CN217962495U - Continuous tubular reaction device for producing polycarbonate polyether polyol - Google Patents
Continuous tubular reaction device for producing polycarbonate polyether polyol Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 34
- 229920000570 polyether Polymers 0.000 title claims abstract description 34
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 31
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 31
- 229920005862 polyol Polymers 0.000 title claims abstract description 31
- 150000003077 polyols Chemical class 0.000 title claims abstract description 29
- 238000003860 storage Methods 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000007670 refining Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 26
- 230000001502 supplementing effect Effects 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- 239000006052 feed supplement Substances 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- 150000002118 epoxides Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 67
- 239000012071 phase Substances 0.000 abstract description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- -1 first reactor (1) Chemical class 0.000 abstract description 3
- 239000007792 gaseous phase Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004593 Epoxy Chemical class 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The utility model relates to a production polycarbonate polyether glycol's continuous tube reaction unit mainly solves among the prior art DMC catalyst activation not in the same direction as or in the twinkling of an eye the activation after easily explode the polymerization, problem that the safety risk is high. The utility model discloses an adopt a continuous tube reaction unit of production polycarbonate polyether polyol, including first reactor (1), tubular reaction unit (2), gaseous phase storage tank (3), second reactor (4), PO storage tank (6), CO 2 Storage tank (7) and separationA refining device (5); wherein the first reactor (1) is communicated with the tubular reaction device (2); the tubular reaction device (2) is communicated with the second reactor (4), the PO storage tank (6) and/or the CO 2 A tank (7); the gas phase storage tank (3) is communicated with the tubular reaction device (2) to realize the circulation of gas phase components, so that the problem is well solved, and the method can be used in the industrial production of the polycarbonate polyether glycol.
Description
Technical Field
The utility model relates to a polyether polyol field especially relates to a continuous tube formula reaction unit of production polycarbonate polyether polyol.
Background
With the use of a large amount of fossil energy, the emission amount of carbon dioxide increases year by year, although plants can absorb part of carbon dioxide through photosynthesis to release oxygen, the effect is very slow, and the effect of relieving global greenhouse effect is not large.
The polycarbonate polyether polyol is prepared by polymerizing carbon dioxide and epoxy compounds, and can be prepared by copolymerizing the epoxy compounds, the carbon dioxide and chain transfer agents containing active H-functional groups, and is a special structural polyol with carbonate groups in molecules and hydroxyl groups at the ends of molecular chains.
The preparation of the polycarbonate polyether polyol has been studied for 40 years at home and abroad, but the reaction of the polycarbonate polyether polyol is exothermic, so that the reactor is required to have good heat exchange performance to ensure that the reaction does not generate temperature runaway, and if the temperature is too high, the content of a carbonic ester chain link is low, the molecular weight distribution is widened, the proportion of a byproduct cyclic carbonic ester is increased, and the quality of a product is reduced; moreover, the DMC catalyst is not activated smoothly or is activated instantly (the concentration of epoxide is too high), so that the explosion polymerization can occur, and the safety accidents of high temperature and high pressure are easily caused.
Chinese patent CN103403060B discloses a process for preparing polyether carbonate polyols by the addition of one or more alkylene oxides and carbon dioxide onto one or more H-functional starter substances in the presence of at least one DMC catalyst, and the addition reaction is carried out in a tubular reactor, and the reaction temperature is controlled, but the process itself involves the risk of DMC catalyst deactivation and PO implosion, but only the choice of reaction equipment is made to reduce the problem of decomposition of the polyether carbonate polyol and/or deactivation of the DMC catalyst due to too high a temperature after implosion.
Chinese patent No. 103214666B discloses a method for preparing aliphatic polycarbonate by a continuous solution polymerization method, which comprises the steps of injecting epoxy monomer, carbon dioxide and catalyst into a loop reactor in a continuous mode, circulating a part of reaction materials back to the loop reactor, allowing a part of reaction materials to enter a tubular reactor for reaction, connecting a discharge end with a flash evaporator, devolatilizing and drying to obtain a polymerization product, improving the conversion rate of the epoxy monomer, and using the circulating flow as the driving force of the loop reactor to solve the problem of limitation of carbon dioxide content on circulating power, but the patent method does not teach how to technically control DMC deactivation and PO implosion risk in the polymerization reaction process.
Chinese patent CN111804218A discloses an industrial continuous production device of polycarbonate polyether polyol, which comprises CO 2 The device comprises an adding device, an epoxide adding device, a chain transfer agent adding device, a catalyst adding device, a premixing kettle and a straight tube reactor; the premix kettle is used for epoxy, chain transfer agent, catalyst and low pressure CO 2 Mixing to form a primary mixture and bringing it to a state to be reacted; straight tube reactor for mixing primary mixture and high-pressure CO 2 Mixing to form a secondary mixture, and making it in a synthesis reaction state, wherein the bottom of the straight tube reactor is communicated with the premixing kettle and the CO 2 An adding device; the problem of scale-up effects in batch processes is mitigated and reaction time is reduced, but it is not mentioned how to avoid the risks of DMC catalyst deactivation and PO implosion during the reaction.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the technical problem that DMC catalyst activation is not in the same direction as or DMC catalyst is easy to explode after the activation in the twinkling of an eye among the prior art and gathers, and the problem that the safety risk is high provides a continuous tubular reaction unit of production polycarbonate polyether polyol, and the device has DMC catalyst and activates in advance, can not explode in the twinkling of an eye and gather, and PO concentration is low in unit time, the unit volume, and the advantage that the safety risk is low.
In order to solve the technical problem, the utility model adopts the following technical scheme: a continuous tubular reaction device for producing polycarbonate polyether polyol comprises a first reactor 1, a tubular reaction device 2, a gas phase storage tank 3, a second reactor 4, a PO storage tank 6, CO 2 A storage tank 7 and a separation and purification device 5; wherein, a stirring device is arranged in the first reactor 1, the top part of the first reactor is provided with an air inlet pipeline 1-1, an emptying pipeline 1-5 and a feeding pipeline, and the bottom part of the first reactor is provided with a material outlet and is communicated with the tubular reaction device 2; the tubular reaction device 2 is provided with a feeding hole and a feeding hole at the bottom, an overflow hole at the side wall, a gas-phase gas outlet at the top, and the feeding hole is communicated with a PO storage tank 6 and/or CO 2 A storage tank 7, an overflow port of which is communicated with the second reactor 4; the tubular reaction device 2 is formed by connecting at least two straight tube reactors in series; the top of the gas phase storage tank 3 is provided with a gas inlet, the bottom of the gas phase storage tank is provided with a gas outlet, the side wall of the gas phase storage tank is provided with a gas supplementing port, and the gas supplementing port and CO are arranged 2 A gas phase pressure control device 3-2 is arranged on a communicating pipeline which is communicated with the storage tank 7 and is close to the gas supplementing port, the gas inlet is communicated with a gas phase outlet of the tubular reaction device 2, and the gas outlet is communicated with a gas supplementing port of the tubular reaction device 2, so that the circulation of gas phase components in the tubular reaction device 2 and the gas phase storage tank 3 is realized; the second reactor 4 is provided with a discharge hole and is communicated with a separation refining device 5.
Further, the tubular reaction device 2 is formed by connecting at least 3 straight tube reactors in series; the first reactor 1 is a kettle type reactor provided with a heat exchange device; the second reactor 4 is a straight tube reactor or a kettle type reactor provided with a heat exchange device.
Further, the tubular reaction device 2 is formed by sequentially connecting a first straight tube reactor 2-1, a second straight tube reactor 2-2 and a third straight tube reactor 2-3 in series; wherein, the bottom feed inlet of the first straight-tube reactor 2-1 is communicated with the first reactor 1, and the feed supplement port is communicated with the PO storage tank 6 and CO 2 A storage tank 7 and a gas phase storage tank 3; a material supplementing port at the bottom of the second straight-tube reactor 2-2 is communicated with a PO storage tank 6 and a gas phase storage tank 3; first, theThe bottom feed supplement ports of the three straight-tube reactors 2-3 are communicated with the gas phase storage tank 3, and the side wall overflow ports are communicated with the second reactor 4; the tops of the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 and the third straight-tube reactor 2-3 are respectively provided with a gas-phase gas outlet which is respectively communicated with a gas inlet at the top of the gas-phase storage tank 3 through a gas-phase pipeline; the second reactor 4 is a straight tube reactor.
Further, a first pressure control device 3-3 is arranged on a gas phase pipeline between the first straight-tube reactor 2-1 and the gas phase storage tank 3; a second pressure control device 3-4 is arranged on a gas phase pipeline between the second straight-tube reactor 2-2 and the gas phase storage tank 3; a third pressure control device 3-5 is arranged on a gas phase pipeline between the third straight-tube reactor 2-3 and the gas phase storage tank 3.
Further, the gas phase pressure control device 3-2, the first pressure control device 3-3, the second pressure control device 3-4 and the third pressure control device 3-5 are all composed of an adjusting valve and a pressure gauge, and the pressure gauge and the adjusting valve are controlled in a linkage mode.
Further, heat exchange devices are arranged on the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 and the third straight-tube reactor 2-3; distribution discs 8 are arranged inside the first straight-tube reactor 2-1, the second straight-tube reactor 2-2, the third straight-tube reactor 2-3 and the second reactor 4 so as to increase the gas-liquid contact area of materials.
Further, the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 and the third straight-tube reactor 2-3 are vertically arranged or arranged at an angle of 0-60 degrees relative to the vertical direction.
Further, the inner diameter of the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 and the third straight-tube reactor 2-3 is 10-300 mm, and the length-diameter ratio is 5-50.
Further, said CO 2 A pressure reducing valve 7-1 is arranged on an air outlet pipeline of the storage tank 7; a pressure pump 3-1 is arranged between the gas outlet of the gas phase storage tank 3 and the tubular reaction device 2; the feed lines to the first reactor 1 include an epoxide feed line 1-2, a chain transfer agent feed line 1-3, and a DMC catalyst feed line 1-4.
The utility model provides a continuous tubular reaction unit of production polycarbonate polyether polyol, including the first reactor that is used for DMC catalyst pre-activation reaction, the tubular reaction unit that is used for continuous tubular reaction, the second reactor that is used for PO end capping reaction, and form the circulation of gaseous phase component between tubular reaction unit and the gaseous phase storage tank, after DMC catalyst pre-activation, will activate basic material, PO, CO in succession again 2 Continuously introducing raw materials into a tubular reactor for PO and CO 2 The copolymerization reaction of (1), and finally, the end-capping polymerization reaction is carried out by using PO to produce and obtain a polycarbonate polyether polyol product; the whole production device avoids the risk of DMC deactivation, and has the advantages of pre-activation of DMC catalyst, no instant implosion, low PO concentration in the reaction kettle in unit time and unit volume, and low safety risk; and the whole reaction process is controllable, and the economic efficiency is high.
The utility model discloses the performance index test method of polycarbonate polyether polyol who makes is as follows:
molecular weight distribution (Mw/Mn): the molecular weight distribution (Mw/Mn) referred to in the present application is determined by GPC measurement, i.e., gel permeation chromatography;
viscosity: GB/T12008.7-2010;
hydroxyl value: GB/T12008.3-2009;
acid value: GB/T12008.5-2010;
moisture content: GB/T22313-2008;
the content of propylene carbonate: performing quantification by using nuclear magnetic hydrogen spectrum;
CO 2 the content is as follows: quantification was performed using nuclear magnetic carbon spectroscopy.
Drawings
FIG. 1 is a schematic structural diagram of a continuous tubular reaction apparatus for producing polycarbonate polyether polyol provided by the present invention.
In the attached figure 1, 1 is a first reactor, 1-1 is an air inlet pipeline, 1-2 is an epoxide feeding pipeline, 1-3 is a chain transfer agent feeding pipeline, 1-4 is a DMC catalyst feeding pipeline, 1-5 is an emptying pipeline, 1-6 is a basic material dropping pump, 2 is a tubular reaction device, 2-1 is a first straight tube reactor,2-2 is a second straight-tube reactor, 2-3 is a third straight-tube reactor, 3 is a gas phase storage tank, 3-1 is a pressure pump, 3-2 is a gas phase pressure control device, 3-3 is a first pressure control device, 3-4 is a second pressure control device, 3-5 is a third pressure control device, 4 is a second reactor, 4-1 is a fourth pressure control device, 5 is a separation and refining device, 6 is a PO storage tank, 6-1 is a first dropping pump, 6-2 is a second dropping pump, 6-3 is a third dropping pump, 7 is CO 2 A storage tank, 7-1 is a pressure reducing valve, and 8 is a distribution disc.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only some embodiments of the present invention, not all embodiments.
[ example 1 ]
A continuous tubular reaction device for producing polycarbonate polyether polyol comprises a first reactor 1, a first straight tube reactor 2-1, a second straight tube reactor 2-2, a third straight tube reactor 2-3, a gas phase storage tank 3, a second reactor 4, a PO storage tank 6, CO 2 A storage tank 7 and a separation and purification device 5 2 A pressure reducing valve 7-1 is arranged on an air outlet pipeline of the storage tank 7;
the first reactor 1 is a kettle type reactor provided with a heating jacket, a stirring device is arranged in the first reactor, the top of the first reactor is provided with an air inlet pipeline 1-1, an emptying pipeline 1-5, an epoxide feeding pipeline 1-2, a chain transfer agent feeding pipeline 1-3 and a DMC catalyst feeding pipeline 1-4, and the bottom of the first reactor is provided with a material outlet;
the top of the gas phase storage tank 3 is provided with a gas inlet, the bottom is provided with a gas outlet, the side wall is provided with a gas supplementing port, and the gas supplementing port and the CO are arranged 2 A gas phase pressure control device 3-2 is arranged on a communicating pipeline communicated with the storage tank 7 and close to the air supplementing port, a pressure pump 3-1 is arranged on a pipeline of the air outlet, and the gas phase components in the gas phase storage tank 3 are pumped to the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 or the third straight-tube reactor 2-3 through the pressure pump 3-1;
the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 and the third straight-tube reactor 2-3 are respectively provided with a heating jacket at the outside and a heating jacket at the bottomThe gas phase circulation reactor is provided with a distribution disc 8, a feed inlet and a feed supplement port, overflow ports are arranged on the side walls, gas phase gas outlets are arranged on the top, the gas phase gas outlets are respectively communicated with a gas inlet on the top of the gas phase storage tank 3 through a gas phase pipeline, and the feed supplement port on the bottom is respectively communicated with a gas outlet on the bottom of the gas phase storage tank 3, so that circulation of gas phase components in the straight-tube reactor and the gas phase storage tank is realized; the bottom feed inlet of the first straight-tube reactor 2-1 is communicated with the material outlet of the first reactor 1, and the feed supplement port is communicated with the PO storage tank 6 and CO 2 A storage tank 7; a feeding port at the bottom of the second straight-tube reactor 2-2 is communicated with the PO storage tank 6; the overflow port on the side wall of the third straight-tube reactor 2-3 is communicated with the second reactor 4; wherein, a first pressure control device 3-3 is arranged on a gas phase pipeline between the first straight-tube reactor 2-1 and the gas phase storage tank 3; a second pressure control device 3-4 is arranged on a gas phase pipeline between the second straight-tube reactor 2-2 and the gas phase storage tank 3; a third pressure control device 3-5 is arranged on a gas phase pipeline between the third straight-tube reactor 2-3 and the gas phase storage tank 3;
the second reactor 4 is a straight tube reactor provided with a distribution disc 8, is provided with a discharge hole and is communicated with the separation and refining device 5, and a fourth pressure control device 4-1 is arranged on a connecting pipeline between the second reactor and the separation and refining device;
the fourth pressure control device 4-1, the gas phase pressure control device 3-2, the first pressure control device 3-3, the second pressure control device 3-4 and the third pressure control device 3-5 are all composed of an adjusting valve and a pressure gauge, and the pressure gauge and the adjusting valve are in linkage control;
the first straight-tube reactor 2-1, the second straight-tube reactor 2-2 and the third straight-tube reactor 2-3 have the inner diameter of 40mm, the length-diameter ratio of 10 and are vertically arranged.
The specific implementation process is as follows:
1) Adding 500g of chain transfer agent (polyether glycol CHE-304 with functionality of 3, molecular weight of 400 and pure PO segment) and 1.2g of DMC catalyst dispersed by tert-butyl alcohol into a first reactor respectively, stirring, degassing for 2h at 115 ℃, introducing nitrogen for replacing and removing oxygen, and keeping a slight positive pressure; raising the temperature to 130 ℃, adding 250g of PO through an epoxide feed line, and indicating that the DMC catalyst is successfully activated when temperature shift occurs in the first reactor and the pressure in the reaction kettle decreases; after pre-activating the DMC catalyst, slowly dripping 150g of PO to keep the activity of the catalyst, and reducing the reaction temperature to 80 ℃ to obtain an activated base material;
2) Continuously pumping the activated base material into a first straight-tube reactor, and according to the activated base material: PO =1:1, continuously feeding PO into a first straight-tube reactor through a first dropping pump, uniformly reacting with the materials in the reactor through a distribution disc, and simultaneously, CO 2 Introducing the mixture into a first straight-tube reactor from the bottom of the reactor through a pressure reducing valve, controlling the reaction temperature to be 85 ℃, controlling the reaction pressure to be 3.5Mpa through a regulating valve, and controlling the retention time to be 8h; with the continuous feeding of the activated base material and PO, the liquid phase in the kettle is gradually increased, the gas phase pressure in the upper space is compressed, when the pressure exceeds the set pressure, the pressure is released to a second straight-tube reactor or a gas phase storage tank by an adjusting valve, and the gas phase component in the gas phase storage tank enters the first straight-tube reactor again through a booster pump for circular reaction;
3) And (3) allowing the liquid-phase material in the first straight-tube reactor to enter a second straight-tube reactor through an overflow port, and activating the basic material: PO =1:1, pumping PO into a second straight-tube reactor by a second dripping pump, controlling the temperature to be 85 ℃, controlling the reaction pressure to be 3.3MPa, and controlling the retention time to be 5.5h; meanwhile, gas-phase components in the pressurized gas-phase storage tank are circulated from the bottom of the reactor to perform a circulating reaction; the liquid phase material is overflowed and then enters a third straight pipe reactor;
4) Once materials are contained in the third straight-tube reactor, gas-phase components with circularly pressurized bottoms enter the reactor from the bottoms to participate in internal pressure reaction, the pressure control mode is the same as that of the first straight-tube reactor and the second straight-tube reactor, the temperature is controlled to be 85 ℃, the reaction pressure is 3.2MPa, and the retention time is 5.5h; after the materials in the third straight-tube reactor are overflowed, the materials are uniformly and continuously discharged through a fourth pressure control device and enter a second reactor;
5) Once the second reactor had material, the ratio of activated base material: PO =3.5:1, pumping PO into a third dropping pump for end-capping reaction at the temperature of 110 ℃ and the reaction pressure of 0.45MPa, and feeding the overflowing material into a separation and refining device; polycarbonate polyether obtained by separation and refining treatmentThe polyol index is: a functionality of 3, a hydroxyl value of 51.48mgKOH/g, an acid value of 0.038mgKOH/g, a water content of 0.03%, a viscosity of 14877mpa · s/25, a propylene carbonate content of 0.70% at DEG C, CO 2 The content was 16.05%, and the molecular weight distribution (Mw/Mn) was 1.48.
Adopt the utility model provides a production polycarbonate polyether glycol's continuous tube formula reaction unit, DMC catalyst activation, reaction material low temperature reaction under the high temperature, PO concentration is low in unit time, the unit volume reation kettle, the risk that PO explodes and gathers can not appear, and factor of safety is high, can be at lower CO 2 The high-content polycarbonate polyether polyol is obtained under pressure, the molecular weight distribution of the prepared polycarbonate polyether polyol is narrow, the content of the propylene carbonate byproduct is low, and the technical effect is good.
Claims (9)
1. A continuous tubular reaction device for producing polycarbonate polyether polyol is characterized by comprising a first reactor (1), a tubular reaction device (2), a gas phase storage tank (3), a second reactor (4), a PO storage tank (6), and CO 2 A storage tank (7) and a separation and purification device (5); wherein,
a stirring device is arranged in the first reactor (1), the top of the first reactor is provided with an air inlet pipeline (1-1), an emptying pipeline (1-5) and a feeding pipeline, and the bottom of the first reactor is provided with a material outlet which is communicated with the tubular reactor (2);
tubular reaction unit (2) bottom be equipped with feed inlet and feed supplement mouth, lateral wall be equipped with the overflow mouth, the top is equipped with the gaseous gas outlet, the feed supplement mouth communicate in PO storage tank (6) and/or CO 2 A storage tank (7), an overflow port of which is communicated with the second reactor (4); the tubular reaction device (2) is formed by connecting at least two straight tube reactors in series;
the top of the gas phase storage tank (3) is provided with a gas inlet, the bottom of the gas phase storage tank is provided with a gas outlet, the side wall of the gas phase storage tank is provided with a gas supplementing port, and the gas supplementing port and CO are arranged 2 A gas phase pressure control device (3-2) is arranged on a communicating pipe line communicated with the storage tank (7) and close to the gas supplementing port, the gas inlet is communicated with a gas phase gas outlet of the tubular reaction device (2), and the gas outlet is communicated with a gas supplementing port of the tubular reaction device (2), so that the tubular reaction device (2) and the gas phase storage are realizedCirculating circulation of gas-phase components in the tank (3);
the second reactor (4) is provided with a discharge hole and is communicated with the separation and refining device (5).
2. The continuous tubular reaction apparatus for producing a polycarbonate polyether polyol according to claim 1, characterized in that: the tubular reaction device (2) is formed by connecting at least 3 straight tube reactors in series; the first reactor (1) is a kettle type reactor provided with a heat exchange device; the second reactor (4) is a straight tube reactor or a kettle type reactor provided with a heat exchange device.
3. The continuous tubular reaction apparatus for producing a polycarbonate polyether polyol according to claim 2, characterized in that: the tubular reaction device is formed by sequentially connecting a first straight-tube reactor (2-1), a second straight-tube reactor (2-2) and a third straight-tube reactor (2-3) in series; wherein, the bottom feed inlet of the first straight-tube reactor (2-1) is communicated with the first reactor (1), and the feed supplement inlet is communicated with the PO storage tank (6) and the CO 2 A storage tank (7) and a gas phase storage tank (3); a feeding port at the bottom of the second straight-tube reactor (2-2) is communicated with the PO storage tank (6) and the gas phase storage tank (3); a bottom feed supplement port of the third straight-tube reactor (2-3) is communicated with the gas phase storage tank (3), and a side wall overflow port is communicated with the second reactor (4); the tops of the first straight-tube reactor (2-1), the second straight-tube reactor (2-2) and the third straight-tube reactor (2-3) are respectively provided with a gas-phase gas outlet which is respectively communicated with a gas inlet at the top of the gas-phase storage tank (3) through a gas-phase pipeline; the second reactor (4) is a straight tube reactor.
4. The continuous tubular reaction apparatus for producing a polycarbonate polyether polyol according to claim 3, characterized in that: a first pressure control device (3-3) is arranged on a gas phase pipeline between the first straight-tube reactor (2-1) and the gas phase storage tank (3); a second pressure control device (3-4) is arranged on a gas phase pipeline between the second straight-tube reactor (2-2) and the gas phase storage tank (3); a third pressure control device (3-5) is arranged on a gas phase pipeline between the third straight-tube reactor (2-3) and the gas phase storage tank (3).
5. The continuous tubular reaction apparatus for producing polycarbonate polyether polyol according to claim 4, characterized in that: the gas phase pressure control device (3-2), the first pressure control device (3-3), the second pressure control device (3-4) and the third pressure control device (3-5) are all composed of a regulating valve and a pressure gauge, and the pressure gauge and the regulating valve are in linkage control.
6. The continuous tubular reaction apparatus for producing a polycarbonate polyether polyol according to claim 3, characterized in that: heat exchange devices are arranged on the first straight-tube reactor (2-1), the second straight-tube reactor (2-2) and the third straight-tube reactor (2-3); distribution discs (8) are arranged in the first straight-tube reactor (2-1), the second straight-tube reactor (2-2), the third straight-tube reactor (2-3) and the second reactor (4) to increase the gas-liquid contact area of materials.
7. The continuous tubular reaction apparatus for producing a polycarbonate polyether polyol according to claim 3, characterized in that: the first straight-tube reactor (2-1), the second straight-tube reactor (2-2) and the third straight-tube reactor (2-3) are vertically arranged or arranged at an angle of 0-60 degrees relative to the vertical direction.
8. The continuous tubular reaction apparatus for producing a polycarbonate polyether polyol according to claim 3, characterized in that: the inner diameters of the first straight-tube reactor (2-1), the second straight-tube reactor (2-2) and the third straight-tube reactor (2-3) are 10-300 mm, and the length-diameter ratio is 5-50.
9. The continuous tubular reaction apparatus for producing polycarbonate polyether polyol according to claim 1, characterized in that: said CO 2 A pressure reducing valve (7-1) is arranged on an air outlet pipeline of the storage tank (7); a pressure pump (3-1) is arranged between the gas outlet of the gas phase storage tank (3) and the tubular reaction device (2); the feed line of the first reactor (1) comprises an epoxide feed line (1-2),A chain transfer agent feed line (1-3), a DMC catalyst feed line (1-4).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202222408913.XU CN217962495U (en) | 2022-09-09 | 2022-09-09 | Continuous tubular reaction device for producing polycarbonate polyether polyol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202222408913.XU CN217962495U (en) | 2022-09-09 | 2022-09-09 | Continuous tubular reaction device for producing polycarbonate polyether polyol |
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