CN105384598B - A kind of method of thing Isolating chlorinated from perchloride - Google Patents
A kind of method of thing Isolating chlorinated from perchloride Download PDFInfo
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- CN105384598B CN105384598B CN201510732306.0A CN201510732306A CN105384598B CN 105384598 B CN105384598 B CN 105384598B CN 201510732306 A CN201510732306 A CN 201510732306A CN 105384598 B CN105384598 B CN 105384598B
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- perchloride
- tetrachloro
- ethylene
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Abstract
This patent application discloses a kind of method of thing Isolating chlorinated from perchloride, mainly include the following steps that：（1）Perchloride waste material is added in evaporator, by the liquid chloride rectifying evaporated, carbon tetrachloride and tetrachloro-ethylene is isolated；（2）Raffinate after being evaporated in step 1 is transferred to distillation kettle, adds and boiling is heated to after water, while being passed through hot nitrogen；（3）Carbon trichloride after being distilled in step 2 is passed through the dissolving of chloroform dissolving tank；（4）Heat filtering is carried out to step 3, and filtrate is subjected to crystallisation by cooling, is centrifuged, crystal is dried and carbon trichloride product is obtained；（5）Kettle liquid in step 2 adds tetrachloro-ethylene and dissolved by heating, and through heat filtering, filtrate crystallisation by cooling, and centrifuges and obtains hexachloro-benzene crude product.The present invention can separate the hexachloro-benzene in perchloride organic hazardous waste, additionally be able to improve the purity for the carbon trichloride product isolated, so as to improve the carbon trichloride product quality isolated.
Description
Technical field
A kind of organic chemistry filed of the present invention, and in particular to method that chloride is isolated from perchloride.
Background technology
During production methane chloride and tetrachloro-ethylene, after chlorination reaction and distilation, it can produce certain
The perchloride organic hazardous waste of amount.After testing, perchloride organic hazardous waste is a kind of having containing various chlorides
The mixture of machine compound, perchloride organic hazardous waste contains chloroform, carbon tetrachloride 2-5%, tetrachloro-ethylene 40-
45%th, carbon trichloride 40-45%, hexachloro-benzene 5-8% and tar, carbon black, mechanical admixture 2-5%.
Patent publication No. " reclaims for CN103787823A's from the rectification residue of methane chloride or/and tetrachloro-ethylene
In the patent of the method for organic chloride ", a kind of method for handling rectification residue is disclosed, this method can be residual from rectifying
Receipts chloroform, carbon tetrachloride and carbon trichloride are isolated in slag.The patent is mainly handled by following steps：
(1) rectification residue of methane chloride or/and tetrachloro-ethylene is passed through in evaporator, is 0.01- in vacuum
0.1MPa, temperature are cold by the volatile component after evaporation for insulation 30 minutes under the conditions of 140-150 DEG C or untill no liquid is evaporated
Congeal into and enter after liquid in trap, obtain residue in light component mixed liquor, evaporator and be transferred to while hot in sublimator；The methane
Chloride rectification residue is by chloroform, carbon tetrachloride, tetrachloro-ethylene, pentachloroethane, carbon trichloride and carbon slag and inorganic matter slag
It is respectively 5.38%, 28.66%, 20.05%, 14.52%, 26.23% and 5.16% in mass ratio；
(2) the light component mixed liquor of 50-70% volume fractions in trap is squeezed into tetrachloro-ethylene distillation system with pump, point
Separate out chloroform, carbon tetrachloride and tetrachloro-ethylene；Simultaneously with heat-conducting oil heating sublimator to 240-250 DEG C, device of sublimating is opened
Cooling water, carbon trichloride first product is obtained after device cooling of sublimating；
(3) remaining light component mixed liquor in trap is passed through in carbon trichloride refining kettle, and added obtained by step (2)
Carbon trichloride first product, is then incubated to carbon trichloride under the conditions of temperature is 45-50 DEG C and all dissolves, turn lysate after dissolving
Into crystallizing pan, it is incubated under the conditions of temperature is 25 DEG C to carbon trichloride crystallization；Crystal is squeezed into centrifugal filter again, received
Collect filter cake and filtrate, filtration cakes torrefaction obtains carbon trichloride, and filtrate is passed through in evaporator and continued cycling through.
Although above-mentioned patent can be handled perchloride organic hazardous waste, still have it is following not
Foot：1st, hexachloro-benzene can not be separated in perchloride organic hazardous waste, can only be used as castoff burning or discharge, hexachloro-benzene tool
There are acute toxicity, teratogenesis, mutagenicity and carcinogenicity, and poisonous corrosive fume is produced by high thermal decomposition, if directly
Connect the harm burned or discharged to environmental and human health impacts very big；2nd, residue in evaporator is transferred to sublimator while hot,
During distillation, the temperature in distillation kettle is difficult to control to, and the impurity in residue can be also sublimated with carbon trichloride,
This will influence the purity of carbon trichloride after separation.
The content of the invention
It is an object of the invention to provide a kind of method that chloride is isolated from perchloride, the separation method can be by height
Hexachloro-benzene in chloride organic hazardous waste is separated, and additionally is able to improve the purity for the carbon trichloride product isolated,
So as to improve the carbon trichloride product quality isolated.
To reach above-mentioned purpose, base case of the invention is as follows：
A kind of method that chloride is isolated from perchloride, is mainly included the following steps that：
(1) the perchloride waste material produced during production methane chloride and tetrachloro-ethylene is added in evaporator, will
The liquid chloride rectifying evaporated, isolates carbon tetrachloride and tetrachloro-ethylene；
(2) raffinate after being evaporated in step 1 is transferred to distillation kettle, adds and boiling is heated to after water, while hot nitrogen is passed through,
The mass ratio of the raffinate and water is 8：1-5；
(3) carbon trichloride after being distilled in step 2 is passed through the dissolving of chloroform dissolving tank, carbon trichloride and chloroform
Mass ratio be 1：1-10；
(4) heat filtering is carried out to step 3, and filtrate is subjected to crystallisation by cooling, centrifuged, crystal is dried and obtained
Carbon trichloride product；
(5) kettle liquid in step 2 adds tetrachloro-ethylene and dissolved by heating, and the mass ratio of kettle liquid and tetrachloro-ethylene is 1：6-15,
Through heat filtering, filtrate crystallisation by cooling, and centrifuge and obtain hexachloro-benzene crude product；
(6) the hexachloro-benzene crude product of step 5 is recrystallized：Add chloroform to be dissolved by heating, hexachloro-benzene crude product and three
The mass ratio of chloromethanes is 1：3-10, through heat filtering, filtrate carries out crystallisation by cooling, centrifuges, and crystal is dried and six are obtained
Chlorobenzene product.
The advantage of this programme is：
1st, in the present invention, hexachloro-benzene crude product can be isolated in kettle liquid through step 5, after being purified through step 6, chlordene benzaldehyde product
Purity can substantially reach 99.9%.Scheme through the present patent application can be by perchloride organic hazardous waste
Hexachloro-benzene is separated, rather than as castoff burning or discharge, it is to avoid burn or discharge to human body or
The harm of environment, additionally is able to the recycling of the tetrachloro-ethylene solution after hexachloro-benzene is separated, saves resource.
2nd, in step 2, water is additionally added in distillation kettle, the mass ratio of raffinate and water is 8：1-5, distillation kettle in add water it
Afterwards, the temperature in distillation kettle can be made to maintain 100 DEG C or so, during distillation, substantially carbon trichloride can only be distilled
Out, the other impurities in raffinate still can be stayed in raffinate, can thus improve the carbon trichloride purity isolated.Three chloromethanes
Alkane solution can be recycled, and save resource.
3rd, in step 3, in sublimation process, have part vapor and be mixed in carbon trichloride, by the carbon trichloride after distillation
It can be dissolved in by blender or injector with entering receiving slit, carbon trichloride after chloroform mixed dissolution with water vapour
In chloroform, but water can not be dissolved in chloroform, by static layering, by the mixing of chloroform and carbon trichloride
Liquid, which is separated from water, to come, so as to improve the product quality for the carbon trichloride isolated.
Chuck is carried out in prioritization scheme 1, the further optimization to base case, step 1 with 0.3Mpa saturated vapor to add
Heat, evaporating temperature is controlled at 135-145 DEG C, after insulation half an hour, temperature is risen into 150-155 DEG C, evaporated.Inventor passes through
Experiment is found, is incubated at 135-145 DEG C, can be evaporated most carbon tetrachloride and tetrachloro-ethylene, temperature is risen to
150-155 DEG C can all be evaporated carbon tetrachloride and tetrachloro-ethylene.
In prioritization scheme 2, the further optimization to base case, step 2, hot nitrogen uses heat-conducting oil heating, conduction oil
Temperature control is at 260-280 DEG C.In this programme, from the efficiency high of heat-conducting oil heating.
In prioritization scheme 3, the further optimization to base case, prioritization scheme 1, step 2, the hot nitrogen air pressure in distillation kettle
Power is maintained at 0.3-0.5Mpa.In this programme, hot nitrogen has two effects, and first, as the thermal source of sublimation process, the
Two, take the carbon trichloride distilled out out of distillation kettle.The hot nitrogen atmospheric pressure distilled in kettle can be taken out of quickly in above range
Carbon trichloride, and be unlikely to make distillation kettle temperature Du Taigao.
In prioritization scheme 4, the further optimization to any one of base case, prioritization scheme 1-3, step 4, -15 are cooled to
DEG C, and crystallize 1 hour.Inventor has found through experiment, when step 4 is carried out under these conditions, can be by carbon trichloride portion big absolutely
Separate, and separative efficiency is of a relatively high.
In prioritization scheme 5, the further optimization to prioritization scheme 4, step 4, the drying is in 40 DEG C of hot water jackets
Vacuum drying, and vacuum is -0.095Mpa, drying time is 4 hours.Inventor has found that step 4 is under these conditions through experiment
During progress, drying efficiency is high.
In prioritization scheme 6, the further optimization to prioritization scheme 5, step 5, the temperature of heat of solution is 120 DEG C (scope).
The boiling point of tetrachloro-ethylene is 121 DEG C, during by the temperature control of heat of solution within the above range, and tetrachloro-ethylene can be completely by flowing back
Dissolve hexachloro-benzene.
In prioritization scheme 7, the further optimization to prioritization scheme 6, step 5, the temperature of crystallisation by cooling is 0 DEG C.Above-mentioned
In temperature range, you can hexachloro-benzene is essentially crystalline out.
In prioritization scheme 8, the further optimization to prioritization scheme 7, step 6, the temperature of heat of solution is 65 DEG C.Chloroform
Boiling point be 61-62 DEG C, in the range of said temperature by backflow can be completely dissolved hexachloro-benzene crude product.
In prioritization scheme 9, the further optimization to prioritization scheme 8, step 6, the temperature of crystallisation by cooling is -15 DEG C.Upper
State in temperature range, you can crystallize out hexachloro-benzene substantially.
Brief description of the drawings
Fig. 1 is a kind of process chart for the embodiment of the method that chloride is isolated from perchloride of the present invention.
Embodiment
Below by embodiment, the present invention is further detailed explanation：
As shown in figure 1, Fig. 1 is the process chart of various embodiments of the present invention.
It is specifically described below by taking embodiment 1 as an example, other embodiment will be presented with table one, other realities in table 1
It is the condition for describing and being distinguished with embodiment 1 to apply example, and other unlisted conditions are same as Example 1.
Embodiment 1
The present embodiment provides a kind of method that chloride is isolated from perchloride, mainly includes the following steps that：
(1) the perchloride waste material produced during production methane chloride and tetrachloro-ethylene is added in evaporator, used
0.3Mpa saturated vapor carries out chuck heating, and evaporating temperature is controlled at 140 DEG C, is finally incubated up to 150 DEG C after half an hour, is steamed
Distribute complete, by the liquid chloride rectifying evaporated, isolate carbon tetrachloride and tetrachloro-ethylene；
(2) raffinate after being evaporated in step 1 is transferred to distillation kettle, adds and boiling is heated to after water, while hot nitrogen is passed through,
Distillation kettle in hot nitrogen atmospheric pressure be maintained at 0.3Mpa, hot nitrogen uses heat-conducting oil heating, conduction oil temperature control at 270 DEG C,
The mass ratio of the raffinate and water is 8:2；
(3) carbon trichloride after being distilled in step 2 is passed through the dissolving of chloroform dissolving tank, carbon trichloride and chloroform
Mass ratio be 1:2；
(4) heat filtering is carried out to step 3, and filtrate is cooled to -15 DEG C, and crystallizes 1 hour, is centrifuged, by crystalline substance
Body is placed in 40 DEG C of hot water jackets and is dried in vacuo, and vacuum is -0.095Mpa, and drying time is 4 hours；
(5) kettle liquid in step 2 adds tetrachloro-ethylene and dissolved by heating, and the mass ratio of kettle liquid and tetrachloro-ethylene is 1:9, thermosol
The temperature of solution is 120 DEG C, and through heat filtering, filtrate crystallisation by cooling, the temperature of crystallisation by cooling is 0 DEG C, is then centrifuged for being isolated
Hexachloro-benzene crude product；
(6) the hexachloro-benzene crude product of step 5 is recrystallized：Add chloroform to be dissolved by heating, hexachloro-benzene and three chloromethanes
Alkane mass ratio 1:5, the temperature of heat of solution is 65 DEG C, through heat filtering, and filtrate carries out crystallisation by cooling, and the temperature of crystallisation by cooling is -15
DEG C, centrifuge, and crystal is dried and chlordene benzaldehyde product is obtained.Chloroform soln can be recycled, and save resource.
Table 1
Waste liquid is detected
Respectively before detection process in perchloride waste material, and through embodiment 1,2,3,4,5 and 6 it is treated after in waste material
Carbon tetrachloride, tetrachloro-ethylene, carbon trichloride, hexachloro-benzene and tar, carbon black, the content of mechanical admixture, the result such as table 2 of detection：
Table 2
Waste liquid test result：
1st, four chlorinations in the waste material before perchloride waste disposal and through embodiment 1,2,3,4,5 and 6 after treated are contrasted
Carbon, tetrachloro-ethylene, carbon trichloride, hexachloro-benzene and tar, carbon black, the content's index of mechanical admixture, it is apparent that waste material
In carbon tetrachloride, tetrachloro-ethylene, carbon trichloride, hexachloro-benzene be substantially separated, good separating effect.
2nd, the purity for the carbon trichloride isolated in comparative example 5 and embodiment 1, embodiment 1 is apparently higher than embodiment 5
In purity, and the embodiment 5 that differs only in of embodiment 5 and embodiment 1 eliminates step 3, does not use chloroform to dissolve
Carbon trichloride, dissolves it can thus be seen that the carbon trichloride after distillation is passed through in chloroform dissolving tank, can effectively improve six
The purity of chloroethanes.
3rd, the purity for the carbon trichloride isolated in comparative example 6 and embodiment 1, embodiment 1 is apparently higher than embodiment 5
In purity, in the step 2 for differing only in embodiment 6 of embodiment 6 and embodiment 1, do not added water in distillation kettle.So as to
Find out, after being added water in distillation kettle, the purity for the carbon trichloride for being finally separating out can be significantly improved.
Above-described is only that the general knowledge such as known characteristic does not make excessive description herein in embodiments of the invention, scheme.
It should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise, some changes can also be made
Shape and improvement, these should also be considered as protection scope of the present invention, these effects and patent for implementing all without the influence present invention
Practicality.The scope of protection required by this application should be based on the content of the claims, the specific embodiment party in specification
Formula etc. records the content that can be used for explaining claim.
Claims (10)
1. a kind of method of thing Isolating chlorinated from perchloride, it is characterised in that mainly include the following steps that：
（1）The perchloride waste material that the process for producing methane chloride and tetrachloro-ethylene is produced is added in evaporator, will be evaporated
The liquid chloride rectifying gone out, isolates carbon tetrachloride and tetrachloro-ethylene；
（2）Raffinate after being evaporated in step 1 is transferred to distillation kettle, adds and boiling is heated to after water, while hot nitrogen is passed through, it is described
The mass ratio of raffinate and water is 8:1-5；
（3）Carbon trichloride after being distilled in step 2 is passed through to the matter of the dissolving of chloroform dissolving tank, carbon trichloride and chloroform
Amount is than being 1:1-10；
（4）Heat filtering is carried out to step 3, and filtrate is subjected to crystallisation by cooling, is centrifuged, crystal is dried and chlordene is obtained
Ethane product；
（5）Kettle liquid in step 2 adds tetrachloro-ethylene and dissolved by heating, and the mass ratio of kettle liquid and tetrachloro-ethylene is 1:6-15, through heat
Filtering, filtrate crystallisation by cooling centrifuges and obtains hexachloro-benzene crude product；
（6）The hexachloro-benzene crude product of step 5 is recrystallized：Add chloroform to be dissolved by heating, hexachloro-benzene crude product and three chloromethanes
The mass ratio of alkane is 1:3-10, through heat filtering, filtrate carries out crystallisation by cooling, centrifuges, and crystal is dried and hexachloro-benzene is obtained
Product.
2. the method for a kind of thing Isolating chlorinated from perchloride according to claim 1, it is characterised in that in step 1
Chuck heating is carried out with 0.3Mpa saturated vapor, evaporating temperature is controlled at 135-145 °C, after insulation half an hour, by temperature liter
To 150-155 °C, evaporate.
3. the method for a kind of thing Isolating chlorinated from perchloride according to claim 1, it is characterised in that in step 2,
Hot nitrogen uses heat-conducting oil heating, and conduction oil temperature control is at 260-280 DEG C.
4. the method for a kind of thing Isolating chlorinated from perchloride according to claim 1, it is characterised in that in step 2,
Hot nitrogen atmospheric pressure in distillation kettle is maintained at 0.3-0.5Mpa.
5. a kind of method of thing Isolating chlorinated from perchloride according to claim any one of 1-4, it is characterised in that
In step 4, -15 DEG C are cooled to, and crystallize 1 hour.
6. the method for a kind of thing Isolating chlorinated from perchloride according to claim 5, it is characterised in that in step 4,
The drying is to be dried in vacuo in 40 DEG C of hot water jackets, and vacuum is -0.095Mpa, and drying time is 4 hours.
7. the method for a kind of thing Isolating chlorinated from perchloride according to claim 6, it is characterised in that in step 5,
The temperature of heat of solution is 120 DEG C.
8. the method for a kind of thing Isolating chlorinated from perchloride according to claim 7, it is characterised in that in step 5,
The temperature of crystallisation by cooling is 0 DEG C.
9. the method for a kind of thing Isolating chlorinated from perchloride according to claim 8, it is characterised in that in step 6,
The temperature of heat of solution is 65 DEG C.
10. a kind of method of thing Isolating chlorinated from perchloride according to claim 9, it is characterised in that step 6
In, the temperature of crystallisation by cooling is -15 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510732306.0A CN105384598B (en) | 2015-10-31 | 2015-10-31 | A kind of method of thing Isolating chlorinated from perchloride |
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| CN201510732306.0A CN105384598B (en) | 2015-10-31 | 2015-10-31 | A kind of method of thing Isolating chlorinated from perchloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107573210A (en) * | 2016-07-05 | 2018-01-12 | 东莞东阳光科研发有限公司 | The piece-rate system and separation method of by-product high-boiling components in a kind of tetrachloro-ethylene production |
| CN106478359A (en) * | 2016-09-30 | 2017-03-08 | 王显权 | A kind of preparation method of carbon tetrachloride |
| CN107879892A (en) * | 2017-11-10 | 2018-04-06 | 宁波巨化化工科技有限公司 | Phenyl polychloride crude product refining method of purification |
| CN108147944A (en) * | 2018-02-09 | 2018-06-12 | 文学明 | The method for extracting carbon trichloride with stripping mode from high chlorine |
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| US7112709B2 (en) * | 2003-09-09 | 2006-09-26 | Vulcan Chemicals | Method for reusing heavy end by-products in the manufacture of polychlorinated alkanes |
| CN103086839B (en) * | 2012-12-20 | 2015-03-25 | 山东东岳氟硅材料有限公司 | Production process for production of tetrachloroethylene and coproduction of hexachloroethane by using methane chloride residual liquid |
| CN103787823B (en) * | 2014-02-28 | 2015-04-08 | 重庆海洲化学品有限公司 | Method for recovering organic chloride from rectification residues of methane chloride or/and tetrachloroethylene |
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