A system for the preparation of a deuterated silane catalyst

Abstract

The utility model provides a kind of preparation system of deuterated silane catalyst, it is related to catalyst preparation technical field.A kind of preparation system of deuterated silane catalyst includes heat exchanger, reactor and rectification recovery system connected in turn by heavy water pipeline;Wherein, the outlet of the reactor is connected with circulation pipeline one between the inlet of the heat exchanger, the top of the rectification recovery system is connected with production pipeline, the bottom of the rectification recovery system is connected with heavy water recovery pipeline.This system can be completely exchanged with hydrogen (protium) on the surface of deuterated weak base resin catalyst, improve the deuteration degree of deuterated base resin catalyst.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, and more specifically, to a preparation system for a deuterated silane catalyst. Background Technology

[0002] Deuterated chemicals are an important class of high-value-added chemicals. Deuterium's abundance in the Earth's crust is far lower than that of ordinary hydrogen (protium), and the annual production scale of deuterated chemicals is typically at or below the ton level. Deuterated silanes can not only serve as probes for studying the chemical mechanisms of organosilicones, but also as deuteration reagents to transfer deuterium into organic compounds through mature hydrosilylation reactions. Currently, there are two methods for preparing deuterated silanes: one is the reduction of halosilanes with LiAlD4 or NaBD4. However, the deuteration reducing agents are easily decomposed and unstable, and consume high-purity alkaline earth metals and aluminum powder, resulting in high energy consumption; this is a process route abandoned in the industrial production of ordinary silanes. The other method involves isotopic exchange between the Si-H bonds of silanes and D2 under metal catalysis. Multiple products with different degrees of isotopic exchange have similar properties, making separation difficult. The problems with these preparation technologies affect the utilization rate of deuterium atoms and increase raw material costs.

[0003] Currently, the industrial production of common silanes employs a combination of cold hydrogenation and disproportionation reactions, allowing tetrachlorosilane to be recycled while simultaneously producing silanes using metallurgical silicon and hydrogen as raw materials (CN110963494A).

[0004] Cold hydrogenation reaction:

[0005] Disproportionation reaction:

[0006] Combining mature chlorosilane distillation purification and disproportionation distillation technologies, the production process for ordinary silanes achieves high atom utilization and product purity. However, due to the significant difference in atomic mass between deuterium and protium, the reaction rate of deuterium is slower than that of ordinary hydrogen, resulting in a lower conversion rate. Nevertheless, the aforementioned ordinary silane production process can be appropriately adjusted and optimized for the production of deuterated silanes. However, the weak-base resin catalyst used in the disproportionation reaction contains ordinary hydrogen (protium) atoms. Directly using this catalyst for the production of deuterated silanes will result in isotope exchange, reducing the purity of the deuterated silanes, which is one of the key issues that needs to be addressed.

[0007] The preparation process of weak base resin catalysts is complex, and the direct synthesis of deuterated weak base resin catalysts is costly. Therefore, it is essential to find a process route that has high deuterium atom utilization, is simple and efficient, safe and reliable in production, and suitable for the industrial production of deuterated weak base resin catalysts. Utility Model Content

[0008] The purpose of this invention is to provide a preparation system for a deuterated silane catalyst, which can completely exchange the hydrogen (protium) on the surface of a deuterated weak base resin catalyst, thereby improving the deuteration degree of the deuterated base resin catalyst.

[0009] This utility model is achieved through the following technical solution:

[0010] A system for preparing a deuterated silane catalyst includes a heat exchanger, a reactor, and a distillation recovery system connected in sequence via a heavy water pipeline; wherein a circulation pipeline is connected between the outlet of the reactor and the inlet of the heat exchanger, a collection pipeline is connected to the top of the distillation recovery system, and a heavy water recovery pipeline is connected to the bottom of the distillation recovery system.

[0011] Furthermore, a liquid pump is installed on the heavy water pipeline at the reactor outlet, and the outlet of the liquid pump is connected to the distillation recovery system and the circulation pipeline, respectively.

[0012] Furthermore, the inlet of the heat exchanger is also connected to a heavy water supply pipeline, and the heavy water recovery pipeline is connected to the heavy water supply pipeline.

[0013] Furthermore, the distillation recovery system includes a distillation column, the outlet of the reactor is connected to the middle of the distillation column via a heavy water pipeline, the top of the distillation column is connected to the collection pipeline, and the bottom of the distillation column is connected to the heavy water recovery pipeline.

[0014] Furthermore, the distillation recovery system includes a first distillation column and a second distillation column arranged in series. The outlet of the reactor is connected to the middle of the first distillation column via a heavy water pipeline. The bottom of the first distillation column is connected to the upper part of the second distillation column via a heavy water pipeline. The collection pipeline is connected to the top of the first distillation column, and the heavy water recovery pipeline is connected to the bottom of the second distillation column.

[0015] Furthermore, a second circulation pipeline is connected between the top of the second distillation column and the bottom of the first distillation column.

[0016] The technical solution of this utility model has at least the following advantages and beneficial effects:

[0017] Based on the market size of deuterated silanes and the characteristics of isotope exchange, this invention designs and develops a deuterated weak base resin catalyst preparation system suitable for ton-scale industrial production of deuterated silanes. Using ordinary weak base resin catalysts as raw materials, heavy water is used in a reactor to modify them into deuterated weak base resin catalysts through isotope exchange. The overall process is simple and efficient, with low equipment investment and low energy consumption, enabling large-scale industrial production. This system features high deuterium atom utilization and high deuteration degree of the deuterated weak base resin catalyst. Theoretically, hydrogen (protium) on the surface of the deuterated weak base resin catalyst can be completely exchanged, resulting in high catalyst preparation efficiency and high deuterated silane abundance. The preparation system is simple and efficient, and the production process is safe and reliable, meeting the industrial-scale production needs of high-purity deuterated silanes. Attached Figure Description

[0018] To more clearly illustrate the technical solutions of the embodiments of this utility model, the drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this utility model and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic diagram of the structure of the preparation system for the deuterated silane catalyst provided in Embodiment 1 of this utility model;

[0020] Figure 2 This is a schematic diagram of the preparation system for the deuterated silane catalyst provided in Embodiment 2 of this utility model.

[0021] Icons: 1-Heat exchanger, 2-Reactor, 3-Distillation column, 4-Liquid pump, 5-Circulation line one, 6-Production line, 7-Heavy water recovery line, 8-Heavy water makeup line, 9-Distillation column one, 10-Distillation column two, 11-Circulation line two;

[0022] Among them, S1 is the replenished heavy water, S2 is the heavy water stream after isotope exchange, S3 is the circulating heavy water stream after isotope exchange, S4 is the heavy water stream entering the heavy water distillation recovery system, S5 is the heavy water circulating stream after H2O removal, S6 is the heavy water stream entering distillation column two, and S7 is the heavy water circulating stream entering the bottom of distillation column one. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of this utility model clearer, the technical solutions of the embodiments of this utility model will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this utility model, and not all embodiments. The components of the embodiments of this utility model described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0024] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0025] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0026] In the description of this utility model, it should be noted that if terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer" appear to indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product is in use, they are only for the convenience of describing this utility model and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this utility model.

[0027] In the description of this utility model, it should also be noted that, unless otherwise explicitly specified and limited, the terms "set," "install," "connect," and "link" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this utility model based on the specific circumstances.

[0028] Example 1

[0029] Reference Figure 1This embodiment provides a preparation system for a deuterated silane catalyst, including a heat exchanger 1, a reactor 2, and a distillation recovery system connected in sequence via a heavy water pipeline; wherein, a circulation pipeline 5 is connected between the outlet of the reactor 2 and the inlet of the heat exchanger 1, a collection pipeline 6 is connected to the top of the distillation recovery system, and a heavy water recovery pipeline 7 is connected to the bottom of the distillation recovery system.

[0030] Based on the market size of deuterated silanes and the characteristics of isotope exchange, a deuterated weak base resin catalyst preparation system suitable for ton-scale industrial production of deuterated silanes was designed and developed. Using ordinary weak base resin catalysts as raw materials, heavy water is used in reactor 2 to modify them into deuterated weak base resin catalysts through isotope exchange. The overall process route is simple and efficient, with low equipment investment and low energy consumption, enabling large-scale industrial production. This system exhibits high deuterium atom utilization and high deuteration degree of the deuterated weak base resin catalyst. Theoretically, hydrogen (protium) on the surface of the deuterated weak base resin catalyst can be completely exchanged, resulting in high catalyst preparation efficiency and high abundance of deuterated silanes. The preparation system is simple and efficient, and the production process is safe and reliable, meeting the industrial-scale production needs of high-purity deuterated silanes.

[0031] In a preferred embodiment of this invention, a liquid pump 4 is provided on the heavy water pipeline at the outlet of the reactor 2, and the outlet of the liquid pump 4 is connected to the distillation recovery system and the circulation pipeline 5, respectively.

[0032] In a preferred embodiment of this invention, the inlet of the heat exchanger 1 is also connected to a heavy water supply pipeline 8, and the heavy water recovery pipeline 7 is connected to the heavy water supply pipeline 8.

[0033] The heavy water stream S1 enters heat exchanger 1, is preheated to the required temperature by heat exchanger 1, and then enters reactor 2. After isotope exchange in reactor 2, the heavy water stream S2 is pumped by liquid pump 4 and divided into two streams, S3 and S4. Stream S3 returns to heat exchanger 1 through circulation pipeline 5, while stream S4 enters the distillation recovery system to separate water (H2O) from the heavy water. The recovered heavy water S5 is returned to heat exchanger 1 through heavy water recovery pipeline 7.

[0034] When using heavy water with a purity of less than 99%, the reaction temperature is 60-120℃, and the average residence time of heavy water S1 in isotope exchange reactor 2 is 10-30 min. When using high-purity heavy water, the reaction temperature is gradually reduced from 60-120℃ to 30-50℃, and the average residence time of heavy water S1 in isotope exchange reactor 2 is 30-60 min.

[0035] The heavy water isotope exchange process can be carried out continuously, that is, heavy water S1 is continuously introduced and S4 is continuously removed from the isotope exchange reactor 2, and the average residence time of the heavy water in reactor 2 is controlled by the flow rate of S1 or S4. The heavy water isotope exchange process can also be carried out intermittently, in which case the heavy water is introduced into the isotope exchange reactor 2 through S1 and maintains a certain average residence time, and then the water is drained through S4 before being reintroduced.

[0036] In a preferred embodiment of this invention, the distillation recovery system includes a distillation column 3. The outlet of the reactor 2 is connected to the middle of the distillation column 3 via a heavy water pipeline. The top of the distillation column 3 is connected to the collection pipeline 6, and the bottom of the distillation column 3 is connected to the heavy water recovery pipeline 7. The distillation column 3 uses high-performance packing with a theoretical plate count of 350.

[0037] The operation process is as follows:

[0038] First, heavy water S1 is conditioned and then fed into isotope exchange reactor 2. After circulating for a certain period of time, it is drawn out via heavy water S4 and fed into the middle of distillation column 3. The heavy water (containing a small amount of HDO) at the bottom of distillation column 3 is returned to isotope exchange reactor 2 after temperature conditioning. The water collected from the top of distillation column 3 (containing a small amount of HDO, H2O) is collected. The operation is divided into two stages:

[0039] (1) Preliminary water separation stage: 98% of the heavy water S1 is controlled at 80-100℃ by heat exchanger 1, intermittently introduced into isotope exchange reactor 2 and circulated for 20 minutes, and then led out through S4 and introduced into the middle of distillation column 3; water (H2O) and a small amount of HDO are separated from the resin residue and isotope exchange at the top of distillation column 3, and deuterium atoms (heavy water D2O) are added to the system. The reflux ratio is gradually increased from 30 to 300 to ensure that the HDO concentration in the top stream does not exceed 1% (or the deuterium atom concentration does not exceed 0.5% of the hydrogen element); the reboiling ratio at the bottom is not less than 50 to ensure that the HDO concentration in the bottom recycled heavy water stream does not exceed 1%;

[0040] (2) Later stage of water separation: Heavy water S1 with a concentration of over 99% is controlled at 80-100℃ by heat exchanger 1, intermittently introduced into isotope exchange reactor 2 and circulated for 50 minutes, and then led out through S4 into the middle of distillation column 3; distillation column 3 maintains a high reflux ratio of 300 and the HDO concentration at the top of the column exceeds 1%, so it switches to full reflux mode, and intermittently collects the mixed liquid of water and HDO from the top of the column, and replenishes the system with deuterium atoms (heavy water D2O); the reboiling ratio of distillation column 3 is increased to ensure that the concentration of heavy water D2O collected from the bottom stream S5 is not less than 99.99%; when the HDO concentration in the top stream of distillation column 3 exceeds 10%, the top collection is stopped, and the heavy water entering isotope exchange reactor 2 is gradually reduced to 45℃ by heat exchanger 1. After the top collection is stopped, the system is maintained for 5 hours.

[0041] In this process, the semi-heavy water HDO undergoes the following reversible disproportionation reaction in distillation column 3: It is continuously generated and consumed automatically.

[0042] The isotope-exchanged resin is dried in a low-temperature inert atmosphere to remove heavy water from the modified resin catalyst without damaging its spatial structure. The purity of the low-temperature inert atmosphere is not less than 99.999%, the temperature of the low-temperature inert atmosphere is 60-120℃, and the final water content in the low-temperature inert atmosphere is less than 1ppm.

[0043] Example 2

[0044] Reference Figure 2 In this embodiment, the distillation recovery system includes a first distillation column 9 and a second distillation column 10 arranged in series. The outlet of the reactor 2 is connected to the middle of the first distillation column 9 through a heavy water pipeline. The bottom of the first distillation column 9 is connected to the upper part of the second distillation column 10 through a heavy water pipeline. The collection pipeline 6 is connected to the top of the first distillation column 9, and the heavy water recovery pipeline 7 is connected to the bottom of the second distillation column 10.

[0045] In a preferred embodiment of this invention, a circulation pipeline 21 connects the top of distillation column 210 and the bottom of distillation column 19. Both distillation column 19 and distillation column 210 use high-performance packing with a theoretical plate number of 200.

[0046] The operation process is as follows:

[0047] First, heavy water S4 is continuously fed into the lower part of distillation column 9. Low-deuterium water (H2O) is collected from the top of distillation column 9, and liquid S6 from the bottom of distillation column 9 is fed into the upper part of distillation column 10. The vapor stream S7 from the top of distillation column 10 is fed into the reboiler of distillation column 9, serving as a (large) portion of the reboiling heat source for distillation column 9. Heavy water S5 (containing a small amount of semi-heavy water HDO) from the bottom of distillation column 10 is continuously returned to isotope exchange reactor 2 after temperature adjustment. The operation is divided into two stages:

[0048] (1) Initial continuous water separation stage: Heavy water is controlled at 80-100℃ by heat exchanger 1 and enters isotope exchange reactor 2. The average residence time of heavy water in isotope exchange reactor 2 is 20 minutes. Part S4 from the outlet of reactor 2 enters the middle of distillation column 9. Water (H2O) remaining in the resin and generated by isotope exchange is continuously separated from the top of distillation column 9, and deuterium atoms (heavy water D2O) are added to the system. The reflux ratio of distillation column 9 is gradually increased from 30 to 200 to ensure that the top stream of the column produces low deuterium water (half-heavy water HDO content is less than 1%). The heavy water and half-heavy water at the bottom of distillation column 9 enter the top or upper part of distillation column 10. The reboiling ratio of distillation column 10 is not less than 20 to ensure that the bottom stream S5 produces heavy water D2O concentration not less than 99% (containing a small amount of half-heavy water HDO).

[0049] The semi-heavy water HDO undergoes the following disproportionation reaction during the circulation process in distillation column 9 and distillation column 10: And it is constantly and automatically generated and consumed;

[0050] (2) Later intermittent water separation stage: Distillation column 9 maintains a high reflux ratio of 200, but low deuterium water (half-heavy water HDO content exceeds 1%) cannot be collected from the top of the column. The full reflux mode is switched to intermittent collection of water and HDO mixture from the top of the column, and deuterium atoms (heavy water D2O) are added to the system. The average circulation residence time of heavy water in isotope exchange reactor 2 is 40 minutes. The HDO concentration at the top of distillation column 9 gradually increases to more than 10% (or deuterium atoms account for one-quarter of hydrogen elements), and the collection from the top of the column is stopped. At the same time, the reboiling ratio of distillation column 10 is increased to ensure that the concentration of heavy water D2O collected from the bottom stream S5 is not less than 99.99%. The temperature of the heavy water entering isotope exchange reactor 2 is gradually reduced to 40°C by heat exchanger 1. After the collection from the top of the column is stopped, the system is maintained for 3 hours.

[0051] The isotope-exchanged resin is dried in a low-temperature inert atmosphere to remove heavy water from the modified resin catalyst without damaging its spatial structure. The purity of the low-temperature inert atmosphere is not less than 99.999%, the temperature of the low-temperature inert atmosphere is 60-120℃, and the final water content in the low-temperature inert atmosphere is less than 1ppm.

[0052] The above are merely preferred embodiments of this utility model and are not intended to limit the scope of this utility model. Various modifications and variations can be made to this utility model by those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of this utility model should be included within the protection scope of this utility model.

Claims

1. A system for preparing a deuterated silane catalyst, characterized in that, It includes a heat exchanger, a reactor, and a distillation recovery system connected in sequence via a heavy water pipeline; wherein, a circulation pipeline is connected between the outlet of the reactor and the inlet of the heat exchanger, a collection pipeline is connected to the top of the distillation recovery system, and a heavy water recovery pipeline is connected to the bottom of the distillation recovery system.

2. The preparation system for the deuterated silane catalyst according to claim 1, characterized in that, A liquid pump is installed on the heavy water pipeline at the reactor outlet, and the outlet of the liquid pump is connected to the distillation recovery system and the circulation pipeline.

3. The preparation system for the deuterated silane catalyst according to claim 1, characterized in that, The inlet of the heat exchanger is also connected to a heavy water supply pipeline, and the heavy water recovery pipeline is connected to the heavy water supply pipeline.

4. The preparation system for the deuterated silane catalyst according to claim 1, characterized in that, The distillation recovery system includes a distillation column. The outlet of the reactor is connected to the middle of the distillation column via a heavy water pipeline. The top of the distillation column is connected to the collection pipeline, and the bottom of the distillation column is connected to the heavy water recovery pipeline.

5. The preparation system for the deuterated silane catalyst according to claim 1, characterized in that, The distillation recovery system includes a first distillation column and a second distillation column arranged in series. The outlet of the reactor is connected to the middle of the first distillation column via a heavy water pipeline. The bottom of the first distillation column is connected to the top of the second distillation column via a heavy water pipeline. The top of the first distillation column is connected to the collection pipeline, and the bottom of the second distillation column is connected to the heavy water recovery pipeline.

6. The preparation system for the deuterated silane catalyst according to claim 5, characterized in that, A second circulation pipeline is connected between the top of the second distillation column and the bottom of the first distillation column.

Images