CN111298754B - Reactor and process for continuously producing polycarbonate oligomer - Google Patents
Reactor and process for continuously producing polycarbonate oligomer Download PDFInfo
- Publication number
- CN111298754B CN111298754B CN202010099824.4A CN202010099824A CN111298754B CN 111298754 B CN111298754 B CN 111298754B CN 202010099824 A CN202010099824 A CN 202010099824A CN 111298754 B CN111298754 B CN 111298754B
- Authority
- CN
- China
- Prior art keywords
- reactor
- liquid
- stage
- liquid inlet
- polycarbonate oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 61
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 212
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000010924 continuous production Methods 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 16
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical group 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003795 chemical substances by application 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
- 239000000758 substrate Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000010586 diagram Methods 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000009977 dual effect Effects 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 4
- 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
- 239000012634 fragment Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000000203 mixture 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
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/242—Tubular reactors in series
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A reactor and a 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 the external circulation of liquid, and the liquid circulation flow in the reactor is amplified through the mode that the Venturi mixed flow nozzle and the inner sleeve are used in a combined mode, so that the uniform mixing of liquid-liquid phases in the production process of the polycarbonate oligomer is realized, the structure of the reactor is simple, and the tightness is ensured. Through multistage series connection, a plurality of steps in the polycondensation or end capping process of the polycarbonate oligomer are realized in one reaction tower, so that the space utilization rate of a factory is improved; the stirring paddle moving part is not needed, and a larger space is provided for the heat exchange inner member in the reactor, so that the large-scale production is facilitated; realizes continuous operation of the polycondensation and 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 used as a flame retardant in fireproof materials in various industries. The polycarbonate oligomer is mainly bisphenol A type polycarbonate, wherein tetrabromobisphenol A polycarbonate oligomer is brominated bisphenol A type polycarbonate, and is suitable for processing PBT, PET, PBT/PET blend resin, polysulfone resin, SAN and various laminated resins due to the unique combination property. The production process of the polycarbonate oligomer mainly comprises a phosgene method and a non-phosgene method, and the reaction process of different production processes generally mainly comprises two steps: polycondensation process and capping process. Wherein, the polycondensation process is that bisphenol A and other polycondensation raw materials are subjected to polycondensation reaction under the action of a catalyst to form polycondensation fragments, and the end capping process is that the polycondensation fragments and phenol are subjected to further end capping reaction to form polycarbonate oligomer. The two steps of reaction processes are liquid-liquid multiphase reaction systems, on one hand, the reactor is required to have strong liquid-liquid mixing performance so as to ensure that the reaction is fully carried out, and on the other hand, the reactor is required to have high tightness so as to avoid leakage of reaction substances.
In order to ensure uniform mixing of liquid-liquid phases, stirred tanks are generally used at home and abroad as reactors for producing polycarbonate. Patent CN208894224U discloses a vertical efficient homogeneous homogenizing reactor for producing polycarbonate, patent CN209715090U discloses a polycarbonate reactor, and patent CN110270289a discloses an ultra-high sealing polycarbonate reaction device. These reactors, without exception, achieve strong mixing of the liquid-liquid phases by mechanical stirring with stirring paddles. When the additional mechanical stirring is adopted, the turbulence of the liquid phase is intense, and the mixing characteristic is good. However, the stirred tanks have the following significant disadvantages when used for the production of polycarbonate oligomers: 1) The stirring kettle is generally used for intermittent operation, so that 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 severe; 3) The heat exchange components of the stirred tank are limited by the stirring paddles, making it difficult to achieve larger scale production with a single reactor. Furthermore, the polycarbonate oligomer polycondensation and endcapping reaction process involves multiple steps, with different operating conditions and processing parameters for the different steps. At present, a plurality of stirring kettles are adopted for series intermittent production in industrial production, but the series connection of a plurality of stirring kettles leads to complex operation process, and the space utilization rate of a factory is reduced.
In addition to achieving strong mixing by mechanical stirring, a tubular static mixer was used as a mixing reactor in the "continuous process for producing polycarbonate oligomer" published in patent CN101356213 a. The static mixer achieves strong mixing through the mixing elements in the reaction tube, avoiding some of the drawbacks of mechanical stirring. However, the static mixer has small volume, complex internal mixing component structure, and is difficult to realize large-scale production, and meanwhile, the static mixer is generally an integrated component, and is difficult to clean and maintain once blocked.
In summary, developing a novel reactor with good liquid-liquid multiphase mixing performance, simple structure and suitability for continuous production of 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 polycarbonate oligomer by using the reactor. The reactor has no mechanical stirring 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 continuous production of polycarbonate oligomers. Comprising the following steps: the device 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 noted that the reactor may comprise only the first liquid inlet 11, and that the second liquid inlet 7 may be provided as desired.
The reactor at least comprises two stages, liquid flow is realized between the stages of the reactor through an interstage overflow pipe, and the total cross section area of the overflow pipe accounts for 0.1-10% of the cross section area of the reactor bed body.
Each stage of reactor carries energy through liquid external circulation, and the liquid circulation flow in the reactor is amplified through a mode that a Venturi mixed flow nozzle is combined with an 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 consists of a liquid distributor main pipe and one or more liquid distribution pipes, one end of each liquid distribution pipe is connected with holes of the liquid distributor main pipe, and the other end of each liquid distribution pipe is connected with the 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 pipe and a heat exchange jacket.
Preferably, the method comprises the steps of,
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 necking part 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 second liquid inlet (b) of the venturi mixed flow nozzle through the liquid distributor, and the circulating liquid inlet (1) is connected with the first liquid inlet (a) of the venturi mixed flow nozzle through the liquid distributor, so that efficient dispersion and rapid mixing between the liquid entering from the second liquid inlet (7) and the liquid entering from the circulating liquid inlet (1) are enhanced.
In another aspect, the present invention provides a process for continuously producing polycarbonate oligomers.
The process comprises a polycondensation reaction process and a capping reaction process, wherein the polycondensation reaction process is carried out in a first reactor, the capping reaction process is carried out in a second reactor, and the first reactor and the second reactor are reactors provided by the invention.
During the polycondensation reaction, a portion of the reaction mass is premixed and fed into the first reactor from one or more of its first liquid inlets (11); the rest of the reaction materials enter the first reactor from one or more of the second liquid inlets (7) of the first reactor after being premixed; the 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 capping agent material enters the second reactor from one or more of its second liquid inlets (7).
According to a preferred embodiment of the process provided by the invention, the polycarbonate oligomer is tetrabromobisphenol a polycarbonate oligomer.
In this preferred embodiment, the reaction process includes a polycondensation reaction process and a capping reaction process. In the polycondensation reaction process, tetrabromobisphenol A, methylene dichloride and sodium hydroxide alkali liquor are mixed in advance and then enter the first reactor from one or more of the first liquid inlets (11) of the first reactor; triphosgene and methylene dichloride are pre-mixed 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 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 fed into the second reactor from one or more of the second liquid inlets (7) of the second reactor.
In the preferred embodiment, the reactor bed temperature of each stage is independently controlled by the heat exchange means of the present stage. In the polycondensation reaction process, the temperature of the bottommost primary bed layer of the first reactor is 15-35 ℃, and the temperature of other reactors at all levels is 5-30 ℃; in the end capping reaction process, the temperature of the bottommost primary bed layer of the second reactor is 25-50 ℃, and the temperature of other reactors at all levels is 5-30 ℃.
The beneficial effects of the invention are as follows:
the reactor provided by the invention realizes the uniform mixing of liquid-liquid phases in the production process of the polycarbonate oligomer by combining the liquid external circulation, the venturi mixed flow nozzle and the inner sleeve for diversion, has high efficiency, replaces a stirred tank reactor in the production process of the polycarbonate oligomer, and has simple structure and better guarantee of tightness.
The reactor provided by the invention realizes a plurality of steps in the polycondensation or end capping process of the polycarbonate oligomer in one reaction tower through multistage series connection, and improves the space utilization rate of a factory.
The reactor provided by the invention has no stirring paddle moving part, and a larger space is provided for the heat exchange inner member in the reactor, so that the large-scale production of the polycarbonate oligomer is facilitated.
The reactor provided by the invention realizes 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 views showing the structure of a three-stage reactor for continuously producing a polycarbonate oligomer.
FIG. 3 is a schematic view of a venturi mixed flow nozzle.
Fig. 4 is a schematic diagram of the arrangement of liquid distribution pipes of the liquid distributor.
Fig. 5 is a schematic view of an interstage overflow tube arrangement.
FIG. 6 is a schematic diagram of a dual liquid flash mixing reactor configuration.
FIG. 7 is a schematic illustration of a dual liquid inlet venturi mixed flow nozzle configuration.
FIG. 8 is a schematic diagram of a four-stage reactor structure for continuous production of polycarbonate oligomer.
In the figure: the device comprises a 1-circulating liquid inlet, a 2-bottom base plate, a 3-liquid distributor, a 4-Venturi mixed flow nozzle, a 5-liquid outlet, a 6-inner sleeve, a 7-second liquid inlet, an 8-reactor bed body, a 9-circulating pump, a 10-liquid outer circulating channel, a 11-first liquid inlet, a 12-inner overflow pipe, a 13-overflow pipe and a 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 views showing the structure of a three-stage reactor for continuously producing a polycarbonate oligomer. In the reactor of the embodiment, the reactors are three stages in series, and the reactors are a first stage, a second stage and a third stage in sequence 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 of the reactor realizes uniform mixing of liquid phases in the reactor through carrying energy by liquid external circulation, and the external circulation liquid further amplifies the liquid circulation flow in the reactor stage in a mode of combining a Venturi mixed flow nozzle with an inner sleeve. As shown in FIG. 1, the reaction liquid in the present stage reactor is led out from the middle position of the side wall of the reactor, passes through the liquid external circulation channel (10) and is conveyed to the circulating liquid inlet (1-1) by the 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 flow speed of the liquid at the necking position 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 necking position of the Venturi mixed flow nozzle is higher.
In the reactor of this example, the flow pattern of the reaction liquid was: the first reaction liquid enters the first-stage reactor from a first liquid inlet (11-3), and the second reaction liquid enters the first-stage reactor from a second liquid inlet (7-3); more preferably, a portion of the first reaction liquid may enter the second stage reactor and the third stage reactor from the first liquid inlets (11-2) and (11-1), respectively, and a portion of the second reaction liquid may enter the second stage reactor and the third stage reactor from the second liquid inlets (7-2) and (7-1), respectively; the reaction liquid of the first-stage reactor overflows to the second-stage reactor through an interstage overflow pipe; the reaction liquid of the second-stage reactor overflows to the 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 fig. 1 and an outer overflow pipe (13) shown in fig. 2; an inner overflow pipe (12) passes through the bottom substrate of the upper primary reactor, so that liquid flows from the upper primary reactor into the annular space flow area of the lower primary reactor; the overflow flows out from the upper primary reactor through the connecting pipe, flows downwards through the overflow pipe arranged outside the reactor main body, and flows into the lower primary reactor through the connecting pipe of the lower primary reactor.
Fig. 3 and fig. 4 are a schematic view of a venturi mixed flow nozzle structure and a schematic view of liquid distribution pipes of a liquid distributor, respectively. The liquid distributor consists of a liquid distributor main pipe and a plurality of liquid distribution pipes (14), wherein 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, and more preferably, 0.2-0.4 of the inner diameter of the end, when the inner diameter of the end, connected with the venturi mixed flow nozzle, of the liquid distribution pipe is more preferably 0.2-0.4 of the inner diameter, liquid in the circulating liquid inlet (1) can be uniformly distributed to each liquid distribution pipe and flows into the venturi mixed flow nozzle.
FIG. 5 is a schematic diagram of the arrangement of overflow tubes within the reactor interstage. The liquid from the upper stage reactor overflows to the lower stage through an inter-stage inner overflow pipe (12). The inner overflow pipes are uniformly distributed on a plurality of concentric circumferences in the annular space area of the reactor, and the number of the overflow pipes is regulated according to the design requirement of the reactor, when the total cross-sectional area of the overflow pipes accounts for 0.1-25 percent, preferably 0.5-12 percent of the cross-sectional area of the reactor, the liquid flow from the lower stage to the upper stage is little, and the reaction liquid overflows from the upper stage to the lower stage in a substantially unidirectional manner.
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 three stages in series, the reactors were first, second and third stages in this order from top to bottom, and the liquid circulation in each stage of the reactor was the same as in example 1.
In the reactor of this embodiment, 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 (7-6); more preferably, a portion of the first reaction liquid may enter the second stage reactor and the third stage reactor from the first liquid inlets (11-2) and (11-1), respectively, and a portion of the second reaction liquid may enter the second stage reactor and the third stage reactor from the second liquid inlets (7-5) and (7-4), respectively.
In the reactor of this embodiment, the reactor circulating liquid inlets (1-1), (1-2) and (1-3) are connected to the nozzle first liquid inlet (a) of the venturi mixing nozzle of FIG. 7 through a liquid distributor, and the reactor second liquid inlets (7-4), (7-5) and (7-6) are connected to the nozzle second liquid inlet (b) of the venturi mixing nozzle of FIG. 7 through a liquid distributor to enhance efficient dispersion and rapid mixing between the liquid entering from the second liquid inlet (7) and the liquid entering from the circulating liquid inlet (1)
In the reactor of this example, the overflow of the inter-stage liquid was carried out in the same manner as in example 1.
FIG. 7 is a schematic illustration of two configurations of a dual liquid inlet venturi mixed flow nozzle. The dual liquid inlet 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 necking part of the venturi mixed flow nozzle.
Example 3
FIG. 8 is a schematic diagram of a four-stage reactor structure for continuous production of polycarbonate oligomer. In the reactor of this example, four stages are connected in series, and the reactor is sequentially a first stage, a second stage, a third stage and a fourth stage from top to bottom, and the liquid circulation and the inter-stage liquid overflow in each stage of the reactor are the same as in example 1.
In the reactor of this embodiment, a first reaction liquid enters the first-stage reactor from a first liquid inlet (11-4), and a second reaction liquid enters the first-stage reactor from a second liquid inlet (7-4); more preferably, a portion of the first reaction liquid may enter the second, third and fourth stage reactors from the first liquid inlets (11-3), (11-2) and (11-1), respectively, and a portion of the second reaction liquid may enter the second, third and fourth stage reactors from the second liquid inlets (7-3), (7-2) and (7-1), respectively.
The reactor of embodiments 1-3 comprises a heat exchange member by which the reactor controls bed temperature, the heat exchange member being one or a combination of heat exchange tubes or heat exchange jackets.
Example 4
A process for continuously producing a polycarbonate oligomer using the reactor described in examples 1 to 3. The process includes a polycondensation reaction process and a capping reaction process.
In the process of this example, the polycondensation reaction process is conducted in a first reactor, which is one of the reactors described in examples 1-3. During the polycondensation reaction, a portion of the polycondensation reaction material is pre-mixed and fed into the first reactor from one or more of the first liquid inlets (11); the rest of the reaction materials enter the first reactor from one or more of the second liquid inlets (7) of the first reactor after being premixed; the 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 the liquid outlet (5) of the first reactor.
In the process of this example, the capping reaction process is carried out in a second reactor, which is one of the reactors described in examples 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 capping agent material enters the second reactor from one or more of its second liquid inlets (7). The reaction liquid containing polycarbonate oligomer flows out of the reactor from the liquid outlet (5) of the second reactor.
Example 5
A process for continuously producing a polycarbonate oligomer using the reactor described in examples 1 to 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 example, the polycondensation reaction process is conducted in a first reactor, which is one of the reactors described in examples 1-3. In the polycondensation reaction process, tetrabromobisphenol A, methylene dichloride and sodium hydroxide alkali liquor are mixed in advance and then enter the first reactor from one or more of the first liquid inlets (11) of the first reactor; triphosgene and methylene dichloride are pre-mixed 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 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 the liquid outlet (5) of the first reactor.
In the process of this example, the capping reaction process is carried out in a second reactor, which is one of the reactors described in examples 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 fed into the second reactor from one or more of the second liquid inlets (7) of the second reactor. The reaction solution containing tetrabromobisphenol A polycarbonate oligomer flows out of the reactor from a liquid outlet (5) of the second reactor.
In the process of this embodiment, the reactor bed temperature at each stage is independently controlled by the heat exchange means at the present stage. In the polycondensation reaction process, the temperature of the bottommost primary bed layer of the first reactor is 15-35 ℃, and the temperature of other reactors at all levels is 5-30 ℃; during the end capping reaction, the temperature of the bottom primary bed layer of the second reactor is 25-50 ℃, and the temperature of the other reactors at each stage is 5-30 ℃.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (12)
1. A reactor for continuous production of polycarbonate oligomers, comprising: 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); the reactor at least comprises a first-stage reactor and a second-stage reactor, liquid flow is realized between each stage of the reactor through an interstage overflow pipe,
each stage of reactor carries energy through liquid external circulation, and the liquid circulation flow in the reactor is amplified through a mode that a Venturi mixed flow nozzle is combined with 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: the reaction liquid in the stage reactor is led out from the side wall of the stage reactor, passes through a liquid external circulation channel (10) and is conveyed to a circulating liquid inlet (1) of the stage reactor by a circulating pump (9);
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 consists of a liquid distributor main pipe and one or more liquid distribution pipes, one end of each liquid distribution pipe is connected with holes of the liquid distributor main pipe, and the other end of each liquid distribution pipe is connected with the Venturi mixed flow nozzle.
2. The reactor for continuous production of polycarbonate oligomer according to claim 1, wherein: 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 necking part of the venturi mixed flow nozzle.
3. The reactor for continuous production of polycarbonate oligomer according to claim 2, 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 venturi mixed flow nozzle of claim 2 through a liquid distributor, the circulating liquid inlet (1) is connected with the first liquid inlet (a) of the venturi mixed flow nozzle of claim 2 through the liquid distributor so as to strengthen the efficient dispersion and rapid mixing between the liquid entering from the second liquid inlet (7) and the liquid entering from the circulating liquid inlet (1),
the inter-stage overflow pipe is an inner overflow pipe (12) or an outer overflow pipe (13); an inner overflow pipe (12) passes through the bottom substrate of the upper primary reactor, so that liquid flows from the upper primary reactor into the annular space flow area of the lower primary reactor; the overflow means allows the liquid to flow out of the upper primary reactor through the connection pipe, down through the overflow pipe (13) arranged outside the reactor body, and into the lower primary reactor through the connection pipe of the lower primary reactor.
4. The reactor for continuous production of polycarbonate oligomer according to claim 1, wherein: the reactor also 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 pipe and a heat exchange jacket.
5. The reactor for continuous production of polycarbonate oligomer according to claim 1, wherein: the interstage flow of liquid is realized by an interstage overflow pipe between two adjacent stages of reactors, and the total sectional area of the overflow pipe accounts for 0.1-10% of the sectional area of the reactor bed body.
6. The reactor for continuous production of polycarbonate oligomer of claim 1, wherein the polycarbonate oligomer is tetrabromobisphenol a polycarbonate oligomer.
7. A process for continuously producing a polycarbonate oligomer using the reactor of any one of claims 1 to 5, characterized in that: the process comprises a polycondensation reaction process carried out in the first stage reactor according to any one of claims 1 to 5 and a capping reaction process carried out in the second stage reactor according to any one of claims 1 to 5.
8. The continuous process for producing a polycarbonate oligomer according to claim 7, wherein the polycarbonate oligomer is tetrabromobisphenol a polycarbonate oligomer.
9. The process of claim 7, wherein the first stage reactor and the second stage reactor are the reactors of claim 3, the process characterized by:
during the polycondensation reaction, a portion of the reaction mass is premixed and fed into the first stage reactor from one or more of the first liquid inlets (11) of the first stage reactor; the rest of the reaction materials enter the first-stage reactor from one or more of the second liquid inlets (7) of the first-stage reactor after being premixed; catalyst enters the first stage reactor from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first stage reactor;
during the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second stage reactor through one or more of the first liquid inlets (11) of the second stage reactor; the capping agent material enters the second stage reactor from one or more of its second liquid inlets (7).
10. The continuous process for producing tetrabromobisphenol a polycarbonate oligomer according to claim 8, 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 primary bed layer is 15-35 DEG o C, the temperature of other reactors at each level is 5-30 o C, performing operation; when the reactor is used in the end capping process, the temperature of the bottommost primary bed layer is 25-50 DEG o C, the temperature of other reactors at each level is 5-30 o C。
11. A process for continuously producing tetrabromobisphenol a polycarbonate oligomer using the reactor of claim 3, characterized in that:
the process comprises a polycondensation reaction process and a capping reaction process, wherein the polycondensation reaction process is carried out in the first stage reactor according to claim 3, and the capping reaction process is carried out in the second stage reactor according to claim 3;
in the polycondensation reaction process, tetrabromobisphenol A, methylene dichloride and sodium hydroxide alkali liquor are mixed in advance and then enter the first-stage reactor from one or more of the first liquid inlets (11) of the first-stage reactor; triphosgene and methylene dichloride are pre-mixed and then enter the first-stage reactor from one or more of the second liquid inlets (7) of the first-stage reactor; triethylamine enters the first stage reactor as a catalyst from one or more of the first liquid inlet (11) or the second liquid inlet (7) of the first stage reactor;
during the end-capping reaction, the polycondensation liquid produced during the polycondensation reaction enters the second stage reactor through one or more of the first liquid inlets (11) of the second stage reactor; phenol and sodium hydroxide lye are premixed and then fed into the second stage reactor from one or more of the second liquid inlets (7) of the second stage reactor.
12. The process for continuously producing tetrabromobisphenol a polycarbonate oligomer by means of a reactor according to claim 11, 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 primary bed layer is 15-35 DEG o C, the temperature of other reactors at each level is 5-30 o C, performing operation; when the reactor is used in the end capping process, the temperature of the bottommost primary bed layer is 25-50 DEG o C, the temperature of other reactors at each level is 5-30 o C。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010099824.4A CN111298754B (en) | 2020-02-18 | 2020-02-18 | Reactor and process for continuously producing polycarbonate oligomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010099824.4A CN111298754B (en) | 2020-02-18 | 2020-02-18 | Reactor and process for continuously producing polycarbonate oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111298754A CN111298754A (en) | 2020-06-19 |
| CN111298754B true CN111298754B (en) | 2024-04-05 |
Family
ID=71161677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010099824.4A Active CN111298754B (en) | 2020-02-18 | 2020-02-18 | Reactor and process for continuously producing polycarbonate oligomer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111298754B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102876A (en) * | 1985-04-01 | 1986-09-17 | 化学工业部晨光化工研究院一分院 | The serialization of one-step synthesis of polycarbonic ester (one) |
| CN2204197Y (en) * | 1994-10-25 | 1995-08-02 | 上海石油化工股份有限公司 | External circulation gas-liquid reactor for ethoxylation reaction |
| US6362304B1 (en) * | 2000-11-29 | 2002-03-26 | General Electric Company | Resin preheating for steam precipitation jet polycarbonate resin isolation |
| CN1923351A (en) * | 2006-09-01 | 2007-03-07 | 清华大学 | Staged reactor |
| CN207614848U (en) * | 2017-11-29 | 2018-07-17 | 中蓝晨光化工研究设计院有限公司 | A kind of vertical reactor continuously preparing makrolon suitable for ester-interchange method |
| CN212524111U (en) * | 2020-02-18 | 2021-02-12 | 清华大学 | Reactor for continuously producing polycarbonate oligomer |
-
2020
- 2020-02-18 CN CN202010099824.4A patent/CN111298754B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102876A (en) * | 1985-04-01 | 1986-09-17 | 化学工业部晨光化工研究院一分院 | The serialization of one-step synthesis of polycarbonic ester (one) |
| CN2204197Y (en) * | 1994-10-25 | 1995-08-02 | 上海石油化工股份有限公司 | External circulation gas-liquid reactor for ethoxylation reaction |
| US6362304B1 (en) * | 2000-11-29 | 2002-03-26 | General Electric Company | Resin preheating for steam precipitation jet polycarbonate resin isolation |
| CN1923351A (en) * | 2006-09-01 | 2007-03-07 | 清华大学 | Staged reactor |
| CN207614848U (en) * | 2017-11-29 | 2018-07-17 | 中蓝晨光化工研究设计院有限公司 | A kind of vertical reactor continuously preparing makrolon suitable for ester-interchange method |
| CN212524111U (en) * | 2020-02-18 | 2021-02-12 | 清华大学 | Reactor for continuously producing polycarbonate oligomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111298754A (en) | 2020-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN212524111U (en) | Reactor for continuously producing polycarbonate oligomer | |
| KR100925931B1 (en) | Method and device for producing polyesters, copolyesters and polycarbonates | |
| KR102524564B1 (en) | Built-in micro interfacial enhanced reaction system and process for pta production with px | |
| AU632645B2 (en) | Multistage reactor | |
| CN111135778A (en) | Strong mixing reactor | |
| CN111298754B (en) | Reactor and process for continuously producing polycarbonate oligomer | |
| US3752653A (en) | Continuous-flow agitated reactor | |
| CN105771868A (en) | Esterification and polymerization double-kettle apparatus | |
| KR100962873B1 (en) | Method and device for the continuous production of polyesters | |
| CN212492861U (en) | Strong mixing reactor | |
| CN109621873B (en) | Esterification reaction device | |
| CN1321990C (en) | Apparatus and method for monotubular multi-spiral static mixed tube style chlorohydrination of propene for production of epoxypropane | |
| CN108311088B (en) | Jet loop reactor and method for preparing butyl rubber polymer | |
| CN112221459B (en) | Polyether neutralization reactor | |
| CN108543506B (en) | Reactor for recovering acetonitrile as by-product in acrylonitrile production process | |
| CN210357184U (en) | Coil pipe in synthetic kettle and synthetic kettle | |
| CN205650187U (en) | Esterify and get together two cauldron devices | |
| CN112755926B (en) | Device and method for enhancing liquid-liquid reaction | |
| CN205761054U (en) | Gas-liquid-solid phase reaction device | |
| CN115282918B (en) | Tubular reactor | |
| CN100450983C (en) | Single-tube multiple rotary static and mixed-piping reacotr with vinyl chlorination and method thereof | |
| CN216573099U (en) | Multistage type of reinforceing mass transfer stirred tank that admits air | |
| CN218609359U (en) | Polyether reactor | |
| JPH1128350A (en) | Process container and process performed therein | |
| CN1279083C (en) | New type non-agitating kettle with two regions for esterifying polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100084 Tsinghua University, Beijing, Haidian District Applicant after: TSINGHUA University Applicant after: Shandong XURUI New Material Co.,Ltd. Address before: 100084 Tsinghua University, Beijing, Haidian District Applicant before: TSINGHUA University Applicant before: SHANDONG SUNRIS CO.,LTD. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |