CN117861251A - Device and method for producing high-purity silane from trichlorosilane - Google Patents
Device and method for producing high-purity silane from trichlorosilane Download PDFInfo
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- CN117861251A CN117861251A CN202311843542.0A CN202311843542A CN117861251A CN 117861251 A CN117861251 A CN 117861251A CN 202311843542 A CN202311843542 A CN 202311843542A CN 117861251 A CN117861251 A CN 117861251A
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 81
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 182
- 239000007791 liquid phase Substances 0.000 claims abstract description 33
- 238000009833 condensation Methods 0.000 claims abstract description 26
- 230000005494 condensation Effects 0.000 claims abstract description 26
- 238000007323 disproportionation reaction Methods 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 14
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 12
- 239000005049 silicon tetrachloride Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000066 reactive distillation Methods 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000005046 Chlorosilane Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- -1 machinery Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention discloses a device for producing high-purity silane by trichlorosilane, which comprises a reaction rectifying tower, an auxiliary reaction system, a multi-stage condensation system, a booster pump and a rectifying system, wherein the auxiliary reaction system is connected with the side line of the reaction rectifying tower in a drawing way, a feed inlet of the multi-stage condensation system is connected with the top of the reaction rectifying tower, and a liquid phase discharge port of the multi-stage condensation system is connected with the reaction rectifying tower; the invention also discloses a method for producing high-purity silane by using the device. The method has the advantages of low energy consumption, high reaction efficiency, safety, environmental protection and high product purity.
Description
Technical Field
The invention relates to the technical field of silane, in particular to a device and a method for producing high-purity silane from trichlorosilane.
Background
Silane, also known as monosilane, silane, tetrahydrosilane, amorphous semiconductor amorphous silicon, has become the most predominant specialty gas used in semiconductor microelectronics processes for the preparation of various microelectronic films including monocrystalline films, crystallites, polycrystals, silicon oxide, silicon nitride, metal silicides, and the like. The use of silanes as silicon-containing films and coatings has expanded from the traditional microelectronics industry to various fields of steel, machinery, chemical and optics. Silane has a potential application in the manufacture of high performance ceramic engine parts, particularly in the manufacture of silicides (Si 3 N 4 SiC, etc.) micropowder technology is becoming more and more important.
The main preparation methods of silane can be classified into a silicon-magnesium alloy method, a sodium aluminum hydride method, a Trichlorosilane (TCS) disproportionation method, and the like. Wherein the trichlorosilane disproportionation method is developed by united states carbide corporation (UCC corporation). The main process comprises the steps of carrying out hydrogenation reaction on Silicon Tetrachloride (STC) to generate trichlorosilane, then carrying out disproportionation reaction on the trichlorosilane to generate Dichlorosilane (DCS), and carrying out disproportionation reaction on the dichlorosilane again to generate silane. The disproportionation reaction is carried out in the tower reactor, which is very suitable for large-scale production, and has high production efficiency and low cost. The reaction product and the silane are easy to separate, high-purity silane can be obtained, the reaction condition is mild, the energy consumption is low, the operation and the control are easy, and the method becomes a main stream method for producing the silane.
For example, CN103172071B discloses a device and a method for preparing high-purity silane by disproportionation reaction and rectification of trichlorosilane, which are formed by connecting a disproportionation reaction and rectification process, a silicon tetrachloride absorption process, a fixed bed absorption process and a product canning process; the mixed gas of silane and dichlorosilane is finally obtained at the top of the tower by using two-step disproportionation reaction and utilizing the rectification separation function of a reactive rectification tower, and the high-purity silane product is obtained through the subsequent separation procedures of absorption, adsorption and the like.
As another example, CN106241813B discloses a system and method for producing high purity silane from trichlorosilane, comprising a reaction column, a multistage condenser, a compressor, a light ends removal column and a product column. The characteristic of larger boiling point difference between silane and other components in a reaction system is utilized, a multistage condenser is adopted to replace a rectifying section at the upper part of a reaction tower in the prior art, the height of the reaction tower is reduced, and the equipment investment is saved; the multistage condenser is matched with cold sources with different temperatures and tastes, so that gas phase from the reaction tower is subjected to multistage partial condensation, the cryogenic load is reduced, and the operation cost and the energy consumption are effectively reduced.
As another example, CN218620354U discloses a device for producing high-purity silane from ten thousand tons of trichlorosilane, which at least comprises a reactive rectifying tower, a condensing system, a silane rectifying tower and a condensing and pressurizing system; the device reasonably utilizes the cold source, adopts a multi-stage condensing system to perform condensation heat exchange for multiple times, gradually increases the grade of the cold source, gradually reduces the flow of cooled crude silane, gradually increases the purity, ensures that the power of the high-grade cold source at low temperature reaches the minimum value, and improves the energy utilization rate.
As another example, CN103241743B discloses a reactive distillation method and apparatus for preparing silane by directly disproportionating trichlorosilane, which is formed by connecting a trichlorosilane baffle rectifying tower, a disproportionation rectifying tower, a silane purifying tower and a silicon tetrachloride separating tower. The invention realizes one-step disproportionation reaction in one reaction rectifying tower, simplifies equipment, simultaneously avoids a large amount of material separation and circulation reaction, shortens the flow, saves energy and reduces consumption, and ensures that the purity of the silane product is higher.
The above patents all adopt reaction rectifying towers as reactors, but the temperature of the upper part of the reaction rectifying towers is lower than the temperature of the lower part of the reaction rectifying towers due to different temperatures in the towers, so that the temperature of the reaction sections of the reaction rectifying towers is inconsistent, the temperature of the lower parts of the reaction sections is high, the temperature of the upper parts of the reaction sections is low, the catalyst efficiency in a low-temperature area is low, the disproportionation reaction is incomplete, and the reaction conversion rate is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a device and a method for producing high-purity silane by using trichlorosilane, which take the trichlorosilane as a raw material and prepare the high-purity silane by utilizing a reaction rectification technology. The method has the characteristics of low energy consumption, high reaction efficiency, safety, environmental protection, high product purity and the like.
In order to solve the technical problems, the invention adopts the following technical scheme: the device for producing high-purity silane by trichlorosilane comprises a reaction rectifying tower, an auxiliary reaction system, a multi-stage condensation system, a booster pump and a rectifying system, wherein a side line of the reaction rectifying tower is connected with the auxiliary reaction system, a feed inlet of the multi-stage condensation system is connected with the top of the reaction rectifying tower, and a liquid phase discharge outlet of the multi-stage condensation system is connected with the reaction rectifying tower; the discharge port of the multistage condensing system is connected with the feed port of the booster pump, and the discharge port of the booster pump is connected with the rectification system.
As a preferred embodiment of the invention, the reaction rectifying tower consists of a rectifying section, a reaction section and a stripping section, wherein the rectifying section is arranged at the upper part of the reaction rectifying tower, the reaction section is arranged at the middle part of the reaction rectifying tower, and the stripping section is arranged at the lower part of the reaction rectifying tower; the reaction section is provided with a disproportionation catalyst, and the rectifying section and the stripping section are provided with fractionation filler; the bottom of the reaction rectifying tower is provided with a reaction rectifying tower reboiler, and trichlorosilane raw materials enter the reaction rectifying tower from the reaction section.
As a preferred embodiment of the invention, the auxiliary reaction system comprises a pump, a primary heat exchanger, a secondary heat exchanger and an auxiliary reactor which are sequentially connected in series, wherein a measuring line extraction outlet of the reaction rectifying tower is connected with a feed inlet of the pump, a discharge outlet of the auxiliary reactor is connected with the middle part of the reaction rectifying tower through the primary heat exchanger, and a reaction product of the auxiliary reactor enters the reaction rectifying tower after exchanging heat with the primary heat exchanger.
As a preferred embodiment of the invention, the auxiliary reaction system comprises a condenser, a storage tank, a pump, a primary heat exchanger, a secondary heat exchanger and an auxiliary reactor which are sequentially connected in series, wherein a line sampling outlet of the reaction rectifying tower is connected with a feed inlet of the condenser, a discharge outlet of the auxiliary reactor is connected with the middle part of the reaction rectifying tower through the primary heat exchanger, and a reaction product of the auxiliary reactor enters the reaction rectifying tower after exchanging heat with the primary heat exchanger.
As a preferred embodiment of the invention, the multistage condensing system comprises a first-stage condenser, a second-stage condenser, a third-stage condenser, an economizer and a chiller which are sequentially connected in series, wherein a gas-phase feed port of the first-stage condenser is connected with the top of the reactive distillation column, a liquid-phase discharge port of the first-stage condenser, the second-stage condenser and the third-stage condenser is connected with the upper part of the reactive distillation column, a discharge port of the chiller is connected with a feed port of a booster pump, a discharge port of the booster pump is connected with the rectification system through the economizer, and materials subjected to pressure boosting by the booster pump enter the rectification system after heat exchange with the economizer.
As a preferred embodiment of the invention, the rectification system comprises a first rectification tower and a second rectification tower, wherein the top of the first rectification tower is provided with a first rectification tower condenser, and the bottom of the first rectification tower is provided with a first rectification tower reboiler; the top of the second rectifying tower is provided with a second rectifying tower condenser, and the bottom of the second rectifying tower is provided with a second rectifying tower reboiler; the bottom of the second rectifying tower is connected with the discharge port of the primary heat exchanger in parallel.
The invention also provides a method for producing high-purity silane by using the device, which comprises the following steps:
(1) Introducing trichlorosilane into the reaction rectifying tower, performing disproportionation reaction, rectifying and purifying to obtain crude silane at the tower top, and extracting liquid silicon tetrachloride at the tower bottom; feeding the materials extracted from the side line of the reaction section of the reactive rectifying tower into the auxiliary reactor for further reaction and returning the materials to the reactive rectifying tower;
(2) Feeding the crude silane obtained from the top of the reactive rectifying tower into the condensing system to obtain condensate and liquid-phase crude silane, and refluxing the condensate to the reactive rectifying tower to continue disproportionation reaction;
(3) And (3) feeding the liquid-phase crude silane obtained in the step (2) into the booster pump, and feeding the boosted liquid-phase crude silane into the rectification system for purification to obtain a high-purity silane product.
As a preferred embodiment of the present invention, the pressure of the reactive distillation column is 0.3-0.8 MPa and the temperature is 50-160 ℃.
As a preferred embodiment of the present invention, the reaction temperature of the auxiliary reaction system is 80-180 ℃ and the pressure is 1.0-3.0 MPa.
As a preferable embodiment of the invention, the pressure of the booster pump is 1.5-5.0 MPa; the pressure of the rectification system is 1.5-4.0 MPa, and the temperature is-20-90 ℃.
Aiming at the problems of incomplete disproportionation reaction and low reaction conversion rate caused by the low temperature of the catalyst in a low temperature area due to the fact that the temperature in the reaction rectifying tower is different, the temperature in the upper part is lower than the temperature in the lower part, which results in inconsistent temperature of a reaction section of the reaction rectifying tower, the temperature in the lower part of the reaction section is high, the temperature in the upper part of the reaction section is low, and the disproportionation reaction is easier to perform by conveniently regulating and controlling the reaction temperature through optimizing a production device; meanwhile, the load of the reaction rectifying tower is reduced, the utilization rate of the catalyst is further improved, and the problem of low-temperature efficiency is well solved. In addition, the auxiliary reaction system is adopted, so that the height of the reaction rectifying tower is effectively reduced, and the equipment investment cost is saved. In actual production, the side extraction of the reactive rectifying tower can be gas phase or liquid phase or gas-liquid phase mixed extraction, the gas phase or gas-liquid phase mixed extraction is stored in a storage tank after being condensed by a condenser, and then enters an auxiliary reactor after being subjected to heat exchange by a pump, a primary heat exchanger and a secondary heat exchanger in sequence. The liquid phase extraction can be directly pumped or stored in a storage tank. The number and size of the condensers and the storage tanks can be set according to actual production requirements.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages that the reaction efficiency is high, the product quality is good, and the auxiliary reaction system is arranged by optimizing the production device, so that the disproportionation reaction can be more easily carried out by conveniently regulating and controlling the reaction temperature, the occurrence of side reaction is reduced, the reaction efficiency and the product quality are obviously improved, and the product purity can reach 99.9999%; meanwhile, the load of the reaction rectifying tower is reduced, the utilization rate of the catalyst is further improved, and the problem of low-temperature efficiency is well solved.
2. The invention has low energy consumption, the cold source is reasonably utilized by arranging the multi-stage condensation system, the multi-stage condensation system is utilized for carrying out condensation heat exchange for multiple times, the grade of the cold source is gradually increased, the flow of the cooled crude silane is gradually reduced, the purity is gradually increased, the power of the high-grade cold source at the low temperature reaches the minimum value, and the energy utilization rate is obviously improved; the discharge port of the auxiliary reactor is connected with the middle part of the reaction rectifying tower through a primary heat exchanger, so that heat is effectively recovered; the discharge port of the booster pump is connected with the rectification system through the economizer, so that the material cooled by the refrigerator can be used as a cold source of the economizer, and the energy consumption is further reduced.
3. The invention has the advantages of low investment and low cost, and the auxiliary reaction system is arranged by optimizing the production device, so that the height of the reaction rectifying tower is effectively reduced, and the equipment investment cost is saved.
4. The method is safe and environment-friendly, and the reaction temperature can be conveniently and fast regulated and controlled by arranging the auxiliary reaction system, so that the disproportionation reaction is stably carried out, and the safety of the reaction is greatly improved; the bottom of the second rectifying tower is connected with the discharge port of the primary heat exchanger in parallel, so that heavy components in the bottom of the second rectifying tower can be returned to the auxiliary reactor for recycling, the three wastes discharge is effectively reduced, and the production cost is reduced.
Drawings
FIG. 1 is a schematic view of an apparatus according to example 1 of the present invention;
FIG. 2 is a schematic view of the apparatus of example 2 of the present invention;
fig. 3 is a schematic view of the apparatus of example 3 of the present invention.
Wherein: 1 represents a reactive rectifying tower, 2 represents an auxiliary reactor, 3 represents a first rectifying tower, 4 represents a second rectifying tower, 5 represents a primary condenser, 6 represents a secondary condenser, 7 represents a tertiary condenser, 8 represents an economizer, 9 represents a cryogenic, 10 represents a booster pump, 11 represents a first rectifying tower condenser, 12 represents a second rectifying tower condenser, 13 represents a reactive rectifying tower reboiler, 14 represents a first rectifying tower reboiler, 15 represents a second rectifying tower reboiler, 16 represents a secondary heat exchanger, 17 represents a primary heat exchanger, 18 represents a pump, 19 represents a storage tank, and 20 represents a condenser.
Detailed Description
The technical scheme of the invention is clearly and completely described below with reference to the accompanying drawings and examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1, a device for producing high-purity silane from trichlorosilane comprises a reaction rectifying tower 1, an auxiliary reaction system, a multi-stage condensation system, a booster pump 10 and a rectifying system; the auxiliary reaction system comprises a pump 18, a primary heat exchanger 17, a secondary heat exchanger 16 and an auxiliary reactor 2 which are sequentially connected in series; the multistage condensation system comprises a first-stage condenser 5, a second-stage condenser 6, a third-stage condenser 7, an economizer 8 and a chiller 9 which are sequentially connected in series; the rectification system comprises a first rectification tower 3 and a second rectification tower 4, wherein a first rectification tower condenser 11 is arranged at the top of the first rectification tower 3, and a first rectification tower reboiler 14 is arranged at the bottom of the first rectification tower; the top of the second rectifying tower 4 is provided with a second rectifying tower condenser 12, and the bottom of the second rectifying tower is provided with a second rectifying tower reboiler 15; the upper part of the reaction rectifying tower 1 is provided with a rectifying section, the middle part is provided with a reaction section, the lower part is provided with a stripping section, the reaction section is filled with four sections of disproportionation reaction catalysts (alkaline anion exchange resin), the rectifying section and the stripping section are filled with fractionation fillers (structured fillers), unreacted chlorosilane can be recovered in the rectifying section, TCS and STC can be primarily separated in the stripping section, the bottom of the reaction rectifying tower 1 is provided with a reaction rectifying tower reboiler 13, and trichlorosilane raw materials enter the reaction rectifying tower 1 from the middle reaction section; the middle part of the reaction rectifying tower 1 is provided with a side-draw outlet for extracting a liquid phase reaction mixture, the side-draw outlet of the reaction rectifying tower 1 is connected with a feed inlet of a pump 18, a discharge outlet of the auxiliary reactor 2 is connected with a reaction section of the reaction rectifying tower 1 through a primary heat exchanger 17, and a reaction product of the auxiliary reactor 2 enters a reaction section of the reaction rectifying tower 1 for continuous reaction after exchanging heat with the primary heat exchanger 17; the gas phase feed inlet of the first-stage condenser 5 is connected with the top gas phase discharge outlet of the reactive rectifying tower 1, the liquid phase discharge outlets of the first-stage condenser 5, the second-stage condenser 6 and the third-stage condenser 7 are respectively connected with the upper condensate reflux inlet of the reactive rectifying tower 1, and the discharge outlet of the chiller 9 is connected with the feed inlet of the booster pump 10; a discharge port of the booster pump 10 is connected with a middle feed port of the first rectifying tower 3 through an economizer 8, a material subjected to pressure boosting by the booster pump 10 is subjected to heat exchange with the economizer 8 and then enters the first rectifying tower 3 for separation, and the economizer 8 is subjected to heat exchange by taking the material cooled by the chiller 9 as a cold source; the tower bottom liquid discharge port of the second rectifying tower 4 is connected in parallel with the discharge port of the primary heat exchanger 17.
The technological process for producing high-purity silane by using the device comprises the following steps:
(1) Introducing trichlorosilane into a reaction rectifying tower from a middle reaction section, performing disproportionation reaction, rectifying and purifying to obtain crude silane at the tower top, and extracting liquid silicon tetrachloride at the tower bottom; the liquid phase material extracted from the side line of the reaction section of the reactive rectifying tower is preheated by a primary heat exchanger and a secondary heat exchanger and then is introduced into an auxiliary reactor for further reaction, and the product obtained by the reaction is returned to the reaction section of the reactive rectifying tower after heat exchange and heat recovery of the primary heat exchanger;
(2) The crude silane obtained from the top of the reactive rectifying tower is cooled by a first-stage condenser, a second-stage condenser and a third-stage condenser in sequence to obtain condensate liquid and gas-phase crude silane containing unreacted trichlorosilane, dichlorosilane and trichlorosilane (MCS) products, and the condensate liquid flows back to the reactive rectifying tower to continue disproportionation reaction;
(3) Sequentially feeding the gas-phase crude silane obtained by condensation in the step (2) into an economizer and a cryocooler, and obtaining liquid-phase crude silane after condensation;
(4) Feeding the liquid phase crude silane obtained in the step (3) into a booster pump, pressurizing, feeding the booster pump into a first rectifying tower for rectifying, discharging light component impurities from the top of the first rectifying tower, feeding the light component impurities into a second rectifying tower for rectifying, wherein the first rectifying tower bottom is a liquid phase after light removal; and (3) returning heavy components (TCS, DCS, MCS mixture) separated from the bottom of the second rectifying tower to the auxiliary reactor, and obtaining a high-purity silane product at the top of the tower.
The technological parameters are controlled as follows:
the temperature of the reaction rectifying tower is controlled to be 50 ℃, and the pressure is controlled to be 0.3MPa;
the temperature of the auxiliary reactor is controlled to be 80 ℃ and the pressure is controlled to be 1.0MPa;
the operation pressure of the first rectifying tower is 1.5MPa, the temperature of the top of the tower is-20 ℃, and the temperature of the bottom of the tower is 20 ℃;
the operating pressure of the second rectifying tower is 1.5MPa, the temperature of the top of the tower is-20 ℃, and the temperature of the bottom of the tower is 20 ℃.
Results: the reaction process is stable and controllable, and the high-purity silane product with the purity of 99.9999 percent is obtained
Example 2
As shown in fig. 2, a device for producing high-purity silane from trichlorosilane comprises a reaction rectifying tower 1, an auxiliary reaction system, a multi-stage condensation system, a booster pump 10 and a rectifying system; the auxiliary reaction system comprises a condenser 20, a storage tank 19, a pump 18, a primary heat exchanger 17, a secondary heat exchanger 16 and an auxiliary reactor 2 which are sequentially connected in series; the multistage condensation system comprises a first-stage condenser 5, a second-stage condenser 6, a third-stage condenser 7, an economizer 8 and a chiller 9 which are sequentially connected in series; the rectification system comprises a first rectification tower 3 and a second rectification tower 4, wherein a first rectification tower condenser 11 is arranged at the top of the first rectification tower 3, and a first rectification tower reboiler 14 is arranged at the bottom of the first rectification tower; the top of the second rectifying tower 4 is provided with a second rectifying tower condenser 12, and the bottom of the second rectifying tower is provided with a second rectifying tower reboiler 15; the upper part of the reaction rectifying tower 1 is provided with a rectifying section, the middle part is provided with a reaction section, the lower part is provided with a stripping section, the reaction section is filled with four sections of disproportionation reaction catalysts (alkaline anion exchange resin), the rectifying section and the stripping section are filled with fractionation fillers (structured fillers), unreacted chlorosilane can be recovered in the rectifying section, TCS and STC can be primarily separated in the stripping section, the bottom of the reaction rectifying tower 1 is provided with a reaction rectifying tower reboiler 13, and trichlorosilane raw materials enter the reaction rectifying tower 1 from the reaction section; the reaction rectifying tower 1 is provided with a side-draw outlet for extracting gas phase reaction mixture, the side-draw outlet of the reaction rectifying tower 1 is connected with the feed inlet of the condenser 20, the discharge outlet of the auxiliary reactor 2 is connected with the reaction section of the reaction rectifying tower 1 through the primary heat exchanger 17, and the reaction product of the auxiliary reactor 2 enters the reaction section of the reaction rectifying tower 1 for continuous reaction after exchanging heat with the primary heat exchanger 17; the gas phase feed inlet of the first-stage condenser 5 is connected with the top gas phase discharge outlet of the reactive rectifying tower 1, the liquid phase discharge outlets of the first-stage condenser 5, the second-stage condenser 6 and the third-stage condenser 7 are respectively connected with the upper condensate reflux inlet of the reactive rectifying tower 1, and the discharge outlet of the chiller 9 is connected with the feed inlet of the booster pump 10; a discharge port of the booster pump 10 is connected with a middle feed port of the first rectifying tower 3 through an economizer 8, a material subjected to pressure boosting by the booster pump 10 is subjected to heat exchange with the economizer 8 and then enters the first rectifying tower 3 for separation, and the economizer 8 is subjected to heat exchange by taking the material cooled by the chiller 9 as a cold source; the tower bottom liquid discharge port of the second rectifying tower 4 is connected in parallel with the discharge port of the primary heat exchanger 17.
The technological process for producing high-purity silane by using the device comprises the following steps:
(1) Introducing trichlorosilane into a reaction rectifying tower from a middle reaction section, performing disproportionation reaction, rectifying and purifying to obtain crude silane at the tower top, and extracting liquid silicon tetrachloride at the tower bottom; the gas phase material extracted from the side line of the reaction section of the reactive rectifying tower is cooled into a liquid phase through a condenser, preheated by a primary heat exchanger and a secondary heat exchanger and then introduced into an auxiliary reactor for further reaction, and a product obtained by the reaction is returned to the reaction section of the reactive rectifying tower after heat exchange and heat recovery of the primary heat exchanger;
(2) The crude silane obtained from the top of the reactive rectifying tower is cooled by a first-stage condenser, a second-stage condenser and a third-stage condenser in sequence to obtain condensate liquid and gas-phase crude silane containing unreacted trichlorosilane, dichlorosilane and trichlorosilane (MCS) products, and the condensate liquid flows back to the reactive rectifying tower to continue disproportionation reaction;
(3) Sequentially feeding the gas-phase crude silane obtained by condensation in the step (2) into an economizer and a cryocooler, and obtaining liquid-phase crude silane after condensation;
(4) Feeding the liquid phase crude silane obtained in the step (3) into a booster pump, pressurizing, feeding the booster pump into a first rectifying tower for rectifying, discharging light component impurities from the top of the first rectifying tower, feeding the light component impurities into a second rectifying tower for rectifying, wherein the first rectifying tower bottom is a liquid phase after light removal; and (3) returning heavy components (TCS, DCS, MCS mixture) separated from the bottom of the second rectifying tower to the auxiliary reactor, and obtaining a high-purity silane product at the top of the tower.
The technological parameters are as follows:
the temperature of the reaction rectifying tower is controlled to be 100 ℃, and the pressure is controlled to be 0.5MPa;
the temperature of the auxiliary reactor is controlled to be 120 ℃, and the pressure is controlled to be 2.0MPa;
the operating pressure of the first rectifying tower is 2.5MPa, the temperature of the top of the tower is-50 ℃, and the temperature of the bottom of the tower is 50 ℃;
the operating pressure of the second rectifying tower is 2.5MPa, the temperature of the top of the tower is-50 ℃, and the temperature of the bottom of the tower is 50 ℃.
Results: the reaction process is stable and controllable, and the high-purity silane product with the purity of 99.9999 percent is obtained.
Example 3
As shown in fig. 3, a device for producing high-purity silane from trichlorosilane comprises a reaction rectifying tower 1, an auxiliary reaction system, a multi-stage condensation system, a booster pump 10 and a rectifying system; the auxiliary reaction system comprises a condenser 20, a storage tank 19, a pump 18, a primary heat exchanger 17, a secondary heat exchanger 16 and an auxiliary reactor 2 which are sequentially connected in series; the multistage condensation system comprises a first-stage condenser 5, a second-stage condenser 6, a third-stage condenser 7, an economizer 8 and a chiller 9 which are sequentially connected in series; the rectification system comprises a first rectification tower 3 and a second rectification tower 4, wherein a first rectification tower condenser 11 is arranged at the top of the first rectification tower 3, and a first rectification tower reboiler 14 is arranged at the bottom of the first rectification tower; the top of the second rectifying tower 4 is provided with a second rectifying tower condenser 12, and the bottom of the second rectifying tower is provided with a second rectifying tower reboiler 15; the upper part of the reaction rectifying tower 1 is provided with a rectifying section, the middle part is provided with a reaction section, the lower part is provided with a stripping section, the reaction section is filled with four sections of disproportionation reaction catalysts (alkaline anion exchange resin), the rectifying section and the stripping section are filled with fractionation fillers (structured fillers), unreacted chlorosilane can be recovered in the rectifying section, TCS and STC can be primarily separated in the stripping section, the bottom of the reaction rectifying tower 1 is provided with a reaction rectifying tower reboiler 13, and trichlorosilane raw materials enter the reaction rectifying tower 1 from the reaction section; the reaction rectifying tower 1 is provided with a first side line outlet and a second side line outlet, the first side line outlet is used for collecting a gas phase reaction mixture, the second side line outlet is used for collecting a liquid phase reaction mixture, the first side line outlet is connected with a feed inlet of the condenser 20, the second side line outlet is connected with a middle feed inlet of the storage tank 19, a discharge port of the auxiliary reactor 2 is connected with a reaction section of the reaction rectifying tower 1 through the primary heat exchanger 17, and a reaction product of the auxiliary reactor 2 enters the reaction section of the reaction rectifying tower 1 for continuous reaction after heat exchange with the primary heat exchanger 17; the gas phase feed inlet of the first-stage condenser 5 is connected with the top gas phase discharge outlet of the reactive rectifying tower 1, the liquid phase discharge outlets of the first-stage condenser 5, the second-stage condenser 6 and the third-stage condenser 7 are respectively connected with the upper condensate reflux inlet of the reactive rectifying tower 1, and the discharge outlet of the chiller 9 is connected with the feed inlet of the booster pump 10; a discharge port of the booster pump 10 is connected with a middle feed port of the first rectifying tower 3 through an economizer 8, a material subjected to pressure boosting by the booster pump 10 is subjected to heat exchange with the economizer 8 and then enters the first rectifying tower 3 for separation, and the economizer 8 is subjected to heat exchange by taking the material cooled by the chiller 9 as a cold source; the tower bottom liquid discharge port of the second rectifying tower 4 is connected in parallel with the discharge port of the primary heat exchanger 17.
The technological process for producing high-purity silane by using the device comprises the following steps:
(1) Introducing trichlorosilane into a reaction rectifying tower from a middle reaction section, performing disproportionation reaction, rectifying and purifying to obtain crude silane at the tower top, and extracting liquid silicon tetrachloride at the tower bottom; the gas phase materials extracted from the first side line extraction port of the reaction section of the reaction rectifying tower are cooled into liquid phase by a condenser and then enter a storage tank, the liquid phase materials extracted from the second side line extraction port of the reaction section of the reaction rectifying tower directly enter the storage tank, the materials in the storage tank are preheated by a primary heat exchanger and a secondary heat exchanger and then are introduced into an auxiliary reactor for further reaction, and the products obtained by the reaction are returned to the reaction section of the reaction rectifying tower after heat exchange and heat recovery of the primary heat exchanger;
(2) The crude silane obtained from the top of the reactive rectifying tower is cooled by a first-stage condenser, a second-stage condenser and a third-stage condenser in sequence to obtain condensate liquid and gas-phase crude silane containing unreacted trichlorosilane, dichlorosilane and trichlorosilane (MCS) products, and the condensate liquid flows back to the reactive rectifying tower to continue disproportionation reaction;
(3) Sequentially feeding the gas-phase crude silane obtained by condensation in the step (2) into an economizer and a cryocooler, and obtaining liquid-phase crude silane after condensation;
(4) Feeding the liquid phase crude silane obtained in the step (3) into a booster pump, pressurizing, feeding the booster pump into a first rectifying tower for rectifying, discharging light component impurities from the top of the first rectifying tower, feeding the light component impurities into a second rectifying tower for rectifying, wherein the first rectifying tower bottom is a liquid phase after light removal; heavy components (TCS, DCS, MCS mixture) separated from the bottom of the second rectifying tower are returned to the auxiliary reactor, and the high-purity silane product is obtained at the top of the tower
The technological parameters are as follows:
the temperature of the reaction rectifying tower is controlled to 160 ℃, and the pressure is controlled to 0.8MPa;
the temperature of the auxiliary reactor is controlled to be 180 ℃ and the pressure is controlled to be 3.0MPa;
the operation pressure of the first rectifying tower is 4MPa, the temperature of the top of the tower is-90 ℃, and the temperature of the bottom of the tower is 90 ℃;
the operating pressure of the second rectifying tower is 4MPa, the temperature of the top of the tower is-90 ℃, and the temperature of the bottom of the tower is 90 ℃.
Results: the reaction process is stable and controllable, and the high-purity silane product with the purity of 99.9999 percent is obtained.
Claims (10)
1. The device for producing the high-purity silane by the trichlorosilane comprises a reaction rectifying tower, an auxiliary reaction system, a multi-stage condensation system, a booster pump and a rectifying system, and is characterized in that a side line of the reaction rectifying tower is connected with the auxiliary reaction system, a feed inlet of the multi-stage condensation system is connected with the top of the reaction rectifying tower, and a liquid phase discharge port of the multi-stage condensation system is connected with the reaction rectifying tower; the discharge port of the multistage condensing system is connected with the feed port of the booster pump, and the discharge port of the booster pump is connected with the rectification system.
2. The device for producing high-purity silane from trichlorosilane according to claim 1, wherein the reaction rectifying tower consists of a rectifying section, a reaction section and a stripping section, wherein the rectifying section is arranged at the upper part of the reaction rectifying tower, the reaction section is arranged at the middle part of the reaction rectifying tower, and the stripping section is arranged at the lower part of the reaction rectifying tower; the reaction section is provided with a disproportionation catalyst, and the rectifying section and the stripping section are provided with fractionation filler; the bottom of the reaction rectifying tower is provided with a reaction rectifying tower reboiler, and trichlorosilane raw materials enter the reaction rectifying tower from the reaction section.
3. The apparatus for producing high purity silane from trichlorosilane according to claim 1, wherein the auxiliary reaction system comprises a pump, a primary heat exchanger, a secondary heat exchanger and an auxiliary reactor which are sequentially connected in series, a line sampling outlet of the reaction rectifying tower is connected with a feeding port of the pump, a discharging port of the auxiliary reactor is connected with the middle part of the reaction rectifying tower through the primary heat exchanger, and a reaction product of the auxiliary reactor enters the reaction rectifying tower after exchanging heat with the primary heat exchanger.
4. The apparatus for producing high purity silane from trichlorosilane according to claim 1, wherein the auxiliary reaction system comprises a condenser, a storage tank, a pump, a primary heat exchanger, a secondary heat exchanger and an auxiliary reactor which are sequentially connected in series, a line sampling outlet of the reaction rectifying tower is connected with a feed inlet of the condenser, a discharge outlet of the auxiliary reactor is connected with the middle part of the reaction rectifying tower through the primary heat exchanger, and a reaction product of the auxiliary reactor enters the reaction rectifying tower after exchanging heat with the primary heat exchanger.
5. The apparatus according to claim 1, wherein the multistage condensing system comprises a first condenser, a second condenser, a third condenser, an economizer and a chiller which are sequentially connected in series, a gas phase feed port of the first condenser is connected with the top of the reactive distillation column, a liquid phase discharge port of the first condenser, the second condenser and the third condenser is connected with the upper part of the reactive distillation column, a discharge port of the chiller is connected with a feed port of the booster pump, a discharge port of the booster pump is connected with the rectification system through the economizer, and the material after being pressurized by the booster pump enters the rectification system after heat exchange with the economizer.
6. The apparatus for producing high purity silane from trichlorosilane according to claim 3 or 4, wherein the rectification system comprises a first rectification column and a second rectification column, a first rectification column condenser is arranged at the top of the first rectification column, and a first rectification column reboiler is arranged at the bottom of the first rectification column; the top of the second rectifying tower is provided with a second rectifying tower condenser, and the bottom of the second rectifying tower is provided with a second rectifying tower reboiler; the bottom of the second rectifying tower is connected with the discharge port of the primary heat exchanger in parallel.
7. A method for producing high purity silane from trichlorosilane using the apparatus of claim 1, comprising the steps of:
(1) Introducing trichlorosilane into the reaction rectifying tower, performing disproportionation reaction, rectifying and purifying to obtain crude silane at the tower top, and extracting liquid silicon tetrachloride at the tower bottom; feeding the materials extracted from the side line of the reaction section of the reactive rectifying tower into the auxiliary reactor for further reaction and returning the materials to the reactive rectifying tower;
(2) Feeding the crude silane obtained from the top of the reactive rectifying tower into the condensing system to obtain condensate and liquid-phase crude silane, and refluxing the condensate to the reactive rectifying tower to continue disproportionation reaction;
(3) And (3) feeding the liquid-phase crude silane obtained in the step (2) into the booster pump, and feeding the boosted liquid-phase crude silane into the rectification system for purification to obtain a high-purity silane product.
8. The method for producing high purity silane from trichlorosilane according to claim 7, wherein the pressure of the reactive rectifying tower is 0.3-0.8 MPa, and the temperature is 50-160 ℃.
9. The method for producing high purity silane from trichlorosilane according to claim 7, wherein the reaction temperature of the auxiliary reaction system is 80-180 ℃ and the pressure is 1.0-3.0 MPa.
10. The method for producing high purity silane from trichlorosilane according to claim 7, wherein the booster pump has a pressure of 1.5 to 5.0MPa; the pressure of the rectification system is 1.5-4.0 MPa, and the temperature is-20-90 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2023113362283 | 2023-10-13 | ||
| CN202311336228 | 2023-10-13 |
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| CN202311843542.0A Pending CN117861251A (en) | 2023-10-13 | 2023-12-28 | Device and method for producing high-purity silane from trichlorosilane |
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