CN215026208U - Preparation device of electronic grade ethyl orthosilicate - Google Patents
Preparation device of electronic grade ethyl orthosilicate Download PDFInfo
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- CN215026208U CN215026208U CN202120830663.1U CN202120830663U CN215026208U CN 215026208 U CN215026208 U CN 215026208U CN 202120830663 U CN202120830663 U CN 202120830663U CN 215026208 U CN215026208 U CN 215026208U
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Abstract
The utility model provides a preparation facilities of electronic grade tetraethoxysilane. The preparation device comprises an industrial grade ethyl orthosilicate supply unit, a multi-grade microporous membrane coupling adsorption column, a light component removal rectifying tower and a heavy component removal rectifying tower; the multistage microporous membrane coupling adsorption column comprises a cylindrical hollow shell, chelate adsorption resin is filled in the cylindrical hollow shell, and microporous membranes are arranged at two ends of the hollow shell; all stages of microporous membrane coupling adsorption columns are arranged in series and/or in parallel according to the material flow sequence, and the inlet of the microporous membrane coupling adsorption column positioned at the first stage is connected with an industrial grade tetraethoxysilane supply unit; the number of theoretical plates of the light-weight removal rectifying tower is 10-30, and the number of theoretical plates of the heavy-weight removal rectifying tower is 20-50. The utility model discloses in using electron level tetraethoxysilane preparation with microporous membrane and liquid phase adsorption coupling technology to further combine to take off light, take off heavy rectification edulcoration, gain fine edulcoration effect, can purify preparation electron level tetraethoxysilane, and manufacturing cost is lower.
Description
Technical Field
The utility model relates to a material purification technical field particularly, relates to a preparation facilities of electron level tetraethoxysilane.
Background
High-purity electronic gas is an essential raw material in the manufacturing process of integrated circuits, and is widely applied to other fields such as photoelectrons, compound semiconductors, solar photovoltaic cells, liquid crystal displays, optical fiber manufacturing and the like. The purity of high purity electronic gas directly affects the performance, integration, and yield of integrated circuits. With the development of integrated circuit manufacturing processes and technologies, the chip size is increasing, the feature size line width is decreasing, and the quality purity and specific technical indexes of various electronic gases for integrated circuit manufacturing processes are required to be improved. Electronic grade Tetraethoxysilane (TEOS) is used as one of many electronic gases, is mainly used for a chemical vapor deposition process in the manufacturing process of IC wafers, has strict requirements on the purity, the purity needs more than 8N, each impurity needs less than 1 ppb, and particularly metal ion impurities (Na, K, Mg, Fe, Ca, Al and the like) are electrically active impurities, so that the insulating property of a silicon dioxide thin film layer deposited on a semiconductor device is reduced, micron-sized circuits are communicated with one another, and a circuit board is scrapped. Among them, the non-electroactive impurities, such as moisture, organic substances, and particles, affect the uniformity and flatness of the deposited film. The general technical grade tetraethoxysilane has 99.8 percent of component and contains more ionic impurities (Na, K, Mg, Al, Fe, Ca, B, P) and particles, so the development of the preparation process of the electronic grade tetraethoxysilane is urgent.
At present, the preparation process mainly adopted by domestic enterprises is the combination of complex rectification, adsorption rectification, vacuum rectification and various coupling technologies. Patent No. CN 109748931A mentions a preparation method and a production system of high-purity ethyl orthosilicate, which comprises the following process steps: mixing high-purity silicon tetrachloride and high-purity ethanol for reaction and rectification to obtain crude TEOS and crude HCl; then, the crude TEOS is subjected to decoloration adsorption treatment and alkaline adsorption treatment, then lightness-removing vacuum rectification is carried out, and the TEOS subjected to lightness-removing vacuum rectification is subjected to heavy-removing vacuum rectification after being subjected to treatment of boron-phosphorus adsorption resin and metal ion adsorption resin to obtain high-purity TEOS (5N +). Patent No. CN 103772424B mentions a preparation method of 8N electronic grade ethyl orthosilicate, which is to use a complexing agent (ethylene diamine tetraacetic acid) to complex most of metal impurities in raw materials and then use a 0.1 micron microporous filter for filtration; removing trace metal impurities, ethanol, organic impurities and water by a cation exchange tower, a quartz plate distillation tower and a sub-boiling distiller under strictly controlled temperature to obtain TEOS product with purity of not less than 99.999999%, organic impurity content of less than 1ppm and water content of less than 0.3 ppm. CN 109575065A mentions a production method and a production system of high-purity tetraethoxysilane, firstly, after a tetraethoxysilane crude product with the purity of 99% is vaporized, alcohol impurities and ether impurities are removed by two-stage series adsorption under an electric field environment (1000-2000V/m), and adsorbents are 4A molecular sieves and/or 5A molecular sieves; drying by using a 3A molecular sieve to remove water, adsorbing by using a silicon-aluminum gel modified by loading metal oxides to remove metal ions to obtain adsorbed gaseous tetraethoxysilane, and condensing to obtain the high-purity tetraethoxysilane, wherein the product comprises 99.999 percent of components, 50ppb of chloride, 5ppm of water and less than 0.5ppb of metal ion impurities.
However, the main disadvantages in the current preparation process of electronic grade ethyl orthosilicate are: the added related complex reaction is purified, although the impurity removal effect can be achieved, the cleanliness of the complexing agent possibly cannot meet the requirement, new impurities can be introduced, and certain difficulty is brought to subsequent purification and separation; the complexing reaction speed of the complexing agent and the raw materials is slow, the reaction time is long, the continuous operation can not be carried out, and the industrialized large-scale production can not be realized; in addition, the processes of reduced pressure distillation and sub-boiling distillation are adopted, so that gas-liquid entrainment cannot be avoided, gas and liquid cannot be completely separated, and impurities are difficult to remove; on the other hand, the requirements on equipment and automation control are higher, the production cost is increased, and the method is not suitable for industrial mass production.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a preparation facilities of electron level tetraethoxysilane to when solving among the prior art purification production electron level tetraethoxysilane, reaction rectification complex time is long and the condition is difficult for control, metallic impurity and granule get rid of difficult, the cost scheduling problem on the high side.
In order to achieve the above object, according to one aspect of the present invention, there is provided an apparatus for preparing electronic grade tetraethoxysilane, comprising: the industrial-grade ethyl orthosilicate supply unit is used for supplying industrial-grade ethyl orthosilicate; the multi-stage microporous membrane coupling adsorption column comprises a cylindrical hollow shell, chelate adsorption resin is filled in the cylindrical hollow shell, and microporous membranes are arranged at two ends of the hollow shell; all stages of microporous membrane coupling adsorption columns are arranged in series and/or in parallel according to the material flow sequence, and the inlet of the microporous membrane coupling adsorption column positioned at the first stage is connected with an industrial grade tetraethoxysilane supply unit; the light component removal rectifying tower is provided with a light component removal tower inlet, a light component removal tower top outlet and a light component removal tower kettle outlet, wherein the light component removal tower inlet is connected with the last microporous membrane coupling adsorption column outlet, and the number of theoretical plates of the light component removal rectifying tower is 10-30; the heavy component removal rectifying tower is provided with a heavy component removal tower inlet, a tower top electronic grade ethyl orthosilicate outlet and a heavy component removal tower kettle outlet, wherein the heavy component removal tower inlet is connected with the light component removal tower kettle outlet, and the number of theoretical plates of the heavy component removal rectifying tower is 20-50.
Further, according to the material flow sequence, in the two adjacent stages of microporous membrane coupled adsorption columns, the pore diameter of the microporous membrane positioned at the upstream of the microporous membrane coupled adsorption column is larger than that of the microporous membrane positioned at the downstream of the microporous membrane coupled adsorption column.
Furthermore, the aperture of the microporous membrane coupling adsorption column is 0.05-0.5 μm.
Furthermore, the microporous membrane coupling adsorption column comprises two stages which are connected in series, the pore diameter of a microporous membrane of the first stage microporous membrane coupling adsorption column is 0.1-0.3 mu m, and the pore diameter of a microporous membrane of the second stage microporous membrane coupling adsorption column is 0.05-0.1 mu m.
Furthermore, the thickness of the microporous membrane is 0.2-0.3 mm, and the microporous membrane is a polytetrafluoroethylene membrane.
Further, the height-diameter ratio of the microporous membrane coupling adsorption column is 5-10.
Further, the preparation apparatus further includes: the microporous filtering unit comprises a filtering cavity and a filtering membrane positioned in the filtering cavity, the filtering membrane is a polytetrafluoroethylene microporous membrane with the aperture of 0.05-0.1 mu m, and an inlet of the filtering cavity is connected with an outlet of the electronic-grade ethyl orthosilicate on the top of the tower.
Further, the light component removal rectifying tower and the heavy component removal rectifying tower are both filled towers, and the adopted filler is stainless steel theta ring filler, triangular spiral filler or glass spring filler.
The utility model provides a preparation facilities of electron level tetraethoxysilane utilizes the device, can adsorb the edulcoration through multistage packing with industrial level tetraethoxysilane earlier the microporous membrane coupling adsorption column that chelate adsorption resin, both ends were provided with the microporous membrane. In the process, the chelating adsorption resin can be used for adsorbing and removing trace metal ions and non-metal ions in the industrial-grade ethyl orthosilicate, and the microporous membrane is used for removing particle impurities in the industrial-grade ethyl orthosilicate. The ethyl orthosilicate after adsorption and impurity removal can be sequentially subjected to light removal to remove low-boiling substances (trace water, ethanol and other low-component substances) and heavy removal to remove high-boiling substances (ethyl orthosilicate tripolymer and the like) and particles through a light removal rectifying tower and a heavy removal rectifying tower.
The utility model discloses in using electron level tetraethoxysilane preparation with microporous membrane and liquid phase adsorption coupling technology to further combine to take off light, take off heavy rectification edulcoration, gain fine edulcoration effect, can purify preparation electron level tetraethoxysilane, and manufacturing cost is lower. Meanwhile, the device is used for purifying the ethyl orthosilicate, the operation time is short, the conditions are easy to control, the production is stable and high in efficiency, new impurities cannot be introduced, and the device is very suitable for industrial large-scale application.
Drawings
The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic structural diagram of a preparation device of electronic grade ethyl orthosilicate according to an embodiment of the invention.
Wherein the figures include the following reference numerals:
10. an industrial grade ethyl orthosilicate supply unit; 20. a microporous membrane coupling adsorption column; 30. a light component removal rectifying tower; 301. an inlet of the light component removal tower; 302. an outlet at the top of the light component removal tower; 303. an outlet of the lightness-removing tower kettle; 40. a heavy component removal rectifying tower; 401. an inlet of a de-weighting tower; 402. an outlet of the tower top electronic grade ethyl orthosilicate; 403. an outlet of the de-weighting tower kettle; 50. a microporous filtration unit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
"technical grade ethyl orthosilicate" refers to ethyl orthosilicate with a purity of more than 99%, and "electronic grade ethyl orthosilicate" refers to ethyl orthosilicate with a purity of 99.999% or more.
As described in the background art, the prior art has the problems of new impurity introduction, long treatment time, incomplete impurity removal and the like when the electronic grade ethyl orthosilicate is purified and produced.
In order to solve the above problems, the present invention provides a preparation device of electronic grade ethyl orthosilicate, as shown in fig. 1, the preparation device comprises an industrial grade ethyl orthosilicate supply unit 10, a multi-stage microporous membrane coupling adsorption column 20, a light component removal rectification column 30 and a heavy component removal rectification column 40; the industrial grade tetraethoxysilane supply unit 10 is used for supplying industrial grade tetraethoxysilane; the multistage microporous membrane coupling adsorption column 20 comprises a cylindrical hollow shell, chelate adsorption resin is filled in the cylindrical hollow shell, and microporous membranes are arranged at two ends of the hollow shell; all stages of microporous membrane coupling adsorption columns 20 are arranged in series and/or in parallel according to a material flow sequence, and the inlet of the microporous membrane coupling adsorption column 20 positioned at the first stage is connected with an industrial grade tetraethoxysilane supply unit 10; the light component removal rectifying tower 30 is provided with a light component removal tower inlet 301, a light component removal tower top outlet 302 and a light component removal tower kettle outlet 303, wherein the light component removal tower inlet 301 is connected with an outlet of the last microporous membrane coupling adsorption column 20; the heavy component removal rectifying tower 40 is provided with a heavy component removal tower inlet 401, a tower top electronic grade ethyl orthosilicate outlet 402 and a heavy component removal tower kettle outlet 403, wherein the heavy component removal tower inlet 401 is connected with the light component removal tower kettle outlet 303.
By utilizing the device, industrial-grade ethyl orthosilicate can be adsorbed and decontaminated through a microporous membrane coupling adsorption column which is filled with chelate adsorption resin in a multistage way and is provided with microporous membranes at two ends. In the process, the chelating adsorption resin can be used for adsorbing and removing trace metal ions and non-metal ions in the industrial-grade ethyl orthosilicate, and the microporous membrane is used for removing particle impurities in the industrial-grade ethyl orthosilicate. The ethyl orthosilicate after adsorption and impurity removal can be sequentially subjected to light removal to remove low-boiling substances (trace water, ethanol and other low-component substances) and heavy removal to remove high-boiling substances (ethyl orthosilicate tripolymer and the like) and particles through a light removal rectifying tower and a heavy removal rectifying tower. Particularly, the number of theoretical plates of the light component removal rectifying tower 30 is 10-30, and the number of theoretical plates of the heavy component removal rectifying tower 40 is 20-50. The theoretical plate numbers of the two are set to be in the ranges, so that the light and heavy removal and impurity removal can be carried out more fully on the basis of saving energy consumption as much as possible.
The utility model discloses in using electron level tetraethoxysilane preparation with microporous membrane and liquid phase adsorption coupling technology to further combine to take off light, take off heavy rectification edulcoration, gain fine edulcoration effect, can purify preparation electron level tetraethoxysilane, and manufacturing cost is lower. Meanwhile, the device is used for purifying the ethyl orthosilicate, the operation time is short, the conditions are easy to control, the production is stable and high in efficiency, new impurities cannot be introduced, and the device is very suitable for industrial large-scale application.
In order to make the chelating adsorption resin more fully adsorb metal ion impurities, non-metal ion impurities and the like in the contact process of the chelating adsorption resin and industrial-grade ethyl orthosilicate so as to further improve the impurity removal effect, in a preferred embodiment, the chelating adsorption resin is polystyrene macroporous iminodiacetic acid chelating resin (preferably bleaching MTS9300 type chelating resin), polystyrene and divinyl macroporous aminophosphonic acid chelating resin (preferably bleaching MTS9500 type chelating resin), sulfonated styrene-divinyl resin (preferably Rohm Hass resin)
563、
572、
600, etc.).
In practical application, a person skilled in the art can select the number of stages and the serial-parallel connection form of the microporous membrane coupled adsorption columns 20, and in a preferred embodiment, in the two adjacent stages of the microporous membrane coupled adsorption columns 20 in the material flow order, the pore diameter of the microporous membrane coupled adsorption column 20 located at the upstream is larger than that of the microporous membrane coupled adsorption column 20 located at the downstream. Therefore, on one hand, most of metal ion impurities and non-metal ion impurities are removed by the first-stage microporous membrane coupling adsorption column 20 in an adsorption mode, and after large particle impurities are removed by the microporous membranes, the remaining metal ion impurities, non-metal ion impurities and small particle impurities can be further removed by the second-stage microporous membrane coupling adsorption column 20. On the other hand, the arrangement ensures higher processing efficiency. More preferably, the pore diameter of the microporous membrane coupling adsorption column 20 is 0.05 to 0.5 μm.
In a preferred embodiment, the microporous membrane coupling adsorption column 20 comprises two stages arranged in series, and the pore diameter of the microporous membrane of the first stage microporous membrane coupling adsorption column 20 is 0.1 to 0.3 μm, and the pore diameter of the microporous membrane of the second stage microporous membrane coupling adsorption column 20 is 0.05 to 0.1 μm. The microporous membrane filtration and liquid phase adsorption impurity removal effects of the two-stage microporous membrane coupling adsorption column 20 can be more fully exerted, the synergistic interaction effect is more obvious, and the impurity removal effect of the tetraethoxysilane is further improved. More preferably, the thickness of the microporous membrane is 0.2-0.3 mm, and the microporous membrane is a polytetrafluoroethylene membrane.
After entering the microporous membrane coupling adsorption column 20, the industrial-grade ethyl orthosilicate can contact with the chelating adsorption resin therein, and impurities are removed through liquid phase adsorption. For the purpose of further improving the contact surface and the adsorption performance, in a preferred embodiment, the height-diameter ratio of the microporous membrane coupled adsorption column 20 is 5 to 10.
In a preferred embodiment, the above preparation apparatus further comprises: and the microporous filtering unit 50 comprises a filtering cavity and a filtering membrane positioned in the filtering cavity, the filtering membrane is a polytetrafluoroethylene microporous membrane with the aperture of 0.05-0.1 mu m, and the inlet of the filtering cavity is connected with the outlet 402 of the electronic-grade tetraethoxysilane at the top of the tower. Thus, after the heavy metal removal and rectification, the tetraethoxysilane can be further introduced into the microporous filtering unit 50 for filtering, and the residual trace metal impurities and particles are removed, so that the impurity removal effect is further improved. In the actual operation process, the addition of the microporous filtering unit 50 further ensures the production stability of the electronic grade ethyl orthosilicate, so that the product has higher purity stability in the continuous purification process.
More preferably, both the light component removal rectification column 30 and the heavy component removal rectification column 40 are packed columns, and the adopted packing is stainless steel theta ring packing, triangular spiral packing or glass spring packing. The use of these fillers can further increase the contact area, and improve the kinetic conditions of light and heavy removal, thereby further improving the effect of impurity removal.
In the actual operation process, the top of the light component removal rectifying tower 30 (light component removal atmospheric tower) and the top of the heavy component removal rectifying tower 40 (heavy component removal atmospheric tower) are both provided with condensation reflux equipment, such as cooling water condensation equipment, and part of condensation reflux is extracted from part of the top of the tower; the bottoms of the light-component removing rectifying tower 30 and the heavy-component removing rectifying tower 40 can be heated by adopting heat conducting oil.
According to another aspect of the present invention, there is provided a method for preparing electronic grade ethyl orthosilicate, comprising the following steps: adsorbing and removing impurities from industrial-grade ethyl orthosilicate by a multistage microporous membrane coupling adsorption column 20 to obtain primary impurity-removed ethyl orthosilicate, wherein the microporous membrane coupling adsorption column 20 comprises a columnar hollow shell, chelating adsorption resin is filled in the columnar hollow shell, and microporous membranes are arranged at two ends of the hollow shell; the microporous membrane coupling adsorption columns 20 at all levels are arranged in series and/or in parallel according to the material flow sequence; removing light and impurities from the primary impurity-removed tetraethoxysilane by a light and impurity removal rectifying tower 30 to obtain secondary impurity-removed tetraethoxysilane; and (4) removing the weight and impurities of the secondary impurity-removed ethyl orthosilicate by a weight-removing rectifying tower 40 to obtain the electronic grade ethyl orthosilicate.
By utilizing the method, industrial-grade ethyl orthosilicate is firstly subjected to adsorption impurity removal through a microporous membrane coupling adsorption column which is filled with chelate adsorption resin in a multistage manner and is provided with microporous membranes at two ends. In the process, the chelating adsorption resin can be used for adsorbing and removing trace metal ions and non-metal ions in the industrial-grade ethyl orthosilicate, and the microporous membrane is used for removing particle impurities in the industrial-grade ethyl orthosilicate. The ethyl orthosilicate after adsorption and impurity removal can be sequentially subjected to light removal to remove low-boiling substances (trace water, ethanol and other low-component substances) and heavy removal to remove high-boiling substances (ethyl orthosilicate tripolymer and the like) and particles through a light removal rectifying tower and a heavy removal rectifying tower.
The utility model discloses in using electron level tetraethoxysilane preparation with microporous membrane and liquid phase adsorption coupling technology to further combine to take off light, take off heavy rectification edulcoration, gain fine edulcoration effect, can purify preparation electron level tetraethoxysilane, and manufacturing cost is lower. Meanwhile, the device is used for purifying the ethyl orthosilicate, the operation time is short, the conditions are easy to control, the production is stable and high in efficiency, new impurities cannot be introduced, and the device is very suitable for industrial large-scale application.
In order to make the chelating adsorption resin more fully adsorb metal ion impurities, non-metal ion impurities and the like in the contact process of the chelating adsorption resin and industrial-grade ethyl orthosilicate so as to further improve the impurity removal effect, in a preferred embodiment, the chelating adsorption resin is polystyrene macroporous iminodiacetic acid chelating resin (preferably bleaching MTS9300 type chelating resin), polystyrene and divinyl macroporous aminophosphonic acid chelating resin (preferably bleaching MTS9500 type chelating resin), sulfonated styrene-divinyl resin (preferably Rohm Hass resin)
563、
572、
600, etc.).
In practical application, a person skilled in the art can select the number of stages and the serial-parallel connection form of the microporous membrane coupled adsorption columns 20, and in a preferred embodiment, in the two adjacent stages of the microporous membrane coupled adsorption columns 20 in the material flow order, the pore diameter of the microporous membrane coupled adsorption column 20 located at the upstream is larger than that of the microporous membrane coupled adsorption column 20 located at the downstream. Therefore, on one hand, most of metal ion impurities and non-metal ion impurities are removed by the first-stage microporous membrane coupling adsorption column 20 in an adsorption mode, and after large particle impurities are removed by the microporous membranes, the remaining metal ion impurities, non-metal ion impurities and small particle impurities can be further removed by the second-stage microporous membrane coupling adsorption column 20. On the other hand, the arrangement ensures higher processing efficiency. More preferably, the pore diameter of the microporous membrane coupling adsorption column 20 is 0.05 to 0.5 μm.
In a preferred embodiment, the microporous membrane coupling adsorption column 20 comprises two stages arranged in series, and the pore diameter of the microporous membrane of the first stage microporous membrane coupling adsorption column 20 is 0.1 to 0.3 μm, and the pore diameter of the microporous membrane of the second stage microporous membrane coupling adsorption column 20 is 0.05 to 0.1 μm. The microporous membrane filtration and liquid phase adsorption impurity removal effects of the two-stage microporous membrane coupling adsorption column 20 can be more fully exerted, the synergistic interaction effect is more obvious, and the impurity removal effect of the tetraethoxysilane is further improved. Further preferably, the thickness of the microporous membrane is 0.2-0.3 mm, and the microporous membrane is a polytetrafluoroethylene membrane.
After entering the microporous membrane coupling adsorption column 20, the industrial-grade ethyl orthosilicate can contact with the chelating adsorption resin therein, and impurities are removed through liquid phase adsorption. For the purpose of further improving the contact surface and the adsorption performance, in a preferred embodiment, the height-diameter ratio of the microporous membrane coupled adsorption column 20 is 5 to 10.
In a preferred embodiment, in the adsorption impurity removal process, the adsorption temperature is 10-60 ℃, and is preferably room temperature; the flow rate of the industrial grade ethyl orthosilicate in the microporous membrane coupling adsorption column 20 is 10-100 ml/min, and preferably 20-40 ml/min; the adsorption pressure is 0.1-0.3 MPa. Under the process condition, the industrial-grade ethyl orthosilicate can be in more sufficient contact with the chelating adsorption resin, and more metal ion impurities, non-metal ion impurities and the like can be removed through adsorption.
In a preferred embodiment, the preparation method further comprises a step of washing the chelate adsorption resin before the adsorption impurity removal process is carried out, and the washing step comprises: washing the chelating adsorption resin by using 18M pure water (the resistance value of the water is 18.2M omega cm, and the impurities of the 18M pure water are all below 100 ppt), and drying in a vacuum drying oven, wherein the drying temperature is 50-80 ℃. Thus, the chelate adsorption resin can be washed in advance, and the introduction of impurities can be further avoided.
More preferably, after the step of removing heavy impurities, the preparation method further comprises: further filtering and impurity removing are carried out on the secondary impurity-removed tetraethoxysilane after the weight removal and impurity removal through a microporous filtering unit 50, so as to obtain electronic grade tetraethoxysilane; the microporous filtering unit 50 comprises a filtering cavity and a filtering membrane positioned in the filtering cavity, wherein the filtering membrane is a polytetrafluoroethylene microporous membrane with the aperture of 0.05-0.1 mu m. Thus, after the heavy metal removal and rectification, the tetraethoxysilane can be further introduced into the microporous filtering unit 50 for filtering, and the residual trace metal impurities and particles are removed, so that the impurity removal effect is further improved. In the actual operation process, the addition of the microporous filtering unit 50 further ensures the production stability of the electronic grade ethyl orthosilicate, so that the product has higher purity stability in the continuous purification process.
In order to further improve the impurity removal effect in the light-component removal rectification and the heavy-component removal rectification processes, in a preferred embodiment, the number of theoretical plates of the light-component removal rectification tower 30 is 10-30; the theoretical plate number of the heavy component removal rectifying tower 40 is 20-50. In the actual operation process, the top of the light component removal rectifying tower 30 (light component removal atmospheric tower) and the top of the heavy component removal rectifying tower 40 (heavy component removal atmospheric tower) are both provided with condensation reflux equipment, such as cooling water condensation equipment, and part of condensation reflux is extracted from part of the top of the tower; the bottoms of the light-component removing rectifying tower 30 and the heavy-component removing rectifying tower 40 can be heated by adopting heat conducting oil. More preferably, in the light component removal and impurity removal step, the pressure at the top of the light component removal rectifying tower 30 is 30KPa to 50KPa, the temperature at the top of the tower is 178 to 184 ℃, and the reflux feed ratio is 5 to 15; preferably, in the step of removing the heavy impurities, the top pressure of the heavy-ends removing rectifying tower 40 is 40-60 Kpa, the top temperature is 181-186 ℃, and the reflux feed ratio is 10-20.
In a preferred embodiment, the number of theoretical plates of the light component removal rectifying tower 30 is 10 to 30, and the number of theoretical plates of the heavy component removal rectifying tower 40 is 20 to 50. The theoretical plate numbers of the two are set to be in the ranges, so that the light and heavy removal and impurity removal can be carried out more fully on the basis of saving energy consumption as much as possible. More preferably, both the light component removal rectification column 30 and the heavy component removal rectification column 40 are packed columns, and the adopted packing is stainless steel theta ring packing, triangular spiral packing or glass spring packing. The use of these fillers can further increase the contact area, and improve the kinetic conditions of light and heavy removal, thereby further improving the effect of impurity removal.
In a word, the preparation process of the electronic grade ethyl orthosilicate has the following advantages:
(1) the utility model provides a serialization production technology is fit for large-scale production to can effective reduction in production cost.
(2) The utility model discloses a microporous membrane and absorption coupling technology have improved the area of contact of adsorption resin and ethyl orthosilicate and impurity ion's the effect of getting rid of, and edulcoration efficiency obviously promotes, greatly reduced manufacturing cost.
(3) The utility model discloses an adsorption equipment simple structure, the operation is overhauld conveniently.
(4) Preferably, the utility model discloses the micropore filtration unit who uses after the heavy rectification of taking off has played better effect to product quality's stability.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The preparation device shown in fig. 1 is used for treating industrial-grade ethyl orthosilicate, and comprises the following specific steps:
and sequentially passing the industrial-grade tetraethoxysilane with the purity of 99.5% through a two-stage microporous membrane coupling adsorption column to obtain the primary impurity-removed tetraethoxysilane. Wherein the first stage microporous membrane coupling adsorption column is filled with a bleached MTS9500 type macroporous chelating adsorption resin, and two ends are polytetrafluoroethylene microporous membranes with the aperture of 0.1 mu m and the thickness of 0.25 mm; the second-stage microporous membrane coupling adsorption column is filled with a blanc MTS9300 type macroporous chelating adsorption resin, and two ends of the second-stage microporous membrane coupling adsorption column are polytetrafluoroethylene microporous membranes with the aperture of 0.05 mu m and the thickness of 0.25 mm; the diameter and the length of the two-stage microporous membrane coupling adsorption column are both 50mm and 500mm, the height-diameter ratio is 10, and the material is 316L stainless steel. The macroporous chelate adsorption resin is washed by 18M pure water before being filled, and then is dried in a vacuum drying oven, wherein the drying temperature is 80 ℃. In the process of adsorption and impurity removal, the adsorption temperature is room temperature, the adsorption pressure is 0.15Mpa, and the flow rate is controlled to be 30 ml/min.
And (3) sending the primary impurity-removed tetraethoxysilane into a light component removal rectifying tower to obtain secondary impurity-removed tetraethoxysilane. Wherein the theoretical plate number of the light component removal rectifying tower is 20, the packing is theta ring metal packing of 5x5mm, the tower pressure is controlled to be 40kpa, the top temperature is 181 ℃, the reflux feed ratio is 10, and low-boiling substances are extracted from the tower top.
And (4) feeding the secondary impurity-removed ethyl orthosilicate into a heavy-weight removal rectifying tower to obtain the heavy-weight-removed impurity-removed ethyl orthosilicate. Wherein the theoretical plate number of the heavy-duty rectifying tower is 30, the filler is theta ring metal filler of 5x5mm, the tower pressure is controlled to be 50kpa, the top temperature is controlled to be 184 ℃, the reflux feed ratio is 15, and high-boiling substances and solid particles with relatively high content of enriched metal impurities are discharged from the tower kettle;
and filtering the product at the top of the de-heavy rectifying tower by a polytetrafluoroethylene microporous membrane with the pore diameter of 0.05 mu m to obtain an electronic grade ethyl orthosilicate product.
After GC-MS detection, the purity of the product reaches 99.999 percent, after ICP-MS detection, the total amount of impurities of the product is 4ppbw, and the number of particles (more than or equal to 0.2 mu m) is 8/ml. The requirements of electronic grade products are met.
Example 2
And sequentially passing the industrial-grade tetraethoxysilane with the purity of 99.0% through a two-stage microporous membrane coupling adsorption column to obtain the primary impurity-removed tetraethoxysilane. Wherein the first stage microporous membrane coupling adsorption column is provided with
600 type adsorption resin, wherein two ends of the adsorption resin are polytetrafluoroethylene microporous membranes with the aperture of 0.1 mu m and the thickness of 0.3 mm; the second-stage microporous membrane coupling adsorption column is filled with a blanc MTS9500 type macroporous chelating adsorption resin, and two ends of the second-stage microporous membrane coupling adsorption column are polytetrafluoroethylene microporous membranes with the aperture of 0.05 mu m and the thickness of 0.3 mm; the diameter and the length of the two-stage microporous membrane coupling adsorption columns are both 50mm and 500mm, the height-diameter ratio is 5, and the material is 316L stainless steel. The adsorbent resin was washed with 18M pure water before packing and then dried in a vacuum oven at 80 ℃. In the process of adsorption and impurity removal, the adsorption temperature is room temperature, the adsorption pressure is 0.2Mpa, and the flow rate is controlled to be 20 ml/min.
And (3) sending the primary impurity-removed tetraethoxysilane into a light component removal rectifying tower to obtain secondary impurity-removed tetraethoxysilane. Wherein the theoretical plate number of the light component removal rectifying tower is 10, the packing is theta ring metal packing of 5x5mm, the tower pressure is controlled to be 30kpa, the top temperature is 178 ℃, the reflux feed ratio is 15, and low-boiling substances are extracted from the tower top.
And (4) feeding the secondary impurity-removed ethyl orthosilicate into a heavy-weight removal rectifying tower to obtain the heavy-weight-removed impurity-removed ethyl orthosilicate. Wherein the theoretical plate number of the heavy-duty rectifying tower is 20, the filler is theta ring metal filler of 5x5mm, the tower pressure is controlled to be 50kpa, the top temperature is controlled to be 184 ℃, the reflux feed ratio is 20, and high-boiling substances and solid particles with relatively high content of enriched metal impurities are discharged from the tower kettle;
and filtering the product at the top of the de-heavy rectifying tower by a polytetrafluoroethylene microporous membrane with the pore diameter of 0.05 mu m to obtain an electronic grade ethyl orthosilicate product.
After GC-MS detection, the purity of the product reaches 99.999 percent, after ICP-MS detection, the total amount of impurities of the product is 3ppbw, and the number of particles (more than or equal to 0.2 mu m) is 7/ml. The requirements of electronic grade products are met.
Example 3
And sequentially passing the industrial-grade tetraethoxysilane with the purity of 99.5% through a two-stage microporous membrane coupling adsorption column to obtain the primary impurity-removed tetraethoxysilane. Wherein the first stage microporous membrane coupling adsorption column is provided with a bleached MTS9300 type macroporous chelating adsorption resin, and two ends are polytetrafluoroethylene microporous membranes with the aperture of 0.1 mu m and the thickness of 0.2 mm; the second-stage microporous membrane coupling adsorption column is provided with
572 type adsorption resin, two ends are polytetrafluoroethylene microporous membrane with aperture of 0.05 μm and thickness of 0.2 mm; the diameter and the length of the two-stage microporous membrane coupling adsorption columns are both 50mm and 500mm, the height-diameter ratio is 8, and the material is 316L stainless steel. The adsorbent resin was washed with 18M pure water before packing and then dried in a vacuum oven at 80 ℃. In the process of adsorption and impurity removal, the adsorption temperature is room temperature, the adsorption pressure is 0.20Mpa, and the flow rate is controlled to be 40 ml/min.
And (3) sending the primary impurity-removed tetraethoxysilane into a light component removal rectifying tower to obtain secondary impurity-removed tetraethoxysilane. Wherein the theoretical plate number of the light component removal rectifying tower is 20, the packing is theta ring metal packing of 5x5mm, the tower pressure is controlled to be 30kpa, the top temperature is 178 ℃, the reflux feed ratio is 20, and low-boiling substances are extracted from the tower top.
And (4) feeding the secondary impurity-removed ethyl orthosilicate into a heavy-weight removal rectifying tower to obtain the heavy-weight-removed impurity-removed ethyl orthosilicate. Wherein the theoretical plate number of the heavy-duty rectifying tower is 40, the filler is theta ring metal filler of 5x5mm, the tower pressure is controlled to be 40kpa, the top temperature is controlled to be 181 ℃, the reflux feed ratio is 20, and high-boiling substances and solid particles with relatively high content of enriched metal impurities are discharged from the tower kettle;
and filtering the product at the top of the de-heavy rectifying tower by a polytetrafluoroethylene microporous membrane with the pore diameter of 0.05 mu m to obtain an electronic grade ethyl orthosilicate product.
After GC-MS detection, the purity of the product reaches 99.999 percent, after ICP-MS detection, the total amount of impurities of the product is 4ppbw, and the number of particles (more than or equal to 0.2 mu m) is 6/ml. The requirements of electronic grade products are met.
Example 4
And sequentially passing the industrial-grade tetraethoxysilane with the purity of 99.0% through a two-stage microporous membrane coupling adsorption column to obtain the primary impurity-removed tetraethoxysilane. Wherein the first stage microporous membrane coupling adsorption column is provided with
600 type adsorption resin, wherein two ends of the adsorption resin are polytetrafluoroethylene microporous membranes with the aperture of 0.1 mu m and the thickness of 0.3 mm; the second-stage microporous membrane coupling adsorption column is provided with
572 type adsorption resin, two ends are polytetrafluoroethylene microporous membrane with aperture of 0.05 μm and thickness of 0.3 mm; the diameter and the length of the two-stage microporous membrane coupling adsorption columns are both 50mm and 500mm, the height-diameter ratio is 7, and the material is 316L stainless steel. The adsorbent resin was washed with 18M pure water before packing and then dried in a vacuum oven at 80 ℃. In the process of adsorption and impurity removal, the adsorption temperature is room temperature, the adsorption pressure is 0.15Mpa, and the flow rate is controlled to be 25 ml/min.
And (3) sending the primary impurity-removed tetraethoxysilane into a light component removal rectifying tower to obtain secondary impurity-removed tetraethoxysilane. Wherein the theoretical plate number of the light component removal rectifying tower is 20, the packing is theta ring metal packing of 5x5mm, the tower pressure is controlled to be 25kpa, the top temperature is 177 ℃, the reflux feed ratio is 15, and low-boiling substances are extracted from the tower top.
And (4) feeding the secondary impurity-removed ethyl orthosilicate into a heavy-weight removal rectifying tower to obtain the heavy-weight-removed impurity-removed ethyl orthosilicate. Wherein the theoretical plate number of the heavy-duty rectifying tower is 40, the filler is theta ring metal filler of 5x5mm, the tower pressure is controlled to be 45kpa, the top temperature is controlled to be 182 ℃, the reflux-feed ratio is 20, and high-boiling substances and solid particles with relatively high content of enriched metal impurities are discharged from the tower kettle;
and filtering the product at the top of the de-heavy rectifying tower by a polytetrafluoroethylene microporous membrane with the pore diameter of 0.05 mu m to obtain an electronic grade ethyl orthosilicate product.
After GC-MS detection, the purity of the product reaches 99.999 percent, after ICP-MS detection, the total amount of impurities of the product is 4ppbw, and the number of particles (more than or equal to 0.2 mu m) is 8/ml. The requirements of electronic grade products are met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation facilities of electronic grade tetraethoxysilane, which is characterized by comprising:
an industrial grade tetraethyl orthosilicate supply unit (10) for providing industrial grade tetraethyl orthosilicate;
the adsorption column comprises a multistage microporous membrane coupling adsorption column (20), wherein the microporous membrane coupling adsorption column (20) comprises a cylindrical hollow shell, chelate adsorption resin is filled in the cylindrical hollow shell, and microporous membranes are arranged at two ends of the hollow shell; the microporous membrane coupling adsorption columns (20) at all levels are arranged in series and/or in parallel according to the material flow sequence, and the inlet of the microporous membrane coupling adsorption column (20) at the first level is connected with the industrial ethyl orthosilicate supply unit (10);
the light component removal rectifying tower (30) is provided with a light component removal tower inlet (301), a light component removal tower top outlet (302) and a light component removal tower kettle outlet (303), wherein the light component removal tower inlet (301) is connected with an outlet of the microporous membrane coupling adsorption column (20) at the last stage, and the theoretical plate number of the light component removal rectifying tower (30) is 10-30;
the heavy component removal rectifying tower (40) is provided with a heavy component removal tower inlet (401), a tower top electronic grade ethyl orthosilicate outlet (402) and a heavy component removal tower kettle outlet (403), wherein the heavy component removal tower inlet (401) is connected with the light component removal tower kettle outlet (303), and the theoretical plate number of the heavy component removal rectifying tower (40) is 20-50.
2. The preparation device of electronic grade tetraethoxysilane according to claim 1, wherein in the two adjacent stages of the microporous membrane coupled adsorption columns (20) in the material flow sequence, the pore diameter of the microporous membrane of the upstream microporous membrane coupled adsorption column (20) is larger than that of the downstream microporous membrane coupled adsorption column (20).
3. The preparation device of electronic grade tetraethoxysilane according to claim 2, wherein the aperture of the microporous membrane coupling adsorption column (20) is 0.05-0.5 μm.
4. The preparation device of electronic grade tetraethoxysilane according to claim 3, wherein the microporous membrane coupling adsorption column (20) comprises two stages arranged in series, the pore diameter of the microporous membrane of the first stage microporous membrane coupling adsorption column (20) is 0.1-0.3 μm, and the pore diameter of the microporous membrane of the second stage microporous membrane coupling adsorption column (20) is 0.05-0.1 μm.
5. The preparation device of electronic grade tetraethoxysilane according to any one of claims 1 to 4, wherein the thickness of the microporous membrane is 0.2-0.3 mm, and the microporous membrane is a polytetrafluoroethylene membrane.
6. The preparation device of the electronic grade tetraethoxysilane of any one of claims 1 to 4, wherein the height-diameter ratio of the microporous membrane coupling adsorption column (20) is 5-10.
7. The apparatus according to any one of claims 1 to 4, further comprising:
the microporous filtering unit (50) comprises a filtering cavity and a filtering membrane positioned in the filtering cavity, the filtering membrane is a polytetrafluoroethylene microporous membrane with the aperture of 0.05-0.1 mu m, and an inlet of the filtering cavity is connected with an outlet (402) of the electronic-grade ethyl orthosilicate on the top of the tower.
8. The preparation device of electronic grade tetraethoxysilane according to any one of claims 1 to 4, wherein the light component removal rectification tower (30) and the heavy component removal rectification tower (40) are both packed towers, and the adopted packing is stainless steel theta ring packing, triangular spiral packing or glass spring packing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121583A (en) * | 2021-04-21 | 2021-07-16 | 洛阳中硅高科技有限公司 | Preparation device and preparation method of electronic-grade ethyl orthosilicate |
| CN114504872A (en) * | 2022-02-15 | 2022-05-17 | 北京袭明科技有限公司 | Method and device for producing high-purity electronic grade ethylene glycol |
| CN117398707A (en) * | 2023-09-07 | 2024-01-16 | 湖北兴福电子材料股份有限公司 | Electronic grade hexamethyldisilazane purification device and purification method |
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2021
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121583A (en) * | 2021-04-21 | 2021-07-16 | 洛阳中硅高科技有限公司 | Preparation device and preparation method of electronic-grade ethyl orthosilicate |
| CN113121583B (en) * | 2021-04-21 | 2024-07-05 | 洛阳中硅高科技有限公司 | Preparation device and preparation method of electronic grade ethyl orthosilicate |
| CN114504872A (en) * | 2022-02-15 | 2022-05-17 | 北京袭明科技有限公司 | Method and device for producing high-purity electronic grade ethylene glycol |
| CN117398707A (en) * | 2023-09-07 | 2024-01-16 | 湖北兴福电子材料股份有限公司 | Electronic grade hexamethyldisilazane purification device and purification method |
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