CN101759189B - Method for preparing trichlorosilane - Google Patents
Method for preparing trichlorosilane Download PDFInfo
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- CN101759189B CN101759189B CN2009101787992A CN200910178799A CN101759189B CN 101759189 B CN101759189 B CN 101759189B CN 2009101787992 A CN2009101787992 A CN 2009101787992A CN 200910178799 A CN200910178799 A CN 200910178799A CN 101759189 B CN101759189 B CN 101759189B
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Abstract
The invention relates to a method for preparing trichlorosilane. The method comprises the step that silicon tetrachloride and hydrogen react with optional hydrogen chloride and silicon powder by adopting at least one main catalyst selected from copper halide and nickel halide and at least one auxiliary catalyst selected from alkali metal compounds. Compared with the prior art, the method for preparing the trichlorosilane has the advantages of low preparing cost, simple and easy technique and high per-pass conversion rate of the silicon tetrachloride.
Description
Technical field
The present invention relates to a kind of method of manufacture of trichlorosilane, relate to the method that a kind of catalytic hydrogenation through silicon tetrachloride is made trichlorosilane especially.
Background technology
Polysilicon is the starting material of solar photovoltaic assembly, and along with the release of photovoltaic industry policy favourable, photovoltaic industry will start upsurge, and market also can increase for the demand of polysilicon is inevitable thereupon.
At present, in the world the polysilicon manufacturing technology use more than 70% be the improvement Siemens Method.It mainly is to get in the silicon wicking surface through trichlorosilane and hydrogen high temperature deposition in reduction furnace that the improvement Siemens Method is made polysilicon.Wherein the output polysilicon time, the silicon tetrachloride that by-product is a large amount of, the polysilicon of average every manufacturing 1t will consume 15～20t trichlorosilane, go back by-product 15～20t silicon tetrachloride simultaneously.Silicon tetrachloride very easily generates silicon-dioxide and hydrogenchloride with the water reaction, and directly discharging will have a strong impact on ecotope.Along with expanding production continuously of domestic and international polysilicon enterprise, a large amount of silicon tetrachloride problems of by-product become the bottleneck of polysilicon industry gradually.
Current, silicon tetrachloride mainly contains the processing approach of two kinds of less expensives: first, fourth silicon chlorides is made WHITE CARBON BLACK as raw material.Silicon tetrachloride pyrohydrolysis in oxyhydrogen flame can generate thermal silica (nano level white SiO 2 powder), and silicon tetrachloride per ton can generate the 0.35t WHITE CARBON BLACK, and the existing minority polysilicon enterprise of China intends and adopts this technology to solve the by-produced tetrachlorosilane problem.But because the expanding production in a large number of polysilicon, the by-product amount of silicon tetrachloride head and shoulders above the manufacturing capacity of white carbon black technique, and the market of WHITE CARBON BLACK is limited, makes WHITE CARBON BLACK and can not solve root problem so depend merely on.The second, carry out hydrogenation and be converted into the raw material trichlorosilane that Siemens Method is made polysilicon with virgin gas such as hydrogen.Utilize the hydrogenation of silicon tetrachloride as by-product to make trichlorosilane; The manufacturing cost that can save polysilicon widely on the one hand; The handling problem that has simultaneously solved the silicon tetrachloride by product has well also realized the closed loop manufacturing of polysilicon, has avoided by product to be difficult to handle the environmental pollution that brings.
Usually, the method for hydrogenation of silicon tetrachloride manufacturing trichlorosilane mainly contains hot hydride process and cold hydride process (chlorine hydride process).
According to said hot hydride process, silicon tetrachloride and hydrogen are reacted under 900-1200 ℃ temperature generate trichlorosilane and hydrogenchloride.This technology must be aided with gas separation unit with reaction product isolated and processing hydrogenchloride, so its investment is big, occupation of land is many.In addition, also there is following shortcoming in hot hydrogenation technology: temperature of reaction is high, technical process is complicated, the device operation easier is big; Well heater adopts carbon-carbon composite, can only introduce, and cost is high; Material purity is required height, can't solve the dichlorosilane of by-product in the polysilicon manufacturing processed; Transformation efficiency is low, energy consumption is high, average every manufacturing 1t trichlorosilane power consumption 3200～3500kwh.
According to said cold hydride process, make the reaction under 500 ℃ or higher temperature of silicon tetrachloride, hydrogenchloride, hydrogen and silica flour generate trichlorosilane.This technology has the following advantages: install single, investment is little, it is few to take up an area of; Low, the stable operation of temperature of reaction; Low to the material purity requirement, the dichlorosilane of by-product can generate trichlorosilane with silicon tetrachloride generation disproportionation reaction in the polysilicon manufacturing processed; Transformation efficiency is high, energy consumption is low, every manufacturing 1t trichlorosilane power consumption 850～1000kwh.
The open JP63025211 of Japanese patent application discloses the method that a kind of catalytic hydrogenation of utilizing silicon tetrachloride is made trichlorosilane.Wherein, make silicon tetrachloride and hydrogen, under the catalysis of nonporous silicon load platinum group metal composite catalyst, catalytic hydrogenations take place and generate high-purity trichlorosilane in 500～1100 ℃ by 0.5～40 mixed.But this technological temperature of reaction is higher, and transformation efficiency is lower, is generally 10～20%, and used noble metal catalyst costs an arm and a leg, and cost is higher.
The open CN1157259A of one Chinese patent application discloses the method that a kind of catalytic hydrogenation of utilizing silicon tetrachloride is made trichlorosilane.Wherein, silicon particle, silicon tetrachloride and hydrogen are reacted in the presence of the catalyzer that contains copper silicide that adds on fluidized-bed in 400～700 ℃.Though this method temperature of reaction is not high, transformation efficiency is still lower, and transformation efficiency is generally 9～22.5%.
The open CN1436725A of one Chinese patent application discloses the method that a kind of catalytic hydrogenation of utilizing silicon tetrachloride is made trichlorosilane.According to this method, the powder nickel catalyzator is mixed by a certain percentage equably, with silica flour then at H
2Under the atmosphere and being changed to continuously from 20 ℃ under 420 ℃ the temperature condition mixture that is obtained is carried out activation treatment.Then, make H
2And SiCl
4Mixed gas flow through the said mixture bed of material of activated processing, make SiCl thus
4Catalytic hydrogenation is a trichlorosilane.The temperature of reaction of this moment is 400～500 ℃, reaction pressure 1.2～1.5MPa.
The open CN101143723A of one Chinese patent application discloses the method that a kind of catalytic hydrogenation of utilizing silicon tetrachloride is made trichlorosilane.According to this method, with the metalluragical silicon reactor drum of packing into, feed silicon tetrachloride gas, hydrogen and the hydrogenchloride of vaporization, nickel catalyzator with (or) under the katalysis of palladium catalyst, hydrogenation of silicon tetrachloride is become trichlorosilane.Wherein, the mol ratio of hydrogen and silicon tetrachloride is 1～5: 1, and the mol ratio of hydrogenchloride and silicon tetrachloride is 1: 1～20, makes reactor drum remain on 400-600 ℃ temperature and the pressure of 1.0～3.0MPa.
Mainly there is following problem in the art methods of making trichlorosilane through the catalytic hydrogenation of silicon tetrachloride:
1. contain noble metal component in the employed catalyzer when making trichlorosilane, so the catalyzer cost is higher, causes the manufacturing cost of trichlorosilane higher thus;
2. when making trichlorosilane according to hot hydride process, because temperature of reaction is higher, so production operation difficulty and production cost are higher;
3. when making trichlorosilane, because this method is higher to the purity requirement of raw material, if, be difficult to directly utilize the sub product (such as silicon tetrachloride and hydrogenchloride etc.) of association in the production of polysilicon therefore without in advance processing according to hot hydride process; With
4. no matter be to make trichlorosilane according to hot hydride process or cold hydride process, all lower from silicon tetrachloride to the per pass conversion of trichlorosilane, generally be merely 17-25%, still there is very big room for promotion.
Therefore; The present present situation of prior art is; Still need a kind of method of manufacture of new trichlorosilane, it can overcome the aforementioned technical problem that exists in the prior art, and has characteristics such as low cost of manufacture, simple for process and silicon tetrachloride per pass conversion height.
Summary of the invention
The inventor through diligent discovering, comes the catalytic hydrogenation silicon tetrachloride through using a kind of specific catalyst system on the basis of existing technology, just can solve foregoing problems, and accomplish the present invention thus.
Particularly, the present invention relates to the content of following aspect:
1. the method for manufacture of a trichlorosilane; Said method comprise make silicon tetrachloride, hydrogen and optional hydrogenchloride and silica flour be selected from the halid at least a Primary Catalysts of copper halide and nickel and be selected from alkali metal cpd at least a promotor (catalyst combination) in the presence of react, to make the step of trichlorosilane.
2. according to aspect 1 described method, it is characterized in that said being reflected in the fluidized-bed reactor carried out.
3. according to the described method in aforementioned arbitrary aspect, it is characterized in that said Primary Catalysts is selected from cuprous chloride (I), cupric chloride (II), nickelous chloride or its combination.
4. according to the described method in aforementioned arbitrary aspect; It is characterized in that; Said promotor is selected from alkali metal halide, alkaline carbonate, alkali metal hydrocarbonate, alkalimetal oxide, basic metal oxalate, alkali metal hydroxide or its combination, and wherein said basic metal is selected from lithium, sodium and potassium.
5. according to the described method in aforementioned arbitrary aspect, it is characterized in that said promotor is selected from alkali metal halide.
6. according to the described method in aforementioned arbitrary aspect, it is characterized in that said promotor is selected from sodium-chlor, Repone K or its combination.
7. according to the described method in aforementioned arbitrary aspect, it is characterized in that, carry out under the said condition that is reflected at reaction pressure 1.8-3.5MPa and temperature of reaction 400-600 ℃.
8. according to the described method in aforementioned arbitrary aspect, it is characterized in that said reaction pressure is 2.0-3.0MPa, and said temperature of reaction is 450-550 ℃.
9. according to the described method in aforementioned arbitrary aspect, it is characterized in that the mol ratio of hydrogen and silicon tetrachloride is 1.0-4.0.
10. according to the described method in aforementioned arbitrary aspect, it is characterized in that the said mol ratio of hydrogen and silicon tetrachloride is 2.0-3.0.
11., it is characterized in that the weight ratio of hydrogenchloride and silicon tetrachloride is 0.1-10: 100 according to the described method in aforementioned arbitrary aspect.
12., it is characterized in that the said weight ratio of hydrogenchloride and silicon tetrachloride is 1-5: 100 according to the described method in aforementioned arbitrary aspect.
13., it is characterized in that the weight ratio of said Primary Catalysts and said silica flour is 0.1-2.0 according to the described method in aforementioned arbitrary aspect: 100, the weight ratio of said promotor and said Primary Catalysts is 10-50: 100.
14., it is characterized in that the weight ratio of said Primary Catalysts and said silica flour is 0.5-1.5 according to the described method in aforementioned arbitrary aspect: 100, the weight ratio of said promotor and said Primary Catalysts is 20-30: 100.
The invention effect
According to the method for manufacture of trichlorosilane of the present invention, owing to do not contain noble metal component in the employed catalyst system, therefore compare with the method for manufacture of prior art, can reduce the manufacturing cost of trichlorosilane greatly.
Method of manufacture according to trichlorosilane of the present invention; Compare with the hot hydride process of prior art; Owing to significantly reduced temperature of reaction, so the production operation difficulty is lower with production cost, and owing to lower to the purity requirement of raw material (especially gas raw material); Can directly utilize of the charging of the sub product of association in the production of polysilicon, so be to solve the polysilicon industry good solution of the aforementioned bottleneck problem of existence at present as reaction.
According to the method for manufacture of trichlorosilane of the present invention, compare with the method for manufacture of prior art, can significantly improve the per pass conversion of silicon tetrachloride, such as improving at least 2% to 10% on year-on-year basis.
Description of drawings
Fig. 1 is the generalized schematic of a kind of fluidized-bed reactor of using in the trichlorosilane method of manufacture of the present invention.
Embodiment
Be elaborated below in conjunction with the accompanying drawing specific embodiments of the invention, but it is pointed out that protection scope of the present invention does not receive the restriction of these embodiments, but confirm by claims of appendix.
As previously mentioned; The invention provides a kind of method of manufacture of trichlorosilane; Said method comprise make silicon tetrachloride and hydrogen (and optional hydrogenchloride) and silica flour the specific catalyst system (be selected from copper halide and nickel halid at least a be Primary Catalysts; To be selected from least a of alkali metal cpd as promotor) existence under react, to make the step of trichlorosilane.
According to the present invention one preferred embodiment, said being reflected in the fluidized-bed reactor carried out, but is not limited to this sometimes.Such as, as the case may be, as long as adopted specific catalyst system of the present invention, said reaction also can be carried out in fixed-bed reactor, and does not influence the realization of effect of the present invention.
In addition, as long as adopted specific catalyst system of the present invention, said reaction can be carried out according to successive mode (making reaction product continuously), also can carry out according to the mode of batch (being interrupted), does not have special restriction.
In following content, be that example describes method of manufacture of the present invention with the continuous mode, but this is not intended that the invention be limited to this.
Owing to the present invention relates to make the improvement of the method for trichlorosilane in the prior art through the catalytic hydrogenation of silicon tetrachloride; Therefore except the following content that spells out; Interior perhaps explanation that other are not shown clearly all directly be suitable in this area conventional known those, and have no particular limits.
According to the present invention, said fluidized-bed reactor can be to make in the method for trichlorosilane the conventional any kind that uses or the fluidized-bed reactor of structure through the catalytic hydrogenation of silicon tetrachloride in this area, does not have special restriction.About one type fluidized-bed reactor, such as can be referring to the accompanying drawing 1 of CN1157259A, this paper be incorporated herein by reference with regard to it at this in full.
Provided the generalized schematic of this fluidized-bed reactor among Fig. 1, but in fact the present invention is not limited to this.
Below be that example comes method of manufacture of the present invention is specified with the fluidized-bed reactor of structure shown in Figure 1, but this and do not mean that the present invention is limited to this.Those skilled in the art can expect fully that based on following explanation method of manufacture of the present invention obviously can be carried out in the reactor drum (such as fixed-bed reactor) of other types.
According to Fig. 1; Said fluidized-bed reactor 1 comprises the main body that is made up of top superelevation part 2 and fluidized-bed part 3, also comprises gas raw material feed-pipe 4, solid material feed-pipe 5, reaction product delivery pipe 6, gas raw material breaker plate 7 simultaneously and is arranged on said reaction product delivery pipe 6 or the gas-solid separating device 8 of terminal (among Fig. 1 for terminal) etc. midway.
According to this Fig. 1; Gas raw material gets into said gas raw material feed-pipe 4 with predetermined flow velocity; After by said gas dispersion plate 7 homodisperse, get into said fluidized-bed reactor 1; Make the solid material that has got into said fluidized-bed part 3 through said solid material feed-pipe 5 be in fluidized state (boiling state), form fluidized-bed layer thus.Said gas raw material fully contacts for some time (residence time) with said solid material and reacts in this fluidized-bed, the reaction product that is generated is discharged said fluidized-bed reactor 1 and got into next step operation via said reaction product delivery pipe 6.
Owing to carried a part of solid material particle secretly in this reaction product, therefore said reaction product delivery pipe 6 midway or end be provided with said gas-solid separating device 8 (such as cyclonic separator).
According to the practical situation of producing; Gas raw material feed-pipe (or solid material feed-pipe) can be provided with one or more; In order to difference one or more gas raw materials of charging (or solid material), do not have special restriction, and the position that is provided with of said gas raw material feed-pipe (or solid material feed-pipe) is also had no particular limits; Need only the accords with production actual needs, might not be arranged on the bottom (or top) of said fluidized-bed reactor.
According to the present invention one preferred embodiment, said gas raw material feed-pipe only is provided with one.At this moment, all gas raw materials are being pre-mixed evenly after get into said fluidized-bed reactor by a said gas raw material feed-pipe.
According to the present invention another preferred embodiment, said solid material feed-pipe only is provided with one.At this moment, all solid materials are being pre-mixed evenly after get into said fluidized-bed reactor by a said solid material feed-pipe.But according to practical situation, some solid material (such as catalyzer) also can get in (being blown into by gas raw material) said fluidized-bed reactor via said gas raw material feed-pipe.
According to the present invention; The specification of said fluidized-bed reactor and auxiliary equipment and pipeline etc., type and structure and their operation and drive manner etc.; All be known to those skilled in the art, can directly know, do not give unnecessary details at this with reference to the pertinent literature of prior art.
According to the present invention, said gas raw material comprises silicon tetrachloride and hydrogen, and can also comprise hydrogenchloride in some cases.
As required, can also contain the rare gas element (not having reactive behavior) that is used to form fluidized-bed or is used for conditioned reaction pressure in the said gas raw material, such as nitrogen or argon gas etc., this is that those skilled in the art can obviously understand.
According to the present invention; Source to silicon tetrachloride, hydrogen, hydrogenchloride and rare gas element has no particular limits; Can directly obtaining perhaps through any known method, by-product needs only and does not wherein contain the deleterious impurity of said catalytic hydrogenation to silicon tetrachloride from any method.
Be easily; Preferred said silicon tetrachloride, hydrogen and hydrogenchloride are the sub products (sub product that from production of polysilicon, reclaims) of production of polysilicon, can solve the aforementioned bottleneck problem that exists in the present polysilicon industry (sub product but lacks valid approach consumption such as the quantum of output of silicon tetrachloride is excessive) thus effectively.
Therefore; Method of manufacture according to trichlorosilane of the present invention; Compare with the hot hydride process of prior art; Purity requirement to gas raw material is lower, can directly utilize the gas feed of the sub product of association in the production of polysilicon as reaction, therefore is to solve the polysilicon industry good solution of the aforementioned bottleneck problem of existence at present.
Because silicon tetrachloride be liquid at normal temperatures, therefore according to the present invention, before using as gas raw material, with said silicon tetrachloride through any routine the type of heating vaporization and be preheated to 300-600 ℃ (preferably 450-550 ℃, but be not limited to this sometimes).
In addition,, before using, hydrogen, optional hydrogenchloride and the optional rare gas element type of heating through any routine is preheated to 300-600 ℃ as gas raw material according to the present invention, preferred 450-550 ℃, but be not limited to this sometimes.
One preferred embodiment is pre-mixed these gas raw materials together according to predetermined ratio according to the present invention, forms uniform gaseous mixture.Obviously, said gaseous mixture is before using as gas raw material, and the type of heating through any routine is preheated to 300-600 ℃, and preferred 450-550 ℃, but be not limited to this sometimes.Then, make this gaseous mixture get into said fluidized-bed reactor 1 via said gas raw material feed-pipe 4 according to predetermined flow velocity.
Flow velocity to silicon tetrachloride, hydrogen, hydrogenchloride, rare gas element or said gaseous mixture has no particular limits, as long as can guarantee generally in said fluidized-bed reactor 1, to form fluidized-bed layer, is generally 30-80Nm
3/ h, but be not limited to this sometimes.
According to the present invention,, use the hydrogen of 1.0-4.0mol (preferred 2.0-3.0mol) with respect to the 1mol silicon tetrachloride.When using hydrogenchloride,, use the hydrogenchloride of 0.1-10 weight part (preferred 1-5 weight part) with respect to 100 weight part silicon tetrachlorides as gas raw material.
According to the present invention; If with the sub product of production of polysilicon as said gas raw material, so owing to contained a certain amount of silicon tetrachloride, hydrogen and/or hydrogenchloride in this sub product, therefore be easily; Concrete composition situation according to this sub product; Through to the silicon tetrachloride, hydrogen and/or the hydrogenchloride that wherein add the amount of supplying,, be deployed into aforesaid gaseous mixture thus to satisfy the aforementioned consumption that the present invention is directed to these gas raw material regulations.
According to the present invention, the consumption of said rare gas element is had no particular limits, those skilled in the art can carry out appropriate selection and adjusting according to its application target fully to this, do not have special qualification.Certainly, the use of this rare gas element is not necessary.
According to the present invention, silica flour is sent into said fluidized-bed part 3 as solid material via said solid material feed-pipe 5.In this part, silica flour is got into the gas raw material fluidisation of this part and is formed fluidized-bed.Under fluidized state; Silicon tetrachloride in the said gas raw material fully contacts for some time (residence time) with hydrogen (and optional hydrogenchloride) with silica flour and reacts; The product that is generated (wherein containing reaction product trichlorosilane, unreacted gas raw material and entrained solid particle) is discharged said fluidized-bed reactor 1 and is got into next step operation via said reaction product delivery pipe 6 (after through necessary gas solid separation), preferably after through necessary trichlorosilane purification step, gets into the manufacturing process such as polysilicon.
According to the present invention, the reaction pressure of said reaction (catalytic hydrogenation) is 1.8-3.5MPa, preferred 2.0-3.0MPa, temperature of reaction is 400-600 ℃, preferred 450-550 ℃, and the residence time be 20-30s,
Therefore, according to the method for manufacture of trichlorosilane of the present invention, compare with the hot hydride process of prior art, owing to significantly reduced temperature of reaction, so production operation difficulty and production cost are lower.
According to the present invention, carry out under the said existence that is reflected at the specific catalyst system.Wherein, said catalyst system be selected from copper halide and nickel halid at least a be Primary Catalysts, to be selected from least a of alkali metal cpd as promotor.
Embodiment preferred according to the present invention, said Primary Catalysts are selected from cuprous chloride (I), cupric chloride (II), nickelous chloride or its combination, preferred cuprous chloride (I).
Embodiment preferred according to the present invention; Said promotor is selected from alkali metal halide, alkaline carbonate, alkali metal hydrocarbonate, alkalimetal oxide, basic metal oxalate, alkali metal hydroxide or its combination, and wherein said basic metal is selected from lithium, sodium and potassium.Preferably, said promotor is selected from alkali metal halide, is preferably selected from sodium-chlor, Repone K or its combination, more preferably sodium-chlor.
Therefore,, do not contain noble metal component in the employed catalyst system,, can reduce the manufacturing cost of trichlorosilane greatly so compare with the method for manufacture of prior art according to the method for manufacture of trichlorosilane of the present invention.
According to the present invention; Said Primary Catalysts, said promotor and silica flour can be used as solid material and join respectively in the said fluidized-bed reactor; Can certainly earlier said Primary Catalysts and said promotor be formed catalyst mixture according to predetermined ratio uniform mixing together, then this catalyst mixture and silica flour joined respectively in the said fluidized-bed reactor.Under both of these case, said catalyzer or catalyst mixture all can get into (being blown into by gas raw material) said fluidized-bed reactor via said gas raw material feed-pipe.
Perhaps; Convenient and accurate in order to measure, preferably, in advance be metered in silica flour according to predetermined ratio said Primary Catalysts and said promotor; Be deployed into solid mixture, and then it is added in the said fluidized-bed reactor via said solid material feed-pipe 5.
No matter under any situation; Said solid material (comprising said Primary Catalysts, said promotor and silica flour) is before getting into said fluidized-bed reactor; All remove air and moisture in the silica flour through baking powder stove; And be preheated to 300-600 ℃ through the type of heating of routine, preferred 400-500 ℃.
According to the present invention, the mean particle size of said Primary Catalysts and said promotor is had no particular limits, but be generally the 10-80 micron, preferred 15-50 micron.The purity that said Primary Catalysts and said promotor have technical grade gets final product, and does not have special restriction.
According to the present invention, the source and the mean particle size of said silica flour had no special restriction, so long as this area when making trichlorosilane through the catalytic hydrogenation of silicon tetrachloride conventional use those get final product.For example, as said silica flour, preferably use the metallurgical grade silica flour, wherein silicone content is at least 75 weight %, preferably at least 95 weight %.And as the mean particle size of said silica flour, such as can enumerating the 50-250 micron, preferred 150-200 micron, but be not limited to this sometimes.
According to context of the present invention, said mean particle size is measured through the laser particle size method.
In addition,, the particle form of said Primary Catalysts, said promotor and silica flour is had no particular limits according to the present invention,, amorphous spherical etc. such as enumerating, but from easy formation fluidized-bed and mobile angle easily, preferably spherical.
Method as the aforementioned solid mixture of allotment does not have special restriction.Such as enumerating; The said Primary Catalysts of predetermined amount and the said promotor of predetermined amount are added in the silica flour of predetermined amount; Through modes such as grinding or high speed dispersion it being mixed then gets final product; Preferred mix time enough so that said Primary Catalysts and said promotor are uniformly distributed in the silica flour and/or the surface of silica flour on.
According to the present invention, with respect to 100 weight part silica flours, the consumption of said Primary Catalysts is the 0.1-2.0 weight part; Preferred 0.5-1.5 weight part; And with respect to the said Primary Catalysts of 100 weight parts, the consumption of said promotor is the 10-50 weight part, preferred 20-30 weight part.
According to the present invention, the consumption of silica flour is had no particular limits, as long as it can be kept certain fluidized bed layer height and (refer to the height of emulsion zone 10 in the fluidized-bed, be equivalent to use among Fig. 1 h in said fluidized-bed part 3
5The height of expression) gets final product.About how confirming the height of this emulsion zone 10, and how to confirm this emulsion zone 10 and freeboard of fluidized bed 9 in the fluidized-bed, such as can be referring to " Fluidization Engineering principle "; Chief editors such as Jin Yong, Zhu Jingxu, Wang Zhanwen; Press of Tsing-Hua University, 18-19 page or leaf, calendar year 2001.
As the bed height of this fluidized-bed, such as the 5-30% of the total height that can enumerate said fluidized-bed part 3, preferred 10-20%, but be not limited to this sometimes.
In addition, as the addition manner of silica flour (and aforementioned solid mixture), such as enumerating and continuous addition manner, but preferred (being interrupted) mode of adding according to the consumption of silica flour or spending rate and in batches according to the consumption in the manufacturing processed or spending rate.
Shown in following embodiment, according to the method for manufacture of trichlorosilane of the present invention, compare with the method for manufacture of prior art, can significantly improve the per pass conversion of silicon tetrachloride, such as improving at least 2% to 10% on year-on-year basis.
Embodiment
Following examples are to further specify of the present invention, rather than restriction the present invention.
In following all embodiment and comparative example, all used fluidized-bed reactor shown in Figure 1.The principal dimension of this fluidized-bed reactor is following:
h
1(height of fluidized-bed top superelevation part): 1100mm;
h
2(height of fluidized-bed upper inclined surface part): 500mm;
h
3(height of the bottom of the big flange of fluidized-bed hypocentrum top to fluidized-bed part): 3300mm;
h
4(the vertical height in vertebra angle under the big flange of fluidized-bed hypocentrum bottom to the fluidized-bed): 800mm;
h
5(bed height of fluidised solid particulate in the fluidized-bed): about 1100mm;
d
1(internal diameter of fluidized-bed part): 330mm; With
d
2(internal diameter of fluidized-bed top superelevation part): 450mm.
Hydrogen, silicon tetrachloride gas and optional hydrogenchloride are in the same place according to the amount ratio uniform mixing of stipulating in embodiment and the comparative example, then the gaseous mixture that is obtained are preheated to 500 ℃.Then, with the gaseous mixture of this preheating with 55Nm
3The flow of/h infeeds in the said fluidized-bed reactor 1 via said gas raw material feed-pipe 4 continuously.
(purity is 98% the spherical silica flour of metallurgical grade with Primary Catalysts (mean particle size is about 30 microns), promotor (mean particle size is about 30 microns) and silica flour; Mean particle size is about 200 microns) mix according to the amount ratio of stipulating in embodiment and the comparative example; After using high speed dispersor fully to disperse 12 hours, the solid mixture that is obtained is preheated to 500 ℃ in baking powder stove.Then; The solid mixture of this preheating is infeeded in the said fluidized-bed part 3 via said solid material feed-pipe 5; Initially amount of infeeding (being about 45kg) and the mode through intermittently replenishing at any time through controlling said solid mixture make the bed height of said fluidized-bed always remain h
5(about 1100mm).
According to following method method of manufacture of the present invention is estimated.
After reaction is uninterruptedly carried out 10 hours continuously; Basicly stable from reaction product delivery pipe expellant gas component; Make from end (exit end) the expellant gas product of said reaction product delivery pipe 6 and discharge through the tap line (not shown) and be depressurized to normal pressure, be cooled to 80-100 ℃; After removing by filter wherein the entrained solid particle, detect the content of trichlorosilane in the said gaseous product and the content of silicon tetrachloride, represent with molar percentage (mol%) respectively with gas chromatograph.
Based on the trichlorosilane content detection data that obtained, according to following chemical equation, it is scaled the silicon tetrachloride amount that is converted into trichlorosilane, represent with molar percentage (mol%).
The per pass conversion of silicon tetrachloride calculates according to following calculating formula:
The per pass conversion of silicon tetrachloride=(changing into silicon tetrachloride amount (mol%)/(the changing into the content (mol%) of silicon tetrachloride amount (the mol%)+aforementioned silicon tetrachloride that records of trichlorosilane) of trichlorosilane) * 100%.
The mol ratio that said gaseous mixture was pressed 2.0: 1 by hydrogen and silicon tetrachloride constitutes.
As Primary Catalysts, as promotor, and with respect to 100 weight part silica flours, the consumption of said CuCl is 1.5 weight parts with NaCl with CuCl, and the consumption of said NaCl is 0.2 weight part.
Reaction pressure is 2.0MPa, and temperature of reaction is 500 ℃, and the residence time is 26s.
After reaction is carried out 10 hours, gaseous product is analyzed, found that the molar content of trichlorosilane in the gaseous product is 24.7%, the molar content of silicon tetrachloride is 74.6%, can know that through calculating the per pass conversion of silicon tetrachloride is 19.89%.
Comparative example 1
The mol ratio that said gaseous mixture was pressed 2.0: 1 by hydrogen and silicon tetrachloride constitutes.
As catalyzer, and with respect to 100 weight part silica flours, the consumption of said CuCl is 1.5 weight parts with CuCl.
Reaction pressure is 2.0MPa, and temperature of reaction is 500 ℃, and the residence time is 26s.
After reaction is carried out 10 hours, gaseous product is analyzed, found that the molar content of trichlorosilane in the gaseous product is 20.3%, the molar content of silicon tetrachloride is 79.2%, can know that through calculating the per pass conversion of silicon tetrachloride is 16.12%.
The mol ratio that said gaseous mixture was pressed 2.0: 1 by hydrogen and silicon tetrachloride constitutes.
As Primary Catalysts, as promotor, and with respect to 100 weight part silica flours, the consumption of said CuCl is 1.5 weight parts with NaCl with CuCl, and the consumption of said NaCl is 0.75 weight part.
Reaction pressure is 2.2MPa, and temperature of reaction is 510 ℃, and the residence time is 24s.
After reaction is carried out 10 hours, gaseous product is analyzed, found that the molar content of trichlorosilane in the gaseous product is 30.6%, the molar content of silicon tetrachloride is 68.5%, can know that through calculating the per pass conversion of silicon tetrachloride is 25.10%.
Said gaseous mixture is made up of hydrogen, silicon tetrachloride and the hydrogenchloride mol ratio by 14: 7: 1.
With NiCl
2As Primary Catalysts, with KCl as promotor, and with respect to 100 weight part silica flours, said NiCl
2Consumption be 1.8 weight parts, the consumption of said KCl is 0.5 weight part.
Reaction pressure is 2.0MPa, and temperature of reaction is 500 ℃, and the residence time is 26s.
After reaction is carried out 10 hours, gaseous product is analyzed, found that the molar content of trichlorosilane in the gaseous product is 34.7%, the molar content of silicon tetrachloride is 64.2%, can know that through calculating the per pass conversion of silicon tetrachloride is 28.84%.
Said gaseous mixture is made up of hydrogen, silicon tetrachloride and the hydrogenchloride mol ratio by 14: 7: 1.
As Primary Catalysts, as promotor, and with respect to 100 weight part silica flours, the consumption of said CuCl is 2.0 weight parts with potassium oxalate with CuCl, and the consumption of said potassium oxalate is 0.4 weight part.
Reaction pressure is 2.7MPa, and temperature of reaction is 480 ℃, and the residence time is 26s.
After reaction is carried out 10 hours, gaseous product is analyzed, found that the molar content of trichlorosilane in the gaseous product is 33.1%, the molar content of silicon tetrachloride is 65.9%, can know that through calculating the per pass conversion of silicon tetrachloride is 27.36%.
Although given to describe in detail and explanation above with reference to the accompanying drawing specific embodiments of the invention; But should indicatedly be; Those skilled in the art can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and modification; When the function that it produced does not exceed spiritual that specification sheets contains yet, all should be within protection scope of the present invention.
Claims (10)
1. the method for manufacture of a trichlorosilane; Said method comprise make silicon tetrachloride, hydrogen and optional hydrogenchloride and silica flour be selected from the halid at least a Primary Catalysts of copper halide and nickel and be selected from alkali metal cpd at least a promotor in the presence of react; To make the step of trichlorosilane; The weight ratio of wherein said Primary Catalysts and said silica flour is 0.1-2.0: 100, and the weight ratio of said promotor and said Primary Catalysts is 20-50: 100.
2. method according to claim 1 is characterized in that, said being reflected in the fluidized-bed reactor carried out.
3. method according to claim 1 is characterized in that, said Primary Catalysts is selected from cuprous chloride (I), cupric chloride (II), nickelous chloride or its combination.
4. method according to claim 1; It is characterized in that; Said promotor is selected from alkali metal halide, alkaline carbonate, alkali metal hydrocarbonate, alkalimetal oxide, basic metal oxalate, alkali metal hydroxide or its combination, and wherein said basic metal is selected from lithium, sodium and potassium.
5. method according to claim 4 is characterized in that said promotor is selected from alkali metal halide.
6. method according to claim 5 is characterized in that, said promotor is selected from sodium-chlor, Repone K or its combination.
7. method according to claim 1 is characterized in that, carries out under the said condition that is reflected at reaction pressure 1.8-3.5MPa and temperature of reaction 400-600 ℃.
8. method according to claim 1 is characterized in that, the mol ratio of hydrogen and silicon tetrachloride is 1.0-4.0.
9. method according to claim 1 is characterized in that, the weight ratio of hydrogenchloride and silicon tetrachloride is 0.1-10: 100.
10. method according to claim 1 is characterized in that, the weight ratio of said Primary Catalysts and said silica flour is 0.5-1.5: 100, and the weight ratio of said promotor and said Primary Catalysts is 20-30: 100.
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| CN101941702B (en) * | 2010-09-08 | 2012-09-05 | 洛阳晶辉新能源科技有限公司 | Method for producing trichlorosilane by converting silicon tetrachloride |
| EP2621626B1 (en) * | 2010-09-27 | 2015-01-28 | GTAT Corporation | Heater and related methods therefor |
| CN103055867B (en) * | 2011-10-21 | 2015-04-29 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
| CN103449446B (en) * | 2013-08-23 | 2015-05-20 | 中国恩菲工程技术有限公司 | Method for preparing trichlorosilane |
| CN105536789A (en) * | 2015-12-10 | 2016-05-04 | 辽宁石油化工大学 | Method for preparing trichlorosilane catalyst through hydrogenation dechlorination of silicon tetrachloride |
| CN113387362B (en) * | 2021-05-08 | 2022-11-29 | 内蒙古新特硅材料有限公司 | Improved method and device for synthesizing trichlorosilane by cold hydrogenation |
| CN114558593A (en) * | 2022-01-18 | 2022-05-31 | 石河子大学 | Catalyst composition for preparing trichlorosilane by cold hydrogenation of silicon tetrachloride |
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