CN102304041B - Solvent-free esterification-distillation integrated process - Google Patents
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Abstract
The invention discloses a solvent-free esterification-distillation integrated process. In the process, a high feeding tank, an esterification kettle, a storage tank and a thin-film evaporator are connected in series; aliphatic alcohol and acid raw materials which is subjected to pretreatment is fed into the circulating esterification kettle with a catalyst fixed bed from the high tank; an esterification is accomplished by means of circulating esterification, and water generated in the reaction is evaporated out by means of constantly vacuumizing to promote the esterification to advance in a forward direction; after the esterification is accomplished, the coarse product is delivered by the circulating pump to the thin-film evaporator from the nitrogen protected storage tank; unreacted excessive organic materials with small molecular weights are evaporated out; and through refining, the pure product is obtained. Compared with the conventional process, the process disclosed by the invention has the advantages that: solvent is not needed in the whole process; excessive organic raw materials with small molecular weights can be recycled; and the process is an energy-saving, emission-reducing and environment-friendly esterification synthesis process.
Description
Technical field:
The present invention relates to a kind of solvent-free esterification-distillation integral process, this process application is combined in the fatty alcohol acid esters, has energy-saving and emission-reduction, the characteristics of green non-pollution.
Background technology:
Esterification generally by the aliphatics alcohols and fatty carboxylic acids in the presence of catalyzer, dehydration reaction generates aliphatic ester.The tradition esterification technique is divided into two kinds: a kind of for solvent method is arranged, aliphatics alkyd adopts homogeneous phase or heterogeneous catalyst, esterification under solvent condition, solvent can form azeotropic with water, constantly water is taken out of from reaction system, promote reaction forward to carry out, toluene, dimethylbenzene etc. can be arranged as the solvent with aqua.The esterification part that comes with some shortcomings is arranged under the solvent condition, because solvent reflux condensation mode constantly, the part heat is taken away by the mode by heat exchange in band water process, increased energy consumption, after simultaneous reactions was finished, solvent must be steamed from reaction system and be reclaimed, in the removal process of solvent, have partial loss, toluene, dimethylbenzene equal solvent cost costliness cause the products production cost to increase, and the use of solvent brings pollution to environment, and partial solvent is poisonous, and operator are damaged.
Another kind method is solventless method, no-solvent process is divided into again two kinds, excessive organic constituent is as the band aqua in a kind of employing esterification, usually this excessive organic constituent and the consistency bad (such as butanols) of water can form azeotropic with water, or employing constantly blasts organic constituent steam (such as methyl alcohol) in reaction system, organic constituent steam will react the water that generates and take away, promote esterification to carry out, this kind method is had relatively high expectations for esterification feed, and range of application is narrower; Another kind method is for to vacuumize reaction system, and the water that reaction is generated steams, and this method generally need to be used the system soluble catalyst, and causes easily degree of esterification not high, and esterification time is long.
Summary of the invention:
The object of the invention is to; a kind of solvent-free esterification-distillation integral process is provided; this technique is by header tank; reaction kettle of the esterification; hold-up vessel; the thin film evaporation instrument is composed in series; the fatty alcohol acid starting material is entered into in the catalyst fixed bed reaction kettle of the esterification capable of circulation through pre-treatment by header tank; adopt the method for circulating esterification to finish esterification; and the method for taking constantly to vacuumize will be reacted the water that generates and be steamed and remove; promote the esterification forward to carry out; after esterification is finished; crude product is through the hold-up vessel of nitrogen protection; be recycled and be pumped in the thin-film evaporator; steaming obtains pure product through making with extra care again except after participating in the excessive small molecular weight organic raw material of reaction.The present invention compares with traditional esterification technique, and whole process need not solvent and participates in, and excessive small molecules organic raw material recoverable is energy-saving and emission-reduction, the esterification synthesis technique of green non-pollution.
A kind of solvent-free esterification of the present invention-distillation integral process, this technique is the aliphatic ester synthesis technique, is to be composed in series by feed intake groove, reaction kettle of the esterification, hold-up vessel, thin-film evaporator of a high position, concrete operations follow these steps to carry out:
A, esterification feed is added respectively a high position feed intake in groove (1), (2), (3), (4), (5), be filled with nitrogen protection and start heating system, after raw material fully dissolves, enter in the reaction kettle of the esterification (12) by vacuum system (19), wherein the adding of esterification bed material contains a kind of liquid starting material at least, boiling point under its normal pressure≤500 ℃;
B, open condenser (15) and high temperature resistant recycle pump (17), material is pumped by reaction kettle of the esterification (12) kettle by high temperature resistant recycle pump (17), by catalyst fixed bed (14), then flowed back in the reaction kettle of the esterification (12) by spray header (13) spraying, in working cycle, react, and constantly circulation, finish esterification, obtain crude product, crude product is pumped in the hold-up vessel (22), be filled with nitrogen protection, wherein esterification reaction temperature is 100 ℃-150 ℃;
Crude product in c, the hold-up vessel (22) is pumped in the thin-film evaporator (26) through high temperature resistant recycle pump (24), open condenser (28), vacuum system (27) and high temperature resistant recycle pump (33), 140 ℃ of temperature, vacuum pressure 300pa, steam except the excessive small molecular weight organic raw material of not participating in reaction, recycling thin film evaporation instrument (26) is made with extra care and is obtained pure product, condenser (28) is condensed into liquid state, flows into receiving tank (29).
Step a esterification technique carries out solvent-free vacuumizing under the condition, and the vacuum pressure of vacuum system (19) and (27) is 300-3000pa.
Step a reaction system raw material uses soluble catalyst to be tosic acid.
At also continuous circulation time, pass through simultaneously vacuum system (19) and take out negative pressure among the step b, the water vapor that reaction generates is by extraction in kettle (12), and process condenser (15) is cooled to liquid state, flows into receiving tank (20).
Immobilized solid catalyst is MCM-41 mesopore molecular sieve or resin cation (R.C.) D001, LSCA-30 or LSI-600 among the step b catalyst fixed bed (14).
Related device is by the high position groove that feeds intake in this technique, reaction kettle of the esterification, hold-up vessel, thin-film evaporator is composed in series, at the high position groove (1) that feeds intake, (2), (3), (4) and respectively carry heating unit on (5), and discharge port each with a valve (6), (7), (8), (9) and (10), a high position feeds intake and is state in parallel between the groove, be connected with reaction kettle of the esterification (12) by pipe connecting, reaction kettle of the esterification (12) bottom is connected with catalyst fixed bed (14) by high temperature resistant recycle pump (17), the spray header (13) of one end of catalyst fixed bed (14) is fixed in the reaction kettle of the esterification (12), upper end at reaction kettle of the esterification (12) is connected with receiving tank (20) by condenser (15), the top of receiving tank (20) is vacuum system (19) fixedly, high temperature resistant recycle pump (17) is connected with hold-up vessel (22) by pipe connecting, the discharge port of the bottom of hold-up vessel (22) is connected with thin-film evaporator (26) by high temperature resistant recycle pump (24), one end of high temperature circulation pump (33) is connected with the top opening for feed of thin-film evaporator (26), the other end connects the bottom of thin-film evaporator (26), top at thin-film evaporator (26) is connected with receiving tank (29) by condenser (28), and the top of receiving tank (29) is vacuum system (27) fixedly.
A high position feeds intake groove (1), (2), (3), (4) and (5) for using separately or using simultaneously.
A kind of solvent-free esterification of the present invention-distillation integral process, its characteristics are: after material enters esterifying kettle, adopt the method for solvent-free circulating esterification to finish esterification, reaction kettle of the esterification is with circulation device, catalyst fixed bed and spray header and vacuum condensation system, material is pumped by high temperature resistant recycle pump in reaction kettle of the esterification, it is catalyst fixed bed to flow through, after in catalyst fixed bed, reacting, be injected in the esterifying kettle by spray header, continuous circulating esterification, the water that generates at the esterifying kettle internal reaction simultaneously is drawn out of system by the vacuum condensation system, promote reaction to carry out, after esterification is finished, pump in the thin-film evaporator capable of circulation through hold-up vessel, steam except refining behind the excessive unreacted small molecular weight organic constituent through thin-film evaporator, the effect of dehydration is constantly to promote that the esterification forward carries out, compare with traditional solvent esterification technique that has, whole process need not solvent and participates in, excessive small molecules organic raw material recoverable, energy-saving and emission-reduction, the esterification synthesis technique of green non-pollution.
Process application of the present invention is combined in the fatty alcohol acid esters, adopt the mode of the excessive adding of small molecular weight organic constituent, the excessive small molecules organic constituent of circulating esterification parallel-series thin-film evaporator circularly removing under condition of no solvent, again product is made with extra care, reach the purpose of purified product, only be that at least a liquid starting material participates in to ingredient requirement wherein, boiling point under its normal pressure≤500 ℃ get final product, because catalyst fixed bed use, make esterification can be applied to homogeneous catalytic reaction and heterogeneous catalytic reaction system, more traditional solvent-free esterification technique purposes is more extensive.
Technique of the present invention if use soluble catalyst in the esterification system, needs catalyzer is directly added in the esterification feed, if use solid catalyst, needs by catalytic fixed bed immobilized.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
Embodiment
Technique of the present invention will be for illustration and explanation by following examples, and these embodiment limit the invention.
Device involved in the present invention is by the high position groove that feeds intake, reaction kettle of the esterification, hold-up vessel, thin-film evaporator is composed in series, the high position groove 1 that feeds intake, 2,3,4 and 5 is to use separately or use simultaneously, at the high position groove 1 that feeds intake, 2,3, respectively carry heating unit on 4 and 5, and discharge port each with a valve 6,7,8,9 and 10, a high position feeds intake and is state in parallel between the groove, be connected with reaction kettle of the esterification 12 by pipe connecting, reaction kettle of the esterification 12 bottoms are connected with catalyst fixed bed 14 by high temperature resistant recycle pump 17, the spray header 13 of an end of catalyst fixed bed 14 is fixed in the reaction kettle of the esterification 12, upper end at reaction kettle of the esterification 12 is connected with receiving tank 20 by condenser 15, the top of receiving tank 20 is vacuum system 19 fixedly, high temperature resistant recycle pump 17 is connected with hold-up vessel 22 by pipe connecting, the discharge port of the bottom of hold-up vessel 22 is connected with thin-film evaporator 26 by high temperature resistant recycle pump 24, one end of high temperature circulation pump 33 is connected with the top opening for feed of thin-film evaporator 26, the other end connects the bottom of thin-film evaporator 26, top at thin-film evaporator 26 is connected with receiving tank 29 by condenser 28, and the top of receiving tank 29 is vacuum system 27 fixedly.
Embodiment 1 (synthesizing of trimethylolpropane tri-heptanoate):
A, at high position groove 1 interior adding raw material TriMethylolPropane(TMP) 134kg and the catalyzer tosic acid 2kg that feed intake, the header tank 2 interior adding enanthic acid 400kg that feed intake, the high position groove 1 that feeds intake is filled with nitrogen protection and starts heating system, TriMethylolPropane(TMP) and tosic acid are dissolved, after raw material fully dissolves, open vacuum system 19, vacuum pressure is 1000pa, valve-off 18 and 21 is opened valve 6,7 simultaneously, 11 and 16, a high position feed intake groove 1 and 2 in raw materials under the condition of negative pressure, be inhaled in the reaction kettle of the esterification 12, wait raw material to be inhaled into fully after, valve-off 11;
B, open vacuum system 19, open simultaneously condenser 15 and high temperature resistant recycle pump 17, material pumps from reaction kettle of the esterification 12 by high temperature resistant recycle pump 17, by catalyst fixed bed 14, this moment catalyst fixed bed not infill system insoluble solid catalyzer, flowed back in the reaction kettle of the esterification 12 by spray header 13 sprayings, in working cycle, react, and constantly circulation, esterification finished, esterification temperature is 100 ℃, obtain crude product, the water that reaction generates is collected into receiving tank 20 by the vacuum condensation system, after the water in receiving tank is collected 53-54kg, esterification finishes, stop vacuum system 19 and condenser 15, valve-off 16,21, open valve 18, the esterification crude product is pumped into hold-up vessel 22, and the inflated with nitrogen protection;
C, open valve 23,25 and 30, valve-off 31 and 32, the crude product in the hold-up vessel 22 is pumped in the thin-film evaporator 26 valve-off 25 through high temperature resistant recycle pump 24, start simultaneously thin-film evaporator 26, and open condenser 28, vacuum system 27, and high temperature resistant recycle pump 33 are under 140 ℃ of temperature, vacuum pressure 300pa, enanthic acid is distilled out of, and flows into receiving tank 29 by the vacuum condensation system, till no longer including enanthic acid and being distilled out of, after utilizing thin-film evaporator 26 to take off enanthic acid, valve-off 30 is opened valve 32, and product is pumped out refining, after the process thin-film evaporator removes enanthic acid, obtain thick product 465kg, product is light yellow transparent, and acid number is 0.8, product acid number 0.05 after refining, sticking refer to 174.5, pour point-59 ℃, 228 ℃ of flash-points.
Embodiment 2 (synthesizing of trimethylolpropane tri-heptanoate):
A, at the high position groove 1 interior adding raw material TriMethylolPropane(TMP) 134kg that feeds intake, the header tank 2 interior adding enanthic acid 400kg that feed intake, the high position groove 1 that feeds intake is filled with nitrogen protection and starts heating system, TriMethylolPropane(TMP) is dissolved, after raw material fully dissolves, open vacuum system 19, vacuum pressure is 2000pa, valve-off 18 and 21 is opened valve 6,7 simultaneously, 11 and 16, a high position feed intake groove 1 and 2 in raw materials under the condition of negative pressure, be inhaled in the reaction kettle of the esterification 12, wait raw material to be inhaled into fully after, valve-off 11;
B, open vacuum system 19, open simultaneously condenser 15 and high temperature resistant recycle pump 17, material pumps from reaction kettle of the esterification 12 by high temperature resistant recycle pump 17, by catalyst fixed bed 14, at catalyst fixed bed 14 interior filling 5kg resin cation (R.C.) LSI-600, flowed back in the reaction kettle of the esterification 12 by spray header 13 sprayings, in working cycle, react, and constantly circulation, esterification finished, esterification temperature is 120 ℃, obtain crude product, the water that reaction generates is collected into receiving tank 20 by the vacuum condensation system, after the water in receiving tank is collected 53-54kg, esterification finishes, stop vacuum system 19 and condenser 15, valve-off 16,21, open valve 18, the esterification crude product is pumped into hold-up vessel 22, and the inflated with nitrogen protection;
C, open valve 23,25 and 30, valve-off 31 and 32, the crude product in the hold-up vessel 22 is pumped in the thin-film evaporator 26 valve-off 25 through high temperature resistant recycle pump 24, start simultaneously thin-film evaporator 26, and open condenser 28, vacuum system 27, and high temperature resistant recycle pump 33 are under 140 ℃ of temperature, vacuum pressure 300pa, enanthic acid is distilled out of, and flows into receiving tank 29 by the vacuum condensation system, till no longer including enanthic acid and being distilled out of, after utilizing thin-film evaporator 26 to take off enanthic acid, valve-off 30 is opened valve 32, and product is pumped out refining, after the process thin-film evaporator removes enanthic acid, obtain thick product 460kg, product is light yellow transparent, and acid number is 0.2, product acid number 0.05 after refining, sticking refer to 174.5, pour point-59 ℃, 228 ℃ of flash-points.
Embodiment 3 (dumbbell shape product 2-TriMethylolPropane(TMP)-hexanodioic acid-4-enanthic acid ester synthesis):
A, at the high position groove 1 interior adding raw material TriMethylolPropane(TMP) 134kg that feeds intake, header tank feeds intake and 2 adds hexanodioic acid 73kg, header tank 3 drops into the 280kg enanthic acid, the high position groove 1 and 2 that feeds intake is filled with nitrogen protection and starts heating system, TriMethylolPropane(TMP) and tosic acid are dissolved, after raw material fully dissolves, open vacuum system 19, vacuum pressure is 3000pa, simultaneously valve-off 18 and 21, open valve 6,7,11 and 16, a high position feed intake groove 1 and 2 in raw materials under the condition of negative pressure, be inhaled in the reaction kettle of the esterification 12, after raw material is inhaled into fully, valve-off 11;
B, open vacuum system 19, open simultaneously condenser 15 and high temperature resistant recycle pump 17, material pumps from reaction kettle of the esterification 12 by high temperature resistant recycle pump 17, by catalyst fixed bed 14, at catalyst fixed bed 14 interior filling 5kg resin cation (R.C.) LSCA-30, flowed back in the reaction kettle of the esterification 12 by spray header 13 sprayings, in working cycle, react, and constantly circulation, esterification finished, esterification temperature is 140 ℃, obtain crude product, the water that reaction generates is collected into receiving tank 20 by the vacuum condensation system, after the water in receiving tank is collected 53-54kg, esterification finishes, stop vacuum system 19 and condenser 15, valve-off 16,21, open valve 18, the esterification crude product is pumped into hold-up vessel 22, and the inflated with nitrogen protection;
C, open valve 23,25 and 30, valve-off 31 and 32, the crude product in the hold-up vessel 22 is pumped in the thin-film evaporator 26 valve-off 25 through high temperature resistant recycle pump 24, start simultaneously thin-film evaporator 26, and open condenser 28, vacuum system 27, and high temperature resistant recycle pump 33 are under 150 ℃ of temperature, vacuum pressure 500pa, enanthic acid is distilled out of, and flows into receiving tank 29 by the vacuum condensation system, till no longer including enanthic acid and being distilled out of, after utilizing thin-film evaporator 26 to take off enanthic acid, valve-off 30 is opened valve 32, and product is pumped out refining, after the process thin-film evaporator removes enanthic acid, obtain thick product 405kg, product is light yellow transparent, and acid number is 1.2, product acid number 0.3 after refining, sticking refer to 171.2, pour point-55 ℃, 242 ℃ of flash-points.
Embodiment 4 (dumbbell shape product 2-TriMethylolPropane(TMP)-hexanodioic acid-2-oleic acid-2 enanthic acid ester synthesis):
A, at the high position groove 1 interior adding raw material TriMethylolPropane(TMP) 134kg that feeds intake, header tank feeds intake and 2 adds hexanodioic acid 73kg, feed intake groove 3 of a high position adds oleic acid 282kg, and the high position groove 4 that feeds intake adds enanthic acid 140kg, and the high position groove 1 and 2 that feeds intake is filled with nitrogen protection and starts heating system, TriMethylolPropane(TMP) and tosic acid are dissolved, after raw material fully dissolves, open reaction kettle of the esterification 12, by vacuum system 19, vacuum pressure is 1500pa, valve-off 18,21 is opened valve 6 simultaneously, 7,11,16, at this moment the raw material in high-order feed intake groove 1 and 2 is inhaled in the kettle of reaction kettle of the esterification 12 under the condition of negative pressure, after raw material is inhaled into fully, valve-off 11;
B, open condenser 15 and high temperature resistant recycle pump 17, material is pumped by reaction kettle of the esterification 12 kettlies by high temperature resistant recycle pump 17, by catalyst fixed bed 14, at catalyst fixed bed 14 interior filling 5kg resin cation (R.C.) D001, then flowed back in the reaction kettle of the esterification 12 by spray header 13 sprayings, in working cycle, react, and constantly circulation, finish esterification, esterification temperature is 110 ℃, obtains crude product, and the water that reaction generates is collected into receiving tank 20 by vacuum condensation 15 systems, when treating that receiving tank 20 no longer include water and are distilled out of, open valve 8 and 11, oleic acid is sucked esterifying kettle 12, valve-off 11, continue circulating esterification and be distilled out of inflow receiving tank 20 until no longer include water, open valve 9 and 11, enanthic acid is sucked reaction kettle of the esterification 12, continue esterification and be distilled out of to no longer including water, esterification stops, stop vacuum system 19 and condenser 15, valve-off 16 and 21 is opened valve 18, the esterification crude product is pumped into hold-up vessel 22, and the inflated with nitrogen protection;
C, open valve 23,25 and 30, valve-off 31 and 32, crude product in the hold-up vessel 22 is pumped in the thin-film evaporator 26 through high temperature resistant recycle pump 24, and valve-off 25 is opened condenser 28, vacuum system 27 and high temperature resistant recycle pump 33,160 ℃ of temperature, vacuum pressure 600pa, enanthic acid is distilled out of, and is that 28 systems flow into receiving tank 29 by vacuum condensation, till no longer including enanthic acid and being distilled out of, utilize the thin film evaporation instrument to take off valve-off 30 behind the enanthic acid, open valve 32, product is pumped out refining, after the process thin-film evaporator removes enanthic acid, obtain thick product 549kg, the product yellow transparent, acid number is 1.5, product acid number 0.5 after refining, sticking refer to 185.3, pour point-45 ℃, 268 ℃ of flash-points.
Embodiment 5 (dumbbell shape product 2-TriMethylolPropane(TMP)-hexanodioic acid-1-oleic acid-1-palmitinic acid-2 enanthic acid ester synthesis):
A, at the high position groove 1 interior adding raw material TriMethylolPropane(TMP) 134kg that feeds intake, header tank feeds intake and 2 adds hexanodioic acid 73kg, feed intake groove 3 of a high position adds oleic acid 142kg, feed intake groove 4 of a high position adds palmitinic acid 126.5kg, feed intake groove 5 of a high position adds enanthic acid 140kg, to the high position groove 1 that feeds intake, 2 and 4 are filled with nitrogen protection and start heating system, TriMethylolPropane(TMP) and tosic acid are dissolved, after raw material fully dissolves, open reaction kettle of the esterification 12, by vacuum system 19, vacuum pressure is 2500pa, simultaneously valve-off 18,21, open valve 6,7,11,16, at this moment the raw material in high-order feed intake groove 1 and 2 is inhaled under the condition of negative pressure in the reaction kettle of the esterification 12, after raw material is inhaled into fully, and valve-off 11;
B, open condenser 15 and high temperature resistant recycle pump 17, material is pumped by reaction kettle of the esterification 12 kettlies by high temperature resistant recycle pump 17, by catalyst fixed bed 14, at catalyst fixed bed 14 interior filling 5kgMCM-41 mesopore molecular sieves, then flowed back in the reaction kettle of the esterification 12 by spray header 13 sprayings, in working cycle, react, and constantly circulation, finish esterification, esterification temperature is 150 ℃, obtain crude product, the water that reaction generates is collected into receiving tank 20 by vacuum condensation 15 systems, when treating that receiving tank 20 no longer include water and are distilled out of, open valve 8 and 11, oleic acid is sucked esterifying kettle 12, valve-off 11, continue circulating esterification and be distilled out of inflow receiving tank 20 until no longer include water, open valve 9 and 11, palmitinic acid is sucked reaction kettle of the esterification 12, continue esterification and be distilled out of to no longer including water, flow into receiving tank 20, open valve 10 and valve 11, enanthic acid is sucked in the reaction kettle of the esterification 12, continue esterification and be distilled out of to no longer including water, esterification stops, stop vacuum system 19 and condenser 15, valve-off 16 and 21 is opened valve 18, the esterification crude product is pumped into hold-up vessel 22, and the inflated with nitrogen protection;
C, open valve 23,25 and 30, valve-off 31 and 32, crude product in the hold-up vessel 22 is pumped in the thin-film evaporator 26 through high temperature resistant recycle pump 24, and valve-off 25 is opened condenser 28, vacuum system 27 and high temperature resistant recycle pump 33,140 ℃ of temperature, vacuum pressure 300pa, enanthic acid is distilled out of, and is that 28 systems flow into receiving tank 29 by vacuum condensation, till no longer including enanthic acid and being distilled out of, utilize the thin film evaporation instrument to take off valve-off 30 behind the enanthic acid, open valve 32, product is pumped out refining, after the process thin-film evaporator removes enanthic acid, obtain thick product 521kg, the product yellow transparent, acid number is 1.3, product acid number 0.6 after refining, sticking refer to 181.4, pour point-39.5 ℃, 277 ℃ of flash-points.
Claims (6)
1. solvent-free esterification-distillation integral process, it is characterized in that device related in this technique is by the high position groove that feeds intake, reaction kettle of the esterification, hold-up vessel, thin-film evaporator is composed in series, at the high position groove 1 (1) that feeds intake, 2 (2), 3 (3), respectively carry heating unit on 4 (4) and 5 (5), and discharge port each with a valve 1 (6), 2 (7), 3 (8), 4 (9) and 5 (10), a high position feeds intake and is state in parallel between the groove, be connected with reaction kettle of the esterification (12) by pipe connecting, reaction kettle of the esterification (12) bottom is connected with catalyst fixed bed (14) by high temperature resistant recycle pump (17), the spray header (13) of one end of catalyst fixed bed (14) is fixed in the reaction kettle of the esterification (12), upper end at reaction kettle of the esterification (12) is connected with receiving tank (20) by condenser (15), the top of receiving tank (20) is vacuum system (19) fixedly, high temperature resistant recycle pump (17) is connected with hold-up vessel (22) by pipe connecting, the discharge port of the bottom of hold-up vessel (22) is connected with thin-film evaporator (26) by high temperature resistant recycle pump (24), one end of high temperature circulation pump (33) is connected with the top opening for feed of thin-film evaporator (26), the other end connects the bottom of thin-film evaporator (26), top at thin-film evaporator (26) is connected with receiving tank (29) by condenser (28), the top of receiving tank (29) is vacuum system (27) fixedly, and concrete operations follow these steps to carry out:
A, esterification feed is added respectively a high position feed intake in the groove 1 (1), 2 (2), 3 (3), 4 (4) and 5 (5), be filled with nitrogen protection and start heating system, after raw material fully dissolves, enter in the reaction kettle of the esterification (12) by vacuum system (19), wherein the adding of esterification feed contains a kind of liquid starting material at least, boiling point under its normal pressure≤500 ℃;
B, open condenser (15) and high temperature resistant recycle pump (17), material is pumped by reaction kettle of the esterification (12) kettle by high temperature resistant recycle pump (17), by catalyst fixed bed (14), then flowed back in the reaction kettle of the esterification (12) by spray header (13) spraying, in working cycle, react, and constantly circulation, finish esterification, obtain crude product, crude product is pumped in the hold-up vessel (22), be filled with nitrogen protection, wherein esterification reaction temperature is 100 ℃-150 ℃;
Crude product in c, the hold-up vessel (22) is pumped in the thin-film evaporator (26) through high temperature resistant recycle pump (24), open condenser (28), vacuum system (27) and high temperature resistant recycle pump (33), 140 ℃ of temperature, vacuum pressure 300pa, steam except the excessive small molecular weight organic raw material of not participating in reaction, recycling thin film evaporation instrument (26) is made with extra care and is obtained pure product, condenser (28) is condensed into liquid state, flows into receiving tank (29).
2. technique according to claim 1 is characterized in that step a esterification technique carries out solvent-free vacuumizing under the condition, and the vacuum pressure of vacuum system (19) and (27) is 300-3000pa.
3. technique according to claim 1 is characterized in that step a reaction system raw material uses soluble catalyst to be tosic acid.
4. technique according to claim 1, it is characterized in that among the step b at also continuous circulation time, pass through simultaneously vacuum system (19) and take out negative pressure, the water vapor that reaction generates is extracted out in kettle (12), through condenser (15), be cooled to liquid state, flow into receiving tank (20).
5. technique according to claim 1 is characterized in that immobilized solid catalyst is MCM-41 mesopore molecular sieve or resin cation (R.C.) D001, LSCA-30 or LSI-600 among the step b catalyst fixed bed (14).
6. technique according to claim 1 is characterized in that a high position feeds intake groove 1 (1), 2 (2), 3 (3), 4 (4) and 5 (5) for using separately or using simultaneously.
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| CN104745647B (en) * | 2013-12-31 | 2020-11-27 | 丰益(上海)生物技术研发中心有限公司 | Method for processing grease through enzymatic esterification and grease prepared by method |
| CN104745646B (en) * | 2013-12-31 | 2019-12-10 | 丰益(上海)生物技术研发中心有限公司 | Equipment for treating grease by enzymatic esterification |
| CN104557526A (en) * | 2014-11-27 | 2015-04-29 | 浙江金科过氧化物股份有限公司 | Method for preparing ortho-methylcyclohexyl acetate under solvent-free conditions |
| CN109232241A (en) * | 2018-09-21 | 2019-01-18 | 浙江皇马科技股份有限公司 | A kind of preparation method of trihydroxymethylpropanyl ester |
| CN114044740B (en) * | 2021-11-22 | 2024-01-05 | 中国石油大学(北京) | Ester base oil with ultrahigh viscosity index and preparation method thereof |
| CN114349639A (en) * | 2022-01-17 | 2022-04-15 | 徐州彰梁生化科技有限公司 | Novel method for applying solid acid catalyst to esterification reaction |
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| CN101050178A (en) * | 2006-04-07 | 2007-10-10 | 花王株式会社 | Method of preparing ester |
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| CN101050178A (en) * | 2006-04-07 | 2007-10-10 | 花王株式会社 | Method of preparing ester |
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