CN1067973C - Process for preparing chlorohydrin in tubular reactor - Google Patents
Process for preparing chlorohydrin in tubular reactor Download PDFInfo
- Publication number
- CN1067973C CN1067973C CN98110163A CN98110163A CN1067973C CN 1067973 C CN1067973 C CN 1067973C CN 98110163 A CN98110163 A CN 98110163A CN 98110163 A CN98110163 A CN 98110163A CN 1067973 C CN1067973 C CN 1067973C
- Authority
- CN
- China
- Prior art keywords
- pipeline reactor
- chlorine
- raw material
- reaction
- pipeline
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a reaction process for preparing chlorohydrin in a tubular reactor. For enhancing the mass transfer efficiency of a gas phase and a liquid phase, a static mixing element is arranged in the tubular reactor. Used raw material is C2-C4 olefin or C2-C4 haloolefin and chlorine. Chlorine is dissolved and reacts with the raw material at normal pressure, and the defect of the low dissolvability of the chlorine in water at normal pressure is overcome by the circulation of reaction liquid. A device volume can be reduced by using the process of the present invention. The conversion rate of the C2-C4 olefin or the C2-C4 haloolefin can achieve more than 98 %. The selectivity of chlorohydrination can achieve more than 91 %.
Description
The present invention relates to the chlorohydrination pipe reaction technology of a kind of hydro carbons and chlorine reaction, specifically, the present invention adopts a kind of pipeline reactor with the static mixing device to carry out molten chlorine and reaction.
Produce in the technology of propylene oxide, epoxy chloropropane at chlorohydrination, chlorohydrin action is the key of this technology.In chlorohydrin action, no matter be gas circulation method or liquid phase circulation method, what extensively adopt is tower bubbling bed reactor.Though tower bubbling bed reactor is simple in structure, and is easy to make, with regard to the characteristics of chlorohydrin action,, cause its throughput lower because its gas-liquid two-phase mass-transfer efficiency is low, equipment volume is excessive.
Purpose of the present invention is exactly to improve the mass-transfer efficiency of chlorohydrin action gas-liquid two-phase, thereby improves its throughput.
In order to realize above-mentioned goal of the invention, the present invention has developed the processing method of carrying out chlorohydrin action in normal pressure, novel pipeline reactor, be about to raw material chlorine G﹠W is equipped with the static mixing device in reactor front end opening for feed enters a pipe pipeline reactor, thorough mixing; And raw material C
2～C
4Alkene or C
2～C
4Haloolefin enters this pipeline reactor through the middle part of reactor opening for feed, carries out chlorohydrin action; The product of chlorohydrin action draws off from the afterbody discharge port of this pipeline reactor, enters a gas-liquid separator; In gas-liquid separator, tail gas is by the top emptying, and reaction solution is flowed out by the bottom, and the part of reaction solution loops back pipeline reactor by reactor front end opening for feed, and another part is then collected as product.
In pipeline reactor of the present invention, the static mixing device of being adorned can be the Kenics type, also can be the Sulger type, or other pattern, and purpose is to make pipeline reactor have the good mixing performance, promptly improves its mass transfer, heat transfer property.The static mixing device etching problem that do not have under the chlorohydrin action condition is as selecting macromolecular material or corrosion-resistant metal materials.The outward appearance of pipeline reactor can be straight, also can bend to other different shape.The total length of pipeline reactor should be greater than 11 meters, and to guarantee the efficient of one way chlorohydrin action, reactor middle part opening for feed is at least 3 meters apart from its front end opening for feed, has adequate time and space to mix molten chlorine to guarantee the chlorine G﹠W.
In the present invention, raw material chlorine, C
2～C
4Alkene or C
2～C
4The working pressure of haloolefin is controlled in 1～8 normal atmosphere (absolute pressure); C
2～C
4Alkene or C
2～C
4The mol ratio of haloolefin and chlorine is 0.9: 1 to 1.1: 1; The temperature of reaction is controlled in 30～80 ℃ the scope; In addition, in order to guarantee the complete of molten chlorine, the apparent linear speed of liquid should be not less than 0.4 meter per second in the raw material, is preferably 0.4～0.6 meter per second.
In the superincumbent invention scheme, pipeline reactor front end opening for feed to a section of middle part opening for feed is to carry out molten chlorine basically; After the opening for feed of middle part is to react basically.Thereby another embodiment of the present invention is the molten chlorine of above-mentioned pipeline reactor and reaction to be divided carry out in two reactors, be that raw material chlorine G﹠W enters first pipeline reactor that the static mixing device is housed and carries out molten chlorine, the molten chlorine liquid and the raw material C that come out from first pipeline reactor
2～C
4Alkene or C
2～C
4Haloolefin enters second pipeline reactor that the static mixing device is housed; The reaction product of second pipeline reactor draws off from the afterbody opening for feed, enters a gas-liquid separator; In gas-liquid separator, tail gas is by the top emptying, and reaction solution is flowed out by the bottom, and the part of reaction solution loops back pipeline reactor by the opening for feed of first pipeline reactor, and another part is collected as product.
The static mixing device of being adorned in first, second pipeline reactor in this scheme is identical with last scheme, and complete in order to guarantee molten chlorine, and the length of first pipeline reactor should be greater than 3 meters; In order to guarantee the efficient of chlorohydrin action, the length of second pipeline reactor should be greater than 8 meters.The working pressure of chlorine and alkene is controlled in 1～8 normal atmosphere (absolute pressure) in the raw material, and the mol ratio of alkene and chlorine is 0.9: 1 to 1.1: 1; The temperature of reaction is controlled in 30～80 ℃ of scopes; The apparent linear speed of liquid is not less than 0.4 meter per second in the raw material, is preferably 0.4～0.6 meter per second.
In normal pressure chlorohydrination pipe reaction technology, sufficient reaction solution circulation must be arranged, to increase the meltage of chlorine.But the selectivity of chlorohydrin action reduces with the increase of chloropharin concentration, and when chloropharin concentration within the specific limits the time, it is less that reaction preference increases the amplitude that reduces with chloropharin concentration, after chloropharin concentration surpasses certain value, and the amplitude increase that selectivity reduces.In order to keep higher reaction preference, another embodiment of the present invention is that the above-mentioned pipeline reaction process with two sections or multistage is connected in series, wherein each section is made up of one or two pipeline reactors and a gas-liquid separator again, the reaction solution part that generated the last period is in this section circulation, and another part enters next section continuation reaction.
Adopt technical scheme of the present invention, C
2～C
4Alkene or C
2～C
4The transformation efficiency of haloolefin can reach more than 98%, and the selectivity of chlorohydrin action surpasses 91%.
The present invention is described in further detail below in conjunction with drawings and Examples.
Fig. 1 is the process flow sheet that carries out molten chlorine and reaction in a pipeline reactor simultaneously;
Fig. 2 is the process flow sheet that carries out molten chlorine, reacts at another pipeline reactor at a pipeline reactor;
Fig. 3 is the process flow sheet of three sections chlorohydrin actions.
In technological process shown in Figure 1, fresh water (FW) after the preheating is entered the pipeline reactor 14 that the static mixing device is housed through pipeline 11 by front end charging aperture A, chlorine enters pipeline reactor 14 through pipeline 12 by front end charging aperture A, and raw material olefin or alkenyl halide enter pipeline reactor 14 through pipeline 13 by middle part charging aperture B. Basically be to carry out molten chlorine in the front portion of pipeline reactor 14, the rear portion is to react basically. Reactant liquor and tail gas enter gas-liquid separator 17 through pipeline 16, tail gas is emptying by the top of gas-liquid separator 17, reactant liquor is flowed out by its bottom, and a part loops back pipeline reactor 14 through pipeline 18 by front end charging aperture A, another part through pipeline 19 as product-collecting.
In technological process shown in Figure 2, the fresh water (FW) after the preheating enters the pipeline reactor 24 of in-built static mixing device through pipeline 21, and chlorine enters the first pipeline reactor 24 through pipeline 22, is to carry out molten chlorine basically in the first pipeline reactor 24; Raw material olefin or alkenyl halide enter the second pipe reactor 25 of in-built static mixing device through pipeline 23, are to react basically in reactor 25; Reactant liquor and tail gas enter gas-liquid separator 27 through pipeline 26, and tail gas is emptying by the top of separator 27, and reactant liquor is flowed out by its bottom, and a part loops back the first pipeline reactor 24 through pipeline 28, another part through pipeline 29 as product-collecting.
Technological process shown in Figure 3 is actually three sections technological processes is as shown in Figure 1 coupled together. Raw material reacts in the pipeline reactor 31 of first paragraph, enters the gas-liquid separator 34 of first paragraph; Reactant liquor part from gas-liquid separator 34 loops back pipeline reactor 31, and another part enters and continues reaction in the pipeline reactor 32 of second segment; Equally, loop back pipeline reactor 32 from the reactant liquor part of the gas-liquid separator 35 of second segment, another part then enters in the 3rd section the pipeline reactor 33 and continues reaction; Loop back the 3rd section pipeline reactor 33 from the reactant liquor part of the 3rd section gas-liquid separator 36, another part is as product-collecting.
Embodiment
Adopt technical process shown in Figure 1, the filling material is the static mixing device of tetrafluoroethylene in the pipe, makes raw material with the propylene of purity 〉=96% and the chlorine of purity 〉=99%, produces propylene chlorohydrin by following processing condition, and experimental scale is 250 tons/year:
The technology water yield: 0.7m
3/ h, internal circulating load: 5.3m
3/ h
Propylene feed amount: 6.2m
3/ h,
Chlorine feed amount: 7.8～7.9m
3/ h,
Drop temperature: 59 ℃
Test-results is listed in the table below
| Experiment numbers | Propylene pressure (MPa) | Chlorine gas pressure (MPa) | The propylene temperature (℃) | Chlorine temperature (℃) | Tail gas amount (m 3/h) | Fluid analysis (mass percent) | Tails assay (volume percent) | ||||
| Propylene chlorohydrin | Propylene dichloride | Monochloroacetone | Dichloroisopropyl ether | Propylene dichloride (g/L) | Propylene | ||||||
| 1 | 0.195 | 0.325 | 25.00 | 26.00 | 0.4 | 4.15 | 0.384 | 0.02 | 0.066 | 0.224 | 0.14 |
| 2 | 0.200 | 0.326 | 27.00 | 25.00 | 0.4 | 4.21 | 0.300 | 0.022 | 0.069 | 0.159 | 0.13 |
| 3 | 0.200 | 0.326 | 22.50 | 23.50 | 0.2 | 4.57 | 0.402 | 0.026 | 0.066 | 0.199 | 0.21 |
| 4 | 0.200 | 0.327 | 21.00 | 21.00 | 0.2 | 4.53 | 0.336 | 0.024 | 0.084 | 0.198 | 0.15 |
Calculated and can be got by testing data: through single hop chlorohydrin action technical process test, the mean concns of propylene chlorohydrin is 4.365%, and average selectivity is 91.48%, and propylene conversion is greater than 99%.
Claims (7)
1, a kind of pipe reaction technology of chlorohydrination comprises:
(1) raw material chlorine G﹠W is equipped with the pipeline reactor of static mixing device, raw material C in the front end opening for feed enters a pipe
2～C
4Alkene or C
2～C
4Haloolefin enters above-mentioned pipeline reactor through the middle part opening for feed;
(2) reaction product of above-mentioned pipeline reactor draws off from the afterbody discharge port, enters a gas-liquid separator;
(3) in above-mentioned gas-liquid separator, tail gas is by the top emptying, and reaction solution is flowed out by the bottom, and the part of reaction solution is circulated to pipeline reactor by the front end opening for feed, and another part is collected as product.
2, the technology described in the claim 1, the length that it is characterized in that described pipeline reactor are greater than 11 meters, and the middle part opening for feed is in the position of distance front end opening for feed greater than 3 meters.
3, the processing method described in the claim 1 or 2 is characterized in that the working pressure of raw material is controlled at 1～8 normal atmosphere (definitely), C
2～C
4Alkene or C
2～C
4The mol ratio of haloolefin and chlorine is 0.9: 1 to 1.1: 1, and temperature of reaction is 30～80 ℃, and the apparent linear speed of liquid is not less than 0.4 meter per second.
4, a kind of pipe reaction technology of chlorohydrination comprises:
(1) raw material chlorine G﹠W enters first pipeline reactor and carries out molten chlorine, the molten chlorine liquid and the raw material C that come out from first pipeline reactor
2～C
4Alkene or C
2～C
4Haloolefin enters second pipeline reactor;
The reaction product of (2) second pipeline reactors draws off from the afterbody discharge port, enters a gas-liquid separator;
(3) in described gas-liquid separator, tail gas is by the top emptying, and reaction solution is flowed out by the bottom, and the part of described reaction solution loops back pipeline reactor by the opening for feed of first pipeline reactor, and another part is collected as product.
5, the described technology of claim 4, the length that it is characterized in that first pipeline reactor is greater than 3 meters, and the length of second pipeline reactor is greater than 8 meters.
6, the processing method described in the claim 4 or 5 is characterized in that the working pressure of raw material is controlled at 1～8 normal atmosphere (definitely), raw material C
2～C
4Alkene or C
2～C
4The mol ratio of haloolefin and chlorine is 0.9: 1 to 1.1: 1, and temperature of reaction is 30～80 ℃, and the apparent linear speed of liquid is not less than 0.4 meter per second in the raw material.
7, a kind of pipe reaction technology of chlorohydrination is characterized in that this technology is to be connected to form as claim 1 or the described pipe reaction process section of claim 4 by two or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110163A CN1067973C (en) | 1998-04-14 | 1998-04-14 | Process for preparing chlorohydrin in tubular reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110163A CN1067973C (en) | 1998-04-14 | 1998-04-14 | Process for preparing chlorohydrin in tubular reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1232011A CN1232011A (en) | 1999-10-20 |
| CN1067973C true CN1067973C (en) | 2001-07-04 |
Family
ID=5220238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110163A Expired - Fee Related CN1067973C (en) | 1998-04-14 | 1998-04-14 | Process for preparing chlorohydrin in tubular reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1067973C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014079163A1 (en) * | 2012-11-20 | 2014-05-30 | Yu Jiaquan | Method for increasing chlorhydrin concentration in chlorohydrination reaction by means of cyclic reaction |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7157609B2 (en) | 2002-05-21 | 2007-01-02 | Tokuyama Corporation | Process for producing propylene chlorohydrin |
| CN1321732C (en) * | 2004-12-17 | 2007-06-20 | 沈阳化工学院 | Tubular chlorine quick dissolving reactor for production of propylene oxide by chlorohydrination and generation of hypochlorous acid |
| CN102241647B (en) * | 2011-05-24 | 2013-05-22 | 淄博永大化工有限公司 | Preparation technology of propylene oxide |
| CN103044359B (en) * | 2013-01-30 | 2016-03-09 | 淄博永大化工有限公司 | A kind of two step extraction processs produce the preparation technology of propylene oxide |
| CN105664830B (en) * | 2016-02-04 | 2017-12-12 | 河南心连心化肥有限公司 | Integrated tube type reaction unit and its reaction method |
| CN106518589B (en) * | 2016-03-14 | 2019-09-06 | 江西苏克尔新材料有限公司 | A method of preparing halogenohydrin and epoxides |
| CN108059586B (en) * | 2017-12-12 | 2021-08-17 | 浙江镇洋发展股份有限公司 | Method for preparing dichloropropanol by glycerol chlorination |
| CN111099964B (en) * | 2018-10-25 | 2022-10-21 | 中国石油化工股份有限公司 | Chlorohydrination reaction system and reaction method |
| CN111099963A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Chlorohydrination reaction system and reaction method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD144907A1 (en) * | 1979-07-16 | 1980-11-12 | Kuessner Karl Heinz | METHOD FOR THE CONTINUOUS PREPARATION OF WAESSED PROPYLENEHLORHYDRIN SOLUTIONS |
| CN1051550A (en) * | 1989-11-06 | 1991-05-22 | 中国石油化工总公司上海石油化工研究所 | The improvement of olefin chlorine alcoholization process |
-
1998
- 1998-04-14 CN CN98110163A patent/CN1067973C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD144907A1 (en) * | 1979-07-16 | 1980-11-12 | Kuessner Karl Heinz | METHOD FOR THE CONTINUOUS PREPARATION OF WAESSED PROPYLENEHLORHYDRIN SOLUTIONS |
| CN1051550A (en) * | 1989-11-06 | 1991-05-22 | 中国石油化工总公司上海石油化工研究所 | The improvement of olefin chlorine alcoholization process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014079163A1 (en) * | 2012-11-20 | 2014-05-30 | Yu Jiaquan | Method for increasing chlorhydrin concentration in chlorohydrination reaction by means of cyclic reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1232011A (en) | 1999-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1067973C (en) | Process for preparing chlorohydrin in tubular reactor | |
| CN109134231B (en) | Device and process for continuously producing chloroacetic acid by differential circulation | |
| CN1119341C (en) | Method for the continuous production of 1,3-dioxolan-2-ones | |
| CN1984858B (en) | Method and device for producing 1,2-dichlorethane by means of direct chlorination | |
| US20220410104A1 (en) | Gas-liquid bubbling bed reactor, reaction system, and process for synthesizing carbonate ester | |
| CN110981846B (en) | Method for preparing ethylene carbonate by adopting tubular reactor with static mixer | |
| CN104250210A (en) | Method for production of acetic acid by methanol carbonylation | |
| CN106242961A (en) | Production of chloroacetic acid equipment | |
| CN109364868A (en) | A kind of continous way chloro thing process units | |
| CN113045391B (en) | Gas-liquid dual-cycle hydroformylation continuous reaction device and process | |
| CN108499508B (en) | A kind of multipoles reactors and the method for preparing cycocel using the device | |
| CN212119062U (en) | Nitric acid recovery unit in adipic acid production | |
| CN1330624C (en) | Process for the preparation of monochloroacetic acid | |
| CN101657400B (en) | Process and apparatus for producing chlorohydrin | |
| CN205295183U (en) | Energy -saving ultra -large methanol synthesis device of production different brackets steam | |
| CN214937128U (en) | Liquid-liquid heterogeneous continuous reaction system | |
| CN105367379A (en) | Method using cycle reaction for preparation of hexafluoroethane | |
| CN1148341C (en) | Process for synthesizing diisopropylamine | |
| CN112552176B (en) | Synthesis process of methyl chloroformate | |
| CN104387258B (en) | A kind of production of chloroacetic acid method and chlorination reactor | |
| Scott et al. | Pilot scale electrosynthesis of alkene oxides by direct and indirect oxidation in a sieve plate electrochemical reactor | |
| CN111138267A (en) | Method for preparing low carbonic acid by using low carbon aldehyde through air oxidation | |
| CN1164544C (en) | Process for dichloroethane by direct chlorization | |
| CN104788284B (en) | The continuous producing method of low carbon alcohol by synthetic gas | |
| CN118221614A (en) | Preparation method of 1, 2-epoxypropane and micro-channel reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |