CN111298754A - Reactor and process for continuously producing polycarbonate oligomer - Google Patents
Reactor and process for continuously producing polycarbonate oligomer Download PDFInfo
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- CN111298754A CN111298754A CN202010099824.4A CN202010099824A CN111298754A CN 111298754 A CN111298754 A CN 111298754A CN 202010099824 A CN202010099824 A CN 202010099824A CN 111298754 A CN111298754 A CN 111298754A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 59
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 213
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000010924 continuous production Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000012295 chemical reaction liquid Substances 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 16
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 description 10
- 230000009977 dual effect Effects 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/242—Tubular reactors in series
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/205—General preparatory processes characterised by the apparatus used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
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Abstract
A reactor and process for the continuous production of polycarbonate oligomers. The reactor comprises a circulating liquid inlet, a bottom base plate, a liquid distributor, a Venturi mixed flow nozzle, a liquid outlet, an inner sleeve, a liquid inlet, a reactor bed body and a liquid outer circulating channel. The reactor carries energy through liquid external circulation, and liquid circulation flow in the reactor is amplified through a mode that the Venturi mixed flow nozzle and the inner sleeve are jointly used, so that liquid-liquid multiphase uniform mixing in the production process of the polycarbonate oligomer is realized, the structure of the reactor is simple, and the sealing property is more guaranteed. Multiple steps in the polycondensation or end capping process of the polycarbonate oligomer are realized in one reaction tower through multistage series connection, so that the space utilization rate of a factory is improved; no stirring paddle moving part is arranged, and the interior of the reactor provides a larger space for heat exchange internal components, thereby being beneficial to large-scale production; realizes the continuous operation of the polycondensation and the end capping reaction process of the polycarbonate oligomer, and improves the reaction efficiency and the product quality.
Description
Technical Field
The present invention relates to a reactor and process for the continuous production of polycarbonate oligomers.
Background
Polycarbonate oligomer is a thermoplastic high polymer material, and the material is widely applied to fire-proof materials in various industries as a fire retardant. The polycarbonate oligomer is mainly bisphenol A polycarbonate, wherein the tetrabromobisphenol A polycarbonate oligomer is brominated bisphenol A polycarbonate, and is suitable for processing PBT, PET, PBT/PET blended resin, polysulfone resin, SAN and various laminated resins due to the unique comprehensive performance. The production process of the polycarbonate oligomer mainly comprises a phosgene method and a non-phosgene method, and the reaction processes of different production processes generally mainly comprise two steps: a polycondensation process and an end-capping process. The end capping process is that the end capping reaction is further carried out on the condensation segment and phenol to form polycarbonate oligomer. The two reaction processes are both liquid-liquid multiphase reaction systems, on one hand, the reactor is required to have strong liquid-liquid mixing performance to ensure that the reaction is fully carried out, and on the other hand, the reactor is required to have high tightness to avoid the leakage of reaction substances.
In order to ensure the uniform mixing of liquid-liquid multiple phases, stirred tanks are generally used at home and abroad as reactors for producing polycarbonate. Patent CN208894224U discloses a vertical high-efficient homogeneity homothermal reactor of production polycarbonate, patent CN209715090U discloses a polycarbonate reactor, patent CN110270289A discloses an ultra-high sealed polycarbonate reaction unit. The reactors are not exclusively used for realizing strong mixing of liquid-liquid multiple phases by means of mechanical stirring of stirring paddles. When external mechanical stirring is adopted, the liquid phase is turbulent violently, and the liquid phase has better mixing characteristics. However, the following significant disadvantages are apparent when the stirred tank is used for the production of polycarbonate oligomers: 1) the stirred tank is generally used for intermittent operation, and continuous production of polycarbonate is difficult to realize; 2) the stirring kettle has a stirring paddle rotating part, so that the sealing requirement of the reaction kettle is more strict; 3) the heat exchange component of the stirring kettle is limited by the stirring paddle, and the larger-scale production is difficult to realize through a single reactor. In addition, the polycarbonate oligomer polycondensation and end-capping reaction process involves multiple steps, with different steps differing in operating conditions and processing parameters. At present, a plurality of stirring kettles are connected in series for intermittent production in industrial production, but the operation process is complicated due to the fact that too many stirring kettles are connected in series, and the space utilization rate of a factory is reduced.
In addition to the intensive mixing by mechanical stirring, a static mixer of a tubular type was used as a mixing reactor in the "continuous production method of a polycarbonate oligomer" disclosed in patent CN 101356213A. The static mixer realizes strong mixing through a mixing component in the reaction tube, and avoids some defects of mechanical stirring. However, the static mixer is small in size, the structure of an internal mixing component is complex, large-scale production is difficult to realize, and the static mixer is generally an integrated part and is difficult to clean and maintain once being blocked.
In conclusion, the development of a novel reactor which has good liquid-liquid multiphase mixing performance and simple structure and is suitable for continuously producing the polycarbonate oligomer has important industrial application value.
Disclosure of Invention
The invention aims to provide a reactor for continuously producing polycarbonate oligomer and a process for continuously producing the polycarbonate oligomer by using the reactor. The reactor has no mechanical stirring moving part, has good liquid-liquid multiphase mixing effect, high reaction efficiency and simple structure, and is easy to realize the large-scale production of the polycarbonate oligomer.
In a first aspect, the present invention provides a reactor for the continuous production of polycarbonate oligomers. The method comprises the following steps: the reactor comprises a circulating liquid inlet (1), a bottom base plate (2), a liquid distributor (3), a Venturi mixed flow nozzle (4), a liquid outlet (5), an inner sleeve (6), liquid inlets (11, 7), a reactor bed body (8) and a liquid outer circulating channel (10). It is to be noted that the reactor may comprise only the first liquid inlet 11 and also the second liquid inlet 7, if desired.
The reactor at least comprises two stages, liquid flow is realized among the stages of the reactor through an interstage overflow pipe, and the total cross-sectional area of the overflow pipe accounts for 0.1-10% of the cross-sectional area of a reactor bed body.
Each stage of the reactor carries energy through liquid external circulation, and the liquid circulation flow in the reactor is amplified in a mode of combining the Venturi mixed flow nozzle and the inner sleeve, so that the liquid-liquid multiphase in the reactor is quickly and uniformly mixed; the external circulation liquid inlet is connected with a liquid distributor, and the liquid distributor is connected with a Venturi mixed flow nozzle; the liquid distributor is composed of a liquid distributor main pipe and one or more liquid distribution pipes, one end of each liquid distribution pipe is connected with a hole of the liquid distributor main pipe, and the other end of each liquid distribution pipe is connected with a Venturi mixed flow nozzle.
The reactor comprises a heat exchange component, the temperature of the bed layer of the reactor is controlled by the heat exchange component, and the heat exchange component is one or a combination of a heat exchange tube or a heat exchange jacket.
Preferably, the first and second electrodes are formed of a metal,
the venturi mixed flow nozzle comprises a nozzle first liquid inlet (a) and a nozzle second liquid inlet (b), and the nozzle second liquid inlet (b) is connected to the throat of the venturi mixed flow nozzle.
The reaction liquid inlet of the reactor comprises a first liquid inlet (11) and a second liquid inlet (7); the first liquid inlet (11) is arranged on the side wall of the reactor; the second liquid inlet (7) is connected with the nozzle second liquid inlet (b) of the Venturi mixed flow nozzle through a liquid distributor, and the circulating liquid inlet (1) is connected with the nozzle first liquid inlet (a) of the Venturi mixed flow nozzle through a liquid distributor so as to enhance the efficient dispersion and the rapid mixing between the liquid entering from the second liquid inlet (7) and the liquid entering from the circulating liquid inlet (1).
In another aspect, the present invention provides a process for the continuous production of polycarbonate oligomers.
The process comprises a polycondensation reaction process and a terminal blocking reaction process, wherein the polycondensation reaction process is carried out in a first reactor, the terminal blocking reaction process is carried out in a second reactor, and the first reactor and the second reactor are the reactors provided by the invention.
During the polycondensation reaction, a part of the reaction materials are mixed in advance and then enter the first reactor through one or more first liquid inlets (11) of the first reactor; the rest of the reaction materials are mixed in advance and then enter the first reactor from one or more of the second liquid inlets (7) of the first reactor; catalyst enters the first reactor from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first reactor.
During the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second reactor through one or more of the first liquid inlets (11) of the second reactor; the mass of blocking agent enters the second reactor from one or more of the second liquid inlets (7) of the second reactor.
According to a preferred embodiment of the process provided by the present invention, the polycarbonate oligomer is a tetrabromobisphenol a polycarbonate oligomer.
In the preferred embodiment, the reaction process includes a polycondensation reaction process and a capping reaction process. In the polycondensation reaction process, tetrabromobisphenol A, dichloromethane and sodium hydroxide alkali liquor are mixed in advance and then enter a first reactor from one or more of first liquid inlets (11) of the first reactor; triphosgene and dichloromethane are premixed and then enter the first reactor from one or more of the second liquid inlets (7) of the first reactor; triethylamine enters the first reactor as a catalyst from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first reactor. During the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second reactor through one or more of the first liquid inlets (11) of the second reactor; phenol and sodium hydroxide lye are premixed and then enter the second reactor from one or more of the second liquid inlets (7) of the second reactor.
In the preferred embodiment, the reactor bed temperatures of each stage are independently controlled by the heat exchange means of the stage. In the polycondensation reaction process, the temperature of the first-stage bed layer at the bottommost part of the first reactor is 15-35 ℃, and the temperature of other reactors at all stages is 5-30 ℃; in the end-capping reaction process, the temperature of the first-stage bed layer at the bottommost part of the second reactor is 25-50 ℃, and the temperature of other reactors in different stages is 5-30 ℃.
The invention has the beneficial effects that:
the reactor provided by the invention realizes the uniform mixing of liquid-liquid multiphase in the production process of the polycarbonate oligomer by liquid external circulation and combining with the Venturi mixed flow nozzle and the inner sleeve for flow guiding, has high efficiency, replaces a stirred tank reactor in the production process of the polycarbonate oligomer, and has simple structure and better sealing property.
The reactors provided by the invention realize multiple steps in the polycondensation or end capping process of the polycarbonate oligomer in one reaction tower through multi-stage series connection, and the space utilization rate of a factory is improved.
The reactor provided by the invention has no stirring paddle moving part, provides a larger space for heat exchange internal components in the reactor, and is beneficial to large-scale production of polycarbonate oligomer.
The reactor provided by the invention realizes the continuous operation of the polycondensation and end capping reaction process of the polycarbonate oligomer, and improves the reaction efficiency and the product quality.
Drawings
FIGS. 1 and 2 are schematic diagrams of a three-stage reactor configuration for the continuous production of polycarbonate oligomers.
FIG. 3 is a schematic diagram of a venturi mixed flow nozzle.
Fig. 4 is a schematic view of the arrangement of the liquid distribution pipes of the liquid distributor.
Figure 5 is a schematic view of the interstage downcomer arrangement.
FIG. 6 is a schematic diagram of a dual liquid flash mixing reactor configuration.
FIG. 7 is a schematic view of a dual liquid inlet venturi mixing nozzle configuration.
FIG. 8 is a schematic diagram of a four-stage reactor configuration for the continuous production of polycarbonate oligomers.
In the figure: 1-circulating liquid inlet, 2-bottom base plate, 3-liquid distributor, 4-Venturi mixed flow nozzle, 5-liquid outlet, 6-inner sleeve, 7-second liquid inlet, 8-reactor bed body, 9-circulating pump, 10-liquid external circulating channel, 11-first liquid inlet, 12-internal overflow pipe, 13-external overflow pipe and 14-liquid distribution pipe.
Detailed Description
Embodiments of various preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Example 1
FIGS. 1 and 2 are schematic diagrams of a three-stage reactor configuration for the continuous production of polycarbonate oligomers. In the reactor of the embodiment, the reactor is in three-stage series connection, and the reactor is sequentially provided with a first stage, a second stage and a third stage from top to bottom; the reactor comprises a circulating liquid inlet (1), a bottom base plate (2), a Venturi mixed flow nozzle (4), a liquid outlet (5), an inner sleeve (6), a first liquid inlet (11), a second liquid inlet (7), a reactor bed body (8), a circulating pump (9) and a liquid outer circulating channel (10).
In the reactor of the embodiment, each stage reactor carries energy through liquid external circulation to realize uniform mixing of liquid phases in the reactor, and the external circulation liquid is further used in combination with an inner sleeve through a Venturi mixed flow nozzle to amplify the circulation flow of the liquid in the reactor stage. As shown in figure 1, the reaction liquid in the reactor of the present stage is led out from the middle position of the side wall of the reactor, passes through a liquid external circulation channel (10) and is conveyed to a circulating liquid inlet (1-1) by a circulating pump (9). The circulating liquid inlet (1-1) is connected with a liquid distributor (3), and the liquid distributor is connected with a Venturi mixed flow nozzle (4). When the liquid flow speed at the throat of the Venturi mixed flow nozzle is 4-20 m/s, preferably 8-12 m/s, the efficiency of sucking surrounding fluid into the Venturi mixed flow nozzle by the negative pressure of the throat of the Venturi mixed flow nozzle is high.
In the reactor of this example, the reaction liquid was flowed in the following manner: a first reaction liquid enters the first-stage reactor from a first liquid inlet (11-3), and a second reaction liquid enters the first-stage reactor from a second liquid inlet (7-3); more preferably, a portion of said first reaction liquid may enter the second and third reactors from first liquid inlets (11-2) and (11-1), respectively, and a portion of said second reaction liquid may enter the second and third reactors from second liquid inlets (7-2) and (7-1), respectively; the reaction liquid of the first-stage reactor overflows to a second-stage reactor through an interstage overflow pipe; the reaction liquid of the second-stage reactor overflows to a third-stage reactor through an interstage overflow pipe; the reaction liquid of the third-stage reactor flows out of the reactor from a liquid outlet (5). The interstage overflow pipe has two modes of an inner overflow pipe (12) shown in figure 1 and an outer overflow pipe (13) shown in figure 2; an internal overflow pipe (12) passes through the bottom substrate of the upper stage reactor to make liquid flow from the upper stage reactor into the annular flow area of the lower stage reactor; the overflow pipe flows out of the upper stage reactor through the connecting pipe, flows downwards through the overflow pipe arranged outside the reactor main body, and flows into the lower stage reactor through the connecting pipe of the lower stage reactor.
Fig. 3 and 4 are a structural schematic diagram of a venturi mixed flow nozzle and a liquid distribution pipe arrangement schematic diagram of a liquid distributor respectively. The liquid distributor consists of a liquid distributor main pipe and a plurality of liquid distribution pipes (14), and the liquid distribution pipes (14) are uniformly distributed on a plurality of concentric circumferences of the distributor main pipe. One end of the liquid distribution pipe is connected with the main pipe of the liquid distributor, the other end of the liquid distribution pipe is connected with the Venturi mixed flow nozzle, the inner diameter of the end, connected with the main pipe of the liquid distributor, of the liquid distribution pipe is 0.12-0.5 of the inner diameter of the end, connected with the Venturi mixed flow nozzle, of the liquid distribution pipe, and when the inner diameter is more preferably 0.2-0.4, liquid in the circulating liquid inlet (1) can be uniformly distributed to the liquid distribution pipes and flows into the Venturi mixed flow nozzle.
FIG. 5 is a schematic diagram of the arrangement of overflow pipes in the reactor stages. The liquid from the reactor of the upper stage overflows to the lower stage through an inter-stage internal overflow pipe (12). The inner overflow pipes are uniformly distributed on a plurality of concentric circumferences in the annular space area of the reactor, the number of the overflow pipes is adjusted according to the design requirement of the reactor, when the total cross-sectional area of the overflow pipes accounts for 0.1-25%, preferably 0.5-12% of the cross-sectional area of the reactor, the liquid streaming from the lower stage to the upper stage is less, and the reaction liquid basically overflows from the upper stage to the lower stage in a one-way mode.
Example 2
FIG. 6 is a schematic diagram of a dual liquid flash mixing reactor configuration. In the reactor of this example, the reactors were connected in series in three stages, the reactors were a first stage, a second stage, and a third stage in this order from top to bottom, and the intra-stage liquid circulation of each stage reactor was the same as in example 1.
In the reactor of this embodiment, a first reaction liquid is introduced into the first-stage reactor from the first liquid inlet (11-3), and a second reaction liquid is introduced into the first-stage reactor from the second liquid inlet (7-6); more preferably, a portion of said first reaction liquid may enter the second and third reactors from first liquid inlets (11-2) and (11-1), respectively, and a portion of said second reaction liquid may enter the second and third reactors from second liquid inlets (7-5) and (7-4), respectively.
In the reactor of this embodiment, the circulating liquid inlets (1-1), (1-2) and (1-3) of the reactor are connected to the first liquid inlet (a) of the nozzle of the mixed flow nozzle of FIG. 7 through a liquid distributor, and the second liquid inlets (7-4), (7-5) and (7-6) of the reactor are connected to the second liquid inlet (b) of the nozzle of the mixed flow nozzle of FIG. 7 through a liquid distributor, so as to enhance the efficient dispersion and rapid mixing between the liquid introduced from the second liquid inlet (7) and the liquid introduced from the circulating liquid inlet (1)
In the reactor of this example, the interstage liquid was overflowed in the same manner as in example 1.
FIG. 7 is two schematic structural views of a dual liquid inlet venturi mixing nozzle. The dual liquid inlet venturi mixing nozzle includes a nozzle first liquid inlet (a) and a nozzle second liquid inlet (b) connected to a throat of the venturi mixing nozzle.
Example 3
FIG. 8 is a schematic diagram of a four-stage reactor configuration for the continuous production of polycarbonate oligomers. In the reactor of this example, the reactors are four stages connected in series, the reactors are a first stage, a second stage, a third stage and a fourth stage from top to bottom, and the manner of the intra-stage liquid circulation and the inter-stage liquid overflow of each stage reactor is the same as that of example 1.
In the reactor of this embodiment, a first reaction liquid is introduced into the first-stage reactor from the first liquid inlet (11-4), and a second reaction liquid is introduced into the first-stage reactor from the second liquid inlet (7-4); more preferably, a portion of said first reaction liquid may enter the second, third and fourth reactors through first liquid inlets (11-3), (11-2) and (11-1), respectively, and a portion of said second reaction liquid may enter the second, third and fourth reactors through second liquid inlets (7-3), (7-2) and (7-1), respectively.
The reactor described in embodiment 1-3 includes a heat exchange member, the reactor controls the bed temperature through the heat exchange member, and the heat exchange member is one or a combination of a heat exchange tube and a heat exchange jacket.
Example 4
A process for the continuous production of a polycarbonate oligomer using the reactors described in examples 1-3. The process comprises a polycondensation reaction process and an end-capping reaction process.
In the process of this embodiment, the polycondensation reaction is carried out in a first reactor, which is one of the reactors described in embodiments 1-3. During the polycondensation reaction, a part of the polycondensation reaction materials are mixed in advance and then enter the first reactor through one or more first liquid inlets (11); the rest of the reaction materials are mixed in advance and then enter the first reactor from one or more of the second liquid inlets (7) of the first reactor; catalyst enters the first reactor from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first reactor. The polycondensation liquid produced by the polycondensation reaction flows out of the reactor from a liquid outlet (5) of the first reactor.
In the process of this embodiment, the end-capping reaction is performed in a second reactor, which is one of the reactors described in embodiments 1-3. During the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second reactor through one or more of the first liquid inlets (11) of the second reactor; the mass of blocking agent enters the second reactor from one or more of the second liquid inlets (7) of the second reactor. The reaction liquid containing the polycarbonate oligomer flows out of the reactor from the liquid outlet (5) of the second reactor.
Example 5
A process for the continuous production of a polycarbonate oligomer using the reactors described in examples 1-3. The polycarbonate oligomer is tetrabromobisphenol A polycarbonate oligomer, and the reaction process of the tetrabromobisphenol A polycarbonate oligomer comprises a polycondensation reaction process and an end-capping reaction process.
In the process of this embodiment, the polycondensation reaction is carried out in a first reactor, which is one of the reactors described in embodiments 1-3. In the polycondensation reaction process, tetrabromobisphenol A, dichloromethane and sodium hydroxide alkali liquor are mixed in advance and then enter a first reactor from one or more of first liquid inlets (11) of the first reactor; triphosgene and dichloromethane are premixed and then enter the first reactor from one or more of the second liquid inlets (7) of the first reactor; triethylamine enters the first reactor as a catalyst from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first reactor. The polycondensation liquid produced by the polycondensation reaction flows out of the reactor from a liquid outlet (5) of the first reactor.
In the process of this embodiment, the end-capping reaction is performed in a second reactor, which is one of the reactors described in embodiments 1-3. During the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second reactor through one or more of the first liquid inlets (11) of the second reactor; phenol and sodium hydroxide lye are premixed and then enter the second reactor from one or more of the second liquid inlets (7) of the second reactor. The reaction liquid containing tetrabromobisphenol A polycarbonate oligomer flows out of the reactor from a liquid outlet (5) of the second reactor.
In the process of this example, the reactor bed temperatures of the stages are independently controlled by the heat exchange means of the stage. In the polycondensation reaction process, the temperature of the first-stage bed layer at the bottommost part of the first reactor is 15-35 ℃, and the temperature of other reactors at all stages is 5-30 ℃; in the end-capping reaction process, the temperature of the first-stage bed layer at the bottommost part of the second reactor is 25-50 ℃, and the temperature of other reactors in different stages is 5-30 ℃.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (14)
1. A reactor for the continuous production of polycarbonate oligomers, comprising: the reactor comprises a circulating liquid inlet (1), a bottom base plate (2), a liquid distributor (3), a Venturi mixed flow nozzle (4), a liquid outlet (5), an inner sleeve (6), liquid inlets (11, 7), a reactor bed body (8) and a liquid external circulating channel (10); the reactor comprises at least two stages, and liquid flow is realized between each stage of the reactor through an interstage overflow pipe.
2. The reactor for continuously producing a polycarbonate oligomer according to claim 1, wherein:
energy is carried by each stage of reactor through external circulation of liquid, and the circulation flow of the liquid in the reactor is amplified in a mode of combining a Venturi mixed flow nozzle and an inner sleeve, so that the liquid-liquid multiphase in the reactor is quickly and uniformly mixed;
the liquid external circulation is realized by the following modes: reaction liquid in the reactor is led out from the side wall of the reactor, passes through the liquid external circulation channel (10) and is conveyed to the circulating liquid inlet (1) of the reactor by the circulating pump (9).
3. The reactor for continuously producing a polycarbonate oligomer according to claim 1 or 2, characterized in that:
the circulating liquid inlet (1) is connected with a liquid distributor (3), and the liquid distributor is connected with a Venturi mixed flow nozzle (4);
the liquid distributor is composed of a liquid distributor main pipe and one or more liquid distribution pipes, one end of each liquid distribution pipe is connected with a hole of the liquid distributor main pipe, and the other end of each liquid distribution pipe is connected with a Venturi mixed flow nozzle.
4. The reactor for continuously producing a polycarbonate oligomer according to claim 1 or 2, characterized in that: the venturi mixed flow nozzle comprises a nozzle first liquid inlet (a) and a nozzle second liquid inlet (b), and the nozzle second liquid inlet (b) is connected to the throat of the venturi mixed flow nozzle.
5. The reactor for continuously producing a polycarbonate oligomer according to claim 1, 2 or 4, wherein:
the reaction liquid inlet comprises a first liquid inlet (11) and a second liquid inlet (7);
the first liquid inlet (11) is arranged on the side wall of the reactor;
the second liquid inlet (7) is connected with the second liquid inlet (b) of the nozzle of the Venturi mixed flow nozzle in claim 4 through a liquid distributor, and the circulating liquid inlet (1) is connected with the first liquid inlet (a) of the nozzle of the Venturi mixed flow nozzle in claim 4 through a liquid distributor, so that the efficient dispersion and the rapid mixing between the liquid entering from the second liquid inlet (7) and the liquid entering from the circulating liquid inlet (1) are enhanced.
6. The reactor for continuously producing a polycarbonate oligomer according to claim 1 or 2, characterized in that: the reactor also comprises a heat exchange component, the temperature of the bed layer is controlled by the reactor through the heat exchange component, and the heat exchange component is one or the combination of a heat exchange tube or a heat exchange jacket.
7. The reactor for continuously producing a polycarbonate oligomer according to claim 1 or 2, characterized in that: the interstage flow of liquid is realized between two adjacent stages of reactors through an interstage overflow pipe, and the total sectional area of the overflow pipe accounts for 0.1-10% of the sectional area of a reactor bed body.
8. The reactor for continuously producing a polycarbonate oligomer according to claim 1 or 2, which is a tetrabromobisphenol a polycarbonate oligomer.
9. A process for continuously producing a polycarbonate oligomer using the reactor of any one of claims 1 to 7, wherein: the process comprises a polycondensation reaction process and an end-capping reaction process, wherein the polycondensation reaction process is carried out in the first reactor of any one of claims 1 to 7, and the end-capping reaction process is carried out in the second reactor of any one of claims 1 to 7.
10. The continuous process for producing a polycarbonate oligomer of claim 9, which is a tetrabromobisphenol a polycarbonate oligomer.
11. The process according to claim 9, the first and second reactors utilized being the reactor of claim 5, the process characterized in that:
during the polycondensation reaction, a part of the reaction materials are mixed in advance and then enter the first reactor through one or more first liquid inlets (11) of the first reactor; the rest of the reaction materials are mixed in advance and then enter the first reactor from one or more of the second liquid inlets (7) of the first reactor; catalyst enters the first reactor from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first reactor;
during the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second reactor through one or more of the first liquid inlets (11) of the second reactor; the mass of blocking agent enters the second reactor from one or more of the second liquid inlets (7) of the second reactor.
12. The process for continuously producing tetrabromobisphenol a polycarbonate oligomer according to claim 10, wherein: the bed temperature of each stage of reactor is independently controlled by the heat exchange component of the stage; when the reactor is used in the polycondensation process, the temperature of the bottommost first-stage bed layer is 15-35 ℃, and the temperature of other reactors in all stages is 5-30 ℃; when the reactor is used for the end-capping process, the temperature of the first-stage bed layer at the bottommost part is 25-50 ℃, and the temperature of other reactors at all stages is 5-30 ℃.
13. A process for continuously producing tetrabromobisphenol A polycarbonate oligomer by using the reactor of claim 5, wherein:
the process comprises a polycondensation reaction process and an end-capping reaction process, wherein the polycondensation reaction process is carried out in the first reactor of claim 5, and the end-capping reaction process is carried out in the second reactor of claim 5;
in the polycondensation reaction process, tetrabromobisphenol A, dichloromethane and sodium hydroxide lye are mixed in advance and then enter a first reactor from one or more of first liquid inlets (11) of the first reactor; triphosgene and dichloromethane are premixed and then enter the first reactor from one or more of the second liquid inlets (7) of the first reactor; triethylamine as a catalyst enters the first reactor from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first reactor;
during the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second reactor through one or more of the first liquid inlets (11) of the second reactor; phenol and sodium hydroxide lye are premixed and then enter the second reactor from one or more of the second liquid inlets (7) of the second reactor.
14. The process for the continuous production of tetrabromobisphenol a polycarbonate oligomer as claimed in claim 13, wherein: the bed temperature of each stage of reactor is independently controlled by the heat exchange component of the stage; when the reactor is used in the polycondensation process, the temperature of the bottommost first-stage bed layer is 15-35 ℃, and the temperature of other reactors in all stages is 5-30 ℃; when the reactor is used for the end-capping process, the temperature of the first-stage bed layer at the bottommost part is 25-50 ℃, and the temperature of other reactors at all stages is 5-30 ℃.
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