CN101781164B - Preparation method of difluoromono-chloroethane - Google Patents
Preparation method of difluoromono-chloroethane Download PDFInfo
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- CN101781164B CN101781164B CN 201010108206 CN201010108206A CN101781164B CN 101781164 B CN101781164 B CN 101781164B CN 201010108206 CN201010108206 CN 201010108206 CN 201010108206 A CN201010108206 A CN 201010108206A CN 101781164 B CN101781164 B CN 101781164B
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- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 44
- 239000000460 chlorine Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000007791 liquid phase Substances 0.000 claims abstract description 35
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000007906 compression Methods 0.000 claims abstract description 14
- 230000006835 compression Effects 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 230000008016 vaporization Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000009834 vaporization Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 87
- 239000000463 material Substances 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 38
- 230000003287 optical effect Effects 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 239000010962 carbon steel Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 31
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000007872 degassing Methods 0.000 abstract 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 23
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 23
- 241000282326 Felis catus Species 0.000 description 13
- 238000005070 sampling Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of difluoromono-chloroethane; in the method, liquid-phase difluoroethane and chlorine are used as raw materials and are mixed according to a certain proportion after vaporization and preheating are carried out, and then the mixture is reacted in a dry-method photochlorination reactor to generate crude difluoromono-chloroethane; and then the finished difluoromono-chloroethane is obtained after compression, multistage degasification, liquid phase washing, neutralization, rectification and drying; and the difluoromono-chloroethane preparation method has simple process, compact structure, high reaction conversion percentage, less side reaction, high raw material recovery rate, low liquid caustic soda consumption, low energy consumption, high economic benefit of side products, good operating stability and high safety factor.
Description
Technical field
The present invention relates to a kind of preparation method of difluoromono-chloroethane, belong to the fluorine chemical technical field.
Technical background
The production method of difluoromono-chloroethane (R142b) is except because of reactor light source arrangement difference, apparatus-form, mode of connection difference, the type of cooling difference, all can be referred to as after all light chlorination process and prepare difluoromono-chloroethane, its purpose all is the control temperature of reaction, improve selectivity, reduce the generation of by product, reduce to produce consuming, increasing economic efficiency.After its unusual part of the present invention is to adopt the dry method light chlorination process to prepare the difluoromono-chloroethane crude product, first take off light separation through multistage, and then carry out liquid phase washing, neutralization, rectifying, drying process and make the difluoromono-chloroethane finished product.
Chinese patent file CN101456788A (200810120170.8) discloses a kind of method and apparatus of preparing difluoromonochloroetbyne byne photochemical catalyst, the production technique of difluoromono-chloroethane is wherein reacted (referred to as the wet method optical chlorinating reaction) after adopting R152a and chlorine to mix in interior optical chlorinating reaction device with spray equipment, outer wall belt heat exchange jacket, reacted mixture makes the difluoromono-chloroethane finished product through gas phase washing, alkali cleaning, compression, degassed, rectifying, drying successively.The photo catalysis reactor that adopts during reaction, the cylindrical shell that comprises outer wall belt heat exchange jacket, interior wall liner impregnating material, described cylinder top and bottom are provided with the material mouth, the cylindrical shell inner top is provided with spray equipment, the following part of spray equipment is saved to be communicated with up and down by four sections towers and assembles, and each tower joint is equipped with four ultraviolet lamps arranging up and down; Three temperature-measuring ports and a liquid C2H4F2 C2H4F2 opening for feed of arranging up and down.The first scale flush away that this invention is adopted is except unreacted chlorine, not only need consume a large amount of liquid caustic soda, improve raw-material consumption, and chlorine and alkaline reaction generate unsettled clorox, discharge easily oxygen, become on the one hand the hidden danger of production system, because incondensable gas need efflux, wherein the content of C2H4F2 C2H4F2 and difluoromono-chloroethane can be up to more than 85% on the other hand, not only make to produce to consume and strengthen, the more important thing is that contaminate environment is serious.
Chinese patent file CN200942338Y (200620085158.4) provides a kind of device of producing difluoromono-chloroethane, is the applicant's utility model patent, and it comprises heat sink, light supply apparatus, main reaction device three parts.Inside at reaction tower arranges spray equipment, lowers the temperature by the spray refrigerant, and this device increases heat interchanging area, can in time discharge reaction heat.The arrangement fluorescent tube of different angles has strengthened the illuminating area of reaction in the light source arrangement.This optical chlorinating reaction device and above-mentioned CN101456788A (200810120170.8) are for the wet method optical chlorinating reaction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of dry process difluoromono-chloroethane, have that raw materials consumption is low, transformation efficiency is high, the characteristics that reaction preference is strong, by-products content is few, technical process is simple, safety coefficient is high can be used for large-scale commercial production.
It is that the light-catalyzed reaction of raw material dry method obtains the crude product difluoromono-chloroethane that the present invention adopts C2H4F2 C2H4F2 and chlorine, and then through overdraft, multistagely take off the method that light separation, liquid phase washing, neutralization, rectifying, drying make the finished product difluoromono-chloroethane.
The term explanation: R152a is writing a Chinese character in simplified form of C2H4F2 C2H4F2, and R142b is writing a Chinese character in simplified form of difluoromono-chloroethane.
Technical scheme of the present invention is described in detail as follows:
A kind of method for preparing difluoromono-chloroethane: comprise feed vaporization preheating, optical chlorinating reaction, compression, multistage light separation, liquid phase washing, liquid phase neutralization, rectifying and the drying of taking off, it is characterized in that: optical chlorinating reaction adopts the dry method optical chlorinating reaction, the optical chlorinating reaction device is tower reactor, the gas phase mixture material of C2H4F2 C2H4F2 and chlorine enters from optical chlorinating reaction device bottom, under UV-light or fluorescent lamp irradiation, carry out catalyzed reaction, the heat that reaction discharges is taken away by external circulation cooling system, and material does not directly contact with heat-eliminating medium.
In the above method, preferably the processing condition of each operation are as follows:
(1) feed vaporization preheating
Raw material chlorine and C2H4F2 C2H4F2 all adopt liquid phase material, vaporize respectively, preheating, the preheating temperature of control chlorine is between 40～90 ℃, and the C2H4F2 C2H4F2 preheating temperature is controlled between 50～100 ℃, then the C2H4F2 C2H4F2 after the preheating and chlorine 1: 0.75 in molar ratio～0.9 is mixed.
The mixing of above-mentioned C2H4F2 C2H4F2 and chlorine is to carry out in mixing tank, preferred mixing tank adopts impregnating material, carbon steel or other alloy materials to make, the mixing tank of its medium carbon steel or other alloy materials can add corrosion-proof lining, filler is housed, the optional strand sheet of filler, screen waviness packings etc. in the mixing tank.
(2) dry method optical chlorinating reaction
C2H4F2 C2H4F2 and chlorine enter dry method optical chlorinating reaction device after mixing, and temperature of reaction is controlled between 60～110 ℃, and reaction pressure is between 0.05～0.12Mpa, and the raw material reaction residence time is 60～90s, and transformation efficiency is 60%～80%.
(3) compression
Reacted mixed gas is cooled to first-10～15 ℃, compresses, liquefies, and compression can be adopted high pressure compressed or stage compression, and material is liquefied as much as possible fully, and the compression top hole pressure is controlled between 0.8～2.0MPa.
(4) take off light separation
Adopt the multistage light separation of taking off, the liquid material that compression is obtained by taking off HCl tower, dechlorinator, taking off the R152a tower and take off light separation, reclaims by product HCl and unreacted chlorine and the C2H4F2 C2H4F2 of reaction successively.
The described HCl of taking off tower is internal reflux stainless steel casting packing tower, the optional Stainless Steel Wire corrugated wire gauze packing of filler or Pall ring; This tower working pressure is 1.5～2.0MPa, the still temperature: 40～65 ℃ of top temperature :-25～-5 ℃, the high-purity HCl of overhead collection purity more than 98% absorbs the byproduct hydrochloric acid of making purity 〉=30% through water.
Described dechlorinator is the Carbon steel stuffing material tower, the optional Stainless Steel Wire corrugated wire gauze packing of filler or Pall ring; Working pressure is made as 1.0～1.5MPa, 40～80 ℃ of still temperature, and the most of unreacted chlorine of overhead collection and a small amount of C2H4F2 C2H4F2, the light echo chlorination system reacts again, and wherein purity of chlorine gas feeding can reach more than 95%.
The described R152a of taking off tower is the Carbon steel stuffing material tower, the optional Stainless Steel Wire corrugated wire gauze packing of filler or Pall ring; Working pressure is 0.8～1.2MPa, 45～65 ℃ of still temperature, and overhead collection C2H4F2 C2H4F2 purity 〉=95%, chlorine can reclaim fully, tower reactor C2H4F2 C2H4F2 content≤0.05%.
(5) liquid phase washing and liquid phase neutralization
Take off the liquid phase material (mainly take R142b as main, containing a small amount of chlorine and high boiling material) after the light separation, remove acidic substance residual in the material by liquid phase washing, liquid phase neutralization, make material be weakly alkaline, the pH value is between 8-10.
The washing of described liquid phase is to carry out in water wash column, and the liquid phase material that takes off after the light separation enters from the water wash column top, and water enters from the water wash column bottom.Material and water carry out countercurrent exchange according to density difference and absorb in water wash column, residual HCL and a small amount of chlorine leach form hydrochloric acid in the material in water, be collected in the salt acid storage tank from the overflow of water wash column top, the material after the washing goes out tower from the water wash column bottom and goes to neutralize.Wherein water wash column is the packing tower of carbon steel, inside lining anti-corrosive material.
Described liquid phase neutralization is to carry out in the alkali separator, material after the washing is in the top enters the alkali separator, alkali lye enters the bottom by alkali separator top bottom insert canal, in the alkali separator, mix layering by the proportion difference, material after neutralization and the layering enters subsequent processing (decanting vessel) by alkali separator bottom, and alkali lye is discharged from the top and recycled.
(6) rectifying and drying
Material after washing, the neutralization enters rectifying tower and carries out rectifying, rectifying tower working pressure: 0.25～0.55MPa, and 35～80 ℃ of still temperature, 25～40 ℃ of top temperature, the difluoromono-chloroethane of overhead extraction purity 〉=99.9% is collected in the pan tank after drying.Tower reactor difluoromono-chloroethane residual quantity≤3%.
The invention provides that a kind of technique is simple, compact construction, reaction conversion ratio is high, side reaction is few, the starting material recovery utilization rate is high, liquid caustic soda consumes lowly, energy consumption is few, byproduct economic benefit height and operational stability is good, safety coefficient is high difluoromono-chloroethane production method.
Institute's employing equipment mainly contains dry method optical chlorinating reaction device, multistage light separating device (take off HCl tower, dechlorinator, take off the R152a tower), liquid phase water wash column, alkali separator, rectifying tower, moisture eliminator and the pan tank of taking off in the inventive method.Except dry method optical chlorinating reaction device, other equipment are prior art, and task is as follows:
Described optical chlorinating reaction device is tower dry method optical chlorinating reaction device, and reaction heat is taken away by external circulation cooling system, and the control temperature of reaction is in controlled area charactert, and side reaction product content is between 0.2%-1.1%.
The described multistage light separating device that takes off namely adopts dehydrochlorination tower, dechlorinator, takes off the R152a tower, isolates successively hydrogenchloride, chlorine and C2H4F2 C2H4F2 in the rear mixture of reaction.Described these three towers, the operating unit of respectively doing for oneself operates according to separately operational requirement, reaches to remove as much as possible hydrogenchloride and make high-purity hydrochloric acid, and reclaims highly purified starting material chlorine and C2H4F2 C2H4F2 as much as possible fully.
Described washing, the N-process material is liquid phase, at the liquid phase water wash column, finish in the alkali separator, be different from Chinese patent CN101456788A (200810120170.8) etc. in the past the gas phase scale in the difluoromono-chloroethane production method wash, material of the present invention is liquid phase, according to material and water, the alkali unmixing, and the relation that density difference is larger, the acidic substance such as hydrogenchloride residual in the material are removed, its advantage is: one, through multistage take off after the light processing thick material middle acid substance content seldom, alleviated washing, the operating load of neutralized system and water, the consumption of liquid caustic soda, the consumption of washing alkali lye than in the past traditional gas phase scale has reduced more than 90%, reduce production costs, two, can not enter because of a large amount of chlorine scale and wash system and generate unsettled hypochlorous acid and decomposite simultaneously oxygen, cause potential safety hazard.
Dry method optical chlorinating reaction device of the present invention, structure as shown in Figure 2, described dry method optical chlorinating reaction device comprises reaction tower joint, two kinds of towers joints of outer circulation temperature-reducing tower joint.The reaction tower joint comprises intermediate reaction tower joint, upper reaction tower joint, lower reaction tower joint.The intermediate reaction tower joint is provided with fluorescent tube interface, temperature-measuring port.Upper reaction tower joint is provided with material outlet, fluorescent tube interface, temperature-measuring port, mouth for subsequent use, and lower reaction tower joint is provided with material inlet, drain hole, temperature-measuring port, fluorescent tube interface.The outer circulation cooling system is provided with water-in, water outlet, mouth for subsequent use.The bearing installation site arranges according to the framework situation.This reactor is connected to form by some tower joints.The tower internode is bolted up and down.
Refer to intermediate reaction tower joint and the arrangement of outer circulation temperature-reducing tower septa intersegmental by the combination of some tower joints in the described dry method optical chlorinating reaction device, can select a joint intermediate reaction tower joint and a joint outer circulation temperature-reducing tower septa intersegmental combination, but also the multistage intermediate reaction tower saves the combination that adds a joint outer circulation temperature-reducing tower joint.
Described dry method optical chlorinating reaction device, reactor column selected parts are with the lining impregnating material or select that corrosion-resistant material is upright to connect making.Walk material in outer circulation temperature-reducing tower joint employing pipe is, shell side is walked temperature lowering water.Tube side, shell side can adopt shell and tube combination or the combination of nahlock hole.
The production method of difluoromono-chloroethane of the present invention is a kind of not only economy but also rational production method, and it is mainly manifested in: 1, raw-material transformation efficiency, recovery utilization rate height, the reaction preference of difluoromono-chloroethane is high.2, the liquid caustic soda consumption is little, the byproduct economic benefit high.3, system's oxygen level is low, and stream coefficient is high, has avoided because of high high flow rate and the environmental pollution that needs discharging to cause of oxygen level
Good characteristics of the present invention is summarized as follows:
On the prior art basis, innovate by production practice, after employing dry method optical chlorinating reaction obtains the difluoromono-chloroethane crude product, adopt first after compression the multistage light separation of taking off, reclaim unreacted starting material chlorine and C2H4F2 C2H4F2 as far as possible fully, thereby reduce raw materials consumption; In addition, multistagely take off the highly purified hydrogenchloride that dehydrochlorination column overhead in the light separation is collected, can be made into the byproduct hydrochloric acid of purity 〉=30% through water absorption, improved economic benefit.Make purity up to 99.9% difluoromono-chloroethane through liquid phase water, neutralization, rectifying, drying successively again through the multistage crude product difluoromono-chloroethane that takes off after the light separation.Technical process of the present invention is brief, wash with gas phase scale on year-on-year basis and to produce difluoromono-chloroethane with degassed rectification method and compare the consumption that starting material liquid chlorine, C2H4F2 C2H4F2 and liquid caustic soda are arranged and all significantly reduce, the market competitiveness has also obtained large change, and the recovery of byproduct hydrochloric acid has also increased the productive profit point.Because raw materials consumption is low, the byproduct rate of recovery is high, and the fully recovery because of unreacted starting material chlorine, the first scale flush away of having avoided Chinese patent CN101456788A (200810120170.8) to adopt removes unreacted chlorine, not only need consume a large amount of liquid caustic soda, improved raw-material consumption, and chlorine and alkaline reaction generate unsettled clorox, discharge easily oxygen, become on the one hand the hidden danger of production system, need efflux owing to incondensable gas on the other hand, wherein the content of C2H4F2 C2H4F2 and difluoromono-chloroethane be the more important thing is contaminate environment up to can not only having improved and produce consumption more than 85%.The present invention adopts first degassed rear scale to wash, and is all removed because chlorine has been close in the dechlorinator, can not wash and produce unsettled hypochlorous acid in the N-process and discharge oxygen carrying out scale, and production safety is threatened.
Description of drawings
Fig. 1 is that the present invention prepares the difluoromono-chloroethane process flow diagram, among the figure: 1, liquid phase R152a charging, 2, the liquid chlorine charging, 3, the R152a pre-heating system of vaporizing, 4, liquid chlorine vaporization pre-heating system, 5, static mixer, 6, the optical chlorinating reaction device, 7, gas holder, 8, compressor, 9, take off the HCl tower, 10, HCl graphitic absorber, 11, the dechlorinator, 12, take off the R152a tower, 13, water wash column, 14, the alkali separator, 15, decanting vessel, 16, rectifying tower, 17, moisture eliminator, 18, pan tank.
Fig. 2 is dry method optical chlorinating reaction device structural representation of the present invention.Dry method optical chlorinating reaction device among the present invention can be selected a joint intermediate reaction tower joint and a joint outer circulation temperature-reducing tower septa intersegmental combination, also but multistage intermediate reaction tower joint adds the combination of a joint outer circulation temperature-reducing tower joint, and this structural representation is with the example that is combined as of a joint intermediate reaction tower joint and a joint outer circulation temperature-reducing tower septa intersegmental.21. material outlets among the figure; 22. for subsequent use mouthful; 23-1,23-2,23-3 are temperature-measuring ports; 24. bearing; 25. water outlet; 26. water-in; 27. drain hole; 28. material inlet; 29. fluorescent tube interface; 30. for subsequent use mouthful.A represents the reaction tower joint among the figure; B outer circulation temperature-reducing tower joint; C intermediate reaction tower joint; Reaction tower joint under the D.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited to this.The dry method optical chlorinating reaction device structure of using among the embodiment comprises reaction tower joint, two kinds of tower joints of outer circulation temperature-reducing tower joint B as shown in Figure 2.The reaction tower joint comprises intermediate reaction tower joint C, upper reaction tower joint A, lower reaction tower joint D.Intermediate reaction tower joint C is provided with fluorescent tube interface 29, temperature-measuring port 23-1.Upper reaction tower joint A is provided with material outlet 21, fluorescent tube interface 29, temperature-measuring port 23-2, mouth 22 for subsequent use, and lower reaction tower joint D is provided with material inlet 28, drain hole 27, temperature-measuring port 23-3, fluorescent tube interface 29.The outer circulation cooling system is provided with water-in 26, water outlet 25, mouth 30 for subsequent use.The bearing installation site arranges according to the framework situation.This reactor is connected to form by some tower joints.The tower internode is bolted up and down.
Embodiment 1:
The dry method light chlorination process is produced difluoromono-chloroethane, adopts first the multistage light separation of taking off after the reaction, carries out liquid phase washing, neutralization again, removes the acidity of material, then carries out rectifying, drying makes the difluoromono-chloroethane finished product.Concrete operations are as follows:
1, raw-material vaporization, preheating refer to the preheating of vaporizing respectively of liquid chlorine and liquid phase C2H4F2 C2H4F2, temperature is 40～60 ℃ after the preheating of control chlorine, the preheating of C2H4F2 C2H4F2 is that temperature is 50～70 ℃, be 1: 0.75～0.8 to mix C2H4F2 C2H4F2 and chlorine by the mole proportioning by static mixer 5, send tower optical chlorinating reaction device 6 reactions of dry method to, feed pressure is 0.05～0.06MPa.
2, optical chlorinating reaction adopts dry method tower reactor 6, UV-light or the irradiation of common fluorescent lamp, and reaction heat is taken away by external circulation cooling system (outer circulation temperature-reducing tower joint B), and the control temperature of reaction is at 60～75 ℃, and the raw material reaction residence time is 60～70s.Sampling detects difluoromono-chloroethane content 60～65wt%, high boiling material content 0～0.8%.
3, multistagely take off light separation and adopt and take off HCl tower, dechlorinator and take off three grades of separation of R152a tower, gather successively and reclaim light constituent hydrogenchloride, chlorine, C2H4F2 C2H4F2.
A, take off HCl tower 9: tower reactor pressure: 1.8～2.0MPa, the tower reactor temperature: 60～65 ℃, cat head :-10～-5 ℃; The cat head sampling detects: HCl content 〉=98%.
B, dechlorinator 11: tower reactor pressure: 1.3～1.5MPa, the tower reactor temperature: 70～80 ℃, cat head: 50～55 ℃; The cat head sampling detects: chlorine content 〉=96%.
C, take off R152a tower 12: tower reactor pressure: 1.1～1.2MPa, tower reactor temperature: 60～65 ℃.Sampling detects: cat head R152a content 〉=98%, tower reactor is without R152a.
4, liquid phase washing: the washing water enters from water wash column 13 bottom sides, and liquid phase material is from water wash column 13 top fed, and countercurrent exchange absorbs in tower.
5, liquid phase neutralization: material and in and alkali lye entered by alkali separator 14 tops, in alkali separator 14, press the density difference layering.In and alkali lye discharge from the top, material enters decanting vessel 15 by bottom discharge, material pH8-9.
6, rectifying, drying: rectifying tower 16 tower reactor pressure: 0.45～0.55MPa, 35～40 ℃ of tower top temperatures are collected in pan tank 18 after the difluoromono-chloroethane of overhead extraction purity 〉=99.9% (R142b) drying device 17 dryings.
Embodiment 2:
As described in Example 1, difference is:
1, temperature is 60～75 ℃ after the preheating of control chlorine, and temperature is 70～80 ℃ after the C2H4F2 C2H4F2 preheating, and the mole proportioning of C2H4F2 C2H4F2 and chlorine is that 1: 0.8～0.85 mixing is reacted, and feed pressure is 0.06～0.08MPa.
2, the optical chlorinating reaction temperature is 75～90 ℃, and the raw material reaction residence time is 70～80s, sampling analysis: difluoromono-chloroethane content 65%～73%, high boiling material content 0～1.1%
3, multistagely take off light separation and adopt and take off HCl tower, dechlorinator and take off three grades of separation of R152a tower, gather successively and reclaim light constituent hydrogenchloride, chlorine, C2H4F2 C2H4F2.
A, take off the HCl tower: tower reactor pressure: 1.5～1.8MPa, the tower reactor temperature: 50～60 ℃, tower top temperature :-20～-10 ℃, the cat head sampling detects: HCl content 〉=98%.
B, dechlorinator: tower reactor pressure: 1.1～1.3MPa, the tower reactor temperature: 55～70 ℃, tower top temperature: 40～50 ℃, the cat head sampling detects: chlorine content 〉=96%.
C, take off the R152a tower: tower reactor pressure: 0.9～1.1MPa, the tower reactor temperature: 50～60 ℃, sampling detects: cat head R152a content 〉=98%, tower reactor is without R152a.
4, described rectifying, drying: tower bottom of rectifying tower pressure: 0.35～0.45MPa, 30～35 ℃ of tower top temperatures, tower reactor R142b residual quantity≤3%.
5, more than the R142b purity to 99.9% of overhead extraction.
Embodiment 3:
As described in Example 1, difference is:
1, temperature is 75～90 ℃ after the preheating of control chlorine, and the preheating of C2H4F2 C2H4F2 is that temperature is 80～100 ℃, and the mole proportioning of C2H4F2 C2H4F2 and chlorine is to mix between 1: 0.85～0.9 to react, and feed pressure is 0.08～0.12MPa.
2, the optical chlorinating reaction temperature is 90～110 ℃, and reaction time is 80～90s, sampling difluoromono-chloroethane content 73%～80%, and high boiling material content is 0～2%.
3, describedly multistagely take off light separation and adopt and take off HCl tower, dechlorinator and take off three grades of separation of R152a tower, gather successively and reclaim light constituent hydrogenchloride, chlorine, C2H4F2 C2H4F2.
A, take off the HCl tower: tower reactor pressure: 1.3～1.5MPa, the tower reactor temperature: 40～50 ℃, cat head :-25～-20 ℃, the cat head sampling detects: HCl content 〉=98%.
B, dechlorinator: tower reactor pressure: 1.0～1.1MPa, the tower reactor temperature: 40～55 ℃, cat head: 30～40 ℃, the cat head sampling detects: chlorine content 〉=96%.
C, take off the R152a tower: tower reactor pressure: 0.8～0.9MPa, the tower reactor temperature: 45～50 ℃, sampling detects: cat head R152a content 〉=98%, tower reactor is without R152a.
4, described rectifying, drying: tower bottom of rectifying tower pressure: 0.25～0.35MPa, 25～30 ℃ of tower top temperatures, tower reactor R142b residual quantity≤3%.
5, the R142b purity of overhead extraction is more than 99.9%.
Claims (8)
1. the production method of a difluoromono-chloroethane, comprise feed vaporization preheating, optical chlorinating reaction, compress, take off light separation, liquid phase washing, liquid phase neutralization, rectifying and drying, it is characterized in that: optical chlorinating reaction adopts the dry method optical chlorinating reaction, the gas phase mixture material of C2H4F2 C2H4F2 and chlorine enters from optical chlorinating reaction device bottom, under UV-light or fluorescent lamp irradiation, carry out catalyzed reaction, the heat that reaction discharges is taken away by external circulation cooling system, and material does not directly contact with heat-eliminating medium;
Described feed vaporization preheating is:
Raw material chlorine and C2H4F2 C2H4F2 all adopt liquid phase material, vaporize respectively, preheating, the preheating temperature of control chlorine is between 40～90 ℃, and the C2H4F2 C2H4F2 preheating temperature is controlled between 50～100 ℃, then with C2H4F2 C2H4F2 and in molar ratio 1:0.75-0.9 mixing of chlorine;
Described dry method optical chlorinating reaction is:
The gas mixture of C2H4F2 C2H4F2 and chlorine carries out in the optical chlorinating reaction device, and temperature of reaction is controlled between 60～110 ℃, reaction pressure between 0.05～0.12MPa, the raw material reaction residence time 60～90s.
2. the production method of difluoromono-chloroethane as claimed in claim 1, it is characterized in that, described compression is that reacted mixed gas is cooled to first 10～15 ℃ of ﹣, compress again, liquefy, compression can be adopted high pressure compressed or stage compression, and the compression top hole pressure is controlled between 0.8～2.0MPa.
3. the production method of difluoromono-chloroethane as claimed in claim 1, it is characterized in that, describedly take off light separation and adopt the multistage light separation of taking off, the liquid material that compression is obtained by taking off HCl tower, dechlorinator, taking off the R152a tower and take off light separation, reclaims unreacted chlorine and C2H4F2 C2H4F2 successively.
4. the production method of difluoromono-chloroethane as claimed in claim 3, it is characterized in that, the described HCl of taking off tower is internal reflux stainless steel casting packing tower, this tower working pressure is 1.5～2.0MPa, still temperature: 40～65 ℃, the top temperature :-25～-5 ℃, the high-purity HCl of overhead collection purity more than 98% absorbs the byproduct hydrochloric acid of making purity 〉=30% through water.
5. the production method of difluoromono-chloroethane as claimed in claim 3, it is characterized in that, described dechlorinator is the Carbon steel stuffing material tower, working pressure is made as 1.0～1.5MPa, 40～80 ℃ of still temperature, the most of unreacted chlorine of overhead collection and a small amount of C2H4F2 C2H4F2, the light echo chlorination system reacts again, and wherein purity of chlorine gas feeding can reach more than 95%.
6. the production method of difluoromono-chloroethane as claimed in claim 3, it is characterized in that, the described R152a of taking off tower is the Carbon steel stuffing material tower, working pressure is 0.8～1.2MPa, 45～65 ℃ of still temperature, overhead collection C2H4F2 C2H4F2 purity 〉=95%, chlorine can reclaim fully, tower reactor C2H4F2 C2H4F2 content≤0.05%.
7. the production method of difluoromono-chloroethane as claimed in claim 1 is characterized in that, the liquid phase material that takes off after the light separation removes acidic substance residual in the material by liquid phase washing, liquid phase neutralization, makes material pH value between 8～10;
The washing of described liquid phase is to carry out in water wash column, and the liquid phase material that takes off after the light separation enters from the water wash column top, and water enters from the water wash column bottom;
Described liquid phase neutralization is to carry out in the alkali separator, material after the washing is in the top enters the alkali separator, alkali lye enters the bottom by alkali separator top bottom insert canal, in the alkali separator, mix layering by the proportion difference, material after neutralization and the layering enters subsequent processing by alkali separator bottom, and alkali lye is discharged from the top and recycled.
8. the production method of difluoromono-chloroethane as claimed in claim 1 is characterized in that, described rectifying and drying are:
Material after washing, the neutralization enters rectifying tower and carries out rectifying, rectifying tower working pressure: 0.25～0.55MPa, and 35～80 ℃ of still temperature, 25～40 ℃ of top temperature, the difluoromono-chloroethane of overhead extraction purity 〉=99.9% is collected in the pan tank after drying; Tower reactor difluoromono-chloroethane residual quantity≤3%.
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| CN103012054A (en) * | 2012-12-18 | 2013-04-03 | 泰兴市梅兰化工有限公司 | Device and method for preparing ultra-high purity difluoromono-chloroethane |
| CN107200674A (en) * | 2017-05-04 | 2017-09-26 | 常熟三爱富中昊化工新材料有限公司 | A kind of method of fluorine-containing halogenated alkane reaction system complex optimum |
| CN107056581B (en) * | 2017-05-22 | 2020-03-27 | 山东东岳化工有限公司 | Method for separating high-boiling residues in 1-chloro-1, 1-difluoroethane production process |
| CN111099961A (en) * | 2018-10-26 | 2020-05-05 | 中昊晨光化工研究院有限公司 | Rectification method and system for production of difluoroethane and difluoromono-chloroethane |
| CN109364847A (en) * | 2018-11-28 | 2019-02-22 | 内蒙古三爱富万豪氟化工有限公司 | Optical chlorinating reaction device and the method for preparing difluoromono-chloroethane |
| CN117380117B (en) * | 2023-12-08 | 2024-03-22 | 泰兴市梅兰化工有限公司 | Photochlorination reactor for producing high-energy recycling of difluorochloroethane |
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| CN101456788A (en) * | 2008-07-31 | 2009-06-17 | 浙江大学 | Method and equipment for preparing difluoromonochloroethane by photochemical catalyst |
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