CN1275914C - Preparation method of difluoro-chloroethane - Google Patents
Preparation method of difluoro-chloroethane Download PDFInfo
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- CN1275914C CN1275914C CN 200410015778 CN200410015778A CN1275914C CN 1275914 C CN1275914 C CN 1275914C CN 200410015778 CN200410015778 CN 200410015778 CN 200410015778 A CN200410015778 A CN 200410015778A CN 1275914 C CN1275914 C CN 1275914C
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- reactor
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- chlorine
- still
- temperature
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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 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- 238000007872 degassing Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 230000004907 flux Effects 0.000 claims abstract description 11
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 44
- 230000003287 optical effect Effects 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 238000004458 analytical method Methods 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000008676 import Effects 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 abstract 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 abstract 1
- 239000003507 refrigerant Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 8
- 230000009466 transformation Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of difluoro-chloroethane and production equipment thereof. The invention aims to solve the problems that difluoroethane and chlorine gas are used for producing difluoromonochloroethane through a kettle type multi-stage reaction, the conversion rate of difluoroethane, the selectivity and the purity of difluoromonochloroethane are improved, and the generation of high chloride is reduced. The technical scheme for solving the problem is as follows: the device is provided with a reaction kettle, the top of which is provided with a feeding pipe and a discharging pipe, and is characterized in that the diameter of the reaction kettle is larger, a plurality of glass tubes are vertically fixed on the top of the reaction kettle through fasteners, and the glass tubes are internally provided with lamp tubes; the discharge pipe is connected with a mixer through an elbow, and the outlet of the mixer is connected with the next-stage reaction kettle. The preparation method comprises mixing difluoroethane and chlorine in proportion, feeding into a first-stage photochemical reactor, a second-stage photochemical reactor and a third-stage photochemical reactor, adjusting luminous flux to make the sample have high-boiling-point substance peaks with different peak heights on a chromatogram, and then performing acid removal, alkali washing, compression, degassing, rectification and drying treatment. The invention is suitable for the refrigerant production industry.
Description
Technical field
The present invention relates to a kind of preparation method of producing the difluoro monochlorethane, particularly a kind of method of utilizing C2H4F2 C2H4F2 under action of ultraviolet light, to give birth to the difluoro monochlorethane with chlorine generation optical chlorinating reaction.
Background technology
Routine utilize C2H4F2 C2H4F2 under action of ultraviolet light and the chlorine generation optical chlorinating reaction method of producing the difluoro monochlorethane have: 1, light source is gone into illumination from the reactor outside the outer photochmeical reaction method the reactor, require the light transmission of reactor good like this, usually with glass and silica glass manufacturing, therefore, conversion unit is all less, in use damages easily, simultaneously in reaction process, chlorine and some products make reactor wall form one deck Coloured film, influence the amount of being shining into of light; 2, in tubular type or the tower interior actinic reactor light source is housed, as shown in Figure 1, by reactor 1 ', fastening piece 2 ', Glass tubing 3 ' and fluorescent tube 4 ' form, and tubular type or tower reactor diameter are less and highly very big, represent with L/D with length-to-diameter ratio, can reach 10-20, and material ethylene dichloride and chlorine add reactor from the bottom, product is overflowed from the top.Because mixture adds from the bottom, material has only top-down motion in reactor, do not have or seldom have level to transverse movement, the homogeneity of storeroom is relatively poor, in case regional area chlorine is excessive, will produce perchloride, in order to reduce the generation of perchloride, often adopt low-conversion in the operation and try to achieve the method for higher yield, low and tubular type of transformation efficiency or tower reactor optical throughput are difficult to regulation and control like this.
Therefore the above-mentioned background technology exists outer photochmeical reaction method to be subjected to the influence of translucent material, and incompatibility is produced greatly; And tubular type or tower in the photochmeical reaction method exist transformation efficiency and selectivity low, defective such as optical throughput is wayward.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of method of producing the difluoro monochlorethane through still formula reaction of high order with C2H4F2 C2H4F2 and chlorine is provided, improves the transformation efficiency of C2H4F2 C2H4F2, the selectivity and the purity of difluoro monochlorethane, reduce the generation of perchloride.
Solution of the present invention is: adopt C2H4F2 C2H4F2 and chlorine under action of ultraviolet light, optical chlorinating reaction takes place, adopt still formula staged reactor, the chlorine classification adds, and the disposable input of C2H4F2 C2H4F2 reaches its purpose thereby separate drying treatment through deacidification at last.Therefore, the inventive method comprises:
A kind of production unit of producing the difluoro monochlorethane has reactor, and the top is provided with feed-pipe and discharge nozzle, it is characterized in that the diameter of reactor is bigger, vertically fixes some Glass tubings at the top of reactor by fastening piece, and Glass tubing is built-in with fluorescent tube; Discharge nozzle connects mixing tank by elbow, and the outlet of mixing tank connects the next stage reactor.
It is cylindric that reactor is, the circular setting of described Glass tubing and fluorescent tube.Fluorescent tube is ultraviolet lamp or fluorescent lamp.
Filling can strengthen mixed object in the described mixing tank.Object can be fill out circle, silk screen, strand sheet any.
A kind of preparation method of difluoro monochlorethane is characterized in that this method comprises:
1) with C2H4F2 C2H4F2 and chlorine by weight 1: 0.8-0.9 mixes in the back adding one-level actinic reactor, and the temperature of reactor is controlled at 45-55 ℃, and reaction time is 40-80 second; Regulating optical throughput makes sample the high boiling material peak of 0-2mm peak height occur on stratographic analysis figure;
2) material with above-mentioned A reactor imports in the second order reaction still through pipe connecting, adds the 10-20% of A reactor amount of chlorine, and the temperature of reactor is controlled at 45-55 ℃, and reaction time is 40-80 second; Regulating optical throughput makes sample the high boiling material peak of 2-4mm peak height occur on stratographic analysis figure;
3) material with above-mentioned second reactor imports in the third order reaction still through pipe connecting, adds the 5-10% of A reactor amount of chlorine, and the temperature of reactor is controlled at 45-55 ℃, and reaction time is 40-80 second; Regulating optical throughput makes sample the high boiling material peak of 2-6mm peak height occur on stratographic analysis figure;
4) separating treatment:
A, removal HCL: the material in the third order reaction still is absorbed HCL, water spray flux 4-6m through the graphite absorption tower
3/ hr makes content≤10% of HCL;
B, alkali cleaning: will carry out alkali cleaning through the material after the graphite absorption tower absorbs, with the NaOH of 15 weight % concentration, spray flux 4-5m
3/ hr removes remaining CL
2And HCL, enter air reservoir;
C, compression: enter Fen Youta after the compressed tower of the material of air reservoir is compressed into liquid phase, enter medial launder after the oil removing;
D, the degassing: degassing tower pressure 0.3-0.6Mpa, tower still temperature is 40-60 ℃, sloughs low-boiling-point substances such as unreacted C2H4F2 C2H4F2;
E, rectifying: from the difluoro monochlorethane of overhead collection purity 〉=99.9%, 30-40 ℃ of still temperature, pressure is 0.25-0.5Mpa, discharges high boiling material from the tower still;
F, drying treatment: input moisture eliminator adsorption dry to water content equals 20ppm after 0.2-0.3Mpa pressure lower compression.
Described material can directly enter separating treatment without the third order reaction still behind the second order reaction still.
Described degassing tower and rectifying tower are the corrugated wire gauze packing tower.
But but both also second reactor of three reactor of above-mentioned still formula staged reactor.And described degassing tower and rectifying tower are the corrugated wire gauze packing tower.
The inventive method C2H4F2 C2H4F2 transformation efficiency can be up to 87%, and difluoro monochlorethane selectivity is greater than 99%, and object difluoro monochlorethane purity 90% (V/V) that obtain, unit consumption is low, and optical throughput control is convenient, can satisfy big requirement of producing.
Description of drawings:
Fig. 1 is prior art constructions figure of the present invention.
Fig. 2 is a structure iron of the present invention.
Fig. 3 is the vertical view of reactor among the present invention.
Embodiment
Present embodiment has reactor 1, and the top is provided with feed-pipe 6 and discharge nozzle 7, and it is cylindric that reactor is, its diameter is bigger, some Glass tubings 3 are vertically fixed by fastening piece 2 in top at reactor, and Glass tubing is built-in with fluorescent tube 4, the circular setting of Glass tubing and fluorescent tube.Discharge nozzle 7 connects mixing tank 5 by elbow 8, and the outlet of mixing tank connects the next stage reactor.
In order to improve the homogeneity of material, make its thorough mixing, reduce the generation of perchloride, filling can strengthen mixed object 9 in mixing tank 5, as fills out circle, silk screen, strand sheet etc.
Preparation method of the present invention describes in detail with following each embodiment.
Embodiment 1:
Present embodiment still formula staged reactor adopts three reactor.Its technical process is:
A, with C2H4F2 C2H4F2 and chlorine by weight 85: 75Kg mixes in the back adding one-level actinic reactor, and the temperature of reactor is controlled at 55 ℃, and reaction time is 40 seconds; Regulating optical throughput makes sample the high boiling material peak of 0-2mm peak height occur on stratographic analysis figure;
In B, the material process pipe connecting importing second order reaction still with above-mentioned A reactor, add chlorine 10Kg, the temperature of reactor is controlled at 55 ℃, and reaction time is 40 seconds; Regulating optical throughput makes sample the high boiling material peak of 2-4mm peak height occur on stratographic analysis figure;
In C, the material process pipe connecting importing third order reaction still with above-mentioned second reactor, add chlorine 5Kg, the temperature of reactor is controlled at 55 ℃, and reaction time is 40 seconds; Regulating optical throughput makes sample the high boiling material peak of 2-6mm peak height occur on stratographic analysis figure;
D, separating treatment:
A removes HCL: the material in the third order reaction still is absorbed HCL, water spray flux 6m through the graphite absorption tower
3/ hr;
B alkali cleaning: will carry out alkali cleaning through the material after the graphite absorption tower absorbs, with the NaOH of 15 weight % concentration, spray flux 5m
3/ hr removes remaining CL
2And HCL, enter air reservoir;
C compresses: enter Fen Youta after the compressed tower of the material of air reservoir is compressed into liquid phase, enter medial launder after the oil removing;
The d degassing: degassing tower pressure 0.6Mpa, tower still temperature is 60 ℃;
E rectifying: 40 ℃ of still temperature, pressure are 0.31Mpa,
The f drying treatment: the adsorption dry of input moisture eliminator is to moisture 20ppm after 0.3Mpa pressure lower compression.
Embodiment 2:
Present embodiment still formula staged reactor adopts second reactor.Its technical process is:
A, with C2H4F2 C2H4F2 and chlorine by weight 65: 60Kg mixes in the back adding one-level actinic reactor, and the temperature of reactor is controlled at 50 ℃, and reaction time is 50 seconds; Regulating optical throughput makes sample the high boiling material peak of 0-2mm peak height occur on stratographic analysis figure;
In B, the material process pipe connecting importing second order reaction still with above-mentioned A reactor, add chlorine 10Kg, the temperature of reactor is controlled at 50 ℃, and reaction time is 50 seconds; Regulating optical throughput makes the chromatogram of sample the 4mm peak occur;
C, separating treatment:
A removes HCL: the material in the third order reaction still is absorbed HCL, water spray flux 5m through the graphite absorption tower
3/ hr;
B alkali cleaning: will carry out alkali cleaning through the material after the graphite absorption tower absorbs, with the NaOH of 15 weight % concentration, spray flux 4.5m
3/ hr removes remaining CL
2And HCL, enter air reservoir;
C compresses: enter Fen Youta after the compressed tower of the material of air reservoir is compressed into liquid phase, enter medial launder after the oil removing;
The d degassing: degassing tower pressure 0.5Mpa, tower still temperature is 50 ℃;
E rectifying: 35 ℃ of still temperature, pressure are 0.28Mpa,
The f drying treatment: the adsorption dry of input moisture eliminator is to moisture 20ppm after 0.2Mpa pressure lower compression.
Embodiment 3:
Present embodiment still formula staged reactor adopts three reactor.Its technical process is:
A, with C2H4F2 C2H4F2 and chlorine by weight 60: 50Kg mixes in the back adding one-level actinic reactor, and the temperature of reactor is controlled at 45 ℃, and reaction time is 60 seconds; Regulating optical throughput makes sample the high boiling material peak of 0-2mm peak height occur on stratographic analysis figure;
In B, the material process pipe connecting importing second order reaction still with above-mentioned A reactor, add chlorine 10Kg, the temperature of reactor is controlled at 45 ℃, and reaction time is 60 seconds; Regulating optical throughput makes sample the high boiling material peak of 2-4mm peak height occur on stratographic analysis figure;
In C, the material process pipe connecting importing third order reaction still with above-mentioned second reactor, add chlorine 4Kg, the temperature of reactor is controlled at 45 ℃, and reaction time is 60 seconds; Regulating optical throughput makes sample the high boiling material peak of 2-6mm peak height occur on stratographic analysis figure;
D, separating treatment:
A removes HCL: the material in the third order reaction still is absorbed HCL, water spray flux 4m through the graphite absorption tower
3/ hr;
B alkali cleaning: will carry out alkali cleaning through the material after the graphite absorption tower absorbs, with the NaOH of 15 weight % concentration, spray flux 4m
3/ hr removes remaining CL
2And HCL, enter air reservoir;
C compression:, enter medial launder after the oil removing with being compressed into liquid phase behind the compressed tower of the material of air reservoir and entering Fen Youta;
The d degassing: degassing tower pressure 0.48Mpa, tower still temperature is 45 ℃;
E rectifying: 38 ℃ of still temperature, pressure are 0.3Mpa,
The f drying treatment: input moisture eliminator adsorption dry to water content equals 20ppm after 0.25Mpa pressure lower compression.
Claims (3)
1, a kind of preparation method of difluoro monochlorethane is characterized in that this method comprises:
1) with C2H4F2 C2H4F2 and chlorine by weight 1: 0.8-0.9 mixes in the back adding one-level actinic reactor, and the temperature of reactor is controlled at 45-55 ℃, and reaction time is 40-80 second; Regulating optical throughput makes sample the high boiling material peak of 0-2mm peak height occur on stratographic analysis figure;
2) material with above-mentioned A reactor imports in the second order reaction still through pipe connecting, adds the 10-20% of A reactor amount of chlorine, and the temperature of reactor is controlled at 45-55 ℃, and reaction time is 40-80 second; Regulating optical throughput makes sample the high boiling material peak of 2-4mm peak height occur on stratographic analysis figure;
3) separating treatment:
A, removal HCL: the material in the third order reaction still is absorbed HCL, water spray flux 4-6m through the graphite absorption tower
3/ hr makes content≤10% of HCL;
B, alkali cleaning: will carry out alkali cleaning through the material after the graphite absorption tower absorbs, with the NaOH of 15 weight % concentration, spray flux 4-5m
3/ hr removes remaining CL
2And HCL, enter air reservoir;
C, compression: enter Fen Youta after the compressed tower of the material of air reservoir is compressed into liquid phase, enter medial launder after the oil removing;
D, the degassing: degassing tower pressure 0.3-0.6Mpa, tower still temperature is 40-60 ℃, sloughs unreacted C2H4F2 C2H4F2 low-boiling-point substance;
E, rectifying: from the difluoro monochlorethane of overhead collection purity 〉=99.9%, 30-40 ℃ of still temperature, pressure is 0.25-0.5Mpa, discharges high boiling material from the tower still;
F, drying treatment: input moisture eliminator adsorption dry to water content equals 20ppm after 0.2-0.3Mpa pressure lower compression.
2, the method for producing the difluoro monochlorethane according to claim 1, it is characterized in that: will be from step 2) material of second reactor imports the third order reaction still through pipe connecting, the 5-10% that adds the A reactor amount of chlorine, the temperature of reactor is controlled at 45-55 ℃, and reaction time is 40-80 second; Regulating optical throughput makes sample the high boiling material peak of 2-6mm peak height occur on stratographic analysis figure.
3, the method for producing the difluoro monochlorethane according to claim 1 is characterized in that: described degassing tower and rectifying tower are the corrugated wire gauze packing tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410015778 CN1275914C (en) | 2004-01-09 | 2004-01-09 | Preparation method of difluoro-chloroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410015778 CN1275914C (en) | 2004-01-09 | 2004-01-09 | Preparation method of difluoro-chloroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1556083A CN1556083A (en) | 2004-12-22 |
| CN1275914C true CN1275914C (en) | 2006-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410015778 Expired - Lifetime CN1275914C (en) | 2004-01-09 | 2004-01-09 | Preparation method of difluoro-chloroethane |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101822B (en) * | 2009-12-16 | 2013-08-28 | 中化蓝天集团有限公司 | Liquid phase purification method for 1,1- difluoroethane |
| CN102101823B (en) * | 2009-12-16 | 2013-08-28 | 中化蓝天集团有限公司 | Gas phase purification method for 1,1-difluoroethane |
| CN101948367A (en) * | 2010-09-06 | 2011-01-19 | 浙江巍华化工有限公司 | Preparation method taking 1,1,1-trifluoroethane as raw material |
| 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 |
| CN103012053A (en) * | 2012-12-18 | 2013-04-03 | 泰兴市梅兰化工有限公司 | Method for preparing ultra-high purity difluoromono-chloroethane |
| CN106431819A (en) * | 2016-09-05 | 2017-02-22 | 山东华安新材料有限公司 | Preparation method of difluoro-monochloroethane |
| CN107382661B (en) * | 2017-06-09 | 2020-07-10 | 浙江三美化工股份有限公司 | Recovery method of difluoro-chloroethane |
| CN110963884B (en) * | 2019-12-16 | 2022-05-06 | 上海华谊三爱富新材料有限公司 | Preparation method of 1,1,1, 2-tetrachloro-2, 2-difluoroethane |
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- 2004-01-09 CN CN 200410015778 patent/CN1275914C/en not_active Expired - Lifetime
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