CN110116007A - A kind of wastewater from chemical industry catalytic ozonation catalysts for treating and preparation method - Google Patents

A kind of wastewater from chemical industry catalytic ozonation catalysts for treating and preparation method Download PDF

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Publication number
CN110116007A
CN110116007A CN201810118624.1A CN201810118624A CN110116007A CN 110116007 A CN110116007 A CN 110116007A CN 201810118624 A CN201810118624 A CN 201810118624A CN 110116007 A CN110116007 A CN 110116007A
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oxide
carrier
catalyst
quality
maceration extract
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杜汉桥
李光辉
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ZHEJIANG CATHAYRIPE ENVIRONMENTAL ENGINEERING Co Ltd
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ZHEJIANG CATHAYRIPE ENVIRONMENTAL ENGINEERING Co Ltd
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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
    • 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
    • B01J23/84—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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • 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
    • 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
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

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

Abstract

The invention discloses a kind of wastewater from chemical industry catalytic ozonation catalysts for treating and preparation method, which includes carrier and active component, and wherein active component is metallic copper, iron, nickel, manganese, cerium oxide.Catalyst of the invention is high to TDS content, and the catalytic ozonation processing of the high high salinity and chlorine wastewater from chemical industry of chloride ion content has good catalytic activity, and wastewater COD removal rate reaches 40% or more.Catalyst of the invention is suitable for the advanced treating of bio-chemical effluent of the sewage treatment plant containing high salinity and chlorine.

Description

A kind of wastewater from chemical industry catalytic ozonation catalysts for treating and preparation method
Technical field
The present invention relates to catalyst of a kind of advanced treatment of industrial waste water and preparation method thereof, in particular to a kind of Industry Waste The catalyst and preparation method thereof of water-ozone catalytic oxidation treatment, belongs to water process and catalytic field.
Background of invention
High salinity and chlorine wastewater from chemical industry refers to that the total dissolved solid content of chemical enterprise emission is higher than 5000mg/L, chloride ion Content is higher than 2000mg/L, the waste water containing hardly degraded organic substance.The total dissolubility of the bio-chemical effluent of certain Craft in Chemical Industrial Area sewage treatment plant is solid Body (TDS) content about 12000mg/L, chloride ion content about 6000mg/L, COD value meet height with high salt between 80~120mg/L The feature of chloride wastewater.Reverse osmosis technology is widely applied in engineering fields such as coal chemical industry wastewater zero emissions.Part reverse osmosis concentrated water Feature with high salinity and chlorine waste water.Because COD value of waste water is higher than the level-one A of " urban wastewater treatment firm pollutant emission standard " Standard, such waste water need advanced treating.Catalytic ozonation method is one for the treatment of process of industrial application.It is with technique letter Advantage single, reaction is mild, without secondary pollution.
Chloride ion, sulfate ion etc. have inhibition to make the active group hydroxyl radical free radical generated in catalytic ozonation With, many catalyst of good performance in less salt waste water by ozone oxidation process are often lower to the activity of high salinity and chlorine waste water, Stability is insufficient.It develops and is suitble to the ozone catalytic oxidation catalyst of high salinity and chlorine Sewage advanced treatment particularly important.
Mehdi Ahmadi has reported a kind of activated carbon supported Fe3O4Catalyst (Separation and Purification Technology, 2017,177:293-303).The catalyst is to total dissolved solid content 37000mg/ L, the petrochemical wastewater of COD value 360mg/L has greater activity.However exists using active carbon as the mechanical strength of the catalyst of carrier and lack It falls into, will appear damaged loss in operation.
For a long time in ozone oxidation environment after use, the surface chemical property of active carbon can change, catalytic activity by It gradually reduces, needs regular regeneration (Chinese water supply and drainage, 2010,26 (4): 6-9,14).
Patent 201510508937.4 discloses a kind of halophilic ozone catalytic oxidation catalyst.By CuO, TiO2Load In the activated alumina ball of 2-4mm.The catalyst is evaluated under dynamic continuous flow operational mode, ozone dosage 100mg/L, Wastewater volume air speed 1h-1, waste water TDS about 3500mg/L, COD about 350mg/L.Measuring wastewater COD removal rate is 31%.Water outlet COD233mg/L is higher than discharge level-one A standard.The catalyst can only be useless no more than 8000mg/L in total dissolved solid content Normal use in water.
Patent 201610067240.2 discloses a kind of ozone catalytic oxidation catalyst for handling reverse osmosis concentrated water.With dipping The nitrate such as titanium, manganese, iron, potassium are supported on the alumina support through peracid or alkali process by method, are made through health, drying, roasting Obtain catalyst.Test condition is that the mass concentration of waste water chloride ion is 2500mg/L, COD200mg/L.Wastewater volume air speed 2h -1, ozone usage 860mg/L, wastewater COD removal rate 60%, water outlet COD, which is still higher than, discharges level-one A standard.Ozone dosage is big, It is economically uneconomical.
Summary of the invention
The purpose of the present invention is deposit in the catalytic ozonation treatment process for existing degradation high salinity and chlorine wastewater from chemical industry The technical issues of, a kind of high salinity and chlorine wastewater from chemical industry catalytic ozonation catalysts for treating and preparation method thereof is provided.This The catalyst of invention is high to the COD removal efficiency of high salinity and chlorine chemical industrial organic wastewater；Stability is high；Compression strength is high.Catalyst Preparation method simple process, can accurately control the load capacity of active component, and active component is uniformly dispersed, in preparation process No waste residue, waste water generate, preparation process low pollution.
Three kinds of reaction paths are existed simultaneously in ozone heterogeneous catalytic oxidation reaction system.1, the ozone of water phase ontology is direct Oxidation reaction；2, the HO indirect oxidation reaction of water phase ontology；3, the ozone of the organic species of catalyst surface absorption and absorption Between reaction.When water phase ontology contains the Cl of high concentration-When, such as reaction equation (1), chloride ion consumes hydroxyl radical free radical, The reaction of HO indirect oxidation is suppressed, thus the third reaction just seems more important.The group that the present invention passes through regulation catalyst At and preparation method, the surface texture of catalyst obtained be conducive to adsorb waste water in solubilised state organic matter and ozone, strengthen The reaction of the third approach realizes qualified discharge to remove the COD of waste water with less ozone usage.
HO·+Cl-→Cl·+OH- (1)
To achieve the purpose of the present invention, one aspect of the present invention provides a kind of processing of wastewater from chemical industry catalytic ozonation with urging Agent, including catalyst carrier and catalytic active component, wherein the active component is the oxidation of metallic copper, iron, nickel, manganese, cerium Object.
Wherein, the wastewater from chemical industry is high salinity and chlorine organic wastewater.
In particular, the high salinity and chlorine organic wastewater refers in water that TDS content is≤15000mg/L, preferably 2000~ 15000mg/L；Chloride ion content >=1000mg/L, preferably 1000~6000mg/L；COD >=70mg/L, preferably 70~ The waste water of 120mg/L.
In particular, the catalyst is that high salinity and chlorine wastewater from chemical industry carries out catalytic ozonation catalysts for treating.
Wherein, the carrier selective oxidation aluminium, molecular sieve, haydite, zirconium oxide, preferably aluminium oxide and haydite, it is further excellent It is selected as aluminium oxide.
In particular, the aluminium oxide can be γ-Al2O3、α-Al2O3、δ-Al2O3、η-Al2O3、θ-Al2O3, preferably brilliant Type is γ-Al2O3。
Especially, the γ-Al2O3Carrier specific surface area be 150~400m2/ g, preferably 220~320m2/g.Carrier 0.2~0.5cm of Kong Rongwei3/ g, preferably 0.38~0.43cm3/g；Carrier compression strength >=130N/.
Especially, the support shapes can be spherical, bar shaped, cylinder, trilobal, honeycomb etc., preferably spherical, Bar shaped, it is further preferably spherical.
In particular, the diameter of the ball type carrier is 2~8mm, preferably 3~5mm.
Because the aperture of catalyst, in 2 times of target molecule diameters, the absorption property of catalyst is best, while industrial application It has higher requirements to the mechanical strength of catalyst, the γ-Al that the present invention uses2O3Preferably specific standard, i.e. specific surface area 220- 320m2/ g, Kong Rong 0.38-0.43cm3/ g, compression strength are greater than the spherical gamma-Al of 130N/, partial size 3-5mm2O3。
Wherein, metallic copper in the active component, iron, nickel, manganese, cerium oxide be respectively CuO, Fe2O3、NiO、MnO2、 CeO2。
In particular, the weight of the activity component metal Cu oxide and catalyst is (0.1-1.5): 100, it is excellent It is selected as (0.5-1.5): 100, further preferably (0.5-1.0): 100；The weight of metal ferriferous oxide and catalyst For (0.1-1.5): 100, preferably (0.25-1.1): 100, further preferably (0.25-0.9): 100；Metal nickel oxide Weight with catalyst is (0.1-1.5): 100, preferably (0.3-1.0): 100；Metal manganese oxide and catalyst Weight be (0.5-3): 100, preferably (1.5-3.0): 100；The parts by weight of metallic cerium oxide and catalyst are matched Than for (0.05-0.7): 100, preferably (0.2-0.7): 100, further preferably (0.2-0.5): 100.
Especially, the weight of the metallic copper, iron, nickel, manganese, the total weight parts of cerium oxide and catalyst is (3-6): 100, preferably (3-5.5): 100, further preferably (3.8-5.5): 100, it is still more preferably (3.8- 5.05):100。
Another aspect of the present invention provides a kind of preparation method of catalytic ozonation processing wastewater from chemical industry catalyst, including The step of following sequence carries out:
1) water absorption rate (Y, %) of carrier is measured；
2) it is weighed to calculate institute for the catalyst carrier of accurate weighing certain mass, and the water absorption rate measured according to step 1) Catalyst carrier carries out the volume of maceration extract required when incipient impregnation processing；
3) active component precursors are added to the water dissolution, precursor maceration extract is made；Wherein, the active component precursors choosing Select the salt compounds of metallic copper, iron, nickel, manganese, cerium；
4) active component precursors maceration extract prepared by step 3) step 2) is carried on using incipient impregnation facture to claim In the carrier of amount；
5) carrier after impregnation is successively dried, calcination process.
Wherein, the wastewater from chemical industry is high salinity and chlorine organic wastewater.
In particular, the high salinity and chlorine organic wastewater refers in water that TDS content is≤15000mg/L, preferably 2000~ 15000mg/L；Chloride ion content >=1000mg/L, preferably 1000~6000mg/L；COD >=70mg/L, preferably 70~ The waste water of 120mg/L.
Wherein, the aluminium of carrier selective oxidation described in step 1), molecular sieve, haydite, zirconium oxide, preferably aluminium oxide and haydite, Further preferably aluminium oxide.
In particular, the aluminium oxide can be γ-Al2O3、α-Al2O3、δ-Al2O3、η-Al2O3、θ-Al2O3, preferably brilliant Type is γ-Al2O3。
Especially, the crystal form is γ-Al2O3Carrier be spherical shape.
Wherein, the water absorption rate of catalyst carrier is measured in step 1) in accordance with the following steps, accurately weighs sample 50g (m, essence Really to 0.01g)；It is put into beaker, adds water to submerge, constantly stir, separated water with sample with funnel after 1h, place 10min, then Weigh sample quality (m after absorbing water1, it is accurate to 0.01g)；The water absorption rate (Y, %) of carrier is calculated according to formula (1),
Y=(m1-m)/m×100 (1)
Wherein, m1 is the quality (g) of carrier after water suction, and m is the quality (g) of carrier.
In particular, the water absorption rate is the quality (g) for the moisture that every 100g catalyst carrier absorbs.
Usually by weight of the volume of every 1g water carries out for 1ml, therefore the water absorption rate is the suction of every 100g catalyst carrier The volume (ml) of the moisture of receipts.
For example, accurately weighing the quality (M, g) of catalyst carrier, then when carrying out incipient impregnation processing, institute in step 2) The volume of the maceration extract needed is (M × Y/100, ml).
Wherein, the salt compounds of metal described in step 3) are nitrate, acetate or formates.
Especially, active component precursors select metallic copper (2+), iron (3+), nickel (2+), manganese (2+), cerium (3+) salt chemical combination Object.
In particular, the salt compounds of the metallic copper are copper nitrate or copper acetate or copper formate；The salt of metallic iron Conjunction object is ferric nitrate；The salt compounds of metallic nickel are nickel nitrate or nickel acetate；The salt compounds of manganese metal are 50% (w/w) Manganese nitrate aqueous solution or manganese acetate；The salt compounds cerous nitrate or cerous acetate of metallic cerium.
Wherein, the salt compounds for the active component precursors metallic copper being add to deionized water in step 3) are converted into gold Carrier (γ-the Al that quality and step 2) after belonging to oxide (CuO) weigh2O3) and the metal oxygen that is converted into of active component precursors Compound (CuO, Fe2O3、NiO、MnO2、CeO2) quality summation ratio be (0.1-1.5): 100, preferably (0.5- 1.5): 100, further preferably (0.5-1.0): 100；The salt compounds of metallic iron are converted into metal oxide (Fe2O3) after Quality and step 2) weigh carrier (γ-Al2O3) and active component precursors metal oxide (CuO, Fe for being converted into2O3、 NiO、MnO2、CeO2) quality summation ratio be (0.1-1.5): 100, preferably (0.25-1.1): 100, further it is excellent It is selected as (0.25-0.9): 100；The salt compounds of metallic nickel are converted into the quality after metal oxide (NiO) and step 2) claims Carrier (γ-the Al of amount2O3) and active component precursors metal oxide (CuO, Fe for being converted into2O3、NiO、MnO2、CeO2) matter The ratio of the summation of amount is (0.1-1.5): 100, preferably (0.3-1.0): 100；The salt compounds of manganese metal are converted into gold Belong to oxide (MnO2) after quality and step 2) weigh carrier (γ-Al2O3) and the metal oxygen that is converted into of active component precursors Compound (CuO, Fe2O3、NiO、MnO2、CeO2) quality summation ratio be (0.5-3): 100, preferably (1.5-3.0): 100；The salt compounds of metallic cerium are converted into metal oxide (CeO2) after quality and step 2) weigh carrier (γ- Al2O3) and active component precursors metal oxide (CuO, Fe for being converted into2O3、NiO、MnO2、CeO2) quality summation ratio Example is (0.05-0.7): 100, preferably (0.2-0.7): 100, further preferably (0.2-0.5): 100.
Such as: it is A1 that the salt compounds of active component precursors metallic copper, which are converted into the quality after metal oxide (CuO), The salt compounds of metallic iron are converted into metal oxide (Fe2O3) after quality A2, the salt compounds of metallic nickel are converted into gold Quality A3 after belonging to oxide (NiO), the salt compounds of manganese metal are converted into metal oxide (MnO2) after quality A4, gold The salt compounds for belonging to cerium are converted into metal oxide (CeO2) after quality A5, step 2) weigh carrier quality be B, then A1/ (A1+A2+A3+A4+A5+B) is (0.1-1.5): 100, preferably (0.5-1.5): 100；Other active component irons, nickel, Manganese, proportion of oxide of cerium and so on.
Especially, the metallic copper, iron, nickel, manganese, cerium salt compounds be converted into metal oxide (CuO, Fe2O3、 NiO、MnO2、CeO2) gross mass and step 2) weigh carrier (γ-Al2O3) and the metal oxygen that is converted into of active component precursors Compound (CuO, Fe2O3、NiO、MnO2、CeO2) quality summation ratio be (3-6): 100, preferably (3-5.5): 100, Further preferably (3.8-5.5): 100, it is still more preferably (3.8-5.05): 100.
Wherein, weighed carrier carries out incipient impregnation in the volume and step 2) of the precursor maceration extract of step 3) preparation The volume of required maceration extract is identical when processing.
In particular, precursor maceration extract described in step 3) is prepared in accordance with the following steps: successively by active component precursors It is add to deionized water, stirs, then dissolution adds deionized water to the load with the weighing being calculated in step 2) again Body carries out the volume of maceration extract required when incipient impregnation processing.
Especially, the sequence that 5 kinds of active component precursors are add to deionized water is successively are as follows: the salt of manganese metal Close the salt of object, the salt compounds of metallic iron, the salt compounds of metallic nickel, the salt compounds of metallic cerium, metallic copper Close object.
Manganese metal salt compound dosage is larger in the present invention, and rate of dissolution is slow in water, during preparation maceration extract first Manganese metal salt compound is added and is conducive to being completely dissolved for 5 kinds of active component precursors compounds, is particularly due to manganese acetate in water Rate of dissolution is lower, and dissolution manganese salt first is conducive to reach being completely dissolved for salt compounds as early as possible；If containing second in solution And then compound nantokite is added in acid ion, will generate the lesser copper acetate of solubility, the stability of maceration extract is caused to subtract It is weak, therefore during preparing maceration extract, it needs finally to add compound nantokite.
Wherein, incipient impregnation facture described in step 4) is that the active component precursors maceration extract for preparing step 3) sprays On the carrier for pouring step 2) weighing；Or active component precursors maceration extract prepared by step 3) is poured into the carrier of step 2) weighing In, so that active component precursors maceration extract is adsorbed on carrier.
In particular, static placement 3-12h is preferably quiet during impregnation after precursor maceration extract is adsorbed on carrier Only place 6-10h.
Wherein, drying temperature described in step 5) is 100-120 DEG C；Drying time is at least 2h, preferably 2-7h.
In particular, preferably 120 DEG C of the drying temperature；It is 4 hours dry or more, preferably 4-7h.
Wherein, calcination process described in step 5) is to roast 1-2h at 300-350 DEG C, then heats to 400~550 DEG C Roast 3-5h.
In particular, calcination process described in step 5) carries out in accordance with the following steps:
5-1) by the carrier after impregnation with the heating rate of≤10 DEG C/min from room temperature to 300-350 DEG C, and 1-2h is kept under conditions of 300-350 DEG C；
It 5-2) is warming up to 400-550 DEG C with the rate of≤10 DEG C/min again, and keeps 3- under conditions of 400-550 DEG C 5h。
In particular, step 5-1) described in heating rate be preferably 4-5 DEG C/min；Step 5-2) described in heating rate it is excellent It is selected as 2.5-5 DEG C/min, further preferably 4-5 DEG C/min.
In particular, step 5-1) in keep 1-1.5h under conditions of 350 DEG C；Step 5-2) in preferably with 4-5 DEG C/min Rate be warming up to 400-550 DEG C, and keep 3-5h under conditions of 400-550 DEG C.
Especially, step 5-2) in be preferably warming up to 460-500 DEG C with the rate of 4-5 DEG C/min, and at 460-500 DEG C Under the conditions of keep 3-5h.
Another aspect of the invention provides a kind of catalytic ozonation processing wastewater from chemical industry being prepared according to the method described above Use catalyst.
Compared with prior art, the present invention having the advantage that and effect:
1, in catalytic ozonation processing high salinity and chlorine waste water reaction, catalyst of the present invention is to organic matter in wastewater from chemical industry Adsorption strength be greater than organic species and absorption that catalyst surface absorption is promoted to the adsorption strength of chloride ion ozone it Between reaction, 15000mg/L is not more than to TDS content, chloride ion content goes out no more than sewage treatment plant's biochemistry of 6000mg/L Water COD removal rate reaches 40% or more；
2, the preparation method of catalyst of the invention is simple, easy to operate, not only can accurately control the negative of active component Carrying capacity, and active component is uniformly dispersed, and generates in preparation process without waste residue, waste water, preparation process low pollution；
3, the catalyst compression strength of catalytic ozonation of the invention is high, and the compression strength of catalyst is greater than 100N/, Conducive to long-lasting catalytic use；
4, the preparation method of catalyst of the present invention is conducive to the content for accurately controlling active component in catalyst, obtained to urge Agent Active components distribution is uniform, and copper oxide, di-iron trioxide, nickel monoxide, manganese dioxide, ceria play collaboration effect It answers, improves the activity of catalyst, increase the COD removal efficiency to wastewater from chemical industry.
Specific embodiment
Present invention will be further explained below with reference to specific examples, the advantages and features of the present invention will be with description and It is apparent.But examples are merely exemplary for these, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art Member it should be understood that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form into Row modifications or substitutions, but these modifications and replacement are fallen within the protection scope of the present invention.
Metal salt compound used in the embodiment of the present invention is purchased from Shanghai fuzz Chemical Co., Ltd.；Carrier γ- Al2O3Particle is purchased from Zibo Ying He Chemical Co., Ltd., and carrier has the feature that
150~400m of carrier specific surface area2/ g carrier hole holds 0.38~0.43cm3/g
Compression strength >=130N/
The measurement of 1 carrier water absorption rate of embodiment
Weigh carrier γ-Al2O3Particle 50g (m is accurate to 0.01g)；It is put into beaker, adds water to submerge, constantly stir, 1h Water is separated with funnel with sample afterwards, places 10min, then weighs sample quality after water suction (m1 is accurate to 0.01g).According to public affairs The water absorption rate (Y, %) of formula (1) calculating carrier.
Carrier γ-Al in embodiment of the present invention2O3The water absorption rate of particle is 55.0%, i.e., every 100g carrier (γ- Al2O3) amount of moisture is fully absorbed as 55ml.
2 catalyst preparation of embodiment
1,380g carrier γ-Al is weighed2O3, spare.
It 2, is 55% according to the carrier water absorption rate Y that embodiment 1 measures, by weight of the volume of every 1g water carries out for 1ml, because The water absorption rate of this carrier is that the volume for the moisture that every 100g catalyst carrier absorbs is 55ml, then 380g catalytic pretreatment carries The volume that body carries out the solution of incipient impregnation weighing is 380 × 55/100=209ml.
3, maceration extract is prepared
Portions of de-ionized water is taken, 50% manganese nitrate aqueous solution (49.4g), nine water ferric nitrates (5.1g), six water are sequentially added Nickel nitrate (4.7g), cerium nitrate hexahydrate (5.3g), nitrate trihydrate copper (12.2g) stir 30 minutes, are completely dissolved solid, then plus Enter deionized water, until the total volume of mixed solution is 209ml, maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract) be made, Spare, wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract, ferric nitrate is converted into iron oxide (Fe2O3) matter Amount, nickel nitrate is converted into the quality of nickel oxide (NiO), manganese nitrate is converted into manganese oxide (MnO2) quality, cerous nitrate is converted into Cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, the quality of cerium oxide and title The summation of the carrier quality (380g) taken) mass ratio be respectively 1:100,0.25:100,0.3:100,3:100,0.5: 100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel prepared by step 3-cerium salt maceration extract (209ml) spray arrives the accurate weighed catalyst of step 1 On carrier, rotation dipping carries out incipient impregnation processing, so that maceration extract, by carrier uniform adsorption, maceration extract substantially uniformity is inhaled By the carrier for having adsorbed maceration extract standing 8h, (usually 3-12h divides maceration extract component uniformly on carrier after being attached on carrier Cloth), load maceration extract carrier is made；Or
Copper-iron-manganese-nickel-cerium salt maceration extract (209ml) prepared by step 3 pours into the accurate weighed catalyst of step 1 and carries In body, rotation dipping carries out incipient impregnation processing, so that maceration extract is by carrier uniform adsorption, the absorption of maceration extract substantially uniformity By the carrier for having adsorbed maceration extract standing 8h, (usually 3-12h divides maceration extract component uniformly on carrier after on to carrier Cloth), load maceration extract carrier is made；
5, it is dried
Load maceration extract carrier is laid in pallet, the baking oven that temperature is 120 DEG C (usually 100-120 DEG C) is put into In, the dry 4h (usually >=2h, preferably 2-7h) at 120 DEG C；
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate keeps 1h under conditions of 300 DEG C from room temperature to 300 DEG C；Then again with the heating rate of 5 DEG C/min from 300 DEG C are warming up to 500 DEG C, and keep 3h at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
In catalyst preparation process of the present invention, maturing temperature influences the property (such as activity etc.) and active component of catalyst Dispersion degree, first segment maturing temperature control at 300-350 DEG C so that active component precursors are decomposed into corresponding oxidation in advance Object.Second stage maturing temperature is controlled at 400-550 DEG C, is conducive to active component, carrier interaction, is formed optimal surface Structure is firmly combined between active component and carrier.If temperature is higher than 550 DEG C, carrier γ-Al2O3Physical property may become Change.Heating rate control is to avoid generating to guarantee catalyst thermally equivalent lower than 10 DEG C/min during calcination process Big stress and the intensity for reducing catalyst.
Supported copper manufactured in the present embodiment, iron, nickel, manganese, cerium catalyst in the content of copper oxide be 1%, iron oxide Content is 0.25%, and the content of nickel oxide is 0.3%, and the content of manganese oxide is 3%, and the content of cerium oxide is 0.5%.
3 catalyst preparation of embodiment
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, four water manganese acetates (33.8g), nine water ferric nitrates (5.1g), four water nickel acetates are sequentially added (4.0g), cerous acetate (4.5g), a water copper acetate (10g) stir 30 minutes, are completely dissolved solid, add deionized water, Until the total volume of mixed solution is 209ml, it is made maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract), it is spare, wherein soaking Copper acetate is converted into the quality of copper oxide (CuO) in stain liquid, ferric nitrate is converted into iron oxide (Fe2O3) quality, nickel acetate conversion Manganese oxide (MnO is converted at the quality of nickel oxide (NiO), manganese acetate2) quality, cerous acetate be converted into cerium oxide (CeO2) Quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, the quality of cerium oxide and weighed carrier quality The summation of (380g)) mass ratio be respectively 1:100,0.25:100,0.3:100,3:100,0.5:100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel-cerium salt maceration extract (209ml) prepared by step 3 pours into the accurate weighed catalyst of step 1 and carries In body, rotation dipping carries out incipient impregnation processing, so that maceration extract is by carrier uniform adsorption, the absorption of maceration extract substantially uniformity By the carrier for having adsorbed maceration extract standing 10h, (usually 3-12h divides maceration extract component uniformly on carrier after on to carrier Cloth), load maceration extract carrier is made；
5, it is dried
Load maceration extract carrier is laid in pallet, the baking oven that temperature is 110 DEG C (usually 100-120 DEG C) is put into In, the dry 7h (usually >=2h, preferably 2-7h) at 110 DEG C；
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 5 DEG C/min from 350 DEG C are warming up to 490 DEG C, and keep 3h at 490 DEG C；Then it is down to room temperature naturally from 490 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
Supported copper manufactured in the present embodiment, iron, nickel, manganese, cerium catalyst in the content of copper oxide be 1%, iron oxide Content is 0.25%, and the content of nickel oxide is 0.3%, and the content of manganese oxide is 3%, and the content of cerium oxide is 0.5%.
4 catalyst preparation of embodiment
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, 50% manganese nitrate aqueous solution (32.9g), nine water ferric nitrates (6.1g), six water are sequentially added Nickel nitrate (4.7g), cerium nitrate hexahydrate (2.0g), nitrate trihydrate copper (12.2g) stir 30 minutes, are completely dissolved solid, then plus Enter deionized water, until the total volume of mixed solution is 209ml, maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract) be made, Spare, wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract, ferric nitrate is converted into iron oxide (Fe2O3) matter Amount, nickel nitrate is converted into the quality of nickel oxide (NiO), manganese nitrate is converted into manganese oxide (MnO2) quality, cerous nitrate is converted into Cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, the quality of cerium oxide and title The summation of the carrier quality (380g) taken) mass ratio be respectively 1:100,0.3:100,0.3:100,2:100,0.2:100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel prepared by step 3-cerium salt maceration extract (209ml) spray arrives the accurate weighed catalyst of step 1 On carrier, rotation dipping carries out incipient impregnation processing, so that maceration extract, by carrier uniform adsorption, maceration extract substantially uniformity is inhaled By the carrier for having adsorbed maceration extract standing 8h, (usually 3-12h divides maceration extract component uniformly on carrier after being attached on carrier Cloth), load maceration extract carrier is made；
Or copper-iron-manganese-nickel-cerium salt the maceration extract (209ml) for preparing step 3 pours into the accurate weighed catalyst of step 1 In carrier, rotation dipping carries out incipient impregnation processing, so that maceration extract, by carrier uniform adsorption, maceration extract substantially uniformity is inhaled By the carrier for having adsorbed maceration extract standing 8h, (usually 3-12h divides maceration extract component uniformly on carrier after being attached on carrier Cloth), load maceration extract carrier is made；
5, it is dried
Load maceration extract carrier is laid in pallet, the baking oven that temperature is 120 DEG C (usually 100-120 DEG C) is put into In, the dry 5h (usually >=2h, preferably 2-7h) at 120 DEG C；
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with 4.5 DEG C/min's during calcination process Heating rate from room temperature to 300 DEG C, and under conditions of 300 DEG C under keep 1h；Then again with the heating speed of 4.5 DEG C/min Rate is warming up to 460 DEG C from 300 DEG C, and keeps 5h at 460 DEG C；Then it is down to room temperature naturally from 460 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
Supported copper manufactured in the present embodiment, iron, nickel, manganese, cerium catalyst in the content of copper oxide be 1%, iron oxide Content is 0.3%, and the content of nickel oxide is 0.3%, and the content of manganese oxide is 2%, and the content of cerium oxide is 0.2%.
5 catalyst preparation of embodiment
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, four water manganese acetates (22.5g), nine water ferric nitrates (6.1g), four water nickel acetates are sequentially added (4.0g), cerium nitrate hexahydrate (5.3g), nitrate trihydrate copper (12.20g) stir 30 minutes, are completely dissolved solid, add Ionized water is made maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract) until the total volume of mixed solution is 209ml, spare, Wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract, ferric nitrate is converted into iron oxide (Fe2O3) quality, acetic acid Nickel is converted into the quality of nickel oxide (NiO), manganese acetate is converted into manganese oxide (MnO2) quality, cerous nitrate be converted into cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, cerium oxide quality and weighed load The summation of weight (380g)) mass ratio be respectively 1:100,0.3:100,0.3:100,2:100,0.5:100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel-cerium salt maceration extract (209ml) prepared by step 3 pours into the accurate weighed catalyst of step 1 and carries In body, rotation dipping carries out incipient impregnation processing, so that maceration extract is by carrier uniform adsorption, the absorption of maceration extract substantially uniformity By the carrier for having adsorbed maceration extract standing 12h, (usually 3-12h divides maceration extract component uniformly on carrier after on to carrier Cloth), load maceration extract carrier is made；
5, it is dried
Load maceration extract carrier is laid in pallet, the baking oven that temperature is 120 DEG C (usually 100-120 DEG C) is put into In, the dry 4h (usually >=2h, preferably 2-7h) at 120 DEG C；
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 5 DEG C/min from 350 DEG C are warming up to 500 DEG C, and keep 3h at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
Supported copper manufactured in the present embodiment, iron, nickel, manganese, cerium catalyst in the content of copper oxide be 1%, iron oxide Content is 0.3%, and the content of nickel oxide is 0.3%, and the content of manganese oxide is 2%, and the content of cerium oxide is 0.5%.
6 catalyst preparation of embodiment
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, 50% manganese nitrate aqueous solution (32.9g), nine water ferric nitrates (18.2g), four water are sequentially added Nickel acetate (13.3g), cerium nitrate hexahydrate (4.0g), nitrate trihydrate copper (6.1g) stir 30 minutes, are completely dissolved solid, then plus Enter deionized water, until the total volume of mixed solution is 209ml, maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract) be made, Spare, wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract, ferric nitrate is converted into iron oxide (Fe2O3) matter Amount, nickel acetate is converted into the quality of nickel oxide (NiO), manganese nitrate is converted into manganese oxide (MnO2) quality, cerous nitrate is converted into Cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, the quality of cerium oxide and title The summation of the carrier quality (380g) taken) mass ratio be respectively 0.5:100,0.9:100,1:100,2:100,0.4:100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel prepared by step 3-cerium salt maceration extract (209ml) spray arrives the accurate weighed catalyst of step 1 On carrier, rotation dipping carries out incipient impregnation processing, so that maceration extract, by carrier uniform adsorption, maceration extract substantially uniformity is inhaled By the carrier for having adsorbed maceration extract standing 6h, (usually 3-12h divides maceration extract component uniformly on carrier after being attached on carrier Cloth), load maceration extract carrier is made；
5, it is dried
Load maceration extract carrier is laid in pallet, the baking oven that temperature is 120 DEG C (usually 100-120 DEG C) is put into In, the dry 5h (usually >=2h, preferably 2-7h) at 120 DEG C；
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 4 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 4.5 DEG C/min It is warming up to 475 DEG C from 350 DEG C, and keeps 4h at 475 DEG C；Then it is down to room temperature naturally from 475 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
Supported copper manufactured in the present embodiment, iron, nickel, manganese, cerium catalyst in the content of copper oxide be 0.5%, iron oxide Content be 0.9%, the content of nickel oxide is 1%, and the content of manganese oxide is 2%, and the content of cerium oxide is 0.4%.
7 catalyst preparation of embodiment
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, four water manganese acetates (16.9g), nine water ferric nitrates (18.2g), four water nickel acetates are sequentially added (13.3g), cerium nitrate hexahydrate (3.0g), nitrate trihydrate copper (6.1g) stir 30 minutes, are completely dissolved solid, add Ionized water is made maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract) until the total volume of mixed solution is 209ml, spare, Wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract, ferric nitrate is converted into iron oxide (Fe2O3) quality, acetic acid Nickel is converted into the quality of nickel oxide (NiO), manganese acetate is converted into manganese oxide (MnO2) quality, cerous nitrate be converted into cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, cerium oxide quality and weighed load The summation of weight (380g)) mass ratio be respectively 0.5:100,0.9:100,1:100,1.5:100,0.3:100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel prepared by step 3-cerium salt maceration extract (209ml) spray arrives the accurate weighed catalyst of step 1 On carrier, rotation dipping carries out incipient impregnation processing, so that maceration extract, by carrier uniform adsorption, maceration extract substantially uniformity is inhaled By the carrier for having adsorbed maceration extract standing 9h, (usually 3-12h divides maceration extract component uniformly on carrier after being attached on carrier Cloth), load maceration extract carrier is made；
5, it is dried
Load maceration extract carrier is laid in pallet, the baking oven that temperature is 120 DEG C (usually 100-120 DEG C) is put into In, the dry 5h (usually >=2h, preferably 2-7h) at 120 DEG C；
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1.5h；Then again with the heating rate of 4 DEG C/min It is warming up to 490 DEG C from 350 DEG C, and keeps 4h at 490 DEG C；Then it is down to room temperature naturally from 490 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
Supported copper manufactured in the present embodiment, iron, nickel, manganese, cerium catalyst in the content of copper oxide be 0.5%, iron oxide Content be 0.9%, the content of nickel oxide is 1%, and the content of manganese oxide is 1.5%, and the content of cerium oxide is 0.3%.
Reference examples 1
Certain commercially available commodity ozone catalytic oxidation catalyst is chosen as reference examples 1, which prepared using mixing method, Carrier is alumina globule, and active component is copper oxide.Ozone catalytic oxidation catalyst 4wt%CuO/ γ-Al2O3, partial size 3- 5mm。
Reference examples 2
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, four water manganese acetates (22.5g), nine water ferric nitrates (6.1g), four water nickel acetates are successively entered (4.0g), cerium nitrate hexahydrate (19.9g), nitrate trihydrate copper (12.2g) stir 30 minutes, are completely dissolved solid, add Ionized water is made maceration extract (i.e. copper-iron-manganese-nickel-cerium salt maceration extract) until the total volume of mixed solution is 209ml, spare, Wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract, ferric nitrate is converted into iron oxide (Fe2O3) quality, acetic acid Nickel is converted into the quality of nickel oxide (NiO), manganese acetate is converted into manganese oxide (MnO2) quality, cerous nitrate be converted into cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, manganese oxide, cerium oxide quality and weighed load The summation of weight (380g)) mass ratio be respectively 1:100,0.3:100,0.3:100,2:100,2:100；
4, incipient impregnation is handled
Copper-iron-manganese-nickel-cerium salt maceration extract (209ml) prepared by step 3 pours into the accurate weighed catalyst of step 1 and carries In body, rotation dipping carries out incipient impregnation processing, so that maceration extract is by carrier uniform adsorption, the absorption of maceration extract substantially uniformity By the carrier for having adsorbed maceration extract standing 10h, (usually 3-12h divides maceration extract component uniformly on carrier after on to carrier Cloth), load maceration extract carrier is made；
5, it is dried
It is same as Example 4
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 5 DEG C/min from 350 DEG C are warming up to 500 DEG C, and keep 4h at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3- NiO-MnO2-CeO2/γ-Al2O3Catalyst).
This reference examples preparation supported copper, iron, nickel, manganese, cerium catalyst in copper oxide content be 1%, iron oxide Content is 0.3%, and the content of nickel oxide is 0.3%, and the content of manganese oxide is 2%, and the content of cerium oxide is 2%.
Reference examples 3
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, four water manganese acetates (22.5g), nine water ferric nitrates (6.1g), four water nickel acetates are sequentially added (4.0g), nitrate trihydrate copper (12.2g) stirs 30 minutes, is completely dissolved solid, adds deionized water, until mixing molten The total volume of liquid is 209ml, maceration extract (i.e. copper-iron-manganese-nickel salt maceration extract) is made, spare, wherein copper nitrate changes in maceration extract It is counted as the quality of copper oxide (CuO), ferric nitrate is converted into iron oxide (Fe2O3) quality, nickel acetate be converted into nickel oxide (NiO) Quality, manganese acetate be converted into manganese oxide (MnO2) quality quality and catalyst total amount (i.e. copper oxide, iron oxide, oxidation Nickel, manganese oxide quality and weighed carrier quality (380g) summation) mass ratio be respectively 1:100,0.3:100, 0.3:100,2:100；
4, incipient impregnation is handled
Copper-iron-manganese prepared by step 3-nickel salt maceration extract (209ml) spray is carried to the accurate weighed catalyst of step 1 On body, rotation dipping carries out incipient impregnation processing, so that maceration extract is by carrier uniform adsorption, the absorption of maceration extract substantially uniformity By the carrier for having adsorbed maceration extract standing 10h, (usually 3-12h divides maceration extract component uniformly on carrier after on to carrier Cloth), load maceration extract carrier is made；
5, it is dried
It is same as Example 4
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 5 DEG C/min from 350 DEG C are warming up to 500 DEG C, and keep 3h at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), manganese oxide (MnO2) catalyst (i.e. CuO-Fe2O3-NiO-MnO2/γ- Al2O3Catalyst).
This reference examples preparation supported copper, iron, nickel, manganese catalyst in copper oxide content be 1%, the content of iron oxide It is 0.3%, the content of nickel oxide is 0.3%, and the content of manganese oxide is 2%.
Reference examples 4
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, nine water ferric nitrates (6.1g), four water nickel acetates (4.0g), cerium nitrate hexahydrate are sequentially added (2.0g), nitrate trihydrate copper (12.2g) stirs 30 minutes, is completely dissolved solid, adds deionized water, until mixing molten The total volume of liquid is 209ml, maceration extract (i.e. copper-iron-nickel-cerium salt maceration extract) is made, spare, wherein copper nitrate changes in maceration extract It is counted as the quality of copper oxide (CuO), ferric nitrate is converted into iron oxide (Fe2O3) quality, nickel acetate be converted into nickel oxide (NiO) Quality, cerous nitrate be converted into cerium oxide (CeO2) quality and catalyst total amount (i.e. copper oxide, iron oxide, nickel oxide, oxidation The summation of the quality of cerium and weighed carrier quality (380g)) mass ratio be respectively 1:100,0.3:100,0.3:100, 0.2:100；
4, incipient impregnation is handled
Copper-iron-nickel prepared by step 3-cerium salt maceration extract (209ml) spray is carried to the accurate weighed catalyst of step 1 On body, rotation dipping carries out incipient impregnation processing, so that maceration extract is by carrier uniform adsorption, the absorption of maceration extract substantially uniformity By the carrier for having adsorbed maceration extract standing 10h, (usually 3-12h divides maceration extract component uniformly on carrier after on to carrier Cloth), load maceration extract carrier is made；
5, it is dried
It is same as Example 4
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 5 DEG C/min from 350 DEG C are warming up to 500 DEG C, and keep 3h at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, obtains loaded copper oxide (CuO), iron oxide (Fe2O3), nickel oxide (NiO), cerium oxide (CeO2) catalyst (i.e. CuO-Fe2O3-NiO-CeO2/γ- Al2O3Catalyst).
This reference examples preparation supported copper, iron, nickel, cerium catalyst in copper oxide content be 1%, the content of iron oxide It is 0.3%, the content of nickel oxide is 0.3%, and the content of cerium oxide is 0.2%.
Reference examples 5
Steps 1 and 2 are same as Example 2；
3, maceration extract is prepared
Portions of de-ionized water is taken, four water manganese acetates (22.5g), four water nickel acetates (4.0g), cerium nitrate hexahydrate are sequentially added (2.0g), nitrate trihydrate copper (12.2g) stirs 30 minutes, is completely dissolved solid, adds deionized water, until mixing molten The total volume of liquid is 209ml, maceration extract (i.e. copper-nickel-manganese-cerium salt maceration extract) is made, spare, wherein copper nitrate changes in maceration extract It is counted as the quality of copper oxide (CuO), nickel acetate is converted into the quality of nickel oxide (NiO), manganese acetate is converted into manganese oxide (MnO2)、 Cerous nitrate is converted into cerium oxide (CeO2) quality and catalyst total amount (the i.e. matter of copper oxide, nickel oxide, manganese oxide, cerium oxide Amount and the summation of weighed carrier quality (380g)) mass ratio be respectively 1:100,0.3:100,2:100,0.2:100；
4, incipient impregnation is handled
Copper-nickel-manganese prepared by step 3 -- cerium salt maceration extract (209ml) pours into the accurate weighed catalyst carrier of step 1 In, rotation dipping carries out incipient impregnation processing, so that maceration extract, by carrier uniform adsorption, maceration extract substantially uniformity is adsorbed onto By the carrier for having adsorbed maceration extract standing 10h, (usually 3-12h divides maceration extract component uniformly on carrier after on carrier Cloth), load maceration extract carrier is made；
5, it is dried
It is same as Example 4
6, calcination process
Dried catalyst is placed in Muffle furnace and carries out calcination process, with the liter of 5 DEG C/min during calcination process Warm rate from room temperature to 350 DEG C, and under conditions of 350 DEG C under keep 1h；Then again with the heating rate of 5 DEG C/min from 350 DEG C are warming up to 500 DEG C, and keep 4h at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, obtains loaded copper oxide, oxygen Change catalyst (the i.e. CuO-NiO-MnO of nickel, manganese oxide, cerium oxide2-CeO2/γ-Al2O3Catalyst).
This reference examples preparation supported copper, nickel, manganese, cerium catalyst in iron oxide content be 1%, the content of nickel oxide It is 0.3%, the content of manganese oxide is 2%, and the content of cerium oxide is 0.2%.
The catalytic ozonation purified treatment of 1 high salinity and chlorine wastewater from chemical industry of test example
The present invention evaluates the activity of catalyst in a manner of continuously flowing
Embodiment 2-7, reference examples 2-5 are respectively charged into internal diameter 30mm × height 800mm stainless steel column shaped reaction device Catalyst (500mL) ozone catalytic oxidation catalyst of preparation, the commercial catalyst (500ml) of reference examples 1, then to reactor It is inside passed through high salinity and chlorine organic wastewater and ozone, ozone is entered by aeration head by bottom, and waste water is added by the top of reactor, Gas-liquid counter current contact；Wherein:
The water quality of high salinity and chlorine organic wastewater is as follows: COD 81mg/L, chloride ion content 6000mg/L, TDS 12000mg/L；
Flow of inlet water is 8mL/min.Ozone inlet gas concentration is 70mg/L, and ozone charge flow rate is 10mL/min.Water inlet stops Stay time 60min.
Wastewater volume air speed 1h-1, ozone dosage 100mg/L, the water sampling after reacting 3h, 120h, measurement water outlet COD value.
Wherein, according to the side of professional standard " the measurement chlorine correction method of HJ/T 70-2001 chemical oxygen demand of high-chloride wastewater " Method measures the COD of waste water, and measurement result is as shown in table 1.
Calculate COD removal rate (η) according to formula (2): calculated result is as shown in table 1.
η=(C1-C2)/C1×100 (2)
In formula: η-COD removal rate, %；C1- influent COD, mg/L；C2- water outlet COD, mg/L.
The intensity test of the ozone catalytic oxidation catalyst of 2 high salinity and chlorine wastewater from chemical industry of test example
The method measurement 2-7 of the embodiment of the present invention of reference chemical standard " HG/T 3927-2007 industrial activated alumina ", The compression strength of the catalyst of reference examples 1-5.Measurement result is as shown in table 1.
1. taking catalyst sample one to be measured, it is placed on the pressure-bearing top of intensity measuring device, presses startup button, until is broken into Only, the reading in digital display field is write down, is repeated said determination 20 times.
2. compression strength is remembered with F, numerical value is indicated with N/, is calculated by formula (3)
In formula: Pi: the numerical value for the compression strength that each catalyst sample is measured, unit N；20: sample particle number.
The Contrast on effect of 1. different catalysts O3 catalytic oxidation high salinity and chlorine waste water of table

Claims (10)

1. a kind of wastewater from chemical industry catalytic ozonation catalysts for treating, characterized in that including catalyst carrier and active component, Wherein the active constituent is the oxide of metallic copper, iron, nickel, manganese, cerium.
2. catalyst as described in claim 1, characterized in that the carrier selective oxidation aluminium, molecular sieve, haydite, zirconium oxide.
3. catalyst as claimed in claim 1 or 2, characterized in that metallic copper object is CuO, gold in the active component Category ferriferous oxide is Fe2O3, metal nickel oxide be NiO, metal manganese oxide MnO2, metallic cerium oxide CeO2。
4. catalyst as claimed in claim 1 or 2, characterized in that the activity component metal Cu oxide and catalyst Weight is (0.1-1.5): 100；The weight of metal ferriferous oxide and catalyst is (0.1-1.5): 100；Gold The weight for belonging to nickel oxide and catalyst is (0.1-1.5): 100；Metal manganese oxide and the parts by weight of catalyst are matched Than for (0.5-3): 100；The weight of metallic cerium oxide and catalyst is (0.05-0.7): 100.
5. a kind of preparation method of catalytic ozonation processing wastewater from chemical industry catalyst, characterized in that including following sequence into Capable step:
1) water absorption rate (Y, %) of carrier is measured；
2) catalyst carrier of accurate weighing certain mass, and the water absorption rate measured according to step 1) calculate the weighed catalysis of institute Agent carrier carries out the volume of maceration extract required when incipient impregnation processing；
3) active component precursors are added to the water after dissolution, add water the bodies such as the catalyst carrier being calculated into step 2) The volume of required maceration extract, is made precursor maceration extract when product impregnation；Wherein, the active component precursors select metal Copper, iron, nickel, manganese, cerium salt compounds；
4) active component precursors maceration extract prepared by step 3) is carried on by step 2) weighing using incipient impregnation facture In carrier；
5) carrier after impregnation is successively dried, calcination process.
6. preparation method as claimed in claim 5, characterized in that the aluminium of carrier selective oxidation described in step 1), molecular sieve, pottery Grain, zirconium oxide.
7. preparation method as claimed in claim 5, characterized in that the salt compounds of metal described in step 3) are nitric acid Salt, acetate or formates.
8. preparation method as claimed in claim 5, characterized in that before the active component being add to deionized water in step 3) The salt compounds of body metallic copper are converted into the carrier and active component precursors that the quality after metal oxide and step 2) weigh The ratio of the summation of the quality for the metal oxide being converted into is (0.1-1.5): 100；The salt compounds of metallic iron are converted into The quality for the metal oxide that the carrier and active component precursors that quality and step 2) after metal oxide weigh are converted into The ratio of summation is (0.1-1.5): 100；The salt compounds of metallic nickel are converted into quality and step 2) after metal oxide The ratio of the summation of the quality for the metal oxide that the carrier and active component precursors of weighing are converted into is (0.1-1.5): 100； The salt compounds of manganese metal are converted into the carrier that the quality after metal oxide is weighed with step 2) and active component precursors change The ratio of the summation of the quality for the metal oxide being counted as is (0.5-3): 100；The salt compounds of metallic cerium are converted into metal The summation of the quality for the metal oxide that the carrier and active component precursors that quality and step 2) after oxide weigh are converted into Ratio be (0.05-0.7): 100.
9. preparation method as claimed in claim 5, characterized in that active component precursors described in step 3) are converted into metal oxygen The quality for the metal oxide that the carrier and active component precursors that quality sum after compound and step 2) weigh are converted into it is total The ratio of sum is (3-6): 100.
10. preparation method as claimed in claim 5, characterized in that drying temperature described in step 5) is 100-120 DEG C；It is dry At least 2h of dry time.
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CN113318747A (en) * 2021-06-11 2021-08-31 浙江中凯瑞普环境工程股份有限公司 High-salt and high-chlorine tolerant supported catalyst and preparation method and application thereof
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