CN114478183A - 143a and 142b processes for preparing VDF - Google Patents
143a and 142b processes for preparing VDF Download PDFInfo
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- CN114478183A CN114478183A CN202210155009.4A CN202210155009A CN114478183A CN 114478183 A CN114478183 A CN 114478183A CN 202210155009 A CN202210155009 A CN 202210155009A CN 114478183 A CN114478183 A CN 114478183A
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a method for preparing VDF by 143a and 142b, which comprises the following steps: 1) checking the pressure and the air tightness of the pipeline; 2) performing thermal cracking treatment on the mixture of 143a and 142b 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 a residual liquid, and the residual liquid flows out from the bottom of the absorption tower; 5) the product enters an alkaline washing box to remove HCl in the mixture; 6) and (4) opening the product, and enabling the product to enter a collection box through a dryer for collection to obtain a target product VDF. The invention can control the output quantities of 143a and 142b according to the design requirements, reduce the carbon deposition 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 by-products in VDF.
Description
Technical Field
The present invention relates to methods 143a and 142b for preparing VDF.
Background
Vinylidene fluoride (VDF) is an important chemical monomer for producing fluorine-containing polymers, VDF can synthesize polyvinylidene fluoride (PVDF) by homopolymerization or copolymerization with other fluorine-containing vinyl, and can prepare Fluororubber (FKM) by binary copolymerization with hexafluoropropylene or ternary copolymerization with hexafluoropropylene and tetrafluoroethylene.
At present, a great deal of research is carried out on the preparation process of the vinylidene fluoride monomer, the vinylidene fluoride monomer is prepared by adopting different processes according to different raw materials, and the vinylidene fluoride monomer is prepared by cracking reaction in an empty tube at 700-1000 ℃ by using chlorodifluoroethane (142b) as the raw material commonly used in industry.
The aesthetic patent US 3996301 utilizes the cracking of tetrafluorocyclobutane to prepare VDF, the tetrafluorocyclobutane reacts in a cracking tube at 500-900 ℃, inert gases such as helium, nitrogen and carbon tetrafluoride can be introduced, the operation is facilitated at low pressure, and the retention time is 1 s-10 min. The main by-products 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 ℃, the high pressure is favorable for dimerization reaction, so the pressure in the dimerization 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 stays for a longer time at low temperature, and the residence time is 1-200 h. The purity of VDF prepared by the method is high, generally can reach more than 95% without rectification treatment, but the VDF has the problems of more byproducts, low selectivity, high energy consumption, easy carbon deposition in a cracking tube, difficult cleaning and the like.
Disclosure of Invention
The invention aims to provide the technical scheme of the method for preparing VDF from 143a and 142b aiming at the defects in the prior art, not only can control the output quantity of 143a and 142b according to design requirements and reduce the purposes of carbon deposition and coking in a cracking device, but also can not influence the selectivity of VDF, is beneficial to removing HF and HCl in reactants, inhibits side reaction and effectively reduces byproducts in VDF.
In order to solve the technical problems, the invention adopts the following technical scheme:
143a and 142b, characterized in that it comprises the following steps:
1) firstly, connecting a first storage bottle, a second storage bottle and a nitrogen steel bottle with a cracking device through pipelines, connecting the cracking device with an absorption tower through a cooling tank, connecting the absorption tower with a dryer through an alkaline washing box, connecting the dryer with a collecting box, opening a third valve connected with the nitrogen steel bottle, and checking the pressure and the air tightness of a pipeline;
2) then, the third valve is closed, the first valve and the second valve which are connected with the first storage bottle and the second storage bottle are opened, the output pressure of 143a and 142b is controlled, the fourth valve and the flowmeter are opened at the same time, the 143a and 142b enter a cracking device while being mixed, and the mixture of 143a and 142b is heated and cracked by 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 a residual liquid, and enabling the residual liquid to flow out from the bottom of the absorption tower;
5) opening a seventh valve, and enabling the product to enter an alkaline washing tank to remove HCl in the mixture;
6) and opening an eighth valve to enable the product to enter a collection box through a dryer for collection, so as to obtain a target product VDF.
The VDF prepared by the process steps can control the output quantities of 143a and 142b according to design requirements, reduce the purposes of carbon deposition and coking in a cracking device, does 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.
Furthermore, the set temperature of the cracking device is 450-600 ℃.
Further, the cracker includes pyrolysis furnace and nickel pyrolysis tube, and in the pyrolysis furnace was located to nickel pyrolysis tube, be equipped with temperature sensor and heating mechanism in the pyrolysis furnace, the design of nickel pyrolysis tube can have certain inhibitory action to taking off HCl side reaction, and heating mechanism can heat the pyrolysis furnace, makes the pyrolysis furnace take off HF and take off the HCl reaction under high temperature, and temperature sensor can the temperature in the real-time supervision pyrolysis furnace, improves the control accuracy to the temperature.
Further, the nickel cracking tube is a planar annular coil or a conical annular coil.
Further, the heating mechanism comprises a base plate, a middle plate and a top plate, the top plate is movably connected with the base plate through the middle plate, a lifting assembly is arranged between the top plate and the base plate, a first cavity is arranged in the base plate, a first positioning ring is arranged on the middle plate and matched with the first cavity, a second cavity is arranged in the middle plate, a second positioning ring is arranged on the top plate and matched with the second cavity, a controller and a power supply interface are arranged in the base plate, can drive the overhead pan and the interveterbral dish through lifting unit reciprocates, satisfy and heat nickel pyrolysis tube, improve heating efficiency, first holding ring and second holding ring can guarantee that interveterbral dish and overhead pan move along first cavity and second cavity stability respectively, have improved whole heating mechanism's stability, and the controller is preferred to be the PLC controller, can control heating mechanism, and 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 disk, be equipped with third heating ring and second S-shaped heating pipe on the top dish, first heating ring, the 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 be followed vertical direction and heated nickel pyrolysis tube, first S-shaped heating pipe and second S-shaped heating pipe can be followed the horizontal direction and heated nickel pyrolysis tube, improve the heating efficiency to nickel pyrolysis tube, further improve pyrolysis efficiency.
Further, lifting unit includes the mount, the carriage, cylinder and lifter, and in the chassis was located to the mount, be equipped with the slide rail in the chassis, carriage sliding connection was on the slide rail, and the cylinder passes through the piston rod and connects the carriage, and mount and carriage all connect the overhead gage through the lifter, and the mount can play the effect that the location supported to the lifter, drives carriage horizontal migration through the piston rod through the cylinder, can realize that the lifter carries out jacking or descends to the overhead gage, adjusts the high position of overhead gage and interveterbral disc.
Furthermore, a first air inlet pipe, a first air outlet pipe and a cooling assembly are arranged on the cooling tank, the first air inlet pipe and the first air outlet pipe are respectively arranged at the top and the bottom of the cooling tank, the cooling assembly comprises a cooling water inlet, a cooling water outlet, a first cooling disc, a second cooling disc and a third cooling disc, the first cooling disc is fixed in the cooling tank through a support, the first cooling disc is communicated with the cooling water inlet, the second cooling disc is connected above the first cooling disc through a first cooling pipe, the third cooling disc is connected above the second cooling disc through a second cooling pipe, the third cooling disc is communicated with the cooling water outlet through a first water outlet pipe, the second cooling disc is connected with a first water outlet pipe through a second water outlet pipe, 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, the cooling water flows into first cooling plate through the cooling water input port, and flow to the third cooling plate through first cooling tube and second cooling pipe, export by the cooling water delivery outlet through first outlet pipe, realize the rapid cooling to the mist, when needs slow down the cooling rate to the mist, the cooling water flows into first cooling plate through the cooling water input port, and flow to the second cooling plate through first cooling tube, export through the cooling water delivery outlet through the second outlet pipe, it is nimble convenient to control.
Further, be equipped with the splitter box in the second cooling pan, water inlet and delivery port, the water inlet passes through the splitter box and communicates the 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 the cooling water through delivery port input second cooling tube or from 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.
Furthermore, a second air inlet pipe, a second air outlet pipe, a deionized water inlet port and a residual liquid outlet port are arranged on the absorption tower, the second air inlet pipe is arranged on the side surface of the absorption tower, the second air outlet pipe is arranged at the top of the absorption tower, the residual liquid outlet port is arranged at the bottom of the absorption tower, the deionized water inlet port is connected with a first spray disc through a deionized water guide pipe, the first spray disc is fixed in the absorption tower, the first spray disc is connected with a second spray disc through an adapter pipe, the second spray disc is fixed in the absorption tower, the cooled mixed gas is input into the absorption tower through the second air inlet pipe, meanwhile, the deionized water is continuously introduced into the deionized water inlet port, the mixed gas is sprayed through the first spray disc and the second spray disc to remove HF gas in the mixed gas, a pressurization cavity is arranged in the first spray disc and is communicated with the deionized water guide pipe, and spray holes are arranged at the bottom of the first spray disc, the spraying holes are communicated with the pressurizing cavity through a second shunt pipe, and the second spraying plate is of a structure similar to the first spraying plate and is not provided with a connecting pipe.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. the VDF prepared by the process steps can control the output quantities of 143a and 142b according to design requirements, reduce the purposes of carbon deposition and coking in a cracking device, does 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.
2. The design of nickel pyrolysis tube can have certain inhibitory action to taking off HCl side reaction, and heating mechanism can heat the pyrolysis furnace, makes the pyrolysis furnace take off HF and take off the HCl reaction under high temperature, and temperature sensor can real-time supervision temperature in the pyrolysis furnace, improves the control accuracy to the temperature.
3. Can drive the overhead pan and the interverterbral dish through lifting unit and reciprocate, satisfy and heat nickel pyrolysis tube, improve heating efficiency, first holding ring and second holding ring can guarantee that interverterbral dish and overhead pan move along first cavity and second cavity stability respectively, have improved whole heating mechanism's stability.
4. First intake pipe is used for inputing the mist in the cooling tank, the mist after the cooling passes through the output of second outlet duct, when needs are with higher speed to the cooling rate of mist, the cooling water flows into first cooling tray through the cooling water input port, and flow to the third cooling tray through first cooling tube and second cooling tube, export by the cooling water delivery outlet through first outlet pipe, the realization is to the rapid cooling of mist, when needs slow down the cooling rate to mist, the cooling water flows into first cooling tray through the cooling water input port, and flow to the second cooling tray through first cooling tube, export through the cooling water delivery outlet through the second outlet pipe, it is nimble convenient to control.
Drawings
The invention will be further described with reference to the accompanying drawings in which:
FIG. 1 is a process flow diagram of a process for preparing VDF according to 143a and 142b of the present invention;
FIG. 2 is a schematic view showing the connection between a nickel pyrolysis tube and a pyrolysis furnace according to example 1 of the present invention;
FIG. 3 is a schematic view showing the connection between a nickel pyrolysis tube and a pyrolysis furnace in example 2 of the present invention;
FIG. 4 is an effect diagram of the heating mechanism of the present invention;
FIG. 5 is a schematic view of the heating mechanism according to the present invention;
FIG. 6 is a schematic view of the structure of a cooling tank according to the present invention;
FIG. 7 is a schematic view of a second cooling plate according to the present invention;
FIG. 8 is a schematic view of the structure of an absorption column in the present invention;
FIG. 9 is a schematic view of the structure of the first shower plate according to the present invention.
In the figure: 1-a first storage bottle; 2-a second storage bottle; 3-a flow meter;
4-a cracking furnace; 401-temperature sensor; 402-a heating mechanism; 403-a chassis; 404-intermediate disk; 405-top disk; 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 positioning ring; 420-a fixing frame; 421-a slide rail; 422-sliding rack; 423-air cylinder; 424-piston rod; 425-a lifter;
5-a nickel cracking tube;
6-cooling the tank; 601-a first intake pipe; 602-a first outlet duct; 603-a cooling water input port; 604-cooling water outlet; 605-a first cooling pan; 606-a second cooling plate; 607-a third cooling plate; 608-a first cooling tube; 609-a second cooling tube; 610-a first water outlet pipe; 611-a second water outlet pipe; 612-a splitter box; 613-water inlet; 614-water outlet; 615-a first shunt tube; 616-a first solenoid valve; 617-second solenoid valve;
7-an absorption column; 701-a second air inlet pipe; 702-a deionized water input port; 703-a raffinate discharge; 704-a second outlet duct; 705-a first spray tray; 706-a second spray tray; 707-a linkage pipe; 708-a deionized water draft tube; 709-a booster cavity; 710-spray holes; 711-a second shunt tube;
8-alkali washing box; 9-a dryer; 10-a collection box; 11-nitrogen cylinder; 12-a first valve; 13-a second valve; 14-a third valve; 15-a fourth valve; 16-a fifth valve; 17-a sixth valve; 18-a seventh valve; 19-eighth valve.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terms first, second and the like in the description and in the claims, and in the drawings, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. Furthermore, the terms "comprising" and "having," as well as any variations thereof, are intended to cover non-exclusive inclusions.
Example 1
As shown in fig. 1, fig. 2, and fig. 4 to fig. 9, the method for preparing VDF according to the present invention 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 pipelines, 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 alkali washing box 8, connecting the dryer 9 with a collecting box 10, opening a third valve 14 connected with the nitrogen steel bottle 11, and checking the pressure and the air tightness of a pipeline;
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 143a and 142b is controlled, the fourth valve 15 and the flow meter 3 are opened at the same time, the 143a and 142b are mixed and enter the cracking device, and the mixture of 143a and 142b is heated and cracked by 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, 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 inhibiting effect on HCl side reaction, the heating mechanism 402 can heat the cracking furnace 4, HF and HCl reaction are removed from the cracking furnace 4 at high temperature, the temperature sensor 401 can monitor the temperature in the cracking furnace 4 in real time, and the control precision of the temperature is improved.
The nickel cracking tube 5 is a planar annular coil.
The heating mechanism 402 comprises a bottom plate 403, an intermediate plate 404 and a top plate 405, the top plate 405 is movably connected with the bottom plate 403 through the intermediate plate 404, a lifting assembly is arranged between the top plate 405 and the bottom plate 403, a first cavity 416 is arranged in the bottom plate 403, a first positioning ring 417 is arranged on the intermediate plate 404, the first positioning ring 417 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, the second positioning ring 419 is matched with the second cavity 418, a controller 414 and a power interface 415 are arranged in the bottom plate 403, the lifting assembly can drive the top plate 405 and the intermediate plate 404 to move up and down, the nickel cracking tube 5 is heated, the 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 stably move along the first cavity 416 and the second cavity 418 respectively, and the stability of the whole heating mechanism 402 is improved, the controller 414 is preferably a PLC controller 414 that controls the heating mechanism 402, and a power interface 415 for connecting to an external power source.
The bottom plate 403 is provided with a first heating ring 406, the middle plate 404 is provided with a second heating ring 407 and a first S-shaped heating pipe 409, the top plate 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 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.
Lifting unit includes mount 420, carriage 422, cylinder 423 and lifter 425, mount 420 is located in chassis 403, be equipped with slide rail 421 in the chassis 403, carriage 422 sliding connection is on slide rail 421, cylinder 423 connects carriage 422 through piston rod 424, mount 420 and carriage 422 all connect top plate 405 through lifter 425, mount 420 can play the effect that the location was supported to lifter 425, drive carriage 422 horizontal migration through cylinder 423 through piston rod 424, can realize lifter 425 and carry out jacking or decline to top plate 405, adjust the high position of top plate 405 and well disc 404.
3) Opening a fifth valve 16 to enable the cracked product to enter a 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 assembly, 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 assembly comprises a cooling water inlet 603, a cooling water outlet 604, a first cooling disc 605, a second cooling disc 606 and a third cooling disc 607, the first cooling disc 605 is fixed in the cooling tank 6 through a bracket, the first cooling disc 605 is communicated with the cooling water inlet 603, the second cooling disc 606 is connected above the first cooling disc 605 through a first cooling pipe 608, the third cooling disc 607 is connected above the second cooling disc 606 through a second cooling pipe 609, the third cooling disc 607 is communicated with the cooling water outlet 604 through a first water outlet pipe 610, the second cooling disc 606 is connected with a first 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, cooling water flows into the first cooling disc 605 through the cooling water input port 603, flows to the third cooling disc 607 through the first cooling pipe 608 and the second cooling pipe 609, is output from the cooling water output port 604 through the first water outlet pipe 610, and is used for rapidly cooling the mixed gas.
A diversion channel 612, a water inlet 613 and a water outlet 614 are arranged in the second cooling disc 606, the water inlet 613 is communicated with the water outlet 614 through the diversion channel 612, a first electromagnetic valve 616 is arranged on the water outlet 614, the diversion channel 612 is communicated with a second water outlet pipe 611 through a first diversion pipe 615, a second electromagnetic valve 617 is arranged on the first diversion pipe 615, cooling water in the first cooling pipe 608 can enter the diversion channel 612 through the water inlet 613, the diversion channel 612 can input the cooling water into the second cooling pipe 609 through the water outlet 614 or divert the cooling water from the first diversion pipe 615 to the second water outlet pipe 611 according to actual process requirements, the first electromagnetic valve 616 is used for controlling the opening and closing of the water outlet 614, and the second electromagnetic valve 617 is used for controlling the opening and closing of the first diversion pipe 615.
4) Opening a sixth valve 17, enabling 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 a residual liquid, and enabling the residual liquid to flow out from the bottom of the absorption tower 7;
a second gas inlet pipe 701, a second gas outlet pipe 704, a deionized water inlet port 702 and a raffinate outlet port 703 are arranged on the absorption tower 7, the second gas inlet pipe 701 is arranged on the side surface of the absorption tower 7, the second gas outlet pipe 704 is arranged on the top of the absorption tower 7, the raffinate outlet port 703 is arranged at the bottom of the absorption tower 7, the deionized water inlet 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 an adapter pipe 707, the second spray disk 706 is fixed in the absorption tower 7, the cooled mixed gas is input into the absorption tower 7 through the second gas inlet pipe 701, meanwhile, the deionized water is continuously introduced into the deionized water inlet port 702, the mixed gas is sprayed through the first spray disk 705 and the second spray disk 706 to remove HF gas in the mixed gas, a pressurizing cavity 709 is arranged in the first spray disk 705, the pressure increasing cavity 709 is communicated with a deionized water flow guide pipe 708, the bottom of the first spray disk 705 is provided with spray holes 710, the spray holes 710 are communicated with the pressure increasing cavity 709 through a second flow dividing pipe 711, and the second spray disk 706 adopts a structure similar to the first spray disk 705 and is not provided with an adapter pipe 707.
5) Opening a seventh valve 18, and enabling the product to enter an alkali washing tank 8 to remove HCl in the mixture; the solution in the caustic wash tank 8 is a sodium hydroxide solution.
6) And opening an eighth valve 19 to enable the product to enter the collecting box 10 through the dryer 9 for collection to obtain a target product VDF, wherein anhydrous calcium chloride is filled in the dryer 9.
The VDF prepared by the process steps can control the output quantities of 143a and 142b according to design requirements, reduce the purposes of carbon deposition and coking in a cracking device, does 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.
Analyzing the obtained VDF product by the method comprising
1. Gas chromatography analysis
The method comprises the steps of adopting an FID detector, enabling a chromatographic column to be of a GS-GSPRO type (60m x 0.32mm), enabling carrier gas to be nitrogen (3.0mL/min), enabling the pressure in front of the chromatographic column to be 30kPa, adopting a temperature program to heat, enabling the initial column temperature to be 50 ℃ and to be kept for 4min, enabling the initial column temperature to be heated to be 150 ℃ at a speed of 10 ℃/min and to be kept for 6min, enabling the temperature of a vaporization chamber to be 200 ℃, enabling the temperature of a detector to be 250 ℃ and enabling the sample injection quantity to be 0.1-0.3 mL.
2. GC-MS analysis
The TRACE DSQ II type gas chromatography-mass spectrometer has the MS condition of an EI ion source, the electron energy of 70eV, the temperature of 200 ℃, the interface temperature of 230 ℃, the scanning range of 10-350 m/z, the GC condition of carrier gas He (3.0Ml/min), the pressure in front of a column of 30kPa, the temperature of a vaporization chamber of 200 ℃ and the temperature programming process which is the same as the gas chromatography analysis.
Example 2
As shown in fig. 1, 3 to 9, the method for preparing VDF for 143a and 142b of the present invention comprises 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 pipelines, 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 alkali washing box 8, connecting the dryer 9 with a collecting box 10, opening a third valve 14 connected with the nitrogen steel bottle 11, and checking the pressure and the air tightness of a pipeline;
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 143a and 142b is controlled, the fourth valve 15 and the flow meter 3 are opened at the same time, the 143a and 142b are mixed and enter the cracking device, and the mixture of 143a and 142b is heated and cracked by 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, 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 inhibiting effect on HCl side reaction, the heating mechanism 402 can heat the cracking furnace 4, HF and HCl reaction are removed from the cracking furnace 4 at high temperature, the temperature sensor 401 can monitor the temperature in the cracking furnace 4 in real time, and the control precision of the temperature is improved.
The nickel cracking tube 5 is a conical annular coil.
The heating mechanism 402 comprises a bottom plate 403, an intermediate plate 404 and a top plate 405, the top plate 405 is movably connected with the bottom plate 403 through the intermediate plate 404, a lifting assembly is arranged between the top plate 405 and the bottom plate 403, a first cavity 416 is arranged in the bottom plate 403, a first positioning ring 417 is arranged on the intermediate plate 404, the first positioning ring 417 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, the second positioning ring 419 is matched with the second cavity 418, a controller 414 and a power interface 415 are arranged in the bottom plate 403, the lifting assembly can drive the top plate 405 and the intermediate plate 404 to move up and down, the nickel cracking tube 5 is heated, the 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 stably move along the first cavity 416 and the second cavity 418 respectively, the stability of the whole heating mechanism 402 is improved, the controller 414 is preferably a PLC controller 414 that controls the heating mechanism 402, and a power interface 415 for connecting to an external power source.
The bottom plate 403 is provided with a first heating ring 406, the middle plate 404 is provided with a second heating ring 407 and a first S-shaped heating pipe 409, the top plate 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 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.
Lifting unit includes mount 420, carriage 422, cylinder 423 and lifter 425, mount 420 is located in chassis 403, be equipped with slide rail 421 in the chassis 403, carriage 422 sliding connection is on slide rail 421, cylinder 423 connects carriage 422 through piston rod 424, mount 420 and carriage 422 all connect top plate 405 through lifter 425, mount 420 can play the effect that the location was supported to lifter 425, drive carriage 422 horizontal migration through cylinder 423 through piston rod 424, can realize lifter 425 and carry out jacking or decline to top plate 405, adjust the high position of top plate 405 and well disc 404.
3) Opening a fifth valve 16 to enable the cracked product to enter a 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 assembly, 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 assembly comprises a cooling water inlet 603, a cooling water outlet 604, a first cooling disc 605, a second cooling disc 606 and a third cooling disc 607, the first cooling disc 605 is fixed in the cooling tank 6 through a bracket, the first cooling disc 605 is communicated with the cooling water inlet 603, the second cooling disc 606 is connected above the first cooling disc 605 through a first cooling pipe 608, the third cooling disc 607 is connected above the second cooling disc 606 through a second cooling pipe 609, the third cooling disc 607 is communicated with the cooling water outlet 604 through a first water outlet pipe 610, the second cooling disc 606 is connected with a first 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, cooling water flows into the first cooling disc 605 through the cooling water input port 603, flows to the third cooling disc 607 through the first cooling pipe 608 and the second cooling pipe 609, is output from the cooling water output port 604 through the first water outlet pipe 610, and is used for rapidly cooling the mixed gas.
A diversion channel 612, a water inlet 613 and a water outlet 614 are arranged in the second cooling disc 606, the water inlet 613 is communicated with the water outlet 614 through the diversion channel 612, a first electromagnetic valve 616 is arranged on the water outlet 614, the diversion channel 612 is communicated with a second water outlet pipe 611 through a first diversion pipe 615, a second electromagnetic valve 617 is arranged on the first diversion pipe 615, cooling water in the first cooling pipe 608 can enter the diversion channel 612 through the water inlet 613, the diversion channel 612 can input the cooling water into the second cooling pipe 609 through the water outlet 614 or divert the cooling water from the first diversion pipe 615 to the second water outlet pipe 611 according to actual process requirements, the first electromagnetic valve 616 is used for controlling the opening and closing of the water outlet 614, and the second electromagnetic valve 617 is used for controlling the opening and closing of the first diversion pipe 615.
4) Opening a sixth valve 17, enabling 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 a residual liquid, and enabling the residual liquid to flow out from the bottom of the absorption tower 7;
a second gas inlet pipe 701, a second gas outlet pipe 704, a deionized water inlet port 702 and a raffinate outlet port 703 are arranged on the absorption tower 7, the second gas inlet pipe 701 is arranged on the side surface of the absorption tower 7, the second gas outlet pipe 704 is arranged on the top of the absorption tower 7, the raffinate outlet port 703 is arranged at the bottom of the absorption tower 7, the deionized water inlet 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 an adapter pipe 707, the second spray disk 706 is fixed in the absorption tower 7, the cooled mixed gas is input into the absorption tower 7 through the second gas inlet pipe 701, meanwhile, the deionized water is continuously introduced into the deionized water inlet port 702, the mixed gas is sprayed through the first spray disk 705 and the second spray disk 706 to remove HF gas in the mixed gas, a pressurizing cavity 709 is arranged in the first spray disk 705, the pressure increasing cavity 709 is communicated with a deionized water flow guide pipe 708, the bottom of the first spray disk 705 is provided with spray holes 710, the spray holes 710 are communicated with the pressure increasing cavity 709 through a second flow dividing pipe 711, and the second spray disk 706 adopts a structure similar to the first spray disk 705 and is not provided with an adapter pipe 707.
5) Opening a seventh valve 18, and enabling the product to enter an alkali washing tank 8 to remove HCl in the mixture; the solution in the caustic wash tank 8 is a sodium hydroxide solution.
6) And opening an eighth valve 19 to enable the product to enter the collecting box 10 through the dryer 9 for collection to obtain a target product VDF, wherein anhydrous calcium chloride is filled in the dryer 9.
The VDF prepared by the process steps can control the output quantities of the 143a and the 142b according to design requirements, reduce the purposes of carbon deposition and coking in the cracking device, does 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.
Analyzing the obtained VDF product by the method comprising
1. Gas chromatography analysis
A FID detector is adopted, a chromatographic column is of a GS-GSPRO type (60m x 0.32mm), carrier gas is nitrogen (3.0mL/min), the pressure in front of the column is 30kPa, the temperature is programmed, the initial column temperature is 50 ℃ and is kept for 4min, the temperature is increased to 150 ℃ at the speed of 10 ℃/min and is kept for 6min, the temperature of a vaporization chamber is 200 ℃, the temperature of a detector is 250 ℃, and the sample injection amount is 0.1-0.3 mL.
2. GC-MS analysis
The TRACE DSQ II type gas chromatography-mass spectrometer has the MS condition of an EI ion source, the electron energy of 70eV, the temperature of 200 ℃, the interface temperature of 230 ℃, the scanning range of 10-350 m/z, the GC condition of carrier gas He (3.0Ml/min), the pressure in front of a column of 30kPa, the temperature of a vaporization chamber of 200 ℃ and the temperature programming process which is the same as the gas chromatography analysis.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (10)
1.143a and 142b a process for the preparation of VDF, characterized in that it comprises the following steps:
1) firstly, connecting a first storage bottle, a second storage bottle and a nitrogen steel bottle with a cracking device through pipelines, connecting the cracking device with an absorption tower through a cooling tank, connecting the absorption tower with a dryer through an alkaline washing box, connecting the dryer with a collecting box, opening a third valve connected with the nitrogen steel bottle, and checking the pressure and the air tightness of a pipeline;
2) then, the third valve is closed, the first valve and the second valve which are connected with the first storage bottle and the second storage bottle are opened, the output pressure of 143a and 142b is controlled, the fourth valve and the flowmeter are opened at the same time, the 143a and 142b enter a cracking device while being mixed, and the mixture of 143a and 142b is heated and cracked by 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 a residual liquid, and enabling the residual liquid to flow out from the bottom of the absorption tower;
5) opening a seventh valve, and enabling the product to enter an alkaline washing tank to remove HCl in the mixture;
6) and opening an eighth valve to enable the product to enter a collection box through a dryer for collection, so as to obtain a target product VDF.
2. The process of 143a and 142b for preparing VDF according to claim 1, wherein: the set temperature of the cracking device is 450-600 ℃.
3. The process of 143a and 142b for preparing VDF according to claim 1, wherein: 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.
4. The process of claim 3, 143a and 142b for preparing VDF, wherein: the nickel cracking tube is a planar annular coil or a conical annular coil.
5. The process of claim 3, 143a and 142b for preparing VDF, wherein: the heating mechanism comprises a base plate, an intermediate plate and a top plate, the top plate is movably connected with the base plate through the intermediate plate, a lifting assembly is arranged between the top plate and the base plate, a first cavity is arranged in the base plate, a first positioning ring is arranged on the intermediate plate and matched with the first cavity, a second cavity is arranged in the intermediate plate, a second positioning ring is arranged on the top plate, and the second positioning ring is arranged on the second positioning ring
The positioning ring is matched with the second cavity, and a controller and a power supply interface are arranged in the chassis.
6. The process of claim 5, 143a and 142b for preparing VDF, wherein: the base plate 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.
7. The process of claim 5, 143a and 142b for preparing VDF, wherein: the lifting assembly comprises a fixing frame, a sliding frame, a cylinder and a lifting rod, the fixing frame is arranged in the chassis, a sliding rail is arranged in the chassis, the sliding frame is connected to the sliding rail in a sliding mode, the cylinder is connected with the sliding frame through a piston rod, and the fixing frame and the sliding frame are connected through the lifting rod to the top plate.
8. The process of 143a and 142b for preparing VDF according to claim 1, 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 pan, second cooling pan and third cooling pan, first cooling pan is fixed in through the support in the cooling tank, first cooling pan intercommunication the cooling water input port, the second cooling pan is in through first cooling union coupling the top of first cooling pan, the third cooling pan is in through the second cooling union coupling the top of second cooling pan, the third cooling pan is through first outlet pipe intercommunication the cooling water delivery outlet, the second cooling pan is through the second outlet pipe connection first outlet pipe.
9. The process according to claim 8 for preparing VDF by 143a and 142b, wherein: be equipped with splitter box, water inlet and delivery port in the second cooling pan, the water inlet passes through the splitter box intercommunication the delivery port, be equipped with first solenoid valve on the delivery port, the splitter box passes through first shunt tubes intercommunication the second outlet pipe, be equipped with the second solenoid valve on the first shunt tubes.
10. The process of 143a and 142b for preparing VDF according to claim 1, 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, the deionized water input port passes through the first shower dish of deionized water honeycomb duct connection, first shower dish is fixed in the absorption tower, first shower dish is through linking pipe connection second shower dish, the second shower dish is fixed in the absorption tower.
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