CN109607694A - A kind of kasugarnycin raw medicine workshop condensed water recycling device and method - Google Patents
A kind of kasugarnycin raw medicine workshop condensed water recycling device and method Download PDFInfo
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- CN109607694A CN109607694A CN201811608840.0A CN201811608840A CN109607694A CN 109607694 A CN109607694 A CN 109607694A CN 201811608840 A CN201811608840 A CN 201811608840A CN 109607694 A CN109607694 A CN 109607694A
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- kasugarnycin
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- PVTHJAPFENJVNC-MHRBZPPQSA-N kasugamycin Chemical compound N[C@H]1C[C@H](NC(=N)C(O)=O)[C@@H](C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H]1O PVTHJAPFENJVNC-MHRBZPPQSA-N 0.000 description 1
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- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
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- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 description 1
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- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
-
- 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention relates to a kind of kasugarnycin workshop concentration water cycle utilization device and desalination process, the device is made of DC power supply, peristaltic pump, CDI, concentration pond, the desalter is to carry out desalination to the condensed water of kasugarnycin raw medicine workshop based on electrochemistry and capacitive couplings, this kind of device of the present invention can remove the various salt ions in the condensed water of kasugarnycin workshop well, effluent quality is set to meet greening water supply standard, while the water handled is Ke Xunhuanliyong.
Description
Technical field
The invention belongs to the technical fields of antibiotic water process, and in particular to a kind of kasugarnycin workshop condensed water is followed
Ring utilizes device and desalination process.
Background technique
Kasugarnycin (Kasugamycin) is called kasugarnycin, kasumin, be bySterptomyces Kasugaensis
OrSterptomycesmicroaureusFerment the secondary metabolite generated, it is a kind of micro- life for preventing and treating corps diseases
Material resource disinfectant use in agriculture, entitled (5- amino-2-methyl -6-(2,3,4,5, the 6- hydroxy-cyclohexyl oxos) oxinane-of chemistry
3- yl) amino-α-amine acetic acid, molecular formula C14H25N3O9, molecular weight 379.4.Kasugarnycin sterling is white crystals；Hydrochloric acid
Salt is white needles or flaky crystal, and sterling fusing point: 236~239 DEG C are decomposed, HCI m. p: 202~204 DEG C (decomposition), easily
It is dissolved in water, dissolves 12.5%(W/V in 25 DEG C of water), insoluble in organic solvents such as methanol, ethyl alcohol, acetone, benzene.Kasugarnycin tool
There is very strong interior suction permeability, while there is preventive and therapeutic action, therapeutic effect is more significant, and the mechanism of action is albumen
Matter synthetic inhibitor.There is inhibitory activity to bacterium, fungi, especially has excellent preventive effect to rice blast fungus, to watermelon
The diseases such as bacterial angular leaf spot, peach gummosis, citrus bacterial canker disease also have special efficacy.It is main to collect since kasugarnycin is found
The research of middle following aspect: 1, kasugarnycin context of detection, such as the long group of ox determine kasugarnycin using the analysis of RP-HPLC method
Content in fermentation liquid.Wu Guoxu etc. based on the above method, in conjunction with itself instrument trait, divides than right different quality
Influence of several SDS to kasugarnycin appearance time.The study found that when the mass fraction of SDS is 1.0, when obtained appearance
Between more be suitable for, detection effect is more satisfactory；Zhang Chuntaos etc. are built by optimizing processing to analysis method and pre-treating method
It has found ion and has changed resin solid phase extraction-residue analysis method of the Ion-pair HPLC kasugarnycin in environmental water sample；Lu
Flower bud etc. analyzes and researches to kasugarnycin wettable powder using LC-MS method, and is selected by the optimization to testing conditions
It selects, establishes the analyzing detecting method of kasugarnycin；It opens clean wait and determines the acquisition of Jiangxi Province's difference rice region using growth rate method
40 rice acne sick seedling strains to the drug resistance of rice acne spirit and kasugarnycin, the results showed that these single armful of mattress strains of rice acne germ are to rice cancer
The resistance of spirit and kasugarnycin is lower, and cultivated rice cancer bacterium does not also cause interactive drug resistance to the spirit of rice acne and kasugarnycin.It is external
There is Lu etc. to have studied degradation status and residual of the kasugarnycin on capsicum and ± earth, remaining kasugarnycin is mentioned from sample
Out, it through Solid Phase Extraction column purification, is finally detected with superelevation Liquid Chromatography-Tandem Mass Spectrometry.The TIANZHU XINGNAO Capsul that this method obtains is
7.782-83.35%, relative standard deviation 2.2%-6.54%.Sheu etc. determines kasugarnycin using detection method analysis and exists
The residual quantity in sight water is filled, this method accuracy, precision are good, and TIANZHU XINGNAO Capsul is between 111.2-111.7%, phase
To standard deviation under 70%；2, it in terms of the strain improvement of streptomyces microaureus, such as pays osmanthus outstanding person and uses N~+ implantation technology
Mutation breeding is carried out to kasugarnycin producing strains, the superior strain fermentation titer that breeding goes out improves 5.44%, constituent content quality
Score improves 4.5%, and strain stability is preferable, and generated economic benefit is also higher；Jinchang is strolled etc. through mutagenic treatment spring thunder
Mycin producing strains have selected high yield seedling strain US95#, the results showed that and producing strain height, genetic stability, tank fermentation level is high,
It is suitble to large-scale production；3, streptomyces microaureus gene studies, such as Zhu pass through the left wing of kasugarnycin biological synthesis gene cluster
Region identifies five genes relevant to kasugarnycin, double groups of valence regulator control system KasW/KasX, MerR family transcriptional controls
The KasS of factor K asV, approach specific regulatory control factor K asT and coding isoprene cysteine carboxymethyl transferase.As a result
Show: 3 times of output increased of high expressing K asT gene kasugarnycin.Kasugarnycin biology in KasW, X, V and S deletion mutation strain
The yield of synthesis has been respectively increased 112,119,294 and 122%；By knocking out KasW/KasX genetic method, kasugarnycin yield
58% is improved, but after knocking out KasV gene, high expressing K asT, kasugarnycin yield does not have significant change, knocks out the KasS gene spring
Thunder mycin yield has dropped 43%；4, in terms of kasugarnycin interworking, as kasugarnycin and tricyclazole, kasugarnycin and Ningnanmycin,
Kasugarnycin and Prochloraz, kasugarnycin and pyraclostrobin etc..
Although related kasugarnycin detection, strain improvement, streptomyces microaureus gene regulation, kasugarnycin and other drugs
It is relatively more to be mutually used in disease of agricultural plants prevention and treatment report, and is generated during kasugarnycin fermentation and separation purifying technique useless
How water handles lacking for report, and especially production kasugarnycin raw medicine workshop condensed water recycles aspect, so far without correlation
Patent and report.Domestic and international kasugarnycin raw medicine workshop condensed water usually with washing water in workshop, ion exchange waste water,
Nanofiltration membrane waste water is directly discharged into sewage treatment plant through sewage conduct, on the one hand increases sewage treatment plant's processing processing waste water
Load, on the other hand also increase kasugarnycin wastewater treatment expense.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides a kind of kasugarnycin workshop condensed water
The kasugarnycin workshop condensed water recycling device is handled kasugarnycin workshop by recycling device and desalination process
Condensed water of the tap water workshop pipeline through reverse osmosis membrane, and to its tap water through reverse osmosis concentration water process.The present invention utilizes should
Kasugarnycin workshop condensed water recycling device can handle the condensed water in kasugarnycin workshop well, use water quality and meet factory
Water supply standard is afforested on ground, and the low reduction kasugarnycin wastewater treatment expense of high degree meets the requirement of national energy conservation and emission reduction.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of kasugarnycin raw medicine workshop condensed water recycling device, including CDI device and condensed water pond, CDI device
Inlet and outlet are communicated with condensed water pond respectively, which is characterized in that the electrode material in the CDI device is active carbon
Material, conductive agent and binder after the weight ratio mixing of 20:3:2 to be made.
The absorbent charcoal material is capacitance carbon.
The binder is Kynoar.
The CDI device includes capacitive deionization unit and electrochemical oxidation unit, the electrochemical oxidation unit and electricity
Hold deionization unit to be connected, condensed water passes sequentially through capacitive deionization unit and electrochemical oxidation unit after entering CDI device.
The capacitive deionization unit includes central gasket, and central gasket center is provided with treatment trough, the side for the treatment of trough
On be provided with two apertures communicated with gasket side, respectively as the inlet and outlet of capacitive deionization unit, gasket
Two sides be respectively arranged with collector, two-side current collecting body is provided with electrode material towards gasket on one side.
The electrochemical oxidation unit includes intermediate washer, and intermediate washer center is provided with oxidation trough, the side of oxidation trough
On be provided with two apertures communicated with intermediate washer side, respectively as the inlet and outlet of electrochemical oxidation unit,
The two sides of intermediate washer are fitted with anode plate and cathode plate, and the cathode plate is made of outside fitting electrode material in collector,
Cathode plate is fitted with PMMA flow-field plate far from the side of intermediate washer.
The PMMA flow-field plate includes plate body, and flow field grooves are arranged towards the side of cathode plate in plate body, and the side of flow field grooves is set
It is equipped with the opening communicated with plate body side, respectively air inlet and air outlet, by air inlet and air outlet to electrochemical oxidation
Unit cathodes area is passed through oxygen, for aoxidizing the organic matter in water.
It is described center gasket or intermediate washer with a thickness of 2mm.
The method that water desalination is concentrated in kasugarnycin workshop is carried out using above-mentioned apparatus the present invention also provides a kind of,
It is characterized in that, the flow that condensed water enters CDI device is 2-10mL/min, and the operation voltage of CDI device is 1.0-2.0V.
The salinity of the condensed water into CDI device is controlled in 100-400mg/L.
Compared with the prior art, the advantages of the present invention are as follows:
1, the device is good through the resulting condensed water of reverse osmosis membrane treated desalting effect to kasugarnycin workshop, water-flowing amount is high and
Low energy consumption.
2, the service using life is long, desalting effect is reproducible, the device is in desorption process, which is alternatively arranged as
Battery uses.
3, the Na in effluent quality+、K+、Ca2+、Mg2+It is all using water quality standard and lasting desalination time extension etc. to meet greening
More advantages.
Detailed description of the invention
Fig. 1 is condensed water recycling device structural schematic diagram in kasugarnycin workshop of the present invention；
Fig. 2 is the structural schematic diagram of capacitive deionization unit of the present invention；
Fig. 3 is the structural schematic diagram of electrochemical oxidation unit of the present invention；
Fig. 4 is the appearance diagram of absorbent charcoal material；
Fig. 5 is the absorbent charcoal material micromorphology schematic diagram under scanning electron microscope；
Fig. 6 is the electrode micromorphology schematic diagram under environmental scanning electronic microscope；
Fig. 7 is scanning speed when being 2mv/s, conventional activated carbon (conventional AC) and capacitance carbon (capacitive AC)
Cyclic voltammetry curve；
Fig. 8 is the different conventional activated carbons (conventional AC) swept under speed and capacitance carbon (capacitive AC) than electricity
Capacity；
Fig. 9 is the adsorbance change curve of conventional activated carbon (conventional AC) and capacitance carbon (capacitive AC)；
Figure 10 is scanning speed when being 10mv/s, uses polyvinyl alcohol (PVA) and sodium carboxymethylcellulose (CMC-Na) following not
Ring volt-ampere curve；
Figure 11 is scanning speed when being 5mv/s, and Kynoar makees the cyclic voltammetry curve of binder；
Figure 12 is scanning speed when being 5mv/s, the cyclic voltammetry curve under different composition ratio；
Figure 13 is that sodium chloride content changes over time curve in pond under different operation voltage；
Figure 14 is that electrode adsorption amount changes over time curve under different initial concentrations；
Figure 15 is that the conductivity of different ions solution changes over time curve.
Specific embodiment
Method and effect of the invention are described in further detail in the following with reference to the drawings and specific embodiments.
The present invention provides a kind of kasugarnycin raw medicine workshop condensed water recycling device, the structure of the device such as Fig. 1
It is shown, including condensed water pond 1, peristaltic pump 2, CDI device 3, DC power supply 4 and conductivity meter 5, there is water inlet on CDI device
Mouth and water outlet, the inlet and outlet of CDI device pass through pipeline respectively and communicate with condensed water pond 1, wherein with water inlet
Peristaltic pump 2 is provided on connected pipeline, CDI device is connected with DC power supply 4, and DC power supply 4 provides direct current for CDI device
Pressure, conductivity meter 5 are used for the conductivity tested in condensed water pond.
The CDI device includes capacitive deionization unit, and condensed water passes through electricity after peristaltic pump enters in CDI device
It is desalted after holding deionization unit.
As shown in Fig. 2, the capacitive deionization unit includes central gasket 11, central 11 center of gasket is provided with treatment trough
110, two apertures communicated with 11 side of central gasket are provided on the side for the treatment of trough 110, respectively as capacitive deionization
The water inlet 111 and water outlet 112 of unit, the two sides of central gasket 11 are respectively arranged with collector 12, and collector 12 is in
Centre gasket 11 is provided with electrode material 13 on one side, and the side of collector 12 outwardly is provided with end plate 14, end plate 14 and collector
It is provided with gasket 15 between 12, diaphragm 16, central gasket 11, diaphragm 16, collection are provided between collector 12 and central gasket 11
Capacitive deionization unit is formed by way of being bonded to each other between fluid 12, gasket 13 and end plate 14.Electricity on collector 12
Pole material side is anode plate, and other side is cathode plate, is connected respectively with the anode and cathode of DC power supply.Condensed water from into
The mouth of a river 111 enters in treatment trough 110, and condensed water flows through between electrode, under the action of the DC voltage, in condensed water sun from
Son is attracted to negative terminal surface, while chloride ion etc. and is attracted to positive electrode surface, as ion is constantly adsorbed, the concentration of solution
It gradually decreases, to realize the removing of effects of ion.
When the close saturation of absorption, electrode is shorted, due to the presence of potential difference, the ion for being adsorbed on electrode surface can be released
It is put into solution, as solution flows out, realizes electrode regeneration.
The CDI device further includes electrochemical oxidation unit, and electrochemical oxidation unit is connected with capacitive deionization unit, dense
Shrink, which is rushed after capacitive deionization unit comes out, enters electrochemical oxidation unit.
As shown in figure 3, electrochemical oxidation unit includes intermediate washer 21, gasket center is provided with oxidation trough 210, oxidation trough
Two apertures communicated with intermediate washer side are provided on 210 side, respectively as the water inlet of electrochemical oxidation unit
211 and water outlet 212, the two sides of intermediate washer 21 are fitted with anode plate 22 and cathode plate 23, and the cathode plate 23 is by collector
Interior outside fitting electrode material composition, cathode plate 23 are provided with PMMA flow-field plate 24, flow-field plate far from the side of intermediate washer 21
24 center is provided with flow field grooves 240, and the side of flow field grooves 240 is provided with two communicated with 24 side of PMMA flow-field plate and opens
Mouth, respectively air inlet 241 and gas outlet 242.Flow-field plate effect is to be passed through oxygen, is aoxidized in electrochemical oxidation unit cathodes area
Organic matter in water.Anode plate 22 is provided with end plate 25 far from the side of intermediate washer 21, sets between end plate 25 and anode plate 22
It is equipped with gasket 26.
From capacitive deionization unit water outlet come out condensed water from the water inlet 211 of electrochemical oxidation unit enter to
Electrochemical oxidation unit, electrochemical oxidation process are the effects by applying direct current electric field, generate hydroxyl radical free radical in electrode surface,
H2O or OH- in solution discharge on anode generates the hydroxyl radical free radical [OH] of ADSORPTION STATE, MOX+H2O → MOX [OH]+H
++ with organic matter (R) electrochemical oxidation reactions (complete oxidation) can occur for the hydroxyl radical free radical (OH) of e-, ADSORPTION STATE.
On the direction that condensed water is advanced, since ion is constantly removed, the conductivity of solution is lower and lower, in direct current
Water, which can be dissociated, under the action of pressure maintains the magnitude of current of system to generate enough H+ and OH-ion, in electrochemistry oxygen
Changing OH- in unit can be aoxidized with the organic matter in water, on the one hand in addition to having to desalination in water in electrochemical oxidation unit
Certain effect, moreover it is possible to remove Organic substance in water effect.Electrochemical cell still further aspect maintains system H+ and OH-, in turn
The magnitude of current of the system is maintained, to guarantee that capacitive desalination is normally carried out in the system.
In said structure, it is made after cathode plate and anode plate are mixed by electrode material with conductive agent and bonding agent.
In order to determine which kind of electrode material is CDI optimum electrode material, most start to attempt to make using graphite carbon felt in experiment
Main body, the reason is that the electric conductivity and hydrophily of graphite carbon felt are all fine, but almost without effect on adsorption effect, the reason is that stone
Black felt does not have adsorption site, and hydrophily is fine, and ion is not able to maintain the state being adsorbed on thereon.
Then electrode material is turned to active carbon, active carbon has very strong adsorptivity, and all the time, the application of active carbon
All be especially extensively, it is also commonplace in water process.This time two kinds of active carbon (conventional activated carbons have been selected in experiment
Conventional AC and capacitance carbon capacitive AC) it is compared, conventional activated carbon mesh number is in 200 mesh, partial size
74m, and capacitance carbon partial size is 10 to 11 μm, specific surface area can achieve 1800m2/g.Concrete outcome is shown in Fig. 4, Fig. 5 and Fig. 6.Point
Conductive agent is not added according to the ratio with both different absorbent charcoal materials and electrode is made in binder, electrochemistry is carried out to electrode
Can test, cyclic voltammetry curve comparison as shown in fig. 7, pass through cyclic voltammetry curve it can be concluded that specific capacitance size,
When sweep speed is 2mv/s, conventional activated carbon specific capacitance only 40F/g, and capacitance carbon has reached about 110F/g.Difference sweeps speed
The comparison of lower specific capacitance size is as shown in Figure 8.And desalting effect pair is carried out with the electrode that both absorbent charcoal materials are produced
Than being all 400mg/L, flow 5mL/min in initial concentration, in the case that voltage is 1.2V, as shown in figure 9, regular activated
The saturated extent of adsorption of charcoal is 3.2mg/g, and the saturated extent of adsorption of capacitance carbon is 6.8mg/g.It is found after Fig. 9 is compared, capacitance carbon
It is more suitably applied to capacitive desalination than conventional activated carbon, the preferred capacitor activated carbon of final result does electrode material.
In order to determine the optimal selection of binder, the binder of use has Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol
And sodium carboxymethylcellulose, Kynoar and polytetrafluoroethylene (PTFE) belong to hydrophobic material, and polyvinyl alcohol and carboxymethyl cellulose
Plain sodium belongs to water wetted material.
Polytetrafluoroethylene (PTFE), english abbreviation PTFE, using is ptfe emulsion, content 60%, is molten with water
Agent.In ptfe emulsion after taking a certain amount of active carbon powder and acetylene black to be added to dilution, make after mixing evenly
Electrode finds that, when the selection of binder ratio is lower, electrode adhesion is bad after testing, and there is cracking after drying and falls off
The case where, one piece of complete carbon film only is produced when consumption of binder reaches very high Shi Caineng, but when consumption of binder is very high
When, carbon film extreme hydrophobic, and electric conductivity also can be very poor, is not suitable for the electrode demand of capacitive desalination.As capacitive desalination method
Electrode, electrode must electric conductivity it is good and hydrophily is fine, so the PTFE that draws a conclusion is not suitable for use in capacitive deionization skill
The binder of electrode in art.
Sodium carboxymethylcellulose, English abbreviation CMC-Na, it all can serve as to glue as carboxymethyl cellulose (CMC)
Agent is tied to use.Sodium carboxymethylcellulose is a kind of very hydrophilic binder, and water can be used as sodium carboxymethylcellulose powder
Solvent, it is soluble easily in water under powdered sodium carboxymethylcellulose room temperature.Because sodium carboxymethylcellulose hydrophily is fine, easy under room temperature
It is dissolved in water, in test loop volt-ampere curve, electrode constantly starts shedding off manufactured electrode due to steeping in the solution.And
Another question using sodium carboxymethylcellulose is the sodium when electrode touches salt water to be processed, on carboxymethyl cellulose
Ion can dissolve into solution rapidly, generate very big influence to the ion concentration of itself in solution.Polyvinyl alcohol is also one
The common binder of kind, english abbreviation PVA, water can be used as its solvent, but be insoluble in water under room temperature, in the water closely boiled
Long agitation can dissolve.Laboratory have it is cotton-shaped and two kinds powdered, dissolubility and dispersibility on, it is cotton-shaped to be more soluble in water
And it is well dispersed, but in bonding degree it is powdered be better than it is cotton-shaped.Select cotton-shaped polyvinyl alcohol that electrode test is made as binder
Its cyclic voltammetry curve is as shown in Figure 10, and cyclic voltammetry curve is undesirable, and the binder as electrode is also not good enough.
Kynoar, english abbreviation PVDF select organic solvent n,N-dimethylacetamide as Kynoar
Solvent and dispersing agent.The addition of a small amount of Kynoar can be prepared by certain hydrophily and the bonding good electrode of degree,
And the chemical property of electrode is tested, result is ideal, as shown in figure 11.
In order to determine that the ratio of active carbon, conductive agent and binder three affects the performance of electrode.Work as consumption of binder
When more, then electrode is hydrophobic, and electric conductivity can also reduce；When consumption of binder is few, electrode adhesion degree is inadequate, is easy to fall off；When
When conductive agent adds few, electrode conductivuty is poor；When conductive agent is added, electrode efficiency decline.Different groups has been attempted in this experiment
Composition and division in a proportion example produces electrode with different portfolio ratios and carries out cyclic voltammetry curve test, such as Figure 12, has finally chosen and wherein imitate
The optimal one group of conduct of fruit prepares electrode.
From cyclic voltammetry curve as can be seen that might not have better effect when the additive amount of conductive agent is big, because
Conductive agent specific gravity increases, then the specific gravity of active carbon reduces.And when binder ratio increases, electrode hydrophily and electric conductivity have
Declined.It is therefore desirable to binder be added less under caking property enough situations, in the case where guaranteeing the normal situation of electric conductivity
Less plus conductive agent.As can be seen from Figure 12, active carbon: conductive agent: the best proportion of binder is 20:3:2, can all be adopted in this experiment
This ratio is taken to continue to test.
In order to determine optimum electrode spacing, selected 1mm, 2mm, 3mm silica gel piece, can by change the thickness of gasket with
And the number of plies of non-woven fabrics carrys out coordination electrode spacing.When using 1mm gasket, the situation of short circuit, institute are easy to appear in CDI reactor
When to use 2mm gasket instead, there is good treatment effect when using 2mm gasket, and using the gasket of 3mm then treatment effect can under
There are many drop, very unsatisfactory, and free-moving water in reactor can be made to increase.In consideration of it, optimum electrode spacing is selected
2mm。
The present invention also provides the application method of above-mentioned apparatus, this method includes determining voltage, determining flow of inlet water, is determined
Initial salt concentration.
Capacitance method desalination is the Electrostatic Absorption by applying direct current electric field, so applied voltage has the removal effect of ion
Very big influence, change voltage influence the ability of electrode adsorption ion.Theoretically, applied voltage is bigger, the electric double layer of formation
Thickness is bigger, and electric double layer thickness means that greatly the ion of absorption is more, so facilitating the removal of ion.But in practical operation
In, the decomposition voltage of sodium chloride solution is in 1.7V, in order to avoid the electrolysis because of sodium chloride influences the change of effects of ion content
Change, voltage must not exceed 1.7V；The decomposition voltage of water is 1.23V, in order to reduce electric energy loss, reduces faradic currents as far as possible
Generation, while solution concentration can also change and interfere the measurement of conductivity in the case where electrolysis water, voltage no more than
The decomposition voltage of water should be controlled in 1.2V and following.
Select initial concentration 400mg/L sodium chloride solution, flow of inlet water 5mL/min, by change operation voltage come
Influence of the different operation voltage to ion remaval effect is observed, 1.2V, 1.0V, 0.8V tri- different operation electricity are had chosen
Pressure, sodium chloride content changes with time relationship in pond under different voltages for measurement, and concrete outcome is as shown in Figure 13.From figure
As can be seen that the adsorbance of electrode will increase, and adsorption rate also will increase and open from absorption with the increase of operation voltage
The time for beginning to reach adsorption saturation can shorten.When operate voltage control 1.2V and it is following when, 1.2V can reach optimization process
Effect, so 1.2V should be used by operating voltage in capacitive deionization experimental system.
In order to determine best flow of inlet water, the revolving speed for changing peristaltic pump is adjustable the variation of flow, selectes a series of differences
The comparison of flow progress capacitive deionization performance.Since this experimental provision effective area is small and treating capacity is little, in experiment
Flow is all set in lesser range, and final choice is surveyed under tetra- kinds of flows of 2mL/min, 5mL/min, 8mL/min, 10mL/min
Determine the situation of change of sodium chloride content in pond, operation voltage is 1.2V, and sodium chloride solution initial concentration is 400mg/ in pond
L, sodium chloride content changes with time relationship in pond under different flow for measurement, obtains Figure 14.It can be found that inhaling from figure
Time required for attached completion shortens with the increase of flow of inlet water.When flow of inlet water is 5mL/min, solution can reach most
Good treatment effect；When flow of inlet water is less than 5mL/min, treatment effect slightly declines；When flow of inlet water is greater than 5mL/min,
Treatment effect is greatly reduced.Analysis the reason is that because, when flow of inlet water is big, the residence time of solution in a device is too short,
Ion in solution is not adsorbed on electrode completely just as solution flows out；And when flow of inlet water is too small, because of hydraulic pressure
Very little leads to solution flowing instability between electrode, and electrode adsorption amount reduces, and since flow is too small so that electrode is in unit
Processing water is too small in time.In conclusion flow of inlet water control is in 5mL/min or so, capacitive deionization effect is best.
In order to determine optimal initial salinity, according to adsorption dynamics adsorption kinetics process it is recognised that effects of ion number not
Together, influence whether the size of adsorbance, thus under should also investigating different influent concentrations in current test adsorbance change
Change situation.During test, constant control flow of inlet water is 5mL/min, and setting operation voltage is 1.2V, and 400mg/ is respectively configured
L, the sodium chloride solution of tri- kinds of concentration of 200mg/L, 100mg/L is successively handled three kinds of various concentration solution with CDI reactor,
Recording electrode adsorbance changes with time relationship, such as Figure 14.
By Figure 14, it is not difficult to find out that, with the raising of initial concentration, the saturated extent of adsorption of electrode be will increase, and adsorb
The time of Cheng Suoxu greatly shortens, the reason is that the solution ion concentration of Electrode treatment is higher in the unit time, concentration difference is bigger, electrode
There are more chances to remove the ion in adsorbent solution, the adsorption process this demonstrates capacitive deionization is to meet adsorption dynamics adsorption kinetics
Process.But the concentration too high service life for influencing the device, therefore condensed water salinity should select a certain range (100-
400mg/L), it if condensed water salinity is higher than 400mg/L, is generally diluted within the scope of 100-400mg/L with tap water, when
When concentration salinity water is 200mg/L, the service using life is best.
Ionic species is to desalination, in addition to sodium ion and chloride ion in condensed water, there is also some other ion in salt water,
Inspecting electrode is necessary to the adsorptivity of other ions.Also, there is centainly ion of different nature in electrode
Adsorption law.This experiment has chosen K+And SO4 2-Carry out inspecting electrode to the adsorption capacity of other ions, and experimental study list
One variable selects potassium chloride and anhydrous sodium sulfate to configure solution, and single research cation is different or what anion difference has
Changing rule, and sulfate radical is negative divalent, while can observe influence of the valence state to absorption.In experiment test, voltage is operated
It is 1.2V, flow of inlet water 5mL/min, is configured to initial concentration 200mg/L solution, since mass fraction is different, in solution
Initial conductivity is not identical, observes the relationship of the variation of electrical conductivity of solution in pond at any time, records different moments solution
Conductivity, as shown in figure 15.
Prove that electrode all has adsorptivity for different ions from Figure 15 measurement result, electrode can be used for handling rich in more
The solution of kind inorganic ions, but experimental result adsorbance and adsorption rate difference are unobvious.By consulting related data, adsorbed
Journey is related with ionic nature, and adsorption rate is related with the charge-mass ratio of ion, and valence state, the hydration radius of saturated extent of adsorption and ion have
It closes.
In order to determine the Na by the device to kasugarnycin workshop condensed water+、K+、Ca2+、Mg2+Removal effect, choosing
With operation voltage 1.2V, flow of inlet water 5mL/min, electrode material is capacitive carbon, binder PVDF, the results showed that spring thunder is mould
The Na of plain workshop condensed water+、K+、Ca2+、Mg2+After the device desalination, successively removal rate be respectively 99.5%, 98.5%,
98.4% and 99.2%.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of kasugarnycin raw medicine workshop condensed water recycling device, including CDI device and condensed water pond, CDI device
Inlet and outlet communicated respectively with condensed water pond, which is characterized in that electrode material in the CDI device is activity
Carbon Materials, conductive agent and binder after the weight ratio mixing of 20:3:2 to be made.
2. a kind of kasugarnycin raw medicine workshop as described in claim 1 condensed water recycling device, which is characterized in that described
Absorbent charcoal material is capacitance carbon.
3. a kind of kasugarnycin raw medicine workshop as described in claim 1 condensed water recycling device, which is characterized in that described
Binder is Kynoar.
4. a kind of kasugarnycin raw medicine workshop as described in claim 1 condensed water recycling device, which is characterized in that described
CDI device includes capacitive deionization unit and electrochemical oxidation unit, the electrochemical oxidation unit and capacitive deionization unit
It is connected, condensed water passes sequentially through capacitive deionization unit and electrochemical oxidation unit after entering CDI device.
5. a kind of kasugarnycin raw medicine workshop as claimed in claim 4 condensed water recycling device, which is characterized in that described
Capacitive deionization unit includes central gasket, and central gasket center is provided with treatment trough, is provided with and pads on the side for the treatment of trough
Two apertures that piece side communicates, respectively as the inlet and outlet of capacitive deionization unit, the two sides of gasket are set respectively
It is equipped with collector, two-side current collecting body is provided with electrode material towards gasket on one side.
6. a kind of kasugarnycin raw medicine workshop as claimed in claim 4 condensed water recycling device, which is characterized in that described
Electrochemical oxidation unit includes intermediate washer, and intermediate washer center is provided with oxidation trough, is provided with on the side of oxidation trough
Between two apertures communicating of gasket side, respectively as the inlet and outlet of electrochemical oxidation unit, the two of intermediate washer
Side is fitted with anode plate and cathode plate, and the cathode plate is made of outside fitting electrode material in collector, and cathode plate is far from
Between the side of gasket be fitted with PMMA flow-field plate.
7. a kind of kasugarnycin raw medicine workshop as claimed in claim 6 condensed water recycling device, which is characterized in that described
PMMA flow-field plate includes plate body, and flow field grooves are arranged towards the side of cathode plate in plate body, and the side of flow field grooves is provided with and plate body side
The opening that face communicates, respectively air inlet and air outlet, it is logical to electrochemical oxidation unit cathodes area by air inlet and air outlet
Enter oxygen, for aoxidizing the organic matter in water.
8. such as a kind of kasugarnycin raw medicine workshop described in claim 5 or 6 condensed water recycling device, which is characterized in that
It is described center gasket or intermediate washer with a thickness of 2mm.
9. a kind of method for carrying out the concentration water desalination of kasugarnycin workshop using device described in claim 1, feature
It is, the flow that condensed water enters CDI device is 2-10mL/min, and the operation voltage of CDI device is 1.0-2.0V.
10. method as claimed in claim 9, which is characterized in that the salinity control of the condensed water into CDI device exists
100-400mg/L。
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| CN106830223A (en) * | 2017-01-18 | 2017-06-13 | 北京理工大学 | A kind of activated carbon electrodes and its preparation method and application |
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| US6602631B1 (en) * | 1999-01-26 | 2003-08-05 | Lynntech Power Systems, Ltd. | Bonding electrochemical cell components |
| CN103184467A (en) * | 2011-12-28 | 2013-07-03 | 上海空间电源研究所 | Oxygen electrochemical purification device for proton exchange membrane |
| KR20170049826A (en) * | 2015-10-29 | 2017-05-11 | 광주과학기술원 | Capacitive deionization electrode comprising activated waste coffee grounds, preparation method thereof and water treatment device comprising the same |
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