, a sodium dihydrogen phosphate solution or an acetic acid aqueous solution.

[0149] In a further embodiment, in the citric acid aqueous solution, sodium dihydrogen phosphate solution or acetic acid aqueous solution, the concentration of the citric acid, sodium dihydrogen phosphate solution or acetic acid is 1-10wt%, preferably 4-6wt%.

[0150] In one embodiment, the mass ratio of the flow rate of the second washing solvent to the feed amount of the fatty alcohol is 0.1 to 1:1, preferably 0.3 to 0.4:1.

[0151] In the above step 3), the third washing solvent for countercurrent washing of the liquid material in the three-stage extraction washing tower is water, which can be used as demineralized water.

[0152] In one embodiment, the mass ratio of the flow rate of the third washing solvent to the feed amount of the fatty alcohol is 0.1 to 1:1, preferably 0.3 to 0.4:1.

[0153] The liquid material is subjected to three-stage extraction countercurrent washing and phase separation to remove impurities and salt residues in the oil phase material, and then the solvent and water removal operation is performed.

[0154] In the above step 3), the pH value of the oil phase material at the top of the three-stage extraction and washing tower is 5-7, preferably 6.5-7.

[0155] In the above step 3), the stirring speed in the primary extraction washing tower, the secondary neutralization washing tower and the tertiary extraction washing tower is 10-100 r / min, preferably 50-60 r / min.

[0156] In the above-mentioned countercurrent washing, the separated oil phase material is continuously fed to the bottom of the primary extraction washing tower, the secondary neutralization washing tower and the tertiary extraction washing tower, the oil phase material is extracted from the top of the primary extraction washing tower, the secondary neutralization washing tower and the tertiary extraction washing tower, and the washed water phase material is discharged from the bottom of the primary extraction washing tower, the secondary neutralization washing tower and the tertiary extraction washing tower.

[0157] In the above step 4), the residence time of the falling film evaporation is 8 to 12 minutes, specifically 8 to 10 minutes, 10 to 12 minutes, and preferably 10 minutes.

[0158] In the above step 4), when the number of series-connected falling film evaporation units is 2, the operating temperature of the oil phase material in the first falling film evaporation unit is 85-105°C, preferably 90-100°C.

[0159] In the above step 4), when the number of series-connected falling film evaporation units is 2, the operating pressure of the oil phase material in the first falling film evaporation unit is 8 to 30 kPaA, preferably 10 to 20 kPaA.

[0160] In the above step 4), when the number of series-connected falling film evaporation units is 2, the operating temperature of the oil phase material in the two-stage falling film evaporation unit is 130-150°C, specifically 135-145°C, preferably 140°C.

[0161] In the above step 4), when the number of series-connected falling film evaporation units is 2, the operating pressure of the oil phase material in the two-stage falling film evaporation unit is 1-5 kPaA, preferably 2-3 kPaA.

[0162] In the above step 4), the organic solvent includes but is not limited to toluene, etc., preferably toluene.

[0163] In the above step 4), the organic solvent is returned to step 3) as a return liquid to be mixed with the liquid material and then subjected to countercurrent washing to separate the phases.

[0164] In one embodiment, the organic solvent is returned as a return liquid to step 3) and mixed with the liquid material, and then subjected to countercurrent washing in an extraction scrubber to separate the phases.

[0165] In a further embodiment, the organic solvent is refluxed through the first liquid return branch pipe, the second liquid return branch pipe, and the liquid return main pipe.

[0166] In one embodiment, the feed rate of the return liquid is 5-10 g / min, preferably 7 g / min.

[0167] In the above falling film evaporation, the washed oil phase material is continuously fed into the falling film evaporation unit, the organic solvent and water in the oil phase material are removed by evaporation, and the evaporated oil phase material is continuously discharged. The organic solvent removed in the falling film evaporation is returned to the primary extraction washing tower from the top of the falling film evaporation unit as return liquid.

[0168] The third aspect of the present invention provides an aliphatic epoxy diluent prepared by the above production process.

[0169] In one embodiment, the aliphatic epoxy diluent is selected from at least one of a monoglycidyl ether epoxy diluent, a diglycidyl ether epoxy diluent, or a polyglycidyl ether epoxy diluent, specifically, C 12～14 Alcohol monoglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, octyl glycidyl ether, benzyl glycidyl ether, triethylene glycol diglycidyl ether, glycerol triglycidyl ether.

[0170] The following describes the embodiments of the present invention through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

[0171] In the following examples, the raw materials used are conventional commercially available raw materials in the art unless otherwise specified.

[0172] Example 1

[0173] A continuous production process of epoxy diluent 1,4-butanediol diglycidyl ether, the process adopts the following technical means:

[0174] (1) A continuous etherification reaction was carried out in an etherification reactor (single reaction tube, tube diameter 1 / 8, length 20 m), the feed rate of epichlorohydrin was 5.2 g / min (the feed rate per minute was 5.2 / 92.5=0.0562 mol), the feed rate of 1,4-butanediol was 2.4 g / min, the catalyst was boron trifluoride etherate, the addition amount of which was 0.5 wt % of the feed amount of fatty alcohol, and the catalyst was continuously added into the etherification reactor through a pump for etherification reaction, the reaction temperature was 80° C., the residence time was 35 min, and the etherification reaction material obtained after the reaction was completed was analyzed by gas chromatography, and the conversion rate of epichlorohydrin was ≥99%, and the conversion rate of 1,4-butanediol was ≥99%. The etherification reaction material was continuously introduced into the cyclization reactor.

[0175] (2) Cyclization reaction using a continuous tubular reactor: A continuous etherification cyclization reaction was carried out using a tubular reactor (single reaction tube, tube diameter 1 / 64, length 30 m), the material feed for the first step etherification reaction was 10.7 g / min, and then 15% sodium hydroxide aqueous solution was added at 18.0 g / min (as OH) - The feed per minute is 18*0.15 / 40=0.0675 mol), the feed amount of benzyltriethylammonium chloride in 5%wt benzyltriethylammonium chloride aqueous solution is 0.0480 g / min, which is continuously added into the cyclization reactor through a pump for cyclization reaction, the reaction temperature is 40°C, the residence time is 60 min, the cyclization reaction materials are continuously passed into a continuous phase separator and stay for 30 min to complete liquid-liquid separation after phase separation, the obtained liquid materials are continuously discharged into the extraction scrubber, and the waste materials are discharged.

[0176] (3) After the liquid material is mixed with the return liquid, the return liquid is toluene, the feed rate is 7g / min, and enters the lower part of the primary extraction washing tower. The top passes through the secondary neutralization washing tower and the water phase discharged from the bottom of the tertiary extraction washing tower for countercurrent washing. The water phase in the tower bottom is discharged as waste water. The oil phase at the top of the tower enters the lower part of the secondary neutralization washing tower. The top of the secondary neutralization washing tower passes through 0.8g / min of 5wt% citric acid aqueous solution for countercurrent washing. The bottom water phase material goes to the primary extraction washing tower, and the top oil phase material goes to the lower part of the tertiary extraction washing tower. The top of the tertiary extraction washing tower passes through 0.8g / min of water for countercurrent washing to remove impurities and residues in the oil phase. The pH of the oil phase at the top of the tower is 6.5, and desolventization and water operation are performed. The number of plates of the three-stage extraction tower is 40, and they are all rotary disk extraction towers with a stirring speed of 50r / min.

[0177] (4) Stay in the continuous falling film evaporator for 10 minutes to remove toluene and water: the washed oil phase material enters the first falling film evaporator to remove toluene and water, the operating temperature is 95°C, the operating pressure is 10kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid, the oil phase material in the tower bottom enters the second falling film evaporator to continue to remove toluene, the operating temperature is 140°C, the operating pressure is 2kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid. The bottom of the tower produces 5750 products 1#, the production flow rate is 4.83g / min, the volatile matter is 0.18%, the product epoxy value is 0.80mol / 100g, and the yield is 91.5% (based on 1,4-butanediol).

[0178] During the continuous synthesis process, 5 samples were taken at irregular intervals, and the epoxy values ​​of the samples were 0.80 mol / 100 g, 0.80 mol / 100 g, 0.80 mol / 100 g, 0.80 mol / 100 g and 0.80 mol / 100 g, respectively.

[0179] Example 2

[0180] A continuous production process of epoxy diluent 1,6-hexanediol diglycidyl ether, the process adopts the following technical means:

[0181] (1) A continuous etherification reaction was carried out in an etherification reactor (single reaction tube, tube diameter 1 / 4, length 30 m), epichlorohydrin was fed at 4.1 g / min (feed per minute was 4.1 / 92.5=0.0443 mol), 1,6-hexanediol was fed at 2.4 g / min, and the catalyst was niobium pentachloride, the addition amount of which was 0.5 wt % of the fatty alcohol feed amount, which was continuously added into the etherification reactor by a pump for etherification reaction, the reaction temperature was 100° C., the residence time was 30 min, and the etherification reaction material obtained after the reaction was completed was subjected to gas chromatography analysis and determination, the epichlorohydrin conversion rate was ≥99%, and the 1,6-hexanediol conversion rate was ≥99%. The etherification reaction material was continuously introduced into the cyclization reactor.

[0182] (2) Cyclization reaction using a continuous tubular reactor: A continuous cyclization reaction was carried out using a tubular reactor (single reaction tube, tube diameter 1 / 4, length 30 m), the material for the first step etherification reaction was fed at 6.3 g / min, and then 10% sodium hydroxide aqueous solution was added at 30 g / min (as OH) - The feed per minute is 30*0.10 / 40=0.075 mol), the feed amount of benzyltriethylammonium chloride in 5%wt benzyltriethylammonium chloride aqueous solution is 0.0720 g / min, which is continuously added into the cyclization reactor through a pump for cyclization reaction, the reaction temperature is 45°C, the residence time is 40 min, the cyclization reaction materials are continuously passed into a continuous phase separator for phase separation, and liquid-liquid separation is performed to obtain a liquid material that is continuously discharged into an extraction scrubber, and the liquid waste is discharged.

[0183] (3) After the liquid material is mixed with the return liquid, the return liquid is toluene, the feed rate is 7g / min, and enters the lower part of the primary extraction washing tower, the top passes through the secondary neutralization washing tower and the water phase discharged from the bottom of the tertiary extraction washing tower, and countercurrent washing is performed. The water phase in the tower bottom is discharged as waste water, and the oil phase at the top of the tower enters the lower part of the secondary neutralization washing tower. The top of the secondary neutralization washing tower passes through 0.8g / min of 6wt% citric acid aqueous solution for countercurrent washing. The bottom water phase material goes to the primary extraction washing tower, and the top oil phase material goes to the lower part of the tertiary extraction washing tower. The top of the tertiary extraction washing tower passes through 0.8g / min of water for countercurrent washing to remove impurities and residues in the oil phase. The pH of the oil phase at the top of the tower is 6.5, and desolventization and water operation are performed. The number of plates of the three-stage extraction tower is 40, and they are all rotary disk extraction towers with a stirring speed of 60r / min.

[0184] (4) Stay in the continuous falling film evaporator for 10 minutes to remove toluene and water: the washed oil phase material enters the first falling film evaporator to remove toluene and water, the operating temperature is 100°C, the operating pressure is 20kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid, the oil phase material in the tower bottom enters the second falling film evaporator to continue to remove toluene, the operating temperature is 140°C, the operating pressure is 3kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid. The bottom of the tower produces 1,6-hexanediol diglycidyl ether product 2#, the production flow rate is 4.83g / min, the volatile matter is 0.15%, the product epoxy value is: 0.66mol / 100g, and the yield is 91.1% (based on 1,6-hexanediol). This continuous falling film evaporator has the characteristics of high efficiency and energy saving, and can improve the concentration efficiency and stability of the product.

[0185] During the continuous synthesis process, 5 samples were taken at irregular intervals, and the epoxy values ​​of the samples were 0.66 mol / 100 g, 0.66 mol / 100 g, 0.66 mol / 100 g, 0.66 mol / 100 g and 0.66 mol / 100 g, respectively.

[0186] Example 3

[0187] A continuous production process of epoxy diluent octyl glycidyl ether, the process adopts the following technical means:

[0188] (1) A continuous etherification reaction was carried out in an etherification reactor (single reaction tube, tube diameter 1 / 4, length 25 m), epichlorohydrin was fed at 4.7 g / min (feed per minute was 4.7 / 92.5=0.0508 mol), n-octanol was fed at 6.0 g / min, and the catalyst was tin tetrachloride, the addition amount of which was 0.5 wt % of the fatty alcohol feed amount, which was continuously added into the etherification reactor by a pump for etherification reaction, the reaction temperature was 85° C., the residence time was 30 min, and the etherification reaction material obtained after the reaction was completed was analyzed by gas chromatography, and the epichlorohydrin conversion rate was ≥99%, C 12-14 The alcohol conversion rate is ≥99%. The etherification reaction materials are continuously introduced into the cyclization reactor.

[0189] (2) Cyclization reaction using a continuous tubular reactor: A continuous cyclization reaction was carried out using a tubular reactor (single reaction tube, tube diameter 1 / 6, length 40 m), the material feed for the first step etherification reaction was 10.7 g / min, and then 15% sodium hydroxide aqueous solution was added at 16.3 g / min (as OH) -The feed per minute is 16.3*0.15 / 40=0.0611 mol), the feed amount of benzyltrimethylammonium chloride in 5%wt benzyltrimethylammonium chloride aqueous solution is 0.2406 g / min, which is continuously added into the cyclization reactor by a pump for cyclization reaction, the reaction temperature is 40°C, the residence time is 60 min, the cyclization reaction material is continuously passed into the continuous phase separator and stays for 30 min to complete liquid-liquid separation after phase separation, the obtained liquid material is continuously discharged into the extraction scrubber, and the waste material is discharged.

[0190] (3) After the liquid material is mixed with the return liquid, the return liquid is toluene, the feed rate is 7g / min, and enters the lower part of the primary extraction washing tower. The top passes through the secondary neutralization washing tower and the water phase discharged from the bottom of the tertiary extraction washing tower for countercurrent washing. The water phase in the tower bottom is discharged as waste water. The oil phase material at the top of the tower enters the lower part of the secondary neutralization washing tower. The top of the secondary neutralization washing tower passes through 1.8g / min of 4wt% sodium dihydrogen phosphate aqueous solution for countercurrent washing. The bottom water phase material goes to the primary extraction washing tower, and the top oil phase material goes to the lower part of the tertiary extraction washing tower. The top of the tertiary extraction washing tower passes through 2.4g / min of water for countercurrent washing to remove impurities and residues in the oil phase. The pH of the oil phase at the top of the tower is 7, and desolventization and water operation are performed. The number of plates of the three-stage extraction tower is 30, and they are all rotary disk extraction towers with a stirring speed of 60r / min.

[0191] (4) Stay in the continuous falling film evaporator for 10 minutes to remove toluene and water: The washed oil phase material enters the first falling film evaporator to remove water, the operating temperature is 100°C, the operating pressure is 10kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid, the oil phase material in the tower bottom enters the second falling film evaporator to continue to remove toluene, the operating temperature is 140°C, the operating pressure is 3kPaA, and the toluene at the top of the tower is returned to the first extraction washing tower as return liquid. Octyl glycidyl ether product is extracted from the bottom of the tower, with a volatile matter of 0.19%, a product epoxy value of 0.48 mol / 100g, and a yield of 93.1% (based on n-octanol).

[0192] Example 4

[0193] A continuous production process of epoxy diluent benzyl glycidyl ether, the process adopts the following technical means:

[0194] (1) A continuous etherification reaction was carried out in an etherification reactor (single reaction tube, tube diameter 1 / 4, length 25 m), epichlorohydrin feed 4.4 g / min (feed per minute 4.4 / 92.5 = 0.0476 mol), benzyl alcohol feed 4.3 g / min, catalyst tin tetrachloride, the addition amount of which was 0.4 wt % of the fatty alcohol feed, was continuously added to the etherification reactor by a pump for etherification reaction, reaction temperature 83° C., residence time 27 min, after the reaction was completed, the etherification reaction material obtained was subjected to gas chromatography analysis and determination, epichlorohydrin conversion ≥ 99%, benzyl alcohol conversion ≥ 99%. The etherification reaction material was continuously introduced into the cyclization reactor.

[0195] (2) Cyclization reaction using a continuous tubular reactor: A continuous cyclization reaction was carried out using a tubular reactor (single reaction tube, tube diameter 1 / 64, length 30 m), the material feed for the first step etherification reaction was 8.7 g / min, and then 20% sodium hydroxide aqueous solution was added at 18.1 g / min (as OH - The feed per minute is 18.1*0.20 / 40=0.0905 mol), the feed amount of 18-crown-6 ether in 5% wt 18-crown-6 ether aqueous solution is 0.1286 g / min, which is continuously added into the cyclization reactor by a pump for cyclization reaction. The reaction temperature is 43°C and the residence time is 45 min. The cyclization reaction materials are continuously passed into a continuous phase separator and stay for 30 min to complete liquid-liquid separation after phase separation. The obtained liquid materials are continuously discharged into the extraction scrubber, and the waste materials are discharged.

[0196] (3) After the liquid material is mixed with the return liquid, the return liquid is toluene, the feed rate is 7g / min, and enters the lower part of the primary extraction washing tower, the top passes through the secondary neutralization washing tower and the water phase discharged from the bottom of the tertiary extraction washing tower, and countercurrent washing is performed. The water phase in the tower bottom is discharged as waste water, and the oil phase material at the top of the tower enters the lower part of the secondary neutralization washing tower. The top of the secondary neutralization washing tower passes through 1.7g / min of 5wt% sodium dihydrogen phosphate aqueous solution for countercurrent washing. The bottom water phase material goes to the primary extraction washing tower, and the top oil phase material goes to the lower part of the tertiary extraction washing tower. The top of the tertiary extraction washing tower passes through 1.7g / min of water for countercurrent washing to remove impurities and residues in the oil phase. The pH of the oil phase at the top of the tower is 7, and desolventization and water operation are performed. The number of plates of the three-stage extraction tower is 35, and they are all rotary disk extraction towers with a stirring speed of 58r / min.

[0197] (4) Stay in the continuous falling film evaporator for 10 minutes to remove toluene and water: the washed oil phase material enters the first falling film evaporator to remove water, the operating temperature is 90°C, the operating pressure is 10kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid, the oil phase material in the tower bottom enters the second falling film evaporator to continue to remove toluene, the operating temperature is 140°C, the operating pressure is 3kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid. The benzyl glycidyl ether product is extracted from the bottom of the tower, the volatile matter is 0.19%, the product epoxy value is 0.47mol / 100g, and the yield is 92.4% (calculated as benzyl alcohol).

[0198] Example 5

[0199] A continuous production process of epoxy diluent triethylene glycol diglycidyl ether, the process adopts the following technical means:

[0200] (1) A continuous etherification reaction was carried out in an etherification reactor (single reaction tube, tube diameter 1 / 4, length 20 m), epichlorohydrin feed 5.8 g / min (feed per minute is 5.8 / 92.5=0.0627 mol), triethylene glycol feed 3.6 g / min, the catalyst is boron trifluoride ethyl ether, the addition amount of which is 0.5 wt % of the fatty alcohol feed amount, and the etherification reaction was continuously added to the etherification reactor by a pump to carry out the etherification reaction, the reaction temperature was 87° C., the residence time was 33 min, and the etherification reaction material obtained after the reaction was completed was subjected to gas chromatography analysis and determination, the epichlorohydrin conversion rate was ≥99%, and the triethylene glycol conversion rate was ≥99%. The etherification reaction material was continuously introduced into the cyclization reactor.

[0201] (2) Cyclization reaction using a continuous tubular reactor: A continuous cyclization reaction was carried out using a tubular reactor (single reaction tube, tube diameter 1 / 64, length 35 m), the material feed for the first step etherification reaction was 9.4 g / min, and then 15% sodium hydroxide aqueous solution was added at 30.1 g / min (as OH) - The feed per minute is 30.1*0.15 / 40=0.1129 mol), the feed amount of 15-crown-5 ether in 5%wt 15-crown-5 ether aqueous solution is 0.1448 g / min, which is continuously added into the cyclization reactor by a pump for cyclization reaction, the reaction temperature is 50°C, the residence time is 50 min, the cyclization reaction materials are continuously passed into a continuous phase separator and stay for 40 min to complete liquid-liquid separation after phase separation, the obtained liquid materials are continuously discharged into the extraction scrubber, and the waste materials are discharged.

[0202] (3) After the liquid material is mixed with the return liquid, the return liquid is toluene, the feed rate is 7g / min, and enters the lower part of the primary extraction washing tower, the top passes through the secondary neutralization washing tower and the water phase discharged from the bottom of the tertiary extraction washing tower, and countercurrent washing is performed. The water phase in the tower bottom is discharged as waste water, and the oil phase material at the top of the tower enters the lower part of the secondary neutralization washing tower. The top of the secondary neutralization washing tower passes through 1.4g / min of 6wt% acetic acid aqueous solution for countercurrent washing. The bottom water phase material goes to the primary extraction washing tower, and the top oil phase material goes to the lower part of the tertiary extraction washing tower. The top of the tertiary extraction washing tower passes through 1.1g / min of water for countercurrent washing to remove impurities and residues in the oil phase. The pH of the oil phase at the top of the tower is 6.8, and desolventization and water operation are performed. The number of plates of the three-stage extraction tower is 45, and they are all rotary disk extraction towers with a stirring speed of 52r / min.

[0203] (4) Stay in the continuous falling film evaporator for 10 minutes to remove toluene and water: the washed oil phase material enters the first falling film evaporator to remove water, the operating temperature is 100°C, the operating pressure is 20kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid, the oil phase material in the tower bottom enters the second falling film evaporator to continue to remove toluene, the operating temperature is 140°C, the operating pressure is 2kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid. The bottom of the tower produces triethylene glycol diglycidyl ether product, with a volatile matter of 0.14%, a product epoxy value of 0.60 mol / 100g, and a yield of 91.8% (based on triethylene glycol).

[0204] Example 6

[0205] A continuous production process of epoxy diluent glycerol triglycidyl ether, the process adopts the following technical means:

[0206] (1) A continuous etherification reaction was carried out in an etherification reactor (single reaction tube, tube diameter 1 / 4, length 30 m), epichlorohydrin feed 7.8 g / min (feed per minute is 7.8 / 92.5=0.0843 mol), glycerol feed 1.6 g / min, catalyst is niobium pentachloride, the addition amount is 0.5 wt% of the fatty alcohol feed amount, and it is confirmed that the etherification reaction is continuously added into the etherification reactor by a pump, the reaction temperature is 85° C., the residence time is 30 min, and the etherification reaction material obtained after the reaction is completed is analyzed by gas chromatography, and the epichlorohydrin conversion rate is ≥99%, and the glycerol conversion rate is ≥99%. The etherification reaction material is continuously introduced into the cyclization reactor.

[0207] (2) Cyclization reaction using a continuous tubular reactor: A continuous cyclization reaction was carried out using a tubular reactor (single reaction tube, tube diameter 1 / 64, length 25 m), the material for the first step etherification reaction was fed at 9.0 g / min, and then 20% sodium hydroxide aqueous solution was added at 25.6 g / min (as OH) -The feed per minute is 25.6*0.20 / 40=0.128 mol), the feed amount of benzyltriethylammonium chloride in 5%wt benzyltriethylammonium chloride aqueous solution is 0.0327 g / min, which is continuously added into the cyclization reactor by a pump for cyclization reaction, the reaction temperature is 47°C, the residence time is 30 min, the cyclization reaction materials are continuously passed into the continuous phase separator and stay for 45 min to complete liquid-liquid separation after phase separation, the obtained liquid materials are continuously discharged into the extraction scrubber, and the waste materials are discharged.

[0208] (3) After the liquid material is mixed with the return liquid, the return liquid is toluene, the feed rate is 6g / min, and enters the lower part of the primary extraction washing tower, the top passes through the secondary neutralization washing tower and the water phase discharged from the bottom of the tertiary extraction washing tower, and countercurrent washing is performed. The water phase in the tower bottom is discharged as waste water, and the oil phase material at the top of the tower enters the lower part of the secondary neutralization washing tower. The top of the secondary neutralization washing tower passes through 0.7g / min of 5wt% acetic acid aqueous solution for countercurrent washing. The bottom water phase material goes to the primary extraction washing tower, and the top oil phase material goes to the lower part of the tertiary extraction washing tower. The top of the tertiary extraction washing tower passes through 0.7g / min of water for countercurrent washing to remove impurities and residues in the oil phase. The pH of the oil phase at the top of the tower is 6.7, and desolventization and water operation are performed. The number of plates of the three-stage extraction tower is 50, and they are all rotary disk extraction towers with a stirring speed of 50r / min.

[0209] (4) Stay in the continuous falling film evaporator for 10 minutes to remove moisture: the washed oil phase material enters the first falling film evaporator to remove moisture, the operating temperature is 100°C, the operating pressure is 10kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid, the oil phase material in the tower bottom enters the second falling film evaporator to continue to remove toluene, the operating temperature is 140°C, the operating pressure is 2kPaA, the toluene at the top of the tower is returned to the first extraction washing tower as return liquid. The glycerol triglycidyl ether product is extracted from the tower bottom, the volatile matter is 0.15%, the product epoxy value is: 0.69mol / 100g, and the yield is 91.4% (based on glycerol).

[0210] Comparative Example 1

[0211] The process and conditions for preparing aliphatic epoxy diluents in the prior art to obtain product 1*. The intermittent process operating conditions are as follows: 131.88 g (1.463 mol) of 1,4-butanediol is added to a three-necked glass reaction bottle with a mechanical stirrer, a thermometer, and a balanced dropping funnel, and then 0.35 mL of boron trifluoride ether solution is added with a syringe, and the temperature is heated to 50°C under mechanical stirring (heating for 0.5 h), and 281.57 g (3.043 mol) of epichlorohydrin is slowly added dropwise, and a cold water bath is used to cool the internal temperature at any time during the addition process so that the internal temperature does not exceed 60°C (dropping time 1.5 h), and the reaction is continued at 60-65°C for 3 hours after the addition. After the reaction is completed, the gas chromatography analysis shows that the conversion rate of epichlorohydrin is ≥99%, and the conversion rate of 1,4-butanediol is ≥99%.

[0212] The reaction materials were cooled to room temperature, 200 mL of toluene and 0.26 g of benzyltriethylammonium chloride were added to the reaction system through a balanced dropping funnel, and 284.85 g (3.561 mol) of 50% sodium hydroxide solution was added dropwise under strong mechanical stirring (addition time 1.5 h). After the addition was completed, the mixture was kept warm at 40°C for 3 h. After the reaction is completed, the following post-treatment is performed (post-treatment operation time 0.5h): filter out the generated sodium chloride solid, rinse the filter cake with a small amount of toluene, drain, and perform liquid separation operation on the filtrate to separate the lower layer of saline water. The upper organic phase is first washed once with 100mL deionized water, then washed once with a solution of 3.3g citric acid and 50mL water, and finally washed once with 100mL deionized water. The organic phase of the deionized phase is directly subjected to reduced pressure rotary evaporation to evaporate the solvent (rotary evaporation solvent removal operation time 3h), and finally 5750 product 1*250g is obtained, with a yield of 84.53% (based on 1,4-butanediol) and an epoxy value of 0.77mol / 100g. Among them, the total operation time of the intermittent operation is 13h, and the average product output per unit time is 0.32g / min.

[0213] Four batches of products were synthesized according to the above synthesis method, and the epoxy values ​​of the products were 0.76 mol / 100 g, 0.78 mol / 100 g, 0.75 mol / 100 g and 0.77 mol / 100 g, respectively.

[0214] Comparative Example 2

[0215] The process and conditions for preparing aliphatic epoxy diluents in the prior art to obtain product 2*. The intermittent process operating conditions are as follows: 240g (2.031mol) of 1,6-hexanediol is added to a three-necked glass reaction bottle with mechanical stirring, a thermometer, and a balanced dropping funnel, and then 1.2g of boron trifluoride ether solution is added with a syringe, and the temperature is heated to 55°C under mechanical stirring (heating for 0.4h), and 390g (4.215mol) of epichlorohydrin is slowly added dropwise. During the dropping process, a cold water bath is used to cool the internal temperature at any time so that the internal temperature does not exceed 65°C (dropping time 2h), and the reaction is continued at 60-65°C for 3 hours after the dropping. After the reaction is completed, the gas chromatography analysis shows that the conversion rate of epichlorohydrin is ≥99%, and the conversion rate of 1,6-hexanediol is ≥99%.

[0216] The reaction materials were cooled to room temperature, 630 mL of toluene and 4.8 g of benzyltriethylammonium chloride were added to the reaction system through a balanced dropping funnel, and 607 g (7.588 mol) of 50% sodium hydroxide solution was added dropwise under strong mechanical stirring (addition time 2 h). After the addition was completed, the mixture was kept warm at 40°C for 3 h. After the reaction is completed, the following post-treatment is performed (post-treatment operation time 1h): filter out the generated sodium chloride solid, rinse the filter cake with a small amount of toluene, drain, and perform liquid separation operation on the filtrate to separate the lower layer of saline water. The upper organic phase is first washed once with 250mL deionized water, then washed once with a solution of 7.3g citric acid and 100mL water, and finally washed once with 250mL deionized water. The organic phase of the deionized phase is directly subjected to reduced pressure rotary evaporation to evaporate the solvent (rotary evaporation desolventizing operation time 3h), and finally 1,6-hexanediol diglycidyl ether product 2*480g is obtained, with a yield of 86.13% (based on 1,6-hexanediol) and an epoxy value of 0.63mol / 100g. Among them, the total operation time of the intermittent operation is 14.4h, and the average product output per unit time is 0.55g / min.

[0217] Four batches of products were synthesized according to the above synthesis method, and the epoxy values ​​of the products were 0.61 mol / 100 g, 0.64 mol / 100 g, 0.62 mol / 100 g and 0.63 mol / 100 g, respectively.

[0218] Comparative test example 1

[0219] The product 1# obtained in Example 1 was compared with the product 1* obtained in Comparative Example 1, and the specific test results are shown in Tables 1 and 2. Among them, the batch operation kettle is 1L, and the liquid holding volume of the continuous etherification reactor is 220ml. It can be seen from Table 1 that the efficiency of the continuous process production product 1# is significantly improved compared with the product 1* produced by the batch process, the product yield is improved, the epoxy value is also improved, and the amount of washing water is greatly reduced. It can be seen from Table 2 that the stability of the product quality of the continuous process production product 1# is significantly improved compared with the product 1* produced by the batch process.

[0220] Table 1

[0221]

[0222]

[0223] Table 2

[0224] batch 1 2 3 4 5 Example 1 Epoxy value mol / 100g 0.8 0.8 0.8 0.8 0.8 Comparative Example 1 Epoxy Value mol / 100g 0.77 0.76 0.78 0.75 0.77

[0225] Comparative Test Example 2

[0226] The product 2# obtained in Example 2 was compared with the product 2* obtained in Comparative Example 2, and the specific test results are shown in Tables 3 and 4. Among them, the batch operation kettle is 1L, and the liquid holding volume of the continuous etherification reactor is 220ml. It can be seen from Table 3 that the efficiency of the continuous process production of product 2# is significantly improved compared with the product 2* produced by the batch process, the product yield is improved, the epoxy value is also improved, and the amount of washing water is greatly reduced. It can be seen from Table 4 that the stability of the product quality of the continuous process production of product 2# is significantly improved compared with the product 2* produced by the batch process.

[0227] Table 3

[0228] project Example 2 Comparative Example 2 Epichlorohydrin conversion rate % 99 99 1,6-Hexanediol conversion rate % 99 99 Epoxy value mol / 100g 0.66 0.63 Yield % 91.1 86.13 Product output per unit time g / min 4.83 0.55 Washing water volume% (based on 1,6-hexanediol) 66.6％ 250％

[0229] Table 4

[0230] batch 1 2 3 4 5 Example 2 Epoxy value mol / 100g 0.66 0.66 0.66 0.66 0.66 Comparative Example 2 Epoxy Value mol / 100g 0.63 0.61 0.64 0.62 0.63

[0231] The above is only a preferred embodiment of the present invention, and is not any formal or substantial limitation of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and supplements without departing from the method of the present invention, and these improvements and supplements should also be regarded as the protection scope of the present invention. Any technician familiar with this profession, without departing from the spirit and scope of the present invention, can make some changes, modifications and evolutions of the technical content disclosed above, which are equivalent embodiments of the present invention; at the same time, any changes, modifications and evolutions of any equivalent changes made to the above embodiments based on the essential technology of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A full-process continuous production system for aliphatic epoxy diluent, characterized in that: It comprises an etherification reactor, a cyclization reactor, a phase separation component, an extraction scrubber and a falling film evaporator. The etherification reactor, the cyclization reactor, the phase separation component, the extraction scrubber and the falling film evaporator are sequentially connected via pipelines along the production route. The falling film evaporator is also connected to the phase separation component via a pipeline.

2. The full-process continuous production system of aliphatic epoxy diluent according to claim 1, characterized in that: Includes any one or more of the following conditions: A1) the etherification reactor is a reaction tube; A2) the etherification reactor is provided with a heat transfer oil input pipe and a heat transfer oil output pipe; A3) the etherification reactor is provided with a reaction material input pipe; A4) the etherification reactor is connected with the cyclization reactor via a first connecting pipe; A5) the cyclization reactor is a reaction tube; A6) the phase separation component is a phase splitter; A7) the cyclization reactor is connected with the phase separation component via a second connecting pipe; A8) the phase separation component is connected to the extraction scrubber via a third connecting pipe; A9) the extraction scrubber comprises a primary extraction scrubber, a secondary neutralization scrubber, and a tertiary extraction scrubber connected in series; A10) the extracting scrubber is connected to the falling film evaporator via a fourth connecting pipe; A11) The falling film evaporator comprises a plurality of falling film evaporation units connected in series.

3. The full-process continuous production system of aliphatic epoxy diluent according to claim 2, characterized in that: Also includes any one or more of the following conditions: A11) The diameter of the reaction tube of the etherification reactor is 1 / 10-1 / 2; A12) the reaction tube length of the etherification reactor is 15-100m; A21) the heat transfer oil output pipe is arranged at the reaction input end of the etherification reactor, and the heat transfer oil input pipe is arranged at the reaction output end of the etherification reactor; A31) one end of the reaction material input pipe is connected to the reaction input end of the etherification reactor, and the other end of the reaction material input pipe is connected to the epoxy material feed pipe, the fatty alcohol feed pipe, and the first catalyst feed pipe; A41) the first connecting pipe is connected with a liquid alkali feeding pipe and a second catalyst feeding pipe; A42) the first connecting pipe is connected to the material input end of the cyclization reactor; A51) The diameter of the reaction tube of the cyclization reactor is 1 / 10-1 / 2; A52) the reaction tube length of the cyclization reactor is 25-100m; A53) The reaction tube of the cyclization reactor is provided with a circulating water inlet pipe and a circulating water outlet pipe; A61) the phase separator is connected to a sodium chloride liquid output pipe; A71) one end of the second connecting pipe is connected to the material output end of the cyclization reactor, and the other end of the second connecting pipe is connected to the input end of the phase separation component; A81) the output end of the phase separation component is connected to the input end of the primary extraction washing tower via the third connecting pipe; A91) The number of plates of the first-stage extraction washing tower, the second-stage neutralization washing tower, and the third-stage extraction washing tower are all 30-50; A92) The bottom of the primary extraction and washing tower is also connected to a wastewater discharge pipe; A93) the top of the primary extraction washing tower is connected to the lower part of the secondary neutralization washing tower via the first oil phase output pipe; A94) the top of the secondary neutralization washing tower is connected to the lower part of the tertiary extraction washing tower via the second oil phase output pipe; A95) the bottom of the secondary neutralization washing tower is connected to a first water phase output pipe, the bottom of the tertiary extraction washing tower is connected to a second water phase output pipe, the first water phase output pipe and the second water phase output pipe are connected to one end of a countercurrent washing pipe, and the other end of the countercurrent washing pipe is connected to the upper part of the primary extraction washing tower; A96) the upper portion of the secondary neutralization washing tower is connected to a second washing solvent inlet pipe; A97) the upper portion of the three-stage extraction washing tower is connected to a third washing solvent inlet pipe; A101) one end of the fourth connecting pipe is connected to the top of the three-stage extraction washing tower, and the other end of the fourth connecting pipe is connected to the falling film evaporator; A111) the falling film evaporation units of the plurality of stages are connected to a portion of the third connecting pipe close to the phase separation component via a liquid return pipe; A112) The number of series connection stages of the falling film evaporation unit is not less than 2.

4. The full-process continuous production system of aliphatic epoxy diluent according to claim 3, characterized in that: Also includes any one or more of the following conditions: A211) the reaction input end is located at an end away from the end connecting the etherification reactor and the cyclization reactor, and the reaction output end is located at an end close to the end connecting the etherification reactor and the cyclization reactor; A411) the connecting ends of the liquid caustic soda feed pipe, the second catalyst feed pipe and the first connecting pipe are close to the cyclization reactor; A531) the circulating water output pipe is arranged at the reaction input end of the reaction tube, and the circulating water input pipe is arranged at the reaction output end of the reaction tube; A611) the sodium chloride liquid output pipe is arranged at the lower part of the phase separator; A811) the input end of the primary extraction and washing tower is located at the lower part of the primary extraction and washing tower; A1121) When the number of series-connected stages of the falling film evaporation unit is 2, the falling film evaporator comprises a first-level falling film evaporation unit and a second-level falling film evaporation unit connected in series in sequence; the middle part of the first-level falling film evaporation unit is connected to one end of the fourth connecting pipe; the first-level falling film evaporation unit is connected to the second-level falling film evaporation unit via the fifth connecting pipe; the second-level falling film evaporation unit is connected with a product output pipe; the liquid return pipe comprises a first liquid return branch pipe, a second liquid return branch pipe, and a liquid return main pipe, one end of the first liquid return branch pipe is connected to the top of the first-level falling film evaporation unit, one end of the second liquid return branch pipe is connected to the top of the second falling film evaporation unit, the other end of the first liquid return branch pipe and the other end of the second liquid return branch pipe are connected to one end of the liquid return main pipe, and the other end of the liquid return main pipe is connected to the input end of the phase separation component.

5. A full-process continuous production process of an aliphatic epoxy diluent, using the full-process continuous production system of an aliphatic epoxy diluent according to any one of claims 1 to 4, comprising the following steps: 1) subjecting the epoxy material to an etherification reaction with a fatty alcohol to obtain an etherification reaction material; 2) subjecting the etherification reaction product to a cyclization reaction with a base, and performing phase separation on the obtained cyclization reaction material to obtain a liquid material and a waste material; 3) washing the liquid material in countercurrent to separate the phases, and obtaining an oil phase material and a water phase material; 4) The oil phase material is subjected to falling film evaporation to remove the organic solvent and water to provide the desired reaction product.

6. The full-process continuous production process of aliphatic epoxy diluent according to claim 5, characterized in that: The full-process continuous production process of the aliphatic epoxy diluent adopts the full-process continuous production system of the aliphatic epoxy diluent according to any one of claims 1 to 4, comprising the following steps: 11) In step 1), the epoxy material and the fatty alcohol are subjected to an etherification reaction in an etherification reactor to obtain an etherification reaction material; 21) In step 2), the etherification reaction product is subjected to a cyclization reaction with a base in a cyclization reactor, and the obtained cyclization reaction material is separated in a phase separation component to obtain a liquid material and a waste material; 31) In step 3), the liquid material is subjected to countercurrent washing in an extraction scrubber to separate the phases, thereby obtaining an oil phase material and an aqueous phase material; 41) In step 4), the oil phase material is subjected to falling film evaporation in a falling film evaporator to remove the organic solvent and water to provide the desired reaction product.

7. The full-process continuous production process of aliphatic epoxy diluent according to any one of claims 5 or 6, characterized in that: Includes any one or more of the following conditions: B1) In step 1), the epoxy material is epichlorohydrin; B2) In step 1), the fatty alcohol is an alcohol containing at least one hydroxyl group; B3) In step 1), the molar ratio of the epoxy material to the fatty alcohol added per minute is (1-1.5)n:1; B4) in step 1), a first catalyst is further added to the etherification reaction; B5) In step 1), the reaction temperature of the etherification reaction is 70-110°C; B6) In step 1), the reaction time of the etherification reaction is 20-40 min; B7) in step 2), the base is an aqueous sodium hydroxide solution; B8) In step 2), the molar ratio of the base to the epoxy material added per minute is 1 to 2:1; B9) In step 2), a phase transfer catalyst is also added to the cyclization reaction; B10) in step 2), the reaction time of the cyclization reaction is 30-120 min; B11) In step 2), the reaction temperature of the cyclization reaction is 20-60°C; B12) in step 3), the first washing solvent for countercurrent washing of the liquid material in the primary extraction washing tower is the bottom aqueous phase in the secondary neutralization washing tower and the tertiary extraction washing tower; B13) in step 3), the second washing solvent for countercurrent washing of the liquid material in the secondary neutralization washing tower is a weak acid aqueous solution; B14) in step 3), the third washing solvent for countercurrent washing of the liquid material in the three-stage extraction washing tower is water; B15) In step 3), the pH value of the oil phase material at the top of the three-stage extraction washing tower is 5-7; B16) In step 3), the stirring speed in the primary extraction washing tower, the secondary neutralization washing tower, and the tertiary extraction washing tower is 10-100 r / min; B17) In step 4), the residence time of the falling film evaporation is 8 to 12 minutes; B18) In step 4), when the number of series-connected falling film evaporation units is 2, the operating temperature of the oil phase material in the first falling film evaporation unit is 85-105° C.; B19) In step 4), when the number of series-connected falling film evaporation units is 2, the operating pressure of the oil phase material in the first falling film evaporation unit is 8-30 kPaA; B20) In step 4), when the number of series connection of the falling film evaporation unit is 2, the operating temperature of the oil phase material in the secondary falling film evaporation unit is 130-150° C.; B21) In step 4), when the number of series-connected falling film evaporation units is 2, the operating pressure of the oil phase material in the two-stage falling film evaporation unit is 1-5 kPaA; B22) In step 4), the organic solvent is toluene; B23) In step 4), the organic solvent is returned as a return liquid to step 3) and mixed with the liquid material, and then subjected to countercurrent washing to separate the phases.

8. The full-process continuous production process of aliphatic epoxy diluent according to claim 7, characterized in that: Also includes any one or more of the following conditions: B301) When the fatty alcohol is a monohydric alcohol, the molar ratio of the epoxy material to the fatty alcohol added per minute is 1.1-1.5:1; when the fatty alcohol is a polyhydric alcohol, the molar ratio of the epoxy material to the fatty alcohol added per minute is (1-1.5)n:1; B401) the first catalyst is selected from at least one of boron trifluoride etherate, aluminum trichloride, tin tetrachloride, and niobium pentachloride; B402) the first catalyst is added in an amount of 0.1-1wt% of the fatty alcohol feed; B701) The mass percentage concentration of the sodium hydroxide aqueous solution is 5-25%; B801) When the fatty alcohol is a monohydric alcohol, the molar ratio of the base to the epoxy material added per minute is 1.2 to 2:1; when the fatty alcohol is a polyhydric alcohol, the molar ratio of the base to the epoxy material added per minute is 1 to 1.8:1; B901) the phase transfer catalyst is selected from at least one of benzyltriethylammonium chloride, benzyltrimethylammonium chloride or crown ether; B902) the phase transfer catalyst is added in an amount of 1 to 10 wt% of the fatty alcohol feed; B1301) the second washing solvent is selected from at least one of a citric acid aqueous solution, a sodium dihydrogen phosphate solution or an acetic acid aqueous solution; preferably, in the citric acid aqueous solution, the sodium dihydrogen phosphate solution or the acetic acid aqueous solution, the concentration of the citric acid, the sodium dihydrogen phosphate solution or the acetic acid is 1-10wt%; B1302) the mass ratio of the flow rate of the second washing solvent to the feed amount of the fatty alcohol is 0.1 to 1:1; B1401) the mass ratio of the flow rate of the third washing solvent to the feed amount of the fatty alcohol is 0.1 to 1:1; B2301) the organic solvent is returned as a return liquid to step 3) and mixed with the liquid material, and then subjected to countercurrent washing in an extraction scrubber to separate the phases; B2302) The feed rate of the return liquid is 5-10g / min.

9. An aliphatic epoxy diluent prepared by the full-process continuous production process of an aliphatic epoxy diluent according to any one of claims 5 to 8.

10. The aliphatic epoxy diluent according to claim 9, characterized in that The aliphatic epoxy diluent is selected from at least one of monoglycidyl ether epoxy diluent, diglycidyl ether epoxy diluent or polyglycidyl ether epoxy diluent.

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