CN109761812A - Triphosgene prepares reaction unit and preparation process - Google Patents
Triphosgene prepares reaction unit and preparation process Download PDFInfo
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- CN109761812A CN109761812A CN201910148986.XA CN201910148986A CN109761812A CN 109761812 A CN109761812 A CN 109761812A CN 201910148986 A CN201910148986 A CN 201910148986A CN 109761812 A CN109761812 A CN 109761812A
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- gas
- reactor tank
- booster pump
- tank
- triphosgene
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 83
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004148 unit process Methods 0.000 title description 4
- 239000007789 gas Substances 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000112 cooling gas Substances 0.000 claims abstract description 9
- 230000002411 adverse Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 54
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 45
- 239000000460 chlorine Substances 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 30
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 27
- 230000001172 regenerating effect Effects 0.000 claims description 25
- 238000004064 recycling Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000007664 blowing Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 27
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 27
- 239000002245 particle Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 230000036632 reaction speed Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000019771 cognition Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application discloses triphosgenes to prepare reaction unit and triphosgene preparation process, it includes reactor tank that triphosgene, which prepares reaction unit, ultraviolet emission device is set in the reactor tank, it further include blower, water cucurbitula and booster pump, the air inlet of the blower is communicated with reactor tank, cooling gas check valve is provided between the blower and reactor tank, the cooling gas check valve for prevent gas from blower into reactor tank adverse current, the gas outlet of blower connects with the air inlet of water cucurbitula, the gas outlet of water cucurbitula connects with booster pump, the booster pump is further reacted for being pumped into reactor tank after gas boosting with reaction solution, and heat exchanger is provided between booster pump and reactor tank, the heat exchanger is used for the gas heating being pumped into reactor tank.
Description
Technical field
The present invention relates to field of chemical equipment more particularly to a kind of triphosgene to prepare reaction unit and preparation process.
Background technique
Two (trichloromethyl) carbonic esters (being commonly called as triphosgene) have important application in Chemical Manufacture, prepare three light at present
The method of gas is first to put into reaction kettle after measuring dimethyl carbonate, then be passed through chlorine, under ultraviolet irradiation condition, realizes chlorine
With reacting for dimethyl carbonate, two (trichloromethyl) carbonic esters are obtained, 60~80 DEG C of reaction temperature, the reaction time is about 7 hours,
There is a large amount of reactor off-gas (ingredient of exhaust gas is two kinds of ingredients of hydrogen chloride and chlorine) generation during the reaction.Industry at present
It is discarded to be first passed through in clean water that (hydrogen chloride in tail gas is substantially by water whole for this to this discarded processing method in production
Absorb, chlorine only has minute quantity to be only absorbed by the water), chlorine remaining in tail gas is passed through in lye again after clean water absorbs and is inhaled
It receives.
Although realizing the zero-emission of exhaust gas in above-mentioned production process, the chlorine in exhaust gas is reaction raw materials, directly
It is excessively wasted raw material with lye to absorb.
Summary of the invention
The present invention prepares reaction unit and preparation process in view of the above-mentioned problems, proposing a kind of triphosgene.
The technical solution adopted by the present invention is as follows:
A kind of triphosgene prepares reaction unit, including reactor tank, and ultraviolet emission device is arranged in the reactor tank, also wraps
Blower, water cucurbitula and booster pump are included, the air inlet of the blower is communicated with reactor tank, is provided between the blower and reactor tank
Cooling gas check valve, the cooling gas check valve for preventing gas from blower, inhale by the adverse current into reactor tank, the gas outlet of blower and water
The air inlet of tank connects, and the gas outlet of water cucurbitula connects with booster pump, and the booster pump is for will be pumped into reaction after gas boosting
It is further reacted in tank with reaction solution, and is provided with heat exchanger between booster pump and reactor tank, the heat exchanger is for being pumped into
Gas heating in reactor tank.
It should be noted that is put in water cucurbitula is saturated sodium chloride solution, saturated sodium chloride solution has hydrogen chloride gas
There is good absorption, but to chlorine almost without assimilation effect, so saturated sodium chloride solution is arranged herein, in this dress
It sets reaction in middle reactor tank and constantly generates chlorine and hydrogen chloride gas, these mixed gas are by blower extraction tank, gaseous mixture
Body is first via water cucurbitula absorbing hydrogen chloride gas, and then remaining chlorine enters heat exchanger, heat exchanger via booster pump pressurization
Reactor tank is entered back into after the temperature of chlorine is increased further to react with liquid.
The hydrogen chloride generated in reaction process and chlorine can be separately recovered to utilization, chlorine after the recovery is made in the present apparatus
It is further reacted for reaction raw materials, more saving raw material.
Optionally, further include escape pipe, gas-liquid two-phase check valve is provided on the escape pipe, the gas-liquid two-phase is unidirectional
Valve is for preventing liquid by reaction kettle adverse current disengaging tracheae.
Gas-liquid two-phase check valve belongs to existing mature technology, and the effect of specific gas-liquid two-phase check valve is as follows, works as outlet
When air pressure in pipe is lower than rated value, gas-liquid two-phase check valve is in close state, and the gas in escape pipe cannot be introduced into reaction
In tank, when the air pressure in escape pipe reaches at or above rated value, gas-liquid two-phase check valve moment is opened, the gas in escape pipe
It gushs into reactor tank and reaction solution intense contact, because reaction solution is violent compared with chlorine contacts, chlorine can be accelerated in this way
With the reaction speed of reaction solution.The purpose that booster pump is arranged here is just to be able to the gas being gradually slowly increased in reactor tank
Body pressure, while usual heat exchanger need to be better than as the pressure-resistant performance of matching used heat exchanger, because of heat exchanger producer now
It specifically can further be stated according to using the pressure-resistant use demand of client specifically customized so heat exchanging device is not done.
It should be noted that gas-liquid two-phase check valve can be not only used for the one-way conduction between gas-liquid two-phase, can also use
One-way conduction between gas gas two-phase and between liquid-liquid diphase.
Optionally, the reactor tank is the reactor tank of non-ferric material, and the escape pipe is the escape pipe of non-ferric material, and is gone out
It intratracheally is provided with magnet piston, non-ferric material support rod is provided in the reactor tank, is rotatably equipped on the support rod
The rotor plate of non-ferric material is provided with iron shot in the rotor plate；When the magnet piston moves in escape pipe, described turn
Movable plate can be rotated around support rod.
In order to guarantee that magnet piston will not coat some corrosion resistant coatings in the outer surface of magnet piston by chlorine corrosion.
Specific set-up mode of the magnet piston in reactor tank is as follows, because reactor tank is all vertically arranged, escape pipe setting
In the tank bottom of reactor tank, and escape pipe, perpendicular to the tank bottom of reactor tank, the side wall of escape pipe, magnetic is arranged in gas-liquid two-phase check valve
Iron piston movable sealing is set in escape pipe, and when booster pump does not start to inflate into escape pipe, magnet piston is located at escape pipe
Bottom, when booster pump is started to work, at leisure from the bottom of escape pipe to top movements, magnet piston will go out magnet piston
Endotracheal space is divided into air cavity and lower air chamber two spaces (particularly the volume of air cavity and lower air chamber is variable), on
Air cavity volume gradually becomes smaller, and lower air chamber volume becomes larger, and the position of gas-liquid two-phase check valve becomes lower gas by being located at upper air cavity
Chamber, when air pressure reaches the rated value of gas-liquid two-phase check valve in lower air chamber, most of gas moment in lower air chamber gush into
Entering in reaction solution (while gas-liquid two-phase check valve), also moment closes, and magnet piston is made in the pressure of upper air cavity and spontaneous gravity
Under, from the upper end of escape pipe at moved to bottom.
The installation site relationship of rotor plate and support rod is somewhat similarly to seesaw, and rotor plate rotates a little around support rod
It is rotated similar to seesaw around supporting point, because one end of rotor plate is provided with iron ball, and magnet piston always has iron ball
There is sucking action, is constantly transported as seesaw so magnet piston will drive rotor plate during moving in escape pipe
It is dynamic, and rotor plate can constantly stir the liquid in reactor tank during the motion, and liquid can be accelerated instead during the motion
Speed is answered, reaction efficiency is higher, while rotor plate rotation can promote the gas (mixture of chlorine and hydrogen chloride) of liquid to accelerate
Evolution, but hydrogen chloride gas cognition be recovered after send back in reaction solution again because hydrogen chloride actually react after a kind of production
Object can accelerate the conversion ratio of reaction speed and raw material after hydrogen chloride removes according to Le Xiate column balancing shifting principle.
So reaction speed can be greatly improved by the setting of setting magnet piston and rotor plate, turning for raw material is improved
Rate.
Optionally, the support rod is T-shaped support rod, and rotor plate is set in support by the change rotation of itself
Bar, and support rod is the support rod of inner hollow.
Because needing to carry out crystallisation by cooling after reaction, so selecting the support rod of inner hollow, reaction in this way terminates
After can fill water at low temperature into support rod and cool down, so can specifically be arranged in reactor tank in some conduits and support rod
The space in portion is connected, and fills water at low temperature cooling into support rod by conduit.Of course for guarantee crystallisation by cooling effect and
Some condenser pipes can be separately provided in speed in reactor tank.
It optionally, further include recycling can, the recycling can is set between blower and water cucurbitula, and is provided in recycling can
Several adsorption stuffings, the temperature of the adsorption stuffing are 4 DEG C~10 DEG C.
Because entire reaction be 60~80 DEG C at a temperature of carry out, and the boiling point of dimethyl carbonate is 90.1 DEG C, this
Two temperature spots are very close, so necessarily there is part dimethyl carbonate can be with the evolution of steam, so set during the reaction
Closed cans is put back into recycle this part dimethyl carbonate gas, adsorption stuffing is really block, since the temperature of block is very low
(4 DEG C~10 DEG C) after dimethyl carbonate encounters these low temperature blocks, can be adsorbed in fluid form on these blocks.
The prior art since adsorption stuffing being arranged in recycling can, this programme does not do specific statement in detail, while this programme according to
The actual conditions of the present apparatus, provide the implementation of a kind of recycling can and adsorption stuffing, and recycling can is with air inlet and outlet
The corrosion-resistant tank of mouth, adsorption stuffing are common vials, and water (and water temperature is 4 DEG C~10 DEG C) has been filled in sealing in vial,
Vial has filled up corrosion-resistant tank.The liquid carbonic acid dimethyl ester accumulated on the outer wall of vial can be recycled further, thus
Realize the recycling to dimethyl carbonate raw material.
The temperature of present apparatus control adsorption stuffing is because dimethyl carbonate can be with solid lower than 4 DEG C in temperature not less than 4 DEG C
The form of body particle is precipitated, and solid particle may block recycling can.
It optionally, further include triple valve, the triple valve is set between water cucurbitula and booster pump, and two of triple valve
Interface connects with water cucurbitula and booster pump respectively, and regenerating tank, setting in the regenerating tank are connected on another interface of triple valve
There is carbon tetrachloride liquid.
Because the whole process of preparation triphosgene is segmented into reaction, crystallisation by cooling, vacuumize depickling gas and vacuum is dry
It dry four, after the completion of reacting with crystallisation by cooling this two, needs to carrying out vacuumizing depickling gas in reactor tank, and is extracted gas
Body is actually three parts (hydrogen chloride, chlorine and dimethyl carbonate), and dimethyl carbonate can be recovered tank absorption, and hydrogen chloride is by water
Cucurbitula absorbs, and chlorine can be reproduced the absorption of the carbon tetrachloride in tank.Specifically during vacuumizing depickling gas triple valve with
It closes and is not turned between booster pump, and heat exchanger and booster pump are all idle.
Optionally, further include injector mixer and air accumulator, the air inlet of the booster pump respectively with triple valve and mix
Injector connects, and two interfaces of residue of injector mixer connect with air accumulator and regenerating tank respectively, and the injector mixer is used
In by air accumulator gas and regenerating tank in be delivered to booster pump after the gas mixing that is discharged；And injector mixer and gas storage
Control valve is provided between tank and between injector mixer and regenerating tank.
It is solid particle (surface can remain a small amount of drop) entirely substantially after completing crystallisation by cooling, in reactor tank,
Air accumulator in the present apparatus it is built-in be nitrogen (or other similar inert gases), the workflow of above-mentioned design is as follows, gas storage
Nitrogen in tank enters back into after entering heat exchanger heating (nitrogen temperature after heating is between 30 DEG C~35 DEG C) via booster pump
Then escape pipe pushes magnet piston motion in escape pipe, and magnet piston still drives rotor plate movement, and rotor plate is moving
During can disturb solid particle in reactor tank, and the high temperature nitrogen (30 DEG C~35 DEG C) that moment gushs away can be blown
The liquid on dried solid particle surface is momented on one side stir solid particle while in this way with high temperature nitrogen air-blowing, can rapidly be dried up
The liquid of solid particles surface.Simultaneously because this process blower still gas in abstraction reaction tank, the gas that blower extracts
Body includes nitrogen, hydrogen chloride, chlorine and minimal amount of dimethyl carbonate, and hydrogen chloride, chlorine and dimethyl carbonate all can
It is absorbed, and the effect from the nitrogen of regenerating tank Nei Laikai through injector mixer, then enter after being mixed with fresh nitrogen next
Circulation continues operation.The above process is also the vacuum drying to solid particle (i.e. product), but this process of vacuum drying and is passed
There are certain differences for " vacuum drying " of system.
It specifically closes and is not turned between triple valve and booster pump during nitrogen blowing.
It optionally, further include cold blowing pipe, the gas outlet of the booster pump connects with cold blowing pipe and heat exchanger respectively, described cold
Blowpipe both ends connect with booster pump and reactor tank respectively, and control valve, the booster pump and heat exchanger are provided on the cold blowing pipe
Between be provided with control valve.
Most of liquid on solid particle (i.e. product) surface can be dried up with the nitrogen of heat, while can also make solid particle
It is maintained at higher temperature, higher temperature can be unfavorable for the carrying and packaging of product, so product must be carried out at cooling
Reason opens cold blowing pipe so closing between injector mixer and air accumulator and the control valve between injector mixer and regenerating tank
On control valve, keep closing between triple valve and booster pump and be not turned on, then (temperature is 10 DEG C~15 with cold nitrogen
DEG C) blown against solid particle, the temperature of solid particles surface is first reduced, the liquid on grains surface is second thoroughly dried up.
It should be noted simultaneously that blower still needs to open during this, the gas released in reactor tank is needed successively to pass through
The absorption of recycling can, water cucurbitula and regenerating tank, the gas come out out of regenerating tank can direct emission because discharging
It is substantially nitrogen, environmental sound, but for the considerations of economizing on resources, a receipts nitrogen pipe can be connect in regenerating tank again
(receive is also to be equipped with control valve on nitrogen pipe), is delivered to other recycling equipments for nitrogen using nitrogen pipe is received.
Blower in the specific present apparatus is and the tank bottom of cold blowing pipe and reactor tank by connecting at the top of pipeline and reactor tank
Place connects.
Based on above-mentioned apparatus, a kind of triphosgene preparation process based on above equipment is further provided in this programme, including
Following steps:
S1: chlorine is passed through in dimethyl carbonate, and maintaining the temperature of entire reaction system is 60~80 DEG C of reaction temperature, so
Reaction solution is constantly stirred afterwards, and constantly supplements chlorine into reaction solution to while being evacuated to reactor tank, maintains this shape
It state 7 hours, is irradiated with ultraviolet light always in whole process；
S2: crystallisation by cooling vacuumizes reactor tank after the completion of crystallization；
S3: first being blown with 30 DEG C~35 DEG C of nitrogen against crystalline solid after vacuumizing, then with 10 DEG C~15 DEG C of nitrogen
Gas is blown against crystalline solid.
There are following beneficial aspects using this technique preparation triphosgene: can be in time by one of reaction product reactant
It moves away, to improve reaction rate, while greatly improving the conversion ratio of raw material, while product purity obtained is higher.
The beneficial effects of the present invention are: utilization can be separately recovered in the hydrogen chloride generated in reaction process and chlorine, return
Chlorine after receipts is further reacted as reaction raw materials, more saving raw material；And product preparation rate is faster, feed stock conversion
It is high.
Detailed description of the invention:
Fig. 1 is reactor tank internal structure simplified schematic diagram；
Fig. 2 is the matching relationship schematic diagram of rotor plate and support rod；
Fig. 3 is that triphosgene prepares each modular construction simplified schematic diagram of reaction unit；
Fig. 4 is the structure schematic diagram of easy reaction kettle.
Each appended drawing reference in figure are as follows:
1, reactor tank, 101, support rod, 102, rotor plate, 103, iron ball, 104, magnet piston, 105, lower air chamber, 106,
Gas-liquid two-phase check valve, 107, upper air cavity, 108, change, 109, condenser pipe, 1010, ultraviolet emission device, 1011, tail gas goes out
Mouthful, 1012, chlorine inlet, 1013, discharge port, 2, blower, 3, recycling can, 4, water cucurbitula, 5, regenerating tank, 6, air accumulator, 7, control
Valve processed, 8, injector mixer, 9, triple valve, 10, booster pump, 11, preheater, 12, cold blowing pipe, 13, receipts nitrogen pipe, 14, gas list
To valve.
Specific embodiment:
Below with reference to each attached drawing, the present invention will be described in detail.
As shown in attached drawing 1, attached drawing 2 and attached drawing 3, a kind of triphosgene prepares reaction unit, including reactor tank 1, in reactor tank 1
Ultraviolet emission device is set, further includes blower 2, water cucurbitula 4 and booster pump 10, the air inlet of blower 2 is communicated with reactor tank 1,
It is provided with cooling gas check valve 14 between blower 2 and reactor tank 1, cooling gas check valve 14 is for preventing gas from blower 2 to reactor tank 1
The gas outlet of interior adverse current, blower 2 connects with the air inlet of water cucurbitula 4, and the gas outlet of water cucurbitula 4 connects with booster pump 10, pressurization
Pump 10 is further reacted for being pumped into reactor tank 1 after gas boosting with reaction solution, and is set between booster pump 10 and reactor tank 1
It is equipped with heat exchanger 11, heat exchanger 11 is used for the gas heating being pumped into reactor tank 1.
It should be noted that is put in water cucurbitula 4 is saturated sodium chloride solution, saturated sodium chloride solution is to hydrogen chloride gas
With good absorption, but to chlorine almost without assimilation effect, so saturated sodium chloride solution is arranged herein, at this
Reaction constantly generates chlorine and hydrogen chloride gas in reactor tank 1 in device, these mixed gas are mixed by 2 extraction tank 1 of blower
Gas is closed first via 4 absorbing hydrogen chloride gas of water cucurbitula, and then remaining chlorine enters heat exchanger via the pressurization of booster pump 10
11, heat exchanger 11 enters back into reactor tank 1 after increasing the temperature of chlorine and further reacts with liquid.
The hydrogen chloride generated in reaction process and chlorine can be separately recovered to utilization, chlorine after the recovery is made in the present apparatus
It is further reacted for reaction raw materials, more saving raw material.
As shown in attached drawing 1, attached drawing 2 and attached drawing 3, further includes escape pipe, gas-liquid two-phase check valve is provided on escape pipe
106, gas-liquid two-phase check valve 106 is for preventing liquid by reaction kettle adverse current disengaging tracheae.
Gas-liquid two-phase check valve 106 belongs to existing mature technology, and the effect of specific gas-liquid two-phase check valve 106 is as follows,
When the air pressure in escape pipe is lower than rated value, gas-liquid two-phase check valve 106 is in close state, and the gas in escape pipe can not
Into in reactor tank 1, when the air pressure in escape pipe reaches at or above rated value, 106 moment of gas-liquid two-phase check valve is opened, out
Endotracheal gas is gushed into reactor tank 1 and reaction solution intense contact, because reaction solution is violent compared with chlorine contacts, in this way
It can accelerate the reaction speed of chlorine and reaction solution.The purpose that booster pump 10 is arranged here is just to be able to gradually slowly increase
Add the gas pressure intensity in reactor tank 1, while usual heat exchanger 11 need to be better than as the pressure-resistant performance of matching used heat exchanger 11,
Because present 11 producer of heat exchanger can be according to using the pressure-resistant use demand of client specifically customized, so heat exchanging device 11 is not done
Specific further statement.
It should be noted that gas-liquid two-phase check valve 106 can be not only used for the one-way conduction between gas-liquid two-phase, it can also
For the one-way conduction between gas gas two-phase and between liquid-liquid diphase.
As shown in attached drawing 1, attached drawing 2 and attached drawing 3, reactor tank 1 is the reactor tank 1 of non-ferric material, and escape pipe is non-ferric material
Escape pipe, and be provided with magnet piston 104 in escape pipe, non-ferric material support rod 101, support rod be provided in reactor tank 1
It is rotatably equipped with the rotor plate 102 of non-ferric material on 101, is provided with iron shot in rotor plate 102；When magnet piston 104 is in outlet
In pipe when movement, rotor plate 102 can be rotated around support rod 101.
In order to guarantee that magnet piston 104 will not be by chlorine corrosion, in the outer surface of magnet piston 104, coating is some corrosion-resistant
Coating.Specific set-up mode of the magnet piston 104 in reactor tank 1 is as follows, because reactor tank 1 is all vertically arranged,
The tank bottom of reactor tank 1 is arranged in escape pipe, and escape pipe, perpendicular to the tank bottom of reactor tank 1, the setting of gas-liquid two-phase check valve 106 exists
The side wall of escape pipe, 104 movable sealing of magnet piston are set in escape pipe, and booster pump 10 does not start to inflate into escape pipe
When, magnet piston 104 is located at the bottom of escape pipe, and when booster pump 10 is started to work, magnet piston 104 is at leisure by escape pipe
Bottom to top movements, the space in escape pipe is divided into upper air cavity 107 and 105 two skies of lower air chamber by magnet piston 104
Between (particularly the volume of air cavity 107 and lower air chamber 105 is variable), upper 107 volume of air cavity gradually becomes smaller, 105 body of lower air chamber
Product becomes larger, and the position of gas-liquid two-phase check valve 106 becomes lower air chamber 105 by being located at upper air cavity 107, when in lower air chamber 105
When air pressure reaches the rated value of gas-liquid two-phase check valve 106, most of gas moment in lower air chamber 105 gushs into reaction solution
In (while gas-liquid two-phase check valve 106) also moment closing, pressure and spontaneous gravity of the magnet piston 104 in upper air cavity 107
Under effect, from the upper end of escape pipe at moved to bottom.
The installation site relationship of rotor plate 102 and support rod 101 is somewhat similarly to seesaw, and rotor plate 102 is around support
The rotation of bar 101 is somewhat similarly to seesaw and rotates around supporting point, because one end of rotor plate 102 is provided with iron ball 103, and magnetic
Iron piston 104 has sucking action to iron ball 103 always, so can band during magnet piston 104 moves in escape pipe
Turn movable plate 102 is constantly moved as seesaw, and rotor plate 102 can constantly stir reactor tank 1 during the motion
Interior liquid, and liquid can accelerate reaction speed during the motion, reaction efficiency is higher, while the rotation of rotor plate 102 can promote
The gas (mixture of chlorine and hydrogen chloride) of liquid is set to accelerate evolution, but hydrogen chloride gas cognition is sent back to instead again after being recovered
Answer in liquid because hydrogen chloride actually react after a kind of product, according to Le Xiate column balancing shifting principle, hydrogen chloride is removed
Afterwards, the conversion ratio of reaction speed and raw material can be accelerated.
So reaction speed can be greatly improved by the setting of setting magnet piston 104 and rotor plate 102, improve former
The conversion ratio of material.
As shown in attached drawing 1, attached drawing 2 and attached drawing 3, support rod 101 is T-shaped support rod 101, and rotor plate 102 passes through certainly
The rotation of change 108 of body is set in support rod 101, and support rod 101 is the support rod 101 of inner hollow.
Because needing to carry out crystallisation by cooling after reaction, so selecting the support rod 101 of inner hollow, reaction in this way is tied
Water at low temperature can be filled into support rod 101 after beam to cool down, so some conduits and branch can specifically be arranged in reactor tank 1
Space inside strut 101 is connected, and fills water at low temperature cooling into support rod 101 by conduit.Of course for the cooling knot of guarantee
Brilliant effect and speed, can be separately provided some condenser pipes in reactor tank 1.
Further include recycling can 3 as shown in attached drawing 1, attached drawing 2 and attached drawing 3, recycling can 3 be set to blower 2 and water cucurbitula 4 it
Between, and several adsorption stuffings are provided in recycling can 3, the temperature of adsorption stuffing is 4 DEG C~10 DEG C.
Because entire reaction be 60~80 DEG C at a temperature of carry out, and the boiling point of dimethyl carbonate is 90.1 DEG C, this
Two temperature spots are very close, so necessarily there is part dimethyl carbonate can be with the evolution of steam, so set during the reaction
Closed cans 3 is put back into recycle this part dimethyl carbonate gas, adsorption stuffing is really block, since the temperature of block is very low
(4 DEG C~10 DEG C) after dimethyl carbonate encounters these low temperature blocks, can be adsorbed in fluid form on these blocks.
The prior art since adsorption stuffing being arranged in recycling can 3, this programme does not do specific statement in detail, while this programme according to
The actual conditions of the present apparatus, provide the implementation of a kind of recycling can 3 and adsorption stuffing, and recycling can 3 is with air inlet and to go out
The corrosion-resistant tank of port, adsorption stuffing are common vials, and sealing has filled water (and water temperature is 4 DEG C~10 in vial
DEG C), vial has filled up corrosion-resistant tank.The liquid carbonic acid dimethyl ester accumulated on the outer wall of vial can be recycled further, this
Sample is achieved that the recycling to dimethyl carbonate raw material.
The temperature of present apparatus control adsorption stuffing is because dimethyl carbonate can be with solid lower than 4 DEG C in temperature not less than 4 DEG C
The form of body particle is precipitated, and solid particle may block recycling can 3.
It further include triple valve 9 as shown in attached drawing 1, attached drawing 2 and attached drawing 3, triple valve 9 is set to water cucurbitula 4 and booster pump 10
Between, and two interfaces of triple valve 9 connect with water cucurbitula 4 and booster pump 10 respectively, are connected on another interface of triple valve 9
Regenerating tank 5 is provided with carbon tetrachloride liquid in regenerating tank 5.
Because the whole process of preparation triphosgene is segmented into reaction, crystallisation by cooling, vacuumize depickling gas and vacuum is dry
It dry four, after the completion of reacting with crystallisation by cooling this two, needs to carrying out vacuumizing depickling gas in reactor tank 1, and is extracted
Gas is actually three parts (hydrogen chloride, chlorine and dimethyl carbonate), and dimethyl carbonate can be recovered the absorption of tank 3, hydrogen chloride
It is absorbed by water cucurbitula 4, and chlorine can be reproduced the absorption of the carbon tetrachloride in tank 5.Specifically three during vacuumizing depickling gas
It closes and is not turned between port valve 9 and booster pump 10, and heat exchanger 11 and booster pump 10 are all idle.
It further include injector mixer 8 and air accumulator 6, the air inlet of booster pump 10 as shown in attached drawing 1, attached drawing 2 and attached drawing 3
Connect respectively with triple valve 9 and injector mixer 8, two interfaces of residue of injector mixer 8 respectively with air accumulator 6 and regenerating tank
5 connect, injector mixer 8 be used for by air accumulator 6 gas and regenerating tank 5 in be delivered to pressurization after the gas mixing that is discharged
Pump 10；And control valve 7 is provided between injector mixer 8 and air accumulator 6 and between injector mixer 8 and regenerating tank 5.
It is solid particle (surface can remain a small amount of drop) entirely substantially after completing crystallisation by cooling, in reactor tank 1,
Air accumulator 6 in the present apparatus it is built-in be nitrogen (or other similar inert gases), the workflow of above-mentioned design is as follows, gas storage
Nitrogen in tank 6 enters after heat exchanger 11 heats via booster pump 10 enters back into escape pipe, then pushes magnet living in escape pipe
104 movement of plug, and magnet piston 104 still drives rotor plate 102 to move, rotor plate 102 can disturb in the process of movement
Solid particle in reactor tank 1, and the high temperature nitrogen that moment gushs away can dry up the liquid of solid particles surface, such one
Side stirs the high temperature nitrogen air-blowing of solid particle one side moment, can rapidly dry up the liquid of solid particles surface.Simultaneously because
This process blower 2 still gas in abstraction reaction tank 1, the gas that blower 2 extracts include nitrogen, hydrogen chloride, chlorine with
And minimal amount of dimethyl carbonate, and hydrogen chloride, chlorine and dimethyl carbonate can be all absorbed, and opened out of regenerating tank 5
Effect of the nitrogen through injector mixer 8, then enter the continuation operation of next circulation after mixing with fresh nitrogen.The above process
It is the vacuum drying to solid particle (i.e. product), but there are certain for this process of vacuum drying and traditional " vacuum drying "
Difference.
It specifically closes and is not turned between triple valve 9 and booster pump 10 during nitrogen blowing.
Further include cold blowing pipe 12 as shown in attached drawing 1, attached drawing 2 and attached drawing 3, the gas outlet of booster pump 10 respectively with cold blowing pipe
12 and heat exchanger 11 connect, 12 both ends of cold blowing pipe connect with booster pump 10 and reactor tank 1 respectively, and control is provided on cold blowing pipe 12
Valve 7 is provided with control valve 7 between booster pump 10 and heat exchanger 11.
Most of liquid on solid particle (i.e. product) surface can be dried up with the nitrogen of heat, while can also make solid particle
It is maintained at higher temperature, higher temperature can be unfavorable for the carrying and packaging of product, so product must be carried out at cooling
Reason is opened cold so closing between injector mixer 8 and air accumulator 6 and the control valve 7 between injector mixer 8 and regenerating tank 5
Control valve 7 on blowpipe 12, closing is not turned between holding triple valve 9 and booster pump 10, and then with cold nitrogen, (temperature exists
10 DEG C~15 DEG C) it is blown against solid particle, the temperature of solid particles surface is first reduced, grains surface is second thoroughly dried up
Liquid.It should be noted simultaneously that blower 2 still needs to open during this, the gas released in reactor tank 1 is needed
Successively to pass through the absorption of recycling can 3, water cucurbitula 4 and regenerating tank 5, the gas come out out of regenerating tank 5 can direct emission
, because what is discharged is substantially nitrogen, environmental sound, but for the considerations of economizing on resources, can regenerate again
A receipts nitrogen pipe 13 (receive is also to be equipped with control valve 7 on nitrogen pipe 13) is connect on tank 5, and nitrogen is delivered to it using nitrogen pipe 13 is received
His recycling equipment.
Blower 2 in the specific present apparatus is to be connected by pipeline with the top of reactor tank 1, and cold blowing pipe 12 and reactor tank 1
Tank bottom at connect.
Further, the present invention also provides a kind of triphosgene preparation process, include the following steps:
S1: chlorine is passed through in dimethyl carbonate, and maintaining the temperature of entire reaction system is 60~80 DEG C of reaction temperature, so
Reaction solution is constantly stirred afterwards, and constantly supplements chlorine into reaction solution to while being evacuated to reactor tank, maintains this shape
It state 7 hours, is irradiated with ultraviolet light always in whole process；
S2: crystallisation by cooling vacuumizes reactor tank after the completion of crystallization；
S3: first being blown with 30 DEG C~35 DEG C of nitrogen against crystalline solid after vacuumizing, then with 10 DEG C~15 DEG C of nitrogen
Gas is blown against crystalline solid.
It should be further noted that this programme also provides a simplified embodiment, simplified embodiment is used such as 4 institute of attached drawing
The easy reaction kettle shown, the easy reaction kettle include a reactor tank 1, and condenser pipe 109 and ultraviolet light hair are equipped in reactor tank 1
Injection device 1010, is provided with offgas outlet 1011, chlorine inlet 1012 and discharge port 1013 in reactor tank 1, and when installation, tail gas goes out
Mouth 1011 is connected by pipeline with cooling gas check valve 14, and chlorine inlet 1012 connects with cold blowing pipe 12, and discharge port 1013 passes through pipe
Road connects with preheater 11.
The above description is only a preferred embodiment of the present invention, not thereby limits scope of patent protection of the invention, all
It is directly or indirectly to be used in other relevant technologies with equivalent structure transformation made by description of the invention and accompanying drawing content
Field similarly includes within the scope of the present invention.
Claims (9)
1. a kind of triphosgene prepares reaction unit, including reactor tank, ultraviolet emission device, feature are set in the reactor tank
It is, further includes blower, water cucurbitula and booster pump, the air inlet of the blower is communicated with reactor tank, the blower and reactor tank
Between be provided with cooling gas check valve, for preventing gas from blower, the adverse current into reactor tank, blower go out the cooling gas check valve
Port connects with the air inlet of water cucurbitula, and the gas outlet of water cucurbitula connects with booster pump, and the booster pump is used for gas boosting
After be pumped into reactor tank and further reacted with reaction solution, and heat exchanger is provided between booster pump and reactor tank, the heat exchanger
For to the gas heating being pumped into reactor tank.
2. triphosgene as described in claim 1 prepares reaction unit, which is characterized in that it further include escape pipe, the escape pipe
On be provided with gas-liquid two-phase check valve, the gas-liquid two-phase check valve is for preventing liquid by reaction kettle adverse current disengaging tracheae.
3. triphosgene as claimed in claim 2 prepares reaction unit, which is characterized in that the reactor tank is the anti-of non-ferric material
Tank is answered, the escape pipe is the escape pipe of non-ferric material, and magnet piston is provided in escape pipe, is provided in the reactor tank
Non-ferric material support rod is rotatably equipped with the rotor plate of non-ferric material on the support rod, is provided with iron shot in the rotor plate；
When the magnet piston moves in escape pipe, the rotor plate can be rotated around support rod.
4. triphosgene as claimed in claim 3 prepares reaction unit, which is characterized in that the support rod is T-shaped support rod,
And rotor plate is set in support rod by the change rotation of itself, and support rod is the support rod of inner hollow.
5. triphosgene as described in claim 1 prepares reaction unit, which is characterized in that it further include recycling can, the recycling can
It being set between blower and water cucurbitula, and is provided with several adsorption stuffings in recycling can, the temperature of the adsorption stuffing is 4 DEG C~
10℃。
6. triphosgene as claimed in claim 5 prepares reaction unit, which is characterized in that it further include triple valve, the triple valve
It is set between water cucurbitula and booster pump, and two interfaces of triple valve connect with water cucurbitula and booster pump respectively, triple valve
It is connected to regenerating tank on another interface, carbon tetrachloride liquid is provided in the regenerating tank.
7. triphosgene as claimed in claim 6 prepares reaction unit, which is characterized in that further include injector mixer and gas storage
The air inlet of tank, the booster pump connects with triple valve and injector mixer respectively, two interfaces of residue point of injector mixer
Do not connect with air accumulator and regenerating tank, the injector mixer be used for by air accumulator gas and regenerating tank in the gas that is discharged
Booster pump is delivered to after body mixing；And it is provided between injector mixer and air accumulator and between injector mixer and regenerating tank
Control valve.
8. triphosgene as claimed in claim 7 prepares reaction unit, which is characterized in that further include cold blowing pipe, the booster pump
Gas outlet connect respectively with cold blowing pipe and heat exchanger, cold blowing pipe both ends connect with booster pump and reactor tank respectively, described
It is provided with control valve on cold blowing pipe, is provided with control valve between the booster pump and heat exchanger.
9. a kind of triphosgene suitable for as described in claim 1~8 Arbitrary Term prepares the triphosgene preparation process of reaction unit,
It is characterized by comprising the following steps:
S1: chlorine is passed through in dimethyl carbonate, and maintaining the temperature of entire reaction system is 60~80 DEG C of reaction temperature, then not
Disconnected agitation reaction solution, and chlorine is constantly supplemented into reaction solution to while being evacuated to reactor tank, maintain this state 7 small
When, it is irradiated with ultraviolet light always in whole process；
S2: crystallisation by cooling vacuumizes reactor tank after the completion of crystallization；
S3: first being blown with 30 DEG C~35 DEG C of nitrogen against crystalline solid after vacuumizing, then with 10 DEG C~15 DEG C of nitrogen pair
Crystalline solid blow.
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| CN201910148986.XA CN109761812B (en) | 2019-02-28 | 2019-02-28 | Triphosgene preparation process |
| CN202110631854.XA CN113321585B (en) | 2019-02-28 | 2019-02-28 | Triphosgene preparation method based on crystallization drying |
| CN202110633528.2A CN113292428B (en) | 2019-02-28 | 2019-02-28 | Triphosgene preparation method based on nitrogen drying |
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| CN114100323A (en) * | 2021-11-15 | 2022-03-01 | 德沃德科技(重庆)有限责任公司 | Solid phosgene tail gas separation process and equipment |
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| CN113292428A (en) | 2021-08-24 |
| CN109761812B (en) | 2021-07-27 |
| CN113292428B (en) | 2022-03-22 |
| CN113321585A (en) | 2021-08-31 |
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