CN104710058A - Papermaking wastewater treatment method - Google Patents

Papermaking wastewater treatment method Download PDF

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Publication number
CN104710058A
CN104710058A CN201510030737.2A CN201510030737A CN104710058A CN 104710058 A CN104710058 A CN 104710058A CN 201510030737 A CN201510030737 A CN 201510030737A CN 104710058 A CN104710058 A CN 104710058A
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electrode
water
pond
light
enters
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张一梅
聂宇
何理
陆骏
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North China Electric Power University
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North China Electric Power University
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Abstract

The invention discloses a papermaking wastewater treatment method. The method comprises the steps of filtration, gas washing, pH adjustment, flocculating precipitation, decoloring, advanced oxidation and plasma disinfection. The method disclosed in the invention has substantially higher pollutant removal ability than the prior art; and ultraviolet light is introduced into a three dimensional electrode/electro-Fenton reaction system, and an anode plate with an ultraviolet photocatalysis performance and a particle electrode are adopted to substitute traditional electrodes, so the photoelectro-synergistic catalysis reaction of the three dimensional electrode/electro-Fenton reaction system is carried out by using ultraviolet light, the energy consumption of the three dimensional electrode/electro-Fenton reaction system is reduced, a synergistic catalytic oxidation effect is generated, and organic pollutions are efficiently and rapidly degraded. Fire coal flue gas waste is used to purify the papermaking wastewater, the acidic gas SO2 in the flue gas is used to neutralize in order to remove alkaline substances in the wastewater, and flue dust particles in the flue gas are used to remove short fibers and other suspension in the wastewater in order to realize treatment of wastes by using other wastes. Organic matters and other pollutants contained in water are effectively removed through a plasma discharge technology.

Description

A kind for the treatment of process of paper waste
Technical field
The present invention relates to a kind for the treatment of process of paper waste, belong to the water treatment field in environment protection.
Background technology
Paper industry occupies certain status in national economy, the level of consumption of paper and paperboard, is one of important symbol weighing modernization level and civilization degree.Simultaneously well-known, paper industry is water pollutions rich and influential family.Ultraviolet thus, in order to Control pollution, protection of the environment, the problem that paper industry in the urgent need to address develops in harmony with environment protection.
The slurry yield of general chemical pulping, at about 45%-50%, namely has 45%-50% can become waste in pulping process in fibrous material.Even if the BCTMP(bleached chemi-mechanical pulp promoted energetically now) and APMP(APMP) slurry yield uprise, but pulp-making waste-water is still seriously polluted.
Major ingredient in waste water is tiny suspension fiber, papermaking filler, waste paper impurity and a small amount of pectin, wax, carbohydrate, and all kinds of organic and mineral compound added in paper making process.The feature of waste water is, SS, COD are all higher.In the composition of COD, non-solubility COD is higher, accounts for more than 60%, and solvability COD is lower.And solvability COD is comparatively difficult for biological degradation.In existing technique, filler is fixed in the many employings of oxidation pond, and its complex structure, easily blocks, and be not easy to the waste water frothing after clearing up and processing after blocking seriously, decolorizing effect is not obvious, and effluent color dilution is dark, and COD can not qualified discharge.
The treatment process of general waste paper making wastewater can be divided into Physical, combustion by evaporation method, physico-chemical processes, biological process four class.Common method has ultra high efficiency, bio-contact oxidation, anaerobic biological treatment, coagulating sedimentation etc.
One, evaporation-combustion method.The method by waste water through concentrated, burning dry-matter, leaching and reclaim alkali.Though can reclaim alkali, the water colour opacity of discharge water is after treatment still very high, does not reach emission standard, becomes disposal of pollutants.In addition, equipment is complicated, investment is large, and control expense is high, can not process straw pulp, black liquor class paper waste.
Two, biological process.The method by waste water through regulate, primary sedimentation be separated, once oxidation culturing bacterium carries out biological treating, secondary oxidation culturing bacterium carries out biological treating, secondary sedimentation be separated, again by once with being carried out at of mud and the reuse of secondary sedimentation gained, its clear water is discharged.This method advantage is that routine maintenance expense is lower, but the one-time investment of equipment is large, and floor space is large, its regulation effect be bullied gentle pH value change impact, stable treatment effect is very poor, and discharge water colourity is still darker, in brown, be difficult to reach emission standard.Practical application is little.
Three, physico-chemical processes.Technological process is: by waste water, through regulating, throwing in, flocculation agent carries out flocculating, precipitate and separate, by the sludge condensation of precipitation, mummification, is discharged by isolated clear water.The method is flocculation, separation, depositing technology.The regulation effect of this method to waste water is better.But flocculation agent used is the chemicals such as molysite, aluminium salt, hydrochloric acid, nitric acid, poly-bright rare acid amides, water glass, and its price is very high, and facility investment is large, so the difficulty promoted is larger.
Four, the pattern of (flocculation) precipitation pre-treatment+biological treatment+advanced treatment.The processing mode that traditional biological process many employings anaerobic and aerobic microorganism combines, what wherein anaerobic treatment was mainly used is UASB and IC anaerobic reactor, aerobic, adopts activated sludge process.But pulp-making waste-water pollutant load is higher sometimes, load is large, and also has large number of biological compared with the macromolecular substance of difficult degradation, so waste water is also difficult to up to standard after traditional process.
In the advanced treatment of pulp-making waste-water, some high-level oxidation technologies can process the waste water after preliminary treatment further, and common high-level oxidation technology has chemical oxidation techniques, electrochemical oxidation technology, Wet Oxidation Process, supercritical Water Oxidation Technology, photochemical oxidation technology etc.
For the many deficiencies existed in existing pulping wastewater treatment method, the invention provides one can comprehensive multiple treatment process advantage, and Pollutant Treatment ability is strong, can realize the pulping wastewater treatment method of waste water recycling.
Summary of the invention
For prior art Problems existing, the invention provides a kind for the treatment of process of paper waste, comprise the steps:
1) filter: with pump, the waste water in retention basin is pumped into preliminary filter, after 70 mesh screen are separated, filtrate enters
Essence filter tank, after 130 mesh screen are separated, filtrate enters air purge adjusting tower;
2) air purge, pH regulator: the flue gas that given up by fire coal sends into air purge adjusting tower from below by induced draft fan, bottom-up flowing, makes the sour gas SO in flue gas 2neutralize with the alkaline matter in waste water, regulate the pH reducing waste water; The suspended substance that staple fibre etc. in smokeshade absorption waste water meanwhile in flue gas is trickle, formation can sedimented particle, then is filtered; Filtrate enters flocculation basin;
3) flocculation sediment: add flocculation agent by doser in flocculation basin, wastewater streams carries out precipitation through tube settler and divides high, the mud being deposited in settling tank bottom enters concentration basin stop through bottom shore pipe makes sludge condensation in about 4 hours, sent into after drying bed carries out nature mummification by mud after concentrated and burn, the lime-ash after burning is made material of construction and is used; Supernatant liquor enters decolouring pond;
4) decolour: in pond, pass into ozone by the aerator bottom decolouring pond, react 2.5 hours, then static 60-70 hour, adds ClO according to the amount of every cubic metre of 7.5g 2, react 2.5 hours, then static 48-60, clear liquid enters in advanced oxidation pond;
5) advanced oxidation: advanced oxidation is provided with RuO in pond 2-IrO 2-Tio 2/ Ti coated anode, graphite cathode, the distance between plates of two interpolars is 6cm, inside yin, yang pole plate, be provided with 2 insulating barriers, the aperture 2-2.5mm of insulating barrier, activated carbon grain sub-electrode is filled between insulating barrier, aeration is carried out by aerating apparatus anticathode, control aeration rate is 5L/min, and the voltage control between negative electrode and anode is 15V, current density 57.1Ma/cm 2, apply ultraviolet source, be that 45° angle irradiates with positive plate, bottom pond, be provided with ultrasonic generator, composition photoelectricity three-diemsnional electrode-Fenton-ultrasonic reaction system; First waste water be transferred to by sulfuric acid or NaOH solution the pH=4 specified after entering advanced oxidation pond; Then catalyst Fe SO is added 47H 2o, regulates pH to designated value again; Then open aerating apparatus saturated to the dissolved oxygen in solution to aeration in reactor, then energising starts electrolysis; While electrolysis, irradiate by UV-light, light-fenton reaction occurs, impels organic matter degradation mineralising; While electrolysis, carry out cleaning electrode with ultrasonic generator, prevent electrode surface passivation, can also promote the carrying out reacted, the water outlet of advanced oxidation pond enters plasma ion disinfection pond;
6) plasma ion disinfection: general electrode and high-pressure glass double-pipe metal electrode are submerged in the water in plasma ion disinfection pond, insulated column is retained on the water surface, general electrode makes water body form ground-electrode, the two-stage of discharging is formed with the high-pressure metal electrode in high-pressure glass double-pipe metal electrode, air produces high-concentrated ozone after the top of Glass tubing flows under high-frequency high-voltage effect, active ion and UV-light, wherein containing ozone, the air of active ion fully mixes participation oxidative degradation by the aeration tube of bottom with water body, in the process at air water upper reaches, UV-light directly penetrates glass radiation whole water body direct light chemical reaction, in whole degradation process, ozone, UV-light carries out sterilization and disinfection to water body simultaneously, remove peculiar smell, after sterilization, clear water enters clean water basin,
7) discharge is regulated: adjust ph is 6 ~ 9 in clean water basin, becomes Water circulation up to standard or discharge.
Described flocculation agent is one or more in polyacrylamide, polymerize aluminum chloride, bodied ferric sulfate.
Activated carbon grain sub-electrode is that activated carbon supported Fe-Co mixes TiO altogether 2, particle diameter 3-5mm, loading level is 200g/L.
Ultraviolet source send the wavelength of UV-light be 200-270nm.
Ultrasonic frequency is 20KHz ~ 100KHz, and power is 100W ~ 2KW.
The present invention has following advantage compared with prior art:
(1) the present invention compared with prior art contaminant removal capacity significantly improve, COD clearance reaches more than 95%, SS clearance and reaches more than 99%, and chroma removal rate reaches more than 98%.
(2) the present invention UV-light can introduce three-dimensional electrode/electro-Fenton reaction system, there is the positive plate of ultraviolet catalytic performance and granule electrode substitutes traditional electrode by adopting, making three-dimensional electrode/electro-Fenton system that UV-light can be utilized to carry out electrical enhanced photocatalysis reaction; The introducing of UV-light, both facilitates the carrying out of Fenton's reaction, improves the pollution clearance of three-dimensional electrode/electro-Fenton system, and the contaminant degradation rate of 60min improves 44.7%; Again for three-dimensional electrode/electro-Fenton system provides new energy derive, react with anode, granule electrode generation photoelectrocatalysis simultaneously, decrease three-dimensional electrode/electro-Fenton reaction system energy consumption, and produce concerted catalysis oxidation effectiveness, efficient fast degradation organic contamination.
(3) present method adopts titanium base TiO 2electrode and UV radiation modification electrode thereof are as anode, and this electrode is DSA class electrode, and have very long work-ing life, whom stripping hardly, can not cause secondary pollution to; Under UV-light and electric field exist, the effect of UV-light photoelectrocatalysis can occur, its process energy consumption reduces greatly simultaneously.
(4) the present invention adopts activated carbon modified granule electrode, not only increases electrocatalysis efficiency, and this granule electrode, under action of ultraviolet light, surface light electrocatalysis occurs simultaneously, facilitates the regenerative process of reaction process and granule electrode.
(5) the present invention adopts carbonaceous material to be negative electrode, and its oxygen uptake effect and absorption property can generate H2O2 fast at cathode surface, can promote the carrying out of Fenton's reaction.
(6) additionally use Catalyzed by Ultrasonic Wave oxidation technology in reaction, not only can ensure that electrode surface cleans and degasification, prevent electrode surface passivation, prevent electrode corrosion, also produce with electric Fenton, UV-light and act synergistically, accelerate speed of reaction, improve the effect of degradation efficiency.
(7) air purge of the present invention, procedure of pH adjustment, to give up gas cleaning paper waste with fire coal, utilizes the sour gas SO in flue gas 2neutralization and the alkaline matter removed in waste water, use the suspended substances such as the staple fibre in the smokeshade Adsorption waste water in flue gas simultaneously.The method of a kind of " treatment of wastes with processes of wastes against one another ", particularly when adopt the bunker coal in paper-making process give up flue gas time, more can receive the effect made the best of both worlds, while improvement paper waste, also administer papermaking and to give up flue gas.
(8) plasma discharge technology is applied to water treatment, shorten ozone in dielectric barrier discharge process, high energy active particle from producing the time fully contacted with water body, improve itself and water mixture homogeneity, thus improve the utilising efficiency of ozone, active particle, the effect that the pollutents such as the organism contained by effectively removing in water have sterilization and disinfection simultaneously can save subsequent disposal measure, and it is simple to have implementation process, easy for operation, the features such as easy care.
Accompanying drawing explanation
Fig. 1 is the schematic diagram for the treatment of process of the present invention.
Embodiment
Paper waste enters the process through following steps after retention basin:
1) filter: with pump, the waste water in retention basin is pumped into preliminary filter, after 70 mesh screen are separated, filtrate enters
Essence filter tank, after 130 mesh screen are separated, filtrate enters air purge adjusting tower;
2) air purge, pH regulator: the flue gas that given up by fire coal sends into air purge adjusting tower from below by induced draft fan, bottom-up flowing, makes the sour gas SO in flue gas 2neutralize with the alkaline matter in waste water, regulate the pH reducing waste water; The suspended substance that staple fibre etc. in smokeshade absorption waste water meanwhile in flue gas is trickle, formation can sedimented particle, then is filtered; Filtrate enters flocculation basin;
3) flocculation sediment: add one or more in polyacrylamide, polymerize aluminum chloride, bodied ferric sulfate by doser in flocculation basin, wastewater streams carries out precipitation through tube settler and divides high, the mud being deposited in settling tank bottom enters concentration basin stop through bottom shore pipe makes sludge condensation in about 4 hours, sent into after drying bed carries out nature mummification by mud after concentrated and burn, the lime-ash after burning is made material of construction and is used; Supernatant liquor enters decolouring pond;
4) decolour: in pond, pass into ozone by the aerator bottom decolouring pond, react 2.5 hours, then static 60-70 hour, adds ClO according to the amount of every cubic metre of 7.5g 2, react 2.5 hours, then static 48-60, clear liquid enters in advanced oxidation pond;
5) advanced oxidation: advanced oxidation is provided with RuO in pond 2-IrO 2-Tio 2/ Ti coated anode, graphite cathode, the distance between plates of two interpolars is 6cm, 2 insulating barriers are provided with inside yin, yang pole plate, the aperture 2-2.5mm of insulating barrier, activated carbon grain sub-electrode is filled between insulating barrier, and activated carbon grain sub-electrode is that activated carbon supported Fe-Co mixes TiO altogether 2, particle diameter 3-5mm, loading level is 200g/L.Carry out aeration by aerating apparatus anticathode, control aeration rate is 5L/min, and the voltage control between negative electrode and anode is 15V, current density 57.1Ma/cm 2, apply ultraviolet source, be that 45° angle irradiates with positive plate, bottom pond, be provided with ultrasonic generator, composition photoelectricity three-diemsnional electrode-Fenton-ultrasonic reaction system; First waste water be transferred to by sulfuric acid or NaOH solution the pH=4 specified after entering advanced oxidation pond; Then catalyst Fe SO is added 47H 2o, regulates pH to designated value again; Then open aerating apparatus saturated to the dissolved oxygen in solution to aeration in reactor, then energising starts electrolysis; While electrolysis, irradiate by UV-light, light-fenton reaction occurs, and impel organic matter degradation mineralising, the wavelength of the UV-light that ultraviolet source sends is 200-270nm; While electrolysis, carry out cleaning electrode with ultrasonic generator, prevent electrode surface passivation, can also promote the carrying out reacted, ultrasonic frequency is 20KHz ~ 100KHz, and power is 100W ~ 2KW, and the water outlet of advanced oxidation pond enters plasma ion disinfection pond;
6) plasma ion disinfection: general electrode and high-pressure glass double-pipe metal electrode are submerged in the water in plasma ion disinfection pond, insulated column is retained on the water surface, general electrode makes water body form ground-electrode, the two-stage of discharging is formed with the high-pressure metal electrode in high-pressure glass double-pipe metal electrode, air produces high-concentrated ozone after the top of Glass tubing flows under high-frequency high-voltage effect, active ion and UV-light, wherein containing ozone, the air of active ion fully mixes participation oxidative degradation by the aeration tube of bottom with water body, in the process at air water upper reaches, UV-light directly penetrates glass radiation whole water body direct light chemical reaction, in whole degradation process, ozone, UV-light carries out sterilization and disinfection to water body simultaneously, remove peculiar smell, after sterilization, clear water enters clean water basin,
7) discharge is regulated: adjust ph is 6 ~ 9 in clean water basin, becomes Water circulation up to standard or discharge.

Claims (5)

1. a treatment process for paper waste, is characterized in that comprising the steps:
1) filter: with pump, the waste water in retention basin is pumped into preliminary filter, after 70 mesh screen are separated, filtrate enters
Essence filter tank, after 130 mesh screen are separated, filtrate enters air purge adjusting tower;
2) air purge, pH regulator: the flue gas that given up by fire coal sends into air purge adjusting tower from below by induced draft fan, bottom-up flowing, makes the sour gas SO in flue gas 2neutralize with the alkaline matter in waste water, regulate the pH reducing waste water; The suspended substance that staple fibre etc. in smokeshade absorption waste water meanwhile in flue gas is trickle, formation can sedimented particle, then is filtered; Filtrate enters flocculation basin;
3) flocculation sediment: add flocculation agent by doser in flocculation basin, wastewater streams carries out precipitation through tube settler and divides high, the mud being deposited in settling tank bottom enters concentration basin stop through bottom shore pipe makes sludge condensation in about 4 hours, sent into after drying bed carries out nature mummification by mud after concentrated and burn, the lime-ash after burning is made material of construction and is used; Supernatant liquor enters decolouring pond;
4) decolour: in pond, pass into ozone by the aerator bottom decolouring pond, react 2.5 hours, then static 60-70 hour, adds ClO according to the amount of every cubic metre of 7.5g 2, react 2.5 hours, then static 48-60, clear liquid enters in advanced oxidation pond;
5) advanced oxidation: advanced oxidation is provided with RuO in pond 2-IrO 2-Tio 2/ Ti coated anode, graphite cathode, the distance between plates of two interpolars is 6cm, inside yin, yang pole plate, be provided with 2 insulating barriers, the aperture 2-2.5mm of insulating barrier, activated carbon grain sub-electrode is filled between insulating barrier, aeration is carried out by aerating apparatus anticathode, control aeration rate is 5L/min, and the voltage control between negative electrode and anode is 15V, current density 57.1Ma/cm 2, apply ultraviolet source, be that 45° angle irradiates with positive plate, bottom pond, be provided with ultrasonic generator, composition photoelectricity three-diemsnional electrode-Fenton-ultrasonic reaction system; First waste water be transferred to by sulfuric acid or NaOH solution the pH=4 specified after entering advanced oxidation pond; Then catalyst Fe SO is added 47H 2o, regulates pH to designated value again; Then open aerating apparatus saturated to the dissolved oxygen in solution to aeration in reactor, then energising starts electrolysis; While electrolysis, irradiate by UV-light, light-fenton reaction occurs, impels organic matter degradation mineralising; While electrolysis, carry out cleaning electrode with ultrasonic generator, prevent electrode surface passivation, can also promote the carrying out reacted, the water outlet of advanced oxidation pond enters plasma ion disinfection pond;
6) plasma ion disinfection: general electrode and high-pressure glass double-pipe metal electrode are submerged in the water in plasma ion disinfection pond, insulated column is retained on the water surface, general electrode makes water body form ground-electrode, the two-stage of discharging is formed with the high-pressure metal electrode in high-pressure glass double-pipe metal electrode, air produces high-concentrated ozone after the top of Glass tubing flows under high-frequency high-voltage effect, active ion and UV-light, wherein containing ozone, the air of active ion fully mixes participation oxidative degradation by the aeration tube of bottom with water body, in the process at air water upper reaches, UV-light directly penetrates glass radiation whole water body direct light chemical reaction, in whole degradation process, ozone, UV-light carries out sterilization and disinfection to water body simultaneously, remove peculiar smell, after sterilization, clear water enters clean water basin,
7) discharge is regulated: adjust ph is 6 ~ 9 in clean water basin, becomes Water circulation up to standard or discharge.
2. the treatment process of paper waste as claimed in claim 1, is characterized in that: described flocculation agent is one or more in polyacrylamide, polymerize aluminum chloride, bodied ferric sulfate.
3. the treatment process of paper waste as claimed in claim 1, is characterized in that: activated carbon grain sub-electrode is that activated carbon supported Fe-Co mixes TiO altogether 2, particle diameter 3-5mm, loading level is 200g/L.
4. the treatment process of paper waste as claimed in claim 1, is characterized in that: the wavelength of the UV-light that ultraviolet source sends is 200-270nm.
5. the treatment process of paper waste as claimed in claim 1, it is characterized in that: ultrasonic frequency is 20KHz ~ 100KHz, power is 100W ~ 2KW.
CN201510030737.2A 2015-01-22 2015-01-22 Papermaking wastewater treatment method Pending CN104710058A (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN106830209A (en) * 2017-02-28 2017-06-13 齐鲁工业大学 A kind of method for improving coking chemical waste water biodegradability
CN108706693A (en) * 2018-05-24 2018-10-26 天津大学 Handle suspended matter and changeable three electrode reactors of persistent organic pollutants
CN109052762A (en) * 2018-07-09 2018-12-21 上海纳米技术及应用国家工程研究中心有限公司 The treatment process of high-COD waste water zero-emission
CN109205884A (en) * 2018-10-19 2019-01-15 齐鲁工业大学 A kind of paper-making effluent treating process
CN109205823A (en) * 2017-07-06 2019-01-15 荆门市格林美新材料有限公司 A kind of environment-friendly disposal system of consumptive material
CN110523255A (en) * 2019-09-16 2019-12-03 德蓝水技术股份有限公司 A kind of alkali decrement waste water flue gases purification
CN111333214A (en) * 2020-02-29 2020-06-26 华南理工大学 Advanced oxidation treatment method for pulping and papermaking wastewater
CN111632412A (en) * 2020-06-13 2020-09-08 江苏启景环保技术有限公司 Papermaking wastewater treatment process

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106830209A (en) * 2017-02-28 2017-06-13 齐鲁工业大学 A kind of method for improving coking chemical waste water biodegradability
CN109205823A (en) * 2017-07-06 2019-01-15 荆门市格林美新材料有限公司 A kind of environment-friendly disposal system of consumptive material
CN108706693A (en) * 2018-05-24 2018-10-26 天津大学 Handle suspended matter and changeable three electrode reactors of persistent organic pollutants
CN108706693B (en) * 2018-05-24 2021-11-26 天津大学 Switchable three-electrode reactor for treating suspended matters and refractory organic pollutants
CN109052762A (en) * 2018-07-09 2018-12-21 上海纳米技术及应用国家工程研究中心有限公司 The treatment process of high-COD waste water zero-emission
CN109205884A (en) * 2018-10-19 2019-01-15 齐鲁工业大学 A kind of paper-making effluent treating process
CN110523255A (en) * 2019-09-16 2019-12-03 德蓝水技术股份有限公司 A kind of alkali decrement waste water flue gases purification
CN111333214A (en) * 2020-02-29 2020-06-26 华南理工大学 Advanced oxidation treatment method for pulping and papermaking wastewater
CN111632412A (en) * 2020-06-13 2020-09-08 江苏启景环保技术有限公司 Papermaking wastewater treatment process

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Application publication date: 20150617