CN104744680B - A kind of synthesizer of polyester polyol - Google Patents
A kind of synthesizer of polyester polyol Download PDFInfo
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- CN104744680B CN104744680B CN201310755564.1A CN201310755564A CN104744680B CN 104744680 B CN104744680 B CN 104744680B CN 201310755564 A CN201310755564 A CN 201310755564A CN 104744680 B CN104744680 B CN 104744680B
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Abstract
The invention discloses a kind of synthesizers of polyester polyol, including reaction kettle, reflux condenser, pans and the second condenser, reaction kettle has heat conductive oil inlet, conduction oil outlet, there is reflux condenser coolant inlet, coolant outlet, the second condenser to have coolant inlet, coolant outlet；Reaction kettle is connected to pans, and pans are connected with reflux condenser, and pans load absorptive substance；Temperature controlling point is arranged in the exit of reflux condenser；Reflux condenser is connected with the second condenser, and the reaction outlet of the second condenser divides two-way to be respectively communicated with vacuum plant, blow valve.The synthesizer of polyester polyol of the present invention is characterized in increasing the pans of filling absorptive substance between reaction kettle and reflux condenser, compares traditional handicraft device, has the following advantages：Reaction speed is fast, and the reaction time is short；Low energy consumption；Utilization rate of equipment and installations is improved, is reduced investment outlay；Wastewater treatment is simple, and processing cost is low.
Description
Technical field
The invention belongs to the synthesis technical fields of polyester polyol, and in particular to a kind of synthesizer of polyester polyol.
Background technology
Polyester polyol is formed by small molecule polyol and binary acid by polycondensation reaction, this is that a balance can be converse
It answers, the micromolecular water generated when constantly removing reaction in reaction process, destruction of balance, reaction can just continue.To make
Rapid reaction carries out, it is necessary to improve reaction temperature and remove the water generated in reaction process in time.
Binary acid used mainly has：
（1）Saturated fatty acid：One ethanedioic acid, succinic acid, hexanedioic acid, suberic acid etc.；
（2）Unsaturated fatty acid：Along butadiene diacid, anti-butadiene diacid etc.；
（3）Aromatic acid：Terephthalic acid (TPA), M-phthalic acid, O-phthalic acid or anhydride.
Polyalcohol has：
（1）Dihydric alcohol：Ethylene glycol, diglycol, Diethylene Glycol, propylene glycol, butanediol；
（2）Ternary acid：Trimethylolpropane, glycerine, trimethylolethane, triol etc.；
（3）Other alcohol：Sorbierite, pentaerythrite etc..
As shown in schematic diagram 2, the reaction first stage is discharged the basic device of current general synthesizing polyester polyalcohol for nature,
100 DEG C or so of the tops reflux condenser B1 temperature is controlled, the water that reaction generates is made constantly to be discharged in the form of water vapour；React the later stage second
Stage makes water vapour be discharged, also wants temperature control at the top of reflux condenser B1, prevent small molecule polyester using the methods of decompression is vacuumized
Polyalcohol is run out of.
In the reaction first stage, water vapour is coerced when being discharged with a small amount of small molecule polyol, therefore, to control reflux condensation mode
The tops device B1 temperature, the water some that reaction generates in this way is discharged with water vapour, and carries under one's arms a small amount of small molecule polyol of discharge, another portion
Part water vapour and most small molecule polyol flow back into reaction kettle A1 because of condensation；In reaction second stage, also to control back
The tops flow condenser B1 temperature, the water some that reaction generates in this way are discharged with water vapour, and another part water vapour flows back because of condensation
To reaction kettle A1.
There are following defects for above-mentioned apparatus：
1, it is slow to go out water speed.Since in the reaction first stage, the tops reflux condenser B1 temperature cannot be too high, and general control exists
100~105 DEG C, Wen Taigao is pushed up, a large amount of small molecule polyols are carried under one's arms by water vapour, and alcohol loss is very big.
2, a certain amount of small molecule polyol is lost.Even if the top reflux condenser B1 temperature can be precisely controlled in 100~
105 DEG C, but still have a certain amount of small molecule polyol and carried under one's arms by water vapour, so small molecule polyol is than theoretical value
Excessive 5% or so.
3, energy consumption is big.In the reaction first stage, reflux condenser B1 pushes up 100 DEG C or so of temperature control system, and the water for reacting generation steams
Vapour part can be discharged, and part is condensed and flows back into reaction kettle A1, therefore, constantly there is water reflux during the reaction, recirculation water
It is evaporated discharge again, constantly recycles, expends a large amount of energy；In reaction second stage, and so.To cause entirely to react
Process energy consumption is big.
4, the reaction time is long.Condensed water constantly flows back in reaction process, cannot be discharged in time, inhibits reaction, and have water
In the presence of material heating is slow, and material reaction speed is slow, and the reaction time extends.
5, wastewater treatment is costly.The waste water that reaction generates is handled, so that its is free from environmental pollution.And due to quilt
The small molecule polyol COD that water vapour is carried under one's arms is very high, to cause cost for wastewater treatment height.
Some relatively advanced devices are to make the reflux condenser B1 in Fig. 2 into destilling towers at present, can effectively be subtracted
When young molecular polylol is discharged with water vapour, but, the problems such as there is also the reaction time is long, energy consumption is big.
Invention content
To solve above-mentioned technical problem of the existing technology, the present invention provides a kind of synthesis of polyester polyol dresses
It sets.
The present invention takes following technical scheme：A kind of synthesizer of polyester polyol, including reaction kettle, reflux condensation mode
Device, pans and the second condenser, reaction kettle have heat conductive oil inlet, conduction oil outlet, reflux condenser have coolant into
Mouth, coolant outlet, the second condenser have coolant inlet, coolant outlet；Reaction kettle is connected to pans, pans with
Reflux condenser is connected, and pans load absorptive substance；Temperature controlling point is arranged in the exit of reflux condenser；Reflux condenser
It is connected with the second condenser, the reaction outlet of the second condenser divides two-way to be respectively communicated with vacuum plant, blow valve.
Preferably, absorptive substance is molecular sieve, silica gel, anhydrous cupric sulfate, Carbon Dioxide calcium, aluminium oxide or activated carbon.
It is further preferred that absorptive substance is molecular sieve.
Still more preferably, molecular sieve isMolecular sieve.
Preferably, the pans for loading absorptive substance have multiple, and multiple pans are laid side by side, are used alternatingly.
For basic device of the present invention as shown in schematic diagram 1, reaction kettle (A2) has heat conductive oil inlet (1), conduction oil outlet (2),
Reaction kettle (A2) is connected to pans (C), and pans (C) are connected to reflux condenser (B2), the outlet of reflux condenser (B2)
The top of another condenser, reflux condenser (B2) is equipped with temperature controlling point (5).Reflux condenser (B2) have coolant inlet (3),
Coolant outlet (4)；Another condenser has coolant inlet (6), coolant outlet (7) and reaction outlet (8), reaction outlet
(8) two-way is divided to connect vacuum plant (including water collecting tank) (9), blow valve (10).It is discharged at the top of from reflux condenser (B2)
Water vapour enters water collecting tank after being cooled to water by another condenser.
The present invention adds pans (C) between reaction kettle (A2) and reflux condenser (B2), is loaded such as in pans (C)
The absorptive substances such as molecular sieve, silica gel, anhydrous cupric sulfate, Carbon Dioxide calcium, aluminium oxide, activated carbon, the absorptive substance meet
The following conditions：
1, water can be selectively adsorbed, but does not adsorb small molecule polyol and polyester polyol substantially, even if absorbing small
Molecular polylol and polyester polyol can also be replaced by water；
2, it is not dissolved in water；
3, it will not react with the raw materials such as binary acid and small molecule polyol and polyester polyols alcohol and water；
4, water can be desorbed under certain condition, it is reusable.
Through the present invention, experiments have shown that, the absorptive substance is best with molecular sieve, and molecular sieve is good to water adsorptive selectivity, even if
Absorbing small molecule polyol can also be replaced by water, reach 20% or more to the adsorbance of water, desorption is simple, reuses the time
It is long.It is furthermore preferred that withMolecular sieve is best.Below just withIt is illustrated for molecular sieve.
In the reaction first stage, reflux condenser (B2) pushes up temperature control system at 100 DEG C hereinafter, polynary with water vapour and small molecule
Discharge is not advisable alcohol at the top of reflux condenser (B2).The water vapour that reaction generates is adsorbed by molecular sieve, is not inhaled in time on a small quantity
Attached water vapour and small molecule polyol flows back because reflux condenser (B2) is condensed, and recirculation water is adsorbed by molecular sieve again, small point
Sub- polyalcohol then flows back into reaction kettle (A2), and the reaction was continued, and such water does not flow back into reaction kettle (A2) substantially.React second-order
Duan Caiyong vacuum decompression methods, in second stage because reaction is basically completed, the water for reacting generation is few, and steam forces down, water vapour
It cannot be automatically drained out, so that water vapour is discharged by vacuum decompression.Similar with traditional handicraft, decompression process wants incremental, very
Reciprocal of duty cycle steps up.At this point, temperature control is also wanted at the top of reflux condenser (B2), to prevent small molecule polyol and low molecular weight polyester
Polyalcohol is run out of, and the boiling point of reflux condenser (B2) top temperature control system water under vacuum degree at that time is slightly higher to be advisable.Under condensing condition,
Water vapour can also be condensed reflux, and molecular sieve also functions to the effect of absorption water, and condensed water is made not flow back into reaction kettle (A2).
Load absorptive substance pans (C) can with it is multiple side by side, be used alternatingly.Preferably, it is a pans, because
For in the second stage of reaction, water can be desorbed by the negative pressure and the temperature of itself of reaction system in molecular sieve, need not be separately
Dehydration waits for reuse next time, simply and conveniently.
The synthesizer of polyester polyol of the present invention compares traditional handicraft device, has the following advantages：
1, reaction speed is fast, and the reaction time is short.Because the water that reaction generates is adsorbed by molecular sieve, reaction kettle is not flowed back into substantially
A2 will not inhibit to react, and water can be discharged from reaction kettle A2 in time, and material heating is rapid, and reaction temperature is high, accelerates reaction
Process.
2, low energy consumption.Water base of reflux condensation mode does not flow back into reaction kettle A2 in reaction process, and returned cold condensate weight is not present
Multiple distillation process, can be greatly reduced energy consumption；And material heating is rapid, and reaction temperature is high, and energy can be reduced again by accelerating reaction process
Consumption.
3, utilization rate of equipment and installations is improved, is reduced investment outlay.Reaction speed is fast, shortens the reaction time, utilization rate of equipment and installations can be improved, and saves
Investment-saving.
4, wastewater treatment is simple, and processing cost is low.Small molecule polyol is not run out of substantially, and waste water COD is low, wastewater treatment letter
Single, processing cost is low.
The synthesizer reaction time of polyester polyol of the present invention is embodied in big production it is obvious that being suitble to the big life of industrialization
Production demand.
Description of the drawings
Fig. 1 is the structure diagram of the synthesizer of polyester polyol of the present invention.
Fig. 2 is the structure diagram of the synthesizer of conventional polyester polyalcohol.
Specific implementation mode
Following embodiments are described in detail by taking 6000L reaction kettle devices as an example and give comparative illustration.
Embodiment 1
The present embodiment process units is as shown in schematic diagram 1, stainless steel band jacket reactor A2 volumes 6000L, 2 square metres of tubulations
4000kg is housed in formula stainless steel reflux condenser B2,4000L stainless steel pans C, pans CMolecular sieve, W-4 are reciprocal
Formula vacuum system (including water collecting tank), 260 degree of deep fats, nitrogen.
3212kg hexanedioic acids are put into a kettle, and 1488kg ethylene glycol heats up, and material temperature is raised to 100 DEG C and opens stirring, opens back
Flow condenser B2 cooling waters, 90 DEG C of the tops control reflux condenser B2 temperature, when material temperature is raised to 210 DEG C, reflux condenser B2 turns off cold
But vacuum is opened when water top temperature also drops to 60 DEG C, reflux condenser B2 cooling waters is reopened before opening vacuum, control reflux condensation mode
65 DEG C of the tops device B2 temperature, since -0.02MPa, vacuum degree is promoted once reaction system vacuum degree every half an hour, be followed successively by -
0.04MPa, -0.06MPa, -0.08MPa, -0.095MPa.Then vacuum reaction 4.5 hours again.Sampling, acid value 2mgKOH/g.
Total reaction time about 16 hours.Polyester polyol molecule amount 1940.
Embodiment 2
2628kg hexanedioic acids are put into the reaction unit of embodiment 1,2120kg diethylene glycols heat up, and material temperature is raised to 100
DEG C stirring is opened, opens reflux condenser B2 cooling waters, 90 DEG C of the tops control reflux condenser B2 temperature, when material temperature is raised to 210 DEG C, returned cold
Condenser B2, which turns off when cooling water top temperature also drops to 60 DEG C, opens vacuum, and reflux condenser B2 cooling waters are reopened before opening vacuum,
65 DEG C of the tops reflux condenser B2 temperature is controlled, for reaction system vacuum degree since -0.02MPa, vacuum degree promotes one every half an hour
It is secondary, it is followed successively by -0.04MPa, -0.06MPa, -0.08MPa, -0.095MPa.Then vacuum reaction 4.5 hours again.Sampling, acid value
1.85mgKOH/g。
Total reaction time about 16 hours.Polyester polyol molecule amount 2040.
Embodiment 3
3182.8kg hexanedioic acids, 1339.2kg ethylene glycol, 198kg trihydroxy methyls are put into the reaction unit of embodiment 1
Propane, heating, material temperature are raised to 100 DEG C and open stirring, open reflux condenser B2 cooling waters, and the tops control reflux condenser B2 are 90 DEG C warm,
When material temperature is raised to 210 DEG C, reflux condenser B2, which turns off when cooling water top temperature also drops to 60 DEG C, opens vacuum, to be beaten again before opening vacuum
Reflux condenser B2 cooling waters are opened, 65 DEG C of the tops control reflux condenser B2 temperature, reaction system vacuum degree is since -0.02MPa, very
Reciprocal of duty cycle is promoted once every half an hour, is followed successively by -0.04MPa, -0.06MPa, -0.08MPa, -0.095MPa.Then vacuum again
Reaction 4.5 hours.Sampling, acid value 1.81mgKOH/g.
Total reaction time about 16 hours.Polyester polyol molecule amount 2040.
Embodiment 4（Comparative example）
The embodiment uses traditional handicraft device, is comparative example.Its reaction unit is as shown in schematic diagram 2, reaction dress
There is no pans C in setting, it is other same as Example 1.
3212kg hexanedioic acids, 1562.4kg ethylene glycol are put into reaction unit（Ethylene glycol excessive 5%）, heating, material temperature liter
Stirring is opened to 100 DEG C, opens reflux condenser B1 cooling waters, 103~105 DEG C of the tops control reflux condenser B1 temperature, when material temperature is raised to
210 DEG C, reflux condenser B1, which turns off when cooling water top temperature also drops to 60 DEG C, opens vacuum, and reflux condensation mode is reopened before opening vacuum
Device B1 cooling waters, 65 DEG C of the tops control reflux condenser B1 temperature, reaction system vacuum degree is since -0.02MPa, and vacuum degree is every half
Hour is promoted once, is followed successively by -0.04MPa, -0.06MPa, -0.08MPa, -0.095MPa.Then vacuum reaction 8.5 is small again
When.Sampling, acid value 2.2mgKOH/g.
Total reaction time about 24 hours.Polyester polyol molecule amount 1930.
It can be seen that from the comparison of the embodiment and embodiment 1 using present invention process device, total reaction time shortens 8
Hour, shorten about one third.
Those skilled in the art are it should be appreciated that above example is intended merely to illustrate rather than to this hair
Bright restriction, as long as within the scope of the invention, the protection model of the present invention is fallen within to variation, the deformation of above example
It encloses.
Claims (4)
1. a kind of synthesizer of polyester polyol, it is characterized in that including reaction kettle, reflux condenser, pans and the second condensation
There is heat conductive oil inlet, conduction oil outlet, reflux condenser to have coolant inlet, coolant outlet for device, reaction kettle, and second is cold
Condenser has coolant inlet, coolant outlet；Reaction kettle is connected to pans, and pans are connected with reflux condenser, in
Between it is canned fill out absorptive substance, the absorptive substance is molecular sieve, silica gel, anhydrous cupric sulfate, Carbon Dioxide calcium, aluminium oxide
Or activated carbon；Temperature controlling point is arranged in the exit of reflux condenser；Reflux condenser is connected with the second condenser, the second condenser
Reaction outlet divide two-way to be respectively communicated with vacuum plant, blow valve.
2. the synthesizer of polyester polyol as described in claim 1, it is characterised in that：The absorptive substance is molecule
Sieve.
3. the synthesizer of polyester polyol as claimed in claim 2, it is characterised in that：The molecular sieve isMolecule
Sieve.
4. the synthesizer of polyester polyol as described in any one of claims 1-3, it is characterised in that：The filling water imbibition
The pans of substance be equipped with it is multiple, multiple pans are laid side by side.
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| CN106220832B (en) * | 2016-08-15 | 2018-07-20 | 上海回天新材料有限公司 | A kind of method and apparatus producing polyester polyol |
| CN108149322B (en) * | 2018-01-30 | 2023-09-08 | 中国科学院福建物质结构研究所 | Synthetic tank device and synthetic method of high deuterium DKDP crystal raw material |
| CN109078598B (en) * | 2018-09-18 | 2024-09-24 | 重庆华峰化工有限公司 | Polyester polyol synthesis system and synthesis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0618249A2 (en) * | 1993-04-02 | 1994-10-05 | MITSUI TOATSU CHEMICALS, Inc. | Aliphatic polyester and preparation process thereof |
| CN101249317A (en) * | 2008-03-13 | 2008-08-27 | 宁波市启航助剂有限公司 | Water diversion recovering device for polycarboxylic acids series dehydragent macromer preparation |
| CN202849299U (en) * | 2012-10-15 | 2013-04-03 | 镇江利德尔复合材料有限公司 | Reflux device for unsaturated polyester resin reaction kettle |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002088146A (en) * | 2000-09-14 | 2002-03-27 | Teijin Ltd | Method for continuous production of polyester |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0618249A2 (en) * | 1993-04-02 | 1994-10-05 | MITSUI TOATSU CHEMICALS, Inc. | Aliphatic polyester and preparation process thereof |
| CN101249317A (en) * | 2008-03-13 | 2008-08-27 | 宁波市启航助剂有限公司 | Water diversion recovering device for polycarboxylic acids series dehydragent macromer preparation |
| CN202849299U (en) * | 2012-10-15 | 2013-04-03 | 镇江利德尔复合材料有限公司 | Reflux device for unsaturated polyester resin reaction kettle |
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