CN114478183B - 143a and 142b method for preparing VDF - Google Patents
143a and 142b method for preparing VDF Download PDFInfo
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- CN114478183B CN114478183B CN202210155009.4A CN202210155009A CN114478183B CN 114478183 B CN114478183 B CN 114478183B CN 202210155009 A CN202210155009 A CN 202210155009A CN 114478183 B CN114478183 B CN 114478183B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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Abstract
The application discloses a method for preparing VDF by 143a and 142b, which comprises the following steps: 1) Checking the pressure and tightness of the pipeline; 2) Subjecting the mixture of 143a and 142b to a thermal cracking treatment by a cracking device; 3) Cooling the cracked product in a cooling tank; 4) The cooled product enters an absorption tower, deionized water is continuously injected into the absorption tower, HF in the product is removed to form residual liquid, and the residual liquid flows out through the bottom of the absorption tower; 5) The product enters a caustic wash tank to remove HCl in the mixture; 6) And opening the product, and collecting the product in a collecting box through a dryer to obtain a target product VDF. The application can control the output of 143a and 142b according to the design requirement, reduce the coking and coking in the cracking device, does not influence the selectivity of VDF, is beneficial to removing HF and HCl in reactants, inhibits side reaction, and effectively reduces byproducts in VDF.
Description
Technical Field
The present application relates to a process for preparing VDF 143a and 142 b.
Background
Vinylidene fluoride (VDF) is an important chemical monomer for producing fluorine-containing polymers, and VDF can be homo-polymerized by itself or copolymerized with other fluorine-containing vinyl groups to synthesize polyvinylidene fluoride (PVDF), and can also be binary polymerized with hexafluoropropylene or ternary polymerized with hexafluoropropylene and tetrafluoroethylene to prepare Fluororubber (FKM).
The prior vinylidene fluoride monomer preparation process is largely researched, and is prepared by adopting different processes according to different raw materials, and is prepared by carrying out cracking reaction in a hollow tube at 700-1000 ℃ by taking chlorodifluoroethane (142 b) as a raw material commonly used in industry.
The beautiful patent US 3996301 utilizes the cracking of tetrafluorocyclobutane to prepare VDF, the tetrafluorocyclobutane reacts in a cracking tube at 500-900 ℃, and inert gases such as helium, nitrogen, carbon tetrafluoride and the like can be introduced, the operation is facilitated under low pressure, and the residence time is 1 s-10 min. The main byproducts are tetrafluoroethylene and ethylene, and the patent designs a dimerization chamber so that the tetrafluoroethylene and the ethylene react to generate a dimer to achieve the purpose of separation. The temperature of the dimerization chamber is 400-600 ℃, and the high pressure is favorable for dimerization reaction, so that the pressure in the chamber is 50-500 Psig, the residence time of gas in the dimerization chamber is determined by the reaction temperature, the gas stays for 1-20 min at high temperature, and the gas stays for longer time at low temperature for 1-200 h. The VDF prepared by the method has high purity, can reach more than 95% generally under the condition of no rectification treatment, but has the problems of more byproducts, low selectivity, high energy consumption, easy carbonization in a cracking tube, difficult cleaning and the like.
Disclosure of Invention
The application aims to provide a technical scheme of a method for preparing VDF by 143a and 142b, which aims at overcoming the defects of the prior art, not only can control the output quantity of 143a and 142b according to design requirements and reduce the purpose of coking carbon in a cracking device, but also can not influence the selectivity of the VDF, is beneficial to removing HF and HCl in reactants, inhibits side reaction and effectively reduces byproducts in the VDF.
In order to solve the technical problems, the application adopts the following technical scheme:
143a and 142b, characterized by comprising the steps of:
1) The method comprises the steps of connecting a first storage bottle, a second storage bottle and a nitrogen steel bottle with a cracking device through a pipeline, connecting the cracking device with an absorption tower through a cooling tank, connecting the absorption tower with a dryer through an alkaline washing tank, connecting the dryer with a receiving tank, opening a third valve connected with the nitrogen steel bottle, and checking pipeline pressure and tightness;
2) Then, the third valve is closed, the first valve and the second valve connected with the first storage bottle and the second storage bottle are opened, the output pressure of the 143a and the 142b is controlled, the fourth valve and the flowmeter are simultaneously opened, the 143a and the 142b are mixed and enter the cracking device, and the mixture of the 143a and the 142b is subjected to heating cracking treatment through the cracking device;
3) Opening a fifth valve to enable the cracked product to enter a cooling tank for cooling;
4) Opening a sixth valve to enable the cooled product to enter an absorption tower, continuously injecting deionized water into the absorption tower, removing HF in the product to form residual liquid, and enabling the residual liquid to flow out through the bottom of the absorption tower;
5) Opening a seventh valve, and enabling the product to enter a caustic wash tank to remove HCl in the mixture;
6) And opening an eighth valve to enable the product to enter a collecting box through a dryer for collection, so as to obtain a target product VDF.
The VDF is prepared through the process steps, the output of 143a and 142b can be controlled according to the design requirement, the purpose of coking in a cracking device is reduced, the selectivity of the VDF is not affected, HF and HCl in reactants are removed, side reactions are inhibited, and byproducts in the VDF are effectively reduced.
Further, the set temperature of the cracking device is 450-600 ℃.
Further, the pyrolysis device comprises a pyrolysis furnace and a nickel pyrolysis tube, the nickel pyrolysis tube is arranged in the pyrolysis furnace, a temperature sensor and a heating mechanism are arranged in the pyrolysis furnace, the design of the nickel pyrolysis tube can have a certain inhibition effect on HCl removal side reaction, the heating mechanism can heat the pyrolysis furnace, HF and HCl removal reactions of the pyrolysis furnace are carried out at high temperature, the temperature sensor can monitor the temperature in the pyrolysis furnace in real time, and the control accuracy of the temperature is improved.
Further, the nickel cracking tube is a planar annular coil or a conical annular coil.
Further, the heating mechanism includes the chassis, intermediate lamella and footwall, the footwall passes through intermediate lamella removal connection chassis, be equipped with lifting unit between footwall and the chassis, be equipped with first cavity in the chassis, be equipped with first positioning ring on the intermediate lamella, first positioning ring and first cavity phase-match, be equipped with the second cavity in the intermediate lamella, be equipped with the second positioning ring on the footwall, second positioning ring and second cavity phase-match, be equipped with controller and power source in the chassis, can drive footwall and intermediate lamella through lifting unit and reciprocate, satisfy and heat nickel splitting tube, improve heating efficiency, first positioning ring and second positioning ring can guarantee that intermediate lamella and footwall follow first cavity and second cavity stability respectively, the stability of whole heating mechanism has been improved, the controller is preferably the PLC controller, can control heating mechanism, power source is used for connecting external power source.
Further, be equipped with first heating ring on the chassis, be equipped with second heating ring and first S-shaped heating pipe on the intermediate plate, be equipped with third heating ring and second S-shaped heating pipe on the top tray, first heating ring, second heating ring, first S-shaped heating pipe, third heating ring and second S-shaped heating pipe all with controller electric connection, first heating ring, second heating ring and third heating ring can follow vertical direction and heat nickel matter schizolysis pipe, first S-shaped heating pipe and second S-shaped heating pipe can follow the horizontal direction and heat nickel matter schizolysis pipe, improve the heating efficiency to nickel matter schizolysis pipe, further improve schizolysis efficiency.
Further, lifting unit includes mount, carriage, cylinder and lifter, and the mount is located in the chassis, is equipped with the slide rail in the chassis, and carriage sliding connection is on the slide rail, and the cylinder passes through the piston rod and connects the carriage, and the mount all passes through the lifter and connects the footwall with the carriage, and the mount can play the effect of location support to the lifter, drives carriage horizontal migration through the piston rod through the cylinder, can realize that the lifter carries out jacking or decline to the footwall, adjusts the high position of footwall and intermediate lamella.
Further, be equipped with first intake pipe, first outlet duct and cooling module on the cooling tank, top and bottom of cooling tank are located respectively to first intake pipe and first outlet duct, cooling module includes the cooling water input port, the cooling water delivery outlet, first cooling plate, second cooling plate and third cooling plate, first cooling plate is fixed in the cooling tank through the support, first cooling plate intercommunication cooling water input port, the second cooling plate passes through first cooling tube coupling in the top of first cooling plate, the third cooling plate passes through the second cooling tube coupling in the top of second cooling plate, the third cooling plate passes through first outlet pipe intercommunication cooling water delivery outlet, the second cooling plate passes through second outlet pipe coupling first outlet pipe, first intake pipe is used for with the mixed gas input cooling tank in, the mixed gas after the cooling is exported through the second outlet duct, when the cooling rate to the mixed gas is required to be accelerated, the cooling water flows in first cooling plate through the cooling water input port, and through first cooling tube and second cooling plate flow to the third cooling plate, realize the rapid cooling to the mixed gas through the cooling water delivery outlet, realize slowing down the mixed gas through the cooling water delivery outlet, the second cooling plate passes through the first cooling water output port, the first cooling plate is convenient when the mixed gas flows through the first cooling water output port.
Further, be equipped with splitter box, water inlet and delivery port in the second cooling disk, the water inlet passes through splitter box intercommunication delivery port, be equipped with first solenoid valve on the delivery port, the splitter box passes through first shunt tubes intercommunication second outlet pipe, be equipped with the second solenoid valve on the first shunt tubes, the cooling water in the first cooling tube can get into the splitter box through the water inlet, the splitter box can be according to actual technological requirement with cooling water through delivery port input second cooling tube or follow first shunt tubes reposition of redundant personnel to second outlet pipe, first solenoid valve is used for controlling the switch of delivery port, the second solenoid valve is used for controlling the switch of first shunt tubes.
Further, be equipped with second intake pipe, the second outlet duct, deionized water input port and raffinate discharge port on the absorption tower, the second intake pipe is located on the side of absorption tower, the top of absorption tower is located to the second outlet duct, the raffinate discharge port is located the bottom of absorption tower, deionized water input port passes through deionized water honeycomb duct connection first spray dish, first spray dish is fixed in the absorption tower, first spray dish passes through the linking pipe and connects second spray dish, the second spray dish is fixed in the absorption tower, the mixed gas after cooling passes through the second intake pipe input absorption tower, deionized water input port lets in deionized water simultaneously, spray the mixed gas through first spray dish and second spray dish, get rid of the HF gas in the mixed gas, be equipped with the pressure boost chamber in the first spray dish, the pressure boost chamber intercommunication deionized water honeycomb duct, the bottom of first spray dish is equipped with the spray hole, the spray hole passes through second branch flow duct intercommunication pressure boost chamber, the second spray dish adopts the structure of being similar to first spray dish, it does not have the linking pipe.
Due to the adoption of the technical scheme, the application has the following beneficial effects:
1. the VDF is prepared through the process steps, the output of 143a and 142b can be controlled according to the design requirement, the purpose of coking in a cracking device is reduced, the selectivity of the VDF is not affected, HF and HCl in reactants are removed, side reactions are inhibited, and byproducts in the VDF are effectively reduced.
2. The design of the nickel cracking tube can have a certain inhibition effect on HCl removal side reaction, the heating mechanism can heat the cracking furnace, HF and HCl removal reactions are carried out on the cracking furnace at high temperature, the temperature sensor can monitor the temperature in the cracking furnace in real time, and the control accuracy of the temperature is improved.
3. Can drive the top tray and the middle dish reciprocates through lifting unit, satisfy and heat nickel matter schizolysis pipe, improve heating efficiency, first holding ring and second holding ring can guarantee that middle dish and top tray respectively follow first cavity and second cavity and stabilize the removal, have improved whole heating mechanism's stability.
4. The first air inlet pipe is used for inputting mixed gas into the cooling tank, the cooled mixed gas is output through the second air outlet pipe, when the cooling speed of the mixed gas needs to be accelerated, cooling water flows into the first cooling disk through the cooling water input port and flows to the third cooling disk through the first cooling pipe and the second cooling pipe, the mixed gas is output through the cooling water output port through the first water outlet pipe, rapid cooling and cooling of the mixed gas are realized, when the cooling speed of the mixed gas needs to be slowed down, the cooling water flows into the first cooling disk through the cooling water input port and flows to the second cooling disk through the first cooling pipe, and the mixed gas is output through the cooling water output port through the second water outlet pipe, and the control is flexible and convenient.
Drawings
The application is further described below with reference to the accompanying drawings:
FIG. 1 is a process flow diagram of a process for preparing VDF of the application 143a and 142 b;
FIG. 2 is a schematic diagram showing the connection between a nickel cracking tube and a cracking furnace according to example 1 of the present application;
FIG. 3 is a schematic view showing the connection between a nickel cracking tube and a cracking furnace according to example 2 of the present application;
FIG. 4 is a diagram showing the effect of the heating mechanism of the present application;
FIG. 5 is a schematic view of a heating mechanism according to the present application;
FIG. 6 is a schematic view of a cooling tank according to the present application;
FIG. 7 is a schematic view of a second cooling plate according to the present application;
FIG. 8 is a schematic view showing the structure of an absorber column according to the present application;
fig. 9 is a schematic structural view of a first shower tray according to the present application.
In the figure: 1-a first storage bottle; 2-a second storage bottle; 3-a flow meter;
4-cracking furnace; 401-a temperature sensor; 402-a heating mechanism; 403-chassis; 404-middle disk; 405-top plate; 406-a first heating ring; 407-a second heating ring; 408-a third heating ring; 409-a first S-shaped heating tube; 410-a second S-shaped heating tube; 414-a controller; 415-a power interface; 416-a first cavity; 417-a first positioning ring; 418-a second cavity; 419-a second retaining ring; 420-fixing frame; 421-sliding rail; 422-a carriage; 423-cylinder; 424-a piston rod; 425-lifting bar;
a 5-nickel cracking tube;
6-cooling tank; 601-a first air inlet pipe; 602-a first outlet pipe; 603-a cooling water inlet; 604-a cooling water outlet; 605-a first cooling plate; 606-a second cooling pan; 607-a third cooling pan; 608—a first cooling tube; 609-a second cooling tube; 610-a first outlet pipe; 611-a second outlet pipe; 612-shunt grooves; 613-water inlet; 614-water outlet; 615-a first shunt; 616—a first solenoid valve; 617-a second solenoid valve;
7-an absorption tower; 701-a second air inlet pipe; 702-a deionized water input port; 703-a raffinate vent; 704-a second air outlet pipe; 705-a first shower tray; 706-a second spray tray; 707-connecting pipe; 708-deionized water draft tube; 709-pressurizing the cavity; 710-spray holes; 711-second shunt tube;
8-alkali washing box; 9-a dryer; 10-collecting box; 11-nitrogen steel cylinders; 12-a first valve; 13-a second valve; 14-a third valve; 15-fourth valve; 16-fifth valve; 17-sixth valve; 18-seventh valve; 19-eighth valve.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
In order that those skilled in the art will better understand the present application, a technical solution in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, shall fall within the scope of the application.
It should be noted that the terms "first," "second," and the like in the description and claims of the present application and in the above-described figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion.
Example 1
As shown in fig. 1, 2, and 4 to 9, the method for preparing VDF according to the present application 143a and 142b includes the steps of:
1) Firstly, connecting a first storage bottle 1, a second storage bottle 2 and a nitrogen steel bottle 11 with a cracking device through a pipeline, connecting the cracking device with an absorption tower 7 through a cooling tank 6, connecting the absorption tower 7 with a dryer 9 through an alkaline washing tank 8, connecting the dryer 9 with a receiving header 10, opening a third valve 14 connected with the nitrogen steel bottle 11, and checking pipeline pressure and tightness;
2) Then, the third valve 14 is closed, the first valve 12 and the second valve 13 connected with the first storage bottle 1 and the second storage bottle 2 are opened, the output pressure of the 143a and the 142b is controlled, the fourth valve 15 and the flow meter 3 are simultaneously opened, the 143a and the 142b are mixed and enter the cracking device, and the mixture of the 143a and the 142b is subjected to heating cracking treatment through the cracking device; the set temperature of the cracking device is 450-600 ℃.
The cracking device comprises a cracking furnace 4 and a nickel cracking tube 5, wherein the nickel cracking tube 5 is arranged in the cracking furnace 4, a temperature sensor 401 and a heating mechanism 402 are arranged in the cracking furnace 4, the design of the nickel cracking tube 5 can have a certain inhibition effect on HCl removal side reaction, the heating mechanism 402 can heat the cracking furnace 4, the cracking furnace 4 can perform HF removal and HCl removal reactions at high temperature, the temperature sensor 401 can monitor the temperature in the cracking furnace 4 in real time, and the control accuracy of the temperature is improved.
The nickel cracking tube 5 is a planar annular coil.
The heating mechanism 402 comprises a base plate 403, an intermediate plate 404 and a top plate 405, the top plate 405 is movably connected with the base plate 403 through the intermediate plate 404, a lifting assembly is arranged between the top plate 405 and the base plate 403, a first cavity 416 is arranged in the base plate 403, a first positioning ring 417 is arranged on the intermediate plate 404 and is matched with the first cavity 416, a second cavity 418 is arranged in the intermediate plate 404, a second positioning ring 419 is arranged on the top plate 405 and is matched with the second cavity 418, a controller 414 and a power interface 415 are arranged in the base plate 403, the top plate 405 and the intermediate plate 404 can be driven to move up and down through the lifting assembly, heating efficiency is improved, the first positioning ring 417 and the second positioning ring 419 can ensure that the intermediate plate 404 and the top plate 405 respectively move along the first cavity 416 and the second cavity 418, stability of the whole heating mechanism 402 is improved, the controller 414 is preferably a PLC (programmable logic controller) 414 and can control the heating mechanism 402, and the power interface 415 is used for connecting an external power supply.
The chassis 403 is provided with a first heating ring 406, the middle disk 404 is provided with a second heating ring 407 and a first S-shaped heating pipe 409, the top disk 405 is provided with a third heating ring 408 and a second S-shaped heating pipe 410, the first heating ring 406, the second heating ring 407, the first S-shaped heating pipe 409, the third heating ring 408 and the second S-shaped heating pipe 410 are all electrically connected with the controller 414, the first heating ring 406, the second heating ring 407 and the third heating ring 408 can heat the nickel cracking pipe 5 from the vertical direction, the first S-shaped heating pipe 409 and the second S-shaped heating pipe 410 can heat the nickel cracking pipe 5 from the horizontal direction, the heating efficiency of the nickel cracking pipe 5 is improved, and the cracking efficiency is further improved.
The lifting assembly comprises a fixing frame 420, a sliding frame 422, an air cylinder 423 and a lifting rod 425, wherein the fixing frame 420 is arranged in a chassis 403, a sliding rail 421 is arranged in the chassis 403, the sliding frame 422 is slidably connected to the sliding rail 421, the air cylinder 423 is connected with the sliding frame 422 through a piston rod 424, the fixing frame 420 and the sliding frame 422 are connected with a top disc 405 through the lifting rod 425, the fixing frame 420 can play a role in positioning and supporting the lifting rod 425, the sliding frame 422 is driven to horizontally move through the piston rod 424 by the air cylinder 423, the lifting rod 425 can lift or descend the top disc 405, and the height positions of the top disc 405 and the middle disc 404 are adjusted.
3) Opening a fifth valve 16 to enable the cracked product to enter the cooling tank 6 for cooling;
the cooling tank 6 is provided with a first air inlet pipe 601, a first air outlet pipe 602 and a cooling component, the first air inlet pipe 601 and the first air outlet pipe 602 are respectively arranged at the top and the bottom of the cooling tank 6, the cooling component comprises a cooling water input port 603, a cooling water output port 604, a first cooling plate 605, a second cooling plate 606 and a third cooling plate 607, the first cooling plate 605 is fixed in the cooling tank 6 through a bracket, the first cooling plate 605 is communicated with the cooling water input port 603, the second cooling plate 606 is connected above the first cooling plate 605 through a first cooling pipe 608, the third cooling plate 607 is connected above the second cooling plate 606 through a second cooling pipe 609, the third cooling plate 607 is communicated with the cooling water output port 604 through a first water outlet pipe 610, the second cooling plate 606 is connected with the first water outlet pipe 610 through a second water outlet pipe 611, the first air inlet pipe 601 is used for inputting mixed gas into the cooling tank 6, the cooled mixed gas is output through the second air outlet pipe 704, when the cooling speed of the mixed gas needs to be accelerated, the cooling water flows into the first cooling plate 605 through the cooling water input port 603, and the first cooling plate 608 and the second cooling water flow through the second cooling pipe 608 and the second cooling pipe 608 is controlled to the second cooling plate 604, when the mixed gas needs to flow to be fast, the mixed gas is cooled down through the first cooling plate 605, the first cooling water is convenient to flow through the first cooling pipe 604, and the cooling water is cooled down through the second cooling pipe 604, and the first cooling pipe is convenient to realize.
The second cooling disk 606 is internally provided with a diversion groove 612, a water inlet 613 and a water outlet 614, the water inlet 613 is communicated with the water outlet 614 through the diversion groove 612, the water outlet 614 is provided with a first electromagnetic valve 616, the diversion groove 612 is communicated with a second water outlet 611 through a first diversion pipe 615, the first diversion pipe 615 is provided with a second electromagnetic valve 617, cooling water in the first cooling pipe 608 can enter the diversion groove 612 through the water inlet 613, the diversion groove 612 can input the cooling water into the second cooling pipe 609 through the water outlet 614 or is shunted from the first diversion pipe 615 to the second water outlet 611 according to actual technological requirements, the first electromagnetic valve 616 is used for controlling the switch of the water outlet 614, and the second electromagnetic valve 617 is used for controlling the switch of the first diversion pipe 615.
4) Opening a sixth valve 17 to enable the cooled product to enter an absorption tower 7, continuously injecting deionized water into the absorption tower 7, removing HF in the product to form residual liquid, and enabling the residual liquid to flow out through the bottom of the absorption tower 7;
the absorption tower 7 is provided with a second air inlet pipe 701, a second air outlet pipe 704, a deionized water input port 702 and a residual liquid discharge port 703, the second air inlet pipe 701 is arranged on the side surface of the absorption tower 7, the second air outlet pipe 704 is arranged at the top of the absorption tower 7, the residual liquid discharge port 703 is arranged at the bottom of the absorption tower 7, the deionized water input port 702 is connected with a first spray disk 705 through a deionized water guide pipe 708, the first spray disk 705 is fixed in the absorption tower 7, the first spray disk 705 is connected with a second spray disk 706 through a connecting pipe 707, the second spray disk 706 is fixed in the absorption tower 7, cooled mixed gas is input into the absorption tower 7 through the second air inlet pipe 701, simultaneously, the deionized water input port 702 is continuously introduced into deionized water, HF gas in the mixed gas is removed through the first spray disk 705 and the second spray disk 706, the pressurizing cavity 709 is arranged in the first spray disk 705, the pressurizing cavity 709 is communicated with the deionized water guide pipe 708, the bottom of the first spray disk 705 is provided with a spray hole 710, the spray hole 710 is communicated with the pressurizing cavity 709 through the second flow pipe 711, and the second spray disk 706 adopts a structure similar to the first spray disk 705, and the connecting pipe 707 is not provided with the connecting pipe 707.
5) Opening a seventh valve 18, and allowing the product to enter a caustic wash tank 8 to remove HCl in the mixture; the solution in the alkaline washing tank 8 is sodium hydroxide solution.
6) The eighth valve 19 is opened, the product enters the collecting box 10 through the dryer 9 for collecting, and the target product VDF is obtained, and the dryer 9 is filled with anhydrous calcium chloride.
The VDF is prepared through the process steps, the output of 143a and 142b can be controlled according to the design requirement, the purpose of coking in a cracking device is reduced, the selectivity of the VDF is not affected, HF and HCl in reactants are removed, side reactions are inhibited, and byproducts in the VDF are effectively reduced.
The VDF product obtained was analyzed by a method comprising
1. Gas chromatography analysis
Adopting an FID detector, wherein the chromatographic column is GS-GSPRO type (60 m is 0.32 mm), the carrier gas is nitrogen (3.0 mL/min), the pre-column pressure is 30kPa, the temperature is programmed, the initial column temperature is 50 ℃ and kept for 4min, the temperature is increased to 150 ℃ at 10 ℃/min and kept for 6min, the temperature of the vaporization chamber is 200 ℃, the temperature of the detector is 250 ℃, and the sample injection amount is 0.1-0.3 mL.
2. GC-MS analysis
The TRACE DSQII type gas chromatograph-mass spectrometer has the MS condition of EI ion source, electron energy of 70eV, temperature of 200 ℃, interface temperature of 230 ℃, scanning range of 10-350 m/z, GC condition of carrier gas He (3.0 Ml/min), pre-column pressure of 30kPa, vaporization chamber temperature of 200 ℃, and temperature programming process the same as the gas chromatograph analysis.
Example 2
As shown in fig. 1, 3 to 9, a method for preparing VDF according to the present application 143a and 142b includes the steps of:
1) Firstly, connecting a first storage bottle 1, a second storage bottle 2 and a nitrogen steel bottle 11 with a cracking device through a pipeline, connecting the cracking device with an absorption tower 7 through a cooling tank 6, connecting the absorption tower 7 with a dryer 9 through an alkaline washing tank 8, connecting the dryer 9 with a receiving header 10, opening a third valve 14 connected with the nitrogen steel bottle 11, and checking pipeline pressure and tightness;
2) Then, the third valve 14 is closed, the first valve 12 and the second valve 13 connected with the first storage bottle 1 and the second storage bottle 2 are opened, the output pressure of the 143a and the 142b is controlled, the fourth valve 15 and the flow meter 3 are simultaneously opened, the 143a and the 142b are mixed and enter the cracking device, and the mixture of the 143a and the 142b is subjected to heating cracking treatment through the cracking device; the set temperature of the cracking device is 450-600 ℃.
The cracking device comprises a cracking furnace 4 and a nickel cracking tube 5, wherein the nickel cracking tube 5 is arranged in the cracking furnace 4, a temperature sensor 401 and a heating mechanism 402 are arranged in the cracking furnace 4, the design of the nickel cracking tube 5 can have a certain inhibition effect on HCl removal side reaction, the heating mechanism 402 can heat the cracking furnace 4, the cracking furnace 4 can perform HF removal and HCl removal reactions at high temperature, the temperature sensor 401 can monitor the temperature in the cracking furnace 4 in real time, and the control accuracy of the temperature is improved.
The nickel cracking tube 5 is a conical annular coil.
The heating mechanism 402 comprises a base plate 403, an intermediate plate 404 and a top plate 405, the top plate 405 is movably connected with the base plate 403 through the intermediate plate 404, a lifting assembly is arranged between the top plate 405 and the base plate 403, a first cavity 416 is arranged in the base plate 403, a first positioning ring 417 is arranged on the intermediate plate 404 and is matched with the first cavity 416, a second cavity 418 is arranged in the intermediate plate 404, a second positioning ring 419 is arranged on the top plate 405 and is matched with the second cavity 418, a controller 414 and a power interface 415 are arranged in the base plate 403, the top plate 405 and the intermediate plate 404 can be driven to move up and down through the lifting assembly, heating efficiency is improved, the first positioning ring 417 and the second positioning ring 419 can ensure that the intermediate plate 404 and the top plate 405 respectively move along the first cavity 416 and the second cavity 418, stability of the whole heating mechanism 402 is improved, the controller 414 is preferably a PLC (programmable logic controller) 414 and can control the heating mechanism 402, and the power interface 415 is used for connecting an external power supply.
The chassis 403 is provided with a first heating ring 406, the middle disk 404 is provided with a second heating ring 407 and a first S-shaped heating pipe 409, the top disk 405 is provided with a third heating ring 408 and a second S-shaped heating pipe 410, the first heating ring 406, the second heating ring 407, the first S-shaped heating pipe 409, the third heating ring 408 and the second S-shaped heating pipe 410 are all electrically connected with the controller 414, the first heating ring 406, the second heating ring 407 and the third heating ring 408 can heat the nickel cracking pipe 5 from the vertical direction, the first S-shaped heating pipe 409 and the second S-shaped heating pipe 410 can heat the nickel cracking pipe 5 from the horizontal direction, the heating efficiency of the nickel cracking pipe 5 is improved, and the cracking efficiency is further improved.
The lifting assembly comprises a fixing frame 420, a sliding frame 422, an air cylinder 423 and a lifting rod 425, wherein the fixing frame 420 is arranged in a chassis 403, a sliding rail 421 is arranged in the chassis 403, the sliding frame 422 is slidably connected to the sliding rail 421, the air cylinder 423 is connected with the sliding frame 422 through a piston rod 424, the fixing frame 420 and the sliding frame 422 are connected with a top disc 405 through the lifting rod 425, the fixing frame 420 can play a role in positioning and supporting the lifting rod 425, the sliding frame 422 is driven to horizontally move through the piston rod 424 by the air cylinder 423, the lifting rod 425 can lift or descend the top disc 405, and the height positions of the top disc 405 and the middle disc 404 are adjusted.
3) Opening a fifth valve 16 to enable the cracked product to enter the cooling tank 6 for cooling;
the cooling tank 6 is provided with a first air inlet pipe 601, a first air outlet pipe 602 and a cooling component, the first air inlet pipe 601 and the first air outlet pipe 602 are respectively arranged at the top and the bottom of the cooling tank 6, the cooling component comprises a cooling water input port 603, a cooling water output port 604, a first cooling plate 605, a second cooling plate 606 and a third cooling plate 607, the first cooling plate 605 is fixed in the cooling tank 6 through a bracket, the first cooling plate 605 is communicated with the cooling water input port 603, the second cooling plate 606 is connected above the first cooling plate 605 through a first cooling pipe 608, the third cooling plate 607 is connected above the second cooling plate 606 through a second cooling pipe 609, the third cooling plate 607 is communicated with the cooling water output port 604 through a first water outlet pipe 610, the second cooling plate 606 is connected with the first water outlet pipe 610 through a second water outlet pipe 611, the first air inlet pipe 601 is used for inputting mixed gas into the cooling tank 6, the cooled mixed gas is output through the second air outlet pipe 704, when the cooling speed of the mixed gas needs to be accelerated, the cooling water flows into the first cooling plate 605 through the cooling water input port 603, and the first cooling plate 608 and the second cooling water flow through the second cooling pipe 608 and the second cooling pipe 608 is controlled to the second cooling plate 604, when the mixed gas needs to flow to be fast, the mixed gas is cooled down through the first cooling plate 605, the first cooling water is convenient to flow through the first cooling pipe 604, and the cooling water is cooled down through the second cooling pipe 604, and the first cooling pipe is convenient to realize.
The second cooling disk 606 is internally provided with a diversion groove 612, a water inlet 613 and a water outlet 614, the water inlet 613 is communicated with the water outlet 614 through the diversion groove 612, the water outlet 614 is provided with a first electromagnetic valve 616, the diversion groove 612 is communicated with a second water outlet 611 through a first diversion pipe 615, the first diversion pipe 615 is provided with a second electromagnetic valve 617, cooling water in the first cooling pipe 608 can enter the diversion groove 612 through the water inlet 613, the diversion groove 612 can input the cooling water into the second cooling pipe 609 through the water outlet 614 or is shunted from the first diversion pipe 615 to the second water outlet 611 according to actual technological requirements, the first electromagnetic valve 616 is used for controlling the switch of the water outlet 614, and the second electromagnetic valve 617 is used for controlling the switch of the first diversion pipe 615.
4) Opening a sixth valve 17 to enable the cooled product to enter an absorption tower 7, continuously injecting deionized water into the absorption tower 7, removing HF in the product to form residual liquid, and enabling the residual liquid to flow out through the bottom of the absorption tower 7;
the absorption tower 7 is provided with a second air inlet pipe 701, a second air outlet pipe 704, a deionized water input port 702 and a residual liquid discharge port 703, the second air inlet pipe 701 is arranged on the side surface of the absorption tower 7, the second air outlet pipe 704 is arranged at the top of the absorption tower 7, the residual liquid discharge port 703 is arranged at the bottom of the absorption tower 7, the deionized water input port 702 is connected with a first spray disk 705 through a deionized water guide pipe 708, the first spray disk 705 is fixed in the absorption tower 7, the first spray disk 705 is connected with a second spray disk 706 through a connecting pipe 707, the second spray disk 706 is fixed in the absorption tower 7, cooled mixed gas is input into the absorption tower 7 through the second air inlet pipe 701, simultaneously, the deionized water input port 702 is continuously introduced into deionized water, HF gas in the mixed gas is removed through the first spray disk 705 and the second spray disk 706, the pressurizing cavity 709 is arranged in the first spray disk 705, the pressurizing cavity 709 is communicated with the deionized water guide pipe 708, the bottom of the first spray disk 705 is provided with a spray hole 710, the spray hole 710 is communicated with the pressurizing cavity 709 through the second flow pipe 711, and the second spray disk 706 adopts a structure similar to the first spray disk 705, and the connecting pipe 707 is not provided with the connecting pipe 707.
5) Opening a seventh valve 18, and allowing the product to enter a caustic wash tank 8 to remove HCl in the mixture; the solution in the alkaline washing tank 8 is sodium hydroxide solution.
6) The eighth valve 19 is opened, the product enters the collecting box 10 through the dryer 9 for collecting, and the target product VDF is obtained, and the dryer 9 is filled with anhydrous calcium chloride.
The VDF is prepared through the process steps, the output of 143a and 142b can be controlled according to the design requirement, the purpose of coking in a cracking device is reduced, the selectivity of the VDF is not affected, HF and HCl in reactants are removed, side reactions are inhibited, and byproducts in the VDF are effectively reduced.
The VDF product obtained was analyzed by a method comprising
1. Gas chromatography analysis
Adopting an FID detector, wherein the chromatographic column is GS-GSPRO type (60 m is 0.32 mm), the carrier gas is nitrogen (3.0 mL/min), the pre-column pressure is 30kPa, the temperature is programmed, the initial column temperature is 50 ℃ and kept for 4min, the temperature is increased to 150 ℃ at 10 ℃/min and kept for 6min, the temperature of the vaporization chamber is 200 ℃, the temperature of the detector is 250 ℃, and the sample injection amount is 0.1-0.3 mL.
2. GC-MS analysis
The TRACE DSQII type gas chromatograph-mass spectrometer has the MS condition of EI ion source, electron energy of 70eV, temperature of 200 ℃, interface temperature of 230 ℃, scanning range of 10-350 m/z, GC condition of carrier gas He (3.0 Ml/min), pre-column pressure of 30kPa, vaporization chamber temperature of 200 ℃, and temperature programming process the same as the gas chromatograph analysis.
The above is only a specific embodiment of the present application, but the technical features of the present application are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present application to achieve substantially the same technical effects are included in the scope of the present application.
Claims (8)
- A process for preparing VDF according to claims 143a and 142b, comprising the steps of:1) The method comprises the steps of connecting a first storage bottle, a second storage bottle and a nitrogen steel bottle with a cracking device through a pipeline, connecting the cracking device with an absorption tower through a cooling tank, connecting the absorption tower with a dryer through an alkaline washing tank, connecting the dryer with a receiving tank, opening a third valve connected with the nitrogen steel bottle, and checking pipeline pressure and tightness; the cracking device comprises a cracking furnace and a nickel cracking tube, wherein the nickel cracking tube is arranged in the cracking furnace, and a temperature sensor and a heating mechanism are arranged in the cracking furnace; the heating mechanism comprises a chassis, a middle disc and a top disc, wherein the top disc is movably connected with the chassis through the middle disc, a lifting assembly is arranged between the top disc and the chassis, a first cavity is arranged in the chassis, a first positioning ring is arranged on the middle disc and is matched with the first cavity, a second cavity is arranged in the middle disc, a second positioning ring is arranged on the top disc and is matched with the second cavity, and a controller and a power interface are arranged in the chassis;2) Then, the third valve is closed, the first valve and the second valve connected with the first storage bottle and the second storage bottle are opened, the output pressure of the 143a and the 142b is controlled, the fourth valve and the flowmeter are simultaneously opened, the 143a and the 142b are mixed and enter the cracking device, and the mixture of the 143a and the 142b is subjected to heating cracking treatment through the cracking device;3) Opening a fifth valve to enable the cracked product to enter a cooling tank for cooling;4) Opening a sixth valve to enable the cooled product to enter an absorption tower, continuously injecting deionized water into the absorption tower, removing HF in the product to form residual liquid, and enabling the residual liquid to flow out through the bottom of the absorption tower;5) Opening a seventh valve, and enabling the product to enter a caustic wash tank to remove HCl in the mixture;6) And opening an eighth valve to enable the product to enter a collecting box through a dryer for collection, so as to obtain a target product VDF.
- 2. The method of preparing VDF according to claim 1 143a and 142b wherein: the set temperature of the cracking device is 450-600 ℃.
- 3. The method of preparing VDF according to claim 1 143a and 142b wherein: the nickel cracking tube is a planar annular coil or a conical annular coil.
- 4. The method of preparing VDF according to claim 1 143a and 142b wherein: the chassis is provided with a first heating ring, the middle plate is provided with a second heating ring and a first S-shaped heating pipe, the top plate is provided with a third heating ring and a second S-shaped heating pipe, and the first heating ring, the second heating ring, the first S-shaped heating pipe, the third heating ring and the second S-shaped heating pipe are electrically connected with the controller.
- 5. The method of preparing VDF according to claim 1 143a and 142b wherein: the lifting assembly comprises a fixing frame, a sliding frame, an air cylinder and a lifting rod, wherein the fixing frame is arranged in the chassis, a sliding rail is arranged in the chassis, the sliding frame is slidably connected onto the sliding rail, the air cylinder is connected with the sliding frame through a piston rod, and the fixing frame and the sliding frame are connected with the top disc through the lifting rod.
- 6. The method of preparing VDF according to claim 1 143a and 142b wherein: be equipped with first intake pipe, first outlet duct and cooling module on the cooling tank, first intake pipe with first outlet duct is located respectively the top and the bottom of cooling tank, cooling module includes cooling water input port, cooling water delivery outlet, first cooling dish, second cooling dish and third cooling dish, first cooling dish is fixed in through the support in the cooling tank, first cooling dish intercommunication cooling water input port, the second cooling dish is in through first cooling tube connection the top of first cooling dish, the third cooling dish is in through second cooling tube connection the top of second cooling dish, the third cooling dish is through first outlet pipe intercommunication cooling water delivery outlet, the second cooling dish is through second outlet pipe connection first outlet pipe.
- 7. The method of preparing VDF according to claim 6 at 143a and 142b wherein: the second cooling disc is internally provided with a diversion groove, a water inlet and a water outlet, the water inlet is communicated with the water outlet through the diversion groove, a first electromagnetic valve is arranged on the water outlet, the diversion groove is communicated with the second water outlet pipe through a first diversion pipe, and a second electromagnetic valve is arranged on the first diversion pipe.
- 8. The method of preparing VDF according to claim 1 143a and 142b wherein: be equipped with second intake pipe, second outlet duct, deionized water input port and raffinate discharge port on the absorption tower, the second intake pipe is located on the side of absorption tower, the second outlet duct is located the top of absorption tower, the raffinate discharge port is located the bottom of absorption tower, deionized water input port passes through deionized water honeycomb duct and connects first spray dish, first spray dish is fixed in the absorption tower, first spray dish passes through the linking union coupling second spray dish, the second spray dish is fixed in the absorption tower.
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