CN107643245A - A kind of ultraviolet lighting reaction experiment device of coal particle surface processing - Google Patents
A kind of ultraviolet lighting reaction experiment device of coal particle surface processing Download PDFInfo
- Publication number
- CN107643245A CN107643245A CN201710644997.8A CN201710644997A CN107643245A CN 107643245 A CN107643245 A CN 107643245A CN 201710644997 A CN201710644997 A CN 201710644997A CN 107643245 A CN107643245 A CN 107643245A
- Authority
- CN
- China
- Prior art keywords
- coal
- sample
- experiment
- coal sample
- vacuum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
A kind of ultraviolet lighting reaction experiment device of coal particle surface processing, including reactor, cooling water recirculation system, vacuum system and oxygen system；The reactor is made up of upper kettle and lower kettle；Upper kettle is by reacting body and chuck layer into reacting body lower end is provided with core plate, top is provided with uviol lamp；Lower kettle upper end is provided with porous plate；Cooling water recirculation system is made up of water inlet pipe, coil pipe, outlet pipe and entrance throttle, and coil pipe connects with water inlet pipe and outlet pipe；The vacuum system is made up of vacuum tube, sensor, data logger, vavuum pump, vacuum meter and vacuum choke valve；The oxygen supply system is made up of oxygen supplying tube, intake-air throttle valve, mass air flow sensor and air supplying pump；This reaction unit is studied suitable for coal science, is had and is occupied little space, be economical and practical, can rationally utilize lab space, save the characteristics of raw material and scientific research personnel's time.
Description
Technical field
It is especially a kind of to include reactor, cooling water the present invention relates to a kind of coal particle surface ultraviolet lighting reaction unit
The ultraviolet lighting reaction experiment device of the coal particle surface processing of the circulatory system, vacuum system and oxygen system.
Background technology
China's low-order coal and oxidation coal resource storage are abundant, low-order coal and oxidized coal it is reasonable efficiently using for alleviation I
The Pressure on Energy of state's growing tension, reduction energy consumption, environmental protection are significant.Low-order coal and oxidized coal sorting are most at present
Electric coal sale or waste treatment, compared with conventional bituminous coal, anthracite, low-order coal and oxidation are directly done using coarse particle gravity-coal slime
Because of its big porosity and high surface oxygen functional group, during FLOTATION SEPARATION, reagent consumption is big, efficiency is low for coal, and it is low to open up low cost
Rank coal and oxidized coal flotation technology are extremely urgent, because coal is the preferable material of native floatability, so in floatation process, adjust
Economize on coal surface nature, change its hydrophilic and hydrophobic, be the effective way for improving its flotation efficiency.
Flotation efficiency, ore pulp preprocessing means are improved using the method that ore pulp pretreatment is carried out before flotation mostly both at home and abroad
Including physical adjustment method and Chemical Regulation method etc., these supplementary means can act on coal grain, increase the property of mineral particle surface
Matter difference, so as to improve flotation efficiency.Wherein in the majority with Chemical Regulation method, the medicament added by Chemical Regulation method is to initially enter ore deposit
In slurry, acted on indirectly with mineral, when pharmaceutical quantities are excessive, flotation effect can be deteriorated, and some total medicament rests on ore pulp
In, do not work not only and cause to waste, it is also possible to which the quality of coal is impacted；Physical adjustment method will not cause medicine in ore pulp
Thing retains, and it directly acts on mineral surfaces, improves the property of whole ore particle system, for relative chemical regulation method, safety collar
Protect, can avoid wasting.Common physics ameliorative way is as follows：
Upgrading is carried out to low-order coal using evaporation, in dehydration, the physical action of dehydration causes the gel knot of low-order coal
Structure and pore system produce irreversible destruction, inherently change the ature of coal of coal sample, so as to improve the coalification journey of coal sample
Degree, improve flotation efficiency；Change coal and the angle in aqueous phase face using ultrasonic technology, so as to change the contact angle size on coal surface
To change sign of the coal in water；Increase mineral grain size using manual operation to increase the contact area of coal and water, so as to
It is also common methods to increase coal wettability of the surface, wherein relatively conventional method is exactly carrier flotation, and these methods are most
Special instrument is needed, increases the cost of flotation.Therefore, simple, clean, the convenient coal preprocess method of demand one kind just into
In order to it is a kind of there is an urgent need to research.
Correlative study finds that ultraviolet has extremely strong destructive power for hydrocarbon macromolecular, and coal table is destroyed using ultraviolet
The macromolecular in face, lure that the radical reaction in coal is combined into new polycyclic aromatic hydrocarbons (PAH) so as to change the surface nature of coal into, so as to
Reverse flotation can be implemented to high oxidation degree coal sample, so both save reagent consumption while or increased production efficiency；And ultraviolet light
Catalytic oxidation technologies have the advantages that selectivity is good, operating condition is gentle, nontoxic, efficient, therefore various ultraviolet catalytic oxidations
Reaction unit has been applied to laboratory.
However, during using ultraviolet catalytic oxidation reaction unit, it is found that existing ultraviolet catalytic oxidation is anti-
Answer device there are problems that, the FTIR research process of Yang Zhiyuan et al. shenfu coal photocatalytic oxidation degradation processes using
Homemade photochemical reaction experimental rig；Guo Hao et al. ultrasonic wave and ultraviolet ray integral plug flow reactors pilot-plant is used for dirt
Water sterilization；Chen Ping et al. photocatalysis technology degraded indoor formaldehyde research and thank to Han on ultraviolet lamp Patents brief introduction
All show that most ultraviolet lamp device is all to concentrate on water process, purification of air, sterilization etc. at this stage in one text, and coal
The research of charcoal catalysis is all homemade ultraviolet lamp device, ununified standard and parameter, is brought to follow-up research certain
Obstacle.There is no a kind of ultraviolet lamp device for catalytic reaction at present, this to experiment bring certain limitation, from reactor,
Intensity of illumination etc. Shortcomings, constrain the development of coal photocatalysis field.
Device Shortcomings at present：First, equipment volume is larger, shared lab space is big, and experiment materials are more, in light
Catalysis technique is also without in the case of extensive field application, and laboratory should be based on Exploration on mechanism, therefore materials are excessively multipair follow-up
Test has no benefit, and is modified to sample preparation, early stage and brings substantial amounts of work, wastes raw material and scientific research personnel's time；Second,
Device is the deriving device of other field, not for the specific device of coal catalytic reaction, and it is cumbersome, it is expensive；
Become simultaneously for the intensity of illumination required for coal catalytic reaction in experimentation, time, temperature, pressure, air mass flow etc. are related
No suitable range section is measured, it is not easy to operate for trace regulation in coal catalytic process, obstruction can be produced to study mechanism.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art and provides that vdiverse in function, experimental situation is adjustable, space-consuming
A kind of ultraviolet lighting reaction experiment device of small, economical and practical coal particle surface processing.
The purpose of the present invention is achieved through the following technical solutions.
A kind of ultraviolet lighting reaction experiment device of coal particle surface processing, including it is reactor, cooling water recirculation system, true
Empty set is united and oxygen system, it is characterised in that：
The reactor is made up of upper kettle and lower kettle, and the upper kettle is made up of reacting body and its chuck layer, institute
The lower end for stating reacting body is provided with core plate, top is provided with two uviol lamps, and the positive side of upper kettle is provided with door-plate
And its observation window；The upper end of the lower kettle is provided with porous plate；
The cooling water recirculation system is made up of water inlet pipe, coil pipe and outlet pipe, wherein：Entrance section is installed on water inlet pipe
Stream valve is arranged at reactor top；Outlet pipe is arranged on the bottom of reactor；Coil pipe is serpentine-like to be arranged in chuck layer and water inlet
Pipe is connected with outlet pipe；
The vacuum system is made up of vacuum tube, sensor and data logger, wherein, one end of vacuum tube extends reaction
Kettle is interior, the other end is communicated with vavuum pump, and vacuum meter and vacuum choke valve are sequentially installed with vacuum tube；
The oxygen system is to be provided with intake-air throttle valve, mass air flow sensor and air supplying pump from left to right successively by oxygen supplying tube, one
The lower end that end is communicated with lower kettle is formed.
Further, supplementary technology scheme is as follows.
The power of the uviol lamp is 300W, and the wavelength of ultraviolet light is 254nm and 365nm respectively.
The data logger is colorful paper-free recorder, is arranged at the side wall of upper kettle, is set in data logger
Have PLC, the positive side of data logger be provided with display screen, be provided with the downside of display screen input keyboard,
Left side is provided with run switch, and the button switch for controlling uviol lamp is provided with the downside of run switch；
Wherein：The PLC is to be connected by control signal wire with vavuum pump and air supplying pump, controlled by signal wire with passing
Sensor, entrance throttle, vacuum choke valve, intake-air throttle valve, vacuum meter and mass air flow sensor are connected.
The sensor is pressure-temperature integral sensor, on the inwall of reactant.
The water inlet pipe, coil pipe, outlet pipe, vacuum tube and oxygen supplying tube are quality of rubber materials pipes.
A kind of experimental method of the ultraviolet lighting reaction experiment device handled using coal particle surface, the experimental method are
Press step progress：
（1）, the Preparatory work of experiment stage
1）The jet coal for taking -0.5mm particle size fractions, ash content to be 32.27% is raw coal sample, prepares the sample of -0.074mm particle size fractions
Coal, it is standby；
2）The coal samples of different densities, acid treatment coal sample, metal ion-modified coal sample, TiO are prepared with sample coal2Modified coal sample and
Odium stearate is modified coal sample, standby；
Wherein, any one coal sample in metal ion-modified coal sample load Fe3+, Mg2+, Na+, Sn2+；
3）Experimental stage
Ith, 4 parts of steps 1 are weighed）The sample coal prepared is laid on core plate respectively, is opened uviol lamp and is started to test, in experiment
The ultraviolet light time be 1-12h, time step 1h；Irradiation process is carried out in the environment of air circulation, will be real every time
Sample coal recovery after testing, is sealed, and carry out Zeta potential measure, contact angle determination, infrared spectrum respectively with hermetic bag
Analysis and thermogravimetric analysis；
IIth, 4 parts of steps 2 are weighed）The coal sample of the different densities prepared is laid on core plate, and it is real to carry out ultraviolet light respectively
Test, experimental method is identical with step b1, and carries out Zeta potential measure respectively to the sample after recovery experiment, and contact angle is surveyed
It is fixed, infrared spectrum analysis and thermogravimetric analysis；
IIIth, the 4 parts of acid treatment prepared coal samples are weighed and carry out ultraviolet light experiment, experimental method is identical with step II, and right
The sample that sample and acid treatment coal sample after the experiment of recovery do not carry out illumination carries out Zeta potential measure respectively, and contact angle is surveyed
It is fixed, infrared spectrum analysis and thermogravimetric analysis；
IVth, 4 parts of steps 2 are weighed）The metal ion-modified coal sample prepared carries out ultraviolet light experiment, the same step of experimental method
1）, and the sample for not carrying out illumination to the sample after the experiment of recovery and metal ion-modified coal sample carries out Zeta potential respectively
Measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis；
Vth, step 2 is weighed）After the TiO2 modification coal samples prepared are well mixed with former state coal, weigh 4 parts of biased samples and carry out purple
Outer illumination experiment, experimental method and step 1）It is identical, and do not carry out to the biased sample after the experiment of recovery and ultraviolet lighting
Biased sample carry out contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis respectively；
VIth, 4 parts of steps 2 are weighed）The odium stearate prepared is modified coal sample and carries out ultraviolet lighting experiment, the same step of experimental method
1）, and the fakement for not carrying out ultraviolet lighting experiment to the sample after the experiment of recovery and stearic acid sodium modification coal sample is carried out respectively
Contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis；
VIIth, 10g coal samples are weighed, are configured to 100g/L black water, is put into ultrasonic cleaner and carries out ultrasonication,
Ultrasonic frequency is 25kHz, power 300W；Ultraviolet light is carried out while being ultrasonically treated, irradiation time is respectively 1-
12h, time step 1h；Each sample after experiment is separately recovered, load valve bag be sealed, and respectively to processing after
Each sample carries out Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis.
In the above-mentioned technical solutions, it is the sample coal that weighs, different close in the ultraviolet irradiation experimentation carried out every time
The coal sample of degree, acid treatment coal sample, metal ion-modified coal sample, TiO2The weight that modified coal sample and odium stearate are modified coal sample is equal
For 3g.
A kind of ultraviolet lighting reaction experiment device for coal particle surface processing that the invention described above provided is realized, it is and existing
Technology is compared, and its advantage and good effect are as follows.
The ultraviolet lighting reaction unit of this coal particle surface processing is applied to coal light-catalyzed reaction, and economical and efficient, environmental protection are clear
It is clean, easy to operate, while solve the problems such as existing ultraviolet lighting reaction unit volume is big, amount of samples is more, cumbersome,
Lab space is reasonably make use of, has saved raw material and the time of scientific research personnel.
The ultraviolet lighting reaction unit of this coal particle surface processing, uviol lamp are connected in a manner of hickey with reactor,
The condition that can be needed according to coal catalytic reaction changes the ultraviolet lamp tube of different capacity, different wave length, is easy to control light application time, more
Change conveniently.
This coal particle surface processing ultraviolet lighting reaction unit, can according to the varying environment required for coal catalytic reaction,
Select aerobic reaction environment or vacuum environment, it is ensured that good reaction environment and easy to operate.
The ultraviolet lighting reaction unit of this coal particle surface processing, the temperature and pressure of reaction environment can be monitored in real time, and
By the situation of peep hole Real Time Observation reaction environment, to make corresponding adjustment, solve conventional experimental provision and be difficult to control
With monitoring coal light-catalyzed reaction during correlated variables the problem of.
The ultraviolet lighting reaction unit of this coal particle surface processing, can pass through air intake throttle valve adjustment air-flow size.
Can be by flow inlet throttle valve adjustment current size, and then regulation reaction environment temperature, using flexible, controllability are strong.
The ultraviolet lighting reaction unit of this coal particle surface processing, on the basis of early stage a large amount of coal photocatalysis explorative experiments
A kind of reaction unit for the suitable coal subject developed after confirming repeatedly to the condition required for coal catalytic reaction and parameter.
The ultraviolet lighting reaction unit of this coal particle surface processing, is shown experimentally that in different ultraviolet illumination intensity
Under, the time that coal sample contact angle reaches maximum is different, and Maximum Contact angle number is different；Identical UV power irradiates different time
Under, the equilibrium contact angle of coal sample is different, and wetability is different and undulate changes.
Brief description of the drawings
Fig. 1 is the front view of the ultraviolet lighting reaction unit that coal particle surface is handled in the present invention.
Fig. 2 is the internal structure schematic diagram of the ultraviolet lighting reaction unit that coal particle surface is handled in the present invention.
Fig. 3 is the control block diagram of the ultraviolet lighting reaction unit that coal particle surface is handled in the present invention.
In figure：1st, upper kettle；2nd, lower kettle；3rd, door-plate；4th, observation window；5th, reacting body；6th, chuck layer；7th, core plate；
8th, uviol lamp；9th, water inlet pipe；10th, coil pipe；11st, outlet pipe；12nd, entrance throttle；13rd, vacuum tube；14th, sensor；15th, data
Recorder；6th, vavuum pump；17th, vacuum meter；18th, vacuum choke valve；19th, oxygen supplying tube；20th, intake-air throttle valve；21st, air mass flow
Meter；22nd, air supplying pump；23rd, PLC；24th, display screen；5th, keyboard is inputted；6th, run switch；27th, button switch；28th, it is more
Orifice plate.
Embodiment
Implement a kind of ultraviolet lighting reaction experiment device of coal particle surface processing, including reactor, cooling water circulation system
System, vacuum system and oxygen system, specific embodiment are：Reactor is made up of upper kettle 1 and lower kettle 2, it is described on
Kettle 1 is made up of reacting body 5 and its chuck layer 6, and the lower end of the reacting body 5 is provided with core plate 7, top is provided with
Two uviol lamps 8, the positive side of upper kettle 1 is provided with door-plate 3 and its observation window 4；The upper end of the lower kettle 2 is provided with more
Orifice plate 28；
Cooling water recirculation system is made up of water inlet pipe 9, coil pipe 10 and outlet pipe 11, wherein：Entrance is installed on water inlet pipe 9
Choke valve 12 is arranged at reactor top；Outlet pipe 11 is arranged on the bottom of reactor；Coil pipe 10 is serpentine-like to be arranged at chuck layer 6
It is interior to be connected with water inlet pipe 9 and outlet pipe 11；
Vacuum system is made up of vacuum tube 13, sensor 14 and data logger 15, wherein, one end of vacuum tube 13 extends
Reactor is interior, the other end is communicated with vavuum pump 16, and vacuum meter 17 and vacuum choke valve 18 are sequentially installed with vacuum tube 13；
Oxygen system is to be provided with intake-air throttle valve 20, mass air flow sensor 21 and air supplying pump from left to right successively by oxygen supplying tube 19
22, the lower end that one end is communicated with lower kettle 2 is formed.
The scheme of further carrying out is that handle is provided with door-plate 3, and sealing ring is provided between door-plate 3 and reactor；Instead
It is aluminum alloy material to answer kettle, and anti-upper kettle 1 is 30cm × 30cm × 30cm cube structure；Lower kettle 2 is square cone structure,
Face be 20cm × 20cm square, high 10cm；The power of two uviol lamps 6 is 300W, ultraviolet wavelength be respectively 254nm and
365nm；Data logger 15 is colorful paper-free recorder, is arranged in the side wall of upper kettle 1；Sensor 14 is pressure-temperature
Integral sensor, on the inwall of reactant 5；PLC 23, data logger are provided with data logger 15
15 positive side is provided with display screen 24, and the downside of display screen 24 is provided with input keyboard 25, the left side of display screen 24
Run switch 26 is provided with, the downside of run switch 26 is provided with the button switch for controlling uviol lamp (8)（27）；PLC is controlled
Device 23 processed is connected by control signal wire with vavuum pump 16, air supplying pump 22, PLC 23 by signal wire and sensor 14,
Entrance throttle 12, vacuum choke valve 18, intake-air throttle valve 20, vacuum meter 17 and mass air flow sensor 21 are connected；Water inlet pipe, disk
Pipe 10, outlet pipe 11, vacuum tube 13 and oxygen supplying tube 19 are quality of rubber materials.
A kind of ultraviolet lighting reaction unit of particle surface processing, the ultraviolet lighting handled using coal particle surface react dress
The experimental method put, specific experiment method comprise the following steps：
S1, Preparatory work of experiment stage
A1, the jet coal for taking -0.5mm particle size fractions, ash content to be 32.27% are raw coal sample, prepare the sample of -0.074mm particle size fractions
Coal, it is standby；
A2, the coal sample for preparing using sample coal made from step A different densities, acid treatment coal sample, metal ion-modified coal sample,
TiO2Modified coal sample and odium stearate are modified coal sample, standby；
Wherein, any one coal sample in metal ion-modified coal sample load Fe3+, Mg2+, Na+, Sn2+；
S2, experimental stage
B1, weigh the sample coal that 4 parts of step a1 are prepared and be laid in respectively on core plate 7, open uviol lamp 8 and start to test, it is real
The ultraviolet light time in testing is 1-12h, time step 1h；Irradiation process is carried out in the environment of air circulation, will be every
Sample coal recovery after secondary experiment, is sealed with hermetic bag, and difference simultaneously carries out Zeta potential measure respectively, contact angle determination,
Infrared spectrum analysis and thermogravimetric analysis；
B2, the coal sample for weighing the different densities that 4 parts of step a2 are prepared are laid on core plate 7, carry out ultraviolet light respectively
Experiment, experimental method is identical with step b1, and carries out Zeta potential measure, contact angle respectively to the sample after the experiment of recovery
Measure, infrared spectrum analysis and thermogravimetric analysis；
B3, the 4 parts of acid treatment prepared coal samples progress ultraviolet light experiments being weighed, experimental method is identical with step b1, and
The sample for not carrying out illumination to the sample after the experiment of recovery and acid treatment coal sample carries out Zeta potential measure, contact angle respectively
Measure, infrared spectrum analysis and thermogravimetric analysis；
B4, weigh the metal ion-modified coal sample progress ultraviolet light experiment that 4 parts of step a2 are prepared, the same step of experimental method
B1, and the sample for not carrying out illumination to the sample after the experiment of recovery and metal ion-modified coal sample carries out Zeta potential respectively
Measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis；
B5, weigh the TiO2 that step a2 prepares be modified coal sample with former state coal it is well mixed after, weigh 4 parts of biased samples carry out it is purple
Outer illumination experiment, experimental method is identical with step b1, and does not carry out to the biased sample after the experiment of recovery and ultraviolet lighting
Biased sample carry out contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis respectively；
B6, weigh the odium stearate modification coal sample progress ultraviolet lighting experiment that 4 parts of step b2 are prepared, the same step of experimental method
B1, and the fakement for not carrying out ultraviolet lighting experiment to the sample after the experiment of recovery and stearic acid sodium modification coal sample is carried out respectively
Contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis；
B7,10g coal samples are weighed, are configured to 100g/L black water, be put into ultrasonic cleaner and carry out ultrasonication,
Ultrasonic frequency is 25kHz, power 300W；Ultraviolet light is carried out while being ultrasonically treated, irradiation time is respectively 1-
12h, time step 1h.Each sample after experiment is separately recovered, load valve bag be sealed, and respectively to processing after
Each sample carries out Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis.
In the experimental method of the above-mentioned ultraviolet lighting reaction unit handled using coal particle surface, carry out each ultraviolet
In line irradiation experimentation, the sample coal, the coal sample of different densities, acid treatment coal sample, metal ion-modified coal sample, the TiO that weigh2
The weight that modified coal sample and odium stearate are modified coal sample is 3g.
Technical scheme is clearly and completely described below in conjunction with accompanying drawing, it is clear that described is specific
Embodiment is only the part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, sheet
The every other embodiment that field those of ordinary skill is obtained under the premise of creative work is not made, belongs to the present invention
The scope of protection.
Embodiment 1
As illustrated in the accompanying drawings from 1 to 3, a kind of ultraviolet lighting reaction unit of coal particle surface processing, it includes reactor, cooling water follows
Loop system, vacuum system and oxygen system, reactor include upper kettle 1 and lower kettle 2, and the positive side of upper kettle 1 is set
There is door-plate 3, the middle part of door-plate 3 is provided with observation window 4, so as to realize that sample picks and places, while the experimental status in observing response kettle；
Upper kettle 1 is made up of reacting body 5 and chuck layer 6, and the lower end of reacting body 5 is provided with core plate 7, and core plate 7 is used to put
Laboratory sample is put, the top of reacting body 5, which is provided with 2 uviol lamps, 8,2 uviol lamps 8, to carry out purple to laboratory sample respectively
Outside line is irradiated, and can also simultaneously be opened and be carried out ultraviolet irradiation to laboratory sample；The upper end of lower kettle 2 is provided with porous plate 28,
For carrying out air circulation into upper kettle 1；Cooling water recirculation system includes water inlet pipe 9, coil pipe 10 and outlet pipe 11, water inlet
Pipe 9 is arranged on the top of reactor, and entrance throttle 12 is provided with water inlet pipe 9, and outlet pipe 11 is arranged on the bottom of reactor,
Coil pipe 10 is serpentine-like to be arranged in the chuck layer 6, and coil pipe 10 connects with water inlet pipe 9 and outlet pipe 11, so as to adjust upper kettle
Temperature in body 1, it is ensured that the temperature of ultraviolet irradiation remains at less than 120 DEG C；Vacuum system includes vacuum tube 13, sensor
14 and data logger 15, one end of vacuum tube 13 go deep into reactor, the other end of vacuum tube 13 is connected with vavuum pump 16,
Vacuum meter 17 and vacuum choke valve 18 are sequentially installed with the vacuum tube 13 in the left side of vavuum pump 16, so as to be provided for upper kettle 1
Vacuum environment, to meet the needs of the reaction of vacuum environment；Oxygen supply system includes oxygen supplying tube 19, and one end of oxygen supplying tube 19 is connected to lower kettle
The lower end of body 2, oxygen supplying tube are sequentially installed with intake-air throttle valve 20, mass air flow sensor 21 and air supplying pump 22 from left to right, with full
Foot needs the experimentation that aerobic environment is reacted.
In the present embodiment, handle is provided with door-plate 3, sealing ring is provided between door-plate 3 and reactor；Reactor is aluminium
Alloy material, anti-upper kettle 1 are 30cm × 30cm × 30cm cube structure；It is square cone structure to state lower kettle 2, and face is
20cm × 20cm square, high 10cm；The power of 2 uviol lamps 6 is 300W, ultraviolet wavelength be respectively 254nm and
365nm, experiment is irradiated so as to provide the ultraviolet light of two kinds of different wave lengths；Data logger 15 is colorful paper-free recorder,
It is arranged in the side wall of upper kettle 1；Sensor 14 is pressure-temperature integral sensor, on the inwall of reactant 5；
PLC 23 is provided with data logger 15, the positive side of data logger 15 is provided with display screen 24, display screen
24 downside is provided with the input keyboard 25 for setup parameter, and the left side of display screen 24 is provided with run switch 26, operation
The downside of switch 26 is provided with the button switch 27 for controlling uviol lamp 8；PLC 23 is by control signal wire and very
Empty pump 16, air supplying pump 22 are connected, and PLC 23 passes through signal wire and sensor 14, entrance throttle 12, vacuum choke valve
18th, intake-air throttle valve 20, vacuum meter 17 and mass air flow sensor 21 are connected, so as to realize the intelligent control of reaction unit, PLC controls
Device 23 processed judges the reaction environment in upper kettle 1, and then judge whether to need to open according to the data of the sensor 14 received
Water cooling system；Water inlet pipe 9, coil pipe 10, outlet pipe 11, vacuum tube 13 and oxygen supplying tube 19 are quality of rubber materials.
The experimental method of the ultraviolet lighting reaction unit handled using coal particle surface, comprises the following steps：
S1, Preparatory work of experiment stage
A1, the jet coal for taking -0.5mm particle size fractions, ash content to be 32.27% are raw coal sample, prepare the sample of -0.074mm particle size fractions
Coal, it is standby；
A2, the coal sample for preparing using sample coal made from step A different densities, acid treatment coal sample, metal ion-modified coal sample,
TiO2Modified coal sample and odium stearate are modified coal sample, standby；
Wherein, any one coal sample in metal ion-modified coal sample load Fe3+, Mg2+, Na+, Sn2+；
S2, experimental stage
B1, weigh the sample coal that 4 parts of step a1 are prepared and be laid in respectively on core plate 7, open uviol lamp 8 and start to test, it is real
The ultraviolet light time in testing is 1-12h, time step 1h；Irradiation process is carried out in the environment of air circulation, will be every
Sample coal recovery after secondary experiment, is sealed with hermetic bag, and difference simultaneously carries out Zeta potential measure respectively, contact angle determination,
Infrared spectrum analysis and thermogravimetric analysis；
B2, the coal sample for weighing the different densities that 4 parts of step a2 are prepared are laid on core plate 7, carry out ultraviolet light respectively
Experiment, experimental method is identical with step b1, and carries out Zeta potential measure, contact angle respectively to the sample after the experiment of recovery
Measure, infrared spectrum analysis and thermogravimetric analysis；
B3, the 4 parts of acid treatment prepared coal samples progress ultraviolet light experiments being weighed, experimental method is identical with step b1, and
The sample for not carrying out illumination to the sample after the experiment of recovery and acid treatment coal sample carries out Zeta potential measure, contact angle respectively
Measure, infrared spectrum analysis and thermogravimetric analysis；
B4, weigh the metal ion-modified coal sample progress ultraviolet light experiment that 4 parts of step a2 are prepared, the same step of experimental method
B1, and the sample for not carrying out illumination to the sample after the experiment of recovery and metal ion-modified coal sample carries out Zeta potential respectively
Measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis；
B5, weigh the TiO2 that step a2 prepares be modified coal sample with former state coal it is well mixed after, weigh 4 parts of biased samples carry out it is purple
Outer illumination experiment, experimental method is identical with step b1, and does not carry out to the biased sample after the experiment of recovery and ultraviolet lighting
Biased sample carry out contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis respectively；
B6, weigh the odium stearate modification coal sample progress ultraviolet lighting experiment that 4 parts of step b2 are prepared, the same step of experimental method
B1, and the fakement for not carrying out ultraviolet lighting experiment to the sample after the experiment of recovery and stearic acid sodium modification coal sample is carried out respectively
Contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis；
B7,10g coal samples are weighed, are configured to 100g/L black water, be put into ultrasonic cleaner and carry out ultrasonication,
Ultrasonic frequency is 25kHz, power 300W；Ultraviolet light is carried out while being ultrasonically treated, irradiation time is respectively 1-
12h, time step 1h.Each sample after experiment is separately recovered, load valve bag be sealed, and respectively to processing after
Each sample carries out Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis.
In each ultraviolet irradiation experimentation is carried out, the sample coal, the coal sample of different densities, the acid treatment coal that weigh
Sample, metal ion-modified coal sample, TiO2The weight that modified coal sample and odium stearate are modified coal sample is 3g.
According to the experimental procedure of the present embodiment, sample coal is carried out successively and carries out the Zeta potential survey after ultraviolet pre-irradiation
Fixed, contact angle determination, infrared spectrum analysis and thermogravimetric analysis, the coal sample of different densities carry out the Zeta electricity after ultraviolet pre-irradiation
Position-finding, contact angle determination, infrared spectrum analysis and thermogravimetric analysis, acid treatment coal sample carry out the Zeta electricity after ultraviolet pre-irradiation
Position-finding, contact angle determination, infrared spectrum analysis and thermogravimetric analysis, after metal ion-modified coal sample carries out ultraviolet pre-irradiation
Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis, TiO2After modified coal sample carries out ultraviolet pre-irradiation
Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis, odium stearate be modified coal sample carry out ultraviolet photograph
Penetrate front and rear Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis, it is known that：
1st, influence of the coal sample property to coal photooxidation reaction coal wetability is as follows：
（1）, the coal sample contact angle after ultraviolet light reduce, Zeta potential diminishes, and hydrophobicity reduces, i.e. coal sample surface is ultraviolet
Aoxidized under light action, when light application time is 1-2h, ultraviolet light is maximum to the oxidizing intensity of coal sample；
（2）, analyzed by FTIR, ultraviolet light can damage to the aromatic hydrocarbon in coal reservoir, cause coal
The destruction of organic structure, while the ester in coal or ether generation hydrolysis generation-OH and-COOH are catalyzed, these are newly-generated
Oxygen-containing functional group can also occupy part-CH2And-CH3H atom on group, ultimately result in coal surface and be oxidized；
（3）, certain content inorganic mineral facilitation can be played to the catalytic oxidation of ultraviolet light, and work as mineral content mistake
This effect can all weaken when more or very few；
（4）, the aromatic hydrocarbon in coal a variety of multi-forms be present, the ultraviolet light under cryogenic conditions can only be to which part form
Aromatic ring structure damage；And to the aromatic hydrocarbon structural damage in coal caused by hydrochloric Acid Modification, after treatment with ultraviolet light
A certain degree of recovery can be obtained.
2nd, influence of the additive to coal photooxidation reaction coal wetability is as follows：
（1）、Mg2+Carbonyl hydrolysis generation-OH and-COOH are mainly caused in modifying process, and causes methyl and methylene
Radix amount is reduced, therefore, Mg2+Modification can cause the obvious oxidation on coal surface.But during ultraviolet light, Mg2+Presence
Fragrant hydrocarbon structure can be protected, avoids its further destruction by ultraviolet light；
（2）、Fe3+In modifying process in addition to causing carbonyl and hydrolyzing, the fragrant hydrocarbon structure that can also acutely destroy in coal.Fe3+It is modified
During be mainly hydrogenating reduction to the failure mechanism of aromatic hydrocarbon, the irradiation of ultraviolet light can be to a certain extent to this partial aromatic
Hydrocarbon produces dehydrogenation effect, and this oxidation can also make coal sample surface hydrophobic be deteriorated；
（3）、Cu2+The modified mechanism for destroying aromatic hydrocarbon is also to promote aromatic hydrocarbon there occurs hydrogenating reduction, and ultraviolet light can make
This reaction is inversely carried out；
（4）、Na+The key reaction occurred in modifying process is the destruction of aromatic hydrocarbon and increasing for-OH, but response intensity is relatively low.
Meanwhile Na+Presence suppression, further oxygen of the protection coal sample from ultraviolet light can be also produced to the catalysed oxidn of ultraviolet light
Change, therefore, in succession by Na+After modified and ultraviolet light, coal sample surface nature is basically unchanged；
（5）、Sn2+Modified and Mg2+、Fe3+Modification has very big similitude, can cause aromatic hydrocarbon structural damage, and cause ester
Class hydrolyzes, while causes the reduction of methyl, methylene.But Sn2+The degree of oxidation on modified surface is more violent, and hydrophobicity is seriously disliked
Change.Sn2+Modification is similar to the failure mechanism of aromatic hydrocarbon with ultraviolet oxidation；
（6）、TiO2Catalyst action is played in the reaction of ultraviolet oxidation coal reservoir, by oxygen after itself being first reduced
Change, oxygen can be provided for reactant in course of reaction；
（7）, odium stearate is modified can cause the violent improvement of coal surface wettability, while coal sample can be protected in ultraviolet light mistake
It is not oxidized in journey.
3rd, light-influence of the acoustical coupling effect to coal wetability is as follows：
（1）, ultrasonic wave mainly coal sample is cleaned by cavitation etc., crushed in media as well, while increase in medium
Dissolved oxygen amount, so as to aggravate the oxidation of coal sample in medium；
（2）, during ultrasonication, the newly-generated oxygen-containing functional group in coal surface is mainly carbonyl-C=O and hydroxyl-OH；
（3）, ultrasonication and ultraviolet light have synergy in terms of the photooxidation process of coal is strengthened, be efficient photooxidation
The design of reaction unit provides new approaches.
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art,
It can still modify to the technical scheme described in foregoing embodiments, or which part technical characteristic is carried out etc.
With replacing, within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., this should be included in
Within the protection domain of invention.
Claims (7)
1. a kind of ultraviolet lighting reaction experiment device of coal particle surface processing, including reactor, cooling water recirculation system, vacuum
System and oxygen system, it is characterised in that：
The reactor is by upper kettle（1）With lower kettle（2）Form, the upper kettle（1）It is by reacting body（5）And its
Chuck layer（6）Form, the reacting body（5）Lower end be provided with core plate（7）, top be provided with two uviol lamps（8）,
Upper kettle（1）Positive side be provided with door-plate（3）And its observation window（4）；The lower kettle（2）Upper end be provided with porous plate
（28）；
The cooling water recirculation system is by water inlet pipe（9）, coil pipe（10）And outlet pipe（11）Form, wherein：Water inlet pipe（9）
On entrance throttle is installed（12）It is arranged at reactor top；Outlet pipe（11）It is arranged on the bottom of reactor；Coil pipe（10）
It is serpentine-like to be arranged at chuck layer（6）Interior and water inlet pipe（9）And outlet pipe（11）It is connected；
The vacuum system is by vacuum tube（13）And its sensor（14）And data logger（15）Form, wherein, vacuum tube
（13）One end extend in reactor, the other end is communicated with vavuum pump（16）, and in vacuum tube（13）On be sequentially installed with it is true
Empty table（17）With vacuum choke valve（18）；
The oxygen system is by oxygen supplying tube（19）Intake-air throttle valve is installed from left to right successively（20）, mass air flow sensor（21）
And air supplying pump（22）, one end is communicated with lower kettle（2）Lower end form.
2. reaction unit as claimed in claim 1, it is characterised in that：The uviol lamp（8）Power be 300W, ultraviolet light
Wavelength is 254nm and 365nm respectively.
3. reaction unit as claimed in claim 1, it is characterised in that：The data logger（15）It is colored paperless tests
Instrument, it is arranged at upper kettle（1）Side wall, in data logger（15）Inside it is provided with PLC（23）, in data logger
（15）Positive side be provided with display screen（24）, display screen（24）Downside be provided with input keyboard（25）, left side set
There is run switch（26）, in run switch（26）Downside be provided with for controlling uviol lamp（8）Button switch（27）；
Wherein：The PLC（23）It is by control signal wire and vavuum pump（16）And air supplying pump（22）It is connected, control is led to
Cross signal wire and sensor（14）, entrance throttle（12）, vacuum choke valve（18）, intake-air throttle valve（20）, vacuum meter（17）
And mass air flow sensor（21）It is connected.
4. reaction unit as claimed in claim 1, it is characterised in that：The sensor（14）It is that pressure-temperature integral type passes
Sensor, installed in reactant（5）Inwall on.
5. reaction unit as claimed in claim 1, it is characterised in that：The water inlet pipe（9）, coil pipe（10）, outlet pipe（11）、
Vacuum tube（13）And oxygen supplying tube（19）It is quality of rubber materials pipe.
6. reaction unit as claimed in claim 1, it is characterised in that：The ultraviolet lighting handled using coal particle surface reacts real
The experimental method of experiment device, the experimental method press step progress：
（1）, the Preparatory work of experiment stage
1）The jet coal for taking -0.5mm particle size fractions, ash content to be 32.27% is raw coal sample, prepares the sample of -0.074mm particle size fractions
Coal, it is standby；
2）The coal samples of different densities, acid treatment coal sample, metal ion-modified coal sample, TiO are prepared with sample coal2Modified coal sample and
Odium stearate is modified coal sample, standby；
Wherein, any one coal sample in metal ion-modified coal sample load Fe3+, Mg2+, Na+, Sn2+；
3）Experimental stage
Ith, 4 parts of steps 1 are weighed）The sample coal prepared is laid in core plate respectively（7）On, open uviol lamp（8）Start to test,
The ultraviolet light time in experiment is 1-12h, time step 1h；Irradiation process is carried out in the environment of air circulation, will
Sample coal recovery after experiment every time, is sealed with hermetic bag, and carries out Zeta potential measure respectively, and contact angle determination is red
External spectrum is analyzed and thermogravimetric analysis；
IIth, 4 parts of steps 2 are weighed）The coal sample of the different densities prepared is laid in core plate（7）On, ultraviolet lighting is carried out respectively
Experiment is penetrated, experimental method is identical with step b1, and carries out Zeta potential measure, contact angle respectively to the sample after recovery experiment
Measure, infrared spectrum analysis and thermogravimetric analysis；
IIIth, the 4 parts of acid treatment prepared coal samples are weighed and carry out ultraviolet light experiment, experimental method is identical with step II, and right
The sample that sample and acid treatment coal sample after the experiment of recovery do not carry out illumination carries out Zeta potential measure respectively, and contact angle is surveyed
It is fixed, infrared spectrum analysis and thermogravimetric analysis；
IVth, 4 parts of steps 2 are weighed）The metal ion-modified coal sample prepared carries out ultraviolet light experiment, the same step of experimental method
1）, and the sample for not carrying out illumination to the sample after the experiment of recovery and metal ion-modified coal sample carries out Zeta potential respectively
Measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis；
Vth, step 2 is weighed）After the TiO2 modification coal samples prepared are well mixed with former state coal, weigh 4 parts of biased samples and carry out purple
Outer illumination experiment, experimental method and step 1）It is identical, and do not carry out to the biased sample after the experiment of recovery and ultraviolet lighting
Biased sample carry out contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis respectively；
VIth, 4 parts of steps 2 are weighed）The odium stearate prepared is modified coal sample and carries out ultraviolet lighting experiment, the same step of experimental method
1）, and the fakement for not carrying out ultraviolet lighting experiment to the sample after the experiment of recovery and stearic acid sodium modification coal sample is carried out respectively
Contact angle determination, Zeta potential measure, infrared spectrum analysis and thermogravimetric analysis；
VIIth, 10g coal samples are weighed, are configured to 100g/L black water, is put into ultrasonic cleaner and carries out ultrasonication,
Ultrasonic frequency is 25kHz, power 300W；Ultraviolet light is carried out while being ultrasonically treated, irradiation time is respectively 1-
12h, time step 1h；Each sample after experiment is separately recovered, load valve bag be sealed, and respectively to processing after
Each sample carries out Zeta potential measure, contact angle determination, infrared spectrum analysis and thermogravimetric analysis.
7. reaction unit as claimed in claim 6, it is characterised in that：In the ultraviolet irradiation experimentation carried out every time,
Sample coal, the coal sample of different densities, acid treatment coal sample, metal ion-modified coal sample, the TiO weighed2Modified coal sample and tristearin
The weight that sour sodium is modified coal sample is 3g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710644997.8A CN107643245A (en) | 2017-08-01 | 2017-08-01 | A kind of ultraviolet lighting reaction experiment device of coal particle surface processing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710644997.8A CN107643245A (en) | 2017-08-01 | 2017-08-01 | A kind of ultraviolet lighting reaction experiment device of coal particle surface processing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107643245A true CN107643245A (en) | 2018-01-30 |
Family
ID=61110906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710644997.8A Pending CN107643245A (en) | 2017-08-01 | 2017-08-01 | A kind of ultraviolet lighting reaction experiment device of coal particle surface processing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107643245A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111188594A (en) * | 2020-02-22 | 2020-05-22 | 太原理工大学 | Old goaf coal slime water gas-liquid fluidized mining device and method |
| CN112798467A (en) * | 2020-12-15 | 2021-05-14 | 中煤科工集团唐山研究院有限公司 | Intelligent online ash detection device and detection method based on high-speed microscopic vision |
| KR20220073285A (en) * | 2020-11-26 | 2022-06-03 | 현대제철 주식회사 | Evaluation device for dust coal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101495404B1 (en) * | 2012-12-12 | 2015-02-24 | 주식회사 포스코 | Apparatus for preventing clogging in cokes mixer |
| CN204220157U (en) * | 2014-09-15 | 2015-03-25 | 南京信息工程大学 | A kind of use for laboratory ultraviolet lighting case |
| CN105217721A (en) * | 2015-11-04 | 2016-01-06 | 郑州轻工业学院 | A kind of photochemical catalysis composite separating film water treatment device and water treatment system |
| CN205412636U (en) * | 2016-04-01 | 2016-08-03 | 河南理工大学 | Device of vacuum -ultraviolet light degradation coal mine gas |
-
2017
- 2017-08-01 CN CN201710644997.8A patent/CN107643245A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101495404B1 (en) * | 2012-12-12 | 2015-02-24 | 주식회사 포스코 | Apparatus for preventing clogging in cokes mixer |
| CN204220157U (en) * | 2014-09-15 | 2015-03-25 | 南京信息工程大学 | A kind of use for laboratory ultraviolet lighting case |
| CN105217721A (en) * | 2015-11-04 | 2016-01-06 | 郑州轻工业学院 | A kind of photochemical catalysis composite separating film water treatment device and water treatment system |
| CN205412636U (en) * | 2016-04-01 | 2016-08-03 | 河南理工大学 | Device of vacuum -ultraviolet light degradation coal mine gas |
Non-Patent Citations (1)
| Title |
|---|
| 杨志远 等: "神府煤光催化氧化降解过程的FTIR研究", 《煤炭学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111188594A (en) * | 2020-02-22 | 2020-05-22 | 太原理工大学 | Old goaf coal slime water gas-liquid fluidized mining device and method |
| KR20220073285A (en) * | 2020-11-26 | 2022-06-03 | 현대제철 주식회사 | Evaluation device for dust coal |
| KR102504648B1 (en) * | 2020-11-26 | 2023-03-02 | 현대제철 주식회사 | Evaluation device for dust coal |
| CN112798467A (en) * | 2020-12-15 | 2021-05-14 | 中煤科工集团唐山研究院有限公司 | Intelligent online ash detection device and detection method based on high-speed microscopic vision |
| CN112798467B (en) * | 2020-12-15 | 2023-01-31 | 中煤科工集团唐山研究院有限公司 | Intelligent online ash detection device and detection method based on high-speed microscopic vision |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107643245A (en) | A kind of ultraviolet lighting reaction experiment device of coal particle surface processing | |
| Rizwan et al. | Hydrogen-based sono-hybrid catalytic degradation and mitigation of industrially-originated dye-based pollutants | |
| WO2014079170A1 (en) | Distillation-free biodiesel production method and system | |
| CN110156120A (en) | Sewage-treatment plant and processing method | |
| CN202089801U (en) | Ultrasonic sewage treatment unit | |
| CN109911995A (en) | A kind of blue algae resource method having both algae toxin removing and algae solution high-efficiency dehydration | |
| CN209456225U (en) | A kind of organic waste-water treating apparatus | |
| CN208916893U (en) | A kind of catalytic ozonation stirring reactor | |
| CN107364991A (en) | A kind of catalytic ozonation ozone air-float integrated apparatus | |
| CN108218047A (en) | A kind of ocean vessel ballast water for the operation of port area handles barge | |
| CN108298777A (en) | A kind of circulating type multilayer sewage-treatment plant and method | |
| CN207608474U (en) | Reactor for treating excess sludge by cavitation jet | |
| CN106039956B (en) | A kind of energy-saving multi-effect VOCs purification reactors and VOCs purifying treatment methods | |
| CN107731336A (en) | The method that combination of ultrasound wet oxidation Fenton methods handle radioactive wastewater | |
| CN217638234U (en) | Chemical reaction device for preparing carbon-14 sample in water | |
| CN203402985U (en) | Device for degrading microcystic toxins in water by adopting silver phosphate catalyst under condition of simulating visible light | |
| CN215480275U (en) | Integrated accident oil pool of transformer substation | |
| CN206069491U (en) | A kind of waste water automatic processing device based on magnetic nano-catalyst | |
| CN205892984U (en) | Production life effluent disposal system of photovoltaic energy enterprise | |
| CN105439276B (en) | A kind of oxidation catalysis post removes mine water middle and high concentration ferrimanganic device and its processing method | |
| CN105800845B (en) | Mixed catalyst ultrasonic atomizatio organic sewage cleaning system under the conditions of ultraviolet | |
| CN209368028U (en) | Handle the reaction tower of organic wastewater | |
| CN208995315U (en) | A kind of cycling use of water night soil-treatment lavatory of intelligence control | |
| CN206143011U (en) | Contrary recycling treatment device of sewage | |
| CN206328207U (en) | A kind of high efficiency anaerobic reactor for highly concentrated wastewater from chemical industry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180130 |
|
| WD01 | Invention patent application deemed withdrawn after publication |