CN110479215A - A kind of coking waste water treatment method - Google Patents
A kind of coking waste water treatment method Download PDFInfo
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- CN110479215A CN110479215A CN201910727852.3A CN201910727852A CN110479215A CN 110479215 A CN110479215 A CN 110479215A CN 201910727852 A CN201910727852 A CN 201910727852A CN 110479215 A CN110479215 A CN 110479215A
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- China
- Prior art keywords
- coking
- metal
- manganese dioxide
- photochemical catalyst
- coal tar
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- 238000004939 coking Methods 0.000 title claims abstract description 68
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002351 wastewater Substances 0.000 claims abstract description 45
- 239000002028 Biomass Substances 0.000 claims abstract description 40
- 239000011280 coal tar Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003463 adsorbent Substances 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 30
- 241000208671 Campanulaceae Species 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 39
- 241000357613 Platycodon Species 0.000 claims description 27
- 235000006751 Platycodon Nutrition 0.000 claims description 27
- 229930189914 platycodon Natural products 0.000 claims description 27
- 239000006228 supernatant Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000003245 coal Substances 0.000 claims description 22
- 238000000197 pyrolysis Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 238000001085 differential centrifugation Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
- 230000006872 improvement Effects 0.000 description 9
- 230000008901 benefit Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011335 coal coke Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- -1 heterocycle compound Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Analytical Chemistry (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Catalysts (AREA)
Abstract
The present invention proposes a kind of coking waste water treatment method, comprising the following steps: using campanulaceae and certain northern power plant's duff prepare biomass modified coal tar adsorbent, prepare metal-doped manganese dioxide photochemical catalyst, the coking wastewater solution containing phenol is handled using the metal-doped manganese dioxide photochemical catalyst prepared, cooperateing with that treated to metal-doped manganese dioxide photochemical catalyst using the biomass modified coal tar adsorbent prepared, the coking wastewater solution containing phenol carries out collaboration processing；The present invention by first using prepare metal-doped manganese dioxide photochemical catalyst to containing phenol coking wastewater carry out photocatalysis treatment, the biomass modified coal tar adsorbent for recycling campanulaceae and certain northern power plant's duff to prepare carries out adsorption treatment to the coking wastewater containing phenol, the treatment effect of coking wastewater containing phenol will be significantly improved, 90.5% is up to the 50mL coking wastewater solution treatment effeciency for containing the phenol that concentration is 500mg/L.
Description
Technical field
The present invention relates to Technologies of Coke Plant Wastewater Treatment field more particularly to a kind of coking waste water treatment methods.
Background technique
Coking wastewater be coal coke, gas purification and coke chemicals recycling during generate containing volatile phenol,
A kind of high concentrations of the heterocyclic compounds such as polycyclic aromatic hydrocarbon and oxygen, sulphur, nitrogen, non-ideal system, heterogeneous difficult organic work
Industry waste water, BOD5/ COD value is generally 0.28~0.32, and biodegradability is poor, it is more difficult to biochemical degradation.Coking wastewater has pollution
Species are various, complicated component, and containing a large amount of object difficult to degrade, contained pollutant is broadly divided into inorganic pollution and organic dirt
Object is contaminated, organic pollutant category is various, and the form of being primarily present has phenol, paracresol, O-phthalic Benzene and Homologues, in addition,
There are also heterocycle compound, polycyclic aromatic hydrocarbon and aliphatic compounds etc..
The organic pollutant that coking wastewater contains seriously inhibit microorganism growth and normal metabolic activity, cause it can
Biochemical property decline, processing difficulty are very big；Meanwhile containing a large amount of carcinogen polycyclic aromatic hydrocarbons, not only water body is caused seriously
Pollution, and huge harm is caused to the health of the mankind.To promote coking wastewater pollution reduction and coking industry
Sustainable development, enterprise is created after 2015 will execute higher discharge standard, and the implementation of new standard reaches COD in coking wastewater
The difficulty of mark discharge further increases, and develops a kind of new method that can improve Treatment of Coking Effluent efficiency, new technology becomes very
Urgently, therefore, the present invention proposes a kind of coking waste water treatment method, to solve shortcoming in the prior art.
Summary of the invention
In view of the above-mentioned problems, the present invention proposes a kind of coking waste water treatment method, by first metal-doped using preparing
Manganese dioxide photochemical catalyst carries out photocatalysis treatment to the coking wastewater containing phenol, recycles campanulaceae and certain northern power plant's duff
The biomass modified coal tar adsorbent prepared carries out adsorption treatment to the coking wastewater containing phenol, to the coking containing phenol
The treatment effect of waste water will significantly improve, and the coking wastewater solution treatment effeciency for the phenol that concentration is 500mg/L is contained to 50mL
Up to 90.5%.
The present invention proposes a kind of coking waste water treatment method, comprising the following steps:
Step 1: biomass modified coal tar adsorbent, preparation process packet are prepared using campanulaceae and certain northern power plant's duff
It includes:
T1: grinding campanulaceae obtains Platycodon Root, and sieves with 100 mesh sieve processing to Platycodon Root；
T2: Platycodon Root is mixed with certain northern power plant's duff according to the ratio of 7:3；
T3: the mixture of pyrolysis of coal experimental provision processing Platycodon Root and certain northern power plant's duff is utilized；
T4: it carries out cooling treatment for 24 hours, obtains biomass modified coal tar adsorbent；
Step 2: preparing metal-doped manganese dioxide photochemical catalyst, and process includes:
S1: 1.100~1.104g potassium permanganate is weighed in 100mL beaker；
S2: 35~37mL deionized water and 35~37mL ethyl alcohol are added into beaker, it is molten to obtain aubergine after being sufficiently stirred
Liquid；
S3: 2.44~2.50g urea and 0.08~0.12g metal oxide are added into the purplish red solution of S2, obtains
Blend is transferred them in 100mL hydrothermal reaction kettle after ultrasonic treatment, is kept the temperature, to after reaction by blend from
So it is cooled to room temperature；
S4: sufficiently washing the precipitating in blend with deionized water, and 9~11min is centrifuged in differential centrifugation machine, takes
The PH of clear liquid measurement blend；
S5: repeating the process of S4, until PH is neutrality, then products therefrom is dried in an oven；
S6: product grind into powder after will be dry in S5 is to get arriving metal-doped manganese dioxide photochemical catalyst；
Step 3: using the metal-doped manganese dioxide photochemical catalyst prepared to the coking wastewater solution containing phenol into
Row processing；
Step 4: metal-doped manganese dioxide photochemical catalyst is cooperateed with using the biomass modified coal tar adsorbent prepared
Treated, and the coking wastewater solution containing phenol carries out collaboration processing.
Further improvement lies in that: pyrolysis of coal experimental provision processing Platycodon Root and certain electricity of the north are utilized in the step 1 T3
The detailed process of the mixture of factory's duff are as follows: it is first turned on the switch of pyrolysis of coal experimental provision, set temperature, it is warming up to 830~
870 DEG C, nitrogen switch is then opened, is first passed through 8~12min nitrogen, then by the mixing of Platycodon Root and certain northern power plant's duff
Object is put into pyrolysis of coal experimental provision, is kept nitrogen to be passed through, is continued 8~12min of firing, and pyrolysis of coal experimental provision electricity is finally closed
Source switch continues to close nitrogen gas control valve after keeping nitrogen to be passed through 10min.
Further improvement lies in that: in the step 2 S3, by blend using ultrasonic disperse equipment carry out ultrasonic treatment 8~
Transfer them in 100mL hydrothermal reaction kettle after 10min, kept the temperature at 60~80 DEG C again, when heat preservation a length of 9~11h.
Further improvement lies in that: metal oxide is appointing in iron oxide, tin oxide and bismuth oxide in the step 2 S3
It anticipates one kind.
Further improvement lies in that: in the step 2 S5, by PH be neutral blend put dry 10 in an oven~
13h, the temperature in baking oven are controlled at 50~70 DEG C.
Further improvement lies in that: in the step 2 S9, the mixed liquor in S8 is put into baking oven, drying time 11.5
~12.5h, controlling the temperature in baking oven is 55~65 DEG C.
Further improvement lies in that: detailed process in the step 3 are as follows: place the beaker on magnetic stirring apparatus, into beaker
The coking wastewater solution that 50mL contains the phenol that concentration is 500mg/L and the metal-doped manganese dioxide light that 0.2g is prepared is added
Catalyst, and it is put into rotor, magnetic agitation is carried out, fluorescent lamp is opened and carries out light-catalyzed reaction, water sample is extracted after reaction, in the process
Control magnetic stirring apparatus in temperature be constant room temperature, the magnetic agitation time be 3~5min, and control speed of agitator be 100~
110r/min, the power control of fluorescent lamp are 60~70W, and reaction time control is 2.5~3.5h.
Further improvement lies in that: detailed process in the step 4 are as follows: carry out differential centrifugation for water sample is extracted in step 3
After take supernatant, the biomass modified coal tar adsorbent for weighing 0.3g is added in supernatant, and will contain supernatant and biology
Matter modified coal coke adsorbent container is placed in thermostatic control oscillator vibration, allows coking in biomass modified coal tar adsorbent and container
The supernatant of waste water solution vibrates 30min in thermostatic control oscillator vibration, observes processing result.
The invention has the benefit that by first using preparing metal-doped manganese dioxide photochemical catalyst to containing phenol
Coking wastewater carry out photocatalysis treatment, the biomass modified coal tar absorption for recycling campanulaceae and certain northern power plant's duff to prepare
Agent carries out adsorption treatment to the coking wastewater containing phenol, it can be found that first carry out photocatalysis treatment carries out adsorption treatment again, it is right
The treatment effect of coking wastewater containing phenol will significantly improve, and when metal-doped manganese dioxide photochemical catalyst and biomass change
Property coal tar adsorbent synthesis dosage be 0.5g when, to 50mL contain concentration be 500mg/L phenol coking wastewater it is molten
Liquid treatment effeciency is up to 90.5%.
Detailed description of the invention
Fig. 1 is the Treatment of Coking Effluent efficiency schematic diagram adsorbed after the first photocatalysis of the present invention.
Fig. 2 is efficiency comparative's schematic diagram of present invention collaboration processing coking wastewater.
Fig. 3 is the photocatalysis efficiency schematic diagram of manganese dioxide metal composite oxide of the present invention.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention is further described below in conjunction with embodiment, the present embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Embodiment one
According to Fig. 1,2,3, the present embodiment proposes a kind of coking waste water treatment method, comprising the following steps:
Step 1: biomass modified coal tar adsorbent, preparation process packet are prepared using campanulaceae and certain northern power plant's duff
It includes:
T1: grinding campanulaceae obtains Platycodon Root, and sieves with 100 mesh sieve processing to Platycodon Root；
T2: Platycodon Root is mixed with certain northern power plant's duff according to the ratio of 7:3；
T3: using the mixture of pyrolysis of coal experimental provision processing Platycodon Root and certain northern power plant's duff, it is first turned on coal
The switch of Pyrolysis Experiment device, set temperature are warming up to 850 DEG C, then open nitrogen switch, are first passed through 10min nitrogen, then will
The mixture of Platycodon Root and certain northern power plant's duff is put into pyrolysis of coal experimental provision, is kept nitrogen to be passed through, is continued to fire
10min finally closes pyrolysis of coal experimental provision power switch, continues to close nitrogen gas control valve after keeping nitrogen to be passed through 10min；
T4: it carries out cooling treatment for 24 hours, obtains biomass modified coal tar adsorbent；
Step 2: preparing metal-doped manganese dioxide photochemical catalyst, and process includes:
S1: 1.102g potassium permanganate is weighed in 100mL beaker；
S2: 36mL deionized water and 36mL ethyl alcohol are added into beaker, obtains purplish red solution after being sufficiently stirred；
S3: 2.47g urea and 0.10g iron oxide being added into the purplish red solution of S2, obtains blend, by blend benefit
It transfers them in 100mL hydrothermal reaction kettle after carrying out ultrasonic treatment 9min with ultrasonic disperse equipment, is protected at 70 DEG C again
Temperature, when heat preservation a length of 10h, to after reaction by blend cooled to room temperature；
S4: the precipitating in blend is sufficiently washed with deionized water, and is centrifuged 10min in differential centrifugation machine, takes supernatant
The PH of liquid measurement blend；
S5: repeating the process of S4, until PH is neutrality, PH is put for neutral blend and dries 12h, baking oven in an oven
Interior temperature is controlled at 60 DEG C；
S6: product grind into powder after will be dry in S5 is to get arriving metal-doped manganese dioxide photochemical catalyst；
Step 3: using the metal-doped manganese dioxide photochemical catalyst prepared to the coking wastewater solution containing phenol into
Row processing, places the beaker on magnetic stirring apparatus, and it is useless that the coking that 50mL contains the phenol that concentration is 500mg/L is added into beaker
The metal-doped manganese dioxide photochemical catalyst that aqueous solution and 0.2g are prepared, and it is put into rotor, magnetic agitation is carried out, daylight is opened
Lamp carries out light-catalyzed reaction, and water sample is extracted after reaction, and controlling temperature in magnetic stirring apparatus in the process is constant room temperature, magnetic agitation
Time is 4min, and controlling speed of agitator is 105r/min, and the power control of fluorescent lamp is 65W, and reaction time control is 3h；
Step 4: metal-doped manganese dioxide photochemical catalyst is cooperateed with using the biomass modified coal tar adsorbent prepared
Treated, and the coking wastewater solution containing phenol carries out collaboration processing, takes being extracted after water sample carries out differential centrifugation in step 3
Supernatant, the biomass modified coal tar adsorbent for weighing 0.3g are added in supernatant, and will be changed containing supernatant and biomass
Property coal tar absorbent container be placed in thermostatic control oscillator vibration, allow coking wastewater in biomass modified coal tar adsorbent and container
The supernatant of solution vibrates 30min in thermostatic control oscillator vibration, observes processing result.
Embodiment two
According to Fig. 1,2,3, the present embodiment proposes a kind of coking waste water treatment method, comprising the following steps:
Step 1: biomass modified coal tar adsorbent, preparation process packet are prepared using campanulaceae and certain northern power plant's duff
It includes:
T1: grinding campanulaceae obtains Platycodon Root, and sieves with 100 mesh sieve processing to Platycodon Root；
T2: Platycodon Root is mixed with certain northern power plant's duff according to the ratio of 7:3；
T3: using the mixture of pyrolysis of coal experimental provision processing Platycodon Root and certain northern power plant's duff, it is first turned on coal
The switch of Pyrolysis Experiment device, set temperature are warming up to 850 DEG C, then open nitrogen switch, are first passed through 10min nitrogen, then will
The mixture of Platycodon Root and certain northern power plant's duff is put into pyrolysis of coal experimental provision, is kept nitrogen to be passed through, is continued to fire
10min finally closes pyrolysis of coal experimental provision power switch, continues to close nitrogen gas control valve after keeping nitrogen to be passed through 10min；
T4: it carries out cooling treatment for 24 hours, obtains biomass modified coal tar adsorbent；
Step 2: preparing metal-doped manganese dioxide photochemical catalyst, and process includes:
S1: 1.102g potassium permanganate is weighed in 100mL beaker；
S2: 36mL deionized water and 36mL ethyl alcohol are added into beaker, obtains purplish red solution after being sufficiently stirred；
S3: 2.47g urea and 0.10g tin oxide being added into the purplish red solution of S2, obtains blend, by blend benefit
It transfers them in 100mL hydrothermal reaction kettle after carrying out ultrasonic treatment 9min with ultrasonic disperse equipment, is protected at 70 DEG C again
Temperature, when heat preservation a length of 10h, to after reaction by blend cooled to room temperature；
S4: the precipitating in blend is sufficiently washed with deionized water, and is centrifuged 10min in differential centrifugation machine, takes supernatant
The PH of liquid measurement blend；
S5: repeating the process of S4, until PH is neutrality, PH is put for neutral blend and dries 12h, baking oven in an oven
Interior temperature is controlled at 60 DEG C；
S6: product grind into powder after will be dry in S5 is to get arriving metal-doped manganese dioxide photochemical catalyst；
Step 3: using the metal-doped manganese dioxide photochemical catalyst prepared to the coking wastewater solution containing phenol into
Row processing, places the beaker on magnetic stirring apparatus, and it is useless that the coking that 50mL contains the phenol that concentration is 500mg/L is added into beaker
The metal-doped manganese dioxide photochemical catalyst that aqueous solution and 0.2g are prepared, and it is put into rotor, magnetic agitation is carried out, daylight is opened
Lamp carries out light-catalyzed reaction, and water sample is extracted after reaction, and controlling temperature in magnetic stirring apparatus in the process is constant room temperature, magnetic agitation
Time is 4min, and controlling speed of agitator is 105r/min, and the power control of fluorescent lamp is 65W, and reaction time control is 3h；
Step 4: metal-doped manganese dioxide photochemical catalyst is cooperateed with using the biomass modified coal tar adsorbent prepared
Treated, and the coking wastewater solution containing phenol carries out collaboration processing, takes being extracted after water sample carries out differential centrifugation in step 3
Supernatant, the biomass modified coal tar adsorbent for weighing 0.3g are added in supernatant, and will be changed containing supernatant and biomass
Property coal tar absorbent container be placed in thermostatic control oscillator vibration, allow coking wastewater in biomass modified coal tar adsorbent and container
The supernatant of solution vibrates 30min in thermostatic control oscillator vibration, observes processing result.
Embodiment three
According to Fig. 1,2,3, the present embodiment proposes a kind of coking waste water treatment method, comprising the following steps:
Step 1: biomass modified coal tar adsorbent, preparation process packet are prepared using campanulaceae and certain northern power plant's duff
It includes:
T1: grinding campanulaceae obtains Platycodon Root, and sieves with 100 mesh sieve processing to Platycodon Root；
T2: Platycodon Root is mixed with certain northern power plant's duff according to the ratio of 7:3；
T3: using the mixture of pyrolysis of coal experimental provision processing Platycodon Root and certain northern power plant's duff, it is first turned on coal
The switch of Pyrolysis Experiment device, set temperature are warming up to 850 DEG C, then open nitrogen switch, are first passed through 10min nitrogen, then will
The mixture of Platycodon Root and certain northern power plant's duff is put into pyrolysis of coal experimental provision, is kept nitrogen to be passed through, is continued to fire
10min finally closes pyrolysis of coal experimental provision power switch, continues to close nitrogen gas control valve after keeping nitrogen to be passed through 10min；
T4: it carries out cooling treatment for 24 hours, obtains biomass modified coal tar adsorbent；
Step 2: preparing metal-doped manganese dioxide photochemical catalyst, and process includes:
S1: 1.102g potassium permanganate is weighed in 100mL beaker；
S2: 36mL deionized water and 36mL ethyl alcohol are added into beaker, obtains purplish red solution after being sufficiently stirred；
S3: 2.47g urea and 0.10g bismuth oxide being added into the purplish red solution of S2, obtains blend, by blend benefit
It transfers them in 100mL hydrothermal reaction kettle after carrying out ultrasonic treatment 9min with ultrasonic disperse equipment, is protected at 70 DEG C again
Temperature, when heat preservation a length of 10h, to after reaction by blend cooled to room temperature；
S4: the precipitating in blend is sufficiently washed with deionized water, and is centrifuged 10min in differential centrifugation machine, takes supernatant
The PH of liquid measurement blend；
S5: repeating the process of S4, until PH is neutrality, PH is put for neutral blend and dries 12h, baking oven in an oven
Interior temperature is controlled at 60 DEG C；
S6: product grind into powder after will be dry in S5 is to get arriving metal-doped manganese dioxide photochemical catalyst；
Step 3: using the metal-doped manganese dioxide photochemical catalyst prepared to the coking wastewater solution containing phenol into
Row processing, places the beaker on magnetic stirring apparatus, and it is useless that the coking that 50mL contains the phenol that concentration is 500mg/L is added into beaker
The metal-doped manganese dioxide photochemical catalyst that aqueous solution and 0.2g are prepared, and it is put into rotor, magnetic agitation is carried out, daylight is opened
Lamp carries out light-catalyzed reaction, and water sample is extracted after reaction, and controlling temperature in magnetic stirring apparatus in the process is constant room temperature, magnetic agitation
Time is 4min, and controlling speed of agitator is 105r/min, and the power control of fluorescent lamp is 65W, and reaction time control is 3h；
Step 4: metal-doped manganese dioxide photochemical catalyst is cooperateed with using the biomass modified coal tar adsorbent prepared
Treated, and the coking wastewater solution containing phenol carries out collaboration processing, takes being extracted after water sample carries out differential centrifugation in step 3
Supernatant, the biomass modified coal tar adsorbent for weighing 0.3g are added in supernatant, and will be changed containing supernatant and biomass
Property coal tar absorbent container be placed in thermostatic control oscillator vibration, allow coking wastewater in biomass modified coal tar adsorbent and container
The supernatant of solution vibrates 30min in thermostatic control oscillator vibration, observes processing result.
According to embodiment one, embodiment two and embodiment three it can be concluded that, iron oxide, tin oxide and oxygen in the method for the present invention
Change bismuth for it is compound prepare metal-doped manganese dioxide photochemical catalyst after, prepare metal-doped manganese dioxide photochemical catalyst light and urge
Change efficiency is higher, and photocatalysis efficiency is in 70% or so (as shown in Figure 3).
Different collaboration processing sequences is taken, in different biomass modified coal tar adsorbents and metal-doped manganese dioxide
Under photochemical catalyst dosage, the adsorption efficiency for the coking wastewater solution that it contains the phenol that concentration is 500mg/L to 50mL is measured
After obtain result as shown in Figure 2, it can be deduced that, the efficiency of the cooperative processing method adsorbed after first photocatalysis, which is apparently higher than, first to be adsorbed
The efficiency of light-catalysed cooperative processing method afterwards, the metal-doped manganese dioxide photochemical catalyst prepared using hydrothermal reaction at low temperature are to receive
Rice manganese dioxide, needed after carrying out photocatalysis treatment with differential centrifugation could by metal-doped manganese dioxide photochemical catalyst and
Phenol separation in coking wastewater solution, and biomass modified coal tar adsorbent itself has the ability of absorption, photocatalysis in the ban
After when adsorbing, biomass modified coal tar adsorbent can adsorb the manganese dioxide composites of the middle remnants in coking wastewater solution, from
And making the light splitting angle value measured lower, adsorption efficiency is higher.
By first using prepare metal-doped manganese dioxide photochemical catalyst to containing phenol coking wastewater carry out light urge
Change processing, the biomass modified coal tar adsorbent for recycling campanulaceae and certain northern power plant's duff to prepare is to the coking containing phenol
Waste water carries out adsorption treatment, it can be found that first carry out photocatalysis treatment carries out adsorption treatment again, to the coking wastewater containing phenol
Treatment effect to significantly improve, and work as metal-doped manganese dioxide photochemical catalyst and biomass modified coal tar adsorbent synthesis
When dosage is 0.5g, the 50mL coking wastewater solution treatment effeciency for containing the phenol that concentration is 500mg/L is up to
90.5%.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements
It all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (8)
1. a kind of coking waste water treatment method, which comprises the following steps:
Step 1: biomass modified coal tar adsorbent is prepared using campanulaceae and certain northern power plant's duff, preparation process includes:
T1: grinding campanulaceae obtains Platycodon Root, and sieves with 100 mesh sieve processing to Platycodon Root；
T2: Platycodon Root is mixed with certain northern power plant's duff according to the ratio of 7:3；
T3: the mixture of pyrolysis of coal experimental provision processing Platycodon Root and certain northern power plant's duff is utilized；
T4: it carries out cooling treatment for 24 hours, obtains biomass modified coal tar adsorbent；
Step 2: preparing metal-doped manganese dioxide photochemical catalyst, and process includes:
S1: 1.100~1.104g potassium permanganate is weighed in 100mL beaker；
S2: 35~37mL deionized water and 35~37mL ethyl alcohol are added into beaker, obtains purplish red solution after being sufficiently stirred；
S3: 2.44~2.50g urea and 0.08~0.12g metal oxide are added into the purplish red solution of S2, is blended
Object is transferred them in 100mL hydrothermal reaction kettle after ultrasonic treatment, is kept the temperature, to after reaction that blend is naturally cold
But to room temperature；
S4: sufficiently washing the precipitating in blend with deionized water, and 9~11min is centrifuged in differential centrifugation machine, takes supernatant
Measure the PH of blend；
S5: repeating the process of S4, until PH is neutrality, then products therefrom is dried in an oven；
S6: product grind into powder after will be dry in S5 is to get arriving metal-doped manganese dioxide photochemical catalyst；
Step 3: using the metal-doped manganese dioxide photochemical catalyst prepared to the coking wastewater solution containing phenol at
Reason；
Step 4: metal-doped manganese dioxide photochemical catalyst collaboration is handled using the biomass modified coal tar adsorbent prepared
The coking wastewater solution containing phenol afterwards carries out collaboration processing.
2. a kind of coking waste water treatment method according to claim 1, it is characterised in that: utilize coal in the step 1 T3
Pyrolysis Experiment device handles the detailed process of the mixture of Platycodon Root and certain northern power plant's duff are as follows: is first turned on pyrolysis of coal reality
The switch of experiment device, set temperature are warming up to 830~870 DEG C, then open nitrogen switch, are first passed through 8~12min nitrogen, then
The mixture of Platycodon Root and certain northern power plant's duff is put into pyrolysis of coal experimental provision, keeps nitrogen to be passed through, continues firing 8
~12min finally closes pyrolysis of coal experimental provision power switch, continues to close nitrogen gas control valve after keeping nitrogen to be passed through 10min.
3. a kind of coking waste water treatment method according to claim 1, it is characterised in that: in the step 2 S3, will be total to
Mixed object transfers them in 100mL hydrothermal reaction kettle again after carrying out 8~10min of ultrasonic treatment using ultrasonic disperse equipment, 60
Kept the temperature at~80 DEG C, when heat preservation a length of 9~11h.
4. a kind of coking waste water treatment method according to claim 1, it is characterised in that: metal oxygen in the step 2 S3
Compound is any one in iron oxide, tin oxide and bismuth oxide.
5. a kind of coking waste water treatment method according to claim 1, it is characterised in that: in the step 2 S5, by PH
It is put for neutral blend and dries 10~13h in an oven, the temperature in baking oven is controlled at 50~70 DEG C.
6. a kind of coking waste water treatment method according to claim 1, it is characterised in that: in the step 2 S9, by S8
In mixed liquor be put into baking oven, drying time be 11.5~12.5h, control baking oven in temperature be 55~65 DEG C.
7. a kind of coking waste water treatment method according to claim 1, it is characterised in that: detailed process in the step 3
Are as follows: it places the beaker on magnetic stirring apparatus, it is molten that the coking wastewater that 50mL contains the phenol that concentration is 500mg/L is added into beaker
The metal-doped manganese dioxide photochemical catalyst that liquid and 0.2g are prepared, and be put into rotor carries out magnetic agitation, open fluorescent lamp into
Water sample is extracted in row light-catalyzed reaction after reaction, controlling temperature in magnetic stirring apparatus in the process is constant room temperature, magnetic agitation time
For 3~5min, and controlling speed of agitator is 100~110r/min, and the power control of fluorescent lamp is 60~70W, reaction time control
It is made as 2.5~3.5h.
8. a kind of coking waste water treatment method according to claim 1, it is characterised in that: detailed process in the step 4
Are as follows: supernatant is taken by being extracted after water sample carries out differential centrifugation in step 3, the biomass modified coal tar adsorbent for weighing 0.3g is thrown
It is added in supernatant, and will be placed in thermostatic control oscillator vibration containing supernatant and biomass modified coal tar absorbent container, allowed
The supernatant of biomass modified coal tar adsorbent and the coking wastewater solution in container vibrates in thermostatic control oscillator vibration
30min observes processing result.
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