CN109563013A - The preparation method of vinylidene chloride - Google Patents
The preparation method of vinylidene chloride Download PDFInfo
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- CN109563013A CN109563013A CN201780050736.1A CN201780050736A CN109563013A CN 109563013 A CN109563013 A CN 109563013A CN 201780050736 A CN201780050736 A CN 201780050736A CN 109563013 A CN109563013 A CN 109563013A
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- reactor
- vinylidene chloride
- impeller
- aqueous solution
- preparation
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 238000007033 dehydrochlorination reaction Methods 0.000 claims abstract description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical class ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 12
- 230000009257 reactivity Effects 0.000 abstract description 11
- 238000006704 dehydrohalogenation reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- 230000036632 reaction speed Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- 230000002051 biphasic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229960002415 trichloroethylene Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NDLYMVMQUIPGDT-UHFFFAOYSA-M [NH4+].[Cl-].C[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.[Cl-] Chemical compound [NH4+].[Cl-].C[P+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.[Cl-] NDLYMVMQUIPGDT-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance 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
-
- 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
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/04—Chloro-alkenes
- C07C21/073—Dichloro-alkenes
- C07C21/08—Vinylidene chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of vinylidene chloride, pass through the mixing power and alkaline aqueous solution using the continuous stirred tank reactor and the reactor with one or more levels impeller, it can be in the case where being added without phase transfer catalyst, also 1 is improved than now, the reactivity of the dehydrochlorination reaction (dehydrohalogenation) of 1,2- trichloroethanes.
Description
This application claims the priority based on the South Korea patent application on the 22nd of August in 2016 the 10-2016-0106229th,
Full content disclosed in South Korea patent application document is incorporated herein by reference.
Technical field
The present invention relates to a kind of preparation methods of vinylidene chloride, by improving de-hydrogen halide (preferably dechlorination
Hydrogen reaction), reactivity can be improved.
Background technique
In general, preparing inclined dichloro by dehydrochlorination reaction after 1,1,2- trichloroethanes is added in phase transfer catalyst
Ethylene.The vinylidene chloride is used as the additive for being used to prepare various plastic film materials in chemical technology or monomer and removes
Careless agent, pharmaceutical raw material precursor.
For example, U.S. Patent No. 02610214, Japanese Patent Publication the 1981-057721st, Chinese patent disclose
It is all to utilize phase transfer catalyst (phase in alkaline aqueous solution that No. 100868987 and Chinese patent, which disclose No. 100868986,
Transfer catalyst) carry out dehydrochlorination reaction.Used phase transfer catalyst is nitrogen salt form such as quaternary ammonium salt
(quaternary ammonium salt) etc., effect is so that NaOH aqueous solution and 1,1,2- trichloroethanes of organic matter are uniform
Mixing.
However, the phase transfer catalyst being added to improve dehydrochlorination reaction is not only expensive, but also it is difficult to from reaction
Removal is refined in reaction product afterwards.Therefore, it is necessary to develop a kind of new method, phase transfer catalyst is not used, it may have
The reactivity of the dehydrochlorination reaction further improved.
Summary of the invention
Technical problem
The present invention is intended to provide a kind of preparation method of vinylidene chloride, this method is not necessarily to if prior art use is for changing
It is apt to reactive phase transfer catalyst, can also improves the reactivity of dehydrochlorination reaction.
Technical solution
The preparation method that the present invention provides a kind of vinylidene chloride includes: 1,1,2- trichloroethanes and alkaline aqueous solution are added
The step of entering to have continuous stirred tank reactor (CSTR) of impeller；And 500 to 3000W/m3Mixing power under carry out
Dehydrochlorination reaction 1 minute to 60 minutes the step of.
In the reactor, impeller preferably comprises one or more levels and is selected from radial pattern La Shidun turbine (rushton
Turbine, radial type), flat paddle (paddle), oblique paddle (pitched paddle type, axial type), propeller,
At least one of (pfaudler) agitating device is drawn in hydrofoil (hydrofoil) and method Wudu.
The alkaline aqueous solution can be the alkaline water of the NaCl of the weight of NaOH and 0 to 25 % comprising 2 to 15 weight %
Solution.
Relative to 1.0 moles of 1,1,2- trichloroethanes, it is water-soluble that the alkalinity preferably is added according to 1.0 to 1.5 molar ratios
Liquid.
The service condition of the continuous stirred tank reactor preferably at 0barg to 10barg pressure keep 70 to
110 DEG C of temperature.
Invention effect
The present invention utilizes the continuous stirred tank reactor with particular impeller, at the same time suitably controls mixing power
In a certain range, it can be improved 1,1,2- trichloroethanes the reactive of dehydrochlorination reaction so as to provide and prepare inclined two
The effect of vinyl chloride.In addition, 1,1,2- trichloroethanes and NaOH aqueous solution is used only according to the configuration in the present invention, therefore
It is easy to refine after reaction, so as to improve process efficiency, and without using expensive phase transfer catalyst, therefore there is warp
Ji benefit.
Detailed description of the invention
Fig. 1 is the schematic diagram of impeller shape possessed by the reactor of an exemplary implementation scheme according to the present invention.
Fig. 2 is the flow diagram for preparing vinylidene chloride of an exemplary implementation scheme according to the present invention.
Fig. 3 be by comparative example 1 to 5 and embodiment 1 whether addition based on phase transfer catalyst and the difference of mixing power it is anti-
Answer the schematic diagram that speed compares.
Fig. 4 is the schematic diagram for comparing the reaction speed based on mixing power of comparative example 1 and Examples 1 to 2.
Specific embodiment
The present invention is described more particularly below.In addition, the present invention can be subject to various transformation and have various embodiments, because
This exemplifies specific embodiment and is described in detail.However, the present invention is not limited to particular implementation, it is all of the invention
Made all transformation, equipollent or substitute, should all fall within the scope of the present invention under technical idea and technical scope.
In addition, terminology used herein "comprising" of the invention is not to refer specifically to a certain characteristic, field, integer, step
Suddenly, movement, element and/or ingredient, and exclude the presence of other characteristics, field, integer, step, movement, element and/or ingredient
Or it is additional.
It is described in more detail below the system of the currently preferred reactive vinylidene chloride for improving dehydrochlorination reaction
Preparation Method.
The preparation method that an exemplary implementation scheme according to the present invention provides a kind of vinylidene chloride includes: by 1,1,
2- trichloroethanes and alkaline aqueous solution addition have the step of continuous stirred tank reactor (CSTR) of impeller；And 500
The step of being carried out dehydrochlorination reaction 1 minute to 60 minutes under to the mixing power of 3000W/m3.
That is, in order to improve the reactivity of dehydrochlorination reaction, phase transfer catalyst is utilized in existing method
(phase transition catalyst) such as quaternary ammonium salt (quaternary ammonium salt).
However, experimental result confirmation according to the present invention, in the dehydrochlorination reaction for being used to prepare vinylidene chloride, mentions
High mixing power ratio more effectively improves reactivity using phase transfer catalyst, so as to complete the present invention.
Specifically, the present invention prepares 1,1, the 2- trichloroethanes and alkaline aqueous solution as chloride reactant, to implement
Prepare the process of vinylidene chloride.
In particular, using continuous stirred tank reactor (CSTR) in order to carry out dehydrochlorination reaction in the present invention, passing through
The mixing power for suitably controlling this reactor, without using such as existing phase transfer catalyst, only with reactant and alkaline water
The reaction of solution can also show the reactivity of excellent dehydrochlorination reaction.At this point, the continuous stirred tank reactor
It can be multistage reactor, it is characterized in that having impeller.In addition, at least one can be set in the reactor, each other by them
Connection, so that it may carry out continuous processing.Rectifier can connect answers on device described.
In addition, in the description of the invention, impeller refers to that connection is set from the top of the continuous stirred tank reactor
It sets and is formed in the agitating device on agitating shaft.In addition, the agitating shaft may include driving portion, the driving portion includes reactor
In drive shaft for rotating impeller, the drive shaft can drive according to method as known in the art.
Specifically, dehydrochlorination reaction according to the present invention reacts (Liquid-Liquid as liquid-liquid diphase
Biphasic reaction), it is important that the product vinylidene chloride after reaction is sent to the top of reactor.Therefore, at this
It, compared with the existing methods can be more effectively by the rotation and mixing power of impeller possessed by control reactor in invention
Vinylidene chloride is obtained, the top for being then delivered to reactor is easy recycling.
In addition, in the present invention, various forms of impellers can use, as long as mixing power is improved, by using tool
There is the reactor of this impeller, reactivity can be improved.
For example, impeller preferably comprises one or more levels and is selected from radial pattern La Shidun turbine in the reactor
(rushton turbine, radial type), flat paddle (paddle), oblique paddle (pitched paddle type, axial
Type), at least one of (pfaudler) agitating device is drawn in propeller, hydrofoil (hydrofoil) and method Wudu.The impeller is
One or more levels refers to has one or more levels agitating device centered on the agitating shaft of reactor.The flat paddle may include 90 degree
3-6 blade flat paddle (90 ° of 3-6blade Paddle at) type.
The impeller can connect setting above reactor, and may include described in one or more levels centered on agitating shaft
Impeller.As an example, impeller described in level-one or second level can be set in reactor.When in reactor be arranged level-one described in leaf
When wheel, the impeller be can be set in the agitating shaft lower end of reactor.In addition, when impeller described in second level is arranged in reactor,
The impeller can be set in the top and bottom of the point of bisection of reactor agitating shaft.
Additionally, it is preferred that by La Shidun turbine (rushton turbine, radial type), flat paddle (paddle) or oblique paddle
(pitched paddle type, axial type) is used singly or in combination at least one, thus centered on agitating shaft
Include impeller described in level-one or second level.
One example of the reactor comprising impeller of the invention is as shown in Figure 1.
In Fig. 1, (a) is that all have the example of oblique blade impeller in top and bottom centered on reactor agitating shaft
(secondary structure)；It (b) is in upper end centered on reactor agitating shaft with flat blade impeller and lower end has oblique blade impeller
Example (secondary structure)；It (c) is in upper end centered on reactor agitating shaft with oblique blade impeller and lower end has flat paddle
The example (secondary structure) of formula impeller；It (d) is that all there is flat blade impeller in top and bottom centered on reactor agitating shaft
Example (secondary structure)；It (e) is that there is example (the level-one knot of oblique blade impeller in lower end centered on reactor agitating shaft
Structure)；It (f) is that there is the example (primary structure) of flat blade impeller in lower end centered on reactor agitating shaft.In the impeller
In, oblique paddle improves the internal excellent effect of temperature and improves OH- conversion ratio, thus the generation with excellent vinylidene chloride
Effect.In addition, when using the oblique paddle as impeller, it can be smooth by the vinylidene chloride prepared by dehydrochlorination reaction
The top that ground is sent to reactor is easy recycling.In addition, flat paddle formula has the effect of improving reaction speed in the impeller.
In addition, in the present invention, due to using the impeller, can provide little particle reactant uniform effect, so that
Solid NaCl is uniformly dispersed, and successfully recovery product and can prevent the channel of continuous stirred tank reactor
(channeling)。
This impeller preferably passes through the oblique paddle peace paddle of selection and is arranged to level-one or second level.Most preferably, the reaction
Impeller includes level-one or the oblique paddle of second level in device.Therefore, most preferably using the example of (a) and (e) in Fig. 1.
In addition, the invention is characterized in that using the continuous stirred tank reactor with the impeller, while by impeller
Mixing power is controlled in a certain range, to improve reactivity.That is, even if including impeller in reactor, stirred if do not controlled
Power is mixed, then reactivity can excessively decline or the efficiency of reaction process can be very low.
Therefore, in the present invention, it is preferred to 500 to 3000W/m3Mixing power under carry out de-hydrogen halide (that is, dechlorination
Change hydrogen reaction) 1 minute to 60 minutes.It is highly preferred that the mixing power can be 1000 to 3000W/m3.At this point, if described
Mixing power is less than 500W/m3, then the improvement of dehydrochlorination reaction can not be expected slowly due to stirred, and if the mixing power
Greater than 3000W/m3, then exist relative to being stirred to react the inapparent problem of its effect faster.In the description of the invention,
Unit " W/m3" for indicating the mixing power of reactor, it can indicate the stirring power density of impeller possessed by reactor.
In addition, the service condition of the continuous stirred tank reactor is preferably kept at 0barg to 10barg pressure
70 to 110 DEG C of temperature.
In addition, the alkaline aqueous solution can be the alkali of the NaCl of the weight of NaOH and 0 to 25 % comprising 2 to 15 weight %
Property aqueous solution.
For example, the alkaline aqueous solution can be the aqueous solution of the NaCl of the NaOH comprising 2 weight % and 25 weight %, or
Person can be the aqueous solution of the NaOH comprising 15 weight %.
In addition, the alkalinity preferably is added according to 1.0 to 1.5 molar ratios relative to 1.0 moles of 1,1,2- trichloroethanes
Aqueous solution.If the usage amount of the alkaline aqueous solution is less than 1.0 molar ratios, there are the conversion ratio of 1,1,2- trichloroethanes drops
Low problem, and if it is greater than 1.5 molar ratios, then there are problems that generating a large amount of by-products.
In addition, in the present invention, at the end of dehydrochlorination reaction, after reactor recycling vinylidene chloride, by mentioning
Sweetening process can obtain final products.
There is no any restrictions to the refining technique of the vinylidene chloride, can be mentioned according to method well known in the art
Refining.
This method according to the present invention, can be easy to get yield be 90% or more and purity be 99% or more inclined two
Vinyl chloride.
In addition, preparing the process of vinylidene chloride in the present invention, such as can be carried out according to the technique of Fig. 2.
As shown in Fig. 2, preparing two continuous stirred tank reactor 10 with impeller in the present invention, they are connected
Come.In addition, rectifier 20 can connect on the reactor 10.
Specifically, the present invention supplies 1,1,2- trichloroethanes and alkaline aqueous solution to the reactor 10, and carries out dechlorination
Change hydrogen reaction.As described above, dehydrochlorination reaction reacts (Liquid-Liquid biphasic as liquid-liquid diphase
Reaction), it is based on interface reaction kinetics/interfacial area (interfacial reaction kinetics/
Interfacial area) generate vinylidene chloride (VDC) in gaseous form.Then, vinylidene chloride gas warp generated
After crossing upper device (rectifier) and liquefaction, it can save.
In addition, though appended drawing reference is not specifically illustrated in attached drawing, but the one stage impeller for including in the reactor is
Oblique paddle.
Referring to embodiment according to the present invention, the present invention will be described in more detail.But following embodiments are this hair
Bright example, interest field of the invention are not limited to following embodiments.
[comparative example 1]
By tri- chloroethene of alkaline aqueous solution (300mL) and 1,1,2- of the NaCl of the NaOH comprising 10 weight % and 18 weight %
Alkane (100g) is added in continuous stirred tank reactor (0.5L), and applies 339W/m3Mixing power after carry out dehydrochlorination it is anti-
It answers 30 minutes, to prepare vinylidene chloride.
[comparative example 2 to 5]
Following phase transfers that the alkaline aqueous solution for being equivalent to 3000ppm is added under the reaction condition of the comparative example 1 are urged
Agent (phase transition catalyst, hereinafter referred to as PTC).In addition to this, pass through method identical with comparative example 1
It is prepared for vinylidene chloride.
* comparative example 2:BTBAC, benzyl tributyl ammonium chloride (Benzyltributyl ammonium chloride)
* comparative example 3:BTMAC, benzyltrimethylammonium chloride (Benzyltrimethyl ammonium chloride)
* comparative example 4:BTEAC, benzyltriethylammoinium chloride (Benzyltriethyl ammonium chloride)
* comparative example 5:MTOAC, methyltri-n-octylphosphonium chloride ammonium (Methyltri-n-octyl ammonium
chloride)
[embodiment 1]
By tri- chloroethene of alkaline aqueous solution (300mL) and 1,1,2- of the NaCl of the NaOH comprising 10 weight % and 18 weight %
Alkane (100g) be added with radial pattern La Shidun turbine (rushton turbine, radial type) to continuously stir autoclave anti-
It answers in device (0.5L), and applies 1398W/m3Mixing power after carry out dehydrochlorination reaction 30 minutes, to prepare vinylidene chloride.
At this point, the service condition of the continuous stirred tank reactor is the temperature for keeping 80 DEG C under the pressure of 1barg.
[experimental example 1]
It is compared based on PTC type and the reaction speed of mixing power
After the dehydrochlorination reaction speed for measuring the comparative example 1 to 5 and embodiment 1, its result is compared into (figure
3)。
From figure 3 it follows that comparative example 1, since mixing power is low, reactivity is low.In addition, comparative example 2 to 5 is in low mixing power
Under, only addition PTC, reaction speed just increase.
In contrast, mixing power is increased to 1398W/m by the embodiment of the present invention 13, thus even if being added without PTC, reaction
Speed also increases.
[embodiment 2]
In addition to by mixing power from 1398W/m3Increase to 2674W/m3Except, it is taken off by method same as Example 1
Hcl reaction, to prepare vinylidene chloride.
[experimental example 2]
The reaction speed of difference based on mixing power compares
For Examples 1 to 2 and comparative example 1, the reaction speed based on mixing power is compared, the results are shown in Fig. 4
In.
From Fig. 4 it has been confirmed that such as embodiment 1 to 2, mixing power more increases, and reaction speed is faster than comparative example 1.
[embodiment 3 to 8]
Confirmation has been carried out in continuous stirred tank reactor according to impeller-type based on reaction pattern and incorporation time
Conversion ratio experiment.
* reaction condition: product deposition condition is the alkalinity using the NaCl of the NaOH comprising 10 weight % and 18 weight %
Aqueous solution (6L, flow per minute are 100ml) and 1,1,2- trichloroethanes (1.5L, flow per minute are 25ml) is 1barg's
Continuous stirred tank reactor is allowed to run at a temperature of pressure and 80 DEG C.
Oblique paddle (Pi), flat paddle formula (Pa)
[table 1]
[table 2]
| Impeller condition | Conversion ratio (OH-) | Incorporation time (s) | |
| Embodiment 3 | Pi/Pi | 87.3% | 6.1 |
| Embodiment 4 | Pa/Pi | 83.1% | 30.0 |
| Embodiment 5 | Pi/Pa | 85.4% | 7.2 |
| Embodiment 6 | Pa/Pa | 85.1% | 6.6 |
| Embodiment 7 | Pi | 87.2% | 5.6 |
| Embodiment 8 | Pa | 83.0% | 7.2 |
In table 1, OH- conversion ratio indicates the average (MSD maximum standard deviation: 5%) of 20~60 minutes conversion ratio values.In addition,
Incorporation time indicates in reactor according to the concentration standard deviation of any three points of height to be 1e-5At the time of following.
From the point of view of the result of upper table 1, conversion ratio is excellent on the whole for embodiment 3 to 8.In addition, the good sequence of conversion ratio is
Pi/Pi ≒ Pi (embodiment 3,7) > Pi/Pa ≒ Pa/Pa (embodiment 5,6) > Pa/Pi ≒ Pa (embodiment 4,8).From the above
It is found that reaction conversion rate is high when tiltedly blade impeller is located at upper end in the level-one or second level of reactor.In addition, implementation of the invention
Vinylidene chloride, is all successfully moved to the top of reactor by channel of the example due to that can prevent continuous stirred tank reactor,
To be easy recycling through a series of processes by rectifier.
Claims (5)
1. a kind of preparation method of vinylidene chloride, it includes:
1,1,2- trichloroethanes and alkaline aqueous solution addition had into the step of continuous stirred tank reactor of impeller；And
500 to 3000W/m3Mixing power under the step of carrying out dehydrochlorination reaction 1 minute to 60 minutes.
2. the preparation method of vinylidene chloride according to claim 1, wherein
In the reactor, impeller includes that one or more levels is selected from radial pattern La Shidun turbine, flat paddle, oblique paddle, propeller, hydrofoil
And at least one of method Wudu drawing agitating device.
3. the preparation method of vinylidene chloride according to claim 1, wherein
The alkaline aqueous solution is the alkaline aqueous solution of the NaCl of the weight of NaOH and 0 to 25 % comprising 2 to 15 weight %.
4. the preparation method of vinylidene chloride according to claim 1, wherein
Relative to 1.0 moles of 1,1,2- trichloroethanes, the alkaline aqueous solution is added according to 1.0 to 1.5 molar ratios.
5. the preparation method of vinylidene chloride according to claim 1, wherein
The service condition of the continuous stirred tank reactor is the temperature that 70 to 110 DEG C are kept at 0barg to 10barg pressure
Degree.
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| KR10-2016-0106229 | 2016-08-22 | ||
| PCT/KR2017/008977 WO2018038460A1 (en) | 2016-08-22 | 2017-08-17 | Method for producing vinylidene chloride |
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| CN114555218A (en) * | 2019-10-08 | 2022-05-27 | 韩华思路信株式会社 | Continuous stirred tank reactor for aldol condensation reaction |
| WO2025053431A1 (en) * | 2023-09-05 | 2025-03-13 | 한화솔루션 주식회사 | Impeller reactor |
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| CN112774591B (en) * | 2020-12-25 | 2022-09-23 | 北京化工大学 | A kind of continuous preparation system and method of vinylidene chloride |
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| KR20180021646A (en) | 2018-03-05 |
| CN109563013B (en) | 2021-11-02 |
| WO2018038460A1 (en) | 2018-03-01 |
| KR102006819B1 (en) | 2019-08-02 |
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