CN116903653B - Preparation method and production system of high-purity ethyl silicate - Google Patents
Preparation method and production system of high-purity ethyl silicate Download PDFInfo
- Publication number
- CN116903653B CN116903653B CN202310849522.8A CN202310849522A CN116903653B CN 116903653 B CN116903653 B CN 116903653B CN 202310849522 A CN202310849522 A CN 202310849522A CN 116903653 B CN116903653 B CN 116903653B
- Authority
- CN
- China
- Prior art keywords
- rectification
- product
- ethyl silicate
- purity
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 claims abstract description 31
- 239000012043 crude product Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 73
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 26
- 244000060011 Cocos nucifera Species 0.000 claims description 26
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003729 cation exchange resin Substances 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 19
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 17
- 238000011049 filling Methods 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 description 19
- 238000004821 distillation Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- -1 single-walled Chemical compound 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- C07F7/04—Esters of silicic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method and a production system of high-purity ethyl silicate, wherein the preparation method comprises the following steps: (1) Rectifying the crude product of the ethyl orthosilicate for the first time to obtain a product after the first rectification; (2) The product after the first rectification passes through an adsorption tower to obtain an adsorbed product; (3) Rectifying the adsorbed product for the second time to obtain a product after the second rectification; (4) And distilling the product after the second rectification to obtain the high-purity ethyl silicate. The invention provides a preparation method of high-purity ethyl silicate, which is simple to operate, and can prepare electronic-grade tetraethyl silicate with the concentration of not less than 99.9999999% (W/W) by reasonably designing each step and playing a synergistic effect. The aspect provides a production system of high-purity ethyl silicate, which adopts conventional manufacturing equipment, and reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a preparation method and a production system of high-purity ethyl silicate.
Background
Electronic grade tetraethyl orthosilicate (TEOS) is widely used in chemical vapor deposition processes to form silicon dioxide deposited films, thereby blocking contaminants and impurities from entering semiconductor devices, and simultaneously producing conductive or insulating layers, antireflection films to improve absorbance, temporary barrier etching, and the like. The electronic grade tetraethoxysilane is prepared mainly by purifying industrial grade raw materials, and the purity of the industrial tetraethoxysilane is generally 99 percent, and the industrial tetraethoxysilane still contains 1 percent of impurities. The impurities comprise electronically active impurities and non-electronically active impurities, wherein the electronically active impurities are metal ions, so that the insulating property of a SiO 2 film layer deposited on the semiconductor device is reduced, and micron-sized circuits are mutually communicated, so that a circuit board is scrapped; non-electronic impurities in tetraethyl orthosilicate include organics and water, which can affect the physical properties of the film by altering the structural integrity and planar uniformity of the film surface.
In the patent US5840953, tetraethyl orthosilicate is prepared by using gas chromatography, impurities are removed by using lithium hydride, the purity of the obtained product is not lower than 99.999999 percent of tetraethyl orthosilicate, the water content is less than 2ppm, but the gas chromatograph is mainly used for analyzing and detecting trace elements, and the gas chromatograph equipment is expensive, so that the production cost is increased. CN109748931B provides a preparation method of high purity ethyl silicate, comprising: s1) mixing high-purity silicon tetrachloride with high-purity ethanol for reactive distillation to obtain crude ethyl orthosilicate and crude hydrogen chloride; s2) carrying out decolorization adsorption treatment and alkaline adsorption treatment on the crude ethyl orthosilicate, and then carrying out light removal rectification treatment to obtain the ethyl orthosilicate after the light removal treatment and the removed light component; s3) carrying out the weight removal rectification treatment on the ethyl orthosilicate subjected to the weight removal treatment after being treated by the boron-phosphorus adsorption resin and the metal ion adsorption resin, so as to obtain the high-purity ethyl silicate. But in actual production, high-purity silicon tetrachloride reacts with high-purity ethanol, and side reactions have great influence on purity and yield. Therefore, a novel preparation method of high-purity ethyl silicate is needed, the purity of the ethyl silicate is improved, and the production cost is reduced.
Disclosure of Invention
The invention aims at providing a preparation method and a production system of electronic-grade tetraethyl orthosilicate with purity not lower than 99.9999999% (W/W), which adopt conventional manufacturing equipment, are simple to operate and have low production cost.
In order to achieve the above object, the present invention provides the following technical solutions:
The first aspect of the invention provides a preparation method of high-purity ethyl silicate, which comprises the following steps:
(1) Rectifying the crude product of the ethyl orthosilicate for the first time to obtain a product after the first rectification;
(2) The product after the first rectification passes through an adsorption tower to obtain an adsorbed product;
(3) Rectifying the adsorbed product for the second time to obtain a product after the second rectification;
(4) And distilling the product after the second rectification to obtain the high-purity ethyl silicate.
In a preferred embodiment, the reflux ratio of the first rectification is 7 to 10 greater than the reflux ratio of the second rectification.
In a preferred embodiment, the reflux ratio of the first rectification is 15 to 20.
In a preferred embodiment, the reflux ratio of the second rectification is 7 to 13.
Preferably, the reflux ratio of the first rectification is 18. The reflux ratio of the second rectification is 10.
The reflux ratio is the ratio of the reflux flow returned from the top of the rectifying tower to the flow of the product at the top of the rectifying tower, and has important influence on the separation effect in the rectifying process. The inventors found that the reflux ratio of the first rectification of the present invention has a value 7 to 10 greater than that of the second rectification, and can improve the purity of ethyl orthosilicate. The reason is presumed that under this condition, the two distillations can remove the non-electronic impurities in the tetraethoxysilane to the maximum extent, and simultaneously remove part of the metal ions.
In a preferred embodiment, the temperature of the first distillation is 90-110 ℃, and the pressure of the first distillation is-0.8 to-1.2 bar.
In a preferred embodiment, the temperature of the second distillation is 130 to 150 ℃, and the pressure of the second distillation is-0.3 to-0.7 bar.
For better removal of impurities in the system, it is preferred that the temperature of the first distillation is 95 ℃, and the pressure of the first distillation is-0.9 bar; the temperature of the second rectification is 140 ℃, and the pressure of the second rectification is-0.5 bar.
In a preferred embodiment, the adsorption tower is filled with coconut shell activated carbon, cation exchange resin, and carbon nanotubes in that order.
In a preferred embodiment, the volume ratio of the coconut shell activated carbon, the cation exchange resin and the carbon nanotubes is 1:1 to 5:1.
Preferably, the volume ratio of the coconut shell activated carbon to the cation exchange resin to the carbon nano tube is 1:2:1.
The inventor discovers that the purity of the tetraethoxysilane is obviously improved by sequentially using coconut shell activated carbon, cation exchange resin and carbon nano tubes for adsorption. The coconut shell activated carbon is of a small molecular pore structure and has a developed pore structure, and the surface of the coconut shell activated carbon is provided with an acidic functional group, and the special pore structure of the coconut shell activated carbon enables the coconut shell activated carbon to have extremely strong adsorption capacity on electronic active impurities and non-electronic impurities in the system, after the coconut shell activated carbon is adsorbed, a cation exchange resin is used for further removing various metal ions, then a carbon nano tube is used for further adsorbing residual metal ions, and the three are sequentially progressive and play a synergistic effect in the system. The inventor discovers through a large number of experiments that the volume ratio of the coconut shell activated carbon to the ion exchange resin to the carbon nano tube is 1:2:1, the adsorption effect on impurities is best, and the three components in the ratio can absorb different types of impurities respectively, so that the impurities in the system can be more completely adsorbed through reasonable volume ratio, and the purity of the product is highest.
In a preferred embodiment, the granularity of the coconut shell activated carbon is 12-30 meshes, the filling density is 0.45-0.55 g/mL, the moisture is less than or equal to 10%, and the specific surface area is 950-1200 m 2/g. Purchased from Hua Hai activated carbon limited, yixing city.
In a preferred embodiment, the carbon nanotubes, single-walled, octadecylamine functionalized. The diameter is 2-10nm, and the length is 0.5-2 μm. Purchased from merck, model 652482.
In a preferred embodiment, the cation exchange resin is selected from the group consisting of styrenic strongly acidic cation exchange resins, the functional groups are sulfonic acid groups, the total exchange is greater than or equal to 1.8mmol/mL (wet), and the particle size ranges from 0.3 to 1.25mm. Available from Tianjin let-down resin technologies Co., ltd., model Styrene-DVB, 001X 7 strongly acidic cation exchange resin.
The granularity and specific surface area of the coconut shell activated carbon influence the adsorption capacity, and the coconut shell activated carbon selected by the invention has extremely strong adsorption capacity on electronic active impurities and non-electronic impurities. The inventor finds that the styrene strong acid cation exchange resin has strong adsorption capacity to various metal ions by using the functional group of sulfonic acid group, the total exchange capacity is more than or equal to 1.8mmol/mL and the particle size range is 0.3-1.25 mm. After being adsorbed by coconut shell activated carbon and cation exchange resin, the inventor finds that the octadecylamine modified single-walled carbon nanotube can be used for efficiently adsorbing the rest metal ions, and the inventor speculates that after the carbon nanotube is oxidized and modified, the acidic adsorption sites are increased, the adsorption capacity is enhanced, meanwhile, the electrostatic attraction between the single-walled carbon nanotube and the metal ions is stronger, the adsorption quantity is high, and the inventor can realize the adsorption with the best effect by selecting an adsorption tower composed of the three materials.
In a second aspect, the present invention provides a production system of high purity ethyl silicate, the production system comprising:
the first rectifying tower is used for carrying out first rectification on the crude product of the ethyl orthosilicate;
the first rectifying tower is connected with the adsorption tower, and the adsorption tower is used for adsorbing the products after the first rectification;
the adsorption tower is connected with the second rectifying tower, and the second rectifying tower is used for rectifying the adsorbed product for the second time;
And the second rectifying tower is connected with the distillation tower, and the distillation tower is used for distilling the product after the second rectification to obtain high-purity ethyl silicate.
Compared with the prior art, the invention has the advantages that:
1. The invention provides a preparation method of high-purity ethyl silicate, which is simple to operate, and can prepare electronic-grade tetraethyl silicate with the concentration of not less than 99.9999999% (W/W) by reasonably designing each step and simultaneously playing a synergistic effect.
2. The invention greatly improves the purity of the product by designing the reflux ratio of the first rectification and the reflux ratio of the second rectification.
3. The absorption tower is filled with coconut shell activated carbon, cation exchange resin and carbon nano tubes with specific structures and performances, and the three materials are synergistic, so that the adsorption of electronic active impurities and non-electronic impurities is improved.
4. The aspect provides a production system of high-purity ethyl silicate, which adopts conventional manufacturing equipment, and reduces the production cost.
Drawings
FIG. 1 is a schematic diagram of a high purity ethyl silicate production system.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of high-purity ethyl silicate, which comprises the following steps:
(1) Rectifying the crude product of the ethyl orthosilicate for the first time to obtain a product after the first rectification; the crude ethyl orthosilicate has a purity of 99.9% and is purchased from Shanghai Du Yi Utility Co.
(2) The product after the first rectification passes through an adsorption tower to obtain an adsorbed product;
(3) Rectifying the adsorbed product for the second time to obtain a product after the second rectification;
(4) And distilling the product after the second rectification to obtain the high-purity ethyl silicate.
The reflux ratio of the first rectification is 18. The reflux ratio of the second rectification is 10.
The temperature of the first distillation is 95 ℃, and the pressure of the first distillation is-0.9 bar; the temperature of the second rectification is 140 ℃, and the pressure of the second rectification is-0.5 bar.
The adsorption tower is filled with coconut shell activated carbon, cation exchange resin and carbon nano tubes in sequence.
The volume ratio of the coconut shell activated carbon to the cation exchange resin to the carbon nano tube is 1:2:1.
The granularity of the coconut shell activated carbon is 12-30 meshes, the filling density is 0.45-0.55 g/mL, the moisture is less than or equal to 10%, and the specific surface area is 950-1200 m 2/g. Purchased from Hua Hai activated carbon limited, yixing city.
The carbon nanotubes, single-walled, octadecylamine functionalized. The diameter is 2-10nm, and the length is 0.5-2 μm. Purchased from merck, model 652482.
The cation exchange resin is selected from styrene strong acid cation exchange resin, the functional group is sulfonic acid group, the total exchange capacity is more than or equal to 1.8mmol/mL (wet), and the particle size range is 0.3-1.25 mm. Available from Tianjin let-down resin technologies Co., ltd., model Styrene-DVB, 001X 7 strongly acidic cation exchange resin.
As shown in fig. 1, the present embodiment provides a production system of high purity ethyl silicate, the production system comprising:
the first rectifying tower is used for carrying out first rectification on the crude product of the ethyl orthosilicate;
the first rectifying tower is connected with the adsorption tower, and the adsorption tower is used for adsorbing the products after the first rectification;
the adsorption tower is connected with the second rectifying tower, and the second rectifying tower is used for rectifying the adsorbed product for the second time;
And the second rectifying tower is connected with the distillation tower, and the distillation tower is used for distilling the product after the second rectification to obtain high-purity ethyl silicate.
Example 2
This embodiment differs from embodiment 1 in that: the reflux ratio of the first rectification is 15; the reflux ratio of the second rectification is 8.
Example 3
This embodiment differs from embodiment 1 in that: the carbon nanotubes, multiwall, carboxylic acid functionalized, purchased from merck, model 755125.
Comparative example 1
The difference between this comparative example and example 1 is that: the adsorption tower is sequentially filled with coconut shell activated carbon and cation exchange resin. The volume ratio of the coconut shell activated carbon to the cation exchange resin is 1:2.
Comparative example 2
The difference between this comparative example and example 1 is that: the adsorption tower is sequentially filled with non-coconut shell activated carbon, cation exchange resin and carbon nano tubes. The non-coconut shell activated carbon has a particle size of 20-40 meshes and is purchased from merck, 242268.
Comparative example 3
The difference between this comparative example and example 1 is that: the volume ratio of the coconut shell activated carbon to the cation exchange resin to the carbon nano tube is 1:1:5.
Comparative example 4
The difference between this comparative example and example 1 is that: the temperature of the first distillation is 145 ℃, and the pressure of the first distillation is-0.8 bar; the temperature of the second rectification is 90 ℃, and the pressure of the second rectification is-1.1 bar.
Performance testing
The purity and the element content of the ethyl orthosilicates prepared in examples and comparative examples were measured using GC and ICP-MS analysis methods, respectively, and the results are shown in table 1.
Table 1 measurement results
| Project | Unit (B) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Purity of | ％ | 99.9999999 | 99.9999999 | 99.9999999 | 99.999999 | 99.999999 | 99.999999 | 99.999999 |
| Water and its preparation method | ppm | 1.5 | 1.6 | 1.8 | 3.5 | 3.3 | 2.5 | 2.8 |
| Aluminum (Al) | ppb | 0.05 | 0.06 | 0.06 | 0.12 | 0.09 | 0.10 | 0.08 |
| Antimony (Sb) | ppb | 0.07 | 0.08 | 0.09 | 0.15 | 0.14 | 0.12 | 0.13 |
| Arsenic (As) | ppb | 0.01 | 0.01 | 0.01 | 0.03 | 0.03 | 0.02 | 0.03 |
| Boron (B) | ppb | 0.05 | 0.07 | 0.08 | 0.15 | 0.14 | 0.13 | 0.12 |
| Chromium (Cr) | ppb | 0.01 | 0.01 | 0.01 | 0.05 | 0.03 | 0.04 | 0.04 |
| Cobalt (Co) | ppb | 0.01 | 0.01 | 0.01 | 0.05 | 0.02 | 0.04 | 0.02 |
| Copper (Cu) | ppb | 0.01 | 0.01 | 0.01 | 0.04 | 0.02 | 0.04 | 0.03 |
| Iron (Fe) | ppb | 0.01 | 0.01 | 0.01 | 0.06 | 0.03 | 0.04 | 0.05 |
| Manganese (Mn) | ppb | 0.01 | 0.01 | 0.01 | 0.03 | 0.01 | 0.02 | 0.01 |
| Molybdenum (Mo) | ppb | 0.01 | 0.01 | 0.01 | 0.04 | 0.02 | 0.01 | 0.03 |
| Nickel (Ni) | ppb | 0.01 | 0.01 | 0.01 | 0.05 | 0.02 | 0.02 | 0.04 |
| Titanium | ppb | 0.01 | 0.01 | 0.01 | 0.02 | 0.02 | 0.02 | 0.03 |
| Vanadium (V) | ppb | 0.01 | 0.01 | 0.01 | 0.06 | 0.03 | 0.01 | 0.02 |
| Zinc alloy | ppb | 0.01 | 0.01 | 0.01 | 0.03 | 0.01 | 0.01 | 0.02 |
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The preparation method of the high-purity ethyl silicate is characterized by comprising the following steps of:
(1) Rectifying the crude product of the ethyl orthosilicate for the first time to obtain a product after the first rectification;
(2) The product after the first rectification passes through an adsorption tower to obtain an adsorbed product;
(3) Rectifying the adsorbed product for the second time to obtain a product after the second rectification;
(4) Distilling the product after the second rectification to obtain high-purity ethyl silicate;
The reflux ratio of the first rectification is 7-10 larger than the reflux ratio of the second rectification;
The reflux ratio of the first rectification is 15-20;
The reflux ratio of the second rectification is 7-13;
The temperature of the first rectification is 90-110 ℃, and the pressure of the first rectification is-0.8 to-1.2 bar;
the temperature of the second rectification is 130-150 ℃, and the pressure of the second rectification is-0.3 to-0.7 bar;
The adsorption tower is sequentially filled with coconut shell activated carbon, cation exchange resin and carbon nano tubes;
The volume ratio of the coconut shell activated carbon to the cation exchange resin to the carbon nano tube is 1 (1-5): 1.
2. The preparation method of the high-purity ethyl silicate according to claim 1, wherein the granularity of the coconut shell activated carbon is 12-30 meshes, the filling density is 0.45-0.55 g/mL, the moisture is less than or equal to 10%, and the specific surface area is 950-1200 m 2/g.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310849522.8A CN116903653B (en) | 2023-07-11 | 2023-07-11 | Preparation method and production system of high-purity ethyl silicate |
| GBGB2317395.8A GB202317395D0 (en) | 2023-07-11 | 2023-11-14 | A preparation method and production system of high-purity ethyl orthosilicate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310849522.8A CN116903653B (en) | 2023-07-11 | 2023-07-11 | Preparation method and production system of high-purity ethyl silicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116903653A CN116903653A (en) | 2023-10-20 |
| CN116903653B true CN116903653B (en) | 2024-05-24 |
Family
ID=88350424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310849522.8A Active CN116903653B (en) | 2023-07-11 | 2023-07-11 | Preparation method and production system of high-purity ethyl silicate |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN116903653B (en) |
| GB (1) | GB202317395D0 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400637A (en) * | 2018-09-29 | 2019-03-01 | 苏州金宏气体股份有限公司 | A kind of production method and production system of high-purity ethyl orthosilicate |
| CN109748931A (en) * | 2019-02-18 | 2019-05-14 | 苏州金宏气体股份有限公司 | A kind of preparation method and production system of high-purity ethyl orthosilicate |
| CN109912636A (en) * | 2019-04-11 | 2019-06-21 | 苏州金宏气体股份有限公司 | A kind of production method of high-purity ethyl orthosilicate |
-
2023
- 2023-07-11 CN CN202310849522.8A patent/CN116903653B/en active Active
- 2023-11-14 GB GBGB2317395.8A patent/GB202317395D0/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400637A (en) * | 2018-09-29 | 2019-03-01 | 苏州金宏气体股份有限公司 | A kind of production method and production system of high-purity ethyl orthosilicate |
| CN109748931A (en) * | 2019-02-18 | 2019-05-14 | 苏州金宏气体股份有限公司 | A kind of preparation method and production system of high-purity ethyl orthosilicate |
| CN109912636A (en) * | 2019-04-11 | 2019-06-21 | 苏州金宏气体股份有限公司 | A kind of production method of high-purity ethyl orthosilicate |
Non-Patent Citations (1)
| Title |
|---|
| 赵松林主编.《椰子综合加工技术》.中国农业出版社,2007,第58页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB202317395D0 (en) | 2023-12-27 |
| CN116903653A (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103664501B (en) | A kind of purification process of hexafluoroethane | |
| JP5791262B2 (en) | Method for producing high purity N-methyl-2-pyrrolidone | |
| CN105523570A (en) | Preparation method of ppt-scale ultrapure ammonium hydroxide | |
| CN113371683B (en) | Electronic grade hydrogen peroxide production method | |
| CN102485642B (en) | The production method of ultra-pure hydrogen phosphide | |
| CN106380372A (en) | Octafluoropropane purifying method and purifying apparatus thereof | |
| WO2021223145A1 (en) | Improved acetonitrile purification process for ultra-performance liquid chromatography-mass spectrometry instrument | |
| CN112266318A (en) | Method for purifying hexafluoro-1, 3-butadiene in grading manner | |
| CN215026208U (en) | Preparation device of electronic grade ethyl orthosilicate | |
| CN116903653B (en) | Preparation method and production system of high-purity ethyl silicate | |
| CN112938899A (en) | Purification method of high-purity electronic grade hydrogen bromide | |
| JP2023535850A (en) | Separation of HF/HCl Containing Etching Exhaust Gas by FTrPSA and Recovery, Recycling and Reuse Method | |
| CN114504872A (en) | Method and device for producing high-purity electronic grade ethylene glycol | |
| CN114949904A (en) | Production method and device of high-purity electronic grade N-methyl-2-pyrrolidone | |
| CN114470958A (en) | Production method and device of high-purity electronic grade methanol | |
| CN102452671A (en) | Method for continuously producing ultrapure ammonia water | |
| Aimikhe et al. | Development of composite activated carbon from mango and almond seed shells for CO2 capture | |
| CN109912636B (en) | Production method of high-purity ethyl orthosilicate | |
| CN113321184A (en) | High-purity electronic grade chlorine gas purification production device and process thereof | |
| CN116747546A (en) | Purification device and purification method for siloxane compound | |
| CN106276828B (en) | A method of absorption trifluoride by purifying nitrogen | |
| CA2899135A1 (en) | Adsorbing/desorbing agent | |
| CN1189387C (en) | High-purity hydrogen peroxide preparation | |
| CN105621453A (en) | Method for preparing ultrapure boron-free ammonia water | |
| CN116062756A (en) | Process and device for preparing ultra-high purity carbonyl sulfide from industrial carbonyl sulfide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |