CN105417769B - A kind of laboratory carbon tetrachloride separating treatment system and its handling process - Google Patents
A kind of laboratory carbon tetrachloride separating treatment system and its handling process Download PDFInfo
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- CN105417769B CN105417769B CN201510778935.7A CN201510778935A CN105417769B CN 105417769 B CN105417769 B CN 105417769B CN 201510778935 A CN201510778935 A CN 201510778935A CN 105417769 B CN105417769 B CN 105417769B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
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Abstract
The invention discloses a kind of laboratory carbon tetrachloride separating treatment system and its handling process, including the active carbon filtration case containing S-shaped adsorption tank and the treatment region with nano-bubble generator, the two is placed in aerated reaction case, is separated by dividing plate, and connected through mozzle；Active carbon filler is wherein filled inside S-shaped adsorption tank and provided with hanging plate, one end of S-shaped adsorption tank is provided with outlet pipe；One end of aerated reaction case is provided with raffinate water inlet pipe.It the advantage is that：（1）As a result of oxidation, aeration, absorption Combined Treatment mode, its treatment effeciency is high, has higher removal effect for the volatile materials of high concentration laboratory containing tetrachloro raffinate；（2）In charcoal adsorption process, activated carbon Rose Box is suspended plate and is divided into multiple S-shaped adsorption tanks, and the raffinate of laboratory containing carbon tetrachloride is flowed with S-shaped path, adds the time of contact of raffinate and activated carbon, the contact area of raffinate and oxygen is added simultaneously, improves treatment effeciency.
Description
Technical field
The invention belongs to environmental protection treatment technology, it is related to the process field of the organic raffinate of laboratory containing carbon tetrachloride of high concentration,
More particularly to a kind of laboratory carbon tetrachloride separating treatment system and its handling process.
Background technology
Carbon tetrachloride (CCl4) it is a kind of organic chlorohydrocarbon of artificial synthesized low boiling (proportion 1.591g/cm3, boiling point 77
DEG C), it is slightly soluble in water.Foreign study shows：Carbon tetrachloride belongs to typical hepatotoxic agent, during high concentration, is influence maincenter first
Nervous system, then influences liver, kidney.It has persistence, extended residual and bioconcentration in the environment, therefore from 1979
Year has been included in " pollutant of priority acccess control in underground water containing carbon tetrachloride " by U.S. EPA, has also been included in 68 kinds " in water by China
The pollutant of priority acccess control " list.
Eighties of last century the seventies cause some regional underground water by carbon tetrachloride due to largely manufacturing and using agricultural chemicals
Water-bearing layer near pollution, the Michigan water-bearing layer in such as U.S. and Canadian Ottawa by the polluting of carbon tetrachloride (
It exists with nonaqueous phase (NAPL) more in water-bearing layer).
What Fortord Army were caused in military base before the U.S. pollutes CCl in the municipal water supply for causing Marina4It is exceeded,
In August, 2000 measures CCl4Concentration is up to 15 μ g/L.The groundwater monitoring in U.S. Livermore areas finds poisonous and harmful rubbish
Stacking causes CCl4CCl in the generation of pollutant, noxious material percolate4At concentrations up to 500 μ g/L.In April, 2000,
Underground water CCl in MW-10 wells near Hafner＆Sons refuse landfills4Concentration is up to 6.3 μ g/L.
At home, the littoral phreatic water of Xiaoqing River, Shandong Province is once by CCl4Pollution, maximum concentration is up to 380 μ g/
L, contaminated area reaches 80km2.Xiaoqinghe River Ya Wangkou, the measuring point phreatic water CCl of western lock two4Content is 16.0-380.0 μ g/L.
1997, detect CCl in the running water of Zhabei District in Shanghai4Content is 1.17 μ g/L, and Xicheng District of Beijing and Xuanwu District are then divided
Wei not 0.24 and 0.32 μ g/L.Carry out carbon tetrachloride content monitoring to China's somewhere phreatic water within 2000, find southern suburbs
There are 3 wells contaminated in water head site, in May, 2001, existing 53 karstic ground water wells are contaminated, area
Up to 17.5km2, carbon tetrachloride maximum concentration is up to 3909.2 μ g/L in water, more than 1954.6 times of national drinking water standard, serious prestige
Coerce the healthy of regional more than 20 ten thousand people that supply water.
Existing Treatment process
Carbon tetrachloride is to common are organic pollutants in soil and groundwater, is easily made with rainwater or irrigation water by leaching
With entering in soil and groundwater, cause the pollution of soil and groundwater body.Carbon Tetrachloride Contamination is controlled in relevant underground water at present
The conventional method of reason has following several：
1. active carbon adsorption
With the carbon tetrachloride in charcoal absorption water source, without adding any chemical reagent, technical requirements are not high, low concentration
Advantages of good adsorption effect, some materials for being difficult to degrade can be directly adsorbed on activated carbon.By having investigated activated carbon dosage, absorption
Influence of the factors such as time, temperature to removal effect.
This method technical maturity, effect simple to operate is reliable, but adsorption efficiency is unstable, and carbon tetrachloride is in low concentration timeliness
It is really good, handle unstable during high concentration, effectively adsorb short life, carrier needs to carry out secondary desorption that circulating use could be carried out,
And by the solution after solvent desorption, form the mixture containing carbon tetrachloride again, how to be isolated again, it is necessary to further grind
Study carefully.
2. aeration process repairing method
Aeration process, which is repaired to inject compressed air, causes volatility dirty in underground water saturated zone, the upward motion process of gas
Dye thing enters gas phase from the soil body and underground water so that the air containing pollutant rises to unsaturation band, then extracts system by gas phase
System processing removes the purpose of pollutant so as to reach.The in-situ immobilization of this processing underground water saturated zone volatile organic contaminant
Technology, due to can the advantage of construction in situ it is used widely, it is be applied to that molecular weight is smaller, be easily changed into gas phase from liquid phase more
Pollutant.
But aeration process repairing method is easily changed by gas flow shape, number of bubbles, bubble size, gas channel density
Etc. factor influence, while reducing disposal ability because handling process is different.Aeration process repairing method in force, if contaminated area is deposited
In local hypotonicity soil layer, air is difficult to fully contact with pollutant, if underground water saturated zone structural crack occurs or disconnected
Band is split, the air of injection then easily forms preferential stream, causes aeration short circuit, greatly influences process range and treatment effect, pollution
Area hardly results in effective reparation.Simultaneously aeration process repairing method also by soil response type, place homogenieity, level of ground water and
Flowing, the water-soluble of pollutant directly affect with volatile so that remediation efficiency declines, cost increase.
3. in situ chemical oxidation method
Oxidant permanganate, Fenton reagent, hydrogen peroxide and persulfate that in-situ chemical recovery technique is used etc..
Oxidant is injected into underground pollution area, substantial amounts of natural iron mineral is contained in soil and water-bearing layer in itself, in iron ore
In the presence of thing catalysis oxidation reaction can effectively rehabilitating soil and underground water organic pollution.Research shows in-situ chemical reparation
Technology easily makes reparation area soil produce mineralising, makes reparation area soil hardening, bad hydraulic permeability, changes reparation area's soil texture.
4. biological restoration
Using bio-inert and organic clay adsorbed bioactive bacterium, by biological metabolism, underground environment is reduced
In poisonous and harmful compound engineering techniques, biology in situ repairing method can handle large-scale pollutant, and can be complete
Full decomposing pollutant.
Current biology in situ repairing method is an emerging technology for processing underground water Organic Pollution source, biological prosthetic
Key factor be suitable electron acceptor, and the oxygen acceptor that has been best electricity, due to lacking oxygen this electricity in underground environment
Sub- acceptor, while the supply of microbial nutrition material is not enough, also causes the biodegradation of microorganism from lasting.
5. permeable reactive wall repairing method
Using the dependent response area filled with Active reaction medium material, when contaminated underground water by when, it is therein
Polluter occurs the effects such as physics, chemistry and biology with reaction medium and is degraded, adsorbs, precipitates or removes, so that dirty
Water is purified.
But permeable coefficient tensor is in the presence of being easily blocked, its native environmental conditions such as oxidation-reduction potential of underground water are subject to brokenly
Bad, the shortcomings of reaction wall engineering measure and relative complex operation maintenance, it is higher to add bimetallic systems, nanometer technology cost, this
A little factors hinder the further development of permeable coefficient tensor and widelyd popularize.
6. original position aeration repairing method
Aeration process in situ is a kind of based technique for in-situ remediation of emerging underground water volatile organic matter, is injected air into
Below Polluted area, volatile organic compounds are resolved to from underground water to air stream and the in-situ immobilization skill handled on ground is led to
Art, while can provide enough oxygen to deep well injection air for the aerobic microbiological in underground water, promotes the drop of indigenous microorganism
Solution is acted on.The technology can handle more Polluted Groundwater in acceptable cost-range, and system is easily installed and turned
Move, easily used with other technical combinations.
But it is due to that geologic structure is complicated, when injection air runs into complete rock stratum band, loosening crushed zone or flexural deformation band
When, the injection air for carrying volatile organic matter is difficult to penetrate above-mentioned geologic structure, while injecting air runs into above-mentioned geology
During structure, air drag is big, will cause the device to consumption and greatly improves.It is difficult to being neither easy volatilization at biodegradable pollutant
Manage effect less good.
The content of the invention
Present invention solves the technical problem that being：A kind of be used for experiment is provided in order to overcome above the deficiencies in the prior art
The raffinate containing carbon tetrachloride is flowed into aerated reaction case in room, and carbon tetrachloride is realized after the processes such as oxidized, aeration, absorption
Separation, solves the defect of conventional processes presence, and is improved.For follow-up laboratory containing carbon tetrachloride raffinate depth
Reason provides technical scheme and supported.
To achieve the above object, the present invention uses following technical scheme：
A kind of laboratory carbon tetrachloride separating treatment system, including active carbon filtration case and band containing S-shaped adsorption tank
There is the treatment region of nano-bubble generator, the two is placed in aerated reaction case, is separated by dividing plate, and is connected through mozzle；Its
Active carbon filler is filled inside middle S-shaped adsorption tank and provided with hanging plate, one end of S-shaped adsorption tank is provided with outlet pipe；Aeration is anti-
One end of case is answered to be provided with raffinate water inlet pipe.
Further, S-shaped adsorption tank is formed by hanging plate vertical direction Heterogeneous Permutation.
Further, the quantity of hanging plate is at least one.
Further, nano-bubble generator is stretched into aerated reaction case, be divided into high-speed rotor impeller, micro porous aeration head and
Air access tube, wherein micro porous aeration head are located at air access tube exhaust outlet one end, and high-speed rotor impeller is arranged at air access
Guan Shang.
Further, raffinate water inlet pipe is three-way pipe structure, is connected with hydrogen peroxide filler pipe, and pass through raffinate water inlet pipe bottom
Mouth is connected with aerated reaction case.
Further, outlet pipe is divided into porous collector pipe and discharging tube, wherein the quantity of porous collector pipe is at least one.
Further, the packed height of active carbon filler is not less than the height of waterline inside S-shaped adsorption tank.
Further, the packed height of active carbon filler is higher than 10~20 centimetres of waterline inside S-shaped adsorption tank.
Above laboratory carbon tetrachloride separating treatment system carries out the technique of carbon tetrachloride processing, and flow is as follows：Four chlorinations
Carbon raffinate enters aerated reaction case by raffinate water inlet pipe, is aerated while hydrogen peroxide reaction reagent is entered by hydrogen peroxide filler pipe
Reaction chamber, reacts with carbon tetrachloride raffinate；Meanwhile, outside air enters nano-bubble generator by air access tube,
High-speed rotor impeller is rotated with the rotating speed of 3000~9000 revs/min of speed, and the microbubble that micro porous aeration head is produced is smashed into
The bubble that 10~600 nanometers of diameter, is uniformly spread to react box house, and abundant with carbon tetrachloride in aerated reaction case
Reaction；Solution after processing enters activated carbon Rose Box by mozzle, due to being provided with least one inside activated carbon Rose Box
Hanging plate, and in vertical direction Heterogeneous Permutation, promote raffinate that S paths are presented inside active carbon filtration case and reach porous collector pipe
Place, is finally discharged through discharging tube；Wherein control condition be throughput be 80 liters/min, 80 centimetres of water level, temperature be 60 DEG C, exposure
The gas time is 2 hours.
Above-mentioned technical proposal is disclosed to be flowed into during aerated reaction case based on the raffinate of laboratory containing carbon tetrachloride, by tetrachloro
Change carbon separation carbon tetrachloride piece-rate system, using combined type handling process remove laboratory raffinate in carbon tetrachloride it is innoxious
Treatment technology.The pending laboratory raffinate containing carbon tetrachloride is entered into aerated reaction case through raffinate water inlet pipe, while dioxygen
Water is mixed with raffinate, and raffinate is aoxidized；At the same time, fresh air is squeezed into air access tube by air pump, in nano bubble
A large amount of nano bubbles are formed in the presence of generator in aerated reaction case, promote carbon dioxide gasification；It is residual after preliminary treatment
Liquid flows into activated carbon Rose Box through mozzle, is flowed in S-shaped adsorption tank with S-shaped path, so as to add aeration and activated carbon
Adsorption time, promotes carbon tetrachloride to be separated from water body.
Beneficial effect
Laboratory carbon tetrachloride separating treatment system and its handling process disclosed by the invention, the advantage is that：
(1) as a result of oxidation, aeration, absorption Combined Treatment mode, its treatment effeciency is high, contains tetrachloro for high concentration
The volatile materials of laboratory raffinate has higher removal effect；
(2) in charcoal adsorption process, activated carbon Rose Box is suspended plate and is divided into multiple S-shaped adsorption tanks, containing tetrachloro
Change carbon laboratory raffinate to flow with S-shaped path, the time of contact of raffinate and activated carbon is added, while adding raffinate and oxygen
Contact area, improve treatment effeciency.
Brief description of the drawings
Fig. 1 is carbon tetrachloride separating treatment system structure diagram in laboratory of the present invention；
Fig. 2 is laboratory carbon tetrachloride separating treatment system top view of the present invention；
Fig. 3 is laboratory carbon tetrachloride separating treatment system front view of the present invention；
Fig. 4 is laboratory carbon tetrachloride separating treatment system schematic perspective view of the present invention；
Fig. 5 is the service branch structure schematic diagram of carbon tetrachloride separating treatment system in laboratory of the present invention；
Wherein, 1 is nano-bubble generator, and 1-1 is high-speed rotor impeller, and 1-2 is micro porous aeration head, and 1-3 connects for air
Enter pipe, 2 be aerated reaction case, and 3 be mozzle, and 4 be S-shaped adsorption tank, and 5 be dividing plate, and 6 be raffinate water inlet pipe, and 6-1 adds for hydrogen peroxide
Note pipe, 7 be raffinate water inlet pipe base opening, and 8 be active carbon filler, and 9 be hanging plate, and 10 be outlet pipe, and 10-1 is porous collector pipe,
10-2 is discharging tube, and 11 be activated carbon Rose Box, and 12 be waterline.
Embodiment
Carbon tetrachloride separating treatment system in laboratory of the present invention is described in detail below in conjunction with the accompanying drawings.
Embodiment 1
As shown in figure 1, being carbon tetrachloride separating treatment system structure diagram in laboratory of the present invention, it can be seen that
Including the active carbon filtration case 11 containing S-shaped adsorption tank 4 and the treatment region with nano-bubble generator 1, the two is placed in exposure
In solid/liquid/gas reactions case 2, separated, and connected through mozzle 3 by dividing plate 5；Fill active carbon filler 8 simultaneously in the wherein inside of S-shaped adsorption tank 4
Provided with hanging plate 9, one end of S-shaped adsorption tank 4 is provided with outlet pipe 10；One end of aerated reaction case 2 is provided with raffinate water inlet pipe 6.
As shown in figure 3, being laboratory carbon tetrachloride separating treatment system front view of the present invention, it can be seen that S-shaped is inhaled
Attached groove 4 is formed by the hanging vertical direction Heterogeneous Permutation of plate 9, and the quantity of hanging plate 9 is at least one.
In laboratory carbon tetrachloride separating treatment system described in the present embodiment, it is anti-that nano-bubble generator 1 stretches into aeration
Answer in case 2, be divided into high-speed rotor impeller 1-1, micro porous aeration head 1-2 and air access tube 1-3, wherein micro porous aeration head 1-2 is set
In air access tube 1-3 exhaust outlets one end, high-speed rotor impeller 1-1 is arranged on air access tube 1-3.
As shown in figure 4, being laboratory carbon tetrachloride separating treatment system schematic perspective view of the present invention, raffinate water inlet pipe
6 be three-way pipe structure, is connected with hydrogen peroxide filler pipe 6-1, and is connected by raffinate water inlet pipe base opening 7 with aerated reaction case 2.
As shown in figure 5, be the service branch structure schematic diagram of carbon tetrachloride separating treatment system in laboratory of the present invention, can
To find out, 10 points of outlet pipe is porous collector pipe 10-1 and discharging tube 10-2, wherein porous collector pipe 10-1 quantity is at least
One.
In the present embodiment, the packed height of the inside active carbon filler 8 of S-shaped adsorption tank 4 is not less than in the height of waterline, figure
12 are expressed as the waterline during carbon tetrachloride separating treatment.
Embodiment 2
The laboratory raffinate containing carbon tetrachloride is handled using above-mentioned piece-rate system, first, carbon tetrachloride raffinate leads to
Cross raffinate water inlet pipe 6 and enter aerated reaction case 2, while hydrogen peroxide reaction reagent enters aeration instead by hydrogen peroxide filler pipe 6-1
Case 2 is answered, is reacted with carbon tetrachloride raffinate；Meanwhile, outside air enters nano-bubble generator by air access tube 1-3
1, high-speed rotor impeller 1-1 are rotated with the rotating speed of 3000~9000 revs/min of speed, micro- gas that micro porous aeration head 1-2 is produced
Bubble smashes into the bubble of 10~600 nanometers of diameter, is uniformly spread to react box house, and with four in aerated reaction case 2
Chlorination carbon fully reacts.
Solution after processing enters activated carbon Rose Box 11 by mozzle 3, because the inside of activated carbon Rose Box 11 is provided with
At least one hanging plate 9, and in vertical direction Heterogeneous Permutation, promote raffinate that S paths are presented inside active carbon filtration case 11 and arrive
Up at porous collector pipe 10-1, finally discharged through discharging tube 10-2；Wherein control condition is that throughput is 80 liters/min, water level
80 centimetres, temperature be 60 DEG C, aeration time be 2 hours.
For the reasonability of test design, optimal treatment effect is reached, passes through above carbon tetrachloride piece-rate system
Carbon tetrachloride clearance is detected, the reasonability and optimal operating parameter to design are verified, as a result as follows：
In simulation carbon tetrachloride piece-rate system, in the laboratory raffinate containing carbon tetrachloride, the concentration of carbon tetrachloride is 20 μ
G/L, to control simulated system temperature be 60 DEG C, aeration time is 2 hours, throughput is 80 liters/min, 80 centimetres of water level, at a high speed
Impeller of rotor 1-1 is revolved with the rotating speed of 3000 revs/min, 5000 revs/min, 7000 revs/min, 9000 revs/min of speed respectively
Turn, specific testing result is as shown in the table.
Carbon tetrachloride removal effect in the raffinate of laboratory
Claims (2)
1. a kind of laboratory carbon tetrachloride separating treatment system, it is characterised in that including containing S-shaped adsorption tank（4）Activated carbon
Rose Box（11）And with nano-bubble generator（1）Treatment region, the two is placed in aerated reaction case（2）In, pass through dividing plate
（5）Separate, and through mozzle（3）Connection；Wherein S-shaped adsorption tank（4）Inside filling active carbon filler（8）And provided with hanging plate
（9）, S-shaped adsorption tank（4）One end be provided with outlet pipe（10）；Aerated reaction case（2）One end be provided with raffinate water inlet pipe（6）；S
Shape adsorption tank（4）By hanging plate（9）Vertical direction Heterogeneous Permutation is formed；Hanging plate（9）Quantity be at least one；Nano bubble
Generator（1）Stretch into aerated reaction case（2）It is interior, it is divided into high-speed rotor impeller（1-1）, micro porous aeration head（1-2）And air access
Pipe（1-3）, wherein micro porous aeration head（1-2）Located at air access tube（1-3）Exhaust outlet one end, high-speed rotor impeller（1-1）If
It is placed in air access tube（1-3）On；Raffinate water inlet pipe（6）For three-way pipe structure, with hydrogen peroxide filler pipe（6-1）Connection, and lead to
Cross raffinate water inlet pipe base opening（7）With aerated reaction case（2）Connection；Outlet pipe（10）It is divided into porous collector pipe（10-1）And discharging tube
（10-2）, wherein porous collector pipe（10-1）Quantity be at least one；S-shaped adsorption tank（4）Internal active carbon filler（8）Fill out
Fill height and be not less than waterline（12）Height；S-shaped adsorption tank（4）Internal active carbon filler（8）Packed height be higher than water level
Line（12）10 ~ 20 centimetres.
2. a kind of laboratory carbon tetrachloride separating treatment system described in claim 1 carries out the technique of carbon tetrachloride processing, its
It is characterised by, technological process is as follows：Carbon tetrachloride raffinate passes through raffinate water inlet pipe（6）Into aerated reaction case（2）, while dioxygen
Water reaction reagent passes through hydrogen peroxide filler pipe（6-1）Into aerated reaction case（2）, reacted with carbon tetrachloride raffinate；Meanwhile,
Outside air passes through air access tube（1-3）Into nano-bubble generator（1）, high-speed rotor impeller（1-1）With speed 3000 ~
9000 revs/min of rotating speed rotation, by micro porous aeration head（1-2）The microbubble of generation smashes into the gas of 10 ~ 600 nanometers of diameter
Bubble, is uniformly spread to react box house, and in aerated reaction case（2）In fully reacted with carbon tetrachloride；It is molten after processing
Liquid passes through mozzle（3）Into activated carbon Rose Box（11）, due to activated carbon Rose Box（11）Inside is hanging provided with least one
Plate（9）, and in vertical direction Heterogeneous Permutation, promote raffinate in active carbon filtration case（11）Inside is presented S paths and reaches porous collection
Water pipe（10-1）Place, finally through discharging tube（10-2）Discharge；Wherein control condition is that throughput is 80 liters/min, 80 lis of water level
Rice, temperature are 60 DEG C, aeration time is 2 hours.
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| CN106006908B (en) * | 2016-05-24 | 2018-12-21 | 徐州腾睿智能装备有限公司 | A kind of vehicular underground water carbon tetrachloride processing equipment and its process for purifying water |
| CN106045075B (en) * | 2016-05-24 | 2018-11-20 | 徐州腾睿智能装备有限公司 | Carbon tetrachloride device and its minimizing technology in a kind of spiral-flow aeration method processing underground water |
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| CN107569985B (en) * | 2017-09-27 | 2020-09-01 | 徐州工程学院 | Reaction cracker |
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| CN104724818A (en) * | 2015-01-30 | 2015-06-24 | 徐州工程学院 | Carbon tetrachloride separation system and process |
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