CN102304041A - Solvent-free esterification-distillation integrated process - Google Patents
Solvent-free esterification-distillation integrated process Download PDFInfo
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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, can toluene, xylenes etc. be arranged as the solvent of band 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 through the mode of heat exchange in band water process; Increased energy consumption; After reaction was accomplished simultaneously, solvent must be steamed from reaction system and reclaimed, in the removal process of solvent; Have partial loss; Toluene, xylenes 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 a solventless method; No-solvent process is divided into two kinds again; Excessive organic constituent is as the band aqua in a kind of employing esterification; Usually this excessive organic constituent and the consistency bad (like butanols) of water can form azeotropic with water, or employing constantly blasts organic constituent steam (like 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 be used the system soluble catalyst, and causes degree of esterification not high easily, and esterification time is long.
Summary of the invention:
The objective of the invention is to; A kind of solvent-free esterification-distillation integral process is provided; This technology is by header tank; Reaction kettle of the esterification; Hold-up vessel; The thin film evaporation appearance is composed in series; The fatty alcohol acid starting material is entered into and has 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 accomplish esterification; And the method for taking constantly to vacuumize will be reacted the water that generates and steamed and remove; Promote the esterification forward to carry out; After esterification is accomplished; Crude product is through the hold-up vessel of nitrogen protection; Be recycled and be pumped in the thin-film evaporator; After steaming removes the excessive small molecular weight organic raw material of participating in reaction, obtain pure product through making with extra care again.The present invention compares with traditional esterification technology, and whole process need not solvent and participates in, and the recyclable utilization of excessive small molecules organic raw material 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 technology 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 a high position respectively feed intake in groove (1), (2), (3), (4), (5); Charge into nitrogen protection and start heating system; After treating that raw material fully dissolves; Get in the reaction kettle of the esterification (12) through 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 through high temperature resistant recycle pump (17); Through catalyst fixed bed (14), flow back in the reaction kettle of the esterification (12) by spray header (13) spraying then, in working cycle, react; And constantly circulation; Accomplish esterification, obtain crude product, crude product is pumped in the hold-up vessel (22); Charge into 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 and remove the excessive small molecular weight organic raw material of not participating in reaction, utilize thin film evaporation appearance (26) to make with extra care again and obtain 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 vacuum system (19) simultaneously and take out negative pressure among the step b, the water vapor quilt that reaction generates through condenser (15), is cooled to liquid state from the interior extraction of kettle (12), 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 technology; 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 respectively have a valve (6) at discharge port; (7); (8); (9) and (10); A high position feeds intake and is parallelly connected state between the groove; Be connected with reaction kettle of the esterification (12) through pipe connecting; Reaction kettle of the esterification (12) bottom is connected with catalyst fixed bed (14) through 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) through 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) through pipe connecting; The discharge port of the bottom of hold-up vessel (22) is connected with thin-film evaporator (26) through 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) through 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 gets into esterifying kettle; Adopt the method for solvent-free circulating esterification to accomplish esterification; Reaction kettle of the esterification has EGR, catalyst fixed bed and spray head and vacuum condensation system; Material is pumped by high temperature resistant circulating 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 head; Continuous circulating esterification; The water that generates at the esterifying kettle internal reaction is drawn out of system by the vacuum condensation system simultaneously; Promote reaction to carry out; After esterification is accomplished; Pump in the thin film evaporator capable of circulation through holding vessel; Steam except that refining behind the excessive unreacted small-molecular weight organic component 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; The recyclable utilization of excessive little molecular organic raw material; Be energy-saving and emission-reduction, the esterification synthesis technique of green non-pollution.
Process application according to the invention is combined in the aliphatic alcohol acid esters; Adopt the mode of the excessive adding of small-molecular weight organic component; The excessive little molecular organic component of circulating esterification and tandem thin-film evaporimeter 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 charging stock is participated in wherein to ingredient requirement; 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.
Technology of the present invention if use soluble catalyst, needs catalyzer is directly added in the esterification feed in the esterification system, if use solid catalyst, needs through catalytic fixed bed immobilized.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Technology of the present invention will illustrate and explain through 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 respectively have a valve 6 at discharge port; 7; 8; 9 and 10; A high position feeds intake and is parallelly connected state between the groove; Be connected with reaction kettle of the esterification 12 through pipe connecting; Reaction kettle of the esterification 12 bottoms are connected with catalyst fixed bed 14 through 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 through 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 through pipe connecting; The discharge port of the bottom of hold-up vessel 22 is connected with thin-film evaporator 26 through 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 through condenser 28, and the top of receiving tank 29 is vacuum system 27 fixedly.
Embodiment 1 (synthesizing of trimethylolpropane tri-heptanoate):
A,, a high position adds raw material TriMethylolPropane(TMP) 134kg and catalyzer tosic acid 2kg in feeding intake groove 1; Header tank feeds intake and adds enanthic acid 400kg in 2; The high position groove 1 that feeds intake is charged into nitrogen protection and starts heating system; TriMethylolPropane(TMP) and tosic acid are dissolved; After treating that 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 condenser 15 and high temperature resistant recycle pump 17 simultaneously; Material pumps from reaction kettle of the esterification 12 through high temperature resistant recycle pump 17; Through catalyst fixed bed 14; This moment catalyst fixed bed not infill system insoluble solid catalyzer; Flow back in the reaction kettle of the esterification 12 by spray header 13 sprayings; In working cycle, react, and constantly circulation, esterification accomplished; Esterification temperature is 100 ℃; Obtain crude product, the water that reaction generates is collected into receiving tank 20 through the vacuum condensation system, treat that water in the receiving tank is collected 53-54kg after; 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 thin-film evaporator 26 simultaneously; 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 steamed, and flows into receiving tank 29 through the vacuum condensation system, till no longer including enanthic acid and being steamed; 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; Refining back product acid number 0.05; Sticking refer to 174.5, pour point-59 ℃, 228 ℃ of flash-points.
Embodiment 2 (synthesizing of trimethylolpropane tri-heptanoate):
A,, a high position adds raw material TriMethylolPropane(TMP) 134kg in feeding intake groove 1; Header tank feeds intake and adds enanthic acid 400kg in 2; The high position groove 1 that feeds intake is charged into nitrogen protection and starts heating system; TriMethylolPropane(TMP) is dissolved; After treating that 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 condenser 15 and high temperature resistant recycle pump 17 simultaneously; Material pumps from reaction kettle of the esterification 12 through high temperature resistant recycle pump 17; Through catalyst fixed bed 14; In catalyst fixed bed 14, fill 5kg resin cation (R.C.) LSI-600; Flow back in the reaction kettle of the esterification 12 by spray header 13 sprayings; In working cycle, react, and constantly circulation, esterification accomplished; Esterification temperature is 120 ℃; Obtain crude product, the water that reaction generates is collected into receiving tank 20 through the vacuum condensation system, treat that water in the receiving tank is collected 53-54kg after; 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 thin-film evaporator 26 simultaneously; 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 steamed, and flows into receiving tank 29 through the vacuum condensation system, till no longer including enanthic acid and being steamed; 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; Refining back product acid number 0.05; Sticking refer to 174.5, pour point-59 ℃, 228 ℃ of flash-points.
Embodiment 3 (synthesizing of dumbbell shape product 2-TriMethylolPropane(TMP)-hexanodioic acid-4-heptanoate):
A;, a high position adds raw material TriMethylolPropane(TMP) 134kg in feeding intake groove 1; 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 charged into nitrogen protection and starts heating system; TriMethylolPropane(TMP) and tosic acid are dissolved; After treating that 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 treating that raw material is inhaled into fully, valve-off 11;
B; Open vacuum system 19; Open condenser 15 and high temperature resistant recycle pump 17 simultaneously; Material pumps from reaction kettle of the esterification 12 through high temperature resistant recycle pump 17; Through catalyst fixed bed 14; In catalyst fixed bed 14, fill 5kg resin cation (R.C.) LSCA-30; Flow back in the reaction kettle of the esterification 12 by spray header 13 sprayings; In working cycle, react, and constantly circulation, esterification accomplished; Esterification temperature is 140 ℃; Obtain crude product, the water that reaction generates is collected into receiving tank 20 through the vacuum condensation system, treat that water in the receiving tank is collected 53-54kg after; 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 thin-film evaporator 26 simultaneously; 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 steamed, and flows into receiving tank 29 through the vacuum condensation system, till no longer including enanthic acid and being steamed; 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; Refining back product acid number 0.3; Sticking refer to 171.2, pour point-55 ℃, 242 ℃ of flash-points.
Embodiment 4 (synthesizing of dumbbell shape product 2-TriMethylolPropane(TMP)-hexanodioic acid-2-oleic acid-2 heptanoate):
A;, a high position adds raw material TriMethylolPropane(TMP) 134kg in feeding intake groove 1; 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 charged into nitrogen protection and starts heating system; TriMethylolPropane(TMP) and tosic acid are dissolved; After treating that raw material fully dissolves, open reaction kettle of the esterification 12, through vacuum system 19; Vacuum pressure is 1500pa; Valve-off 18,21 is opened valve 6 simultaneously; 7; 11,16, the raw material at this moment 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 treating that 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 through high temperature resistant recycle pump 17; Through catalyst fixed bed 14; In catalyst fixed bed 14, fill 5kg resin cation (R.C.) D001; Flow back in the reaction kettle of the esterification 12 by spray header 13 sprayings then, in working cycle, react, and constantly circulation; Accomplish esterification; Esterification temperature is 110 ℃, obtains crude product, and the water that reaction generates is collected into receiving tank 20 through vacuum condensation 15 systems; When treating that receiving tank 20 no longer include water and steamed; Open valve 8 and 11, oleic acid is sucked esterifying kettle 12, valve-off 11; Continue circulating esterification and steamed inflow receiving tank 20 until no longer including water; Open valve 9 and 11, enanthic acid is sucked reaction kettle of the esterification 12, continue esterification and steamed 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 steamed, and is that 28 systems flow into receiving tank 29 through vacuum condensation; Till no longer including enanthic acid and being steamed; Utilize the thin film evaporation appearance 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; Refining back product acid number 0.5; Sticking refer to 185.3, pour point-45 ℃, 268 ℃ of flash-points.
Embodiment 5 (synthesizing of dumbbell shape product 2-TriMethylolPropane(TMP)-hexanodioic acid-1-oleic acid-1-palmitinic acid-2 heptanoate):
A;, a high position adds raw material TriMethylolPropane(TMP) 134kg in feeding intake groove 1; 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 charge into nitrogen protection and start heating system, and TriMethylolPropane(TMP) and tosic acid are dissolved, treat that raw material fully dissolves after; Open reaction kettle of the esterification 12; Through vacuum system 19, vacuum pressure is 2500pa, simultaneously valve-off 18; 21; Open valve 6,7,11; 16; At this moment the high-order groove 1 that feeds intake is inhaled in the reaction kettle of the esterification 12 under the condition of negative pressure with 2 interior raw materials, treat that raw material is inhaled into fully after, 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 through high temperature resistant recycle pump 17; Through catalyst fixed bed 14; In catalyst fixed bed 14, fill the 5kgMCM-41 mesopore molecular sieve; Flow back in the reaction kettle of the esterification 12 by spray header 13 sprayings then; In working cycle, react; And constantly circulation; Accomplish esterification; Esterification temperature is 150 ℃; Obtain crude product; The water that reaction generates is collected into receiving tank 20 through vacuum condensation 15 systems; When treating that receiving tank 20 no longer include water and steamed; Open valve 8 and 11, oleic acid is sucked esterifying kettle 12, valve-off 11; Continue circulating esterification and steamed inflow receiving tank 20 until no longer including water; Open valve 9 and 11, palmitinic acid is sucked reaction kettle of the esterification 12, continue esterification and steamed 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 steamed 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 steamed, and is that 28 systems flow into receiving tank 29 through vacuum condensation; Till no longer including enanthic acid and being steamed; Utilize the thin film evaporation appearance 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; Refining back product acid number 0.6; Sticking refer to 181.4, pour point-39.5 ℃, 277 ℃ of flash-points.
Claims (7)
1. solvent-free esterification-distillation integral process is characterized in that this technology 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, and concrete operations follow these steps to carry out:
A, esterification feed is added a high position respectively feed intake in groove (1), (2), (3), (4), (5); Charge into nitrogen protection and start heating system; After treating that raw material fully dissolves; Enter in the reaction kettle of the esterification (12) through 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 through high temperature resistant recycle pump (17); Through catalyst fixed bed (14), flow back in the reaction kettle of the esterification (12) by spray header (13) spraying then, in working cycle, react; And constantly circulation; Accomplish esterification, obtain crude product, crude product is pumped in the hold-up vessel (22); Charge into 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 and remove the excessive small molecular weight organic raw material of not participating in reaction, utilize thin film evaporation appearance (26) to make with extra care again and obtain pure product; Condenser (28) is condensed into liquid state, flows into receiving tank (29).
2. technology 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. technology according to claim 2 is characterized in that step a reaction system raw material uses soluble catalyst to be tosic acid.
4. technology according to claim 3, it is characterized in that among the step b and continuous circulation time, pass through vacuum system (19) simultaneously 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. technology according to claim 4 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. technology according to claim 1; It is characterized in that device related in this technology 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) that feeds intake; (2); (3); (4) and respectively carry heating unit on (5); And respectively have a valve (6) at discharge port; (7); (8); (9) and (10); A high position feeds intake and is parallelly connected state between the groove; Be connected with reaction kettle of the esterification (12) through pipe connecting; Reaction kettle of the esterification (12) bottom is connected with catalyst fixed bed (14) through 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) through 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) through pipe connecting; The discharge port of the bottom of hold-up vessel (22) is connected with thin-film evaporator (26) through 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) through condenser (28), and the top of receiving tank (29) is vacuum system (27) fixedly.
7. device according to claim 6 is characterized in that a high position feeds intake groove (1), (2), (3), (4) and (5) for using separately or using simultaneously.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104745646A (en) * | 2013-12-31 | 2015-07-01 | 丰益(上海)生物技术研发中心有限公司 | Apparatus for esterifying oils and fats by use of enzymic method |
| CN104745647A (en) * | 2013-12-31 | 2015-07-01 | 丰益(上海)生物技术研发中心有限公司 | Method for enzymic-method esterification processing of grease and grease prepared by using same |
| 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 |
| CN114044740A (en) * | 2021-11-22 | 2022-02-15 | 中国石油大学(北京) | Ultrahigh-viscosity-index ester base oil 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745646A (en) * | 2013-12-31 | 2015-07-01 | 丰益(上海)生物技术研发中心有限公司 | Apparatus for esterifying oils and fats by use of enzymic method |
| CN104745647A (en) * | 2013-12-31 | 2015-07-01 | 丰益(上海)生物技术研发中心有限公司 | Method for enzymic-method esterification processing of grease and grease prepared by using same |
| 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 |
| 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 |
| 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 |
| CN114044740A (en) * | 2021-11-22 | 2022-02-15 | 中国石油大学(北京) | Ultrahigh-viscosity-index ester base oil and preparation method thereof |
| 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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|---|---|
| CN102304041B (en) | 2013-10-30 |
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