CN1611483A - Internal recycle reactor for synthesizing diphenyl carbonate by ester exchange method - Google Patents
Internal recycle reactor for synthesizing diphenyl carbonate by ester exchange method Download PDFInfo
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- CN1611483A CN1611483A CN 200310110806 CN200310110806A CN1611483A CN 1611483 A CN1611483 A CN 1611483A CN 200310110806 CN200310110806 CN 200310110806 CN 200310110806 A CN200310110806 A CN 200310110806A CN 1611483 A CN1611483 A CN 1611483A
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- reaction
- reaction tubes
- reactor
- pipe
- reaction pipe
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- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 7
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 150000002148 esters Chemical group 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000005204 segregation Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 4
- 238000009884 interesterification Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 11
- 239000002994 raw material Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NHZZUJIRMHDTKR-UHFFFAOYSA-N carbonic acid;toluene Chemical compound OC(O)=O.CC1=CC=CC=C1 NHZZUJIRMHDTKR-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- -1 carbonate ester Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a kind of internal recycling reactor for synthesizing diphenyl carbonate by liquid phase interesterification. The reactor contains a perpendicular reaction pipe, an internal recycling pipe, a spray nozzle, and a separation segment. The reaction pipe is connected with the bottom of separation segment; the underpart of internal recycling pipe is connected with the bottom of reaction pipe through a fixing support; there is a heating or cooling nesting in the outside of reaction pipe; the underpart of reaction pipe is connected with the spray nozzle; the spray nozzle is the inlet of stuff liquor and catalyst; there is a stuff outlet in the middle of reaction pipe; there is a gas outlet in the separation segment. The length of reaction pipe is 1000-7000mm; the length of internal recycling pipe is 1/4-3/4 time of the reaction pipe; the sectional area of separation segment is 2-10 fold of the total sectional area of reaction pipe. The reactor of the invention has great operation elasticity, even liquid phase mixing, and fine mass transfer, and also it adapts to other normal pressure or pressurization liquid phase synthesizing reaction.
Description
The present invention relates to the inner circulation reactor of diphenyl carbonate synthesis (being called for short DPC) normal pressure under the condition that a kind of liquid phase phenol, methylcarbonate and catalyzer exist or compressive reaction.
Reactor with ester-interchange method diphenyl carbonate synthesis under liquid phase phenol, methylcarbonate and the catalyzer existence condition, adopt the synthetic DPC of a plurality of reactors in series mostly, comprise tank reactor and distillation tower, once used 2 or more tank reactor continuously as EP0591923.1994, JP4235951.1992 etc. and synthesize DPC.Because this ester-interchange method exists the system speed of reaction slow, problems such as the reaction volume that needs is big, facility investment big, amplification, especially under pressurized conditions, application will be subjected to certain limitation.
The objective of the invention is to improve at the deficiency of above-mentioned reactor, a kind of inner circulation reactor of liquid phase ester exchange synthesizing diphenyl carbonate is provided, be particularly suitable for compressive reaction, the flow range of this reactor is wide, liquid circulation is abundant, reaction efficiency height, less investment, be convenient to processing and install, heating or good cooling effect.
The inner circulation reactor of ester-interchange method diphenyl carbonate synthesis of the present invention, comprise that a vertical reaction tubes, inner circulating tube, nozzle and segregation section constitute, reaction tubes links to each other with the segregation section bottom, the inner circulating tube bottom links to each other with the reaction tubes bottom by fixed support, heating of reaction tubes peripheral hardware or cooling jacket, and the reaction tubes bottom links to each other with nozzle, nozzle is the import of stock liquid and catalyzer, drain hole is arranged at the reaction tubes bottom, and there is discharge port at the reaction tubes middle part, and segregation section has pneumatic outlet; Reaction tube length 1000-7000mm, inner circulating tube length is the 1/4-3/4 of tube length of reaction tube, the inner circulating tube sectional area is reaction tubes sectional area summation 20-90%, two ends have the groove of 10-80 degree respectively about the inner circulating tube outside pipe, apart from 10-500mm, the perforate aperture diameter of nozzle is 1-10mm between inner circulating tube lower end and the reaction tubes bottom, and the sectional area of segregation section is reaction tubes sectional area summation 2-10 times, in establish the gas-liquid separation baffle plate, this reactor can adopt stainless material to make.
Fig. 1 is the configuration diagram of inner circulation reactor of the present invention
Inner circulation reactor shown in the figure is made of vertical reaction tubes, inner circulating tube, nozzle, a segregation section, reaction tubes links to each other with the segregation section bottom, the inner circulating tube bottom links to each other with the reaction tubes bottom by anchor, heating of reaction tubes peripheral hardware or cooling jacket, the reaction tubes bottom links to each other with nozzle, and nozzle is the import of stock liquid and catalyzer, and drain hole is arranged at the reaction tubes bottom, there is discharge port at the reaction tubes middle part, and segregation section has pneumatic outlet.
Medium phenol when reaction system, methylcarbonate and catalyzer are when liquid phase, enter in the reactor by nozzle ejection through the pump pressurization, by-product carbinol that produces during reaction and raw material dimethyl carbonate azeotropic gas are to segregation section, the segregation section sectional area is reaction tubes sectional area 2-10 times, increase the area that methyl alcohol and methylcarbonate produce steam, separating back gas is the saturation steam of methyl alcohol and methylcarbonate, go out from the side interface of segregation section middle and upper part, can get the liquid of methyl alcohol and methylcarbonate after condensation, the methylcarbonate after the separation enters reactor cycles again with raw material; Because stock liquid sprays through nozzle the reaction tubes bottom liquid is produced adsorption, outside groove is arranged at the inner circulating tube bottom, increased adsorption area to the reaction tubes bottom liquid, rise to reaction tubes top through inner circulating tube, because the groove on inner circulating tube top and liquid enter slowing down of flow velocity behind the reaction tubes, liquid above the reaction tubes produces downward gravity, adds the adsorption of nozzle, thereby realizes the circulation of liquid phase medium.For reaction is carried out continuously, liquid phase comprises unreacted raw material and resultant from reaction tubes middle part extraction in its medium, and the methylcarbonate of additional raw material, catalyzer and recovery adds from nozzle together, thereby reaction is carried out continuously.
Embodiment 1
Adopt accompanying drawing structure of reactor of the present invention, the diameter of the reaction tubes of its reactor is 53 liters of 150mm, length 3000mm, volumes, the diameter of inner circulating tube is 89mm, length 1800mm, the gradient 30 degree of inner circulating tube bottom, long 30mm, the gradient 35 degree on top, long 60mm, apart from 30mm, nozzle perforate aperture diameter is 2mm between inner circulating tube lower end and the reaction tubes bottom, and the diameter of segregation section is 400mm, length 500mm.Earlier at raw material mixer preparation reaction raw materials liquid 60Kg, the mol ratio of methylcarbonate and phenol 1: 1, catalyst content 4Kg, with pump stock liquid is joined in this reactor, feed the steam heating reaction solution to 140C to the reaction tubes chuck, stagnation pressure 0.5Mpa, the reaction beginning, after the condensation of gas that segregation section goes out, collect the azeotropic liquid of methyl alcohol and methylcarbonate, go out methylcarbonate through extracting and separating and enter the reactor cycles use again, after one hour, system enters steady state, and this reactor operation is after 18 hours, get at reactor outlet that the dipheryl carbonate ester content is 24.5% in the thick product, phenol is 48.7%, intermediate methyl benzol carbonate (MPC) is 26.7%, other organic by-products total amount is less than 0.1%, and this reactor operation is after 24 hours, and catalyst production is 0.069gDPC/gcat.hr, move after 72 hours, catalyst production is 0.071gDPC/gcat.hr, moves after 300 hours, and productive rate is 0.065gDPC/gcat.hr.
In the production of ester-interchange method diphenyl carbonate synthesis, adopt inner circulation reactor of the present invention to have following advantage:
1. in the identical situation of reaction volume, the output investment ratio still reaction of inner circulation reactor Device is little, reaction efficiency is high, and especially compressive reaction is more obvious. The adding of heat and adopting Go out to be more prone to.
2. use inner circulation reactor of the present invention, can adopt the circulation continuous processing, from the continuous extraction of reactor head, product improves plant capacity from reactor middle part extraction than tank reactor to by product greatly, saves investment, is convenient to operation with gas phase.
3. the structure formation of inner circulation reactor of the present invention is convenient to processing and is installed, and can be applicable to homogeneous phase and heterogeneous building-up reactions, and is of many uses.
Claims (5)
1. the inner circulation reactor of a liquid phase ester-interchange method diphenyl carbonate synthesis, comprise a vertical reaction tubes (1), inner circulating tube (2), the segregation section (5) that is communicated with reaction tubes (1) in their upper ends, the nozzle (3) of lower end ligation pipe (1) material inlet, heating of reaction tubes (1) peripheral hardware or cooling jacket, reaction tubes (1) bottom has drain hole (11) and middle part that discharge port (13) is arranged, and segregation section (5) has pneumatic outlet (7).
2. inner circulation reactor as claimed in claim 1 is characterized in that inner circulating tube (2) length is the 1/4-3/4 of tube length of reaction tube, and inner circulating tube (2) sectional area is reaction tubes (1) sectional area summation 20-90%.
3. inner circulation reactor as claimed in claim 2 is characterized in that inner circulating tube (2) has the gradient (6) of 10-80 degree respectively in two ends up and down outside pipe, and the length of groove is 10-500mm.
4. inner circulation reactor as claimed in claim 2 is characterized in that between inner circulating tube (2) lower end and reaction tubes (1) bottom apart from 10-500mm.
5. inner circulation reactor as claimed in claim 1, the sectional area that it is characterized in that segregation section (6) be reaction tubes sectional area summation 2-10 doubly, in establish the gas-liquid separation baffle plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101108068A CN100386304C (en) | 2003-10-29 | 2003-10-29 | Internal circulation reactor for synthesizing diphenyl carbonate by ester exchange method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101108068A CN100386304C (en) | 2003-10-29 | 2003-10-29 | Internal circulation reactor for synthesizing diphenyl carbonate by ester exchange method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1611483A true CN1611483A (en) | 2005-05-04 |
| CN100386304C CN100386304C (en) | 2008-05-07 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101108068A Expired - Fee Related CN100386304C (en) | 2003-10-29 | 2003-10-29 | Internal circulation reactor for synthesizing diphenyl carbonate by ester exchange method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100386304C (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1248687B (en) * | 1990-06-04 | 1995-01-26 | Enichem Sintesi | PROCESS FOR THE PRODUCTION OF DIMETHYLCARBONATE AND APPARATUS SUITABLE FOR THE PURPOSE |
| JPH0772158B2 (en) * | 1991-01-11 | 1995-08-02 | 旭化成工業株式会社 | Continuous production method of diaryl carbonate |
| CN1204644A (en) * | 1998-07-09 | 1999-01-13 | 湖北齐跃化工股份有限公司 | Multi-pipe circulating reactor for liquid-phase oxidizing oxonation synthesis of dimethyl carbonate |
| JP2005517003A (en) * | 2002-02-05 | 2005-06-09 | エルジー・ケム・リミテッド | Continuous production method of aromatic carbonate using heterogeneous catalyst and reaction apparatus thereof |
-
2003
- 2003-10-29 CN CNB2003101108068A patent/CN100386304C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN100386304C (en) | 2008-05-07 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20051014 Address after: Beijing City, Dongcheng District No. 16 Andrew intercontinental building Applicant after: PetroChina Company Limited Address before: No. four, South Renmin Road, Sichuan, Chengdu Province nine Applicant before: CHENGDU ORGANIC CHEMICALS Co.,Ltd. CHINESE ACADEMY OF SCIENCES |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080507 Termination date: 20161029 |
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| CF01 | Termination of patent right due to non-payment of annual fee |