CN116925123A - Preparation method of electronic-grade hexamethyldisilazane - Google Patents
Preparation method of electronic-grade hexamethyldisilazane Download PDFInfo
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- CN116925123A CN116925123A CN202310884635.1A CN202310884635A CN116925123A CN 116925123 A CN116925123 A CN 116925123A CN 202310884635 A CN202310884635 A CN 202310884635A CN 116925123 A CN116925123 A CN 116925123A
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- hexamethyldisilazane
- rectifying tower
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 104
- 239000012982 microporous membrane Substances 0.000 claims abstract description 103
- 230000008878 coupling Effects 0.000 claims abstract description 79
- 238000010168 coupling process Methods 0.000 claims abstract description 79
- 238000005859 coupling reaction Methods 0.000 claims abstract description 79
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 238000009835 boiling Methods 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- 239000006227 byproduct Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000000746 purification Methods 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 1
- JZTPOMIFAFKKSK-UHFFFAOYSA-N O-phosphonohydroxylamine Chemical compound NOP(O)(O)=O JZTPOMIFAFKKSK-UHFFFAOYSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- LKCWBDHBTVXHDL-RMDFUYIESA-N amikacin Chemical compound O([C@@H]1[C@@H](N)C[C@H]([C@@H]([C@H]1O)O[C@@H]1[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O1)O)NC(=O)[C@@H](O)CCN)[C@H]1O[C@H](CN)[C@@H](O)[C@H](O)[C@H]1O LKCWBDHBTVXHDL-RMDFUYIESA-N 0.000 description 1
- 229960004821 amikacin Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application relates to a preparation method of electronic-grade hexamethyldisilazane, which comprises the following steps: s1, taking industrial hexamethyldisilazane as a raw material, and introducing the raw material into a multistage microporous membrane coupling adsorption unit to remove metal ions through adsorption; s2, feeding the materials discharged by the multistage microporous membrane coupling adsorption unit into a light component removal rectifying tower, wherein the light component removal rectifying tower adopts silazane sub-boiling point rectifying operation; s3, allowing the hexa-methyl disilazane subjected to light component removal to enter a heavy component removal rectifying tower for rectifying and purifying, wherein the heavy component removal rectifying tower adopts silazane sub-boiling point rectifying operation; s4, the hexamethyldisilazane subjected to the de-duplication treatment enters a filter for filtering and impurity removal, and the electronic-grade hexamethyldisilazane is obtained after the impurity removal by the filter.
Description
Technical Field
The application belongs to the technical field of chemical material purification, and particularly relates to a preparation method of electronic-grade hexamethyldisilazane.
Background
Hexamethyldisilazane (HMDS), a colorless transparent liquid, is an important organosilicon compound, and has wide application in the fields of organosilicon chemistry and organic synthesis. For example, hexamethyldisilazane can be used as a reagent for providing N atoms in a vapor phase process silica surface hydrophobic agent and an organic synthesis reaction; can be used as an auxiliary agent of the silicon carbide fiber to improve the heat resistance and the strength of the silicon carbide fiber; can also be used as an anti-settling agent for coatings and for the preparation of organosilicon compounds. In addition, hexamethyldisilazane is not only a key raw material for synthesizing hexamethyldisilurea (BSU), but also a silylating agent commonly used in organic synthesis, and has important industrial utilization value. Meanwhile, the hexamethyldisilazane can be used as a bonding aid of a photo-etching agent in the semiconductor industry, and the hexamethyldisilazane is also used in the synthesis process of amikacin, penicillin, cephalosporin and the like in the pharmaceutical industry.
Along with the development of scientific technology, the quality, especially the purity, of the raw materials of the hexamethyldisilazane is required to be higher and higher, for example, the hexamethyldisilazane used in the fields of photoresist, chip manufacturing, medicines, new materials and the like is required to reach the quality standard of SEMI-C7/C8/C12 of international chemical electronics. But limited by equipment and technology, the quality of the domestic electronic grade hexamethyldisilazane can only reach SEMI-C1 level or the domestic wet electronic chemical BV-I level, and the domestic electronic grade hexamethyldisilazane is difficult to be a high-grade product and cannot exert and create the maximum economic value. The reason is mainly that the domestic process for producing hexamethyldisilazane and the equipment thereof are relatively imperfect, the content of metal ion impurities in the produced hexamethyldisilazane is difficult to reach the standard requirement, only middle and low grade products can be produced, and high grade products can not be produced.
Thus, there is a great need in the art for a suitable system and process for producing high purity electronic grade hexamethyldisilazane with lower energy consumption and lower capital investment.
Disclosure of Invention
The application aims at solving the technical problems and provides a preparation method of electronic-grade hexamethyldisilazane, which is used for producing high-purity electronic-grade hexamethyldisilazane with lower energy consumption and lower investment.
In view of the above, the present application provides a method for preparing electronic grade hexamethyldisilazane, comprising the steps of:
s1, taking industrial hexamethyldisilazane as a raw material, and introducing the raw material into a multistage microporous membrane coupling adsorption unit to remove metal ions through adsorption;
s2, feeding the materials discharged by the multistage microporous membrane coupling adsorption unit into a light component removal rectifying tower, wherein the light component removal rectifying tower adopts silazane sub-boiling point rectifying operation;
s3, allowing the hexa-methyl disilazane subjected to light component removal to enter a heavy component removal rectifying tower for rectifying and purifying, wherein the heavy component removal rectifying tower adopts silazane sub-boiling point rectifying operation;
s4, the hexamethyldisilazane subjected to the de-duplication treatment enters a filter for filtering and impurity removing, and the electronic-grade hexamethyldisilazane is obtained after the impurity removing by the filter.
Further, in the step S1, the purity of the industrial grade hexamethyldisilazane raw material is more than or equal to 99 percent, and the content of metal ions in the hexamethyldisilazane after passing through the multistage microporous membrane coupling adsorption unit is less than 0.1 ppm.
Further, in the step S2, the pressure in the light component removal rectifying tower is controlled to be 35-55 kpa, the temperature is controlled to be 70-80 ℃, the light component in the hexamethyldisilazane is removed through the top of the tower by the light component removal rectifying tower, and the removed light component is condensed by a first reflux condenser and is used or sold as industrial hexamethyldisilazane.
Further, in the step S3, the pressure in the heavy removal rectifying tower is controlled to be 15-25 kpa, the temperature is controlled to be 70-80 ℃, the heavy components in the hexamethyldisilazane are left in the tower bottom through the heavy removal rectifying tower, and the hexamethyldisilazane after rectification and purification is extracted from the tower top.
Further, in the step S3, the heavy component removed by the heavy component removal rectifying tower is used or sold as technical grade hexamethyldisilazane.
Further, the preparation device adopted by the preparation method of the electronic-grade hexamethyldisilazane comprises the following steps:
a raw material supply unit capable of delivering raw material industrial grade hexamethyldisilazane to the multistage microporous membrane coupled adsorption unit;
the multistage microporous membrane coupling adsorption unit comprises multistage microporous membrane coupling adsorption columns, wherein the microporous membrane coupling adsorption columns at all stages are connected in series according to the material flow sequence, and an inlet of the microporous membrane coupling adsorption column at the first stage is connected with the raw material supply unit;
the light component removing unit comprises a light component removing rectifying tower, a first reboiler and a first reflux condenser, wherein a light component removing rectifying tower inlet, a light component removing rectifying tower top outlet and a light component removing rectifying tower kettle outlet are arranged on the light component removing rectifying tower, the light component removing rectifying tower inlet is connected with an outlet of a microporous membrane coupling adsorption column of the last stage, the light component removing rectifying tower top outlet is connected with the first reflux condenser, the material discharged by the first reflux condenser is divided into two paths, one path of material flows back into the light component removing rectifying tower, and the other path of material discharges byproduct industrial-grade hexamethyldisilazane;
the heavy component removing unit comprises a heavy component removing rectifying tower, a second reboiler and a second reflux condenser, wherein a heavy component removing rectifying tower inlet, a heavy component removing rectifying tower top outlet and a heavy component removing rectifying tower kettle outlet are arranged on the heavy component removing rectifying tower, the heavy component removing rectifying tower inlet is connected with the light component removing rectifying tower kettle outlet, the heavy component removing rectifying tower top outlet is connected with the second reflux condenser, and materials discharged by the second reflux condenser are respectively in two paths, one path of materials flows back into the heavy component removing rectifying tower, and the other path of materials enter the filtering unit;
the filter unit comprises a filter, a feed inlet of the filter is connected with an outlet of the top of the heavy removal rectifying tower, and a discharge outlet of the filter discharges purified electronic-grade hexamethyldisilazane.
Further, the multistage microporous membrane coupled adsorption unit includes:
the device comprises a first-stage microporous membrane coupling adsorption column and a second-stage microporous membrane coupling adsorption column, wherein the inlet of the first-stage microporous membrane coupling adsorption column is connected with a raw material supply pipe, the outlet of the first-stage microporous membrane coupling adsorption column is connected with the inlet of the second-stage microporous membrane coupling adsorption column, and the outlet of the second-stage microporous membrane coupling adsorption column is connected with the inlet of the light component removal rectifying tower;
the pore diameter of the microporous membrane of the first-stage microporous membrane coupling adsorption column is larger than that of the microporous membrane of the second-stage microporous membrane coupling adsorption column;
and chelating adsorption resin is filled in the first-stage microporous membrane coupling adsorption column and the second-stage microporous membrane coupling adsorption column.
Further, the diameter of the microporous membrane of the first-stage microporous membrane coupling adsorption column is 0.1-0.3 um; the aperture of the microporous membrane of the second-stage microporous membrane coupling adsorption column is 0.05-0.1 um;
the length-diameter ratio of the first-stage microporous membrane coupling adsorption column and the second-stage microporous membrane coupling adsorption column is 5-10.
Further, the first reboiler and the second reboiler are heated by siphoning;
the theoretical plate number of the light component removal rectifying tower is 28-35, and the filler of the light component removal rectifying tower is theta-ring metal;
the theoretical plate number of the de-heavy rectifying tower is 35-45, and the packing of the de-heavy rectifying tower is corrugated net packing.
Further, the filter has a filtering precision of 0.03-0.1 um, and the filter element of the filter adopts a PTFE sintered filter rod.
The preparation method of the electronic-grade hexamethyldisilazane has the following advantages:
firstly, the preparation method of the electronic grade hexamethyldisilazane has simple production operation process, continuous production and operation and good refining and purifying effects;
secondly, the application uses industrial hexamethyldisilazane as the raw material, and the source of the raw material is relatively simple;
thirdly, the byproduct generated in the refining and purifying process of the hexamethyldisilazane can be directly used and sold as industrial hexamethyldisilazane, and the whole process has no waste products, little pollution and high product availability;
fourth, the preparation method of the application sequentially uses multistage microporous membrane coupling adsorption units to remove metal ions, uses a light component removal rectifying tower to remove heavy components, uses a heavy component removal rectifying tower to remove impurities, and uses a post filter to filter impurities, so that the whole arrangement is reasonable, the units are mutually matched, and the impurity removal effect is good;
fifth, the light component removing rectifying tower and the heavy component removing rectifying tower adopt siphon heating mode to heat the first reboiler and the second reboiler, so that the energy consumption in the refining and purifying process of hexamethyldisilazane is low.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing electronic grade hexamethyldisilazane according to the present application;
the label in the figure is:
1. a raw material supply pipe; 2. a first stage microporous membrane coupled adsorption column; 3. a second stage microporous membrane coupled to the adsorption column; 4. a light component removing rectifying tower; 5. a first reboiler; 6. a first reflux condenser; 7. a heavy-removal rectifying tower; 8. a transfer pump; 9. a second reboiler; 10. a second reflux condenser; 11. a filter; 12. a by-product discharge pipe; 13. and (5) vacuumizing the system.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which are obtained by a person skilled in the art based on the embodiments of the present application, fall within the scope of protection of the present application.
In the description of the present application, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments in accordance with the present application. For ease of description, the dimensions of the various features shown in the drawings are not drawn to actual scale. Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values. It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further discussion thereof is necessary in subsequent figures.
It should be noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged, as appropriate, such that embodiments of the present application may be implemented in sequences other than those illustrated or described herein, and that the objects identified by "first," "second," etc. are generally of a type, and are not limited to the number of objects, such as the first object may be one or more. Furthermore, in the description and claims, "and/or" means at least one of the connected objects, and the character "/", generally means that the associated object is an "or" relationship.
It should be noted that, in the description of the present application, the terms like "front, rear, upper, lower, left, right", "horizontal, vertical, horizontal", and "top, bottom", etc. generally refer to the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are merely for convenience of describing the present application and simplifying the description, and these orientation terms do not indicate and imply that the apparatus or elements referred to must have a specific orientation or be constructed and operated in a specific orientation, and thus should not be construed as limiting the scope of the present application; the orientation word "inner and outer" refers to inner and outer relative to the contour of the respective component itself.
It should be noted that, in the present application, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Furthermore, it should be noted that the scope of the methods and apparatus in the embodiments of the present application is not limited to performing the functions in the order shown or discussed, but may also include performing the functions in a substantially simultaneous manner or in an opposite order depending on the functions involved, e.g., the described methods may be performed in an order different from that described, and various steps may be added, omitted, or combined. Additionally, features described with reference to certain examples may be combined in other examples.
As shown in fig. 1, a method for preparing electronic grade hexamethyldisilazane comprises the steps of:
s1, taking industrial hexamethyldisilazane as a raw material, and introducing the raw material into a multistage microporous membrane coupling adsorption unit to remove metal ions through adsorption;
s2, feeding materials discharged from the multistage microporous membrane coupling adsorption unit into a light component removal rectifying tower 4, wherein the light component removal rectifying tower 4 adopts silazane sub-boiling point rectifying operation;
s3, allowing the hexa-methyl disilazane subjected to light component removal to enter a heavy component removal rectifying tower 7 for rectifying and purifying, wherein the heavy component removal rectifying tower 7 adopts silazane sub-boiling point rectifying operation;
s4, the hexamethyldisilazane subjected to the de-duplication treatment enters a filter 11 for filtering and impurity removal, and the electronic-grade hexamethyldisilazane is obtained after the impurity removal by the filter 11.
The principle of the sub-boiling point rectification technology is that the low-boiling point liquid and the high-boiling point liquid are mixed together, when the mixed liquid is heated, the saturation limit appears, when the saturation limit is larger than the temperature of the mixed liquid, the liquid in the high-boiling point liquid is crystallized first, so that the high-boiling point liquid is separated, and then the purification of the high-boiling point liquid is realized through vapor diffusion caused by the boiling point difference of the low-boiling point liquid.
Preferably, in the step S1, the content of metal ions after hexamethyldisilazane passes through the multistage microporous membrane coupled adsorption unit may be controlled to be less than 0.1ppm by adjusting parameters such as pressure, temperature, flow rate and the like in the adsorption column.
As some embodiments of the present application, in the step S1, the pressure in the adsorption column is 0.1-0.3 mpa, the temperature is 10-60 ℃, and the flow rate is 0.6-6L/min.
Preferably, in the step S2, the pressure in the light component removal rectifying tower 4 is controlled to be 35-55 kpa, the temperature is controlled to be 70-80 ℃, the light component in the hexamethyldisilazane is removed through the top of the tower by the light component removal rectifying tower 4, and the removed light component is condensed by the first reflux condenser 6 and can be recycled as industrial hexamethyldisilazane for use or sale.
Preferably, in the step S3, the pressure in the heavy ends removal rectifying tower 7 is controlled to be 15-25 kpa, the temperature is controlled to be 70-80 ℃, heavy components and other impurities in the hexamethyldisilazane are left in a tower bottom through the heavy ends removal rectifying tower 7, and the hexamethyldisilazane after rectification and purification is extracted from the tower top.
Further, in the step S3, the heavy component removed by the heavy component removal rectifying tower is used or sold as technical grade hexamethyldisilazane.
Further, the preparation method of the electronic-grade hexamethyldisilazane is performed by adopting a preparation device of the electronic-grade hexamethyldisilazane, and the preparation device of the electronic-grade hexamethyldisilazane comprises the following steps:
a raw material supply unit capable of delivering raw material industrial grade hexamethyldisilazane to the multistage microporous membrane coupled adsorption unit;
the multistage microporous membrane coupling adsorption unit comprises multistage microporous membrane coupling adsorption columns, wherein the microporous membrane coupling adsorption columns at all stages are connected in series according to the material flow sequence, and an inlet of the microporous membrane coupling adsorption column at the first stage is connected with the raw material supply unit;
the light component removing unit comprises a light component removing rectifying tower 4, a first reboiler 5 and a first reflux condenser 6, wherein a light component removing rectifying tower inlet, a light component removing rectifying tower top outlet and a light component removing rectifying tower kettle outlet are arranged on the light component removing rectifying tower 4, the light component removing rectifying tower inlet is connected with the outlet of a microporous membrane coupling adsorption column of the last stage, the light component removing rectifying tower top outlet is connected with the first reflux condenser 6, the material discharged by the first reflux condenser 6 is divided into two paths, one path of material flows back into the light component removing rectifying tower 4, and the other path of material discharges byproduct industrial grade hexamethyldisilazane;
the heavy component removing unit comprises a heavy component removing rectifying tower 7, a second reboiler 9 and a second reflux condenser 10, wherein a heavy component removing rectifying tower inlet, a heavy component removing rectifying tower top outlet and a heavy component removing rectifying tower kettle outlet are arranged on the heavy component removing rectifying tower 7, the heavy component removing rectifying tower inlet is connected with the light component removing rectifying tower kettle outlet, the heavy component removing rectifying tower top outlet is connected with the second reflux condenser 10, and materials discharged by the second reflux condenser 10 are respectively in two paths, one path of materials flows back into the heavy component removing rectifying tower 7, and the other path of materials enter the filtering unit;
the filter unit comprises a filter 11, wherein a feed inlet of the filter 11 is connected with an outlet of the top of the heavy removal rectifying tower, and a discharge outlet of the filter discharges purified electronic-grade hexamethyldisilazane.
As some embodiments of the present application, the raw material supply unit includes:
a raw material storage tank for storing raw material technical grade hexamethyldisilazane;
a raw material supply pipe 1 is provided,
and a feedstock transfer pump for pumping the technical grade hexamethyldisilazane feedstock in the feedstock storage tank into the multistage microporous membrane coupled adsorption unit.
As some embodiments of the present application, the raw material transfer pump is disposed between the raw material storage tank and the raw material supply pipe 1, the raw material storage tank, the raw material transfer pump, and the raw material supply pipe 1 are sequentially connected, and the raw material supply pipe 1 is connected with the multistage microporous membrane coupled adsorption unit.
Preferably, the purity of the industrial grade hexamethyldisilazane raw material conveyed by the raw material supply unit to the multistage microporous membrane coupling adsorption unit is more than or equal to 99%.
Preferably, the multistage microporous membrane coupled adsorption unit comprises:
the light-removal rectifying tower comprises a first-stage microporous membrane coupling adsorption column 2 and a second-stage microporous membrane coupling adsorption column 3, wherein the inlet of the first-stage microporous membrane coupling adsorption column 2 is connected with a raw material supply pipe 1, the outlet of the first-stage microporous membrane coupling adsorption column is connected with the inlet of the second-stage microporous membrane coupling adsorption column 3, and the outlet of the second-stage microporous membrane coupling adsorption column 3 is connected with the inlet of the light-removal rectifying tower 4.
Further, the pore diameter of the microporous membrane of the first-stage microporous membrane coupling adsorption column 2 is larger than that of the microporous membrane of the second-stage microporous membrane coupling adsorption column 3.
Preferably, the aperture of the microporous membrane of the first-stage microporous membrane coupling adsorption column 2 is 0.1-0.3 um; the aperture of the microporous membrane of the second-stage microporous membrane coupling adsorption column 3 is 0.05-0.1 um.
Preferably, the aspect ratio of the first-stage microporous membrane coupling adsorption column 2 and the second-stage microporous membrane coupling adsorption column 3 is 5-10.
Further, the first-stage microporous membrane coupling adsorption column 2 and the second-stage microporous membrane coupling adsorption column 3 are filled with chelating adsorption resin, and the chelating adsorption resin is one or more of diacetic acid chelating resin (type MTS9300 with a large size of Kong Yaan) polystyrene, chelating resin (type MTS9500 with a large size of float), chelating resin of polystyrene and diethylene macroporous amino phosphoric acid, sulfonated styrene divinyl resin and the like.
Further, the preparation device further comprises:
and the vacuumizing unit is respectively connected with the first reflux condenser 6 and the second reflux condenser 10.
Still further, the vacuum pumping unit includes:
a vacuum-pumping system 13 for evacuating the first reflux condenser 6 and the second reflux condenser 10;
and a connecting pipe for connecting the vacuum pumping system 13 and the reflux condenser.
Specifically, the vacuum pumping system 13 is connected to the first reflux condenser 6 and the second reflux condenser 10 through connection pipes, respectively.
Further, a byproduct discharge pipe 12 is disposed at the outlet of the first reflux condenser 6, a part of the material discharged from the outlet of the first reflux condenser 6 is discharged as byproduct industrial grade hexamethyldisilazane through the byproduct discharge pipe 12, and the byproduct industrial grade hexamethyldisilazane discharged from the byproduct discharge pipe 12 can be directly used or sold as industrial grade hexamethyldisilazane.
Still further, one end of the first reboiler 5 is communicated with the outlet of the light-removal rectifying tower kettle, and the other end of the first reboiler is communicated with the light-removal rectifying tower 4, so that the first reboiler 5 and the light-removal rectifying tower 4 can form a loop, one part of materials discharged from the outlet of the light-removal rectifying tower kettle is conveyed to the heavy component removing unit through the conveying pump 8, and the other part of materials enter the light-removal rectifying tower 4 again through the first reboiler 5.
Preferably, the first reboiler 5 is heated by means of siphoning.
Preferably, the theoretical plate number of the light component removal rectifying tower 4 is 28-35, preferably 30; the packing of the light component removal rectifying tower 4 adopts 5 x 5mm theta-ring metal.
Further, the second reboiler 9 is communicated with the outlet of the heavy-removal rectifying tower kettle, and the other end of the second reboiler is communicated with the heavy-removal rectifying tower 7, so that the second reboiler 9 and the heavy-removal rectifying tower 7 form a loop, and at least part of materials discharged from the outlet of the heavy-removal rectifying tower kettle can enter the heavy-removal rectifying tower 7 again through the second reboiler 9.
Preferably, the second reboiler 9 is heated by means of siphoning.
Preferably, the theoretical plate number of the heavy component removal rectifying tower 7 is 35-45, preferably 40; the packing of the heavy-duty stripping rectifying tower 7 adopts corrugated net packing.
As some examples of the present application, the heavy component mixture containing hexamethyldisilazane in the bottom of the de-heavy rectification column 7 can be directly used and sold as technical grade hexamethyldisilazane.
Further, the filter 11 is a high-precision filter, and the filter 11 has a filtration accuracy of 0.03 to 0.1um.
Preferably, the filter element of the filter 11 is a PTFE sintered filter rod with a pore size of 0.05 um.
The high-precision filter adopted by the application has the advantages of high filtering precision, stable performance and repeated use, and the filter element adopts the PTFE sintered filter stick.
Furthermore, in order to reduce the influence of the rectification process on the product, the second reflux condenser 10 and the pipeline connected to the de-duplication rectification tower 7 are made of PTFE or lined with PTFE.
The existing hexamethyldisilazane rectification and purification process generally adopts a normal pressure rectification mode, so that the energy consumption is high, the efficiency is low, the used materials are difficult to meet the production requirements of electronic grade products, the device and the method for removing trace metal ions are absent in the process, the content of the produced hexamethyldisilazane is generally difficult to reach 99.99% or more, the content of the metal ions exceeds 50ppb, the particle size with the diameter of more than 0.5um is more than 25 particles, and the hexamethyldisilazane is difficult to use in the manufacture of large-scale integrated circuits and ultra-large-scale integrated circuits.
In the application, industrial hexamethyldisilazane is used as a raw material (the mass content is 99% or more), metal ions are removed through a two-stage microporous membrane coupling adsorption technology, light components and heavy components are removed through a sub-boiling point rectification technology, and finally impurities are filtered through a high-precision filter made of special materials, so that an electronic-grade hexamethyldisilazane product is obtained.
The following is a specific example of the preparation of electronic grade hexamethyldisilazane according to the present application:
example 1
Industrial hexamethyldisilazane (purity is 99.1%) is taken as a raw material, and is sequentially introduced into the first-stage microporous membrane coupling adsorption column 2 and the second-stage microporous membrane coupling adsorption column 3 to remove metal ions through adsorption; the materials discharged by the multistage microporous membrane coupling adsorption unit enter a light component removal rectifying tower 4, the light component removal rectifying tower 4 adopts silazane sub-boiling point rectifying operation, the pressure in the light component removal rectifying tower 4 is controlled to be 35kpa, the temperature is controlled to be 70 ℃, the light component in hexamethyldisilazane is removed through the top of the tower by the light component removal rectifying tower 4, and the removed light component is recovered to be used as industrial hexamethyldisilazane after being condensed by a first reflux condenser 6; the light hexamethyldisilazane enters a heavy removal rectifying tower 7 for rectifying and purifying, heavy components are removed, the pressure in the heavy removal rectifying tower 7 is controlled to be 15kpa, the temperature is controlled to be 70 ℃, the heavy components and other impurities in the hexamethyldisilazane are left in a tower kettle through the heavy removal rectifying tower 7, and the hexamethyldisilazane after rectifying and purifying is extracted from the tower top; and (3) the de-heavy hexamethyldisilazane enters a filter 11 for filtering and impurity removal, and the electronic-grade hexamethyldisilazane is obtained after the impurity removal by the filter 11.
Example 2
Industrial hexamethyldisilazane (purity is 99.3%) is taken as a raw material, and is sequentially introduced into the first-stage microporous membrane coupling adsorption column 2 and the second-stage microporous membrane coupling adsorption column 3 to remove metal ions through adsorption; the materials discharged by the multistage microporous membrane coupling adsorption unit enter a light component removal rectifying tower 4, the light component removal rectifying tower 4 adopts silazane sub-boiling point rectifying operation, the pressure in the light component removal rectifying tower 4 is controlled to be 42kpa, the temperature is controlled to be 76 ℃, the light component in hexamethyldisilazane is removed through the top of the tower by the light component removal rectifying tower 4, and the removed light component is recovered to be used as industrial hexamethyldisilazane after being condensed by a first reflux condenser 6; the light hexamethyldisilazane enters a heavy removal rectifying tower 7 for rectifying and purifying, heavy components are removed, the pressure in the heavy removal rectifying tower 7 is controlled to be 18kpa, the temperature is controlled to be 74 ℃, the heavy components and other impurities in the hexamethyldisilazane are left in a tower kettle through the heavy removal rectifying tower 7, and the hexamethyldisilazane after rectifying and purifying is extracted from the tower top; and (3) the de-heavy hexamethyldisilazane enters a filter 11 for filtering and impurity removal, and the electronic-grade hexamethyldisilazane is obtained after the impurity removal by the filter 11.
Example 3
Industrial hexamethyldisilazane (purity is 99.1%) is taken as a raw material, and is sequentially introduced into the first-stage microporous membrane coupling adsorption column 2 and the second-stage microporous membrane coupling adsorption column 3 to remove metal ions through adsorption; the materials discharged by the multistage microporous membrane coupling adsorption unit enter a light component removal rectifying tower 4, the light component removal rectifying tower 4 adopts silazane sub-boiling point rectifying operation, the pressure in the light component removal rectifying tower 4 is controlled to be 55kpa, the temperature is controlled to be 80 ℃, the light component in hexamethyldisilazane is removed through the top of the tower by the light component removal rectifying tower 4, and the removed light component is recovered to be used as industrial hexamethyldisilazane after being condensed by a first reflux condenser 6; the light hexamethyldisilazane enters a heavy removal rectifying tower 7 for rectifying and purifying, heavy components are removed, the pressure in the heavy removal rectifying tower 7 is controlled to be 25kpa, the temperature is controlled to be 80 ℃, the heavy components and other impurities in the hexamethyldisilazane are left in a tower kettle through the heavy removal rectifying tower 7, and the hexamethyldisilazane after rectifying and purifying is extracted from the tower top; and (3) the de-heavy hexamethyldisilazane enters a filter 11 for filtering and impurity removal, and the electronic-grade hexamethyldisilazane is obtained after the impurity removal by the filter 11.
The electronic grade hexamethyldisilazane obtained by purification in the above examples 1 to 3 is detected, and the purity of the hexamethyldisilazane treated by the preparation method of the electronic grade hexamethyldisilazane is more than or equal to 99.99%, the metal ion content is less than 10ppb, the particle size is less than 0.05um, and the particle number is less than 10. Meets the international electronic chemical SEMI-C7, C8 and C12 standards or the national wet electronic chemical BV-IV, V and VI product standards of semiconductors, and meets the market application requirements of high-grade electronic grade hexamethyldisilazane.
In summary, it is possible to obtain: the preparation method of the electronic-grade hexamethyldisilazane has the following advantages:
firstly, the preparation method of the electronic grade hexamethyldisilazane has simple production operation process, continuous production and operation and good refining and purifying effects;
secondly, the application uses industrial hexamethyldisilazane as the raw material, and the source of the raw material is relatively simple;
thirdly, the byproduct generated in the refining and purifying process of the hexamethyldisilazane can be directly used and sold as industrial hexamethyldisilazane, and the whole process has no waste products, little pollution and high product availability;
fourth, the preparation method of the application sequentially uses multistage microporous membrane coupling adsorption units to remove metal ions, uses a light component removal rectifying tower to remove heavy components, uses a heavy component removal rectifying tower to remove impurities, and uses a post filter to filter impurities, so that the whole arrangement is reasonable, the units are mutually matched, and the impurity removal effect is good;
fifth, the light component removing rectifying tower and the heavy component removing rectifying tower adopt siphon mode to heat the first reboiler 5 and the second reboiler 9, so that the energy consumption in the refining and purifying process of hexamethyldisilazane is low.
The embodiments of the present application have been described above with reference to the accompanying drawings, in which the embodiments of the present application and features of the embodiments may be combined with each other without conflict, the present application is not limited to the above-described embodiments, which are merely illustrative, not restrictive, of the present application, and many forms may be made by those of ordinary skill in the art without departing from the spirit of the present application and the scope of the claims, which are protected by the present application.
Claims (10)
1. The preparation method of the electronic-grade hexamethyldisilazane is characterized by comprising the following steps:
s1, taking industrial hexamethyldisilazane as a raw material, and introducing the raw material into a multistage microporous membrane coupling adsorption unit to remove metal ions through adsorption;
s2, feeding the materials discharged by the multistage microporous membrane coupling adsorption unit into a light component removal rectifying tower, wherein the light component removal rectifying tower adopts silazane sub-boiling point rectifying operation;
s3, allowing the hexa-methyl disilazane subjected to light component removal to enter a heavy component removal rectifying tower for rectifying and purifying, wherein the heavy component removal rectifying tower adopts silazane sub-boiling point rectifying operation;
s4, the hexamethyldisilazane subjected to the de-duplication treatment enters a filter for filtering and impurity removing, and the electronic-grade hexamethyldisilazane is obtained after the impurity removing by the filter.
2. The method for producing electronic grade hexamethyldisilazane according to claim 1, wherein in the step S1, the purity of the industrial grade hexamethyldisilazane raw material is not less than 99%, and the content of metal ions in hexamethyldisilazane after passing through the multistage microporous membrane coupled adsorption unit is not more than 0.1 ppm.
3. The method for preparing electronic grade hexamethyldisilazane according to claim 1, wherein in the step S2, the pressure in the light component removing rectifying tower is controlled to be 35-55 kpa and the temperature is controlled to be 70-80 ℃, the light component in hexamethyldisilazane is removed through the top of the tower by the light component removing rectifying tower, and the removed light component is condensed by the first reflux condenser and then is used or sold as industrial grade hexamethyldisilazane.
4. The method for producing electronic grade hexamethyldisilazane according to claim 1, wherein in the step S3, the pressure in the stripping and rectifying column is controlled to be 15 to 25kpa and the temperature is controlled to be 70 to 80 ℃, the heavy component in hexamethyldisilazane is left in the column bottom through the stripping and rectifying column, and the purified hexamethyldisilazane is recovered from the column top.
5. The method for producing electronic grade hexamethyldisilazane according to claim 4, wherein the heavy component removed by the de-duplication rectification column is used or sold as industrial grade hexamethyldisilazane in the step S3.
6. The method for preparing electronic grade hexamethyldisilazane according to claim 1, wherein the preparation device used in the method for preparing electronic grade hexamethyldisilazane comprises:
a raw material supply unit capable of delivering raw material industrial grade hexamethyldisilazane to the multistage microporous membrane coupled adsorption unit;
the multistage microporous membrane coupling adsorption unit comprises multistage microporous membrane coupling adsorption columns, wherein the microporous membrane coupling adsorption columns at all stages are connected in series according to the material flow sequence, and an inlet of the microporous membrane coupling adsorption column at the first stage is connected with the raw material supply unit;
the light component removing unit comprises a light component removing rectifying tower, a first reboiler and a first reflux condenser, wherein a light component removing rectifying tower inlet, a light component removing rectifying tower top outlet and a light component removing rectifying tower kettle outlet are arranged on the light component removing rectifying tower, the light component removing rectifying tower inlet is connected with an outlet of a microporous membrane coupling adsorption column of the last stage, the light component removing rectifying tower top outlet is connected with the first reflux condenser, the material discharged by the first reflux condenser is divided into two paths, one path of material flows back into the light component removing rectifying tower, and the other path of material discharges byproduct industrial-grade hexamethyldisilazane;
the heavy component removing unit comprises a heavy component removing rectifying tower, a second reboiler and a second reflux condenser, wherein a heavy component removing rectifying tower inlet, a heavy component removing rectifying tower top outlet and a heavy component removing rectifying tower kettle outlet are arranged on the heavy component removing rectifying tower, the heavy component removing rectifying tower inlet is connected with the light component removing rectifying tower kettle outlet, the heavy component removing rectifying tower top outlet is connected with the second reflux condenser, and materials discharged by the second reflux condenser are respectively in two paths, one path of materials flows back into the heavy component removing rectifying tower, and the other path of materials enter the filtering unit;
the filter unit comprises a filter, a feed inlet of the filter is connected with an outlet of the top of the heavy removal rectifying tower, and a discharge outlet of the filter discharges purified electronic-grade hexamethyldisilazane.
7. The method for preparing electronic grade hexamethyldisilazane according to claim 6, wherein the multistage microporous membrane coupled adsorption unit comprises:
the device comprises a first-stage microporous membrane coupling adsorption column and a second-stage microporous membrane coupling adsorption column, wherein the inlet of the first-stage microporous membrane coupling adsorption column is connected with a raw material supply pipe, the outlet of the first-stage microporous membrane coupling adsorption column is connected with the inlet of the second-stage microporous membrane coupling adsorption column, and the outlet of the second-stage microporous membrane coupling adsorption column is connected with the inlet of the light component removal rectifying tower;
the pore diameter of the microporous membrane of the first-stage microporous membrane coupling adsorption column is larger than that of the microporous membrane of the second-stage microporous membrane coupling adsorption column;
and chelating adsorption resin is filled in the first-stage microporous membrane coupling adsorption column and the second-stage microporous membrane coupling adsorption column.
8. The method for preparing electronic grade hexamethyldisilazane according to claim 7,
the diameter of the microporous membrane of the first-stage microporous membrane coupling adsorption column is 0.1-0.3 um; the aperture of the microporous membrane of the second-stage microporous membrane coupling adsorption column is 0.05-0.1 um;
the length-diameter ratio of the first-stage microporous membrane coupling adsorption column and the second-stage microporous membrane coupling adsorption column is 5-10.
9. The method for preparing electronic grade hexamethyldisilazane according to claim 6,
the first reboiler and the second reboiler are heated by a siphon way;
the theoretical plate number of the light component removal rectifying tower is 28-35, and the filler of the light component removal rectifying tower is theta-ring metal;
the theoretical plate number of the de-heavy rectifying tower is 35-45, and the packing of the de-heavy rectifying tower is corrugated net packing.
10. The method for preparing electronic grade hexamethyldisilazane according to claim 6, wherein the filter has a filtration precision of 0.03-0.1 um, and the filter element of the filter is a PTFE sintered filter rod.
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