CN115744843B - Efficient synthesis system for fluorinated nitroxyl - Google Patents
Efficient synthesis system for fluorinated nitroxyl Download PDFInfo
- Publication number
- CN115744843B CN115744843B CN202211331301.3A CN202211331301A CN115744843B CN 115744843 B CN115744843 B CN 115744843B CN 202211331301 A CN202211331301 A CN 202211331301A CN 115744843 B CN115744843 B CN 115744843B
- Authority
- CN
- China
- Prior art keywords
- nitroxyl
- fluorinated
- gas
- nitrogen dioxide
- inlet
- 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
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a high-efficiency synthesis system of fluorinated nitroxyl, which comprises; the device comprises a feeding section, a heating section and a cooling section which are sequentially arranged; the feeding section is provided with a fluorine gas inlet and a nitrogen dioxide inlet; the nitrogen dioxide inlet further comprises an air outlet baffle plate, a rotary shaft sleeve arranged on the outer surface of the nitrogen dioxide inlet and blades arranged on the rotary shaft sleeve; the air outlet baffle is used for changing the flow direction of nitrogen dioxide gas so as to push the blades to rotate, thereby enabling the blades to realize unpowered rotation.
Description
Technical Field
The invention relates to a high-efficiency synthesis system for fluorinated nitroxyl, in particular to a high-efficiency synthesis system for fluorinated nitroxyl, which is used for preparing fluorinated nitroxyl by directly reacting fluorine gas with nitrogen dioxide.
Background
Fluorinated nitroxyl gases, i.e., nitroxyl fluorides, also known as fluorinated nitroxyl, are colorless gases, liquids or white solids, and are odoriferous and are commonly used as oxidants in rocket propellants.
At present, no report on the preparation method of fluorinated nitroxyl is found at home, and only report on the laboratory preparation method of fluorinated nitroxyl is found abroad, mainly fluorine gas and nitrate (or CoF) 3 The fluoride and the nitrogen oxide) are reacted under specific conditions, the method is only suitable for micro-preparation, and most importantly, the method has high danger and cannot be applied to industry. And at present, no report is known about a synthesis system for preparing fluorinated nitroxyl.
Disclosure of Invention
The invention provides a high-efficiency synthesis system of fluorinated nitroxyl, which can effectively solve the problems.
The invention is realized in the following way:
the invention provides a high-efficiency synthesis system of fluorinated nitroxyl, comprising; the device comprises a feeding section, a heating section and a cooling section which are sequentially arranged;
the feeding section is provided with a fluorine gas inlet and a nitrogen dioxide inlet; the fluorine gas inlet and the nitrogen dioxide inlet are staggered, and the nitrogen dioxide inlet further comprises an air outlet baffle plate, a rotary shaft sleeve arranged on the outer surface of the nitrogen dioxide inlet and blades arranged on the rotary shaft sleeve; the air outlet baffle is used for changing the flow direction of nitrogen dioxide gas so as to push the blades to rotate, thereby enabling the blades to realize unpowered rotation.
The beneficial effects of the invention are as follows: the efficient synthesis system of the fluorinated nitroxyl provided by the invention can be suitable for the efficient synthesis system of the fluorinated nitroxyl in the process of preparing the fluorinated nitroxyl by directly reacting fluorine gas with nitrogen dioxide, and solves the technical limitation problem of preparing the fluorinated nitroxyl by using fluoride and nitrate in the laboratory in the past, thereby enabling the industrialized preparation of the fluorinated nitroxyl to be possible. Further, the flow direction of nitrogen dioxide gas can be changed by the air outlet baffle plate, so that the nitrogen dioxide gas pushes the blades to rotate, and the blades can realize unpowered rotation. Furthermore, as the nitrogen dioxide gas covers the surfaces of the rotating shaft sleeve and the blades, the corrosion of fluorine gas to the rotating shaft sleeve and the blades can be prevented, and the service life of the rotating shaft sleeve and the blades can be prolonged.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing fluorinated nitroxyl gas according to an embodiment of the present invention.
Fig. 2 is a photograph of a fluorine gas-purified adsorbent in the method for producing a fluorinated nitroxyl gas according to the embodiment of the present invention.
FIG. 3 is a schematic structural diagram of a reactor for fluorinated nitroxyl production according to an embodiment of the present invention.
Fig. 4 is a schematic structural diagram of a purifying device for fluorinated nitroxyl according to an embodiment of the present invention.
Fig. 5 is a schematic structural diagram of a condensing unit in a purifying apparatus for fluorinated nitroxyl according to an embodiment of the present invention.
Fig. 6 is a schematic structural diagram of a rectification unit in a purification device for fluorinated nitroxyl provided by the embodiment of the invention.
FIG. 7 is a schematic diagram of a part of the structure of a packing in a purification apparatus for fluorinated nitroxyl according to an embodiment of the present invention.
FIG. 8 is a schematic view showing a part of the structure of a reactor for preparing fluorinated nitroxyl according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing fluorinated nitroxyl gas, comprising the steps of:
s1, fluorine gas and NO 2 Introducing the gas into a reactor, and controlling the reaction temperature to be 300-500 ℃ to obtain the product fluorinated nitroxyl crude gas.
Referring to fig. 3, the reactor is a straight tube type and is divided into a feeding section 10, a heating section 12 and a cooling section 14 in sequence, wherein the length of each section is 100 mm-2000 mm, and the temperature of the heating section 12 is 300-500 ℃. Preferably, each segment has a length of 500mm to 1800mm, and in one embodiment, each segment has a length of about 1500mm. It can be understood that by controlling the length of each section, the raw materials can be fully mixed and reacted, and the conversion efficiency can be improved. The aspect ratio of the straight tube reactor may be 10:1 to 1.5.
Specifically, the fluorine gas inlet 101 and the nitrogen dioxide inlet 102 are formed at one end of the feeding section 10. The length of the feeding section 10 is 100 mm-2000 mm. Preferably, the length of the feeding section 10 is 500mm to 1000mm. In one embodiment, the length of the feed section 10 is 600mm and the diameter is 60mm. The other end of the feeding section 10 is connected with the heating section 12 in a sealing way through a first connecting flange 11. In particular, the first connecting flange 11 may be a male connecting flange, so that a good sealing connection between the feeding section 10 and the heating section 12 is achieved. The use of the connecting flange can lead the reactor of the invention to be convenient to disassemble and maintain.
Referring to fig. 8, the fluorine gas inlet 101 is staggered from the nitrogen dioxide inlet 102, specifically, the fluorine gas inlet 101 is disposed near the closed end of the feeding section 10. The nitrogen dioxide inlet 102 is also disposed toward the closed end of the feed section 10. The nitrogen dioxide inlet 102 further comprises an outlet baffle 1020, a rotating hub 1021 disposed on the outer surface of the nitrogen dioxide inlet 102, and vanes 1022 disposed on the rotating hub 1021. The outlet baffle 1020 is configured to change the flow direction of the nitrogen dioxide gas to push the blades 1022 to rotate, thereby allowing the blades 1022 to rotate without power. Further, since the nitrogen dioxide gas covers the surfaces of the rotating shaft sleeve 1021 and the blades 1022, the corrosion of fluorine gas to the rotating shaft sleeve 1021 can be prevented, and the service life can be prolonged. Further, since the blades 1022 can rotate, the fluorine gas can be driven to move along the closed end of the feeding section 10, so that the fluorine gas and the nitrogen dioxide gas collide and are fully mixed. In other embodiments, the rotational speed of the blade 1022 may be indirectly controlled by controlling the pressure of the nitrogen dioxide gas.
Further, the air outlet baffle 1020 is provided with a plurality of air outlets 1023. The aperture of the air outlet 1023 may be 1-5mm so that a greater pressure may be applied from the air outlet 1023 to thereby urge the blades 1022 to rotate.
The arrangement of the vanes 1022 may be selected according to practical needs, and is not particularly limited, so long as a good fit with the air outlet 1023 is achieved. In one embodiment, the blade 1022 has its face intersecting the axis of the rotation hub 1021.
Still further, the nitrogen dioxide inlet 102 is disposed on the axis of the feeding section 10, and the vanes 1022 are disposed at a predetermined distance from the side wall of the feeding section 10, so that the mixed gas can be sufficiently mixed from both sides and then fed into the heating section 12. The predetermined distance may be 10 to 20mm.
The length of the heating section 12 is 100 mm-2000 mm. Preferably, the length of the heating section 12 is 1000mm to 1500mm. In one embodiment, the heating section 12 has a length of 1200mm and a diameter of about 180 mm. Heating units 121 are arranged around the heating section 12 and used for heating the heating section 12 to a reaction temperature. The middle part of the heating section 12 is further provided with a temperature sensor 122, so that stable temperature control of the heating section 12 can be realized. The heating section 12 is also provided with a second connecting flange 13 at its other end remote from the feed section 10, the second connecting flange 13 being adapted for sealing connection with the cooling section 14. The second connecting flange 13 may also be a convex connecting flange.
The length of the cooling section 14 is 100mm to 2000mm. Preferably, the length of the cooling section 14 is 1500mm to 1800mm. In one embodiment, the cooling section 14 has a length of 1700mm and a diameter of about 200 mm. A cooling coil 141 is disposed around the cooling section 14, and a product gas outlet 144 is disposed at an end of the cooling section 14 remote from the heating section 12. The cooling coil 141 includes a cooling water discharge port 142 and a cooling water inlet 143.
As a further improvement, the reactor preferably employs a nickel-containing alloy. More preferably nickel copper alloy is selected. The nickel base in the nickel-containing alloy can produce passivation reaction with fluorine gas, so that the reactor can be operated for a long time with high efficiency without being corroded. Therefore, as a further improvement, in other embodiments, before step S1, the method may further include:
s11, introducing fluorine-nitrogen mixed gas and pure fluorine gas into the reactor in sequence for pretreatment. The ratio of fluorine to nitrogen in the fluorine-nitrogen mixed gas is 1:3-6. The fluorine-nitrogen mixed gas with lower activity is used for pretreatment, so that excessive corrosion of the reactor in the early stage can be prevented; then the passivation treatment is carried out by pure fluorine gas.
As a further improvement, preferably, the reaction temperature is 300-450 ℃; more preferably, the reaction temperature is 350-400 ℃. In one embodiment, the reaction temperature is controlled in the range of 360-400 ℃.
As a further improvement, the fluorine gas and NO 2 The molar ratio of the gas is 1:1.0 to 3.5. A plurality of experiments prove that the fluorine gas and NO 2 The ratio of the gases has a large influence on the gas yield of the fluorinated nitroxyl crude gas. Preferably, the fluorine gas and NO 2 The molar ratio of the gas is 1:2.0 to 2.5. More preferably, the fluorine gas and NO 2 The molar ratio of the gas is 1:2.0 to 2.3.
As a further improvement, the NO 2 The gas is obtained by the following method:
by mixing industrial liquid N 2 O 4 Heating and gasifying to obtain gas NO 2 Then gasifies the gas NO 2 Passing through calcium fluoride molecular sieve, and heating to 70-110 deg.C. After treatment with calcium fluoride molecular sieves, the gas NO can be made 2 Not less than 90% by volume. Preferably, the gasified gas NO 2 Passing through calcium fluoride molecular sieve and heating to 85-105 deg.C. More preferably, the gasified gas NO 2 Passing through calcium fluoride molecular sieve, and heating to 90-100deg.C. In one embodiment, the gasified gas NO 2 Passing through a calcium fluoride molecular sieve and then heating to about 95 ℃ to obtain gaseous NO 2 The volume content of (a) can reach about 98%, and the contents are shown in Table 1 (the length of the calcium fluoride molecular sieve isAbout 0.5 m, with a pressure of about 0.1 Mpa) at a standard atmospheric pressure, it can be seen from Table 1 that NO increases with increasing temperature 2 Is due to the significant increase in the volume content of calcium fluoride molecules to N with increasing temperature 2 O 4 The adsorption performance of (a) is increased. However, when the temperature reaches 95 ℃, the volume concentration decreases to some extent with the increase of the temperature, which is probably due to the increase of the temperature N 2 O 4 Is desorbed by the calcium fluoride molecular sieve.
TABLE 1
As a further improvement, the fluorine gas is obtained by the following method:
f prepared by an electrolytic cell 2 The fluorine gas with the volume content of about 95-97% is obtained after the hydrogen fluoride impurity is removed from the gas through a cold trap at the temperature of minus 60 ℃ to minus 70 ℃. The fluorine gas raw material can be anode gas (the fluorine gas content is about 90%) obtained by using a medium-temperature electrolytic tank to electrolyze industrial HF. Further, the fluorine gas with the volume content of about 95-97% can be further purified by using an adsorbent, so that the content of the fluorine gas reaches more than 99%. The adsorbent specifically comprises the following components: a particulate, having a plurality of micropores, and comprising: 35-50 parts of sodium fluoride powder, 20-30 parts of potassium fluoride powder and 3-5 parts of binder.
The preparation method of the adsorbent comprises the following steps:
s11, weighing 35-50 parts of sodium fluoride powder, 20-30 parts of potassium fluoride powder, 3-6 parts of binder and 3-8 parts of diluent according to mass fraction, adding into an oil bath pot at 180-200 ℃ for uniform mixing, and melting to form a mixed solution;
s12, placing the mixed solution into a spherical mold, molding in a press at 180-200 ℃, and cooling at room temperature to obtain a spherical fluoride salt mixture, wherein the molding pressure is 0.2-1 Mpa;
s13, placing the spherical fluoride salt mixture into a solvent to extract a diluent, wherein the solvent is a volatile organic solvent;
s14, taking out the extracted spherical fluoride salt, volatilizing a solvent, and finally, blowing nitrogen to the surface of the product to obtain the fluoride salt adsorbent with high porosity.
As a further improvement, in step S11, the binder is selected from binders that can form sodium fluoride powder and potassium fluoride powder into good binding properties, such as polyvinylidene fluoride, styrene-butadiene rubber emulsion, carboxymethyl cellulose, and the like. In one embodiment, the binder is selected from polyvinylidene fluoride, which can provide good binding properties to sodium fluoride powder and potassium fluoride powder. The content of the binder is not too high, and although the binder is effective, the binder tends to block the channels, and it is difficult to form a high porosity.
The diluent is selected from materials which can infiltrate the three materials, such as diphenyl ketone, or other ketone compounds containing benzene rings.
As a further improvement, preferably, 36 to 40 parts of sodium fluoride powder, 22 to 25 parts of potassium fluoride powder, 3 to 6 parts of binder and 5 to 8 parts of diluent are weighed. In one example, 36 parts of sodium fluoride powder, 24 parts of potassium fluoride powder, 5 parts of a binder, and 5 parts of a diluent are weighed.
As a further refinement, it is preferred that the temperature of the oil bath is 185 to 195 ℃, in one embodiment the temperature of the oil bath is about 190 ℃.
In general, to increase the filling rate, it is generally pressed to form a spherical fluoride salt mixture. As a further improvement, in step S12, the mixed solution is placed in a spherical mold having a diameter of 5 to 15 mm. The pressure of the mould pressing needs to be strictly controlled, if the pressure is too high, the formed spherical fluoride salt mixture is too compact, and the later diluent needs a long time to be extracted or is difficult to completely extract; otherwise, if the pressure is too small, the resulting spherical fluoride salt mixture does not have sufficient strength and is liable to crush and clog the adsorbent column. Therefore, the molding pressure is preferably 0.4 to 0.6MPa. In one embodiment, the molding pressure is about 0.55Mpa.
As a further improvement, in step S13, the volatile organic solvent includes ethanol, diethyl ether, and a mixture thereof. The extraction time is 10-20 hours, which can be selected according to the actual inaudible need, and is limited by completely extracting the diluent. In one embodiment, the spherical fluoride salt mixture is placed in ethanol for 18 hours to completely extract the benzophenone.
As a further improvement, the ratio of the volatile organic solvent to the spherical fluoride salt mixture can be controlled to be 10-50 ml/1 mg during the extraction process. Preferably, the ratio of the volatile organic solvent to the spherical fluoride salt mixture can be controlled to be 20-30 ml/1 mg.
In step S14, the extracted spherical fluoride salt is taken out and left at room temperature to evaporate the solvent naturally.
The embodiment of the invention further provides an adsorbent for purifying fluorine gas, which is prepared according to the method. The moisture content of the final product measured by the adsorbent for fluorine gas purification is less than or equal to 0.2%, and the internal porosity can reach more than 50%.
Example A-1
36 g of sodium fluoride powder, 24 g of potassium fluoride powder, 5 g of polyvinylidene fluoride and 5 g of benzophenone are sequentially added into an oil bath pot at 190 ℃ to be stirred uniformly, and the mixture is melted for 1.5 hours to form a mixed solution, and the solution is put intoThe spherical mold of (2) is molded in a press at 190 ℃ under a pressure of 0.55Mpa, cooled at 25 ℃ for 20 hours, molded, the product is extracted in ethanol for 18 hours after molding, the extract is left in air for 36 hours to volatilize ethanol after the extraction is completed, the surface is purged with nitrogen after ethanol volatilization, and the moisture content of the final product is measured to be 0.14% and the internal porosity is 57.6%, see fig. 2.
Example A-2
Substantially the same as in example 1, except that: 30 g of sodium fluoride powder and 20 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.13%, and the internal porosity is measured to be 55.4%.
Example A-3
Substantially the same as in example 1, except that: 50 g of sodium fluoride powder and 30 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.16%, and the internal porosity is measured to be 58.9%.
Comparative example A-4
Substantially the same as in example 1, except that: 25 g of sodium fluoride powder and 15 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.11%, and the internal porosity is measured to be 48.5%.
Comparative example A-5
Substantially the same as in example 1, except that: 55 g of sodium fluoride powder and 35 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.20%, and the internal porosity is measured to be 59.2%.
Comparative example A-6
Substantially the same as in example 1, except that: 25 g of sodium fluoride powder and 35 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.11%, and the internal porosity is measured to be 48.5%.
Comparative example A-7
Substantially the same as in example 1, except that: 55 g of sodium fluoride powder and 15 g of potassium fluoride powder are taken, and the moisture content of the final product is measured to be 0.20%, and the internal porosity is measured to be 59.2%.
The adsorptivity test was performed for examples A-1 to A-3 and comparative examples A-4 to A-7 as follows:
the product is put into a stainless steel adsorption tower, the temperature is controlled at 20 ℃, 95% fluorine gas is introduced, and the flow rate of the fluorine gas is 1m/s. The fluorine gas content and the hydrogen fluoride content (volume content) of the outlet gas components were measured as shown in table 2 below:
table 2 shows the gas contents of examples A-1 to A-3 and comparative examples A-4 to A-7 (the balance being impurity gas)
From the above data, it can be seen that the adsorbent has a large change in adsorption performance for hydrogen fluoride with a change in the ratio of sodium fluoride powder to potassium fluoride powder.
As a further improvement, the preparation method further comprises:
s2, introducing the fluorinated nitroxyl crude gas into a condenser at the temperature of minus 30 ℃ to minus 50 ℃ to remove impurities such as nitrogen dioxide;
s3, introducing the fluorinated nitroxyl gas obtained in the step S2 into a rectifying tower, and further removing FNO and oxygen and nitrogen impurities under the pressure of 0.1-0.3 MPa.
Example B-1
The flow rate of fluorine gas is 0.3kg/h; NO (NO) 2 The flow rate is 0.72kg/h (molar ratio is 1:2);
fluorine gas purification temperature is-80 ℃; fluorine gas purifying pressure is 0.1MPa;
NO 2 the purification temperature is 95 ℃; NO (NO) 2 The purifying pressure is 0.1MPa;
the reaction temperature is 360-400 ℃; the reaction pressure was 0.1MPa
The output of fluorinated nitroxyl in the crude gas is 0.9kg/h; the fluorinated nitroxyl content in the crude gas was 88% (v/v).
Example B-2
The flow rate of fluorine gas is 0.3kg/h; NO (NO) 2 Flow 0.90kg/h (molar ratio 1:2.3);
fluorine gas purification temperature is-80 ℃; fluorine gas purifying pressure is 0.1MPa;
NO 2 the purification temperature is 95 ℃; NO (NO) 2 The purifying pressure is 0.1MPa;
the reaction temperature is 360-400 ℃; the reaction pressure was 0.1MPa
The output of fluorinated nitroxyl in the crude gas is 0.93kg/h; the fluorinated nitroxyl content in the crude gas was 93% (v/v).
Further, introducing the fluorinated nitroxyl crude gas into a condenser at-45 ℃ to remove impurities such as nitrogen dioxide; then controlling the working temperature of the rectifying tower to minus 30 ℃; the working pressure of the rectifying tower is 0.2MPa, and the high-purity fluorinated nitroxyl gas with the purity of more than 99 percent can be obtained.
Example B-3
The flow rate of fluorine gas is 0.3kg/h; NO (NO) 2 Flow 0.60kg/h (molar ratio 1:1.6);
fluorine gas purification temperature is-80 ℃; fluorine gas purifying pressure is 0.1MPa;
NO 2 the purification temperature is 95 ℃; NO (NO) 2 The purifying pressure is 0.1MPa;
the reaction temperature is 360-400 ℃; the reaction pressure was 0.1MPa
The output of fluorinated nitroxyl in the crude gas is 0.7kg/h; the fluorinated nitroxyl content in the crude gas was 78% (v/v).
Example B-4
The flow rate of fluorine gas is 0.3kg/h; NO (NO) 2 The flow rate is 0.37kg/h (molar ratio is 1:1);
fluorine gas purification temperature is-80 ℃; fluorine gas purifying pressure is 0.1MPa;
NO 2 the purification temperature is 95 ℃; NO (NO) 2 The purifying pressure is 0.1MPa;
the reaction temperature is 360-400 ℃; the reaction pressure was 0.1MPa
The output of fluorinated nitroxyl in the crude gas is 0.4kg/h; the fluorinated nitroxyl content in the crude gas was 60% (v/v).
Example B-5
The flow rate of fluorine gas is 0.3kg/h; NO (NO) 2 Flow 1.29kg/h (molar ratio 1:3.5);
fluorine gas purification temperature is-80 ℃; fluorine gas purifying pressure is 0.1MPa;
NO 2 the purification temperature is 95 ℃; NO (NO) 2 The purifying pressure is 0.1MPa;
the reaction temperature is 360-400 ℃; the reaction pressure was 0.1MPa
The output of fluorinated nitroxyl in the crude gas is 0.52kg/h; the fluorinated nitroxyl content in the crude gas was 33% (v/v).
Referring to fig. 4, the embodiment of the invention further provides a purifying device for fluorinated nitroxyl, which specifically includes:
a raw gas storage tank 21 for storing the fluorinated nitroxyl raw gas from the reactor; a condensing unit 23 for condensing the fluorinated nitroxyl crude gas from the crude gas storage tank 21 to remove most of the nitrogen dioxide; a rectifying unit 25 for further rectifying the gas from the condensing unit 23 to remove most of impurities; a product reservoir 27 for storing pure fluorinated nitroxyl from said rectification unit 25.
Referring to fig. 5, the condensing unit 23 includes: a primary condenser 231 and a secondary condenser 233.
The primary condenser 231 comprises a first cylindrical tank 2310, a first isolation plate 2322 arranged in the middle of the first cylindrical tank 2310, a first fluorinated nitroxyl air inlet 2311 and a first fluorinated nitroxyl air outlet 2312 arranged on two sides of the top of the first cylindrical tank 2310, a first cooling jacket 2321 arranged on the outer side of the first cylindrical tank 2310, a first condensing pipe 2313 arranged around two sides of the first isolation plate 2322, a first refrigerant inlet 2315 and a first refrigerant outlet 2314 communicated with two ends of the first condensing pipe 2313, a first nitrogen dioxide discharge outlet 2316 communicated with the bottom of the first cylindrical tank 2310, a first temperature sensor 2317 and a second temperature sensor 2318 used for acquiring the bottom and the top of the first cylindrical tank 2310, a first liquid level sensor 2320 arranged on the bottom of the first cylindrical tank 2310, and a third temperature sensor 2318 arranged on the first refrigerant inlet 2315. The first fluorinated nitroxyl inlet 2311 is in communication with the product gas outlet 144; the first fluorinated nitroxyl outlet 2312 is in communication with the secondary condenser 233.
The first cooling jacket 2321 is provided with a large hot melt coolant, which may be selected from lm-1/lm-2/lm-3/lm-4/lm-5/lm-6/lm-7/lm-8 glacier coolant. The outer layer adopts a medium with large heat capacity as a refrigerant, so that the effects of stabilizing the temperature and preventing the fluorinated nitroxyl from liquefying can be achieved, and the pressure change is prevented from being overlarge due to the liquefaction of the fluorinated nitroxyl and the abrupt change of the temperature. The first condensation pipe 2313 may be a baffle plate structure with a cooling coil. The first condensation pipe 2313 may use liquid nitrogen as a refrigerant. Specifically, the temperature of the primary condenser 231 may be controlled between-30 ℃ and-40 ℃.
In other embodiments, the first stage condenser 231 may further include a pressure sensor (not shown) to obtain the internal pressure of the first cylindrical tank 2310, and warning is provided when the internal pressure of the first cylindrical tank 2310 floats beyond a set value. More preferably, the pressure sensor is disposed at an air intake side of the first cylindrical can 2310. Further, when the internal pressure of the first cylindrical tank 2310 is floating, the pressure exceeds that of the first cylindrical tankWhen the set value is exceeded, the FNO entering the primary condenser 231 can be controlled by an electric control valve 2 Thereby lowering the internal pressure of the first cylindrical can 2310 to a set value. In other embodiments, FNO entering the primary condenser 231 is controlled by an electrically controlled valve 2 The amount of (2) is reduced to 20-50% of the normal amount.
In other embodiments, when the internal pressure of the first cylindrical tank 2310 floats beyond a set value, the FNO entering the primary condenser 231 is controlled by an electrically controlled valve 2 It is also difficult to lower the internal pressure of the first cylindrical tank 2310 to a set value by floating, which means that the first level sensor 2320 may be damaged, and it is difficult to operate normally. This may be due to the fact that after the first liquid level sensor 2320 is damaged, the liquid level rises to the bottom of the first isolation plate 2322 to form a water seal, resulting in a sharp increase of the internal pressure of the first cylindrical tank 2310. At this time, the first nitrogen dioxide discharge port 2316 may be further opened to perform nitrogen dioxide discharge, thereby performing pressure relief. Therefore, the invention can judge under the condition of no need of additional sensor by the linkage control of each device. And further, after the pressure relief is finished, overhauling is carried out.
The secondary condenser 233 comprises a second cylindrical tank 2330, a second isolation plate 2342 arranged in the middle of the second cylindrical tank 2330, a second fluorinated nitroxyl air inlet 2331 and a second fluorinated nitroxyl air outlet 2332 arranged on two sides of the top of the second cylindrical tank 2330, a second cooling jacket 2341 arranged on the outer side of the second cylindrical tank 2330, a second condensing pipe 2333 arranged on two sides of the second isolation plate 2342 in a surrounding manner, a second refrigerant inlet 2335 and a second refrigerant outlet 2334 communicated with two ends of the second condensing pipe 2333, a second nitrogen dioxide outlet 2340 communicated with the bottom of the second cylindrical tank 2330, a fourth temperature sensor 2337 and a fifth temperature sensor 2338 used for acquiring the bottom and the top of the second cylindrical tank 2330, a second liquid level sensor 2340 arranged on the bottom of the second cylindrical tank 2330, a sixth temperature sensor 2318 arranged on the second refrigerant inlet 2335, and a refrigerant outlet 2342 arranged on the bottom of the second cooling jacket 2341. The second fluorinated nitroxyl inlet 2331 is in communication with the first fluorinated nitroxyl outlet 2312; the second fluorinated nitroxyl outlet 2332 is in communication with the rectification unit 25. The second cooling medium outlet 2334 is communicated with the top of the second cooling jacket 2341, so that a cooling medium circulating flow channel is formed between the second condensing pipe 2333 and the second cooling jacket 2341.
The second condensing tube 2333 may be a baffle plate structure with cooling coils. The second condensing tube 2333 and the second cooling jacket 2341 may use liquid nitrogen as a refrigerant. Specifically, the temperature of the secondary condenser 233 may be controlled between-40 ℃ and-50 ℃. Experiments prove that the temperature of the condenser at the later stage is lower than that of the condenser at the previous stage by one grade, namely, the strategy of gradually decreasing the temperature is set to ensure the relative temperature of the temperatures at each stage, so that on one hand, the wide-range fluctuation of the temperature can not occur, the frequent pressure fluctuation is caused, and the safety is ensured; on the other hand, nitrogen dioxide in the fluorinated nitroxyl can be effectively removed, and the nitrogen dioxide in the fluorinated nitroxyl can be controlled at a theoretical minimum.
In other embodiments, the secondary condenser 233 may further include a pressure sensor (not shown) to obtain the internal pressure of the second cylindrical tank 2330, and the warning is given when the internal pressure of the second cylindrical tank 2330 floats beyond a set value. More preferably, the pressure sensor is disposed at an air intake side of the second cylindrical tank 2330.
Further, when the internal pressure of the second cylindrical tank 2330 floats beyond a set value, the FNO entering the second condenser 233 can be controlled by an electrically controlled valve 2 Thereby lowering the internal pressure of the second cylindrical tank 2330 to a set value. In other embodiments, FNO entering the secondary condenser 233 is controlled by an electronically controlled valve 2 The amount of (2) is reduced to 20-50% of the normal amount.
In other embodiments, when the internal pressure of the second cylindrical tank 2330 floats beyond a set value, the FNO entering the second condenser 233 is controlled by an electrically controlled valve 2 Is difficult to make the second columnThe internal pressure of the tank 2330 floats down to the set point, indicating that the second level sensor 2340 may have been damaged and is difficult to operate properly. This may be due to the fact that after the second level sensor 2340 is damaged, the liquid level rises to the bottom of the second isolation plate 2342 to form a water seal, resulting in a sharp increase in the internal pressure of the second cylindrical tank 2330. At this time, the second nitrogen dioxide discharge outlet 2340 may be further opened to perform nitrogen dioxide discharge, thereby performing pressure relief. Therefore, the invention can judge under the condition of no need of additional sensor by the linkage control of each device. And further, after the pressure relief is finished, overhauling is carried out.
In other embodiments, a three-stage condenser 233 may be further included, the three-stage condenser 233 being temperature controlled to be lower than the second condenser pipe 2333.
Referring to fig. 6, the rectification unit 25 includes a reboiler 253, and a condenser 251 disposed at the top of the reboiler 253, where the condenser 251 is fixedly connected with the reboiler 253 through a fixing device.
The condenser 251 comprises a first tower body 2510, a heat exchange straight pipe 2511 vertically arranged in the first tower body 2510, a filler 2521 filled between the first tower body 2510 and the heat exchange straight pipe 2511, a liquid nitrogen inlet 2514 arranged at the bottom of the first tower body 2510, a liquid nitrogen outlet 2514 arranged at the top of the first tower body 2510, a discharge outlet 2513 arranged at the top of the first tower body 2510 and communicated with the material pipe 2510, and a first temperature sensor 2515 arranged in the middle of the first tower body 2510. The bottom of the tube 2510 is in communication with the reboiler 252, and the first temperature sensor 2515 obtains the temperature in the middle of the condenser 251. The condenser 251 further includes: and a buffer chamber 2512 disposed between the heat exchange straight tube 2511 and the discharge port 2513. The buffer cavity 2512 has a dome-shaped structure, the bottom of which is communicated with each heat exchange straight pipe 2511, and the top of which is communicated with the discharge port 2513. The condenser 251 further includes: a return bend 2513 is provided on top of the buffer chamber 2512. The return bend 2513 is a spiral structure, the bottom of the return bend is communicated with the top of the buffer cavity 2512, and the top of the return bend is communicated with the discharge hole 2513. The condenser 251 further includes: a second temperature sensor 2518 for acquiring the temperature of the return bend 2513. In the actual working process, the temperature of the return bend 2513 is controlled between-25 ℃ and-35 ℃ for rectification by acquiring the temperature of the second temperature sensor 2518.
Further, the condenser 251 further includes: a first pressure sensor 2519 for acquiring the pressure of the return bend 2513. And when the pressure change of the return bend 2513 exceeds a set pressure, an alarm is given.
Referring to fig. 7, the filler 2521 may be selected from a wire mesh filler, and the material of the wire mesh filler may be selected from an aluminum alloy material with a large specific heat capacity, so that the condenser 251 may not be easily changed greatly. The mesh of the wire mesh filler is 5 mm-20 mm, so that the refrigerant can be prevented from being blocked.
The primary function of the buffer chamber 2512 is to provide a converging and buffering action, thereby preventing the return bend 2513 from a large pressure change and risk.
The heat exchange straight tube 2511, buffer chamber 2512 and return bend 2513 are preferably formed from a nickel-containing alloy. More preferably nickel copper alloy is selected. The nickel base in the nickel-containing alloy can produce a passivation layer through a passivation reaction with fluorine gas, so that the heat exchange straight pipe 2511, the buffer cavity 2512 and the return bend 2513 can operate efficiently for a long time without being corroded by fluorinated nitroxyl oxidation.
The reboiler 253 includes a second tower 2530, a feed inlet 2351 disposed at an upper portion of the second tower 2530, a heat medium pipe 2538 disposed in the second tower 2530, a second filler 2539 filled in the second tower 2530, a heat medium inlet 2532 and a heat medium outlet 2533 which are communicated with the heat medium pipe 2538, a waste outlet 2534 disposed at a bottom of the second tower 2530, and a third temperature sensor 2535 and a second pressure sensor 2536 for acquiring a temperature and a pressure in a middle portion of the second tower 2530. After being heated by the heat medium pipe 2538, the crude fluorinated nitroxyl gas volatilizes to the condenser 251 to exchange heat, most of impurities are condensed, and discharged from the waste outlet 2534, while the pure fluorinated nitroxyl gas is discharged from the discharge outlet 2513 and stored in the product storage tank 27. The second tower 2530 is preferably made of a nickel-containing alloy. More preferably nickel copper alloy is selected. The nickel base in the nickel-containing alloy can produce a passivation layer through a passivation reaction with fluorine gas, so that the second tower 2530 can operate efficiently for a long time without being corroded by fluorinated nitroxyl oxidation.
The second packing 2539 may be selected from a wire mesh packing, and the material of the wire mesh packing may be selected from a nickel-containing alloy, so that the reboiler 253 may not be easily subjected to a large temperature change, on the one hand, and may not be easily corroded by fluorinated nitroxyl oxidation, on the other hand. More preferably, the nickel-containing alloy is a nickel-containing alloy having a fluorine passivation layer on the surface. In other embodiments, the wire mesh filler material is selected from nickel copper alloys having a fluorine passivation layer on the surface. The mesh of the wire mesh filler is 3mm x 3 mm-10 mm x 10mm, so that the refrigerant can be prevented from being blocked.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A high efficiency synthesis system for fluorinated nitroxyl comprising; the device comprises a feeding section, a heating section and a cooling section which are sequentially arranged;
the feeding section is provided with a fluorine gas inlet and a nitrogen dioxide inlet; the fluorine gas inlet and the nitrogen dioxide inlet are staggered, and the nitrogen dioxide inlet further comprises an air outlet baffle plate, a rotary shaft sleeve arranged on the outer surface of the nitrogen dioxide inlet and blades arranged on the rotary shaft sleeve; the air outlet baffle is used for changing the flow direction of nitrogen dioxide gas so as to push the blades to rotate, thereby enabling the blades to realize unpowered rotation.
2. A high efficiency synthesis system for fluorinated nitroxyl of claim 1, wherein the fluorine gas inlet is disposed proximate the closed end of the feed section and the nitrogen dioxide inlet is also disposed toward the closed end of the feed section.
3. A high efficiency synthesis system for fluorinated nitroxyl of claim 1, wherein the gas outlet baffle is provided with a plurality of gas outlets such that there is a greater pressure from the gas outlets.
4. A high efficiency synthesis system for fluorinated nitroxyl according to claim 3, wherein the gas outlet has a pore size of 1-5mm.
5. A high efficiency synthesis system for fluorinated nitroxyl according to claim 1, wherein the nitrogen dioxide inlet is disposed on the axis of the feed section and the vanes are disposed a predetermined distance from the side wall of the feed section such that the mixed gas can be fed to the heating section after being thoroughly mixed from both sides.
6. The efficient synthesis system for fluorinated nitroxyl of claim 1, further comprising a crude gas storage tank for storing the fluorinated nitroxyl crude gas from the reactor; a condensing unit for condensing the fluorinated nitroxyl crude gas from the crude gas storage tank to remove a majority of the nitrogen dioxide; the rectification unit is used for further rectifying the gas from the condensation unit to remove most of impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211331301.3A CN115744843B (en) | 2022-10-28 | 2022-10-28 | Efficient synthesis system for fluorinated nitroxyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211331301.3A CN115744843B (en) | 2022-10-28 | 2022-10-28 | Efficient synthesis system for fluorinated nitroxyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115744843A CN115744843A (en) | 2023-03-07 |
| CN115744843B true CN115744843B (en) | 2023-07-18 |
Family
ID=85354758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211331301.3A Active CN115744843B (en) | 2022-10-28 | 2022-10-28 | Efficient synthesis system for fluorinated nitroxyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115744843B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107531A (en) * | 2015-08-19 | 2015-12-02 | 杭州茂宇电子化学有限公司 | Catalyst for synthesizing sulfuryl fluoride and preparation method therefor |
| CN206526789U (en) * | 2017-03-07 | 2017-09-29 | 杭州茂宇电子化学有限公司 | Vikane reactor and reaction unit |
| CN114198981A (en) * | 2021-12-31 | 2022-03-18 | 天津海嘉斯迪新材料合伙企业(有限合伙) | Refining and purifying equipment and method for preparing high-purity fluorine gas |
| CN115116825A (en) * | 2021-03-22 | 2022-09-27 | 株式会社国际电气 | Method for manufacturing semiconductor device, substrate processing method, substrate processing system, and recording medium |
-
2022
- 2022-10-28 CN CN202211331301.3A patent/CN115744843B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107531A (en) * | 2015-08-19 | 2015-12-02 | 杭州茂宇电子化学有限公司 | Catalyst for synthesizing sulfuryl fluoride and preparation method therefor |
| CN206526789U (en) * | 2017-03-07 | 2017-09-29 | 杭州茂宇电子化学有限公司 | Vikane reactor and reaction unit |
| CN115116825A (en) * | 2021-03-22 | 2022-09-27 | 株式会社国际电气 | Method for manufacturing semiconductor device, substrate processing method, substrate processing system, and recording medium |
| CN114198981A (en) * | 2021-12-31 | 2022-03-18 | 天津海嘉斯迪新材料合伙企业(有限合伙) | Refining and purifying equipment and method for preparing high-purity fluorine gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115744843A (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100929472B1 (en) | Method for preparing chlorine gas, aqueous sodium hypochlorite solution and liquid chlorine | |
| CN218403687U (en) | Quick detach formula nitryl fluoride synthesizer | |
| CN115744843B (en) | Efficient synthesis system for fluorinated nitroxyl | |
| CN105418430A (en) | Device and method for preparing high-purity dimethyl carbonate through batch rectification | |
| CN111186839A (en) | Reaction system and method for preparing nano-pore carbon material by using ternary low-temperature molten salt | |
| CN115557474B (en) | FNO 2 Method for producing gas | |
| CN115682631B (en) | FNO based on condenser 2 Is purified by the purification device of (2) | |
| CN218853499U (en) | FNO 2 Rectification and purification device | |
| CN102304048A (en) | Method and equipment for refining high-purity diethyl carbonate | |
| CN202379748U (en) | Reverse disproportionation reaction device for preparing trichlorosilane | |
| JP4487103B2 (en) | Highly efficient synthesis method of methanol and apparatus therefor | |
| CN115747833B (en) | High-integration-level high-purity fluorine gas supply system | |
| CN111974411A (en) | Titanium-based heterogeneous amination composite catalyst and preparation method and application thereof | |
| CN115747848B (en) | Safe production method of high-purity fluorine gas | |
| CN103604277B (en) | Carbon dioxide precooling liquefaction purification integration apparatus | |
| CN115650174B (en) | Purifying device for high-purity fluorine gas | |
| CN218609428U (en) | For FNO 2 Reactor for preparation | |
| CN115700301B (en) | High-efficiency control method of electrolytic tank for preparing high-purity fluorine gas | |
| CN115304821B (en) | Method for recovering perfluoro-2- (2-sulfuryl fluoride ethoxy) propyl vinyl ether | |
| CN114408929B (en) | Separation and purification method and system for fluosilicic acid and silicon dioxide mixed slurry | |
| CN115652349A (en) | For pure F 2 Prepared electrolytic cell device | |
| CN210022090U (en) | Device for producing pinacolone by continuous method | |
| CN112121453B (en) | In-tower reactive distillation and membrane coupling process method and device for producing ethyl levulinate | |
| CN115646238A (en) | Fluorine gas static mixing device and gas distribution method thereof | |
| CN101898752B (en) | Method for refining pure krypton and pure xenon from concentrated xenon-krypton liquid |
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 |