CN106824253A - A kind of support type ozone catalyst and preparation and application for dyeing waste water biochemistry pre-treatment - Google Patents

A kind of support type ozone catalyst and preparation and application for dyeing waste water biochemistry pre-treatment Download PDF

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Publication number
CN106824253A
CN106824253A CN201710025112.6A CN201710025112A CN106824253A CN 106824253 A CN106824253 A CN 106824253A CN 201710025112 A CN201710025112 A CN 201710025112A CN 106824253 A CN106824253 A CN 106824253A
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support type
type ozone
ozone catalyst
waste water
dyeing waste
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CN201710025112.6A
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Inventor
何丹农
高小迪
童琴
董亚梅
严良
代卫国
金彩虹
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Shanghai Na Xu Industrial Co Ltd
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Shanghai Na Xu Industrial Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/076Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/36Organic compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a kind of support type ozone catalyst for dyeing waste water biochemistry pre-treatment and preparation and application, multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, zeolite is pre-processed with absolute ethyl alcohol with deionized water, it is standby after dry, calcination activation;By equivalent molar than metal nitrate dissolved after, with NaOH solution regulation system pH to 7 ~ 8,1h is mixed, metal composite oxide precursor solution is obtained, under a certain pressure, by in its vacuum impregnation to Zeolite support, after reaction a period of time is carried out in microwave reactor, take out and repeat this step, finally, catalysis material is placed in 350 DEG C of Muffle kiln roasting 4h, multi-element metal oxide support type ozone catalyst is can obtain after cooling.The problems such as dyeing waste water biodegradability is poor, COD concentration is high can be solved, for water pollution process field.

Description

It is a kind of for dyeing waste water biochemistry pre-treatment support type ozone catalyst and prepare and Using
Technical field
The present invention relates to a kind of support type ozone catalyst for dyeing waste water biochemistry pre-treatment and preparation and application, can To solve the problems such as dyeing waste water biodegradability is poor, COD concentration is high, for water pollution process field.
Background technology
Dyeing is typical highly water intensive industry, and nearly hundred million tons of technique softened water need to be consumed every year.Dyeing waste water comes Source and pollutant component are sufficiently complex, with spies such as change of water quality big, content of organics is high, colourities (predominantly colored dyes) high Point, directly discharge brings high risks to human health and living environment, while causing the waste of water resource.Dyeing waste water is most Processed using biochemical process, especially based on Aerobic biological process method.Biochemical process has BOD5Clearance is high, technical maturity, operation The low advantage of expense.But the progress of the development and finishing process in printing and dye-ing technology with chemical & blended fabric, some new color additives etc. The organic matter of difficult for biological degradation largely enters waste water, and the CODcr for not only causing waste water increases, and makes the biodegradability of waste water Reduce.If only relying on the poor printing and dyeing of aerobic biochemical technique (such as contact oxidation method or activated sludge process) treatment biodegradability to give up Water has been extremely difficult to Expected Results.Therefore, how the larger molecular organicses in waste water are converted into small organic molecule, difficult degradation Material is converted into degradable material, be that subsequent biochemical treatment creates conditions is us so as to improve the removal efficiency of the COD of waste water Key issue to be solved.
There is high-level oxidation technology treatment effect to stablize to dyeing waste water, effluent quality is good, biodegradability can be obtained effectively The advantages of raising, the concern of domestic and foreign scholars is increasingly subject to, be with a wide range of applications.At present, common advanced oxidation skill Art mainly has photocatalysis oxidation technique, Fenton, catalytic ozonation technology etc..With oxidant, electricity, illumination, catalyst etc. Produce the extremely strong hydroxyl radical free radical of activity in the reaction, can be summed up with organic matter, replaced, electro transfer, scission of link, open loop Can be that hardly degraded organic substance macromolecular is degraded to low toxicity or nontoxic small molecule in waste water Deng effect, generation is easy to raw Change the material of degraded, improve the biodegradability of waste water.
Catalytic ozonation is efficient as one kind, fast, the water technology of non-secondary pollution, in drinking water, print The association areas such as dye waste water, leather-making waste water obtain engineer applied, are also received in research field and also carry out bigger concern, but ozone Catalytic oxidation technologies do not obtain the promotion and application of large-scale also at present, main reason is that the system of efficient ozone catalyst Standby is the core and problem of catalytic ozonation technology.
The present invention using with natural micropore structure, bigger serface natural zeolite as carrier, it is true using microwave radiation technology Empty infusion process prepares multi-element metal oxide support type ozone catalyst, and being acted on by the adsorption and enrichment of porous carrier can not only For multi-element metal oxide provides larger effective area, mass transfer rate and catalytic degradation efficiency can be also improved, and enhancing is urged The stability of agent material, the prepared ozone catalyst with high-efficiency catalytic activity effectively increases the removal effect of COD Rate, improves the biodegradability of dyeing waste water, while the recovery for also solving suspended state catalyst is difficult and causes two to water quality The problems such as degree pollution, for the treatment of the industrial wastewater of other difficult degradations provides theoretical foundation.
The content of the invention
It is sufficiently complex it is an object of the invention to be directed to dyeing waste water composition, with change of water quality it is big, content of organics is high, The features such as colourity is high, biodegradability is poor, direct biochemical treatment efficiency is low, makes biochemical processing process organic loading higher, causes out Water COD value can not be up to standard or be unable to stably reaching standard, a kind of support type ozone for improving dyeing waste water biodegradability of proposition Catalyst and preparation and application.Pre-processed to improve the removal efficiency of COD carrying out conventional biochemical process before processing, dropped Low operating cost, it is ensured that the treatment effeciency of subsequent biochemical treatment.The present invention is with the day with natural micropore structure, bigger serface Right zeolite prepares multi-element metal oxide support type ozone catalyst as carrier by microwave radiation technology vacuum impregnation technology, makes work Property component can be homogeneously dispersed in matrix and be distributed densification, with reference to the fuel factor of microwave, may be such that support materials for catalysts Catalysis activity higher is shown, the removal efficiency of COD in dyeing waste water is effectively increased, returning for suspended state catalyst is also solved The problems such as receiving difficulty and not good degradation effect, effectively shortens the reaction time, improves biodegradability, and energy is reduced to greatest extent Consumption, saves material cost and operating cost.
A kind of preparation method of support type ozone catalyst for dyeing waste water biochemistry pre-treatment, it is characterised in that bag Include following steps:
(1)Multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, zeolite is used Absolute ethyl alcohol is pre-processed with deionized water, standby after dry, calcination activation;
(2)By equivalent molar than metal nitrate dissolved after, with NaOH solution regulation system pH to 7 ~ 8, mix 1h, obtains metal composite oxide precursor solution, under a certain pressure, by its vacuum impregnation to Zeolite support, then at micro- After reaction a period of time is carried out in ripple reactor, this step is taken out and repeated, finally, catalysis material is placed in 350 DEG C of Muffle furnaces Middle roasting 4h, multi-element metal oxide support type ozone catalyst is can obtain after cooling.
Metallic element is any two or three in Mn, Fe, Cu and Ni.
Zeolite is 1 with the mass ratio of metal composite oxide presoma:(0.5~1.2), dipping time is 2 ~ 10 times.
Vacuum pressure is 5 ~ 10MPa, and microwave irradiation time is 3 ~ 8min.
A kind of support type ozone catalyst for dyeing waste water biochemistry pre-treatment, it is characterised in that according to any of the above-described Methods described is prepared.
What a kind of support type ozone catalyst for dyeing waste water biochemistry pre-treatment was processed before dyeing waste water biochemistry should With.
The catalytic performance test of ozone catalyst is carried out in ozone catalytic tower, the support type ozone catalyst that will be prepared It is filled in catalytic tower, filling rate is 50 %, and hydraulic detention time maintains 60 min, after ozonation aerated 30 min, determines RhB COD value before and after solution catalyzing, and calculate catalysis degradation modulus of the ozone catalyst to waste water from dyestuff.
The problems such as dyeing waste water biodegradability is poor, COD concentration is high can be solved, for water pollution process field.The present invention Using with natural micropore structure, bigger serface natural zeolite as carrier, prepared using microwave radiation technology vacuum impregnation technology Multi-element metal oxide support type ozone catalyst, can be such that support type ozone catalyst gradually causes in the impregnation pressure for applying certain Densification and active component can be uniformly dispersed in surface and the pore passage structure of Zeolite support, with reference to the fuel factor of microwave, can make work Property component thermally equivalent without reunite.A process for preparing support type ozone catalyst there is good ozone catalytic activity, Dyeing waste water biodegradability is effectively improved, is that subsequent biochemical treatment creates conditions, and it is tired to solve the recovery of suspended state catalyst It is difficult, the problems such as two degree of pollutions and not good degradation effect are caused to water quality, substantially reduce the reaction time, improve going for COD Except efficiency, it is adaptable to large-scale practical application.
The invention has the advantages that:
The preparation method of support type ozone catalyst proposed by the present invention, multi-element metal is prepared using microwave radiation technology vacuum impregnation technology Oxide carried type ozone catalyst, can be such that support type ozone catalyst is gradually densified and living certain impregnation pressure is applied Property component can be uniformly dispersed in surface and the pore passage structure of Zeolite support, with reference to the fuel factor of microwave, active component can be made equal It is even to be heated without reuniting, and support materials for catalysts shows catalysis activity higher.
The preparation method of support type ozone catalyst proposed by the present invention, with natural micropore structure, bigger serface Natural zeolite as carrier, the mass transfer speed of composite particles can be further improved using the adsorption and enrichment effect of porous carrier Rate, drastically increases the oxidative degradation efficiency of organic matter.
Support type ozone catalyst prepared by the present invention not only has good stability, high, living with load capacity Property high, low cost, the features such as COD removal effects are good, and effectively prevent from not exclusively being caused due to separating during catalytic degradation Secondary pollution problem.
Specific embodiment
By embodiment, the present invention is described further.
Embodiment 1:
Multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, by zeolite nothing Water-ethanol is pre-processed with deionized water, standby after dry, calcination activation;
By equivalent molar than Fe (NO3)3·9H2O、Mn(NO3)2·4H2O and Ni (NO3)2·6H2After O is dissolved, NaOH is used Solution regulation system pH to 7 ~ 8 or so, mixes 1h, obtains metal composite oxide precursor solution, under 10MPa, will It is 1 according to mass ratio:1.2 vacuum impregnations after carrying out reaction 5min in microwave reactor, are taken out simultaneously in Zeolite support This step 5 time is repeated, finally, catalysis material 350 DEG C of Muffle kiln roasting 4h is placed in, multi-element metal oxygen is can obtain after cooling Compound support type ozone catalyst Fe2O3-MnO-NiO;The degraded of COD of the prepared support type ozone catalyst to RhB solution Rate is 79.6 %.
Embodiment 2:
Multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, by zeolite nothing Water-ethanol is pre-processed with deionized water, standby after dry, calcination activation;
By equivalent molar than Mn (NO3)2·4H2O and Ni (NO3)2·6H2After O is dissolved, with NaOH solution regulation system pH To 7 ~ 8 or so, 1h is mixed, metal composite oxide precursor solution is obtained, under 8MPa, by its vacuum impregnation to homogeneity Measure in the Zeolite support of ratio, after carrying out reaction 10min in microwave reactor, take out and repeat this step 3 time, finally, will Catalysis material is placed in 350 DEG C of Muffle kiln roasting 4h, and multi-element metal oxide support type ozone catalyst is can obtain after cooling MnO-NiO;The degradation rate of COD of the prepared support type ozone catalyst to RhB solution is 67.2 %.
Embodiment 3:
Multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, by zeolite nothing Water-ethanol is pre-processed with deionized water, standby after dry, calcination activation;
By equivalent molar than Mn (NO3)2·4H2O and Cu (NO3)2·3H2After O is dissolved, with NaOH solution regulation system pH To 7 ~ 8 or so, 1h is mixed, obtain metal composite oxide precursor solution, according to mass ratio be 1 by it under 5MPa: This step 6 time is taken out and repeated to 1.2 vacuum impregnations after carrying out reaction 10min in microwave reactor, in Zeolite support, Finally, catalysis material is placed in 350 DEG C of Muffle kiln roasting 4h, multi-element metal oxide support type ozone is can obtain after cooling Catalyst MnO-CuO;The degradation rate of COD of the prepared support type ozone catalyst to RhB solution is 69.1 %.
Embodiment 4:
Multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, by zeolite nothing Water-ethanol is pre-processed with deionized water, standby after dry, calcination activation;
By equivalent molar than Fe (NO3)3·9H2O、Ni(NO3)2·6H2O and Cu (NO3)2·3H2After O is dissolved, NaOH is used Solution regulation system pH to 7 ~ 8 or so, mixes 1h, obtains metal composite oxide precursor solution, under 10MPa, will Its vacuum impregnation to homogenous quantities than Zeolite support in, after carrying out reaction 10min in microwave reactor, take out and repeat this Step 3 time, finally, 350 DEG C of Muffle kiln roasting 4h is placed in by catalysis material, multi-element metal oxide is can obtain after cooling and is born Load type ozone catalyst Fe2O3-MnO-NiO;The degradation rate of COD of the prepared support type ozone catalyst to RhB solution is 71.3 %。

Claims (5)

1. it is a kind of for dyeing waste water biochemistry pre-treatment support type ozone catalyst preparation method, it is characterised in that including Following steps:
(1)Multi-element metal oxide support type ozone catalyst is prepared using microwave radiation technology vacuum impregnation technology, first, zeolite is used Absolute ethyl alcohol is pre-processed with deionized water, standby after dry, calcination activation;
(2)By equivalent molar than metal nitrate dissolved after, with NaOH solution regulation system pH to 7 ~ 8, mix 1h, obtains metal composite oxide precursor solution, under a certain pressure, by its vacuum impregnation to Zeolite support, then at micro- After reaction a period of time is carried out in ripple reactor, this step is taken out and repeated, finally, catalysis material is placed in 350 DEG C of Muffle furnaces Middle roasting 4h, multi-element metal oxide support type ozone catalyst is can obtain after cooling.
2. it is according to claim 1 it is a kind of for dyeing waste water biochemistry pre-treatment support type ozone catalyst preparation side Method, it is characterised in that metallic element is any two or three in Mn, Fe, Cu and Ni.
3. it is according to claim 1 it is a kind of for dyeing waste water biochemistry pre-treatment support type ozone catalyst preparation side Method, it is characterised in that zeolite is 1 with the mass ratio of metal composite oxide presoma:(0.5~1.2), dipping time is 2 ~ 10 It is secondary.
4. it is according to claim 1 it is a kind of for dyeing waste water biochemistry pre-treatment support type ozone catalyst preparation side Method, it is characterised in that vacuum pressure is 5 ~ 10MPa, microwave irradiation time is 3 ~ 8min.
5. it is a kind of for dyeing waste water biochemistry pre-treatment support type ozone catalyst, it is characterised in that according to claim 1-4 Any methods described is prepared.
CN201710025112.6A 2017-01-13 2017-01-13 A kind of support type ozone catalyst and preparation and application for dyeing waste water biochemistry pre-treatment Pending CN106824253A (en)

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Cited By (7)

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CN108636442A (en) * 2018-05-21 2018-10-12 北京高能时代环境技术股份有限公司 The processing method of support type ozone catalyst, preparation method and applications and acid blue dye pollutant effluents
CN108970621A (en) * 2018-08-08 2018-12-11 芜湖格丰环保科技研究院有限公司 The method of water body COD degradation catalyst is prepared using smelting laterite-nickel ores waste residue and its ozone degradation COD is applied
CN110963617A (en) * 2018-09-28 2020-04-07 宝山钢铁股份有限公司 Device and method for removing benzaldehyde and benzotriazole in cold-rolled biochemical effluent
CN111747560A (en) * 2020-06-04 2020-10-09 广东益诺欧环保股份有限公司 System and method for treating and recycling J acid
CN112408578A (en) * 2020-11-26 2021-02-26 上海绿强新材料有限公司 Catalytic ozone oxidation honeycomb filler and preparation and printing and dyeing wastewater advanced treatment method
CN113648985A (en) * 2021-02-08 2021-11-16 南京理工大学 Two-dimensional catalytic material and preparation and application thereof
CN114713280A (en) * 2022-03-09 2022-07-08 同济大学 Preparation method of supported catalyst for catalytic oxidation treatment of refractory wastewater by ozone

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108636442A (en) * 2018-05-21 2018-10-12 北京高能时代环境技术股份有限公司 The processing method of support type ozone catalyst, preparation method and applications and acid blue dye pollutant effluents
CN108970621A (en) * 2018-08-08 2018-12-11 芜湖格丰环保科技研究院有限公司 The method of water body COD degradation catalyst is prepared using smelting laterite-nickel ores waste residue and its ozone degradation COD is applied
CN108970621B (en) * 2018-08-08 2021-02-26 芜湖格丰环保科技研究院有限公司 Method for preparing water body COD degradation catalyst by using laterite-nickel ore smelting waste residues and application of water body COD degradation catalyst in ozone degradation
CN110963617A (en) * 2018-09-28 2020-04-07 宝山钢铁股份有限公司 Device and method for removing benzaldehyde and benzotriazole in cold-rolled biochemical effluent
CN111747560A (en) * 2020-06-04 2020-10-09 广东益诺欧环保股份有限公司 System and method for treating and recycling J acid
CN112408578A (en) * 2020-11-26 2021-02-26 上海绿强新材料有限公司 Catalytic ozone oxidation honeycomb filler and preparation and printing and dyeing wastewater advanced treatment method
CN113648985A (en) * 2021-02-08 2021-11-16 南京理工大学 Two-dimensional catalytic material and preparation and application thereof
CN113648985B (en) * 2021-02-08 2022-04-01 南京理工大学 Two-dimensional catalytic material and preparation and application thereof
CN114713280A (en) * 2022-03-09 2022-07-08 同济大学 Preparation method of supported catalyst for catalytic oxidation treatment of refractory wastewater by ozone

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Application publication date: 20170613