CN103183701A - Chlorosilane-containing ethylene preparation method - Google Patents
Chlorosilane-containing ethylene preparation method Download PDFInfo
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- CN103183701A CN103183701A CN2011104564692A CN201110456469A CN103183701A CN 103183701 A CN103183701 A CN 103183701A CN 2011104564692 A CN2011104564692 A CN 2011104564692A CN 201110456469 A CN201110456469 A CN 201110456469A CN 103183701 A CN103183701 A CN 103183701A
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Abstract
The invention discloses a chlorosilane-containing ethylene preparation method, which comprises the following steps: hydrogen-containing chlorosilane and acetylene are reacted on the surface of a filling material in a first reaction tower under catalyst effect to obtain a head product containing ethylene and chlorosilane, the head product and acetylene are placed in a second reaction tower filled with the filling material, and rectificated after reacting to obtain the chlorosilane-containing ethylene, wherein, the mass content of chlorosilane-containing ethylene in the first reaction tower and the second reaction tower are 1-15% and 5-60%. According to the invention, the mass content of chlorosilane-containing ethylene in the first reaction tower and the second reaction tower are controlled, the generation rate of twice addition reactions of hydrogen-containing chlorosilane and chlorosilane-containing ethylene in a mixture can be effectively reduced, accordingly, the products has high selectivity, and twice addition by-product is little. The experiment result shows that the selectivity of the chlorosilane-containing ethylene is greater than 98%, and the amount of twice addition product is less than 2%.
Description
Technical field
The present invention relates to the vinyl chlorine-containing silane technical field, more particularly, relate to a kind of preparation method of vinyl chlorine-containing silane.
Background technology
Vinyl chlorine-containing silane is the important monomer of organosilicon industry, mainly utilizes acetylene both at home and abroad and contains silicon hydride chlorid by catalysis addition technology synthesizing vinyl group containing chlorosilane.This method is more difficult to get an adduct of highly selective, the main reason that has following two aspects: on the one hand, acetylene and the addition reaction that contains silicon hydride chlorid mainly are subjected to the influence of catalyst concn, namely produce latter stage at each, the catalyst concn step-down can cause the by product of secondary adduct to increase in the reaction system; On the other hand, in each latter stage production cycle, reaction purpose production concentration increases the by product that causes the secondary adduct and increases.Therefore, the generation that how suppresses the secondary adduct by the control reaction conditions is the problem that numerous enterprises is concerned about and is endeavoured to study.
The preparation method of vinyl chlorine-containing silane has obtained report comparatively widely at present, for example, publication number is the synthetic method that the Chinese patent literature of CN 1228435A has been reported a kind of vinyl trichloro silane, in system, add the reactive behavior that polyvinyl siloxane keeps catalyzer, with the acetylene Bubbling method with contain the silicon hydride chlorid reactant and mix, control contains the content of silicon hydride chlorid and product vinyl trichloro silane and the consumption of the water in the reaction system, alcohols and aminated compounds, makes good catalyst activity and stable.But this method exists acetylene to reclaim difficult shortcoming, and the unit consumption of product height, and environmental benefit is poor.The patent No. is USP 4898961,1990 american documentation literature discloses a kind of method for preparing vinyl silanes, by the alkynes of gaseous state and silane containing hydrogen are mixed, flow, contact reacts in the liquid medium thin and that contain homogeneous catalyst, obtain vinyl silanes.But, this method severe reaction conditions, the equipment requirements height, a transformation efficiency is not high simultaneously.
In the prior art, application number is the synthetic method that the Chinese patent literature of 200710168341.X has been reported a kind of vinyl chlorine-containing silane, enter the mixing raw material that contains silicon hydride chlorid after acetylene and the vaporization in the reaction tower continuously, the quality percentage composition of vinyl chlorosilane is 45～55% in the hierarchy of control, with the chlorohexane mixture as solvent, the reaction pressure of control 0.001～0.03MPa and 50～90 ℃ temperature of reaction.But, carry out owing to this is reflected in the closed unit, thereby along with continuously feeding, the concentration of its still inner catalyst is constantly diluted, influence reaction preference, in addition, because it adopts the mixing raw material porous feed, cause itself and still bottom product to continue addition reaction, by product increases, and selectivity reduces.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of vinyl chlorine-containing silane, the selectivity of product height of this method, and secondary addition by product is few.
In order to solve above technical problem, the invention provides a kind of preparation method of vinyl chlorine-containing silane, may further comprise the steps:
The solvent that will contain silicon hydride chlorid, acetylene respectively and contain catalyzer is continuously in the input in first reaction tower of filling material, describedly contain silicon hydride chlorid and acetylene reacts in described filling surface under the effect of catalyzer, obtain containing the head product of vinyl chlorine-containing silane, the quality percentage composition of vinyl chlorine-containing silane is 1～15% in the described first reaction tower tower reactor;
In second reaction tower with filling material in described head product and the acetylene input, reaction back rectifying obtains vinyl chlorine-containing silane, and the quality percentage composition of the vinyl chlorine-containing silane of the second reaction tower tower reactor is 5～60%.
Preferably, the described mol ratio that contains silicon hydride chlorid and acetylene that enters the reaction of first reaction tower is 1: (0.9～1.1).
Preferably, described catalyzer is platinum complex; Described solvent is monochloroethane, toluene, dimethylbenzene, chlorobenzene or dichlorobenzene.
Preferably, the temperature of reaction of described first reaction tower is 70～92 ℃, and reaction pressure is 0.001～0.05Mpa.
Preferably, the temperature of reaction of described second reaction tower is 70～92 ℃, and reaction pressure is 0.001～0.05Mpa.
Preferably, also comprise:
Get first spray equipment that the described head product of part is delivered to the first reaction tower cat head, described part head product is in the filling surface reaction of described first reaction tower.
Preferably, the specific liquid rate of described first spray equipment is 300～1000m
3/ m
2
Preferably, also comprise: the reaction product of getting described second reaction tower of part is delivered to second spray equipment of the second reaction tower cat head, and the reaction product of described part second reaction tower is reacted at the filling surface of described second reaction tower.
Preferably, the specific liquid rate of described second spray equipment is 300～1000m
3/ m
2
Preferably, described first reaction tower and described second reaction tower comprise 5～20 Jie Tajie respectively, and described tower joint highly is 500～3000mm, and described tower diameter is 500～2500mm.
Preferably, acetylene and contain respectively charging of silicon hydride chlorid, described first reaction tower and the second reaction tower sidewall arrange a plurality of acetylene opening for feeds respectively, in the described first reaction tower cat head, the tower or hydrogeneous chlorosilane feed mouth is set at the bottom of the tower.
Preferably, the described silicon hydride chlorid that contains is in the cat head charging of described first reaction tower.
The invention provides a kind of preparation method of vinyl chlorine-containing silane, may further comprise the steps: will contain silicon hydride chlorid and acetylene and under the effect of catalyzer, react in the filling surface of described first reaction tower, obtain containing the head product of vinyl chlorine-containing silane, in second reaction tower with filling material in described head product and the acetylene input, reaction back rectifying, obtain vinyl chlorine-containing silane, the quality percentage composition of vinyl chlorine-containing silane is respectively 1～15% and 5～60% in described first reaction tower and second reaction tower.Because when containing silicon hydride chlorid and acetylene reaction generation vinyl chlorine-containing silane, the vinyl chlorine-containing silane that generates easily and raw material contain the addition reaction of silicon hydride chlorid generation secondary, cause selectivity of product to reduce, by product increases, therefore, the present invention is by the quality percentage composition of vinyl chlorine-containing silane in control first reaction tower and second reaction tower, effectively reduce the occurrence probability that contains the secondary addition reaction of silicon hydride chlorid and vinyl chlorine-containing silane in the mixture, therefore, the selectivity of product height of this method, secondary addition by product is few.
Description of drawings
Fig. 1 is the preparation flow figure of vinyl chlorine-containing silane disclosed by the invention.
Embodiment
Below the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention discloses a kind of preparation method of vinyl chlorine-containing silane, as shown in Figure 1, the preparation flow figure for vinyl chlorine-containing silane of the present invention may further comprise the steps:
The solvent that will contain silicon hydride chlorid, acetylene respectively and contain catalyzer is continuously in the input in first reaction tower of filling material, describedly contain silicon hydride chlorid and acetylene reacts in described filling surface under the effect of catalyzer, obtain containing the head product of vinyl chlorine-containing silane, the quality percentage composition of vinyl chlorine-containing silane is 1～15% in described first reaction tower;
In second reaction tower with filling material in the described head product input, reaction back rectifying obtains vinyl chlorine-containing silane, and the quality percentage composition of the vinyl chlorine-containing silane at the bottom of the second reaction tower reactor is 5～60%.
The present invention with contain silicon hydride chlorid, acetylene is raw material, describedly contains silicon hydride chlorid and acetylene reacts under the effect of catalyzer, obtains vinyl chlorine-containing silane, the main reaction reaction formula is as follows:
CH≡CH+HSiCl
3→CH
2＝CHSiCl
3
But raw material contains silicon hydride chlorid and the secondary addition reaction takes place the reaction product vinyl chlorine-containing silane easily, causes selectivity of product to reduce, and by product increases, and the side reaction reaction formula is as follows:
CH
2＝CHSiCl
3+HSiCl
3→Cl
3SiCH
2CH
2SiCl
3
According to the present invention, the described silicon hydride chlorid that contains is liquid phase, described liquid phase contains silicon hydride chlorid and preferably enters continuously first reaction tower at the bottom of still top, middle part or the still of first reaction tower, the acetylene raw material is imported in first reaction tower and second reaction tower continuously simultaneously, and the described solvent that contains catalyzer is preferably gone in described first reaction tower through the still jacking of first reaction tower.After respectively raw material being imported in first reaction tower, describedly contain silicon hydride chlorid and acetylene reacts in described filling surface under the effect of catalyzer, obtain containing the head product of vinyl chlorine-containing silane, described head product comprises reaction product vinyl chlorine-containing silane, the intact solvent that contains silicon hydride chlorid, acetylene raw material and contain catalyzer of unreacted.In the step of preparation head product, the mol ratio that contains silicon hydride chlorid and acetylene in described first reaction tower is preferably 1: (0.9～1.1), more preferably 1: (0.9～1.1); Described catalyzer is preferably platinum complex; Described solvent is preferably monochloroethane, toluene, dimethylbenzene, chlorobenzene or dichlorobenzene; The described temperature of stating first reaction tower is preferably 70～92 ℃, and more preferably 75～90 ℃, more preferably 80～85 ℃; The pressure of described first reaction tower is preferably 0.001～0.05Mpa, more preferably 0.005～0.04Mpa, more preferably 0.01～0.03Mpa.
After obtaining head product, to react in second reaction tower with filling material in described head product and the acetylene input, the temperature of described second reaction tower is preferably 70～92 ℃, and more preferably 75～90 ℃, more preferably 80～85 ℃; The pressure of described second reaction tower is preferably 0.001～0.05Mpa, more preferably 0.005～0.04Mpa, more preferably 0.01～0.03Mpa.After the reaction, with reacted material input solvent recovery tower, obtain vinyl by rectifying and contain silicon hydride chlorid in described second reaction tower, the solvent that contains catalyzer reenters first reaction tower continuation catalyzed reaction to carry out.
In order to guarantee that the catalyst concentration in first reaction tower and second reaction tower keeps stable, be not subjected to the influence of reaction time, the present invention preferably adopts following control device, as shown in Figure 1: the part head product that described first reaction tower obtains preferably enters the still top of second reaction tower by recycle pump, another part head product is delivered to first spray equipment on the first reaction tower reactor top, and described part head product is in the filling surface reaction of described first reaction tower.In like manner, the partial reaction product that described second reaction tower obtains preferably partly enters next step solvent recuperation operation by recycle pump, the reaction product of another part second reaction tower is delivered to second spray equipment on the second reaction tower reactor top, and the reaction product of described part second reaction tower is reacted at the filling surface of described second reaction tower.The specific liquid rate of described first spray equipment is preferably 300～1000m
3/ m
2, 500～1000m more preferably
3/ m
2, 600～900m more preferably
3/ m
2The specific liquid rate of described second spray equipment is preferably 300～1000m
3/ m
2, 500～1000m more preferably
3/ m
2, 600～900m more preferably
3/ m
2Above-mentioned preferred control device has guaranteed the catalyst concn that addition reaction needs in the reaction tower, guarantees that addition reaction speed improves the selectivity of principal product vinyl chlorine-containing silane simultaneously.
Owing to contain silicon hydride chlorid and the secondary addition reaction takes place vinyl chlorine-containing silane easily, cause selectivity of product to reduce, by product increases, when in reaction tower, reacting simultaneously, but still have to contain silicon hydride chlorid on a small quantity and be dissolved in the solvent system, increased the reaction chance that at the bottom of still, contains silicon hydride chlorid and vinyl chlorine-containing silane.Therefore, in order to reduce by product, avoid the generation of secondary addition reaction, the present invention is by the quality percentage composition of vinyl chlorine-containing silane in control first reaction tower and second reaction tower, effectively reduce the occurrence probability that contains the secondary addition reaction of silicon hydride chlorid and vinyl chlorine-containing silane in the mixture, thereby the selectivity of product height of this method, secondary addition by product is few.The quality percentage composition of vinyl chlorine-containing silane is preferably 2～15% in described first reaction tower, and more preferably 5～15%; The quality percentage composition of the vinyl chlorine-containing silane of described second reaction at the bottom of the tower reactor is preferably 10～50%, and more preferably 15～25%.
The present invention adopts reaction unit to be made up of the two-stage reaction tower, namely comprises first reaction tower and second reaction tower, and described first reaction tower and described second reaction tower preferably comprise 5～20 Jie Tajie respectively, more preferably comprise 8～15 Jie Tajie respectively; Described every Jie Tajie highly is preferably 500～3000mm, more preferably 1000～2800mm, more preferably 1200～2500mm.Described tower diameter is 500～2500mm, more preferably 600～2200mm, more preferably 800～1500mm.Guarantee that reaction can a thorough selectivity height.Described first reaction tower and the second reaction tower sidewall preferably arrange a plurality of acetylene opening for feeds respectively, can selecting wherein, a plurality of tower joint sidewalls arrange the acetylene opening for feed, also can the acetylene opening for feed all be set each tower joint, be provided with in two-stage reaction column overhead, tower or at the bottom of the tower simultaneously and contain silicon hydride chlorid and acetylene opening for feed, the described silicon hydride chlorid that contains is equipped with filler and redistributor preferably in the first reaction tower cat head charging in the reaction tower; The filler that the present invention adopts is preferably ceramic corrugated plate packing, ceramic raschig rings or poly-saddle ring filler.
In the prior art, adopting parallel feeding can make acetylene and two kinds of raw materials of silane containing hydrogen pass through good gaseous state mixes, other feeding manner has the selectivity of the highest transformation efficiency and an addition relatively, but during this mode charging, gaseous phase partial pressure reduces in tower, contains silicon hydride chlorid in the parallel feeding and directly enters easily at the bottom of the tower, causes reactive behavior to interrupt inadequately because contain silicon hydride chlorid concentration in the reaction mixture material at the bottom of the tower, the proportioning imbalance causes the reaction by-product to increase.Unlike the prior art be, the present invention has taked acetylene and has contained the silicon hydride chlorid mode of charging respectively, contain silicon hydride chlorid simultaneously and pay the utmost attention in the cat head charging, can effectively control since addition reaction when carrying out in the tower gaseous phase partial pressure reduce the problem of the raw material charging shakiness of bringing.Take preferred hydrogeneous chlorosilane feed mouth of the while of charging respectively to be arranged on the mode of cat head, be conducive to contain that silicon hydride chlorid is saturated is dissolved in the solvent, strengthen the mixed effect of raw material in solvent, by the time enough reaction is arranged, can fully react on tower top simultaneously, minimizing in tower reactor with the touch opportunity of vinyl chlorine-containing silane, avoid the generation of secondary addition reaction.
In sum, the present invention adopts the method for continuous synthesis of vinyl chlorosilane, compared with prior art, avoided because of the fluctuation of catalyst concn in the latter stage production cycle reaction system to react influence, reduce the unreacted touch opportunity that contains silicon hydride chlorid and vinyl chlorine-containing silane, effectively avoided the generation of secondary addition reaction, improve one time synthesis of selective, not only really realize continuous industry production, significantly improved reaction yield, and realized the recycling of catalyzer.The preparation method of vinyl chlorine-containing silane provided by the invention has the production efficiency height, process stabilizing, and equipment cost is low, but characteristics such as scale of mass production.Experimental result shows, preparation method's vinyl chlorine-containing silane selectivity provided by the invention greater than 98%, the secondary adduct is less than 2%.
In order to further specify technical scheme of the present invention, be described below in conjunction with the preferred embodiment of the invention of embodiment, but should be appreciated that these describe just to further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
Embodiment 1 continous way double tower lowpressure stream movable bed is produced the preparation method of vinyl trichloro silane
First reaction tower and second reaction tower that present embodiment adopts comprise 10 Jie Tajie respectively, tower joint diameter is 1200mm, the tower joint highly is 2000mm, each tower joint of reaction tower (or a plurality of tower joint) sidewall arranges the acetylene opening for feed, simultaneously be provided with the trichlorosilane opening for feed in the two-stage reaction column overhead, filler and redistributor are housed in the reaction tower; There is material recycle feed mouth on the second reaction tower reactor top.
Step (1) drops into platinum complex in the monochloroethane, and the monochloroethane that will contain platinum complex with pump is delivered to the first reaction tower top at the bottom of the still of first reaction tower, make it at the reaction tower internal recycle;
Step (2) is gone into trichlorosilane in the tower by the first reaction tower jacking, acetylene is imported in the first reaction tower reactor continuously by the first reaction tower side feed opening, make under the katalysis of trichlorosilane, the acetylene platinum complex in monochloroethane and react in filling surface, keep the continuously feeding reaction, the mol ratio of described acetylene and trichlorosilane is 1: 1, the control of vinyl trichloro silane quality percentage composition is 15% in first reaction tower, and the acetylene flow is 20m
3/ h, described filler are ceramic corrugated plate packing, control the first reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 85 ℃, the first reaction tower specific liquid rate 800m
3/ m
2, simultaneously reaction mass at the bottom of the first reaction tower tower reactor is pressed certain flow volume delivery to the second reaction tower top;
Step (3) is continuously imported second reaction tower in by the second reaction tower side feed opening acetylene, reaction mass continues reaction at filling surface at the bottom of making described acetylene and first reaction tower, the control of vinyl trichloro silane content is 20% in the second reaction tower system, and the acetylene flow is 20m
3/ h controls the second reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 85 ℃;
Step (4) with the second reaction tower reactor at the bottom of reaction mass keep specific liquid rate 800m at the bottom of the second reaction tower reactor by certain flow volume delivery to cat head
3/ m
2, be delivered to simultaneously the solvent recuperation cat head according to a certain percentage and carry and distillate vinyl trichloro silane in the crude reaction material;
(5) solvent monochloroethane and platinum complex are reclaimed, crude reaction mass transport to the first reaction tower reactor is pushed up circulating reaction again at the bottom of the reaction tower reactor.
Experimental result shows that the vinyl trichloro silane selectivity 99% of present embodiment, secondary adduct 0.5%, catalyst levels are less than the 10g/ ton.
Embodiment 2 continous way double tower lowpressure stream movable beds are produced the synthetic method of methyl ethylene dichlorosilane
First reaction tower and second reaction tower that present embodiment adopts comprise 10 Jie Tajie respectively, tower joint diameter is 800mm, the tower joint highly is 1500mm, each tower joint of reaction tower (or a plurality of tower joint) sidewall arranges the acetylene opening for feed, simultaneously be provided with the dimethyl dichlorosilane (DMCS) opening for feed in the two-stage reaction column overhead, filler and redistributor are housed in the reaction tower; There is material recycle feed mouth on the second reaction tower reactor top.
Step (1) drops into platinum complex in the monochloroethane, and the monochloroethane that will contain platinum complex with pump is delivered to the first reaction tower top at the bottom of the still of first reaction tower, make it at the reaction tower internal recycle;
Step (2) is gone into dimethyl dichlorosilane (DMCS) in the tower by the first reaction tower jacking, acetylene is imported in the first reaction tower reactor continuously by the first reaction tower side feed opening, make under the katalysis of dimethyl dichlorosilane (DMCS), the acetylene platinum complex in monochloroethane and react in filling surface, keep the continuously feeding reaction, the mol ratio of described acetylene and dimethyl dichlorosilane (DMCS) is 1: 1, the control of methyl ethylene dichlorosilane quality percentage composition is 12% in first reaction tower, and the acetylene flow is 20m
3/ h, described filler are ceramic corrugated plate packing, control the first reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 80 ℃, the first reaction tower specific liquid rate 600m
3/ m
2, simultaneously reaction mass at the bottom of the first reaction tower tower reactor is pressed certain flow volume delivery to the second reaction tower top;
Step (3) is continuously imported second reaction tower in by the second reaction tower side feed opening acetylene, reaction mass continues reaction at filling surface at the bottom of making described acetylene and first reaction tower, the control of methyl ethylene dichlorosilane content is 20% in the second reaction tower system, and the acetylene flow is 20m
3/ h controls the second reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 80 ℃;
Step (4) with the second reaction tower reactor at the bottom of reaction mass keep specific liquid rate 600m at the bottom of the second reaction tower reactor by certain flow volume delivery to cat head
3/ m
2, be delivered to simultaneously the solvent recuperation cat head according to a certain percentage and carry and distillate methyl ethylene dichlorosilane in the crude reaction material;
(5) solvent monochloroethane and platinum complex are reclaimed, crude reaction mass transport to the first reaction tower reactor is pushed up circulating reaction again at the bottom of the reaction tower reactor.
Experimental result shows, the methyl ethylene dichlorosilane selectivity of present embodiment greater than 98%, the secondary adduct less than 2%, catalyst levels is less than the 10g/ ton.
Embodiment 3 continous way double tower lowpressure stream movable beds are produced the synthetic method of methyl ethylene dichlorosilane
First reaction tower and second reaction tower that present embodiment adopts comprise 10 Jie Tajie respectively, tower joint diameter is 800mm, the tower joint highly is 1500mm, each tower joint of reaction tower (or a plurality of tower joint) sidewall arranges the acetylene opening for feed, simultaneously be provided with the dimethyl dichlorosilane (DMCS) opening for feed in the two-stage reaction column overhead, filler and redistributor are housed in the reaction tower; There is material recycle feed mouth on the second reaction tower reactor top.
Step (1) drops into platinum complex in the monochloroethane, and the monochloroethane that will contain platinum complex with pump is delivered to the first reaction tower top at the bottom of the still of first reaction tower, make it at the reaction tower internal recycle;
Step (2) is gone into dimethyl dichlorosilane (DMCS) in the tower by the first reaction tower jacking, acetylene is imported in the first reaction tower reactor continuously by the first reaction tower side feed opening, make under the katalysis of dimethyl dichlorosilane (DMCS), the acetylene platinum complex in monochloroethane and react in filling surface, keep the continuously feeding reaction, the mol ratio of described acetylene and dimethyl dichlorosilane (DMCS) is 1: 1, the control of methyl ethylene dichlorosilane quality percentage composition is 10% in first reaction tower, and the acetylene flow is 20m
3/ h, described filler are ceramic corrugated plate packing, control the first reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 80 ℃, the first reaction tower specific liquid rate 600m
3/ m
2, simultaneously reaction mass at the bottom of the first reaction tower tower reactor is pressed certain flow volume delivery to the second reaction tower top;
Step (3) is continuously imported second reaction tower in by the second reaction tower side feed opening acetylene, reaction mass continues reaction at filling surface at the bottom of making described acetylene and first reaction tower, the control of methyl ethylene dichlorosilane content is 22% in the second reaction tower system, and the acetylene flow is 20m
3/ h controls the second reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 80 ℃;
Step (4) with the second reaction tower reactor at the bottom of reaction mass keep specific liquid rate 600m at the bottom of the second reaction tower reactor by certain flow volume delivery to cat head
3/ m
2, be delivered to simultaneously the solvent recuperation cat head according to a certain percentage and carry and distillate methyl ethylene dichlorosilane in the crude reaction material;
(5) solvent monochloroethane and platinum complex are reclaimed, crude reaction mass transport to the first reaction tower reactor is pushed up circulating reaction again at the bottom of the reaction tower reactor.
Experimental result shows, the methyl ethylene dichlorosilane selectivity of present embodiment greater than 98%, the secondary adduct less than 2%, catalyst levels is less than the 10g/ ton.
Embodiment 4 continous way double tower lowpressure stream movable beds are produced the synthetic method of methyl ethylene dichlorosilane
First reaction tower and second reaction tower that present embodiment adopts comprise 10 Jie Tajie respectively, tower joint diameter is 800mm, the tower joint highly is 1500mm, each tower joint of reaction tower (or a plurality of tower joint) sidewall arranges the acetylene opening for feed, simultaneously be provided with the dimethyl dichlorosilane (DMCS) opening for feed in the two-stage reaction column overhead, filler and redistributor are housed in the reaction tower; There is material recycle feed mouth on the second reaction tower reactor top.
Step (1) drops into platinum complex in the monochloroethane, and the monochloroethane that will contain platinum complex with pump is delivered to the first reaction tower top at the bottom of the still of first reaction tower, make it at the reaction tower internal recycle;
Step (2) is gone into dimethyl dichlorosilane (DMCS) in the tower by the first reaction tower jacking, acetylene is imported in the first reaction tower reactor continuously by the first reaction tower side feed opening, make under the katalysis of dimethyl dichlorosilane (DMCS), the acetylene platinum complex in monochloroethane and react in filling surface, keep the continuously feeding reaction, the mol ratio of described acetylene and dimethyl dichlorosilane (DMCS) is 1: 1, the control of methyl ethylene dichlorosilane quality percentage composition is 8% in first reaction tower, and the acetylene flow is 20m
3/ h, described filler are ceramic corrugated plate packing, control the first reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 80 ℃, the first reaction tower specific liquid rate 600m
3/ m
2, simultaneously reaction mass at the bottom of the first reaction tower tower reactor is pressed certain flow volume delivery to the second reaction tower top;
Step (3) is continuously imported second reaction tower in by the second reaction tower side feed opening acetylene, reaction mass continues reaction at filling surface at the bottom of making described acetylene and first reaction tower, the control of methyl ethylene dichlorosilane content is 18% in the second reaction tower system, and the acetylene flow is 20m
3/ h controls the second reaction tower system pressure automatically at 0.01MPa pressure, and temperature is controlled at 80 ℃;
Step (4) with the second reaction tower reactor at the bottom of reaction mass keep specific liquid rate 600m at the bottom of the second reaction tower reactor by certain flow volume delivery to cat head
3/ m
2, be delivered to simultaneously the solvent recuperation cat head according to a certain percentage and carry and distillate methyl ethylene dichlorosilane in the crude reaction material;
(5) solvent monochloroethane and platinum complex are reclaimed, crude reaction mass transport to the first reaction tower reactor is pushed up circulating reaction again at the bottom of the reaction tower reactor.
Experimental result shows, the methyl ethylene dichlorosilane selectivity of present embodiment greater than 98%, the secondary adduct less than 2%, catalyst levels is less than the 10g/ ton.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments herein.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the wideest scope consistent with principle disclosed herein and features of novelty.
Claims (12)
1. the preparation method of a vinyl chlorine-containing silane may further comprise the steps:
The solvent that will contain silicon hydride chlorid, acetylene respectively and contain catalyzer is continuously in the input in first reaction tower of filling material, describedly contain silicon hydride chlorid and acetylene reacts in described filling surface under the effect of catalyzer, obtain containing the head product of vinyl chlorine-containing silane, the quality percentage composition of vinyl chlorine-containing silane is 1～15% in the described first reaction tower tower reactor;
In second reaction tower with filling material in described head product and the acetylene input, reaction back rectifying obtains vinyl chlorine-containing silane, and the quality percentage composition of the vinyl chlorine-containing silane of the second reaction tower tower reactor is 5～60%.
2. preparation method according to claim 1 is characterized in that, the described mol ratio that contains silicon hydride chlorid and acetylene that enters the reaction of first reaction tower is 1: (0.9～1.1).
3. preparation method according to claim 1 is characterized in that, described catalyzer is platinum complex; Described solvent is monochloroethane, toluene, dimethylbenzene, chlorobenzene or dichlorobenzene.
4. preparation method according to claim 1 is characterized in that, the temperature of reaction of described first reaction tower is 70～92 ℃, and reaction pressure is 0.001～0.05Mpa.
5. preparation method according to claim 1 is characterized in that, the temperature of reaction of described second reaction tower is 70～92 ℃, and reaction pressure is 0.001～0.05Mpa.
6. preparation method according to claim 1 is characterized in that, also comprises:
Get first spray equipment that the described head product of part is delivered to the first reaction tower cat head, described part head product is in the filling surface reaction of described first reaction tower.
7. preparation method according to claim 6 is characterized in that, the specific liquid rate of described first spray equipment is 300～1000m
3/ m
2
8. preparation method according to claim 1, it is characterized in that, also comprise: the reaction product of getting described second reaction tower of part is delivered to second spray equipment of the second reaction tower cat head, and the reaction product of described part second reaction tower is reacted at the filling surface of described second reaction tower.
9. preparation method according to claim 8 is characterized in that, the specific liquid rate of described second spray equipment is 300～1000m
3/ m
2
10. preparation method according to claim 1 is characterized in that, described first reaction tower and described second reaction tower comprise 5～20 Jie Tajie respectively, and described tower joint highly is 500～3000mm, and described tower diameter is 500～2500mm.
11. preparation method according to claim 1, it is characterized in that, acetylene and contain respectively charging of silicon hydride chlorid, described first reaction tower and the second reaction tower sidewall arrange a plurality of acetylene opening for feeds respectively, in the described first reaction tower cat head, the tower or hydrogeneous chlorosilane feed mouth is set at the bottom of the tower.
12. preparation method according to claim 1 is characterized in that, the described silicon hydride chlorid that contains is in the cat head charging of described first reaction tower.
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