CN107473364A - A kind of Fenton fluid bed catalytic type filler and preparation method thereof - Google Patents

A kind of Fenton fluid bed catalytic type filler and preparation method thereof Download PDF

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Publication number
CN107473364A
CN107473364A CN201710646940.1A CN201710646940A CN107473364A CN 107473364 A CN107473364 A CN 107473364A CN 201710646940 A CN201710646940 A CN 201710646940A CN 107473364 A CN107473364 A CN 107473364A
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Prior art keywords
fluid bed
catalytic type
filler
type filler
fenton
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CN201710646940.1A
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CN107473364B (en
Inventor
朱益民
刘伟凤
唐晓佳
尹琳
聂毅兴
吕琦玮
陈涛
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Dalian Maoyuan Technology Co Ltd
Shaoxing Xinyue Environmental Technology Co Ltd
Dalian Maritime University
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Dalian Maoyuan Technology Co Ltd
Shaoxing Xinyue Environmental Technology Co Ltd
Dalian Maritime University
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    • 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
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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

Abstract

The present invention relates to a kind of Fenton fluid bed catalytic type filler and preparation method thereof, belong to field of waste water treatment.The Fenton fluid bed includes porous suspended filler, catalyst layer with catalytic type filler；The catalyst layer is coated on the surface of porous suspended filler；The catalyst layer includes metal salt, activated carbon, binding agent with Fenton's reaction catalytic activity, and the weight ratio of the metal salt, activated carbon and binding agent is 0.3 1.2：6：1.0 1.5, the load capacity of the metal salt on the activated carbon is 5 20%.Fenton fluid bed catalytic type filler of the present invention has the oxidation efficiency and utilization rate that huge catalysis area can effectively improve hydrogen peroxide, hydrogen peroxide decomposition can be reduced, reduce iron containing sludge yield, wastewater treatment efficiency is improved, reduces added amount of chemical and operating cost.

Description

A kind of Fenton fluid bed catalytic type filler and preparation method thereof
Technical field
The present invention relates to a kind of Fenton fluid bed catalytic type filler and preparation method thereof, belong to field of waste water treatment.
Background technology
Fenton oxidation method is a kind of widely used efficient wastewater processing technology, is characterized in hydrogen peroxide (H2O2) in Fe2 +Catalytic action under can produce largely have extremely strong oxidisability hydroxyl radical free radical (OH).In practical engineering application, Fenton Fenton's reaction is applied to fluidized bed reactor system by fluidization, significantly improves Fenton efficiency, have it is simple to operate, It is easy to use, the advantage such as be swift in response.Fenton fluid bed is especially suitable for the treatment of Organic Wastewater containing difficult for biological degradation, and Through gradually applied in the processing engineering of the waste water such as percolate, dyestuff, paper pulp papermaking, daily use chemicals, agricultural chemicals, well should have Use prospect.
The water treatment effect of Fenton fluid bed and the species of filler and performance are closely related.Filler is in fluidized state, The contact probability of hydroxyl free radical caused by hydrogen peroxide and wastewater through organic matter can be greatly increased, improves chemical reaction and mass transfer effect Rate；Being carried on the catalyst on carrier filler surface can participate in that hydrogen peroxide is catalytically decomposed, and reduce dosing, it is dirty to reduce iron content Mud amount and processing cost.But filler generally existing catalysis area at present used in Fenton fluid bed is small, density is not easy to fluidize greatly, The problems such as size is uneven, size is difficult to regulation.Such as：Bed fillers are fluidized as Fenton using quartz sand, zeolite, load iron haydite etc., Specific surface area is smaller, thus catalysis area is small, and catalytic effect is undesirable；Its grain density is greatly, it is necessary to higher upflow velocity Fluidized state can be at, therefore power consumption is higher.In addition, during using natural siliceous sand, zeolite etc. as filler, filler particles Size is difficult to uniformity, causes fluidized state in bed body uneven, and its particle size can not handle need according to actual waste water It is adjusted, also contributes to the treatment effect of Fenton fluid bed.
The content of the invention
The present invention on the surface of porous suspended filler by wrapping up catalyst layer, and making it have catalysis, area is big, density is small Easily fluidisation, the advantages that grain shape is homogeneous, particle size is controllable, solves above mentioned problem.
The invention provides a kind of Fenton fluid bed catalytic type filler, the Fenton fluid bed catalytic type filler includes Porous suspended filler, catalyst layer；
The catalyst layer is coated on the surface of porous suspended filler；
The catalyst layer includes metal salt, activated carbon, binding agent with Fenton's reaction catalytic activity, the metal The weight ratio of salt, activated carbon and binding agent is 0.3-1.2：6：1.0-1.5, the load capacity of the metal salt on the activated carbon are 5- 20%.
Metal salt of the present invention is preferably iron chloride, manganese chloride, cobalt chloride, copper chloride, ferric nitrate, manganese nitrate, nitric acid At least one of cobalt and copper nitrate.
The specific surface area of activated carbon of the present invention is preferably 500-2000m2/g。
Binding agent of the present invention is preferably polytetrafluoroethylene (PTFE) or Kynoar.
The specific surface area of porous suspended filler of the present invention is preferably 400-800m2/g。
Porous suspended filler of the present invention is preferably polypropylene or polyamide.
The particle diameter of porous suspended filler of the present invention is preferably 10-50mm.
Fenton fluid bed of the present invention is 10000-20000m with the specific surface area of catalytic type filler2/m3, it, which is catalyzed, lives Property composition includes activated carbon and Fe2O3、Fe3O4、MnO2, CuO, CoO and Co3O4At least one of.
Another object of the present invention is to provide a kind of preparation method of above-mentioned Fenton fluid bed catalytic type filler, the preparation Method comprises the following steps：
1. metal salt solution and activated carbon are mixed, stand, add cohesive agent emulsion, mix, ultrasound, obtain viscosity and urge Agent slurry；
The mass concentration of the cohesive agent emulsion is 20-60%；
2. porous suspended filler is immersed in sticky catalyst pulp, take out, activation, obtain catalytic type filler.
1. time that step of the present invention is preferably standing is 6-12h, and the ultrasonic time is 60-90min.
2. step of the present invention is preferably that the method activated is：The porous suspended filler of sticky catalyst pulp will be submerged 80-120 DEG C of activation 30-60min in an oven；Or 600-700W activates 15-25min in micro-wave oven.
The present invention has the beneficial effect that：
1. there is Fenton fluid bed catalytic type filler of the present invention huge catalysis area can effectively improve peroxidating The oxidation efficiency and utilization rate of hydrogen, it is possible to reduce hydrogen peroxide decomposition, reduce iron containing sludge yield, improve sewage disposal effect Fruit, reduce added amount of chemical and operating cost；
2. Fenton fluid bed of the present invention is 0.95-1.13 with the density of catalytic type filler, less aeration quantity or stir It is dynamic just it is fully fluidized, it is several that contact of the hydroxyl free radical caused by hydrogen peroxide with wastewater through organic matter can be effectively increased Rate, shorten the reaction time, reduce the volume for the treatment of facility, meanwhile, reduce power consumption and operating cost that system is aerated；
3. Fenton fluid bed of the present invention is homogeneous with the shape of catalytic type filler, be advantageous to reach uniformly good in bed body Good fluidized state；Suitable Fenton fluid bed catalytic type packing material size size is selected, different sewage processing can be met Water quality and water requirement, ensure wastewater treatment efficiency；
4. Fenton fluid bed of the present invention is good with catalytic type filler stability, it may be reused, not easily run off, without two Secondary pollution.
Brief description of the drawings
The width of accompanying drawing 2 of the present invention,
Fig. 1 is the structural representation of Fenton fluid bed catalytic type filler of the present invention；
Fig. 2 is the sectional view of Fenton fluid bed catalytic type filler of the present invention；
Wherein, 1, porous suspended filler, 2, catalyst layer.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with Any mode limits the present invention.
Embodiment 1
A kind of preparation method of Fenton fluid bed catalytic type filler, the preparation method comprise the following steps：
1. the ferric nitrate of equimolar amounts and manganese nitrate is soluble in water, obtain the metal that concentration of metal ions is 10mol/L Salting liquid, addition specific surface area are 1000m2/ g activated carbon mixes, and stands dipping 6h, Fe/Mn ions on the activated carbon negative Carrying capacity is 5%, then the ptfe emulsion that mass concentration is 60wt% is slowly added dropwise and mixes, and ultrasonic 60min, obtains viscosity and urges Agent slurry, wherein, the weight ratio of metal salt, activated carbon and polytetrafluoroethylene (PTFE) is 0.3：6：1；
2. the porous suspended filler of polypropylene that particle diameter is 10mm is immersed in sticky catalyst pulp, make polypropylene porous Sticky catalyst pulp is uniformly wrapped up on the surface of floating stuffing, takes out, and 80 DEG C of activation 60min, make porous suspended fill out in an oven Material and the firm combination of catalyst, meanwhile, the catalytic activity of activated catalyst, catalytic type filler is obtained, wherein, porous suspended filler Specific surface area be 500m2/g。
Embodiment 2
A kind of preparation method of Fenton fluid bed catalytic type filler, the preparation method comprise the following steps：
1. the copper chloride of equimolar amounts and cobalt chloride is soluble in water, obtain the metal that concentration of metal ions is 20mol/L Salting liquid, addition specific surface area are 2000m2/ g activated carbon mixes, and stands dipping 12h, Cu/Co ions on the activated carbon negative Carrying capacity is 20%, then the polyvinylidene fluoride emulsion that mass concentration is 30wt% is slowly added dropwise and mixes, and ultrasonic 90min, obtains viscosity Catalyst pulp, wherein, the weight ratio of metal salt, activated carbon and Kynoar is 1.2：6：1.5；
2. the porous suspended filler of polyamide that particle diameter is 50mm is immersed in sticky catalyst pulp, make polyamide porous Sticky catalyst pulp is uniformly wrapped up on the surface of floating stuffing, takes out, and 700W activates 25min in micro-wave oven, makes porous suspended Filler and the firm combination of catalyst, meanwhile, the catalytic activity of activated catalyst, catalytic type filler is obtained, wherein, it is porous suspended to fill out The specific surface area of material is 800m2/g。
Effect example 1
Using dyeing waste water of the Fenton fluidized bed processing printworks after biochemical treatment, during using traditional catalyst, The dosage of hydrogen peroxide is 0.064mol/L, and hydrogen peroxide is 1.8 with ferrous dosage mol ratio：1, the COD of waste waterCrFrom 520mg/L is down to 364mg/L, clearance 57.0%；And the Fenton fluid bed catalytic type filler prepared using embodiment 1 When, under conditions of identical ferrous iron dosage and filler dosage, the dosage of hydrogen peroxide is down to 0.025mol/L, waste water CODCr98mg/L is down to from 520mg/L, clearance 81.1%, hydrogen peroxide consumption 61% is reduced, improves sewage disposal Efficiency 24.1%.
Effect example 2
Using the pharmacy waste water of Fenton fluidized bed processing pharmaceutical factory, during using traditional catalyst, hydrogen peroxide adds It is 1.3 with ferrous dosage mol ratio to measure as 0.042mol/L, hydrogen peroxide：1, the COD of waste waterCrIt is down to from 491mg/L 198mg/L, clearance 59.7%；And the Fenton fluid bed catalytic type filler prepared using embodiment 2, it is ferrous in identical Under conditions of dosage and filler dosage, the dosage of hydrogen peroxide is down to 0.018mol/L, the COD of waste waterCrFrom 491mg/L 72mg/L is down to, clearance 85.3%, reduces hydrogen peroxide consumption 57.1%, improves sewage treating efficiency 25.6%.

Claims (10)

  1. A kind of 1. Fenton fluid bed catalytic type filler, it is characterised in that：Fenton fluid bed catalytic type filler includes more Hole floating stuffing, catalyst layer；
    The catalyst layer is coated on the surface of porous suspended filler；
    The catalyst layer includes metal salt, activated carbon, binding agent with Fenton's reaction catalytic activity, the metal salt, work The weight ratio of property charcoal and binding agent is 0.3-1.2：6：1.0-1.5, the load capacity of the metal salt on the activated carbon are 5-20%.
  2. 2. Fenton fluid bed catalytic type filler according to claim 1, it is characterised in that：The metal salt be iron chloride, At least one of manganese chloride, cobalt chloride, copper chloride, ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate.
  3. 3. Fenton fluid bed catalytic type filler according to claim 1, it is characterised in that：The specific surface area of the activated carbon For 500-2000m2/g。
  4. 4. Fenton fluid bed catalytic type filler according to claim 1, it is characterised in that：The binding agent is polytetrafluoroethyl-ne Alkene or Kynoar.
  5. 5. Fenton fluid bed catalytic type filler according to claim 1, it is characterised in that：The ratio of the porous suspended filler Surface area is 400-800m2/g。
  6. 6. Fenton fluid bed catalytic type filler according to claim 1, it is characterised in that：The porous suspended filler is poly- Propylene or polyamide.
  7. 7. Fenton fluid bed catalytic type filler according to claim 1, it is characterised in that：The grain of the porous suspended filler Footpath is 10-50mm.
  8. 8. the preparation method of the Fenton fluid bed catalytic type filler of claim 1,2,3,4,5,6 or 7, it is characterised in that： The preparation method comprises the following steps：
    1. metal salt solution and activated carbon are mixed, stand, add cohesive agent emulsion, mix, ultrasound, obtain sticky catalyst Slurry；
    The mass concentration of the cohesive agent emulsion is 20-60%；
    2. porous suspended filler is immersed in sticky catalyst pulp, take out, activation, obtain catalytic type filler.
  9. 9. preparation method according to claim 8, it is characterised in that：The time of the step 1. middle standing is 6-12h, is surpassed The time of sound is 60-90min.
  10. 10. preparation method according to claim 8, it is characterised in that：The method of the step 2. middle activation is：Will submergence The porous suspended filler of sticky catalyst pulp activates 30-60min for 80-120 DEG C in an oven；Or the 600-700W in micro-wave oven Activate 15-25min.
CN201710646940.1A 2017-08-01 2017-08-01 Catalytic filler for Fenton fluidized bed and preparation method thereof Active CN107473364B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109107576A (en) * 2018-09-07 2019-01-01 宜兴市滨元环保设备有限公司 Fenton reactor nickel catalytic filler
CN109772370A (en) * 2019-03-01 2019-05-21 华东理工大学 A kind of water purification beaded catalyst and its preparation method and application
CN113087226A (en) * 2021-05-19 2021-07-09 新疆广汇新能源有限公司 Treatment method for removing COD (chemical oxygen demand) from sewage secondary strong brine

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Publication number Priority date Publication date Assignee Title
CN109107576A (en) * 2018-09-07 2019-01-01 宜兴市滨元环保设备有限公司 Fenton reactor nickel catalytic filler
CN109772370A (en) * 2019-03-01 2019-05-21 华东理工大学 A kind of water purification beaded catalyst and its preparation method and application
CN113087226A (en) * 2021-05-19 2021-07-09 新疆广汇新能源有限公司 Treatment method for removing COD (chemical oxygen demand) from sewage secondary strong brine

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