CN113527034A - Method for synthesizing halogenated hydrocarbon by continuous flow microchannel reactor - Google Patents
Method for synthesizing halogenated hydrocarbon by continuous flow microchannel reactor Download PDFInfo
- Publication number
- CN113527034A CN113527034A CN202110706449.XA CN202110706449A CN113527034A CN 113527034 A CN113527034 A CN 113527034A CN 202110706449 A CN202110706449 A CN 202110706449A CN 113527034 A CN113527034 A CN 113527034A
- Authority
- CN
- China
- Prior art keywords
- microchannel reactor
- reaction
- flow
- hydrogen halide
- olefin
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- 150000008282 halocarbons Chemical class 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 150000001336 alkenes Chemical class 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 17
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 16
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 12
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 claims description 6
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 10
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen halides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of organic synthesis, and discloses a method for synthesizing halogenated hydrocarbon by a continuous flow microchannel reactor, which comprises the following steps: A) introducing olefin and aqueous hydrogen halide solution into a continuous flow microchannel reactor by a metering pump in a two-feed mode; B) the flow of olefin and hydrogen halide water solution is controlled by a metering pump, so that the olefin and the hydrogen halide water solution enter the microchannel reactor to perform mixed reaction according to the set flow velocity, the reaction pressure is controlled by a back pressure valve, the reaction temperature is controlled by an external heat exchanger, a heat exchange medium is heat conduction oil, a product flows out from an outlet of the microchannel reactor, and the product flows into a product collecting region after being cooled for further treatment. The method for synthesizing the halogenated hydrocarbon by the continuous flow microchannel reactor can improve the reaction yield, reduce the use of hydrogen halide, increase the safety and realize continuous intelligent production.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing halogenated hydrocarbon by a continuous flow microchannel reactor.
Background
The halogenated hydrocarbon is an important organic chemical raw material and has wide application in the fields of fine chemical industry, medical and agricultural chemicals, material preparation and the like.
Industrially, the synthesis of halogenated hydrocarbons from olefins and hydrogen halides by addition reaction is an important production process.
The existing production process mainly adopts batch reaction, and has the defects of long production period, low reaction efficiency, low conversion rate and the like. And the olefin with smaller molecular weight has low boiling point, is easy to volatilize, has low flash point, is easy to explode, and has higher danger and great operation difficulty in the large-scale production process.
There is therefore an urgent need for improvement of the conventional techniques for preparing halogenated hydrocarbons.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing halogenated hydrocarbon by using a continuous flow microchannel reactor, which can improve the reaction yield, reduce the use of hydrogen halide, increase the safety and realize continuous intelligent production.
In order to achieve the above purpose, the present invention provides a method for synthesizing halogenated hydrocarbons by using a continuous flow microchannel reactor, comprising the following steps:
A) introducing olefin and aqueous hydrogen halide solution into a continuous flow microchannel reactor by a metering pump in a two-feed mode;
B) the flow of olefin and hydrogen halide water solution is controlled by a metering pump, so that the olefin and the hydrogen halide water solution enter the microchannel reactor to perform mixed reaction according to the set flow velocity, the reaction pressure is controlled by a back pressure valve, the reaction temperature is controlled by an external heat exchanger, a heat exchange medium is heat conduction oil, a product flows out from an outlet of the microchannel reactor, and the product flows into a product collecting region after being cooled for further treatment.
Preferably, in said step A), the olefin is 1-hexene, 2-ethyl-1-butene, 2, 3-dimethyl-2-butene or 2-methyl-1-hexene.
Preferably, in the step a), the hydrogen halide is hydrogen chloride or hydrogen bromide, and the concentration of the aqueous hydrogen halide solution is 25% to 35%.
Preferably, in the step B), the reaction pressure is 0-0.50 MPa, and the reaction temperature is 50-100 ℃.
Preferably, in the step B), the set flow rate of the olefin is 3-10 ml/min, and the flow rate of the hydrogen halide water solution is 8-25 ml/min.
Preferably, in the step B), the time for carrying out the mixing reaction in the microchannel reactor is 10-20 min.
Compared with the prior art, the invention has the following advantages:
1. because the boiling point of the olefin is too low, and the flash point is low and easy to cause explosion, the traditional reaction kettle has greater danger in operation, the invention improves the pressure in the reactor through the back pressure valve, so that the boiling point of the olefin is increased, and the safety of the reaction is improved;
2. the reaction time is short, in the traditional batch reaction, the conversion rate of the olefin is more than 85 percent, which needs about 6 hours, and the invention changes the batch reaction into the continuous reaction, thereby improving the reaction efficiency and reducing the reaction time.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A) Introducing 1-hexene and aqueous hydrogen chloride (25%) into a continuous flow microchannel reactor via a metering pump in two feeds;
B) controlling the flow of 1-hexene and hydrogen chloride water solution by a metering pump, enabling the 1-hexene to enter a microchannel reactor at the flow rate of 5.0ml/min, enabling the hydrogen chloride water solution to enter the microchannel reactor at the flow rate of 12.5ml/min for mixing reaction, controlling the reaction pressure at normal pressure by a backpressure valve, controlling the reaction temperature at 50 ℃ by an external heat exchanger, controlling the reaction temperature to be heat-conducting oil by a heat exchange medium, enabling the reaction residence time to be 15min, enabling a product to flow out of an outlet of the microchannel reactor, cooling, then enabling the product to enter a product collecting region for further treatment, collecting the cooled reaction solution, and enabling the conversion rate of 1-hexene to be 75.3%.
Example 2
A) Introducing 2-ethyl-1-butene and aqueous hydrogen chloride (35%) into a continuous flow microchannel reactor by a metering pump in two feeding ways;
B) controlling the flow of the 2-ethyl-1-butene and the aqueous solution of the hydrogen chloride by a metering pump, enabling the 2-ethyl-1-butene to enter a microchannel reactor at the flow rate of 3.0ml/min and the aqueous solution of the hydrogen chloride to carry out mixing reaction at the flow rate of 8ml/min, controlling the reaction pressure to be 0.22MPa by a backpressure valve, controlling the reaction temperature to be 85 ℃ by an external heat exchanger, controlling the heat exchange medium to be heat conduction oil, controlling the reaction retention time to be 20min, enabling a product to flow out of an outlet of the microchannel reactor, cooling, then enabling the product to enter a product collecting region for further treatment, collecting the cooled reaction liquid, and controlling the conversion rate of the 2-ethyl-1-butene to be 87.6%.
Example 3
A) Introducing 2-hexene and aqueous hydrogen bromide (30%) into a continuous flow microchannel reactor via a metering pump in two feeds;
B) controlling the flow of the 2-hexene and the aqueous hydrogen bromide by a metering pump, enabling the 2-hexene to enter the microchannel reactor at a flow rate of 8.0ml/min, enabling the aqueous hydrogen bromide to enter the microchannel reactor at a flow rate of 20ml/min for mixing reaction, controlling the reaction pressure to be 0.48MPa by a backpressure valve, controlling the reaction temperature to be 100 ℃ by an external heat exchanger, controlling the reaction temperature to be heat-conducting oil by a heat exchange medium, enabling the reaction residence time to be 12min, enabling a product to flow out of an outlet of the microchannel reactor, cooling, then enabling the product to enter a product collecting region for further treatment, collecting the cooled reaction liquid, and enabling the conversion rate of the 2-hexene to be 88.3%.
Example 4
A) Introducing 2-methyl-1-hexene and aqueous hydrogen chloride (35%) into a continuous flow microchannel reactor via a metering pump in two feeds;
B) controlling the flow of the 2-methyl-1-hexene and the aqueous solution of hydrogen chloride by a metering pump, leading the 2-methyl-1-hexene to enter a microchannel reactor for mixing reaction at the flow rate of 3.5ml/min and the aqueous solution of hydrogen chloride to enter the microchannel reactor at the flow rate of 8.5ml/min, controlling the reaction pressure to be 0.28MPa by a backpressure valve, controlling the reaction temperature to be 100 ℃ by an external heat exchanger, taking heat transfer oil as a heat transfer medium, controlling the reaction retention time to be 20min, leading a product to flow out from an outlet of the microchannel reactor, cooling, then leading the product to enter a product collecting region for further treatment, collecting the cooled reaction liquid, and leading the conversion rate of the 2-methyl-1-hexene to be 92.5%.
Example 5
A) Introducing 2, 3-dimethyl-2-butene and aqueous hydrogen bromide (35%) into a continuous flow microchannel reactor by a metering pump in a two-stream feeding manner;
B) controlling the flow of the 2, 3-dimethyl-2-butene and the aqueous hydrogen bromide solution by a metering pump, enabling the 2, 3-dimethyl-2-butene to enter the microchannel reactor at the flow rate of 10ml/min and the aqueous hydrogen bromide solution at the flow rate of 25ml/min for mixing reaction, controlling the reaction pressure to be 0.5MPa by a backpressure valve, controlling the reaction temperature to be 100 ℃ by an external heat exchanger, taking heat transfer oil as a heat transfer medium, controlling the reaction retention time to be 10min, enabling a product to flow out of an outlet of the microchannel reactor, cooling, then enabling the product to enter a product collecting region for further treatment, and collecting the cooled reaction liquid, wherein the conversion rate of the 2, 3-dimethyl-2-butene is 93.8%.
According to the method for synthesizing the halogenated hydrocarbon by the continuous flow microchannel reactor, the pressure in the reactor is increased through the back pressure valve, so that the boiling point of olefin is increased, and the safety of the reaction is improved; the reaction time is short, in the traditional batch reaction, the conversion rate of the olefin is more than 85 percent, which needs about 6 hours, and the invention changes the batch reaction into the continuous reaction, thereby improving the reaction efficiency and reducing the reaction time.
Claims (6)
1. A method for synthesizing halogenated hydrocarbon by a continuous flow microchannel reactor is characterized by comprising the following steps: the method comprises the following steps:
A) introducing olefin and aqueous hydrogen halide solution into a continuous flow microchannel reactor by a metering pump in a two-feed mode;
B) the flow of olefin and hydrogen halide water solution is controlled by a metering pump, so that the olefin and the hydrogen halide water solution enter the microchannel reactor to perform mixed reaction according to the set flow velocity, the reaction pressure is controlled by a back pressure valve, the reaction temperature is controlled by an external heat exchanger, a heat exchange medium is heat conduction oil, a product flows out from an outlet of the microchannel reactor, and the product flows into a product collecting region after being cooled for further treatment.
2. The continuous-flow microchannel reactor of claim 1, wherein the reactor further comprises: in the step A), the olefin is 1-hexene, 2-ethyl-1-butene, 2, 3-dimethyl-2-butene or 2-methyl-1-hexene.
3. The continuous-flow microchannel reactor of claim 1, wherein the reactor further comprises: in the step A), the hydrogen halide is hydrogen chloride or hydrogen bromide, and the concentration of the aqueous hydrogen halide solution is 25-35%.
4. The continuous-flow microchannel reactor of claim 1, wherein the reactor further comprises: in the step B), the reaction pressure is 0-0.50 MPa, and the reaction temperature is 50-100 ℃.
5. The continuous-flow microchannel reactor of claim 1, wherein the reactor further comprises: in the step B), the set flow rate of the olefin is 3-10 ml/min, and the flow rate of the hydrogen halide water solution is 8-25 ml/min.
6. The continuous-flow microchannel reactor of claim 1, wherein the reactor further comprises: in the step B), the time for carrying out the mixing reaction in the microchannel reactor is 10-20 min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110706449.XA CN113527034A (en) | 2021-06-24 | 2021-06-24 | Method for synthesizing halogenated hydrocarbon by continuous flow microchannel reactor |
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| CN202110706449.XA CN113527034A (en) | 2021-06-24 | 2021-06-24 | Method for synthesizing halogenated hydrocarbon by continuous flow microchannel reactor |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429799A (en) * | 2003-01-04 | 2003-07-16 | 大连理工大学 | Synthesis method of 1-bromoane |
| WO2010104742A2 (en) * | 2009-03-12 | 2010-09-16 | Chemtura Corporation | Processes for making alkyl halides |
| US20120141356A1 (en) * | 2004-04-16 | 2012-06-07 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| CN106117128A (en) * | 2016-06-26 | 2016-11-16 | 江苏扬农化工集团有限公司 | A kind of micro passage reaction prepares the method for pyridone chlorine addition product continuously |
-
2021
- 2021-06-24 CN CN202110706449.XA patent/CN113527034A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429799A (en) * | 2003-01-04 | 2003-07-16 | 大连理工大学 | Synthesis method of 1-bromoane |
| US20120141356A1 (en) * | 2004-04-16 | 2012-06-07 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| WO2010104742A2 (en) * | 2009-03-12 | 2010-09-16 | Chemtura Corporation | Processes for making alkyl halides |
| CN106117128A (en) * | 2016-06-26 | 2016-11-16 | 江苏扬农化工集团有限公司 | A kind of micro passage reaction prepares the method for pyridone chlorine addition product continuously |
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Application publication date: 20211022 |