CN103304369B - Method for converting carbon tetrachloride to ethylene tetrachloride - Google Patents
Method for converting carbon tetrachloride to ethylene tetrachloride Download PDFInfo
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- CN103304369B CN103304369B CN201310239672.3A CN201310239672A CN103304369B CN 103304369 B CN103304369 B CN 103304369B CN 201310239672 A CN201310239672 A CN 201310239672A CN 103304369 B CN103304369 B CN 103304369B
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- zellon
- tetracol phenixin
- chlorine
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- reaktionsofen
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Abstract
The invention belongs to the technical field of ethylene tetrachloride preparation and in particular relates to a method for converting carbon tetrachloride to ethylene tetrachloride. The method is characterized in that carbon tetrachloride is subjected to non-catalytic pyrolysis to generate ethylene tetrachloride in the presence of a hydrogen, oxygen and hydrogen chloride combined gas and excessive chlorine. The method has the beneficial effects that new carbon tetrachloride is not generated in the reaction; the heat released in the reaction between hydrogen and chlorine is used in conversion from carbon tetrachloride to ethylene tetrachloride; and the conversion rate is 94-95%.
Description
Technical field
The invention belongs to zellon preparing technical field, be specifically related to a kind of method that tetracol phenixin is converted into zellon.
Background technology
Tetracol phenixin is a kind of halon damaged the ozone layer, because of but a kind of product undesirably obtained.The main application of tetracol phenixin was once used as raw material to produce environmentally harmful perhalide freon, but because the environmentally harmful effect of freon is proved, so the demand of tetracol phenixin is just gradually reducing and is being subject to the strict control of world and China environmental administration.On the other hand, as solvent and the raw material producing other Chemicals, zellon environmental sound, thus expects that the demand of zellon will keep and constantly increase.
Under the raw material mentioned in Chinese patent CN101348414 adopts any one and the chlorine existent condition in monochloro methane, methane and Sweet natural gas, tetracol phenixin generates the method for zellon through non-catalytic pyrolysis, but containing monochloro methane, methane in the raw material of the method, easy and excessive chlorine reacts and regenerates tetracol phenixin, reduce the inversion quantity of raw material tetracol phenixin, due to the gas that Sweet natural gas is also based on methane, the reduction of raw material tetracol phenixin inversion quantity can be caused equally.
Disclose a kind of monochloro methane or Sweet natural gas and excessive chlorine and methane chloride of adopting in Chinese patent CN102816046 and react the method generating zellon, due in raw material also containing monochloro methane or Sweet natural gas or methane chloride (monochloro methane, methylene dichloride, trichloromethane), the reduction of raw material tetracol phenixin inversion quantity can be caused equally.
Summary of the invention
The object of this invention is to provide a kind of method that tetracol phenixin is converted into zellon, in the method, tetracol phenixin generates zellon through non-catalytic pyrolysis, and its transformation efficiency is high and generate without new tetracol phenixin.
Tetracol phenixin of the present invention is converted into the method for zellon, is that tetracol phenixin generates zellon through non-catalytic pyrolysis under the composition gas and excessive chlorine existent condition of hydrogen and oxygen.
Mol ratio 1:2.01 ~ 3.22:0.1 ~ 0.25 of described hydrogen, tetracol phenixin, oxygen.
Described tetracol phenixin is converted into the method for zellon, comprises the following steps:
(1) first the composition gas of hydrogen and oxygen and excessive chlorine are introduced bottom Reaktionsofen and burn, after making Reaktionsofen temperature keep certain temperature and pressure, then introduce overheated tetracol phenixin steam and obtain zellon gas mixture containing tetracol phenixin, chlorine, zellon and hydrogenchloride;
Described temperature of reaction is 560 DEG C ~ 650 DEG C, preferably 545 DEG C ~ 638 DEG C, and described reaction pressure is 0.1 ~ 1.0kg/cm
2, preferably 0.2 ~ 0.8kg/cm
2.
Described overheated tetracol phenixin steam adopts spray regime to spray into Reaktionsofen, and jet velocity is at 40 ~ 60m/s, and the temperature of overheated tetracol phenixin steam is 70 ~ 100 DEG C.
(2) zellon gas mixture is cooled in quenching column, zellon, hydrogenchloride and heavy constituent are separated from mixture, in zellon gas mixture, unreacted tetracol phenixin is separated through resolving with chlorine, tetracol phenixin after separation gets back to Reaktionsofen as raw material, and the chlorine after separation returns chlorine treatment system;
(3) zellon, hydrogenchloride and heavy constituent are separated the zellon crude product obtained through multi-stage condensing, obtain zellon finally by lightness-removing column and rectifying tower.
In the present invention, vaporization chlorine is introduced with certain speed, in the zellon gas mixture gas produced to make Reaktionsofen, the volume content of unreacted chlorine is 1.0 ~ 5.0%, be preferably 2.0 ~ 4.0%, for ensureing that hydrogen complete reaction needs excessive chlorine, the excessive tetracol phenixin that can not cause too much of chlorine is converted into the reduction of the transformation efficiency of zellon, but needs the add-on of raw material chlorine to be reduced according to combustion flame situation, is conducive to economizing on resources.In the present invention, a certain proportion of oxygen and hydrogen reach the object controlling temperature of reaction and speed.
In the present invention, tetracol phenixin comprises two portions, and one is the new tetracol phenixin added, and two is unreacted tetracol phenixin in zellon gas mixture, and the tetracol phenixin after being namely separated with chlorine is got back in Reaktionsofen as raw material, has saved tetracol phenixin.
Compared with prior art, beneficial effect of the present invention is as follows:
The present invention is under hydrogen and oxygen composition gas and excessive chlorine existent condition, tetracol phenixin generates zellon through non-catalytic pyrolysis, a certain proportion of oxygen and hydrogen reach the object controlling temperature of reaction and speed, do not generate new tetracol phenixin in this reaction.The present invention provides tetracol phenixin to transform the heat of zellon by hydrogen and chlorine reaction heat release, and transformation efficiency reaches 94% ~ 95%.
Accompanying drawing explanation
Fig. 1 is Reaktionsofen structural representation of the present invention;
In figure: 1, overheated tetracol phenixin steam; 2, zellon gas mixture; 3, hydrogen and oxygen composition gas; 4, the chlorine of vaporization; I, reaction zone; II, combustion zone.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
As shown in Figure 1, the method that described tetracol phenixin is converted into zellon is as follows:
(1) first hydrogen and oxygen composition gas 3 and excessive vaporization chlorine 4 are introduced Reaktionsofen base burning district II to burn, after making Reaktionsofen temperature keep certain temperature and pressure, then introduce the obtained zellon gas mixture 2 containing tetracol phenixin, chlorine, zellon and hydrogenchloride of overheated tetracol phenixin steam 1;
Overheated tetracol phenixin steam adopts spray regime to spray into Reaktionsofen reaction zone I generation pyrolytic reaction, and Reaktionsofen top sparger jet velocity is at 49m/s, and the temperature of overheated tetracol phenixin steam is 74 DEG C.
Introduce the tetracol phenixin flow of reaction zone I depend on the amount of chlorine of introducing and generate the situation of hydrogenchloride burning, being vaporized before entering Reaktionsofen by tetracol phenixin is conducive to reaction and carries out.
(2) zellon gas mixture is cooled in quenching column, zellon, hydrogenchloride and heavy constituent are separated from mixture, unreacted tetracol phenixin and chlorine are after resolving and being separated, and tetracol phenixin gets back to Reaktionsofen, and the chlorine after separation returns chlorine treatment system;
(3) zellon, hydrogenchloride and heavy constituent are separated the zellon crude product obtained through multi-stage condensing, obtain zellon finally by lightness-removing column and rectifying tower.
In the present invention:
The reaction formula that tetracol phenixin pyrolysis generates zellon is as follows:
This reaction is endothermic equilibrium reaction, and namely I high-temperature low-pressure in reaction zone is conducive to the generation of zellon.
Be thermo-negative reaction owing to reacting 1, heat thus must be provided to maintain temperature of reaction, when hydrogen and chlorine combustion reactions, a large amount of heats can be released.Therefore hydrogen and chlorine can be used as raw material and are fed in Reaktionsofen, for tetracol phenixin pyrolysis provides heat.In hydrogen, add a certain proportion of oxygen reach the object controlling temperature of reaction and speed.
When using hydrogen as raw material, the reaction formula of combustion reactions is as follows:
Cl
2+ △ (photon) → 2Cl
˙(1)
Cl
˙+H
2→HCl+H
˙（2）
H
˙+Cl
2→HCl+Cl
˙（3）
Cl
˙+H
2→HCl+H
˙（4）
Total reaction is:
H
2+Cl
2=2HCl+184.096KJ （5）
Pilot run is as follows:
Charging, kg/h
Hydrogen: 4.45kg
Oxygen: 0.5kg
Chlorine: 82.9kg
Tetracol phenixin: 454kg
Hydrogen/chlorine/tetracol phenixin/oxygen (mol ratio) 1:1.05:2.65:0.11
Reaction conditions:
Temperature, 545 DEG C
Pressure, 0.2kg/cm
2(gauge pressure)
Reaction product:
The zellon generated, 232kg/h;
Change into the tetracol phenixin of zellon, 430kg/h;
Excess chlorine tolerance, the molecular fraction of chlorine in Reaktionsofen Exhaust Gas: 0.05
Tetracol phenixin changes into the transformation efficiency (mol ratio) of zellon: 94.7%
Perchlorobenzene/zellon (weight ratio): < 0.03
As can be seen from the above embodiments, tetracol phenixin pyrolytic reaction heat is provided by combustion reactions under using the composition gas of hydrogen and oxygen and excessive chlorine existent condition, prior art of comparing the transformation efficiency that tetracol phenixin is converted into zellon improves greatly, and compare monochloro methane and excessive chlorine react and regenerate a large amount of tetracol phenixin and more have transformation efficiency and benefit.
Embodiment 2
Step and reaction process are as embodiment 1, and overheated tetracol phenixin steam adopts spray regime to spray into Reaktionsofen reaction zone I generation pyrolytic reaction, and Reaktionsofen top sparger jet velocity is at 43m/s, and the temperature of overheated tetracol phenixin steam is 85 DEG C.
Pilot run is as follows:
Charging, kg/h
Hydrogen: 4.5kg
Oxygen: 0.5kg
Chlorine: 83.9kg
Tetracol phenixin: 363.8kg
Hydrogen/chlorine/tetracol phenixin/oxygen (mol ratio) 1:1.05:2.1:0.11
Reaction conditions:
Temperature, 607 DEG C
Pressure, 0.46kg/cm
2(gauge pressure)
Reaction product:
The zellon generated, 186kg/h;
Change into the tetracol phenixin of zellon, 344.9kg/h;
Excess chlorine tolerance, the molecular fraction of chlorine in Reaktionsofen Exhaust Gas: 0.05
Tetracol phenixin changes into the transformation efficiency (mol ratio) of zellon: 94.8%
Perchlorobenzene/zellon (weight ratio): < 0.03
Embodiment 3
Step and reaction process are as embodiment 1, and overheated tetracol phenixin steam adopts spray regime to spray into Reaktionsofen reaction zone I generation pyrolytic reaction, and Reaktionsofen top sparger jet velocity is at 54m/s, and the temperature of overheated tetracol phenixin steam is 96 DEG C.
Pilot run is as follows:
Charging, kg/h
Hydrogen: 4.5kg
Oxygen: 0.9kg
Chlorine: 83.9kg
Tetracol phenixin: 502.4kg
Hydrogen/chlorine/tetracol phenixin/oxygen (mol ratio) 1:1.05:2.9:0.2
Reaction conditions:
Temperature, 618 DEG C
Pressure, 0.76kg/cm
2(gauge pressure)
Reaction product:
The zellon generated, 256.4kg/h;
Change into the tetracol phenixin of zellon, 475.8kg/h;
Excess chlorine tolerance, the molecular fraction of chlorine in Reaktionsofen Exhaust Gas: 0.04
Tetracol phenixin changes into the transformation efficiency (mol ratio) of zellon: 94.7%
Perchlorobenzene/zellon (weight ratio): < 0.03
Embodiment 4
Step and reaction process are as embodiment 1, and overheated tetracol phenixin steam adopts spray regime to spray into Reaktionsofen reaction zone I generation pyrolytic reaction, and Reaktionsofen top sparger jet velocity is at 58m/s, and the temperature of overheated tetracol phenixin steam is 96 DEG C.
Pilot run is as follows:
Charging, kg/h
Hydrogen: 4.8kg
Oxygen: 0.9kg
Chlorine: 89.5kg
Tetracol phenixin: 587.7kg
Hydrogen/chlorine/tetracol phenixin/oxygen (mol ratio) 1:1.05:3.18:0.2
Reaction conditions:
Temperature, 638 DEG C
Pressure, 0.9kg/cm
2(gauge pressure)
Reaction product:
The zellon generated, 299.3kg/h;
Change into the tetracol phenixin of zellon, 555.3kg/h;
Excess chlorine tolerance, the molecular fraction of chlorine in Reaktionsofen Exhaust Gas: 0.04
Tetracol phenixin changes into the transformation efficiency (mol ratio) of zellon: 94.5%
Perchlorobenzene/zellon (weight ratio): < 0.03.
Claims (8)
1. tetracol phenixin is converted into a method for zellon, it is characterized in that: under the composition gas and excessive chlorine existent condition of hydrogen and oxygen, tetracol phenixin generates zellon through non-catalytic pyrolysis; Comprise the following steps:
(1) first the composition gas of hydrogen and oxygen and excessive chlorine are introduced bottom Reaktionsofen and burn, after making Reaktionsofen temperature keep certain temperature and pressure, then introduce overheated tetracol phenixin steam and obtain zellon gas mixture containing tetracol phenixin, chlorine, zellon and hydrogenchloride; The mol ratio 1: 2.01 ~ 3.22: 0.1 ~ 0.25 of hydrogen, tetracol phenixin, oxygen;
(2) zellon gas mixture is cooled in quenching column, from mixture, be separated zellon, hydrogenchloride and heavy constituent;
(3) zellon, hydrogenchloride and heavy constituent are separated the zellon crude product obtained through multi-stage condensing; The zellon crude product obtained, obtains zellon finally by lightness-removing column and rectifying tower.
2. tetracol phenixin according to claim 1 is converted into the method for zellon, it is characterized in that: temperature of reaction is 520 DEG C ~ 650 DEG C.
3. tetracol phenixin according to claim 2 is converted into the method for zellon, it is characterized in that: temperature of reaction is 545 DEG C ~ 638 DEG C.
4. tetracol phenixin according to claim 1 is converted into the method for zellon, it is characterized in that: reaction pressure is 0.1 ~ 1.0kg/cm
2.
5. tetracol phenixin according to claim 4 is converted into the method for zellon, it is characterized in that: reaction pressure is 0.2 ~ 0.8kg/cm
2.
6. tetracol phenixin according to claim 1 is converted into the method for zellon, it is characterized in that: in step (2) zellon gas mixture, unreacted tetracol phenixin is separated through resolving with chlorine, tetracol phenixin after separation gets back to Reaktionsofen as raw material, and the chlorine after separation returns chlorine treatment system.
7. tetracol phenixin according to claim 1 is converted into the method for zellon, it is characterized in that: overheated tetracol phenixin steam adopts spray regime to spray into Reaktionsofen, and jet velocity is at 40 ~ 60m/s, and the temperature of overheated tetracol phenixin steam is 70 ~ 100 DEG C.
8. tetracol phenixin according to claim 1 is converted into the method for zellon, it is characterized in that: in the zellon gas mixture that Reaktionsofen is discharged, the volume content of unreacted chlorine is 1.0 ~ 5.0%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310239672.3A CN103304369B (en) | 2013-06-17 | 2013-06-17 | Method for converting carbon tetrachloride to ethylene tetrachloride |
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|---|---|---|---|
| CN201310239672.3A CN103304369B (en) | 2013-06-17 | 2013-06-17 | Method for converting carbon tetrachloride to ethylene tetrachloride |
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| CN103304369B true CN103304369B (en) | 2015-02-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2850218A1 (en) * | 2012-07-05 | 2015-03-25 | Siemens Aktiengesellschaft | Method for recovering an electropositive metal from a metal carbonate |
| CN109627142B (en) * | 2018-12-12 | 2021-10-22 | 山东东岳氟硅材料有限公司 | Treatment method and treatment system for byproduct tail gas in tetrachloroethylene production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5315050A (en) * | 1993-02-11 | 1994-05-24 | Vulcan Materials Company | Manufacture of perchloroethylene from carbon tetrachloride in the presence of hydrogen |
| CN101143328A (en) * | 2007-10-26 | 2008-03-19 | 江苏工业学院 | Catalyst used for preparing tetrachloroethylene and its preparation method and use |
| CN101348414A (en) * | 2007-07-20 | 2009-01-21 | 文乃建化学工程公司 | Non-catalytic method of carbon tetrachloride to perchloroethylene |
| CN102816046A (en) * | 2012-08-13 | 2012-12-12 | 自贡鸿鹤化工股份有限公司 | Industrial preparation method for tetrachloroethylene |
-
2013
- 2013-06-17 CN CN201310239672.3A patent/CN103304369B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5315050A (en) * | 1993-02-11 | 1994-05-24 | Vulcan Materials Company | Manufacture of perchloroethylene from carbon tetrachloride in the presence of hydrogen |
| CN101348414A (en) * | 2007-07-20 | 2009-01-21 | 文乃建化学工程公司 | Non-catalytic method of carbon tetrachloride to perchloroethylene |
| CN101143328A (en) * | 2007-10-26 | 2008-03-19 | 江苏工业学院 | Catalyst used for preparing tetrachloroethylene and its preparation method and use |
| CN102816046A (en) * | 2012-08-13 | 2012-12-12 | 自贡鸿鹤化工股份有限公司 | Industrial preparation method for tetrachloroethylene |
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