CN214438885U - Novel preparation device of electronic-grade fluoromethane - Google Patents
Novel preparation device of electronic-grade fluoromethane Download PDFInfo
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- CN214438885U CN214438885U CN202120204051.1U CN202120204051U CN214438885U CN 214438885 U CN214438885 U CN 214438885U CN 202120204051 U CN202120204051 U CN 202120204051U CN 214438885 U CN214438885 U CN 214438885U
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Abstract
The utility model provides a novel preparation facilities of electron level fluoromethane, include: the reaction tank includes: the device comprises a hollow tank body, a top cover detachably arranged at the top of the hollow tank body, a bottom cover detachably arranged at the bottom of the hollow tank body, clapboards respectively arranged between the hollow tank body and the top cover and between the hollow tank body and the bottom cover, catalyst tubes penetrating between the clapboards, a gas material inlet arranged at the top cover and a material outlet arranged at the bottom cover; the heating unit comprises a heating medium pipeline inlet arranged at the bottom of the hollow tank body, a heating medium pipeline outlet arranged at the top of the hollow tank body and a heating medium exhaust port arranged at the top of the hollow tank body; the temperature measuring unit comprises a first temperature sensor, a second temperature sensor and a third temperature sensor which are used for measuring the top, the middle and the bottom of the hollow tank body; and the pressure measuring unit is arranged in the top cover.
Description
Technical Field
The utility model relates to a novel preparation facilities of electron level fluoromethane.
Background
Monofluoromethane (CH3F) is a nontoxic, liquefiable gas at normal temperature and pressure, and is widely used in the semiconductor industry as a plasma etching material for etching thin films of silicon compounds. The current process for the production of monofluoromethane can be produced by the reaction of HF with methanol. However, the prior art does not provide a dedicated apparatus for continuous industrial production of monofluoromethane due to the high corrosiveness of HF.
SUMMERY OF THE UTILITY MODEL
The utility model provides a novel preparation facilities of electron level fluoromethane can effectively solve above-mentioned problem.
The utility model discloses a realize like this:
the utility model provides a novel preparation facilities of electron level fluoromethane, include:
the reaction tank includes: the device comprises a hollow tank body, a top cover detachably arranged at the top of the hollow tank body, a bottom cover detachably arranged at the bottom of the hollow tank body, clapboards respectively arranged between the hollow tank body and the top cover and between the hollow tank body and the bottom cover, catalyst tubes penetrating between the clapboards, a gas material inlet arranged at the top cover and a material outlet arranged at the bottom cover; the outer layer of the hollow tank body is made of carbon steel, and the inner layer of the hollow tank body is made of stainless steel 304; the top cover is also made of stainless steel 304, and the bottom cover is made of Monel;
the heating unit comprises a heating medium pipeline inlet arranged at the bottom of the hollow tank body, a heating medium pipeline outlet arranged at the top of the hollow tank body and a heating medium exhaust port arranged at the top of the hollow tank body;
the temperature measuring unit comprises a first temperature sensor, a second temperature sensor and a third temperature sensor which are used for measuring the top, the middle and the bottom of the hollow tank body;
and the pressure measuring unit is arranged in the top cover.
As a further improvement, the heating unit further comprises a heat medium drain port arranged at the bottom of the hollow tank body.
As a further improvement, the reaction tank comprises a further gas outlet cover, the cover is arranged at the gas material inlet, the gas outlet cover is of an inverted trapezoidal structure, and a plurality of openings are uniformly formed in two side edges of the gas outlet cover.
As a further improvement, the catalyst array pipes are uniformly distributed in the middle of the hollow tank body.
As a further improvement, the catalyst tube comprises catalyst particles filled in the catalyst tube, wherein the catalyst particles are formed by mixing 8-10 parts by weight of chromium trichloride/activated carbon compound and 50-70 parts by weight of aluminum trichloride, and the content of the chromium trichloride in the chromium trichloride/activated carbon compound is 15-25 wt%.
The utility model has the advantages that: the utility model provides a novel preparation facilities can be exclusively used in HF and methyl alcohol serialization industrial production fluoromethane. In addition, the conversion rates of HF and methanol can be remarkably improved by catalyzing the reaction of HF and methanol by the activated novel catalyst, and the conversion rates can respectively reach more than 60% and 70%, so that the utilization rate of raw materials is greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a novel preparation device of electronic-grade fluoromethane according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a part of the components in the novel preparation device for electronic-grade fluoromethane according to the embodiment of the present invention.
Fig. 3 is a flow chart of a preheating activation method of the novel preparation device of electronic-grade fluoromethane according to the embodiment of the present invention.
Fig. 4 is a flow chart of a method for preparing fluoromethane using the novel catalyst according to an embodiment of the present invention.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the drawings of the embodiments of the present invention are combined to clearly and completely describe the technical solutions of the embodiments of the present invention, and obviously, the described embodiments are some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the accompanying drawings, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically limited otherwise.
Referring to fig. 1, an embodiment of the present invention provides a novel apparatus for preparing electronic grade fluoromethane, including:
the reaction tank 10 includes: the device comprises a hollow tank body 101, a top cover 102 detachably arranged at the top of the hollow tank body 101, a bottom cover 103 detachably arranged at the bottom of the hollow tank body 101, partition plates 109 respectively arranged between the hollow tank body 101 and the top cover 102 and between the hollow tank body 101 and the bottom cover 103, a catalyst array pipe 105 penetrating and arranged between the partition plates 109, a gas material inlet 104 arranged at the top cover 102 and a material outlet 106 arranged at the bottom cover 103;
a heating unit 11 including a heat medium pipe inlet 111 provided at the bottom of the hollow tank 101, a heat medium pipe outlet 112 provided at the top of the hollow tank 101, and a heat medium exhaust port 114 provided at the top of the hollow tank 101;
the temperature measuring unit 12 comprises a first temperature sensor 121, a second temperature sensor 122 and a third temperature sensor 123 which are used for measuring the top, the middle and the bottom of the hollow tank body 101;
and a load cell 13 disposed in the top cover 102 for measuring a pressure of the reaction gas in the top cover 102.
The outer layer of the hollow tank body 101 can be made of carbon steel, and the inner layer is made of stainless steel 304. The top cover 102 may be made of stainless steel 304, and the bottom cover 103 may be made of monel. The hydrogen fluoride and the methanol are generated at the bottom and react to generate water, so that the HF is dissolved in the water to form water acid, and the Monel material is selected to prevent high-temperature corrosion and prolong the service life of equipment. The bottom of the bottom cover 103 is further provided with a sewage draining outlet 107. In addition, since the top cover 102 and the bottom cover 103 are both detachable structures, replacement of the catalyst tubes 105 is facilitated.
Referring to fig. 2, as a further improvement, the reaction tank 10 includes a further gas outlet cover 108 covering the gas material inlet 104, wherein the gas outlet cover 108 is of an inverted trapezoidal structure, and two side edges thereof are uniformly provided with a plurality of openings 1082. Correspondingly, the catalyst tubes 105 are uniformly distributed in the middle of the hollow tank 101. It is understood that the above configuration allows sufficient mixing of the reaction gas in the top cover 102.
As a further improvement, the catalyst tube 105 comprises catalyst particles filled in the catalyst tube, the catalyst particles are formed by mixing 8-10 parts by weight of chromium trichloride/activated carbon compound and 50-70 parts by weight of aluminum trichloride, and the content of chromium trichloride in the chromium trichloride/activated carbon compound is 15-25 wt%. In one embodiment, the catalyst particles are formed by mixing 8 parts by weight of chromium trichloride/activated carbon composite and 60 parts by weight of aluminum trichloride, and the content of the chromium trichloride in the chromium trichloride/activated carbon composite is 20 wt%. The chromium trichloride/activated carbon composite can be used for loading the chromium trichloride on the activated carbon by an impregnation method or other methods. Further, the chromium trichloride/activated carbon compound is mixed with the aluminum trichloride to form the chromium trichloride/activated carbon compound.
As a further modification, the heating unit 11 further includes a heat medium discharge port 113 provided at the bottom of the hollow tank 101. When the heating unit 11 is used, heating medium is firstly introduced through the heating medium pipeline inlet 111, the heating medium pipeline outlet 112 and the heating medium exhaust port 114 are opened, and the heating medium exhaust port 114 is higher than the heating medium pipeline outlet 112, so that when the heating medium flows out from the heating medium pipeline outlet 112, the heating medium exhaust port 114 is closed. When the heat medium needs to be discharged, the heat medium exhaust port 114 and the heat medium discharge port 113 need to be opened, so that the heat medium can be discharged.
The first temperature sensor 121 and the third temperature sensor 123 may be directly provided with corresponding holes at the top and the bottom of the hollow tank 101. The second temperature sensor 122 is formed by opening a hole from the top cover 102 and the partition 109, respectively, so as to extend into the middle of the hollow can 101, which is advantageous in that the height of measurement can be adjusted. When the temperature is too high or too low in the reaction process, the reaction temperature can be controlled by adjusting the air input or the heating medium flow.
Referring to fig. 3, an embodiment of the present invention further provides a preheating activation method for the novel electronic-grade fluoromethane preparation apparatus, including the following steps:
s1, introducing N into the catalyst tube nest 1052Heating to 200 ℃ and drying for 5-15 h;
s2, drying, keeping N2Introducing HF for fluorination at the temperature of 200 ℃, gradually increasing the flow of the HF from 5-10 ml/min to 300ml/min, simultaneously monitoring the temperature of a catalyst tube array 105 through a temperature measurement unit 12, controlling the temperature of the catalyst tube array 105 to be 200 +/-5 ℃, and keeping the flow of the HF for 1-3 hours after the flow is stable;
s3, under the temperature of 200 ℃, the HF flow is unchanged, and N is gradually reduced2The flow rate is 0ml/min, meanwhile, the temperature of the catalyst tube array 105 is monitored through the temperature measuring unit 12, the temperature of the catalyst tube array 105 is controlled to be 200 +/-5 ℃, and the temperature is kept for 3-5 hours after stabilization;
s4, heating to raise the temperature of the catalyst tube 105 from 200 ℃ to 260 ℃, and keeping for 3-5 hours after stabilization;
s5, heating to raise the temperature of the catalyst tube 105 from 260 ℃ to 300 ℃, and keeping for 3-5 hours after stabilization;
and S6, heating to raise the temperature of the catalyst tube 105 from 300 ℃ to 350 ℃, keeping the temperature for 20-28 h after stabilization, and reducing the temperature to the reaction temperature to complete preheating and activation.
As a further improvement, in step S1, N is introduced into the catalyst tubes 1052And heating to 200 ℃ and drying for 5-15 h, wherein the steps comprise:
s11, holding N2The flow rate is 200-400 ml/min, the temperature of the catalyst tube array 105 is increased to 100 ℃ at the temperature increase rate of 5-10 ℃/min, and the catalyst tube array is dried for 2-6 h at constant temperature;
and S12, raising the temperature of the catalyst tube array 105 to 200 ℃ at a temperature raising rate of 5-10 ℃/min, and drying for 3-9 h at constant temperature.
As a further modification, in step S2, the HF flow rate is reduced when the temperature of the catalyst tubes 105 is too high. Step S2 is mainly to reduce the activity of HF and prevent reaction runaway during activation.
As a further modification, in step S3, N is increased when the temperature of the catalyst tubes 105 is too high2And (4) flow rate. It will be appreciated that the selectivity and efficiency of the catalyst may be improved by the above-described warm-up activation method.
Referring to fig. 4, the present invention further provides a novel method for preparing fluoromethane using the novel catalyst, comprising: the method comprises the following steps:
s7, introducing a reaction gas of HF and methanol mixed into the catalyst tube 105 from top to bottom, wherein the ratio of the HF to the methanol is 1.05-1.1: 1(HF is partially dissolved in formed water and has no reactivity, so that excessive HF is needed); the catalyst tube 105 comprises activated catalyst particles, wherein the catalyst particles are formed by mixing 8-10 parts by weight of chromium trichloride/activated carbon compound and 50-70 parts by weight of aluminum trichloride, and the content of chromium trichloride in the chromium trichloride/activated carbon compound is 15-25 wt%;
s8, controlling the temperature of the upper part of the catalyst tube 105 to be 190-200 ℃, the temperature of the middle part to be 250-260 ℃, the temperature of the lower part to be 240-250 ℃, the reaction pressure to be 0.05-0.3 Mpa and the retention time to be 30-90S, thereby obtaining the fluoromethane.
In step S8, it is more preferable that the upper temperature of the catalyst tubes 105 is controlled to 195 ± 2 ℃, the middle temperature is controlled to 255 ± 2 ℃, the lower temperature is controlled to 245 ± 2 ℃, the reaction pressure is controlled to 0.07Mpa, and the residence time is controlled to 60 to 70S.
Example 1:
mixing 8 parts by weight of chromium trichloride/activated carbon compound and 60 parts by weight of aluminum trichloride, wherein the content of chromium trichloride in the chromium trichloride/activated carbon compound is 20 wt%, filling the chromium trichloride/activated carbon compound into the catalyst tube 105, and assembling the catalyst tube onto a device for activation; n is a radical of2The flow rate is 300ml/min, the temperature of the catalyst bed layer is increased to 100 ℃ at the heating rate of 10 ℃/min, and the catalyst bed layer is dried for 4 hours at constant temperature; heating the catalyst tube 105 to 200 ℃ at a heating rate of 10 ℃/min, and drying for 6h at constant temperature; after drying at 200 ℃, starting HF fluorination at the temperature; n is a radical of2The flow rate is maintained at 300ml/min, and the HF flow rate is gradually increased from 10ml/min to 300ml/min (which can be adjusted each time)20ml/min), adjusting once every 1 hour, and simultaneously monitoring the temperature of the catalyst tube array 105, so that the reaction hot spot of the catalyst tube array 105 is less than 5 ℃, reducing the HF flow when necessary, and keeping the HF flow for 2 hours after the HF flow is stable; keeping the temperature at 200 ℃ and the HF flow constant, gradually reducing the nitrogen flow to 0ml/min (50 ml/min can be adjusted every time), adjusting every 1 hour, monitoring the temperature of the catalyst tube 105, ensuring that the reaction hot spot of the catalyst tube 105 is less than 5 ℃, and increasing N when necessary2The flow is kept for 4 hours after being stabilized; the temperature of the catalyst tube 105 is increased from 200 ℃ to 260 ℃, the temperature increase rate is 5 ℃/min and then the temperature is kept for 4 h; the temperature of the catalyst tube 105 is increased from 260 ℃ to 300 ℃, the temperature increase rate is 5 ℃/min and then the temperature is kept for 4 h; the temperature of the catalyst tube 105 is increased from 300 ℃ to 350 ℃, the temperature rising rate is 5 ℃/min, the reaction temperature is kept for 24h after the temperature rising rate is stabilized, and the activation is finished. After activation is finished, introducing HF and the methanol in a molar ratio of 1.08:1, controlling the upper temperature of the catalyst tube 105 to be 195 +/-2 ℃, the middle temperature to be 255 +/-2 ℃, the lower temperature to be 245 +/-2 ℃, the reaction pressure to be 0.07Mpa and the residence time to be 60-70 s, and reacting to generate the fluoromethane. The resulting fluoromethane mixture was subjected to quantitative and qualitative analyses by chromatography, as shown in Table 1.
Further, the fluoromethane is washed by water, washed by alkali, dried and rectified, and finally an electronic grade product is obtained.
Example 2:
example 2 is essentially the same as example 1, except that: the temperature of the upper portion of the catalyst tubes 105 was controlled to about 190 c, the temperature of the middle portion was controlled to about 250 c, and the temperature of the lower portion was controlled to about 240 c. The resulting fluoromethane mixture was subjected to quantitative and qualitative analyses by chromatography, as shown in Table 1.
Example 3:
example 3 is essentially the same as example 1, except that: the temperature of the upper portion of the catalyst tubes 105 was controlled to be about 200 c, the temperature of the middle portion was controlled to be about 260 c, and the temperature of the lower portion was controlled to be about 250 c. The resulting fluoromethane mixture was subjected to quantitative and qualitative analyses by chromatography, as shown in Table 1.
Comparative example 1:
comparative example 1 is substantially the same as example 1 except that: the catalysis was not activated.
Table 1 shows the test data of comparative examples and examples
From the table, it can be seen that after the catalyst is activated, the conversion rates of methanol and hydrogen fluoride can be significantly improved, and the conversion rates can be respectively more than 66% and more than 59%. In addition, the selectivity of the catalyst is also obviously improved through activation.
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 (4)
1. A novel preparation facilities of electron-grade fluoromethane, its characterized in that includes:
the reaction tank (10) comprises: the device comprises a hollow tank body (101), a top cover (102) detachably arranged at the top of the hollow tank body (101), a bottom cover (103) detachably arranged at the bottom of the hollow tank body (101), partition plates (109) respectively arranged between the hollow tank body (101) and the top cover (102) and between the hollow tank body (101) and the bottom cover (103), catalyst tubes (105) penetrating and arranged between the partition plates (109), a gas material inlet (104) arranged at the top cover (102), and a material outlet (106) arranged at the bottom cover (103); the outer layer of the hollow tank body (101) is made of carbon steel, and the inner layer of the hollow tank body is made of stainless steel 304; the top cover (102) is also made of stainless steel 304, and the bottom cover (103) is made of Monel;
the heating unit (11) comprises a heat medium pipeline inlet (111) arranged at the bottom of the hollow tank body (101), a heat medium pipeline outlet (112) arranged at the top of the hollow tank body (101) and a heat medium exhaust port (114) arranged at the top of the hollow tank body (101);
the temperature measuring unit (12) comprises a first temperature sensor (121), a second temperature sensor (122) and a third temperature sensor (123) which are used for measuring the top, the middle and the bottom of the hollow tank body (101);
a load cell (13) disposed in the top cover (102) for measuring a reaction pressure of the top cover (102).
2. The novel apparatus for preparing electronic grade fluoromethane according to claim 1, wherein the heating unit (11) further comprises a heat medium drain (113) provided at the bottom of the hollow tank (101).
3. The novel preparation device of electronic-grade fluoromethane according to claim 1, wherein the reaction tank (10) comprises a further gas outlet cover (108) which is covered on the gas material inlet (104), the gas outlet cover (108) has an inverted trapezoidal structure, and a plurality of openings (1082) are uniformly formed on two side edges of the gas outlet cover.
4. The novel preparation device of electronic-grade fluoromethane according to claim 3, characterized in that the catalyst tubes (105) are uniformly arranged in the middle of the hollow tank (101).
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| Application Number | Priority Date | Filing Date | Title |
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| CN202120204051.1U CN214438885U (en) | 2021-01-25 | 2021-01-25 | Novel preparation device of electronic-grade fluoromethane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202120204051.1U CN214438885U (en) | 2021-01-25 | 2021-01-25 | Novel preparation device of electronic-grade fluoromethane |
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| CN214438885U true CN214438885U (en) | 2021-10-22 |
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| CN202120204051.1U Active CN214438885U (en) | 2021-01-25 | 2021-01-25 | Novel preparation device of electronic-grade fluoromethane |
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Address after: No. 6, Gongye Road, Jiaoyang industrial concentration zone, Jiaoyang Town, Shanghang County, Longyan City, Fujian Province, 364204 Patentee after: Fujian del Technology Co.,Ltd. Address before: No. 6, Gongye Road, Jiaoyang industrial concentration zone, Jiaoyang Town, Shanghang County, Longyan City, Fujian Province, 364000 Patentee before: FUJIAN DEER TECHNOLOGY CO.,LTD. |
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