CN109987608B - Method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride - Google Patents
Method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
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Abstract
The invention relates to a method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride, which takes crude trichlorosilane as a raw material and comprises the steps of primary dust removal, gas phase adsorption, primary light component removal, primary heavy component removal, disproportionation, complexing agent addition, secondary dust removal, primary separation, secondary separation treatment, secondary light component removal treatment, secondary heavy component removal treatment, tertiary separation treatment, tertiary light component removal, tertiary heavy component removal, quartic light component removal and the like. The process route of the invention is that on the existing process route for manufacturing the electronic-grade dichlorosilane, the purity requirement of the raw material trichlorosilane is reduced through the change and adjustment of the steps, the electronic-grade dichlorosilane, the electronic-grade trichlorosilane and the electronic-grade silicon tetrachloride which can be obtained simultaneously have low contents of impurities such as metal impurities, chlorosilane impurities, boron and the like, the quality is stable, and the requirements of large-scale integrated circuits on products can be met.
Description
Technical Field
The invention relates to a method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride, belonging to the technical field of chlorosilane production.
Background
The electronic-grade dichlorosilane, the electronic-grade trichlorosilane and the electronic-grade silicon tetrachloride are mainly used for silicon epitaxial growth and silicon sources of large-scale integrated circuits. At present, electronic-grade dichlorosilane and trichlorosilane are mainly monopolized by Japan and other international great monopoles, along with the rapid development of the semiconductor industry in China and the domestic requirements of semiconductor materials, equipment and the like, the monopolization of the electronic-grade dichlorosilane and the electronic-grade trichlorosilane in China is broken, the healthy development of the information industry in China is ensured, and the independent development of the electronic-grade dichlorosilane and the electronic-grade trichlorosilane is imperative. Meanwhile, the electronic grade perhydropolysilazane produced by using the electronic grade dichlorosilane as the raw material is also widely applied to national defense military industry and is also an urgent need of the national defense military industry at present.
At present, electronic-grade dichlorosilane which can really reach the semiconductor grade is not available in domestic markets, the process route is to purify dichlorosilane which is a byproduct of polysilicon or prepare the dichlorosilane by using trichlorosilane as a raw material, but the requirements on the raw material are high, some requirements are more than 4N, some requirements are at least more than 3N, meanwhile, the requirements on metal impurities, boron-phosphorus impurities and other chlorosilane impurities of the electronic-grade dichlorosilane and the trichlorosilane in the electronic industry are extremely high, and the control on the impurities of the electronic-grade dichlorosilane in domestic is unstable; in addition, dichlorosilane which is thrown out from high-boiling or low-boiling substances in the preparation process of dichlorosilane is extremely difficult to treat, so that the industry needs to use low-quality trichlorosilane as a raw material, stably control metal impurities, boron-phosphorus impurities and other chlorosilane impurities of a product, and perfectly understand the process for discharging dichlorosilane in the preparation process.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride, and solving the problems.
The technical scheme for solving the technical problems is as follows: a method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride comprises the following steps:
s1, taking the crude trichlorosilane as a raw material, and carrying out primary dust removal treatment;
s2, performing gas phase adsorption treatment on the trichlorosilane after primary dust removal;
s3, sequentially carrying out primary light component removal treatment and primary heavy component removal treatment on the trichlorosilane after gas phase adsorption;
s4, performing disproportionation reaction on the trichlorosilane after removing the heavy components to obtain a first mixture containing dichlorosilane, trichlorosilane and silicon tetrachloride;
s5, adding a complexing agent into the first mixture, and performing secondary dust removal treatment;
s6, carrying out primary separation on the first mixture subjected to secondary dust removal to obtain a second mixture containing dichlorosilane and trichlorosilane and a third mixture containing trichlorosilane and silicon tetrachloride;
s7, sequentially carrying out secondary separation treatment, secondary light component removal treatment and secondary heavy component removal treatment on the second mixture to obtain electronic-grade dichlorosilane; and carrying out three times of separation treatment on the third mixture to obtain a fourth mixture containing trichlorosilane and a fifth mixture containing silicon tetrachloride, sequentially carrying out three times of light component removal treatment and three times of heavy component removal treatment on the fourth mixture to obtain electronic grade trichlorosilane, and sequentially carrying out four times of light component removal treatment and four times of heavy component removal treatment on the fifth mixture to obtain electronic grade silicon tetrachloride.
The invention has the beneficial effects that: the process route is different from the existing process for independently manufacturing the electronic-grade dichlorosilane or the electronic-grade trichlorosilane, the requirement on the purity of the raw material trichlorosilane is reduced through the change and adjustment of steps on the existing process route for manufacturing the electronic-grade dichlorosilane, the process route is obviously changed and different from other processes, the electronic-grade dichlorosilane, the electronic-grade trichlorosilane and the electronic-grade silicon tetrachloride which can be simultaneously obtained have low content of impurities such as metal impurities, chlorosilane impurities, boron and the like, the quality is stable, and the requirements of large-scale integrated circuits on products can be met.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step S1, the purity of the crude trichlorosilane is 2N (content is more than 99%), the primary dedusting treatment is performed in a raw material dedusting tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the feeding amount is 1896.2kg/h, impurities with boiling points higher than the tower top temperature are removed from the tower kettle, and the impurities are extracted from the tower top.
The method has the advantages that the raw material is trichlorosilane, the trichlorosilane is used for disproportionation reaction, the method is different from the prior other chlorosilane production processes that the raw material is purified polysilicon byproduct dichlorosilane and other trichlorosilane disproportionation processes, the purity of trichlorosilane in other processes is required to be at least 4N (the content is more than 99.99%) or 3N (the content is more than 99.9%), the method provides that the purity of trichlorosilane is only 2N, and the raw materials dichlorosilane, trichlorosilane and silicon tetrachloride in the prior other chlorosilane production processes are probably not obtained from trichlorosilane by using anionic surface tertiary amine exchange resin, so that B, P impurities and the like of products are difficult to remove or cannot be removed by rectification.
Further, in step S2, the gas phase adsorption treatment is performed in an adsorption tower by using molecular sieve for adsorption, the tower pressure is 0.2-0.4MPa, and the tower pressure isThe top temperature was 90 ℃ and the feed rate was 1896.2 kg/h. The particle size of the molecular sieve is 1-3.5mm in diameter, and the dry basis bulk density is 0.45-0.78g/cm3Specific surface area greater than 200m2Per g, pore volume is more than or equal to 0.4cm3/g。
The further scheme has the advantages that the adsorption used in other existing processes is the product purification after disproportionation, and the adsorbent is active carbon, silica gel and the like; the adsorption of the invention is carried out before the raw material trichlorosilane is purified, and the adsorbent is a molecular sieve. Firstly, in the process of producing chlorosilane, all boron and phosphorus impurities come from raw materials, if the raw materials are not well treated, the treatment after purification is obviously primary and secondary inverted, secondly, if boron in the raw materials is not well treated and the adsorption effect is poor, boron trichloride can be generated during disproportionation reaction, the boiling point of the boron trichloride is very close to that of a target product dichlorosilane, and if the adsorption effect is poor, the boron trichloride is difficult to separate through rectification, so that the product contains more impurities and the product quality is reduced.
Further, step S3, the primary light component removal treatment is carried out in a raw material light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the discharged material at the tower top is 240kg/h, 1656.2kg/h is extracted from the tower kettle, and the reflux amount is 12-16m3H; the primary heavy component removal treatment is carried out in a raw material heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the tower bottom discharge is 240kg/h, the tower top discharge is 1416.2kg/h, and the reflux amount is 11-15m3/h。
The method has the advantages that the raw material trichlorosilane is rectified through the light component removal tower and the heavy component removal tower, the parameter control requirements of the light component removal tower and the heavy component removal tower are different from those of the prior art, the gas used for controlling the tower pressure is not nitrogen but other high-purity gas, and the nitrogen is impurity gas for downstream manufacturers in the semiconductor industry, particularly the rear downstream manufacturers of the method, and is doped into the impurity gas to be not beneficial to further processing of the downstream manufacturers, so that other high-purity gas which is not the impurity gas can be adopted in the method.
Further, in step S4, the disproportionation reaction is carried out in a disproportionation reactor with the pressure of 0.2-0.3MPa and the reaction temperature of 60-70 ℃; the disproportionation reactor is a double-tube-plate tube type heat exchanger, water is used in the tube pass, trichlorosilane after heavy components are removed in the shell pass, and macroporous weak-base anion exchange resin A21 with tertiary amino on the surface and the water content of less than 0.3 percent is added as a catalyst; the first mixture comprises 6-7 wt% of dichlorosilane, 80-81 wt% of trichlorosilane, 11-12 wt% of silicon tetrachloride and the balance of other impurities.
The further scheme has the beneficial effects that in the prior art, industrial metal silicon is used as a raw material to obtain trichlorosilane, and the trichlorosilane is purified to prepare electronic-grade trichlorosilane, boron trichloride, phosphorus trichloride and the like contained in the raw material trichlorosilane are difficult to be completely separated in rectification, so that B, P and other impurities in a product influence the resistivity of the product. In the invention, trichlorosilane is selected to pass through macroporous alkalescent anion resin with tertiary amino on the surface, so that boron trichloride and phosphorus trichloride in the trichlorosilane form BH3-PH3A compound which is a low boiling point compound. The boiling point of boron trichloride is 12 ℃, the boiling point of phosphorus trichloride is 76 ℃, the boiling point of silicon tetrachloride produced after disproportionation reaction is 57 ℃, and the boiling point of dichlorosilane is 8.2 ℃. After the trichlorosilane passes through the catalyst, the boron trichloride and the phosphorus trichloride are induced to generate the PH with low boiling point3-BH3The compound is easy to separate by rectification relative to the boiling point of trichlorosilane, so that the electronic-grade trichlorosilane with low boron and phosphorus impurities can be easily obtained, and the effect is obviously better than that of the electronic-grade trichlorosilane obtained by directly rectifying the trichlorosilane.
If the catalyst contains water in the disproportionation reaction, chlorosilane and water react to generate silicic acid substances and generate a large amount of heat in the reaction process, silicic acid and the like generated by the reaction are attached to the surface of the catalyst to block gaps of the catalyst and reduce the reaction activity of the catalyst, and meanwhile, the heat generated by the reaction can cause the catalyst to be overheated and deactivated, so that the catalyst for the disproportionation reaction needs to be fully dried, the water content of the catalyst used in the method disclosed by the invention is less than 0.3 wt%, and the method is different from the method that the nitrogen is simply dried in the prior art, or the silicon tetrachloride or the trichlorosilane enters a device to react with the catalyst to take away the water in the catalyst.
In addition, materials and catalysts are not easy to block in a shell pass, the tube pass is hot water, the temperature of water can be finely controlled through a heat exchanger, meanwhile, the specific heat capacity of the water is large, a stable temperature environment which is not possessed by other media can be provided, the disproportionation reactor adopts a double-tube-plate mode, the possibility of contact between the tube pass water and the shell pass materials is avoided, and great benefits are achieved in the aspects of safety and quality.
Further, in step S5, a step of adding a complexing agent is performed in the chlorosilane intermediate tank, wherein the complexing agent is aromatic aldehyde or an aromatic aldehyde derivative, and the amount of the complexing agent added is 0.08 wt% to 0.15 wt% of the first mixture; the secondary dust removal treatment is carried out in a chlorosilane dust removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 70-95 ℃, the feeding amount is 1416.2kg/h, impurities with boiling points higher than the tower top temperature are removed at the tower bottom by about 0.1kg/h, and 1416.1kg/h of mixed chlorosilane is collected at the tower top.
The beneficial effect of adopting above-mentioned further scheme is that adsorb the impurity in the material with the complexing agent, but because the complexing agent that adds forms solid-state high polymer with metal chlorides such as ferric chloride easily, causes the jam of container or pipeline, in order to clear up these blockages, probably need regularly to stop a vehicle and clear up, causes the system and frequently opens the parking, increases work load simultaneously, and the increase system is opened and is produced more impurity and be difficult to the clean risk of replacement. Therefore, the process of the invention is provided with two sets of dust removal towers, and the dust removal step after complexation can well remove solid substances formed by complexation, thereby avoiding blockage.
Further, in step S6, the first separation is carried out in a No. 1 separation tower with a tower pressure of 0.2-0.4MPa and a tower top temperature of 53-73 ℃, a second mixture 299.1kg/h is obtained at the tower top, a third mixture 1117kg/h is obtained at the tower bottom, and a reflux amount of 7-10m3/h。
Further, step (b)In step S7, the secondary separation treatment is carried out in a No. 2 separation tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the feeding amount is 319.1kg/h, the tower kettle external discharge amount is 200kg/h, the tower top extraction amount is 99.1kg/h, the reflux amount is 2-4m3H; the secondary light component removal treatment is carried out in a DCS light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, 20kg/h of DCS containing heavy component impurities is discharged from the tower top, 79.1kg/h is extracted from the tower bottom, and the reflux quantity is 2-4m3H; the secondary heavy component removal treatment is carried out in a DCS heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, DCS containing light component impurities is discharged from the tower bottom at 16kg/h, electronic-grade dichlorosilane is extracted from the tower top at 63.1kg/h, and the reflux quantity is 2-4m3/h。
Further, pumping the material discharged from the top of the DCS lightness removing tower and the material discharged from the kettle of the DCS heaving tower into an anti-disproportionation reactor, adding crude silicon tetrachloride with the weight 10 times that of the material into the anti-disproportionation reactor, carrying out anti-disproportionation reaction under the action of a catalyst to obtain trichlorosilane, and reusing the trichlorosilane as the raw material in the step S1; the pressure of the reverse disproportionation reactor is 0.5MPa, and the temperature is 70 ℃. The feed composition was DCS36kg/h, STC 360 kg/h.
The method has the advantages that in the existing process for preparing electronic-grade dichlorosilane, the dichlorosilane containing high boiling point or low boiling point discharged in the purification of dichlorosilane is subjected to alkali washing and absorption by the conventional method, so that the cost is increased, and on the other hand, the dichlorosilane is relatively active and dangerous and is relatively unsafe to be subjected to alkali washing. It should be noted that the purpose of the reverse disproportionation is to consume redundant dichlorosilane, avoid additional treatment to increase cost, and obtain trichlorosilane which can be used as a raw material, so as to realize recycling of materials, and the reverse disproportionation is not a theoretical one-to-one reaction, and the concentration of reactants needs to be increased to promote the reaction, and the finally obtained mixture of silicon tetrachloride and trichlorosilane can be simply rectified and separated, and can be reused as a low-purity raw material.
Further, in step S7,the third separation treatment is carried out in a No. 3 separation tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, 850kg/h of fourth mixture is extracted from the tower top, 267g/h of fifth mixture is extracted from the tower bottom, and the reflux amount is 9-11m3H; the third light component removal treatment is carried out in a TCS light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, 200kg/h of impurities are discharged from the tower top, 650kg/h are extracted from the tower bottom, and the reflux amount is 8-10m3H; the third heavy component removal treatment is carried out in a TCS heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the discharged impurities at the tower bottom are 190kg/h, the electronic grade trichlorosilane is 460kg/h and the reflux amount is 8-10m3H; the fourth light component removal treatment is carried out in an STC light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 95-117 ℃, impurities are discharged from the tower top for 127kg/h, the tower bottom is withdrawn for 150kg/h, and the reflux amount is 4-6m3H; the four heavy component removal treatments are carried out in an STC heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 95-117 ℃, 50kg/h of impurities are discharged from the tower bottom, 100kg/h of electronic grade silicon tetrachloride is collected from the tower top, and the reflux amount is 4-6m3/h。
The method has the advantages that the method adopts twice purification for purifying the chlorosilane, one time is at the raw material processing part, the other time is after the disproportionation reaction, the twice purification for the chlorosilane greatly reduces the content of metal and boron-phosphorus impurities in the chlorosilane component, reduces the requirement on equipment materials (the production equipment only needs to use 304L or 316L without electrolytic polishing), and also reduces the load of the equipment (the one-time purification process needs a higher tower and more tower plates, and consequently, higher heat medium consumption and refrigerant consumption are brought)
Regarding the feeding amount, the external discharge amount, the extraction amount and the like in the technical scheme, considering the scale of the equipment, the feeding amount, the external discharge amount, the extraction amount and the like can be changed according to the corresponding proportion, such as the scaling up or scaling down, in addition, the size requirement of the backflow amount greatly affects the quality of the electronic grade product, although the backflow amount of different equipment is changed, the backflow amount of the same equipment design can also greatly affect the quality of the product, the backflow amount can be balanced between the product quality and energy saving in the traditional large chemical industry, but the electronic grade product is not necessarily considered comprehensively according to the equipment and other related factors, and is determined according to experiments. The present invention is only given the preferred examples, which are only used to explain the present invention and not to limit the scope of the present invention.
The invention relates to a new process route for controlling the temperature and pressure of a light component removal tower and a heavy component removal tower in process control to solve the problem that a boron-containing compound is difficult to separate and put forward due to the change of the temperature and the pressure in a rectification process, wherein the equipment part is made of 316L materials, and the other materials are all 304L materials, electrolytic polishing is not needed, and the overall investment of the equipment is reduced. The foreign imported structured packing for the packing ensures the metal impurities of the product.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
In the description of the invention, DCS refers to dichlorosilane, TCS refers to trichlorosilane, STC refers to silicon tetrachloride, E-represents an electronic grade, and the reactor in the figure is a disproportionation reactor.
As shown in fig. 1, the invention relates to a method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride by using trichlorosilane, which comprises the following steps:
s1, taking crude trichlorosilane (with the purity of 2N) as a raw material, and carrying out primary dust removal treatment in a raw material dust removal tower; the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the feeding amount is 1896.2kg/h, impurities with boiling points higher than the tower top temperature are removed from the tower kettle, and the impurities are extracted from the tower top; different from other schemes that raw materials are directly treated and enter a packed tower in the prior art, the dust removal tower is a plate tower, has better adaptability to materials containing particle impurities, and can obviously reduce the requirement on the purity of the trichloro raw materials;
s2, performing gas phase adsorption treatment on the trichlorosilane subjected to primary dust removal in an adsorption tower, and removing impurities in the raw materials by adopting molecular sieve adsorption, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 90 ℃, and the feeding amount is 1896.2 kg/h; the particle size of the molecular sieve is the diameter1-3.5mm, and the dry basis bulk density is 0.45-0.78g/cm3Specific surface area greater than 200m2Per g, pore volume is more than or equal to 0.4cm3(ii)/g; as shown in fig. 1, two sets of adsorption towers can be arranged in parallel, and simultaneously gas phase adsorption treatment is carried out, wherein when one adsorption tower needs to clean a molecular sieve or maintain, the other adsorption tower can still run without stopping the adsorption towers completely;
s3, performing primary light component removal treatment on the trichlorosilane after gas phase adsorption in a raw material light component removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the feeding amount is 1896.2kg/h, the discharged material at the tower top is 240kg/h, the extracted material at the tower bottom is 1656.2kg/h, and the reflux amount is 12-20m3H; then carrying out primary heavy component removal treatment in a raw material heavy component removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the feeding amount is 1656.2kg/h, the tower bottom discharge is 240kg/h, the tower top discharge is 1416.2kg/h, and the reflux amount is 12-20m3/h；
S4, carrying out disproportionation reaction on the trichlorosilane after removing heavy components in a disproportionation reactor under the action of a catalyst, wherein the pressure of the disproportionation reactor is 0.2-0.3MPa, and the reaction temperature is 60-70 ℃, so as to obtain a first mixture containing dichlorosilane, trichlorosilane and silicon tetrachloride; the disproportionation reactor is a double-tube-plate tube-type heat exchanger, water is used in the tube pass, trichlorosilane after heavy components are removed in the shell pass, macroporous weak-base anion exchange resin A21 with tertiary amino on the surface and the water content of less than 0.3 percent is added as a catalyst, and the disproportionation reaction is carried out in the shell pass; the first mixture comprises 6-7 wt% of dichlorosilane, 80-81 wt% of trichlorosilane, 11-12 wt% of silicon tetrachloride and the balance of other impurities;
s5, introducing the first mixture into a chlorosilane intermediate tank, and adding a complexing agent through an intermediate tank feeding pipe, wherein the complexing agent is aromatic aldehyde or an aromatic aldehyde derivative, and the addition amount of the complexing agent is 0.08-0.15 wt% of that of the first mixture; performing secondary dust removal treatment in a chlorosilane dust removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 70-95 ℃, the feeding amount is 1416.2kg/h, impurities with boiling points higher than the tower top temperature are removed at the tower bottom by about 0.1kg/h, and 1416.1kg/h of mixed chlorosilane is extracted from the tower top;
s6, dividing the first mixture (namely the top extraction of the chlorosilane dust removal tower in S5) after the secondary dust removal into 1Separating for the first time from the tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 53-73 ℃, the feeding amount is 1416.1kg/h, 299.1kg/h of a second mixture (comprising part of TCS and almost all DCS) containing dichlorosilane and trichlorosilane is extracted from the tower top, 1117kg/h of a third mixture (the rest of TCS and almost all STC) containing trichlorosilane and silicon tetrachloride is extracted from the tower bottom, and the reflux amount is 7-10m3/h；
S7, sequentially carrying out secondary separation treatment on the second mixture in a No. 2 separation tower (similar to a de-heavy tower), wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the feeding amount is 319.1kg/h, the discharge amount (heavy component impurities and a small amount of DCS) at the tower bottom is 200kg/h, the tower top yield is 99.1kg/h, and the reflux amount is 2-4m3H; performing secondary light component removal treatment in a DCS light component removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the feeding amount is 99.1kg/h, 20kg/h of DCS containing heavy component impurities is discharged from the tower top, 79.1kg/h of DCS is extracted from the tower bottom, and the reflux amount is 2-4m3H; finally, secondary heavy component removal treatment is carried out in a DCS heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the feeding amount is 79.1kg/h, 16kg/h of DCS containing light component impurities is discharged from the tower bottom, 63.1kg/h of electronic-grade dichlorosilane is collected from the tower top, and the reflux amount is 2-4m3Pumping the product extracted from the tower top into an electronic-grade dichlorodihydrogend finished product storage tank;
pumping the material discharged from the top of the DCS lightness-removing tower and the material discharged from the bottom of the DCS heaving tower into an anti-disproportionation reactor, adding crude silicon tetrachloride with the weight 10 times that of the material into the anti-disproportionation reactor, carrying out anti-disproportionation reaction under the action of a catalyst to obtain trichlorosilane, and reusing the trichlorosilane as the raw material in the step S1; the pressure of the anti-disproportionation reactor is 0.5MPa, the temperature is 70 ℃, the feeding material forms DCS36kg/h and STC 360kg/h, and the conversion rate of dichlorosilane is about 95 percent;
the third mixture is separated for three times in a No. 3 separating tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, 850kg/h of a fourth mixture containing trichlorosilane is extracted from the tower top, 267g/h of a fifth mixture containing silicon tetrachloride (a small amount of trichlorosilane is contained in the fifth mixture) is extracted from the tower bottom, and the reflux amount is 9-11m3/h；
Performing light component removal treatment on the fourth mixture in a TCS light component removal tower for three times, wherein the tower pressure is 0.2-0.4MPa, and the tower pressure isThe top temperature is 68-87 ℃, the feeding amount is 850kg/h, the low-boiling TCS200kg/h is discharged from the top of the tower, the TCS 650kg/h is extracted from the bottom of the tower, and the reflux amount is 8-10m3H; carrying out three times of heavy component removal treatment in a TCS heavy component removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the feeding amount is 650kg/h, the high-boiling TCS contained in the discharged high-boiling TCS at the tower bottom is 190kg/h, the electronic grade trichlorosilane is 460kg/h and the reflux amount is 8-10m3Pumping the product extracted from the tower top into an electronic grade trichlorosilane finished product storage tank;
performing four times of light component removal treatment on the fifth mixture in an STC light component removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 95-117 ℃, the feeding amount is 267kg/h, TCS, light components and part of STC are discharged from the tower top, STC is 150kg/h is collected from the tower bottom, and the reflux amount is 4-6m3H; then carrying out four times of heavy component removal treatment in an STC heavy component removal tower, wherein the tower pressure is 0.2-0.4MPa, the tower top temperature is 95-117 ℃, the feeding amount is 150kg/h, the high-boiling STC contained in the discharged material at the tower bottom is 50kg/h, the electronic grade silicon tetrachloride is collected at the tower top for 100kg/h, and the reflux amount is 4-6m3And h, pumping the product extracted from the tower top into an electronic grade silicon tetrachloride finished product storage tank.
For the production method of the present invention, the applicant has conducted a plurality of process experiments, and in the above technical scheme, the column pressure and the column top temperature of each column are subjected to corresponding verification experiments within the limited range (different gradient experiments are conducted from small to large according to data, and gradually increase from the minimum value to the maximum value of each range value), so as to obtain the product of the present invention. The technical scheme described in the applicant adopts appropriate production equipment to obtain the feeding amount, the discharging amount, the extraction amount, the reflux amount and the like, and of course, the production equipment and the scale thereof can be adjusted appropriately by those skilled in the art, and the related amounts can be increased or decreased correspondingly. The key point of the invention is the sequence arrangement of the front and back steps and each technical parameter in the process, each production equipment is selected from the general equipment in the field, but the relevant experimental comparison is also carried out, the most appropriate equipment is selected from various production equipment according to the experimental data and the result analysis, and the best production effect can be achieved by matching with the corresponding steps and the technical parameters.
In the steps, the raw material dust removal tower is a plate tower, the plate tower has better adaptability to materials containing high-boiling-point impurities relative to a packed tower, the quality requirement of the system on the raw material TCS can be obviously reduced, and a reboiler of the raw material dust removal tower is a kettle reboiler, so that the raw material dust removal tower is convenient to overhaul and extract; the height-diameter ratio of the adsorption tower is about 10: 1; the raw material light component removal tower is a packed tower, the packing is plate corrugated regular packing and is made of 316L stainless steel, and the raw material heavy component removal tower is a packed tower.
The catalyst for the disproportionation reaction needs to be strictly dehydrated, and the specific process is as follows: the dry catalyst A-21 was purchased, the water content was required to be less than 0.3 wt%, and the catalyst was charged into the reactor, and the volume of the charged catalyst was confirmed in advance. After the TCS raw material contacts the catalyst, impurities of boron trichloride and phosphorus trichloride in the TCS can form BH3-PH3The compound, which is a low boiling point material, is easily separated from the product in the rectification system.
The invention tests whether the catalyst floats upwards or sinks in alcohols, aromatic hydrocarbons, silicon tetrachloride and trichlorosilane and the expansion state and expansion rate of the catalyst in various volumes through experiments.
The experimental record is as follows:
experiment one
Firstly, the purpose of experiment is as follows:
the swelling ratio of A21 resin in alcohols was measured.
II, experimental equipment:
2L graduated cylinder, glass rod, alcohol (99.7%), basket filter (with filter screen) with modified caliber DN50, high-purity laboratory nitrogen, sealing bag and leather sheath.
Thirdly, experimental contents:
1. taking about 500ML resin, placing the resin in an oven for drying by laboratory analysts, setting the oven at 70 ℃ (surely not over 90 ℃) for three hours, weighing, placing the resin in the oven for drying at 70 ℃, weighing again after half an hour, and taking out the resin until the mass change is less than 0.2% (the mass difference is 0.001g) at half an hour intervals.
2. The laboratory dried A21 resin was removed and poured slowly into a 2L graduated cylinder to measure a resin bulk of 560ML (the cylinder wall slightly adsorbs the resin, allowing the resin to fall off on standing).
3. And (3) slowly pouring 99.7% alcohol into a 2L measuring cylinder to soak the resin in the alcohol solution (the resin gradually changes from white to light yellow), shaking to remove air bubbles, wherein the volume of the expanded resin is 730ML, and the volume of the resin is still 730ML after the resin is sealed and stands for 24 hours.
4. Pouring the resin alcohol mixture into a basket with a filter screen to filter the alcohols, then putting the basket into a basket filter, blowing a sealing cover with nitrogen for drying (bottom inlet side discharge), and putting the filtered residual alcohols into a waste liquid bottle for storage until the residual alcohols are subsequently treated by laboratory personnel.
5. The A21 resin is continuously blown in a basket filter for two days, taken out and bottled, and sent to a laboratory for drying at constant temperature.
6. The dried a21 resin was repeated again for steps 2, 3, 4, and 5, and the whole was repeated three times, and experimental data were recorded.
Fourthly, recording experimental data:
fifth, experimental calculation results
Sixth, conclusion
The expanded volume of the a21 resin in this alcohol was 33.2%.
Experiment two:
firstly, the purpose of experiment is as follows:
the swelling ratio of A21 resin in aromatic hydrocarbons was measured.
II, experimental equipment:
2L graduated cylinder, glass rod, aromatic hydrocarbon (99.5%), basket filter (with filter screen) with modified caliber DN50, high-purity laboratory nitrogen, sealing bag, leather sheath, gas mask and rubber glove.
Thirdly, experimental contents:
1. taking about 500ML resin, placing the resin in an oven for drying by laboratory analysts, setting the oven at 70 ℃ (surely not over 90 ℃) for three hours, weighing, placing the resin in the oven for drying at 70 ℃, weighing again after half an hour, and taking out the resin until the mass change is less than 0.2% (mass difference is 0.001G) at half an hour interval.
2. The laboratory dried A21 resin was removed and slowly poured into a 2L graduated cylinder to measure a resin bulk of 525ML (the cylinder wall was heavily loaded with resin, and the resin was allowed to settle for a longer period of time).
3. And (3) slowly pouring 99.5% aromatic hydrocarbon into a 2L measuring cylinder to soak the resin in the aromatic hydrocarbon solution (the resin gradually changes from white to orange), shaking to remove air bubbles, wherein the volume of the resin after expansion is 660ML, and the resin volume is still 660ML after the opening is sealed and stands for 24 hours.
4. Pouring the resin aromatic hydrocarbon mixture into a basket with a filter screen to filter aromatic hydrocarbons, then putting the basket into a basket filter, blowing a sealing cover with nitrogen for drying (bottom inlet and side discharge), putting the filtered residual aromatic hydrocarbons into a waste liquid bottle, sealing the bottle by a sealing bag, and treating by laboratory staff subsequently.
5. The A21 resin is continuously blown in a basket filter for two days, taken out and bottled, and sent to a laboratory for drying at constant temperature.
6. The dried a21 resin was repeated again for steps 2, 3, 4, and 5, and the whole was repeated three times, and experimental data were recorded.
Fourthly, recording experimental data:
fifth, experimental calculation results
Sixth, conclusion
The expanded volume of the a21 resin in aromatic hydrocarbons was 23.7%.
Experiment three:
firstly, the purpose of experiment is as follows:
the expansion of the a21 resin in silicon tetrachloride was determined.
II, experimental equipment:
2L graduated cylinder, glass rod, silicon tetrachloride, basket filter (with filter screen) with modified caliber DN50, high-purity laboratory nitrogen, sealing bag and leather sheath, gas mask, rubber glove, tail gas treatment device, PH test paper, etc.
Thirdly, experimental contents:
1. taking about 500ML resin, placing the resin in an oven for drying by laboratory analysts, setting the oven at 70 ℃ (surely not over 90 ℃) for three hours, weighing, placing the resin in the oven for drying at 70 ℃, weighing again after half an hour, and taking out the resin until the mass change is less than 0.2% (mass difference is 0.001G) at half an hour interval.
2. The laboratory dried A21 resin was removed and slowly poured into a 2L graduated cylinder to measure a resin bulk volume of 505ML (the cylinder wall adsorbs the resin, and the resin falls off on standing for a period of time).
3. Slowly pouring silicon tetrachloride into a 2L measuring cylinder to ensure that the resin is soaked in the silicon tetrachloride solution (the resin gradually changes from white to dark brown, a large amount of white smoke is generated at the opening of the measuring cylinder, and the resin gradually floats along with the addition of the silicon tetrachloride), shaking to remove air bubbles, wherein the volume of the expanded resin is 540ML, and the volume of the resin is still 540ML after the opening is sealed and stands for 24 hours.
4. Pour resin silicon tetrachloride mixture into the basket of taking the filter screen in with silicon tetrachloride filter, then put the basket in the basket filter, the closing cap leads to nitrogen and weathers (advancing the side row at the end, there is acid gas with PH test paper detection tail gas), and the raffinate silicon tetrachloride that filters is put into high-purity laboratory waste liquid jar, and the seal bag is sealed, treats follow-up the handling by laboratory personnel.
5. And (3) continuously blowing the A21 resin in a basket filter for two days, taking out and bottling the resin after no change is detected by the PH test paper, and carrying out the next experiment.
6. The dried a21 resin was repeated again for steps 2, 3, 4, and 5, and the whole was repeated twice and experimental data was recorded.
Fourthly, recording experimental data:
fifth, experimental calculation results
Sixth, conclusion
The expanded volume of the a21 resin in silicon tetrachloride was 7.3%.
Experiment four:
firstly, the purpose of experiment is as follows:
the swelling rate of the A21 resin in trichlorosilane is measured.
II, experimental equipment:
2L graduated cylinder, glass rod, trichlorosilane, basket filter (with filter screen) with modified caliber DN50, high-purity laboratory nitrogen, sealing bag and leather sheath, gas mask and rubber glove.
Thirdly, experimental contents:
1. the A21 resin dried in the apparatus was taken out and slowly poured into a 2L measuring cylinder to measure a bulk volume of 525ML (the resin was adsorbed on the cylinder wall and allowed to stand for a while, the resin dropped).
2. And slowly pouring trichlorosilane into a 2L measuring cylinder to soak the resin in trichlorosilane solution (the resin gradually changes from white to dark brown, a small amount of white smoke is generated at the opening of the measuring cylinder, and the resin gradually floats along with the addition of silicon tetrachloride), wherein the volume of the expanded resin is 560ML, then a nitrogen pipe is connected into the measuring cylinder, and the opening of the measuring cylinder is fixed by a rubber band. Preventing the build up of gas creating a hazard. (after standing for more than ten minutes, the resin and the trichlorosilane are gradually reacted, bubbles are generated in the resin, the bubbles gradually move upwards from the bottom along with the time until the top is broken, new bubbles are generated in the resin, the circulation is repeated, and the liquid level slowly drops.)
3. After two hours, the internal air bubbles were shaken out, and the volume of the resin after expansion was read again as 570ML (some air bubbles may occupy a part of the volume inside).
4. And (6) finishing and recording experimental data.
Fourthly, recording experimental data:
fifth, experimental calculation results
Sixth, conclusion
The expansion volume of the A21 resin in trichlorosilane was 7.7%.
The quality of products produced by the production process of the invention is closely related to the water-containing treatment and pretreatment of the A-21 catalyst, the prior art only singly produces various electronic grade chlorosilanes, the requirements on the A-21 catalyst are not high, the A-21 catalyst is not treated or is simply heated, and the water content can basically meet the production requirements even if the water content is slightly high, but the invention is a method for simultaneously producing electronic grade dichlorosilane, electronic grade trichlorosilane and electronic grade silicon tetrachloride, and the invention has the advantages of complex working procedures due to the requirement of obtaining three products, high performance requirements on the A-21 catalyst and particularly the requirement on the water content, which is required to be below 3%. If the water content of the catalyst is higher, the production process of the invention is greatly influenced, firstly: the yield of dichlorosilane in the product is reduced; secondly, the method comprises the following steps: low-boiling products such as monochlorotrihydrogen, even monosilane and other impurities can be generated, and the impurities have great influence on electronic gas used in the semiconductor industry; thirdly, the method comprises the following steps: the catalyst is not well treated, so that the catalyst expands and is broken or reacts with water to generate silica or silica gel precipitates, the catalyst pores are occupied, and the catalyst is deactivated.
The above experiments show that the swelling ratios of the A21 resin in alcohols, aromatic hydrocarbons, silicon tetrachloride and trichlorosilane are obtained, so that the swelling ratios are disclosed to calculate the adding volume of the catalyst and protect equipment on the one hand, and the swelling data of various solvents such as alcohols or aromatic hydrocarbons on the other hand, because the catalyst must be treated by the solvents to ensure the performance of the catalyst, and in the process of treating the catalyst by the solvents, different swelling ratios require different adding amounts of the treated catalyst, otherwise, the equipment can be damaged by swelling.
In the production process, before the disproportionation reaction, firstly, in a disproportionation reactor, after a catalyst is filled (the filling amount is determined by combining the expansion rate in each solvent), hot nitrogen (70-80 ℃) is used for drying resin, after 24 hours, 99.5 wt% alcohol solution (such as ethanol solution) is added, and after 24 hours, hot nitrogen is used for drying; adding 99.5 wt% alcohol solution, blowing with hot nitrogen after 24 hr, and repeating the above steps for three times until the water content in alcohol is lower than 500 ppm; and then adding an analytically pure aromatic hydrocarbon solution (such as benzene) into the resin, blowing the solution by hot nitrogen after 24 hours, then adding the analytically pure aromatic hydrocarbon solution, blowing the solution by hot nitrogen after 24 hours, and repeating the cycle for three times to detect that the alcohol content in the aromatic hydrocarbon is less than 0.3 wt% so as to introduce chlorosilane.
The chlorosilane dust removal tower is a plate tower, and a reboiler of the chlorosilane dust removal tower is a kettle-type reboiler, so that the chlorosilane dust removal tower is convenient to overhaul and take out. The invention uses two sets of plate towers for dust removal, and the complexing agent is easy to form solid high polymers with metal chlorides such as ferric chloride and the like after the complexing agent is added into materials, and the blockage of equipment or a pipeline is easy to cause when the conventional packed tower is adopted for separation.
The No. 1 separating tower is a packed tower and is mainly used for separating DCS, TCS and STC. The No. 2 separating tower, the DCS light-removing tower, the DCS heavy-removing tower, the No. 3 separating tower, the TCS light-removing tower, the TCS heavy-removing tower, the STC light-removing tower and the STC heavy-removing tower are all packed towers.
In the anti-disproportionation reactor, the DCS discharged from the inside and the outside of the rectification system is converted into the TCS by the STC with common quality, the cost for treating the DCS is saved, the safety risk in the DCS treatment process is avoided, and the produced TCS can be used for photovoltaic or cyclic utilization.
By adopting the production method, the electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride products which are finally obtained are detected, and the results are as follows:
the detection result of the electronic-grade dichlorosilane is as follows:
| item | Unit of | Index (I) | Item | Unit of | Index (I) |
| Purity of | vol％ | ≥99.99 | Aluminium | ppbw | ≤0.1 |
| Other chlorosilanes | ppmw | ≤1000 | Calcium carbonate | ppbw | ≤0.1 |
| Carbon (C) | ppmw | ≤1 | Cobalt | ppbw | ≤0.1 |
| Phosphorus + arsenic | ppba | ≤0.03 | Copper (Cu) | ppbw | ≤0.1 |
| Boron + aluminum | ppba | ≤0.01 | Resistivity of | Ω.cm | ≥1000 |
| Iron | ppbw | ≤0.1 | Monochloro-hydrosilicon | vol％ | ≤0.01 |
| Nickel (II) | ppbw | ≤0.1 | Trichlorosilane | vol％ | ≤0.001 |
| Chromium (III) | ppbw | ≤0.1 | Silicon tetrachloride | vol％ | ≤0.001 |
The detection result of the electronic grade trichlorosilane is as follows:
| item | Unit of | Index (I) | Item | Unit of | Index (I) |
| Purity of | wt％ | ≥99.999 | Aluminium | ppbw | ≤0.1 |
| Other chlorosilanes | ppmw | ≤100 | Calcium carbonate | ppbw | ≤0.1 |
| Carbon (C) | ppmw | ≤1 | Cobalt | ppbw | ≤0.1 |
| Phosphorus + arsenic | ppba | ≤0.03 | Copper (Cu) | ppbw | ≤0.1 |
| Boron + aluminum | ppba | ≤0.01 | Resistivity of | Ω.cm | ≥500 |
| Iron | ppbw | ≤0.1 | Monochloro-hydrosilicon | wt％ | ≤0.001 |
| Nickel (II) | ppbw | ≤0.1 | Dichlorosilane | wt％ | ≤0.01 |
| Chromium (III) | ppbw | ≤0.1 | Silicon tetrachloride | wt％ | ≤0.01 |
The detection result of the electronic grade silicon tetrachloride is as follows:
| item | Unit of | Index (I) | Item | Unit of | Index (I) |
| Purity of | wt％ | ≥99.999 | Aluminium | ppbw | ≤0.1 |
| Other chlorosilanes | ppmw | ≤100 | Calcium carbonate | ppbw | ≤0.1 |
| Carbon (C) | ppmw | ≤1 | Cobalt | ppbw | ≤0.1 |
| Phosphorus + arsenic | ppba | ≤0.03 | Copper (Cu) | ppbw | ≤0.1 |
| Boron + aluminum | ppba | ≤0.01 | Resistivity of | Ω.cm | ≥1000 |
| Iron | ppbw | ≤0.1 | Monochloro-hydrosilicon | wt％ | ≤0.001 |
| Nickel (II) | ppbw | ≤0.1 | Dichlorosilane | wt％ | ≤0.001 |
| Chromium (III) | ppbw | ≤0.1 | Trichlorosilane | wt％ | ≤0.01 |
The electronic-grade dichlorosilane, the electronic-grade trichlorosilane and the electronic-grade silicon tetrachloride produced by the method can meet the requirements of modern large-scale integrated circuits, and both metal impurities of products and donor-acceptor impurities and other chlorosilane impurities of semiconductors can meet the requirements of electronic grade. The intrinsic resistivity of the epitaxial film grown by using the electronic-grade chlorosilane produced by the method can completely or even far exceed the requirement of the semiconductor industry. By utilizing the production method, the yield of the finished product electronic-grade dichlorosilane can reach about 6 percent, the yield of the finished product electronic-grade trichlorosilane can reach about 25 percent and the yield of the finished product electronic-grade silicon tetrachloride can reach about 8 percent by calculation according to the conservation of the used materials. The intrinsic resistivity of the epitaxial film finally produced by the produced electronic-grade dichlorosilane can reach 3000 omega cm, and no byproduct dichlorosilane with low purity is produced in the production process, because the dichlorosilane discharged by high-boiling and low-boiling points in the production process is completely treated by the final anti-disproportionation reaction, the obtained trichlorosilane can be recycled as the raw material of the invention; the byproduct discharged by high-boiling and low-boiling points in the production process of the invention also contains a mixture containing trichlorosilane and silicon tetrachloride, after the rectification separation step of the invention, the produced trichlorosilane can be used as the raw material of photovoltaic polysilicon, and the produced silicon tetrachloride can be used for producing nano-scale fumed silica on one hand and can be used as the raw material of optical fiber grade silicon tetrachloride on the other hand.
Furthermore, the terms "first," "second," and the like, as well as "primary," "secondary," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first," "second," etc. and "primary," "secondary," etc. may explicitly or implicitly include at least one of the features.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride is characterized by comprising the following steps:
s1, taking the crude trichlorosilane as a raw material, and carrying out primary dust removal treatment;
s2, performing gas phase adsorption treatment on the trichlorosilane after primary dust removal;
s3, sequentially carrying out primary light component removal treatment and primary heavy component removal treatment on the trichlorosilane after gas phase adsorption;
s4, performing disproportionation reaction on the trichlorosilane after removing the heavy components to obtain a first mixture containing dichlorosilane, trichlorosilane and silicon tetrachloride;
s5, adding a complexing agent into the first mixture, wherein the complexing agent is aromatic aldehyde or an aromatic aldehyde derivative, and the addition amount of the complexing agent is 0.08-0.15 wt% of the first mixture, and performing secondary dust removal treatment;
s6, carrying out primary separation on the first mixture subjected to secondary dust removal to obtain a second mixture containing dichlorosilane and trichlorosilane and a third mixture containing trichlorosilane and silicon tetrachloride;
s7, sequentially carrying out secondary separation treatment, secondary light component removal treatment and secondary heavy component removal treatment on the second mixture to obtain electronic-grade dichlorosilane; and carrying out three times of separation treatment on the third mixture to obtain a fourth mixture containing trichlorosilane and a fifth mixture containing silicon tetrachloride, sequentially carrying out three times of light component removal treatment and three times of heavy component removal treatment on the fourth mixture to obtain electronic grade trichlorosilane, and sequentially carrying out four times of light component removal treatment and four times of heavy component removal treatment on the fifth mixture to obtain electronic grade silicon tetrachloride.
2. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 1, wherein in step S1, the purity of the crude trichlorosilane is 2N, the primary dedusting treatment is performed in a raw material dedusting tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, impurities with boiling points higher than that of the tower top are removed from a tower kettle, and the impurities are extracted from the tower top.
3. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 1, wherein in the step S2, the gas-phase adsorption treatment is performed in an adsorption tower by adopting a molecular sieve for adsorption, the tower pressure is 0.2-0.4MPa, and the tower top temperature is 90 ℃.
4. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 1, wherein in step S3, the primary light component removal treatment is carried out in a raw material light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the light component is discharged from the tower top, and the light component is extracted from the tower kettle; the primary heavy component removal treatment is carried out in a raw material heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the tower bottom is discharged outside, and the tower top is extracted.
5. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 1, wherein in the step S4, the disproportionation reaction is carried out in a disproportionation reactor, the pressure of the disproportionation reactor is 0.2-0.3MPa, and the reaction temperature is 60-70 ℃; the disproportionation reactor is a double-tube-plate tube type heat exchanger, water is used in the tube pass, trichlorosilane after heavy components are removed in the shell pass, and macroporous weak-base anion exchange resin A21 with tertiary amino on the surface and the water content of less than 0.3 percent is added as a catalyst; the first mixture comprises 6-7 wt% of dichlorosilane, 80-81 wt% of trichlorosilane and 11-12 wt% of silicon tetrachloride.
6. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 1, wherein the step of adding the complexing agent is performed in a chlorosilane intermediate tank in step S5; the secondary dust removal treatment is carried out in a chlorosilane dust removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 70-95 ℃, impurities with boiling points higher than the tower top temperature are removed in a tower kettle, and the tower top is extracted.
7. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to any one of claims 1 to 6, wherein in the step S6, the primary separation is performed in a No. 1 separation tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 53-73 ℃, the second mixture is extracted from the tower top, and the third mixture is extracted from the tower bottom.
8. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 7 is characterized in that in step S7, the secondary separation treatment is carried out in a No. 2 separation tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the tower bottom is discharged outside, and the tower top is extracted; the secondary light component removal treatment is carried out in a DCS light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the light component is discharged from the tower top, and the light component is extracted from a tower kettle; the secondary heavy component removal treatment is carried out in a DCS heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 41-60 ℃, the tower bottom is discharged, and electronic-grade dichlorosilane is extracted from the tower top.
9. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 8 is characterized in that materials discharged from the top of a DCS lightness-removing tower and materials discharged from the bottom of a DCS heaving tower are pumped into a reverse disproportionation reactor, crude silicon tetrachloride with the weight 10 times that of the materials is added into the reverse disproportionation reactor, and the materials are subjected to reverse disproportionation reaction under the action of a catalyst to obtain trichlorosilane which is reused as a raw material in the step S1; the pressure of the reverse disproportionation reactor is 0.5MPa, and the temperature is 70 ℃.
10. The method for simultaneously producing electronic-grade dichlorosilane, electronic-grade trichlorosilane and electronic-grade silicon tetrachloride according to claim 7 is characterized in that in step S7, the third separation treatment is performed in a No. 3 separation tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, a fourth mixture is extracted from the tower top, and a fifth mixture is extracted from the tower kettle; the third light component removal treatment is carried out in a TCS light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the light component is discharged from the tower top, and the light component is extracted from the tower kettle; the third heavy component removal treatment is carried out in a TCS heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 68-87 ℃, the tower bottom is discharged outside, and electronic-grade trichlorosilane is extracted from the tower top; the fourth light component removal treatment is carried out in an STC light component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 95-117 ℃, the light component is discharged from the tower top, and the light component is extracted from a tower kettle; the four heavy component removal treatments are carried out in an STC heavy component removal tower, the tower pressure is 0.2-0.4MPa, the tower top temperature is 95-117 ℃, the heavy component is discharged from the tower kettle, and electronic grade silicon tetrachloride is collected from the tower top.
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| CN110963494B (en) * | 2019-12-13 | 2023-04-07 | 内蒙古兴洋科技股份有限公司 | System and method for preparing silane |
| CN111548364A (en) * | 2020-05-22 | 2020-08-18 | 江西宏柏新材料股份有限公司 | Synthesis method and device of phenyl chlorosilane |
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