CN107913663A - A kind of method that COD in beneficiation wastewater is removed using flyash - Google Patents

A kind of method that COD in beneficiation wastewater is removed using flyash Download PDF

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Publication number
CN107913663A
CN107913663A CN201711072288.3A CN201711072288A CN107913663A CN 107913663 A CN107913663 A CN 107913663A CN 201711072288 A CN201711072288 A CN 201711072288A CN 107913663 A CN107913663 A CN 107913663A
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China
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flyash
cod
beneficiation wastewater
beneficiation
wastewater
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CN201711072288.3A
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Chinese (zh)
Inventor
王成行
王晨亮
汪泰
李沛伦
宋宝旭
邹坚坚
邱显扬
汤玉和
胡真
李汉文
冉金城
姚艳清
付华
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Guangdong Institute of Resources Comprehensive Utilization
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Guangdong Institute of Resources Comprehensive Utilization
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Priority to CN201711072288.3A priority Critical patent/CN107913663A/en
Publication of CN107913663A publication Critical patent/CN107913663A/en
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    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/78—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 alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • Materials Engineering (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

A kind of method that COD in beneficiation wastewater is removed using flyash, step are as follows：It is 6 ~ 8 to be cleaned original state flyash to pH with distilled water, drying；By 1g:10ml, adds the H of 1mol/L in flyash2SO4Solution, stirs 1h, stands, and filters, and washes, drying；Above-mentioned H is added in beneficiation wastewater2SO4Flyash that solution treatment is crossed, solid FeSO4·7H2The O and H that mass concentration is 1.5%2O2, stir, stand, filtering, the beneficiation wastewater for the COD that is removed.This method preparation process is easy to operate, and raw material is easy to get, and process is easy to control, catalyst reusable edible, non-secondary pollution, can realize effective degraded of COD and qualified discharge in beneficiation wastewater, while reaches the treatment of wastes with processes of wastes against one another, has preferable application prospect.

Description

A kind of method that COD in beneficiation wastewater is removed using flyash
Technical field
The present invention relates to Industrial Wastewater Treatment and solid waste resource recovery to utilize field, more particularly to a kind of to utilize fine coal The method that ash removes beneficiation wastewater COD, this method are suitable for containing chemical agent and the exceeded industrial and mining enterprises' waste discharges of COD.
Technical background
Beneficiation wastewater is a kind of waste water common in mining production, with water is big, water quality is in sour or alkalescence, solid suspension Thing is more, containing heavy metal ion and the features such as remaining beneficiation reagent, its COD generally can be higher, this is primarily due in ore dressing The a large amount of all kinds of beneficiation reagents of Cheng Zhonghui additions, these beneficiation reagents can also remain in while valuable mineral recycling is helped In final beneficiation wastewater so that the reductive organic matter too high levels that can be aoxidized in beneficiation wastewater, cause COD higher.
Currently, the processing for beneficiation wastewater mainly has natural degradation method, acid-base neutralization method, the precipitation method, absorption method and oxygen Change method.Natural degradation method is simple and practicable, but is also easy to produce secondary product, can not discharge usually or directly；Acid-base neutralization method passes through Add acid or alkali carrys out regulating water quality condition, easily implement but not strong to the applicability of waste water quality, while the reason that meets with trouble Waste water often effect unobvious；The processing cost of the precipitation method is high, while also not prominent enough to the treatment effect of the waste water of complicated component Go out, be often used together with other processing methods；Absorption method is mainly by natural or modified adsorbent to nuisance in waste water Adsorbed, process flow is simple, equipment requirement is low, but limited to the water treatment effect of high organic content；Oxidizing process There is preferable treatment effect to the waste water containing organic pollution, but also can there are oxidant utilization it is not high the problems such as.For Reality containing a variety of organic beneficiation reagents, COD high in beneficiation wastewater, selects two kinds for the treatment of technologies to carry out degraded to cooperate with to it and be A kind of relatively good thinking.
Flyash is the solid waste that thermal power plant excludes, its main component is Al2O3、SiO2、Fe2O3, CaO etc., it is more For glass spheres, single powder coal ash particle diameter is about 25 ~ 30 μm, and specific surface area is very big, generally 1600 ~ 3500cm2/ g, Mean specific gravity is 2114g/cm3, volume-weighted average 783kg/m3, aqueous solution is in alkalescence.Since flyash possesses larger ratio surface Product so that it shows higher absorption property.Degraded with flyash collaboration Fenton reagent to COD in beneficiation wastewater, Mainly utilize flyash contained metallic element and the suction-operated of itself in itself.Modified flyash possesses bigger Specific surface area, adsorptivity enhancing, metal active site increases.
The content of the invention
It is an object of the invention to provide a kind of method that beneficiation wastewater COD is removed using flyash, which drops with COD Solution rate is high, easy to operate, the advantages such as cost is low.
The present invention's comprises the following steps that：It is 6 ~ 8 to be cleaned original state flyash to pH with distilled water, drying；By 1g: 10ml, adds the H of 1mol/L in flyash2SO4Solution, stirs 1h, stands, and filters, and washes, drying；Add in beneficiation wastewater Enter above-mentioned H2SO4Flyash that solution treatment is crossed, solid FeSO4·7H2The O and H that mass concentration is 1.5%2O2, stir, stand, Filtering, the beneficiation wastewater for the COD that is removed.
The addition of flyash is 5 ~ 20g in the beneficiation wastewater per 1L.
FeSO in the beneficiation wastewater per 1L4·7H2The addition of O is 1.0 ~ 5.0mmol.
H in the beneficiation wastewater per 1L2O2Addition be 2.0 ~ 15.0mmol.
Flyash is the burning waste of coal-fired plant, and oxide therein is all in stable state so that flyash is answered It is restricted with scope and using efficiency, it is necessary to carry out surface or structurally-modified active to strengthen its.The flyash former ash is main Chemical composition is SiO2, content 42.76%, the Fe at the same time containing ＞ 9.44%2O3With the Al of ＞ 15.36%2O3.To flyash former ash Carry out granulometry, measure its particle size range be mainly 1 μm ~ 40 μm, wherein D10=2.66 μm, D90=17.39 μm, particle mean size D50=7.38μm。
Vitreous surface through the modified flyash of peracid becomes uneven, and many grooves and hole occurs, This increases not only the specific surface area of flyash, improves its adsorption capacity, and enables to the metal inside flyash to live Property site can more expose, and the catalytic performance of flyash has also been obtained further reinforcement.
Embodiment
Following embodiments are intended only as illustrating the present invention, do not represent the limitation applied to the present invention.
Embodiment 1
Take flyash some, add distilled water and clean repeatedly, until pH value of solution=7 or so, filter, are dried for standby；After taking cleaning Flyash it is some, by 1g:10ml, adds the H that concentration is 1mol/L in flyash2SO4, 1h is mixed, filtering, wash, It is dried for standby.
Take COD be 190mg/L beneficiation wastewater 100ml, adjust pH be 4, add the above-mentioned processed flyash of 2g and The solid FeSO of 1.57mmol/L4·7H2O and 9.43mmol/L mass concentrations are 1.5% H2O2, stir 40min, Ran Houjing Put, be layered, filter.The COD contents of processed waste water are measured, it is 92.11% to calculate COD removal rates.
Embodiment 2
Beneficiation wastewater 100ml is taken, it is 4 to adjust pH, adds the flyash of 2g embodiments 1 and the solid FeSO of 4.72mmol/L4· 7H2O and 14.15mmol/L mass concentrations are 1.5% H2O2, 40min is stirred, then stands, be layered, filtering.Measure processing The COD contents of waste water afterwards, it is 90.23% to calculate COD removal rates.
Embodiment 3
Beneficiation wastewater 100ml is taken, it is 4 to adjust pH, adds the flyash of 2g embodiments 1 and the solid FeSO of 1.57mmol/L4· 7H2O and 11.79mmol/L mass concentrations are 1.5% H2O2, 40min is stirred, then stands, be layered, filtering.Measure processing The COD contents of waste water afterwards, it is 92.32% to calculate COD removal rates.
Embodiment 4
Beneficiation wastewater 100ml is taken, it is 4 to adjust pH, adds the flyash of 2g embodiments 1 and the solid FeSO of 1.18mmol/L4· 7H2O and 9.43mmol/L mass concentrations are 1.5% H2O2, 40min is stirred, then stands, be layered, filtering.After measure processing The COD contents of waste water, it is 72.33% to calculate COD removal rates.
Embodiment 5
Beneficiation wastewater 100ml is taken, it is 4 to adjust pH, adds the flyash of 2g embodiments 1 and the solid FeSO of 1.57mmol/L4· 7H2O and 2.36mmol/L mass concentrations are 1.5% H2O2, 40min is stirred, then stands, be layered, filtering.After measure processing The COD contents of waste water, it is 36.87% to calculate COD removal rates.
Embodiment 6
Beneficiation wastewater 100ml is taken, it is 4 to adjust pH, adds the flyash of 1g embodiments 1 and the solid FeSO of 1.57mmol/L4· 7H2O and 9.43mmol/L mass concentrations are 1.5% H2O2, 40min is stirred, then stands, be layered, filtering.After measure processing The COD contents of waste water, it is 80.41% to calculate COD removal rates.

Claims (4)

  1. A kind of 1. method that COD in beneficiation wastewater is removed using flyash, it is characterized in that step is as follows：With distilled water by original state powder It is 6 ~ 8 that coal ash, which is cleaned to pH, drying；By 1g:10ml, adds the H of 1mol/L in flyash2SO4Solution, stirs 1h, stands, Filtering, is washed, drying；Above-mentioned H is added in beneficiation wastewater2SO4Flyash that solution treatment is crossed, solid FeSO4·7H2O and matter Measure the H that concentration is 1.5%2O2, stir, stand, filtering, the beneficiation wastewater for the COD that is removed.
  2. 2. the method according to claim 1 that COD in beneficiation wastewater is removed using flyash, it is characterized in that described select per 1L The addition of flyash is 5 ~ 20g in ore deposit waste water.
  3. 3. the method according to claim 1 that COD in beneficiation wastewater is removed using flyash, it is characterized in that described select per 1L FeSO in ore deposit waste water4·7H2The addition of O is 1.0 ~ 5.0mmol.
  4. 4. the method according to claim 1 that COD in beneficiation wastewater is removed using flyash, it is characterized in that described select per 1L H in ore deposit waste water2O2Addition be 2.0 ~ 15.0mmol.
CN201711072288.3A 2017-11-03 2017-11-03 A kind of method that COD in beneficiation wastewater is removed using flyash Pending CN107913663A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112340824A (en) * 2020-10-28 2021-02-09 贵州中车绿色环保有限公司 Preparation method of modified fly ash and application of modified fly ash in COD (chemical oxygen demand) removal
CN116002919A (en) * 2023-01-10 2023-04-25 天津大学 Method for treating acidic mine wastewater by using fly ash

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101492187A (en) * 2009-03-09 2009-07-29 中国科学院地球化学研究所 Method for treating antimony ore beneficiation wastewater with modified coal ash
CN104310631A (en) * 2014-09-30 2015-01-28 西安华陆环保设备有限公司 Treatment method of acid red dyeing wastewater
CN104310645A (en) * 2014-10-24 2015-01-28 陕西华陆化工环保有限公司 Method for treating papermaking wastewater by using modified fly ash
CN104355350A (en) * 2014-10-13 2015-02-18 陕西华陆化工环保有限公司 Method for removing phosphate by modified fly ash

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101492187A (en) * 2009-03-09 2009-07-29 中国科学院地球化学研究所 Method for treating antimony ore beneficiation wastewater with modified coal ash
CN104310631A (en) * 2014-09-30 2015-01-28 西安华陆环保设备有限公司 Treatment method of acid red dyeing wastewater
CN104355350A (en) * 2014-10-13 2015-02-18 陕西华陆化工环保有限公司 Method for removing phosphate by modified fly ash
CN104310645A (en) * 2014-10-24 2015-01-28 陕西华陆化工环保有限公司 Method for treating papermaking wastewater by using modified fly ash

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112340824A (en) * 2020-10-28 2021-02-09 贵州中车绿色环保有限公司 Preparation method of modified fly ash and application of modified fly ash in COD (chemical oxygen demand) removal
CN116002919A (en) * 2023-01-10 2023-04-25 天津大学 Method for treating acidic mine wastewater by using fly ash

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