CN112076700B - Esterification kettle and application method thereof - Google Patents
Esterification kettle and application method thereof Download PDFInfo
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- CN112076700B CN112076700B CN201911110379.0A CN201911110379A CN112076700B CN 112076700 B CN112076700 B CN 112076700B CN 201911110379 A CN201911110379 A CN 201911110379A CN 112076700 B CN112076700 B CN 112076700B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B01J19/0013—Controlling the temperature of the process
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to an esterification kettle and an application method thereof, wherein an alcohol steam pipe is arranged in an esterification kettle body, an opening at the upper end of the alcohol steam pipe is positioned at the top of the esterification kettle body, a hook-shaped nozzle with an upward opening is arranged at the lower end of the alcohol steam pipe, a vapor-liquid circulating pipe is communicated with the upper part of the opening of the hook-shaped nozzle in a suspending way, and a first hood is arranged above the vapor-liquid circulating pipe in a suspending way; the upper end of the body is provided with a gas distributor comprising a drainage disc, a plurality of through pipes and drainage ports, a second hood is arranged above the through pipes in a suspending manner, the lower end of the drainage port is connected with a crude ester downpipe, and the lower end of the crude ester downpipe is a hook-shaped drainage outlet which is simultaneously communicated with the lower end opening of the gas-liquid circulating pipe and the inside of the body in a suspending manner. Compared with the prior art, the invention ensures that isooctanol gas in the esterification kettle body rises to the esterification tower positioned above to realize continuous esterification reaction with oleic acid, so as to realize the purposes of high yield, simple operation, fully utilized material heat, low cost, material waste avoidance and the like.
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
The isooctyl oleate is obtained by esterifying animal and vegetable oleic acid with isooctyl alcohol, is an intermediate for synthesizing epoxy octyl oleate, and is also used as a main additive of lubricating grease, and has good low-temperature characteristics, high-temperature stability, environmental friendliness and no harm to human bodies, so that the isooctyl oleate is widely applied; wherein the esterification reaction formula of the isooctyl oleate is as follows:
specifically, the esterification process of oleic acid and isooctanol is generally batch type, 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 or p-toluenesulfonic acid and the like), stirred for 4-6 hours, water generated by the esterification reaction is distilled off, and then the finished product is obtained after the procedures of neutralization, water washing, decoloration and the like. However, batch esterification processes suffer from a number of disadvantages: the single kettle is required to be repeatedly operated, the yield is low, the production operation is complex, the heat cannot be fully utilized, and the production cost is high.
In order to solve the technical problems, the continuous esterification of oleic acid and isooctanol is realized by adopting a vapor-liquid countercurrent mode, so that an esterification kettle is required to be provided, isooctanol vapor in the esterification kettle body is lifted to the esterification tower positioned above to realize the continuous esterification reaction with oleic acid, and the purposes of high yield, simplicity in operation, full utilization of material heat, low cost, material waste avoidance and the like are realized.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides an esterification kettle for synthesizing isooctyl oleate and an application method thereof, so that isooctyl alcohol gas in an esterification kettle body rises to an esterification kettle positioned above to realize continuous esterification reaction with oleic acid, thereby achieving the purposes of high yield, simple operation, full and full utilization of material heat, low cost, material waste avoidance and the like.
The technical scheme of the invention is realized as follows:
the esterification kettle comprises an esterification kettle body, wherein an alcohol steam pipe is arranged in the esterification kettle body, an opening at the upper end of the alcohol steam pipe is positioned at the top of the esterification kettle body, a hook-shaped nozzle with an upward opening is arranged at the lower end of the alcohol steam pipe, a vapor-liquid circulating pipe is communicated above the opening of the hook-shaped nozzle in a suspending manner, and a first hood is arranged above the vapor-liquid circulating pipe in a suspending manner; the upper end of the body is provided with a gas distributor which is vertically and internally communicated with the outside, the gas-liquid circulating pipe and the first hood are positioned below the gas distributor, the gas distributor comprises a drainage disc, a plurality of through pipes penetrating through the drainage disc and drainage ports arranged in the middle of the drainage disc, the second hood is arranged above each through pipe in a suspending manner, the lower end of each drainage port is connected with a crude ester downflow pipe, the lower end of the crude ester downflow pipe is a hooked drainage outlet which faces the lower end opening of the gas-liquid circulating pipe, and the hooked drainage outlet is simultaneously communicated with the lower end opening of the gas-liquid circulating pipe and the inside of the body in a suspending manner.
According to the invention, isooctyl alcohol is in a vapor shape through external treatment, and the isooctyl alcohol vapor sequentially enters an alcohol vapor pipe, a vapor-liquid circulating pipe and a vapor distributor and then rises into an esterification tower internally provided with oleic acid, the rising isooctyl alcohol vapor fully and repeatedly contacts with the oleic acid, esterification reaction is carried out under the action of a catalyst, the generated isooctyl oleate and unreacted oleic acid flow into the esterification kettle body through a drainage port until flowing to a hooked drainage outlet and the inner lower part of the body, and the hooked drainage outlet is simultaneously communicated with an opening at the lower end of the vapor-liquid circulating pipe, so that the unreacted oleic acid can further react with the isooctyl alcohol vapor at the opening at the lower end of the vapor-liquid circulating pipe, further the full reaction of the isooctyl alcohol vapor and the oleic acid is realized, the continuous esterification is realized through repeated circulation, the reaction is full and efficient, and the material waste is effectively avoided; in addition, the first hood is arranged, so that isooctyl alcohol gas can conveniently rise upwards to enter the esterification tower along the outer periphery of the first hood, the dispersity of the isooctyl alcohol gas is guaranteed, the isooctyl alcohol gas can conveniently react with oleic acid fully, oleic acid is prevented from dripping into the vapor-liquid circulating pipe, isooctyl alcohol gas after the first hood is dispersed by the second hood is further dispersed, the isooctyl alcohol gas can further conveniently react with oleic acid fully, and oleic acid is prevented from dripping into the pipe; it should be noted that the suspension communication above the opening of the hook-shaped nozzle is provided with a vapor-liquid circulation pipe, which means that the vapor-liquid circulation pipe is not contacted with the esterification kettle body through a connecting piece, and the outer wall of the pipe of the vapor-liquid circulation pipe is connected with the inner wall of the esterification kettle body through a connecting piece, and likewise, the suspension above the vapor-liquid circulation pipe is provided with a first cover cap, the suspension above the through pipe is provided with a second cover cap, which means that a large gap is reserved between the vapor-liquid circulation pipe and the first cover cap, and between the through pipe and the second cover cap, which are connected through a connecting column, so that the stability of the first cover cap and the second cover cap is ensured, and isooctanol vapor is dispersed and lifted up, and the suspension communication between the hook-shaped drainage outlet and the lower end opening of the vapor-liquid circulation pipe and the body is not contacted with the suspension.
Preferably, the vapor-liquid circulating pipe and the first cap 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.
Further ensures that isooctanol gas can enter the through pipe on the gas distributor evenly and dispersedly, and improves the reaction efficiency.
Preferably, the lower end of the vapor-liquid circulating pipe is a horn-shaped opening with a downward opening.
Because the lower end opening of the vapor-liquid circulating pipe is simultaneously communicated with the hooked nozzle and the hooked drainage outlet in a hanging way, a larger horn-shaped opening is needed to ensure that isooctyl alcohol vapor in the hooked nozzle enters the vapor-liquid circulating pipe and that unreacted oleic acid at the hooked drainage outlet is in contact reaction with isooctyl alcohol vapor at the lower end opening of the vapor-liquid circulating pipe and the hooked nozzle.
Preferably, the upper surface of the drainage disc is in an inner low and outer high shape, and the drainage port is positioned at the lowest position of the drainage disc and is positioned at the middle position.
The obtained isooctyl oleate crude ester and unreacted oleic acid are conveniently and more efficiently drained to the drainage port and then flow into the crude ester downpipe.
Preferably, the plurality of through pipes are arranged around the drainage port in a surrounding manner.
So that the through pipe is dispersed around the drainage port, the ascending isooctanol gas is convenient to uniformly disperse, the full reaction with oleic acid is ensured, and the efficiency is high.
Preferably, the pipe diameter of the through pipe is smaller than the pipe diameter of the crude ester downflow pipe and the pipe diameter of the vapor-liquid circulation pipe.
The pipe diameter of the through pipe is smaller, isooctyl alcohol gas can be further dispersed conveniently, the pipe diameter of the crude ester downpipe and the pipe diameter of the vapor-liquid circulating pipe are larger, the crude ester downpipe is convenient for the crude isooctyl oleate and unreacted oleic acid to smoothly flow downwards, and the isooctyl alcohol gas can be more conveniently lifted, so that 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 downflow pipe comprises a first inclined pipe, a fourth vertical pipe and a hooked drainage outlet which are connected end to end from top to bottom.
The structures of the alcohol steam pipe, the vapor-liquid circulating pipe and the crude ester downflow pipe are clearly illustrated.
Preferably, a heat conducting coil is arranged at the inner lower part of the body.
To esterify the oleic acid obtained the octyl ester crude ester provides heat.
Preferably, an overflow pipe is arranged beside the body, an upper end opening of the overflow pipe is communicated with the top of the body, a lower end opening of the overflow pipe is communicated with the bottom of the body, and a crude ester overflow port is formed in the overflow pipe.
The overflow pipe can ensure that the internal pressure of the esterification kettle body is consistent on one hand, and the liquid level of the isooctyl oleate crude ester is kept stable, and on the other hand, the crude ester obtained by esterification can flow into an external storage tank.
Preferably, the upper end opening of the alcohol steam pipe is communicated with an external isooctyl alcohol preheater.
The isooctyl alcohol preheater is convenient for converting isooctyl alcohol into vapor, and isooctyl alcohol vapor enters the esterification kettle body through the alcohol vapor 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 feed is arranged at the upper part in the esterification tower, a plurality of ripple fillers arranged up and down are arranged below the tower top distributor, a heater is arranged between every two adjacent ripple fillers, and the top of the esterification tower is communicated with an alcohol-water separation device positioned outside; during operation, oleic acid feed and isooctanol enter an esterification tower, wherein the oleic acid feed enters a tower top distributor to enable the oleic acid to flow downwards along the surface of the corrugated filler; the isooctyl alcohol in vapor state sequentially enters an alcohol steam pipe, a vapor-liquid circulating pipe and a vapor distributor and rises to the corrugated filler, the rising isooctyl alcohol vapor fully and repeatedly contacts with oleic acid flowing downwards on the surface of the corrugated filler, 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 flowing to a hooked drainage outlet and the inner lower part of the esterification kettle, wherein the unreacted oleic acid can react with isooctyl alcohol vapor at the opening at the lower end of the vapor-liquid circulating pipe, vapor water generated by the esterification reaction and the unreacted isooctyl alcohol vapor continuously rise upwards to the top of the esterification tower to enter an alcohol-water separation device, a water discharge system and anhydrous isooctyl alcohol flow back to the esterification kettle, and continuous esterification is realized by repeated circulation.
The beneficial effects of the invention adopting the technical scheme are as follows:
the invention provides an esterification kettle, which enables isooctanol vapor in the esterification kettle body to rise to the esterification kettle positioned above to realize continuous esterification reaction with oleic acid, so as to realize the purposes of high yield, simple operation, fully utilized material heat, low cost, material waste avoidance and the like.
According to the invention, isooctyl alcohol is in a vapor shape through external treatment, and the isooctyl alcohol vapor sequentially enters an alcohol vapor pipe, a vapor-liquid circulating pipe and a vapor distributor and then rises into an esterification tower internally provided with oleic acid, the rising isooctyl alcohol vapor fully and repeatedly contacts with the oleic acid, esterification reaction is carried out under the action of a catalyst, the generated isooctyl oleate and unreacted oleic acid flow into the esterification kettle body through a drainage port until flowing to a hooked drainage outlet and the inner lower part of the body, and the hooked drainage outlet is simultaneously communicated with an opening at the lower end of the vapor-liquid circulating pipe, so that the unreacted oleic acid can further react with the isooctyl alcohol vapor at the opening at the lower end of the vapor-liquid circulating pipe, further the full reaction of the isooctyl alcohol vapor and the oleic acid is realized, the continuous esterification is realized through repeated circulation, the reaction is full and efficient, and the material waste is effectively avoided; the invention continuously feeds and discharges, fully exchanges and utilizes the heat of materials, automatically controls the heating temperature, has high yield and low cost, and has the advantages of reducing the labor cost of ton consumption of products by more than 60 percent and reducing the energy consumption by about 40 percent through verification.
Drawings
FIG. 1 is a schematic diagram of the overall structure with an esterification kettle structure for continuous esterification;
FIG. 2 is an enlarged schematic view of the portion A in FIG. 1;
FIG. 3 is a schematic diagram of a gas distributor according to the present embodiment;
FIG. 4 is an enlarged schematic view of the portion B in FIG. 1;
description of the drawings: oleic acid sump 10, oleic acid metering pump 11, alkyd heat exchanger 12, oleic acid preheater 13, esterification column 14, overhead distributor 141, corrugated packing 142, heater 143, isooctanol sump 20, isooctanol metering pump 21, alcohol ester heat exchanger 22, isooctanol preheater 23, body 24, alcohol vapor pipe 241, hooked nozzle 2411, first standpipe 2412, horizontal pipe 2413, second standpipe 2414, vapor-liquid circulation pipe 242, flared opening 2421, first hood 243, vapor distributor 244, drain pan 2441, through pipe 2442, drain 2443, second hood 2444, crude ester downcomer 245, hooked drain outlet 2451, first diagonal 2452, fourth standpipe 2453, heat conduction coil 246, overflow pipe 30, crude ester overflow outlet 31, crude ester sump 32, alcohol-water separation column 40, first connection pipe 51, second connection pipe 52, third connection pipe 53, fourth connection pipe 54, fifth connection pipe 55, sixth connection pipe 56, seventh connection pipe 57, eighth connection pipe 58, ninth connection pipe 59, tenth connection pipe 510, eleventh connection pipe 513, twelfth connection pipe 511, longitudinal axis A, thirteenth connection pipe 60.
Detailed Description
The specific embodiments of the present invention are as follows:
the description of the upper, lower, etc. directions according to the present embodiment is described based on the placement position of fig. 1.
1-4, an esterification kettle 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 from top to bottom) is arranged in the body 24, an opening at the upper end of the alcohol steam pipe 241 is positioned at the top of the body 24, a hook-shaped nozzle 2411 with an upward opening is arranged at the lower end of the alcohol steam pipe 241, a vapor-liquid circulating pipe 242 (the vapor-liquid circulating pipe 242 is a third vertical pipe) is in suspension communication above the opening of the hook-shaped nozzle 2411, a first cover cap 243 (the vapor-liquid circulating pipe 242 and the first cover cap 243 are connected through a plurality of connecting columns) is also in suspension above the vapor-liquid circulating pipe 242, so that a gap is reserved between the two, and the rising of isooctanol vapor is ensured; the upper end of the body 24 is provided with a gas distributor 244 which is vertically and internally communicated, the gas-liquid circulation pipe 242 and the first cover cap 243 are positioned under the gas distributor 244, the gas distributor 244 comprises a drainage disk 2441 with the upper surface in an inner low and outer high shape, a plurality of through pipes 2442 penetrating through the drainage disk 2441 (the through pipes 2442 are circumferentially arranged around the drainage port 2443) and the drainage port 2443 arranged in the middle of the drainage disk 2441, the center of the drainage port 2443 and the center of the opening at the upper end 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 of the drainage disk 2441 and is positioned at the middle position, a second cap 2444 is suspended above each through pipe 2442 (the through pipes 2442 and the second caps 2444 are connected through a plurality of connecting columns, so that a gap is reserved between the two caps, isooctanol gas is guaranteed to rise), a crude ester downpipe 245 (comprising a first inclined pipe 2452, a fourth vertical pipe 2453 and a hooked drainage outlet 2451 which are connected end to end from top to bottom) is connected at the lower end of the drainage port 2443, specifically, the lower end of the crude ester downpipe 245 is a hooked drainage outlet 2451 which is opened towards the lower end of the vapor-liquid circulation pipe 242, and the hooked drainage outlet 2451 is simultaneously suspended and communicated with the lower end of the vapor-liquid circulation pipe 242 and the interior of the body 24; further, a heat conducting coil 246 is provided below and within the body 24.
In order to facilitate the isooctanol vapor to effectively enter the vapor-liquid circulation pipe 242, the lower end of the vapor-liquid circulation pipe 242 is provided with a horn-shaped opening 2421 with a downward opening.
In order to facilitate the further dispersion of isooctyl alcohol gas, the smooth and unimpeded downward flow of isooctyl oleate and unreacted oleic acid, and the ascending of more isooctyl alcohol gas, 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 vapor-liquid circulating pipe 242, and the production efficiency is improved.
Further, in order to ensure the pressure in the esterification kettle body 24, the level stability of the crude ester and the extraction of the crude ester, an overflow pipe 30 is provided beside the body 24, an upper opening of the overflow pipe 30 is communicated with the top of the body 24, a lower opening of the overflow pipe 30 is communicated with the bottom of the body 24, and a crude ester overflow port 31 is provided on the overflow pipe 30.
The upper end opening of the alcohol steam pipe 241 communicates with the outside, and an isooctyl alcohol preheater 23 for converting isooctyl alcohol into vapor is provided.
In order to more clearly embody the structure and operation of esterification reactor body 24, the structure associated with esterification reactor body 24 will be further described below and the details of the esterification reaction will be described.
An isooctyl alcohol storage tank 20, an isooctyl alcohol metering pump 21, an alcohol ester heat exchanger 22 and an isooctyl alcohol preheater 23 (the side wall of which is provided with heat transfer oil) which are sequentially connected in series are arranged on the outer side of the esterification kettle body 24; specifically, the isooctyl alcohol storage tank 20 is communicated with the isooctyl alcohol metering pump 21 through a fifth connecting pipe 55, the isooctyl alcohol metering pump 21 is communicated with the alcohol ester heat exchanger 22 through a sixth connecting pipe 56, the alcohol ester heat exchanger 22 is communicated with the isooctyl alcohol preheater 23 through a seventh connecting pipe 57, and the isooctyl alcohol preheater 23 is communicated with the upper end opening of the 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 (the side wall of the esterification kettle is provided with heat conducting oil) and an esterification tower 14 which is in a cylindrical shape as a whole, a tower top distributor 141 communicated with the oleic acid preheater 13 is arranged on the upper inner part of the esterification tower 14, 3 corrugated fillers 142 (each corrugated filler is formed by arranging a plurality of longitudinally arranged stainless steel corrugated sheets) are arranged below the tower top distributor 141, a heater 143 is arranged between every two adjacent corrugated fillers 142, and an alcohol-water separation device positioned on the outside is communicated on the top of the esterification tower 14; specifically, the oleic acid storage tank 10 is communicated with the oleic acid metering pump 11 through a first connecting pipe 51, the oleic acid metering pump 11 is communicated with the alkyd heat exchanger 12 through a second connecting pipe 52, the alkyd heat exchanger 12 is communicated with the oleic acid preheater 13 through a third connecting pipe 53, and the oleic acid preheater 13 is communicated with the tower top distributor 141 through a fourth connecting pipe 54; wherein the diameter of the esterification tower is 1m, the height of the esterification tower is 28m, and the distance between the top of the oleic acid metering pump 11 and the top of the esterification tower 14 is 25m.
More specifically, the gas distributor 244 is located between the esterification tower 14 and the esterification reactor body 24, and is configured to penetrate the esterification tower 14 and the esterification reactor body 24.
The crude ester overflow 31 is communicated with the alcohol ester heat exchanger 22 and the crude ester storage tank 32 in sequence, wherein the crude ester overflow 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 separation of isooctanol vapor and steam water, the alcohol-water separation device comprises an alkyd heat exchanger 12, an alcohol-water separation tower 40 and an isooctyl alcohol storage tank 20 which are sequentially connected in series, wherein 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 isooctyl alcohol storage tank 20 through an eleventh connecting pipe 511.
The working flow and principle of this embodiment lie in that the oleic acid metering pump 11 pumps the oleic acid in the oleic acid storage tank 10, 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, and meanwhile, the isooctanol metering pump 21 pumps the isooctanol in the isooctanol storage tank 20, the isooctanol sequentially passes through the alcohol ester heat exchanger 22 and the isooctanol preheater 23, then the isooctanol in a vapor state sequentially enters the alcohol steam pipe 241, the vapor-liquid circulating pipe 242 and the vapor distributor 244 and rises to the corrugated filler 142, the rising isooctanol vapor fully and repeatedly contacts with the oleic acid flowing downwards along the surface of the corrugated filler 142, esterification reaction occurs under the action of the catalyst, the generated isooctyl oleate and unreacted oleic acid flow downwards to the esterification kettle body 24 through the drainage port 2443 until flowing to the lower part of the hook-shaped drainage outlet 2451 and the esterification kettle body, wherein the unreacted oleic acid can react with the isooctanol at the opening at the lower end of the vapor-liquid circulating pipe 242, and the esterification reaction is carried out by the isooctanol in the vapor-liquid circulating pipe, and the esterification reaction is carried out in the tower top and the esterification system is repeatedly carried out, and the esterification reaction is carried out in the water-free system, and the esterification reaction is carried out in the continuous, and the esterification system is carried out, and the esterification water is discharged again, and the esterification system is not carried out.
More specifically, the specific steps of the continuous esterification process of this embodiment include:
s1: oleic acid, isooctyl alcohol and catalyst are selected
Oleic acid (commercially available) acid value mgKOH/g:195-205;
iodine value gI 2 /100g：110-135；
The water content is less than 0.5;
density of 0.89g/cm 3 ；
The content of isooctanol (commercially available) is more than or equal to 99.5 percent;
boiling point: 183-186 ℃;
density of 0.833g/cm 3 ；
The content of the catalyst (commercially available) tetraalkyl titanate is more than or equal to 99 percent;
boiling point: > 250 ℃;
s2: feeding material
Oleic acid with catalyst: premixing and dissolving oleic acid and a catalyst according to the proportion 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 the average 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 preferably 190 ℃;
isooctanol: putting isooctanol into an isooctanol storage tank 20, and pumping isooctanol into an alcohol steam pipe 241 and a vapor-liquid circulating pipe 242 in an esterification kettle body 24 through an alcohol-ester heat exchanger and an isooctanol preheater 23 at a uniform speed of 110L/h by using an isooctanol metering pump 21, wherein the isooctanol temperature at the outlet of the isooctanol preheater 23 is 200-210 ℃, preferably 210 ℃;
s3: esterification reaction
The premix of oleic acid and catalyst is evenly sprayed and distributed on the surface of the corrugated filler 142 from the top distributor 141, the premix gradually flows downwards along the surface of the corrugated filler 142 under the action of gravity and meets with isooctyl alcohol vapor rising from the esterification kettle body 24, under the action of the catalyst, when the esterification temperature is 190-200 ℃, the oleic acid reacts with isooctyl alcohol to generate isooctyl oleate and water, the isooctyl oleate flows downwards together with unreacted oleic acid and the catalyst, the unreacted oleic acid can further react with isooctyl alcohol vapor rising from below, the vapor water generated by the reaction and part of unreacted isooctyl alcohol vapor continuously rise upwards, the isooctyl alcohol vapor further reacts with oleic acid flowing from above, and the circulation is repeated until excessive isooctyl alcohol vapor and vapor water rise to the top of the tower and enter the alcohol-water separation tower 40, the alcohol-water separation tower 40 separates isooctyl alcohol and water, wherein the water is removed from the esterification system, and the dehydrated isooctyl alcohol is returned to the esterification system to react, namely, the isooctyl alcohol is returned to the isooctyl alcohol storage tank 20.
S4: crude ester discharge
The 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 downflow pipe 245 and the inside of the esterification kettle body 24 through the drainage port 2443, and as the hook-shaped drainage outlet 2451 of the crude ester downflow pipe 245 is simultaneously communicated with the lower end opening of the vapor-liquid circulating pipe 242, the unreacted oleic acid and the obtained isooctyl oleate crude ester can be fully mixed with isooctyl alcohol vapor at the lower end opening of the vapor-liquid circulating pipe 242 for reaction, the esterification rate reaches more than 98.5 percent, and 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, then falls to the temperature of less than 80 ℃ from 210 ℃ and enters the crude ester storage tank 32. ( Quality index (crude ester) of isooctyl oleate obtained: 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. Crude ester water washing: washing the crude ester with hot water at 60 ℃ to remove the catalyst;
b. desolventizing: heating the washed crude ester to 100 ℃, vacuumizing, heating to 120 ℃ when the vacuum residual pressure is less than or equal to 2000Pa, and keeping for more than half an hour, wherein no gas escapes;
c. decoloring: adding 1-5% of active carbon (depending on the color of the crude ester) into the dehydrated and desolventized crude ester, stirring for 1 hour at 120 ℃, and filtering to obtain refined ester;
d. the technical index of the obtained isooctyl oleate is as follows: ester content%: 99.5% or more; free acid content%: less than or equal to 0.3; flash point (open cup, DEG C) is not less than 210.
In the above steps, liquid alkyl titanate is used as a catalyst, the alkyl titanate is miscible with oleic acid, the optimal reaction temperature of the catalyst is 180-200 ℃, the boiling point of the catalyst is higher than 250 ℃, vaporization does not occur in the esterification tower 14, the catalyst does not separate out to block the channels of the corrugated filler 142 like a solid catalyst, the crude ester after the reaction can be washed by water to remove the catalyst, and the finished product can be obtained through refining procedures such as decolorization and the like. The catalyst dosage is optimally 0.8-1% of oleic acid; the molar ratio of alcohol to acid is 1.5-3:1, namely when the feeding amount of oleic acid is 100 parts by mass, isooctanol is 68.7-137.3 parts by mass, when the esterification conversion rate in the esterification tower 14 is 98%, the molar ratio of alcohol to acid in the tower kettle is 75-150:1, and the reaction balance can be fully moved towards the direction of generating ester, so that the oleic acid content in the crude ester overflowed from the esterification reaction kettle is less than 0.3%.
In addition, the influence of the mass ratio of oleic acid to isooctanol on the esterification rate, the influence of the amount of the catalyst on the esterification rate, the influence of the reaction temperature on the esterification rate, and the influence of the height of the esterification stage on the esterification rate are described in tables 1 to 4, respectively, so that a better esterification reaction scheme is conveniently realized.
Table 1: influence of oleic acid to isooctanol mass ratio on esterification rate
Catalyst (in terms of oleic acid mass): 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: influence of the amount of catalyst on the esterification rate
Oleic acid isooctanol=100:110, esterification reaction temperature: 200 ℃, esterification stage height: 15 m
Table 3: influence of the reaction temperature on the esterification rate
Oleic acid isooctanol=100:110, catalyst 0.8%, esterification stage height: 15 m
| Esterification reaction temperature °C | 180 | 190 | 200 | 210 |
| Esterification rate% | 81.3 | 93.5 | 98.1 | 98.5 |
Table 4: influence of the height of the esterification stage on the esterification rate
Oleic acid isooctanol=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 (8)
1. An esterification kettle, which is characterized in that: the esterification kettle comprises an esterification kettle body, wherein an alcohol steam pipe is arranged in the esterification kettle body, an opening at the upper end of the alcohol steam pipe is positioned at the top of the esterification kettle body, a hook-shaped nozzle with an upward opening is arranged at the lower end of the alcohol steam pipe, a vapor-liquid circulating pipe is communicated above the opening of the hook-shaped nozzle in a hanging manner, and a first hood is arranged above the vapor-liquid circulating pipe in a hanging manner; the upper end of the body is provided with a gas distributor which is vertically and internally and externally communicated, the gas-liquid circulating pipe and the first hood are positioned below the gas distributor, the gas distributor comprises a drainage disc, a plurality of through pipes penetrating through 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 suspending manner, the lower end of each drainage port is connected with a crude ester downflow pipe, the lower end of each crude ester downflow pipe is a hook-shaped drainage outlet which faces the lower end opening of the gas-liquid circulating pipe, and the hook-shaped drainage outlet is simultaneously communicated with the lower end opening of the gas-liquid circulating pipe and the inside of the body in a suspending manner; the steam-liquid circulating pipe and the first hood are positioned right below the steam distributor, wherein the center of the drainage port and the center of the opening at the upper end of the steam-liquid circulating pipe are positioned on the same longitudinal axis; the lower end of the vapor-liquid circulating pipe is a horn-shaped opening with a downward opening.
2. The esterification kettle according to claim 1, wherein: the upper surface of the drainage disc is in an inner low and outer high shape, and the drainage port is positioned at the lowest position of the drainage disc and is positioned at the middle position.
3. An esterification kettle according to claim 1 or 2, characterized in that: the plurality of through pipes are circumferentially arranged around the drainage port.
4. The esterification kettle according to claim 1, wherein: the pipe diameter of the through pipe is smaller than the pipe diameter of the crude ester downflow pipe and the pipe diameter of the vapor-liquid circulating pipe.
5. The 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 vapor-liquid circulating pipe is a third vertical pipe, and the crude ester downflow pipe comprises a first inclined pipe, a fourth vertical pipe and a hooked drainage outlet which are connected end to end from top to bottom.
6. The esterification kettle according to claim 1, wherein: the overflow pipe is arranged beside the body, an upper end opening of the overflow pipe is communicated with the top of the body, a lower end opening of the overflow pipe is communicated with the bottom of the body, and a crude ester overflow port is formed in the overflow pipe.
7. The esterification kettle according to claim 1, wherein: the upper end opening of the alcohol steam pipe is communicated with an external isooctyl alcohol preheater.
8. The application method of the esterification kettle is characterized in that: an esterification tower is arranged right above the esterification kettle, a tower top distributor connected with oleic acid feed is arranged at the upper part in the esterification tower, a plurality of ripple fillers arranged up and down are arranged below the tower top distributor, a heater is arranged between every two adjacent ripple fillers, and the top of the esterification tower is communicated with an alcohol-water separation device positioned outside; during operation, oleic acid feed and isooctanol enter an esterification tower, wherein the oleic acid feed enters a tower top distributor to enable the oleic acid to flow downwards along the surface of the corrugated filler; the isooctyl alcohol in vapor state sequentially enters an alcohol steam pipe, a vapor-liquid circulating pipe and a vapor distributor and rises to the corrugated filler, the rising isooctyl alcohol vapor fully and repeatedly contacts with oleic acid flowing downwards on the surface of the corrugated filler, 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 flowing to a hooked drainage outlet and the inner lower part of the esterification kettle, wherein the unreacted oleic acid can react with isooctyl alcohol vapor at the opening at the lower end of the vapor-liquid circulating pipe, vapor water generated by the esterification reaction and the unreacted isooctyl alcohol vapor continuously rise upwards to the top of the esterification tower to enter an alcohol-water separation device, a water discharge system and anhydrous isooctyl alcohol flow back to the esterification kettle, and continuous esterification is realized by repeated circulation.
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