CN112076700A - Esterification kettle and application method thereof - Google Patents
Esterification kettle and application method thereof Download PDFInfo
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- CN112076700A CN112076700A CN201911110379.0A CN201911110379A CN112076700A CN 112076700 A CN112076700 A CN 112076700A CN 201911110379 A CN201911110379 A CN 201911110379A CN 112076700 A CN112076700 A CN 112076700A
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Abstract
The invention relates to an esterification kettle and an application method thereof.A steam alcohol pipe is arranged in an esterification kettle body, the upper end opening of the steam alcohol pipe is positioned at the top of the esterification kettle body, the lower end of the steam alcohol pipe is provided with a hook-shaped nozzle with an upward opening, a steam-liquid circulating pipe is communicated in a hanging manner above the opening of the hook-shaped nozzle, and a first hood is arranged in a hanging manner above the steam-liquid circulating pipe; the upper end part of the body is provided with a steam distributor comprising a drainage disc, a plurality of through pipes and drainage ports, a second hood is arranged above the through pipes in a hanging way, the lower ends of the drainage ports are connected with a coarse ester downpipe, and the lower end part of the coarse ester downpipe is a hook-shaped drainage outlet which is simultaneously communicated with the lower end opening of the steam-liquid circulating pipe and the inside of the body in a hanging way. Compared with the prior art, the method has the advantages that isooctanol vapor in the esterification kettle body rises to the esterification tower above the esterification kettle body to realize continuous esterification reaction with oleic acid, so that the purposes of high yield, simple operation, full utilization of material heat, low cost, material waste avoidance and the like are realized.
Description
Technical Field
The invention relates to the technical field of isooctyl oleate preparation, in particular to an esterification kettle for synthesizing isooctyl oleate and an application method thereof.
Background
Isooctyl oleate is obtained by esterifying animal and vegetable oleic acid and isooctyl alcohol, is an intermediate for synthesizing epoxy octyl oleate, is also used as a main additive of lubricating grease, and is widely applied because of good low-temperature property, high-temperature stability, environmental friendliness and no harm to human bodies; wherein the esterification reaction formula of the isooctyl oleate is as follows:
specifically, the esterification process of oleic acid and isooctyl alcohol is generally intermittent, the molar ratio of alcohol to acid is 1.2:1, the mixture is heated to about 160 ℃ in the presence of an acid catalyst (concentrated sulfuric acid, p-toluenesulfonic acid and the like), stirred for 4-6 hours, water generated by the esterification reaction is evaporated, and the finished product is obtained after the procedures of neutralization, water washing, decoloration and the like. However, the batch esterification method has a plurality of disadvantages: the method needs repeated operation of a single kettle, has low yield, complex production operation, incapability of fully utilizing heat and high production cost.
In order to solve the technical problems, continuous esterification of oleic acid and isooctanol is realized by a vapor-liquid countercurrent mode, and an esterification kettle is needed to be provided, so that isooctanol vapor in an esterification kettle body rises to an esterification tower above the esterification kettle body to realize continuous esterification reaction with oleic acid, and the purposes of high yield, simple operation, full utilization of material heat, low cost, material waste avoidance and the like are achieved.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides the esterification kettle for synthesizing isooctyl oleate and the application method thereof, so that isooctyl alcohol gas in the esterification kettle body rises to the esterification kettle positioned above the esterification kettle to realize continuous esterification reaction with oleic acid, and the purposes of high yield, simple operation, full utilization of material heat, low cost, material waste avoidance and the like are realized.
The technical scheme of the invention is realized as follows:
an esterification kettle comprises an esterification kettle body, wherein an alcohol steam pipe is arranged in the esterification kettle body, the upper end opening of the alcohol steam pipe is positioned at the top of the esterification kettle body, the lower end of the alcohol steam pipe is provided with a hook-shaped nozzle with an upward opening, a vapor-liquid circulating pipe is communicated above the opening of the hook-shaped nozzle in a hanging manner, and a first hood is also arranged above the vapor-liquid circulating pipe in a hanging manner; the steam distributor is characterized in that a steam distributor which is communicated up and down, inside and outside is arranged at the upper end of the body, the steam-liquid circulating pipe and the first hood are located below the steam distributor, the steam distributor comprises a drainage disc, a plurality of through pipes penetrating the drainage disc and drainage ports arranged in the middle of the drainage disc, a second hood is arranged above each through pipe in a hanging mode, a coarse ester downpipe is connected to the lower end of each drainage port, the lower end of each coarse ester downpipe is a hook-shaped drainage outlet facing the lower end opening of the steam-liquid circulating pipe, and the hook-shaped drainage outlet is communicated with the lower end opening of the steam-liquid circulating pipe and the inside of the body in a hanging mode.
According to the invention, isooctanol is in a gas state through external treatment, isooctanol gas sequentially enters an alcohol steam pipe, a vapor-liquid circulating pipe and a vapor distributor and then rises into an esterification tower with built-in oleic acid, the rising isooctanol gas and the oleic acid are in full and repeated contact, an esterification reaction is carried out under the action of a catalyst, the generated isooctyl oleate and unreacted oleic acid flow into an esterification kettle body through a drainage port until the generated isooctyl oleate flows to a hook-shaped drainage outlet and the lower part in the esterification kettle body, and the hook-shaped drainage outlet is communicated with an opening at the lower end of the vapor-liquid circulating pipe at the same time, so that unreacted oleic acid can further react with the isooctanol gas at the opening at the lower end of the vapor-liquid circulating pipe, the full reaction of the isooctanol gas and the oleic acid is further realized, the continuous esterification is realized through repeated circulation, the reaction is full and efficient; in addition, the arrangement of the first hood is convenient for isooctanol gas to rise upwards along the outer periphery of the first hood and enter the esterification tower, so that the dispersibility of the isooctanol gas is ensured, and the sufficient reaction with oleic acid is facilitated; it should be noted that the fact that the steam-liquid circulating pipe is communicated with the opening of the hook-shaped nozzle in a suspended manner means that the steam-liquid circulating pipe is arranged in a suspended manner and is not in contact with the opening of the hook-shaped nozzle in a suspended manner, the steam-liquid circulating pipe can be connected with the inner wall of the esterification kettle body through a connecting piece through the outer wall of the steam-liquid circulating pipe, similarly, the fact that the first hood is arranged above the steam-liquid circulating pipe in a suspended manner, the fact that the second hood is arranged above the through pipe in a suspended manner means that a large gap is reserved between the steam-liquid circulating pipe and the first hood, and between the through pipe and the second hood, the gaps can be connected through a connecting column, the stability of the first hood and the second hood is guaranteed, and the isooctanol gas is dispersed and.
Preferably, the vapor-liquid circulating pipe and the first hood are positioned right below the vapor distributor, wherein the centers of the drainage openings and the centers of the openings at the upper ends of the vapor-liquid circulating pipe are positioned on the same longitudinal axis.
Further ensure that the isooctanol gas can enter the through pipe on the gas distributor uniformly and dispersedly, and improve the reaction efficiency.
Preferably, the lower end of the vapor-liquid circulation pipe is opened in a downward-opening trumpet shape.
Because the lower end opening of the vapor-liquid circulating pipe is simultaneously suspended and communicated with the hook-shaped nozzle and the hook-shaped drainage outlet, a larger horn-shaped opening is needed to ensure that isooctanol gas in the hook-shaped nozzle enters the vapor-liquid circulating pipe and unreacted oleic acid at the hook-shaped drainage outlet is in contact reaction with the isooctanol gas at the lower end opening of the vapor-liquid circulating pipe and the hook-shaped nozzle.
Preferably, the upper surface of the drainage tray is low inside and high outside, and the drainage port of the drainage tray is positioned at the lowest position and at the middle position of the drainage tray.
The obtained isooctyl oleate crude ester and unreacted oleic acid can be more efficiently drained to the drainage port and then flow into the crude ester down-flow pipe.
Preferably, the plurality of through tubes are circumferentially arranged around the drainage opening.
The through pipe is dispersed around the drainage port, so that the rising isooctanol vapor is uniformly dispersed, the full reaction with oleic acid is ensured, and the efficiency is high.
Preferably, the pipe diameter of the through pipe is smaller than that of the crude ester downpipe and that of the vapor-liquid circulating pipe.
The pipe diameter of the through pipe is small, so that isooctyl alcohol gas can be further dispersed conveniently, the pipe diameter of the crude ester downflow pipe is large, so that isooctyl oleate crude ester and unreacted oleic acid can smoothly flow downwards without resistance conveniently, and more isooctyl alcohol gas can conveniently rise conveniently, and the production efficiency is improved.
Preferably, the alcohol steam pipe comprises a first vertical pipe, a horizontal pipe and a second vertical pipe which are connected end to end from top to bottom, the vapor-liquid circulating pipe is a third vertical pipe, and the crude ester downpipe comprises a first inclined pipe, a fourth vertical pipe and a hook-shaped drainage outlet which are connected end to end from top to bottom.
Clearly illustrating the structure of the alcohol steam pipe, the vapor-liquid circulating pipe and the crude ester downpipe.
Preferably, a heat conducting coil is arranged at the inner lower part of the body.
Heat is provided for the crude isooctyl oleate obtained by esterification.
Preferably, an overflow pipe is arranged beside the body, an opening at the upper end of the overflow pipe is communicated with the top of the body, an opening at the lower end of the overflow pipe is communicated with the bottom of the body, and a crude ester overflow outlet is formed in the overflow pipe.
The overflow pipe can guarantee on the one hand that the internal pressure of esterification reactor body is unanimous, keeps the crude ester liquid level of isooctyl oleate stable, and on the other hand can flow into external storage tank with the crude ester that the esterification obtained.
Preferably, the upper end opening of the alcohol steam pipe is communicated with an external isooctanol preheater.
The isooctanol preheater is convenient for convert isooctanol into gas, and the isooctanol gas enters the esterification kettle body through the alcohol steam pipe.
The application method of the esterification kettle comprises the steps that an esterification tower is arranged right above the esterification kettle, a tower top distributor connected with oleic acid feeding is arranged above the esterification tower, a plurality of corrugated fillers arranged up and down are arranged below the tower top distributor, a heater is arranged between every two adjacent corrugated fillers, and the top of the esterification tower is communicated with an alcohol-water separation device positioned outside; when the device works, oleic acid feed and isooctyl alcohol enter an esterification tower, wherein the oleic acid feed enters a tower top distributor, so that the oleic acid flows downwards along the surface of the corrugated packing; the isooctanol in a steam state sequentially enters an alcohol steam pipe, a steam-liquid circulating pipe and a steam distributor and rises to the corrugated packing, the rising isooctanol steam is fully and repeatedly contacted with oleic acid flowing downwards on the surface of the corrugated packing, esterification reaction is carried out under the action of a catalyst, the generated isooctyl oleate and unreacted oleic acid flow downwards together and flow to an esterification kettle through a drainage port until the isooctyl oleate flows to a hook-shaped drainage outlet and the lower part in the esterification kettle, wherein the unreacted oleic acid can react with the isooctanol steam at the lower end opening of the steam-liquid circulating pipe, the steam-state water generated by the esterification reaction and the unreacted isooctanol steam continuously rise to the top of an esterification tower together and enter an alcohol-water separation device, water is discharged out of a system, and anhydrous isooctanol flows back to the esterification kettle again, so that the continuous esterification is realized through repeated circulation.
The beneficial effects of the invention adopting the technical scheme are as follows:
the invention provides an esterification kettle, which enables isooctanol gas in an esterification kettle body to rise to an esterification kettle positioned above the esterification kettle body to realize continuous esterification reaction with oleic acid, so that the purposes of high yield, simple operation, full utilization of material heat, low cost, material waste avoidance and the like are realized.
According to the invention, isooctanol is in a gas state through external treatment, isooctanol gas sequentially enters an alcohol steam pipe, a vapor-liquid circulating pipe and a vapor distributor and then rises into an esterification tower with built-in oleic acid, the rising isooctanol gas and the oleic acid are in full and repeated contact, an esterification reaction is carried out under the action of a catalyst, the generated isooctyl oleate and unreacted oleic acid flow into an esterification kettle body through a drainage port until the generated isooctyl oleate flows to a hook-shaped drainage outlet and the lower part in the esterification kettle body, and the hook-shaped drainage outlet is communicated with an opening at the lower end of the vapor-liquid circulating pipe at the same time, so that unreacted oleic acid can further react with the isooctanol gas at the opening at the lower end of the vapor-liquid circulating pipe, the full reaction of the isooctanol gas and the oleic acid is further realized, the continuous esterification is realized through repeated circulation, the reaction is full and efficient; the invention continuously feeds and discharges materials, fully exchanges and utilizes the heat of the materials, automatically controls the heating temperature, has high yield and low cost, and is verified that the ton labor cost of the product is reduced by more than 60 percent and the energy consumption is reduced by about 40 percent.
Drawings
FIG. 1 is a schematic diagram of the overall structure with an esterification kettle configuration for achieving continuous esterification;
FIG. 2 is an enlarged view of portion A of FIG. 1;
FIG. 3 is a schematic structural diagram of a gas distributor in the present embodiment;
FIG. 4 is an enlarged view of the portion B of FIG. 1;
description of the drawings: the device comprises an oleic acid storage tank 10, an oleic acid metering pump 11, an alkyd heat exchanger 12, an oleic acid preheater 13, an esterification tower 14, a tower top distributor 141, a corrugated packing 142, a heater 143, an isooctanol storage tank 20, an isooctanol metering pump 21, an alcohol ester heat exchanger 22, an isooctanol preheater 23, a body 24, an alcohol steam pipe 241, a hook-shaped nozzle 2411, a first vertical pipe 2412, a horizontal pipe 2413, a second vertical pipe 2414, a vapor-liquid circulating pipe 242, a horn-shaped opening 2421, a first cover cap 243, a vapor distributor 244, a drainage disc 2441, a through pipe 2442, a drainage port 2443, a second cover cap 2444, a crude ester downpipe 245, a hook-shaped drainage outlet 2451, a first inclined pipe 2452, a fourth vertical pipe 2453, a heat-conducting coil 246, an overflow pipe 30, a crude ester overflow port 31, a crude ester storage tank 32, an alcohol-water separation tower 40, a first connecting pipe 51, a second connecting pipe 52, a third connecting pipe 53, a fourth connecting pipe 54, a, Seventh connecting tube 57, eighth connecting tube 58, ninth connecting tube 59, tenth connecting tube 510, eleventh connecting tube 511, twelfth connecting tube 512, thirteenth connecting tube 513, longitudinal axis a 60.
Detailed Description
The specific embodiment of the invention is as follows:
the description of the up, down, etc. directions referred to in the present embodiment is described based on the placement position of fig. 1.
An esterification kettle, as shown in fig. 1-4, comprises an esterification kettle body 24, wherein an alcohol steam pipe 241 (comprising a first vertical pipe 2412, a horizontal pipe 2413 and a second vertical pipe 2414 which are connected end to end from top to bottom) is arranged in the body 24, the upper end opening of the alcohol steam pipe 241 is positioned at the top of the body 24, the lower end of the alcohol steam pipe 241 is a hook-shaped nozzle 2411 with an upward opening, a vapor-liquid circulating pipe 242 (the vapor-liquid circulating pipe 242 is a third vertical pipe) is connected in a hanging manner above the opening of the hook-shaped nozzle 2411, and a first cover cap 243 is also arranged in a hanging manner above the vapor-liquid circulating pipe 242 (the vapor-liquid circulating pipe 242 and the first cover cap 243 are connected through connecting columns, so that a gap is reserved between the vapor; a gas distributor 244 which is through up and down, inside and outside is arranged at the upper end part of the body 24, the gas-liquid circulation pipe 242 and the first cover cap 243 are positioned right below the gas distributor 244, the gas distributor 244 comprises a drainage tray 2441 with the upper surface in a low inside and high outside shape, a plurality of through pipes 2442 (a plurality of through pipes 2442 are arranged around the drainage port 2443) which are arranged on the drainage tray 2441 in a surrounding way, a drainage port 2443 which is arranged at the middle part of the drainage tray 2441, the center of the drainage port 2443 and the center of the upper end opening of the gas-liquid circulation pipe 242 are positioned on the same longitudinal axis A60, the drainage port 2443 is positioned at the lowest position and at the middle position of the drainage tray 2441, a second cover cap 2444 is arranged above each through pipe 2442 in a suspending way (the through connecting columns are connected between the through pipes 2442 and the second cover cap 2444, so that a gap is left between the two to ensure that isooctanol rises), a coarse ester downflow pipe 245 is connected at the lower end of the drainage, A fourth vertical pipe 2453 and a hook-shaped drainage outlet 2451), specifically, the lower end of the coarse ester downpipe 245 is the hook-shaped drainage outlet 2451 which faces the lower end opening of the vapor-liquid circulation pipe 242, and the hook-shaped drainage outlet 2451 is simultaneously communicated with the lower end opening of the vapor-liquid circulation pipe 242 and the interior of the body 24 in a hanging manner; also, a thermally conductive coil 246 is provided below the body 24.
In order to facilitate the isooctanol gas to effectively enter the gas-liquid circulation pipe 242, the lower end of the gas-liquid circulation pipe 242 is provided with a downward opening trumpet-shaped opening 2421.
In order to further disperse isooctanol gas, facilitate smooth downward flow of isooctyl oleate crude ester and unreacted oleic acid, facilitate rising of more isooctanol gas and improve production efficiency, the pipe diameter of the through pipe 2442 is smaller than the pipe diameter of the crude ester downpipe 245 and the pipe diameter of the gas-liquid circulating pipe 242.
Further, in order to ensure the pressure in the esterification reactor body 24, the liquid level of the crude ester to be stable and the extraction of the crude ester, an overflow pipe 30 is arranged beside the body 24, an upper end opening of the overflow pipe 30 is communicated with the top of the body 24, a lower end opening of the overflow pipe 30 is communicated with the bottom of the body 24, and a crude ester overflow port 31 is arranged on the overflow pipe 30.
An isooctanol preheater 23 for converting isooctanol into vapor is connected to the upper end opening of the alcohol steam pipe 241.
In order to more clearly embody the structure and operation principle of esterification reaction vessel body 24, the following description will be further provided in connection with the structure connected to esterification reaction vessel body 24, and the details of the esterification reaction will be explained.
An isooctanol storage tank 20, an isooctanol metering pump 21, an alcohol ester heat exchanger 22 and an isooctanol preheater 23 (the side wall of which is provided with heat conducting oil) which are sequentially communicated in series are arranged on the outer side of the esterification kettle body 24; specifically, the isooctanol storage tank 20 is communicated with an isooctanol metering pump 21 through a fifth connecting pipe 55, the isooctanol metering pump 21 is communicated with an alcohol ester heat exchanger 22 through a sixth connecting pipe 56, the alcohol ester heat exchanger 22 is communicated with an isooctanol preheater 23 through a seventh connecting pipe 57, and the isooctanol preheater 23 is communicated with an upper end opening of an alcohol steam pipe 241 through an eighth connecting pipe 58.
An oleic acid treatment device is arranged on the outer side of the esterification kettle body 24, the oleic acid treatment device comprises an oleic acid storage tank 10, an oleic acid metering pump 11, an alkyd heat exchanger 12, an oleic acid preheater 13 (heat conduction oil is arranged on the side wall), and an integral cylindrical esterification tower 14 which are sequentially communicated in series, a tower top distributor 141 communicated with the oleic acid preheater 13 is arranged above the esterification tower 14, 3 corrugated fillers 142 (each corrugated filler is formed by arranging a plurality of stainless steel corrugated sheets which are longitudinally arranged) which are vertically arranged are arranged below the tower top distributor 141, a heater 143 is arranged between every two adjacent corrugated fillers 142, and the top of the esterification tower 14 is communicated with an alcohol-water separation device positioned outside; specifically, the oleic acid storage tank 10 is communicated with an oleic acid metering pump 11 through a first connecting pipe 51, the oleic acid metering pump 11 is communicated with an alkyd heat exchanger 12 through a second connecting pipe 52, the alkyd heat exchanger 12 is communicated with an oleic acid preheater 13 through a third connecting pipe 53, and the oleic acid preheater 13 is communicated with an overhead distributor 141 through a fourth connecting pipe 54; wherein the diameter of the esterification tower is 1m, the height is 28m, and the distance between the top of the oleic acid metering pump 11 and the top of the esterification tower 14 is 25 m.
More specifically, the vapor distributor 244 is located between the esterification tower 14 and the esterification main body 24, and is used for penetrating the esterification tower 14 and the esterification main body 24.
The crude ester overflow port 31 is sequentially communicated with the alcohol ester heat exchanger 22 and the crude ester storage tank 32, wherein the crude ester overflow port 31 is communicated with the alcohol ester heat exchanger 22 through a twelfth connecting pipe 512, and the alcohol ester heat exchanger 22 is communicated with the crude ester storage tank 32 through a thirteenth connecting pipe 513.
In order to ensure the separation of isooctanol vapor and vaporous water, the alcohol-water separation device comprises the alkyd heat exchanger 12, the alcohol-water separation tower 40 and the isooctanol storage tank 20 which are sequentially communicated in series, the esterification tower 14 is communicated with the alkyd heat exchanger 12 through a ninth connecting pipe 59, the alkyd heat exchanger 12 is communicated with the alcohol-water separation tower 40 through a tenth connecting pipe 510, and the alcohol-water separation tower 40 is communicated with the isooctanol storage tank 20 through an eleventh connecting pipe 511.
The working process and principle of the embodiment are that the oleic acid in the oleic acid storage tank 10 is pumped by the oleic acid metering pump 11, the oleic acid sequentially passes through the alkyd heat exchanger 12, the oleic acid preheater 13 and the tower top distributor 141, so that the oleic acid flows downwards along the surface of the corrugated filler 142, meanwhile, the isooctanol in the isooctanol storage tank 20 is pumped by the isooctanol metering pump 21, the isooctanol sequentially passes through the alcohol ester heat exchanger 22 and the isooctanol preheater 23, then the isooctanol in a steam state sequentially enters the alcohol steam pipe 241, the steam-liquid circulation pipe 242 and the steam distributor 244 and rises to the corrugated filler 142, the rising isooctanol steam is fully and repeatedly contacted with the oleic acid flowing downwards on the surface of the corrugated filler 142, esterification reaction is carried out under the action of the catalyst, the generated isooctanol and unreacted oleic acid flow downwards together and flow to the esterification kettle body 24 through the drainage port 2443 until the oleic acid flows to the hook-shaped drainage outlet port, In the lower part of the esterification reactor body 24, unreacted oleic acid can react with isooctanol vapor at the lower end opening of the vapor-liquid circulation pipe 242, and vapor water generated by the esterification reaction and unreacted isooctanol vapor continuously rise to the top of the esterification tower 14 together and enter the alcohol-water separation device, and water is discharged out of the system, and anhydrous isooctanol flows back into the esterification system again, so that continuous esterification is realized by repeated circulation.
More specifically, the continuous esterification process of the embodiment specifically comprises the following steps:
s1: oleic acid, isooctyl alcohol and catalyst are selected
Oleic acid (commercially available) acid value mgKOH/g: 195-;
iodine value gI2/100g：110-135；
The water content is less than 0.5;
density 0.89g/cm3；
The content of isooctyl alcohol (sold in the market) is more than or equal to 99.5 percent;
boiling point: 183-186 ℃;
density 0.833g/cm3；
The content of catalyst (sold in market) tetra-alkyl titanate is more than or equal to 99 percent;
boiling point: more than 250 ℃;
s2: feeding of the feedstock
Oleic acid with catalyst: premixing and dissolving oleic acid and a catalyst in a ratio of 100:0.8 to obtain a premix, placing the premix into an oleic acid storage tank 10, and pumping the premix into an esterification tower 14 through an alkyd heat exchanger 12 and an oleic acid preheater 13 at a uniform speed of 100L/h by using an oleic acid metering pump 11, wherein the temperature of the premix at the outlet of the oleic acid preheater 13 is 180-210 ℃, and is preferably 190 ℃;
isooctyl alcohol: placing isooctanol into an isooctanol storage tank 20, pumping isooctanol into an alcohol steam pipe 241 and a steam-liquid circulation pipe 242 in an esterification kettle body 24 by using an isooctanol metering pump 21 at the uniform speed of 110L/h through an alcohol-fat heat exchanger and an isooctanol preheater 23, wherein the temperature of the isooctanol at the outlet of the isooctanol preheater 23 is 200-210 ℃, preferably 210 ℃;
s3: esterification reaction
The premixed material of oleic acid and catalyst is uniformly sprayed and distributed on the surface of the corrugated packing 142 from the tower top distributor 141, the premixed material flows downwards gradually along the surface of the corrugated packing 142 under the action of gravity and meets isooctanol gas rising from the esterification kettle body 24, the oleic acid reacts with isooctanol under the action of catalyst at the esterification temperature of 190-, wherein water is removed from the esterification system and dehydrated isooctanol is returned to the esterification system to participate in the reaction, i.e., isooctanol is returned to the isooctanol storage tank 20.
S4: crude ester discharge
Isooctyl oleate generated by the esterification tower 14 and a small amount of unreacted oleic acid flow into the esterification kettle body 24, specifically enter the crude ester downpipe 245 and the esterification kettle body 24 through the drainage port 2443, because the hook-shaped drainage port 2451 of the crude ester downpipe 245 is simultaneously communicated with the opening at the lower end of the vapor-liquid circulation pipe 242, the unreacted oleic acid and the obtained isooctyl oleate crude ester can be further fully mixed and reacted with isooctyl alcohol vapor at the opening at the lower end of the vapor-liquid circulation pipe 242, the esterification rate reaches over 98.5 percent, when the amount of isooctyl oleate in the esterification kettle body 24 reaches the height of an overflow port, the isooctyl oleate crude ester enters an alcohol-ester heat exchanger (with isooctyl alcohol) from the crude ester overflow port 31, is subjected to heat exchange, is reduced to the temperature within 80 ℃ from 210 ℃, and then enters the crude ester storage tank 32. (the quality index (crude ester) of the obtained isooctyl oleate is that the ester value mgKOH/g is less than or equal to 0.5, the flash point (opening, DEG C) is more than or equal to 210℃.)
S5: refining of isooctyl oleate crude ester
a. Washing the crude ester with water: washing the crude ester with 60 deg.C hot water to remove catalyst;
b. desolventizing: heating the washed crude ester to 100 ℃, vacuumizing, heating to 120 ℃ when the residual vacuum pressure is less than or equal to 2000Pa, and keeping the temperature for more than half an hour until no gas escapes;
c. and (3) decoloring: adding activated carbon (determined according to the color and luster of the crude ester) with the weight accounting for 1-5% of the material amount into the dehydrated and desolventized crude ester, stirring for 1 hour at 120 ℃, and filtering to obtain refined ester;
d. the technical indexes of the obtained isooctyl oleate are as follows: ester content%: not less than 99.5%; content of free acid%: less than or equal to 0.3; the flash point (open cup, DEG C) is more than or equal to 210.
In the above steps, liquid alkyl titanate is used as the catalyst, the alkyl titanate is miscible with oleic acid, the optimal reaction temperature of the catalyst is 180-. The optimal dosage of the catalyst is 0.8-1% of the oleic acid; the molar ratio of alcohol to acid is 1.5 to 3:1, that is, when the feed amount of oleic acid is 100 parts by mass, isooctanol is 68.7 to 137.3 parts by mass, and when the conversion of esterification reaction in the esterification column 14 is 98%, the molar ratio of alcohol to acid in the column bottom is 75 to 150:1, the reaction equilibrium is sufficiently shifted to the direction of ester formation, so that the oleic acid content of the crude ester overflowing from the esterification reaction tank is less than 0.3%.
In addition, the following tables 1 to 4 are used to respectively illustrate the influence of the mass ratio of oleic acid to isooctanol on the esterification rate, the influence of the amount of catalyst used on the esterification rate, the influence of the reaction temperature on the esterification rate, and the influence of the esterification section height on the esterification rate, so as to facilitate the realization of a better esterification reaction scheme.
Table 1: effect of oleic acid to isooctanol mass ratio on esterification rate
Catalyst (by mass oleic acid): 0.8%, esterification temperature: 200 ℃, esterification stage height: 15 m
| Acid alcohol | 100:68.7 | 100:82.4 | 100:96.2 | 100:110 | 100:123.7 | 100:136.2 |
| Molar ratio of | 1:1.5 | 1:1.8 | 1:2.1 | 1:2.4 | 1:2.7 | 1:3 |
| Esterification rate% | 87.2 | 93.5 | 97.6 | 98.2 | 98.3 | 98.5 |
Table 2: effect of the amount of catalyst on the esterification Rate
Oleic acid isooctyl alcohol 100:110, esterification reaction temperature: 200 ℃, esterification stage height: 15 m
Table 3: effect of reaction temperature on esterification Rate
Oleic acid, isooctyl alcohol 100:110, catalyst 0.8%, esterification stage height: 15 m
| The esterification reaction temperature is lower | 180 | 190 | 200 | 210 |
| Esterification rate% | 81.3 | 93.5 | 98.1 | 98.5 |
Table 4: influence of esterification section height on esterification rate
Oleic acid, isooctyl alcohol 100:110, catalyst 0.8%, esterification temperature: 200 deg.C
| Height of esterification stage (m) | 6 | 9 | 12 | 15 | 18 | 21 | 24 |
| Esterification rate% | 45.9 | 68.3 | 87.6 | 97.1 | 98.2 | 98.5 | 98.6 |
Claims (10)
1. An esterification kettle is characterized in that: the esterification reaction kettle comprises an esterification kettle body, wherein an alcohol steam pipe is arranged in the esterification kettle body, the upper end opening of the alcohol steam pipe is positioned at the top of the esterification kettle body, the lower end of the alcohol steam pipe is provided with a hook-shaped nozzle with an upward opening, a vapor-liquid circulating pipe is suspended and communicated above the opening of the hook-shaped nozzle, and a first hood is also suspended and arranged above the vapor-liquid circulating pipe; the steam distributor is characterized in that a steam distributor which is communicated up and down, inside and outside is arranged at the upper end of the body, the steam-liquid circulating pipe and the first hood are located below the steam distributor, the steam distributor comprises a drainage disc, a plurality of through pipes penetrating the drainage disc and drainage ports arranged in the middle of the drainage disc, a second hood is arranged above each through pipe in a hanging mode, a coarse ester downpipe is connected to the lower end of each drainage port, the lower end of each coarse ester downpipe is a hook-shaped drainage outlet facing the lower end opening of the steam-liquid circulating pipe, and the hook-shaped drainage outlet is communicated with the lower end opening of the steam-liquid circulating pipe and the inside of the body in a hanging mode.
2. An esterification kettle according to claim 1, wherein: the vapor-liquid circulating pipe and the first hood are positioned right below the vapor distributor, wherein the center of the drainage port and the center of the opening at the upper end of the vapor-liquid circulating pipe are positioned on the same longitudinal axis.
3. An esterification kettle according to claim 1, wherein: the lower end of the vapor-liquid circulating pipe is provided with a horn-shaped opening with a downward opening.
4. An esterification kettle according to claim 1, wherein: the upper surface of the drainage plate is low in inside and high in outside, and a drainage opening of the drainage plate is located at the lowest position of the drainage plate and at the middle position.
5. An esterification kettle according to claim 1 or 4, wherein: the plurality of through pipes are arranged around the drainage opening in a surrounding manner.
6. An esterification kettle according to claim 1, wherein: the pipe diameter of the through pipe is smaller than that of the crude ester downdraft pipe and that of the vapor-liquid circulating pipe.
7. An esterification kettle according to claim 1, wherein: the alcohol steam pipe comprises a first vertical pipe, a horizontal pipe and a second vertical pipe which are connected end to end from top to bottom, the steam-liquid circulating pipe is a third vertical pipe, and the crude ester downpipe comprises a first inclined pipe, a fourth vertical pipe and a hook-shaped drainage outlet which are connected end to end from top to bottom.
8. An esterification kettle according to claim 1, wherein: the side of body is equipped with the overflow pipe, the upper end opening and the top of body intercommunication of overflow pipe, the lower extreme opening and the bottom of body intercommunication of overflow pipe, it has a crude ester overflow mouth to open on the overflow pipe.
9. An esterification kettle according to claim 1, wherein: the upper end opening of the alcohol steam pipe is communicated with an external isooctanol preheater.
10. The application method of the esterification kettle is characterized in that: an esterification tower is arranged right above an esterification kettle, a tower top distributor connected with oleic acid feeding is arranged above the esterification tower, a plurality of corrugated fillers arranged up and down are arranged below the tower top distributor, a heater is arranged between every two adjacent corrugated fillers, and the top of the esterification tower is communicated with an alcohol-water separation device positioned outside; when the device works, oleic acid feed and isooctyl alcohol enter an esterification tower, wherein the oleic acid feed enters a tower top distributor, so that the oleic acid flows downwards along the surface of the corrugated packing; the isooctanol in a steam state sequentially enters an alcohol steam pipe, a steam-liquid circulating pipe and a steam distributor and rises to the corrugated packing, the rising isooctanol steam is fully and repeatedly contacted with oleic acid flowing downwards on the surface of the corrugated packing, esterification reaction is carried out under the action of a catalyst, the generated isooctyl oleate and unreacted oleic acid flow downwards together and flow to an esterification kettle through a drainage port until the isooctyl oleate flows to a hook-shaped drainage outlet and the lower part in the esterification kettle, wherein the unreacted oleic acid can react with the isooctanol steam at the lower end opening of the steam-liquid circulating pipe, the steam-state water generated by the esterification reaction and the unreacted isooctanol steam continuously rise to the top of an esterification tower together and enter an alcohol-water separation device, water is discharged out of a system, and anhydrous isooctanol flows back to the esterification kettle again, so that the continuous esterification is realized through repeated circulation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115124422A (en) * | 2022-06-28 | 2022-09-30 | 珠海谦信新材料有限公司 | Promote equipment of ethyl acetate productivity |
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| CN112076700B (en) | 2023-06-23 |
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