CN113041636A - Continuous bromination addition reaction rectification process and device - Google Patents
Continuous bromination addition reaction rectification process and device Download PDFInfo
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- CN113041636A CN113041636A CN201911375673.4A CN201911375673A CN113041636A CN 113041636 A CN113041636 A CN 113041636A CN 201911375673 A CN201911375673 A CN 201911375673A CN 113041636 A CN113041636 A CN 113041636A
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- 238000007259 addition reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title claims abstract description 19
- 238000005893 bromination reaction Methods 0.000 title claims abstract description 17
- 230000031709 bromination Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 23
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims description 45
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 43
- 239000007791 liquid phase Substances 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000000066 reactive distillation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract 4
- 239000000284 extract Substances 0.000 abstract 1
- 239000013589 supplement Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 6
- DVTKTUMRXCKEEG-UHFFFAOYSA-N 1,2-dibromo-1-chloroethane Chemical compound ClC(Br)CBr DVTKTUMRXCKEEG-UHFFFAOYSA-N 0.000 description 5
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
-
- 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
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a bromination addition reaction rectification process and a bromination addition reaction rectification device, which realize the coupling of a photobromine reaction and product rectification, realize high-efficiency photobromination reaction and solve the problem of difficult subsequent elemental bromine separation. The process enriches the elemental bromine at the top of the tower in a rectification mode, enriches the product at the bottom of the tower, continuously introduces feed gas into the rectification tower to contact with high-concentration bromine at the top of the tower, initiates a photobromination reaction under the illumination condition, continuously extracts the obtained product from the bottom of the tower, and continuously supplements the elemental bromine consumed by the reaction with the elemental bromine. The invention has simple process and stable control, realizes the photobromination reaction and the separation of products in one set of device, and greatly improves the conversion rate of raw materials and the production efficiency.
Description
Technical Field
The invention discloses a device and a reaction process for rectifying the photobromination reaction of olefin or halogenated olefin, which are applicable to the existing photobromination process of olefin and halogenated olefin and the separation process of target products.
Background
The photobromination reaction is one of the important reactions in the chemical production process, and most of the bromine-containing fine chemical products and medical intermediates are subjected to the photobromination reaction.
Among them, the photobromination addition reaction is one of the main reactions of the bromination reaction.
In the bromination addition reaction, the research on the alkene dibromination addition reaction is more, and the alkene dibromination addition reaction is roughly divided into inorganic bromine salt, organic bromine salt, bromine-containing organic matter, simple substance bromine and the like according to the difference of bromination reagents. Among them, elemental bromine has the most extensive and economical application range, and related data reports are also more common.
At present, a common industrial bromination addition reaction process device is that a bromine addition reaction is carried out on a mixture of a simple substance bromine and halogenated olefin under the condition of illumination, the reaction speed is reduced due to the lower concentration of reactants in the later reaction period, and a large amount of unreacted raw materials are recycled in a subsequent separation device. The elemental bromine is difficult to recycle and has low utilization rate, the device flow is long, and the requirement on equipment is high, so that the production cost of the target product is increased.
The brominated addition apparatus described in the literature and patents is of a single reactor type, i.e., only one bromination addition reactor is involved. The technical scheme and the device adopting the reactive distillation are not involved in the relevant documents and patents, and the latter is the main characteristic of the invention.
Disclosure of Invention
The invention aims to provide a continuous bromination addition reaction rectification process and a device, which couple the photobromination addition reaction of olefin and halogenated olefin with the separation of a target product, realize high-efficiency photobromination and solve the problem of difficult subsequent elemental bromine separation. The process and the device achieve better reaction effect and raw material utilization rate than the prior process, and simultaneously have the function of product purification.
According to the first aspect of the invention, the following technical scheme is adopted:
a bromination addition reaction rectification process for olefin and halogenated olefin is characterized in that: the photobromination reaction is separated from the target product to realize coupling, and the coupling is carried out in the same reaction device;
feeding reaction raw material olefin or halogenated olefin at the lower part of the reaction device, and feeding reaction raw material simple substance bromine from the upper part of the feeding part of the olefin or halogenated olefin;
the reaction material enters a reaction device, the bromination reaction is carried out under the illumination condition, and simultaneously, the rectification separation is carried out, unreacted bromine simple substance is concentrated above the simple substance bromine feeding part and then flows back, the reaction with olefin or halogenated olefin is continued, and the concentrated target product is extracted at the bottom of the reaction device.
The feeding mode of the elemental bromine is liquid phase feeding, and the feeding mode of the olefin or halogenated olefin is gas phase feeding.
Preferably, the molar ratio of the reflux amount in the reactive distillation process to the feeding amount of the olefin or the halogenated hydrocarbon is 1-100: 1, and preferably 10: 1.
The lighting conditions include, but are not limited to, natural light, artificial light sources of a particular wavelength, or mixed light sources. Preferably, the light source with a specific wavelength of 350-500 nm is adopted for illumination, and more preferably, a light collecting device is adopted for enabling the illumination to be more uniform.
According to the second aspect of the invention, the invention provides a continuous bromination addition reaction device, which can save a traditional separation device of a target product, adopts a filler section of a filler rectifying tower as a reaction part at the same time, improves the yield of the target product and the conversion rate of raw materials, greatly reduces the investment cost and the operation cost of equipment, and simultaneously can meet the requirements of the photobromination addition reaction of olefin and halogenated olefin and the separation of the target product in the aspects of reaction mass transfer and heat transfer, separation and the like.
According to the second aspect of the invention, the following technical scheme is adopted:
a continuous bromination addition reaction rectifying device is characterized in that an olefin or halogenated olefin gas-phase feed port is arranged at the lower part of the device, a liquid-phase feed port of elemental bromine is arranged above the gas-phase feed port of the device, and a transparent tower section between the gas-phase feed port and the liquid-phase feed port is a filler section; a condensing device is arranged above the liquid-phase feed inlet; a reboiling device is arranged below a liquid-phase feed inlet tower section of olefin or halogenated olefin, and a target product discharge port is arranged at the bottom of the device.
Preferably, the bottom of the transparent tower section is connected with a heating kettle which is used as a reboiling device and a target product collecting device, and the heating kettle is provided with a target product discharge port.
Preferably, the reaction rectifying device adopts an internal condensation mode, the condensing device is arranged in a transparent tower section above the liquid phase feed inlet, and a coil type glass condenser is more preferably adopted.
Preferably, a liquid-phase feed inlet of the elemental bromine is positioned at the upper part of the transparent tower section, and a distributor is arranged at a port; the liquid phase feed inlet for the olefin or haloolefin is located at the lower portion of the column section.
Preferably, the reaction device adopts a rectifying tower, the rectifying tower is a packed tower, and the tower body of the rectifying tower adopts transparent materials, such as glass, PVDF, glass lining, steel lining PTFE and other materials resistant to elemental bromine. The materials of the packing and the inner member include but are not limited to glass, ceramics and plastics, and the form of the packing includes but is not limited to common structured packing and random packing.
Preferably, the target product outlet is located below the liquid level at the bottom of the column.
Preferably, 2-6 liquid redistributors are arranged in the tower, so that the liquid is distributed more uniformly.
The invention has the beneficial effects that: the integration of the photobromination addition reaction of olefin or halogenated olefin and the separation of a target product is realized, the production efficiency is effectively improved, and the production equipment cost and the operation cost are saved; secondly, compared with the traditional device and process, the device and the process realize the high-efficiency utilization of the elemental bromine, the conversion rate of the elemental bromine and the conversion rate of olefin or halogenated olefin reach more than 99 percent, and the comprehensive utilization rate reaches more than 99.8 percent; and extracting a target product at the bottom of the tower, wherein the bromine entrainment in the product is less than 0.1 percent. Therefore, the device and the process have the advantages of high yield of target products, simple flow, low cost and the like, and have good industrial application prospect.
Drawings
FIG. 1 is a schematic view of a reaction process apparatus according to the present invention.
Detailed Description
Reference is made to figure 1. The invention adopts a continuous bromination addition reaction rectifying device, and a tower body 1 of a rectifying tower is transparent. The lower part of the transparent tower body is provided with an olefin or halogenated olefin gas-phase feed port 2, the upper part of the transparent tower body is provided with a liquid-phase feed port 3 of elemental bromine, a transparent tower section between the gas-phase feed port 2 and the liquid-phase feed port 3 is a filler section 4, and the filler is made of transparent materials; the top of the reaction rectifying device adopts an internal condensation mode, the condensing device 5 is arranged in a transparent tower section above the liquid-phase feed inlet 3, and the condensing device 5 adopts a coiled glass condenser.
The bottom of the transparent tower section is connected with a heating kettle 6, the heating kettle 6 is used as a reboiling device and a collecting device of a target product, the heating kettle 6 is provided with a target product discharge port 7, and jacket heating is adopted.
The following is a specific experiment using the above reaction apparatus.
Example 1: preparation of 1, 2-dibromoethane by photobromination addition reaction of ethylene and elemental bromine
Ethylene gas phase feeding is carried out from a gas phase feeding port 2, elemental bromine liquid phase feeding is carried out from a liquid phase feeding port 3, under the condition of light catalysis, the photobromination addition reaction is carried out on the filling section and the parts above the filling section to generate 1, 2-dibromoethane, unreacted elemental bromine is condensed and refluxed at the tower top and continuously reacts with the gas phase ethylene to generate the 1, 2-dibromoethane.
Wherein the feeding speed of ethylene and elemental bromine is 0.5kmol/h, the reaction pressure is normal pressure, the bottom temperature is 115 ℃, the top temperature is 55 ℃, the illumination adopts an artificial light source, and a light collecting device is added to ensure uniform illumination, so that the photobromination reaction is stably carried out.
And continuously discharging the liquid phase of the 1, 2-dibromoethane at the bottom of the tower kettle, wherein the molar concentration of bromine in the 1, 2-dibromoethane is 0.05 percent, the conversion rate of elemental bromine reaches 99.6 percent, and the conversion rate of ethylene reaches 99.0 percent.
Example 2: preparation of 1, 2-dibromo-1-chloroethane by photobromination reaction of chloroethylene and elemental bromine
Feeding chloroethylene gas phase from a gas phase feed port 2, feeding elementary bromine liquid phase from a liquid phase feed port 3, carrying out a photobromination addition reaction on the filling section and the parts above to generate 1, 2-dibromo-1-chloroethane under the condition of illumination catalysis, condensing and refluxing unreacted elementary bromine at the tower top, and continuously reacting with the gas phase chloroethylene to generate the 1, 2-dibromo-1-chloroethane.
Wherein the feeding speed of the chloroethylene and the elemental bromine is 0.7kmol/h, the reaction pressure is normal pressure, the temperature at the bottom of the tower is 170 ℃, the temperature at the top of the tower is 55 ℃, an artificial light source is adopted for illumination, a light collecting device is added to ensure uniform illumination, and the photobromination reaction is carried out stably.
And continuously discharging the 1, 2-dibromo-1-chloroethane liquid phase at the bottom of the tower kettle, wherein the molar concentration of bromine in the 1, 2-dibromo-1-chloroethane is 0.03 percent, the conversion rate of the elemental bromine reaches 99.7 percent, and the conversion rate of the chloroethane reaches 99.1 percent.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, substitution and improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (4)
1. A rectification process of continuous photobromination reaction is characterized in that
Feeding reaction raw material olefin or halogenated olefin at the lower part of the reaction device, and feeding reaction raw material simple substance bromine from the upper part of the feeding part of the olefin or halogenated olefin;
the reaction material enters a reaction device, the bromination reaction is carried out under the illumination condition, and simultaneously, the rectification separation is carried out, unreacted bromine simple substance is concentrated above the simple substance bromine feeding part and then flows back, the reaction with olefin or halogenated olefin is continued, and the concentrated target product is extracted at the bottom of the reaction device.
2. The continuous photobromination rectification process of claim 1, wherein the mixing of the two phases in the rectification column is catalyzed by light irradiation.
3. The reaction process of claim 1, wherein the molar ratio of the reflux amount in the reactive distillation process to the feeding amount of the olefin or the halogenated olefin is 1-100: 1.
4. A continuous bromination addition reaction rectifying device is characterized in that an olefin or halogenated olefin gas-phase feed port is arranged at the lower part of the device, a liquid-phase feed port of elemental bromine is arranged above the gas-phase feed port of the device, and a transparent tower section between the gas-phase feed port and the liquid-phase feed port is a filler section; a condensing device is arranged above the liquid-phase feed inlet; a reboiling device is arranged below a liquid-phase feed inlet tower section of olefin or halogenated olefin, and a target product discharge port is arranged at the bottom of the device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911375673.4A CN113041636A (en) | 2019-12-27 | 2019-12-27 | Continuous bromination addition reaction rectification process and device |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911375673.4A CN113041636A (en) | 2019-12-27 | 2019-12-27 | Continuous bromination addition reaction rectification process and device |
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| CN113041636A true CN113041636A (en) | 2021-06-29 |
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| CN201911375673.4A Pending CN113041636A (en) | 2019-12-27 | 2019-12-27 | Continuous bromination addition reaction rectification process and device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736097A (en) * | 2022-05-13 | 2022-07-12 | 马鞍山昂扬新材料科技有限公司 | High-efficiency synthesis process of dibromoethane micro-channel |
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| CN1316409A (en) * | 2001-04-09 | 2001-10-10 | 中国石油化工集团公司 | Process for preparing benzylchlorine |
| CN102068945A (en) * | 2010-12-15 | 2011-05-25 | 天津大学 | Reactive distillation device and method for separating and purifying methylal |
| CN102093178A (en) * | 2009-12-15 | 2011-06-15 | 上海焦化有限公司 | Method for continuously producing unsaturated aldehyde compound by using reaction and rectification |
| CN102107875A (en) * | 2009-12-24 | 2011-06-29 | 北京有色金属研究总院 | Method for preparing silicon tetrachloride for optical fiber |
| CN102140053A (en) * | 2011-01-29 | 2011-08-03 | 锦州惠发天合化学有限公司 | Method for synthesizing halogenated alkanes |
-
2019
- 2019-12-27 CN CN201911375673.4A patent/CN113041636A/en active Pending
Patent Citations (5)
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|---|---|---|---|---|
| CN1316409A (en) * | 2001-04-09 | 2001-10-10 | 中国石油化工集团公司 | Process for preparing benzylchlorine |
| CN102093178A (en) * | 2009-12-15 | 2011-06-15 | 上海焦化有限公司 | Method for continuously producing unsaturated aldehyde compound by using reaction and rectification |
| CN102107875A (en) * | 2009-12-24 | 2011-06-29 | 北京有色金属研究总院 | Method for preparing silicon tetrachloride for optical fiber |
| CN102068945A (en) * | 2010-12-15 | 2011-05-25 | 天津大学 | Reactive distillation device and method for separating and purifying methylal |
| CN102140053A (en) * | 2011-01-29 | 2011-08-03 | 锦州惠发天合化学有限公司 | Method for synthesizing halogenated alkanes |
Non-Patent Citations (1)
| Title |
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| 郑旭煦: "《化工原理（第二版）》", 30 June 2009 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114736097A (en) * | 2022-05-13 | 2022-07-12 | 马鞍山昂扬新材料科技有限公司 | High-efficiency synthesis process of dibromoethane micro-channel |
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Application publication date: 20210629 |
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