CN110115999A

CN110115999A - Ozone catalytic oxidation catalyst and preparation method thereof for degradation of organic waste water

Info

Publication number: CN110115999A
Application number: CN201810119278.9A
Authority: CN
Inventors: 王凯; 李光辉
Original assignee: ZHEJIANG CATHAYRIPE ENVIRONMENTAL ENGINEERING Co Ltd
Current assignee: ZHEJIANG CATHAYRIPE ENVIRONMENTAL ENGINEERING Co Ltd
Priority date: 2018-02-06
Filing date: 2018-02-06
Publication date: 2019-08-13

Abstract

The invention discloses a kind of preparation methods of ozone catalytic oxidation catalyst for degradation of organic waste water, the catalyst is multicomponent load catalyst, including catalytic carrier, catalytic active component, wherein catalytic active component is multi-component metal oxide, catalyst of the invention carries out high catalytic efficiency in ozone catalytic treatment process in high-chlorine organic wastewater, stability is good, there is good synergistic effect between catalyst activity component, high-chlorine organic wastewater advanced treating efficiency is improved, and catalyst compression strength of the invention is high；It is 70~120mg/L for COD, chloride ion content is not more than the high-chlorine organic wastewater of 8000mg/L, COD content can reach national sewage discharge level-one A standard after catalyst treatment of the present invention, and the preparation method of catalyst of the present invention is simple, the load capacity of active component accurately controls, active component is uniformly dispersed, it is generated in preparation process without waste residue, waste water, prepares pollution-free, environmentally protective.

Description

Ozone catalytic oxidation catalyst and preparation method thereof for degradation of organic waste water

Technical field

The present invention relates to a kind of multicomponent load catalysts of high-chlorine organic wastewater of degrading, and belong to water process and environment is urged Change field.

Background technique

In recent years, with China's industrial boom, contaminated wastewater is also got worse, and water pollution is in organise, is toxic The type and quantity of harmful, organic pollutants are increasing, and Organic substance in water directly affects ecological environment and the mankind Life and health, waste water pollution problem also become major issue urgently to be resolved.Brine waste includes water in water circulating system with water, removes Brine system draining, strong brine of the reverse osmosis discharge of reclaiming system etc..In strong brine TDS (total dissolved solid) it is higher (TDS > 4000mg/L), especially high-chlorine organic wastewater (Cl^-Content is greater than 3500mg/L), the degradation of organic matter has very big difficulty. National requirements for environmental protection is increasingly strict, and sewage discharge must reach national sewage discharge level-one A standard (COD < 50mg/L), and useless Chloride ion content is higher in water, and degradation difficulty is bigger.The COD in the waste water after biochemical treatment is generally in 70~120mg/L at present, Water quality cannot reach national sewage discharge level-one A standard, need to carry out advanced treating.

Catalytic ozonation technology is a kind of efficient Sewage advanced treatment technology.The original substantially of catalytic ozonation technology Reason is O in reaction process₃It decomposes and generates OH, HO₂Free radicals such as (hydrop free radicals), free radical again with organic matter It is reacted, larger molecular organics in water is oxidized to small-molecule substance or even exhaustive oxidation into CO₂、H₂O and other inorganic matters. Primary oxidizers during catalytic ozonation are hydroxyl radical free radicals, and oxidability is only second to fluorine, are had higher than ozone Oxidation-reduction potential, the reaction speed of catalytic ozonation is higher.

Chloride ion has inhibiting effect to catalysis reaction as a kind of free radical inhibitors in high-chloride wastewater, is because from heat Amechanical angle analysis, hydroxyl radical free radical can be by Cl^-It is oxidized to Cl₂, so, when there are a large amount of Cl for system^-When, it can consume a large amount of Free radical keep COD removal effect bad to weaken whole oxidability.Here it is catalytic ozonation processing is high The bottleneck of chlorine organic wastewater.

Chinese patent CN106466603A discloses resistance to ozone catalyst with high salt of one kind and preparation method thereof.This method will live Property alumina particle and copper oxide, titanium dioxide, polyethylene glycol, polyvinyl alcohol mix in stirring mixer, after drying and roasting Obtain resistance to ozone catalyst with high salt.To TDS be 3500mg/L, the RO concentrated water of COD about 350mg/L, ozone dosage 100mg/L, Under conditions of 1 hour residence time, COD removal rate 31%.The catalyst activity component of this method preparation is single, contains to chloride ion Measuring not high waste water has certain effect, but unsatisfactory to the treatment effect of high-chloride wastewater.

Chinese patent CN105618080A disclose it is a kind of handle reverse osmosis concentrated water ozone catalytic oxidation catalyst and its Preparation method.Active component, auxiliary agent and dispersing agent will be supported on the modified support by this method using infusion process.With activity Group be divided into copper, manganese, cerium oxide catalyst treatment COD be 200mg/L, chloride ion content 2500mg/L reverse osmosis concentrated water, It is discharged COD73mg/L, national sewage discharge level-one A standard is still not achieved, it is more undesirable to the treatment effect of high-chloride wastewater.

Chinese patent CN105498777A is announced using alumina silicate as the preparation method of the metal-supported catalyst of carrier.It will Kaolin, aluminium hydroxide, active component, pore creating material are sufficiently mixed, and are conveyed into sugar coating machine, and adhesive molding is added, and are roasted through dry Fire to obtain catalyst.With the reverse osmosis concentrated water of catalyst treatment COD content 183mg/L, effluent COD concentration 101mg/L cannot Reach national sewage discharge level-one A standard.

Chinese patent CN106732792A discloses a kind of processing coal chemical industry high-salt wastewater catalyst and preparation method thereof. The catalyst uses mixing method, and aluminium-hydroxide powder, metal salt, pore creating material, adhesive and catalyst kernel are mixed spheroiding, It is made after drying and roasting.With active constituent be manganese oxide, tin tetrachloride catalyst treatment COD300mg/L, TDS be The reverse osmosis concentrated water of 18800mg/L, ozone dosage 200mg/L are discharged COD150mg/L, cannot reach national sewage discharge one Grade A standard, and ozone concentration is higher, it is at high cost.

There are no the ozone catalytic oxidation catalysts for capableing of efficient degradation high-chlorine organic wastewater currently on the market.For high chlorine Organic wastewater has invented a kind of load multi-component metal oxide catalyst.

Summary of the invention

The purpose of the present invention is present in the catalytic ozonation treatment process for existing degradation high-chlorine organic wastewater Technical problem provides a kind of catalyst and preparation method thereof for ozone degradation high-chlorine organic wastewater, catalyst of the present invention Stability is good, and especially in high-chloride wastewater, the stability of catalyst of the invention is good；Have between catalyst activity component good Synergistic effect, synergistic effect improve advanced treating of the ozone to high-chlorine organic wastewater, the COD removal efficiency of high-chlorine organic wastewater Height, and the catalyst compression strength of catalytic ozonation of the invention is high；The preparation method technique letter of catalyst of the invention Load capacity that is single, can accurately controlling active component, and active component is uniformly dispersed, object waste residue, waste water generate in preparation process, Prepare pollution-free, environmentally protective.

To achieve the purpose of the present invention, one aspect of the present invention provides a kind of catalytic ozonation for degradation of organic waste water Catalyst, including catalytic carrier, catalytic active component, wherein the catalytic active component selects metal oxide.

Wherein, the organic wastewater is high-chlorine organic wastewater.

In particular, the high-chlorine organic wastewater refers to that chloride ion content is 1000~10000mg/L, COD is less than 500mg/L Waste water, preferably chloride ion content be 2000~9000mg/L, COD be less than 200mg/L waste water；Further preferably in water Chloride ion content is the high-chlorine organic wastewater of 3500~8000mg/L, and the COD of organic wastewater is higher than 83mg/L and is less than The waste water of 200mg/L.

In particular, the catalyst is the catalyst that high-chlorine organic wastewater carries out catalytic ozonation processing.

Wherein, the carrier selective oxidation aluminium, silica, active carbon, zeolite, molecular sieve, ceramics, zirconium oxide, preferably Aluminium oxide, ceramics and active carbon, 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。

In particular, the crystal form is γ-Al₂O₃Carrier, carrier specific surface area be 150~600m²/ g, preferably 200~ 300m²/g.It is 0.2~0.5cm that carrier hole, which holds,³/ g, preferably 0.3~0.45cm³/g.Carrier heap density is 0.4~0.8g/cm³, It is preferred that 0.6~0.7g/cm³.Carrier compression strength is 70~300N/, preferably 100~200N/.

Carrier γ-Al of the invention₂O₃If its specific surface area is too small, reactant and active component contact area are small, urge It is low to change activity；If specific surface area is too big, aperture will accordingly become smaller, and the small inside diffusional resistance in aperture increases, and be unfavorable for reacting.Cause This, it is 200~300m that the present invention, which selects specific surface area,²γ-the Al of/g₂O₃。

Carrier γ-Al of the present invention₂O₃Specific surface area be 200~300m²/ g, and aperture is larger, and inside diffusional resistance subtracts It is small, conducive to going on smoothly for catalysis reaction.

Especially, the support shapes can be spherical, bar shaped, cylinder, trilobal, graininess, honeycomb etc., preferably It is further preferably spherical for spherical, bar shaped and graininess.

In particular, the diameter of the ball-type carrier is 2~8mm, preferably 3~7mm.

Wherein, in the oxide of the metal oxide selection metallic copper of the catalytic active component, iron, manganese, nickel or cobalt At least two.

In particular, in the catalytic active component selective oxidation copper, iron oxide, manganese oxide, nickel oxide or cobalt oxide extremely It is two kinds few.

Especially, the copper oxide is CuO；The iron oxide is Fe₂O₃；Manganese oxide is MnO₂；Nickel oxide is NiO, aoxidizes Cobalt is Co₃O₄。

Wherein, the load capacity of the catalytic active component is 1-15%, preferably 1.5-10%, further preferably 2%- 10%, it is still more preferably 3-4%.

Wherein, when the metal oxide of the catalytic active component selects two kinds of metal oxides, the first metal oxide Total load amount with the second metal oxide is 1-15%.Preferably 2-10%, further preferably 3-4%.

In particular, the ratio between the load capacity of first metal oxide and the load capacity of the second metal oxide are (1-4): 1。

Especially, first metal oxide selects CuO, Fe₂O₃、MnO₂, NiO or Co₃O₄, preferably CuO, MnO₂, Further preferably CuO；Second metal oxide selects CuO, Fe₂O₃、MnO₂, NiO or Co₃O₄, preferably Fe₂O₃、 NiO, further preferably Fe₂O₃；And the two is different metal oxide.

Wherein, when the metal oxide of the catalytic active component selects three kinds of metal oxides, first, second, and third The total load amount of metal oxide is 1-15%.Preferably 1.5-10%, further preferably 2-10%, still more preferably for 3-4%.

In particular, the load capacity of first metal oxide, the load capacity of the second metal oxide and third metal oxygen The ratio between load capacity of compound is (2-6): (1-2): 1, preferably (2-4): (1-2): 1, further preferably (2-4): 1:1.

Especially, first metal oxide selects CuO, Fe₂O₃、MnO₂, NiO or Co₃O₄, preferably CuO, MnO₂, Further preferably CuO；Second metal oxide selects CuO, Fe₂O₃、MnO₂, NiO or Co₃O₄, preferably Fe₂O₃、 NiO, further preferably Fe₂O₃；The third metal oxide selects CuO, Fe₂O₃、MnO₂, NiO or Co₃O₄, preferably MnO₂、Co₃O₄, further preferably MnO₂；And three is different metal oxide.

In particular, the first metal oxide CuO of catalytic active component, the second metal oxide Fe₂O₃, third metal oxygen Compound MnO₂, the ratio between load capacity be (2-6): (1-2): 1, preferably (2-4): (1-2): 1, further preferably (2-4): 1: 1。

In particular, further including catalyst aid, the catalyst aid is lanthanide metal oxide.

Wherein, the lanthanide metal oxide selects lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium Or one of lutetium or a variety of oxides, the preferably oxide of lanthanum, cerium, further preferably cerium oxide.

In particular, the lanthana is La₂O₃, cerium oxide CeO₂, praseodymium oxide PrO₂, neodymia Nd₂O₃, promethium oxide For Pm₂O₃, samarium oxide Sm₂O₃, europium oxide Eu₂O₃, gadolinium oxide Gd₂O₃, terbium oxide Tb₂O₃, dysprosia Dy₂O₃, oxygen Change holmium is Ho₂O₃, erbium oxide Er₂O₃, thulium oxide Tm₂O₃, ytterbium oxide Yb₂O₃, luteium oxide Lu₂O₃。

Wherein, the load capacity of the catalyst aid is 0.1%-3%, preferably 0.2%-1%, further preferably 0.4- 1%.

In particular, the load capacity of the catalyst aid lanthanide metal oxide is 0.1-3%, preferably 0.2-1%, into one Step is preferably 0.4-1%.

Another aspect of the present invention provides a kind of preparation method of ozone catalytic oxidation catalyst for degradation of organic waste water, Include the steps that following sequence carries out:

1) water absorption rate (Y, %) of catalytic 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) catalytic active component precursor is added to the water, after dissolution, adds water the catalysis being calculated into step 2) The volume of required maceration extract, is made precursor maceration extract when the processing of agent carrier incipient impregnation；

4) catalytic carrier that step 2) weighs is impregnated in the active component precursors maceration extract of step 3) preparation, carry out etc. Volume impregnation processing；

5) carrier after impregnation is subjected to calcination process.

Wherein, the water absorption rate of catalytic carrier, 1A are measured in step 1) in accordance with the following steps) accurate weighing is dry to constant weight Catalytic carrier；Deionized water 1B) is then added into the catalytic carrier of accurate weighing, and catalytic carrier is made to be soaked in deionized water In at least 1h；It 1C) filters, accurate weighing absorbs the weight of the catalytic carrier after moisture；1D) carrier is calculated according to formula (1) Water absorption rate (Y, %),

Y (%)=(m₁- m)/m × 100% (1)

Wherein, m1 be water suction after catalytic carrier weight (g), i.e. step 1C) weigh water suction after vehicle weight；M is to inhale The vehicle weight weighed to the weight (g) of the catalytic carrier of constant weight, i.e. step 1A) is dried before water.

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.

In particular, the catalytic carrier selective oxidation aluminium, silica, active carbon, zeolite, molecular sieve, ceramics, oxidation Zirconium, preferably aluminium oxide, ceramics and active carbon, further preferably aluminium oxide.

Especially, the aluminium oxide can be γ-Al₂O₃、α-Al₂O₃、δ-Al₂O₃、η-Al₂O₃、θ-Al₂O₃, preferably brilliant Type is γ-Al₂O₃。

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 the selection of active component precursors described in step 3) metallic copper, iron, manganese, nickel or cobalt.

In particular, the salt compounds are nitrate, carbonate, acetate, formates or lactate, preferably nitric acid Salt or acetate.

Especially, the catalytic active component precursor being add to deionized water is converted into quality and step after metal oxide The ratio of the summation of the quality for the metal oxide that the rapid catalytic carrier and catalytic active component precursor 2) weighed is converted into is (1- 15): 100, preferably 1.5-10:100, further preferably (2-10): 100, it is still more preferably (3-4): 100.

Such as: it is A, the catalytic carrier that step 2) weighs that catalytic active component precursor, which is converted into the quality after metal oxide, Quality be B, then A/ (A+B) is (1-15): 100, preferably 1.5-10%, further (2-10): 100, further preferably (3-4): 100.

In particular, the precursor maceration extract of the processing of incipient impregnation described in step 3) is prepared in accordance with the following steps: will Two kinds of active components precursor is add to deionized water, and is stirred, dissolution, the catalysis for then adding deionized water to weigh to step 2) again Volume needed for carrier carries out incipient impregnation processing, two of them active component precursors are converted into the quality of corresponding oxide The ratio between be (1-4): 1, and the quality of two oxides that is converted into of the two kinds of active components precursor being add to deionized water it Ratio with the summation of the quality of the catalytic carrier and the two oxides being converted into that weigh with step 2) is (1-15): 100, it is excellent It is selected as 1.5-10%, further (2-10): 100, further preferably (3-4): 100.

Such as: the quality for the two oxides that two kinds of active components precursor is converted into is respectively A1, A2；What step 2) weighed The quality of catalytic carrier is B, then (A1+A2)/(A1+A2+B) is (1-15): 100, preferably 1.5-10%, further (2- 10): 100, further preferably (3-4): 100.

Especially, the first precursor selects metallic copper (2 in two kinds of active components precursor⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) Or cobalt (2⁺) salt compounds；Second of precursor selects metallic copper (2⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) Salt compounds；And two kinds of active components precursor is the salt of not same metal；Such as the first precursor is the salt of metallic copper Class, then second precursor are the salt of other metallic irons apart from copper, manganese, nickel or cobalt；If the first precursor is the salt of iron Class, then second precursor is the salt of other metallic coppers in addition to iron, manganese, nickel or cobalt；The rest may be inferred for other.

In particular, the first precursor is the salt compounds of metallic copper, iron, manganese, nickel in 2 kinds of active component precursors, The preferably salt compounds of metallic copper, manganese, the further preferably salt compounds of metallic copper；Second of precursor is metal Copper, iron, manganese, nickel salt compounds, the preferably salt compounds of metallic iron, nickel, the further preferably salt of metallic iron Compound.

In particular, the salt compounds selection nitrate, carbonate, acetate, formates or lactate, preferably nitre Hydrochlorate or acetate.

In particular, the precursor maceration extract of the processing of incipient impregnation described in step 3) is prepared in accordance with the following steps: by 3 Kind active component precursors are add to deionized water, and are stirred, and dissolution, the catalysis for then adding deionized water to step 2) to weigh again carries Body carry out incipient impregnation processing needed for volume, wherein three kinds of active component precursors be converted into corresponding oxide quality it Than for (2-6): (1-2): 1；And the matter of three kinds of oxides that three kinds of active component precursors being add to deionized water are converted into The ratio of the summation of the quality of catalytic carrier and three kinds of oxides being converted into that the sum of amount is weighed with step 2) is (1-15): 100, preferably 1.5-10%, further (2-10): 100, further preferably (3-4): 100.

Such as: the quality for 3 kinds of oxides that 3 kinds of active component precursors are converted into is respectively A1, A2, A3；Step 2) weighs Catalytic carrier quality be B, then (A1+A2+A3)/(A1+A2+A3+B) be (1-15): 100, preferably 1.5-10%, into one It walks (2-10): 100, further preferably (3-4): 100.

Especially, the first precursor selects metallic copper (2 in three kinds of active component precursors⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt compounds；Second of precursor selects metallic copper (2⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt compounds；The third described precursor selects metallic copper (2⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt Class compound；And three kinds of active component precursors are the salt of not same metal.Such as the first precursor is the salt, then of metallic copper The salt that second of precursor is the salt of iron, the third precursor is manganese except copper removal, iron, nickel or cobalt；If the first precursor For the salt of iron, then second of precursor is the salt of manganese, the third precursor is the salt of copper in addition to iron, manganese, nickel or cobalt；Its He and so on.

In particular, the first precursor is preferably the salt compounds of metallic copper, manganese in three kinds of active component precursors, it is excellent It is selected as the salt compounds of metallic copper；Second of precursor is preferably the salt compounds of metal patch, nickel, the preferably salt of metallic iron Class compound；The third precursor is preferably the salt compounds of manganese metal, cobalt, preferably the salt compounds of manganese metal.

Especially, the salt compounds selection nitrate, carbonate, acetate, formates or lactate, preferably nitre Hydrochlorate or acetate.

In particular, the first precursor is copper nitrate (Cu (NO in three kinds of active component precursors₃)₂)；Second of precursor nitre Sour iron (III)；The third precursor manganese nitrate (II).

Wherein, the selection of impregnation described in step 4) incipient impregnation processing.

In particular, static placement 2-15h is excellent during impregnation after precursor maceration extract is adsorbed on catalytic carrier Select static placement 3-5h.

Wherein, 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 4-5 DEG C/min from room temperature to 150 DEG C, and 150 1-2h, preferably 1h are kept under conditions of DEG C；

It 5-2) is warming up to 400-500 DEG C with the rate of 2.5-5 DEG C/min again, and keeps 2- under conditions of 400-500 DEG C 5h, preferably 3h.

In particular, step 5-1) in preferably keep 1h under conditions of 150 DEG C；Step 5-2) in preferably with 4.0-5 DEG C/ The rate of min is warming up to 400-500 DEG C, and keeps 3h under conditions of 400-500 DEG C.

In catalyst preparation process of the present invention, maturing temperature influence catalyst activity component dispersion and catalytic property, For maturing temperature at 400-500 DEG C, catalytic active component precursor is decomposed into oxide, and dispersion degree is high, and catalytic activity improves.Temperature When degree is higher than 400-500 DEG C, the grained sintered reunion of catalyst is easily caused, the specific surface area of catalyst is reduced, reduces and urge The contact area of agent and reactant, catalytic activity also will be greatly reduced；Heating rate, which controls, during calcination process is Uniform, tiny catalyst particle is formed when 2.5-5 DEG C/min, is improved the surface area of active component, is improved catalyst Catalytic activity will lead to catalyst crystal grain more than 5 DEG C/min and increase if heating rate is improved, and surface area is accordingly reduced, and is catalyzed Activity reduces.

In particular, further including step 5A before calcination process) place is dried in the catalytic carrier after impregnation Reason, wherein being dried temperature is 100-120 DEG C, preferably 110 DEG C；Drying time is at least 4h.

Further aspect of the present invention provides a kind of preparation method of ozone catalytic oxidation catalyst for degradation of organic waste water, Include the steps that following sequence carries out:

1) water absorption rate (Y, %) of catalytic carrier is measured；

3) catalytic active component precursor and catalyst aid precursor are added to the water, after dissolution, are added water into step 2) The volume of required maceration extract, is made precursor maceration extract when the catalyst carrier incipient impregnation processing being calculated；

5) carrier after impregnation is subjected to calcination process.

Wherein, the salt compounds of the selection of active component precursors described in step 3) metallic copper, iron, manganese, nickel or cobalt；It is described The salt compounds of catalyst aid precursor selection lanthanide series metal.

In particular, the lanthanide series metal selection lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium One of, preferably lanthanum, cerium, further preferably cerium.

Especially, the salt compounds are nitrate, carbonate, acetate, formates or lactate, preferably nitric acid Salt or acetate.

In particular, selecting the salt compounds of lanthanoid metal, cerium, preferably metallic cerium in the catalytic active component precursor Salt compounds.

Especially, the catalytic active component precursor being add to deionized water is converted into quality and step after metal oxide The quality for the metal oxide that the rapid catalytic carrier and catalytic active component precursor 2) weighed is converted into, the conversion of catalyst aid precursor At metal oxide quality summation ratio be (1-15): 100, preferably (1.5-10): 100, preferably (2-10): 100, further preferably (1.7-9): 100, further preferably (3-4): 100；Catalyst aid precursor is converted into metal oxidation The quality for the metal oxide that the catalytic carrier and catalytic active component precursor that quality after object is weighed with step 2) are converted into is urged The ratio for changing the summation of the quality for the metal oxide that auxiliary agent precursor is converted into is (0.1-3): 100, preferably (0.2-1): 100, further preferably 0.4-1%.

Such as: it is A that catalytic active component precursor, which is converted into the quality after metal oxide, and catalyst aid precursor is converted into gold Quality after belonging to oxide is C, and the quality for the catalytic carrier that step 2) weighs is B, then A/ (A+C+B) is (1-15): 100, it is excellent It is selected as (1.5-10): 100, preferably (2-10): 100, further preferably (1.7-9): 100, further preferably (3-4): 100；Then C/ (A+C+B) is (0.1-3): 100, preferably (0.2-1): 100, further preferably 0.4-1%.

In particular, the precursor maceration extract of the processing of incipient impregnation described in step 3) is prepared in accordance with the following steps: will Two kinds of active components precursor, catalyst aid precursor are add to deionized water, and are stirred, then dissolution adds deionized water to step again Volume needed for the rapid catalytic carrier 2) weighed carries out incipient impregnation processing, two of them active component precursors are converted into accordingly The mass ratio of oxide be (1-4): 1, and two kinds that the two kinds of active components precursor being add to deionized water is converted into Quality, the catalytic carrier precursor of catalytic carrier and the two oxides being converted into that the quality sum and step 2) of oxide weigh The ratio for being converted into the summation of the quality of oxide is (1-15): 100, preferably (1.5-10): 100, preferably (2-10): 100, further preferably (1.7-9): 100, further preferably (3-4): 100；The catalyst aid being add to deionized water The quality of catalytic carrier and the two oxides being converted into that the quality sum and step 2) for the oxide that precursor is converted into weigh, The ratio that catalytic carrier precursor is converted into the summation of the quality of oxide is (0.1-3): 100, preferably (0.2-1): 100, into One step is preferably 0.4-1%.

Such as: the quality for the two oxides that two kinds of active components precursor is converted into is respectively A1, A2；Catalyst aid precursor The quality for the oxide being converted into is C, and the quality for the catalytic carrier that step 2) weighs is B, then (A1+A2)/(A1+A2+B+C) is (1-15): 100, preferably (1.5-10): 100, preferably (2-10): 100, further preferably (1.7-9): 100, further Preferably (3-4): 100；Then C/ (A1+A2+B+C) is (0.1-3): 100, preferably (0.2-1): 100, further preferably 0.4-1%.

Especially, the first precursor selects metallic copper (2 in two kinds of active components precursor⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) Or cobalt (2⁺) salt compounds, preferably salt compounds of metallic copper, manganese；Second of precursor selects metallic copper (2⁺)、 Iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt compounds, preferably salt compounds of metallic iron, nickel；And two kinds of work Property component precursor be not same metal salt；Such as the first precursor is the salt of metallic copper, then second of precursor is copper removal Except other metallic irons, manganese, nickel or cobalt salt；If the first precursor is the salt of iron, second of precursor is except iron Except other metallic coppers, manganese, nickel or cobalt salt；The rest may be inferred for other.

In particular, the precursor maceration extract of the processing of incipient impregnation described in step 3) is prepared in accordance with the following steps: by 3 Kind active component precursors, catalyst aid precursor are add to deionized water, and are stirred, then dissolution adds deionized water to step again 2) volume needed for the catalytic carrier weighed carries out incipient impregnation processing, wherein three kinds of active component precursors are converted into accordingly The mass ratio of oxide is (2-6): (1-2): 1, preferably (2-4): (1-2): 1, further preferably (2-4): 1:1, and What the quality sum and step 2) for three kinds of oxides that three kinds of active component precursors being add to deionized water are converted into weighed The quality of catalytic carrier and three kinds of oxides being converted into, catalytic carrier precursor are converted into the ratio of the summation of the quality of oxide For (1-15): 100, preferably (1.5-10): 100, preferably (2-10): 100, further preferably (1.7-9): 100, into one Step is preferably (3-4): 100；The quality sum and step for the oxide that the catalyst aid precursor being add to deionized water is converted into The rapid catalytic carrier 2) weighed and the quality for three kinds of oxides being converted into, catalytic carrier precursor are converted into the quality of oxide The ratio of summation is (0.1-3): 100, preferably (0.2-1): 100, further preferably (0.4-1): 100.

Such as: the quality for 3 kinds of oxides that 3 kinds of active component precursors are converted into is respectively A1, A2, A3；Step 2) weighs The quality of catalytic carrier be B, the quality of the oxide that catalyst aid precursor is converted into is C；Then (A1+A2+A3)/(A1+A2+ A3+B+C) it is (1-15): 100, preferably (1.5-10): 100, preferably (2-10): 100, further preferably (1.7-9): 100, further preferably (3-4): 100；Then C/ (A1+A2+A3+B+C) is (0.1-3): 100, preferably (0.2-1): 100, Further preferably (0.4-1): 100.

Especially, the first precursor selects metallic copper (2 in three kinds of active component precursors⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt compounds, the preferably salt compounds of metallic copper, manganese, further preferably metallic copper salt Close object；Second of precursor selects metallic copper (2⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt compounds, preferably For metallic iron, the salt compounds of nickel, further preferably metallic iron salt compounds；The third described precursor selects metallic gold Belong to copper (2⁺), iron (3⁺), manganese (2⁺), nickel (2⁺) or cobalt (2⁺) salt compounds, preferably salt compounds of manganese metal, cobalt, Further preferably manganese metal salt compounds；And three kinds of active component precursors are the salt of not same metal.Such as the first Precursor is the salt of metallic copper, then second of precursor is the salt of iron, the third precursor is manganese, nickel or cobalt except copper removal, iron Salt；If the first precursor is the salt of iron, second precursor is the salt of manganese, the third precursor be except iron, manganese it The salt of outer copper, nickel or cobalt；Other and so on.

In particular, the first precursor is preferably the salt compounds of metallic copper in three kinds of active component precursors；Second Kind precursor is preferably the salt compounds of metallic iron；The third precursor is preferably the salt compounds of manganese metal.

Another aspect of the invention provides a kind of ozone catalytic oxygen of degradation of organic waste water being prepared according to the method described above Change catalyst.

Compared with prior art, the present invention has the advantage that

1, the catalytic ozonation for high-chlorine organic wastewater of degrading of the invention is multicomponent load catalyst by carrying Body, active component and auxiliary agent composition, catalytic activity is high, significant to the degradation effect of high-chlorine organic wastewater, to high chlorine organic waste The COD removal rate of water is high.

(bicomponent catalyst COD removal rate is in 23%~33%, three component catalyst removal rate 27%~38%, four Component catalyst COD removal rate is 35%~45%.)

2, catalyst of the invention is suitable for the organic wastewater of high chlorinity, and the chlorinity that can degrade is not more than 8000mg/L High-chlorine organic wastewater, and treatment effect stablize.After catalyst long-term operation, it is able to maintain higher COD removal rate, continuously After handling high-chlorine organic wastewater 120h, wastewater COD removal rate is remained unchanged, and catalytic effect is stablized.

3, there is good synergistic effect, synergistic function is improved to high chlorine in catalyst of the invention between active component The advanced treating of organic wastewater, the COD to high-chloride wastewater is 70~120mg/L, chloride ion content is not more than the height of 8000mg/L The COD removal rate of chlorine organic wastewater is higher, reaches 45% or more.

4, the catalyst compression strength for catalytic ozonation of the invention is high, and catalytic stability is good, especially in high chlorine Catalyst stability of the present invention is good in waste water, and catalyst long service life has saved cost for wastewater treatment；

5, 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, object waste residue, waste water generate in preparation process, prepare pollution-free, environmentally protective.

Currently without the ozone oxidation catalyst for finding degradation high-chlorine organic wastewater, four components in catalyst of the invention (i.e. three catalytic active components and a catalyst aid ingredient) catalyst can drop the waste water COD of chlorinity 6000mg/L from 83 More than 40, reach country-level A standard.Influence of the high-chlorine organic wastewater to catalyst is mainly the influence of chloride ion, chloride ion Hydroxyl radical free radical can be consumed, the effect of catalysis reaction is reduced, causes high-chloride wastewater COD difficult to degrade, energy efficient degradation of the present invention is high Organic matter in chloride wastewater.

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.

Copper nitrate, ferric nitrate used in the embodiment of the present invention, manganese nitrate, cerous nitrate are purchased from the limited public affairs of extra large fuzz chemical industry Department；Carrier γ-Al₂O₃Particle is purchased from Zibo Ying He Chemical Co., Ltd., and carrier has the feature that

150~600m of carrier specific surface area²/ g carrier hole holds 0.2~0.5cm³/g

0.4~0.8g/cm of heap density³Compression strength 70~300N/

1 Vehicle element of embodiment

Take γ-Al₂O₃Particle is soaked in deionized water, and at least 20min is shaken in ultrasonic vibration instrument (usually

20-30min), it is cleaned, removes carrier surface dust and impurities；Then carrier is taken out, is put into baking oven and carries out It is dried, wherein controlled drying temperature >=100 DEG C (usually 110 ± 10 DEG C) in drying process process, Yu Wendu >= Dry at least 4h under conditions of 100 DEG C, dry to constant weight, obtained pretreated carrier is spare.

The measurement of 2 carrier water absorption rate of embodiment

Weigh pretreated carrier γ-Al₂O₃Particle 50g (m is accurate to 0.01g) is placed in beaker, then to burning Deionized water is added in cup, and submerges γ-Al₂O₃Particle stirs at least 1h (usually 1h) carrier γ-Al₂O₃Particle is sufficiently inhaled Receive deionized water；Then it filters, water is detached from the carrier, weigh the weight (76g, m1) of the carrier after absorbing moisture；Finally press The water absorption rate (Y, %) of carrier is calculated according to formula (1).

Y (%)=(m₁- m)/m × 100% (1)

The arithmetic mean of instantaneous value for taking parallel determinations is measurement result, and it is little to miss absolute value of the difference for parallel determinations twice In 1%.

Carrier γ-Al in the specific embodiment of the invention is calculated₂O₃The water absorption rate of particle is 52%, i.e., every 100g is carried Body (γ-Al₂O₃) amount of moisture is fully absorbed as 52ml.

3 catalyst preparation of embodiment (double catalytic active components)

1, the catalytic pretreatment carrier γ-Al of the preparation of 350g embodiment 1 is accurately weighed₂O₃, spare.

It 2, is 52% according to the carrier water absorption rate Y that embodiment 2 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 52ml, then 350g catalytic pretreatment carries The volume that body carries out the solution of incipient impregnation weighing is 350 × 52/100=182ml.

3, maceration extract is prepared

Copper nitrate (29.53g) and ferric nitrate (24.6g) are added in a small amount of deionized water, stirs, is added after dissolution Until the total volume of mixed solution is 182ml maceration extract is made, i.e. copper nitrate-ferrous solution (182ml) in deionized water, spare, Wherein copper nitrate is converted into the quality of copper oxide (CuO) in maceration extract and ferric nitrate is converted into iron oxide (Fe₂O₃) mass ratio For 2:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (i.e. copper oxide, iron oxide quality with it is weighed The summation of carrier quality (350g)) 4%.

The oxide precursor object that maceration extract uses in the embodiment of the present invention is illustrated by taking nitrate as an example, in addition to nitrate Except, other are suitable for the present invention such as acetate, soluble carbonate salt, formates, lactate.

4, incipient impregnation is handled

The weighed catalyst pretreated carrier of step 1 is poured into copper nitrate-iron maceration extract (182ml) prepared by step 3, Carrier is soaked in maceration extract, carries out incipient impregnation processing, and be stirred continuously, shake (so that maceration extract is uniformly inhaled by carrier It is attached), after stirring, oscillation 10min (usually 5-10min), maceration extract substantially uniformity is adsorbed on carrier；Then leaching will have been adsorbed The carrier of stain liquid stands 15h (usually 2-25h is uniformly distributed maceration extract component on carrier), and load maceration extract is made and carries Body；

Equi-volume impregnating: it is added after the ability of measured in advance carrier inhalation solution needed for just making carrier thorough impregnation Amount of solution, this method are known as equi-volume impregnating.Both the volume of carrier absorption moisture content determines the volume of solution allocation, make It is equal.

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 4h (usually >=4h, preferably 4-5h) at 110 DEG C, every 20min is stirred once in the drying process, with guarantee Grain is heated evenly, and dry impregnated carrier is made；

6, calcination process

Dry impregnated support particles are placed in Muffle furnace and carry out calcination process, with 5 DEG C/min during calcination process Heating rate from room temperature to 150 DEG C, and under conditions of 150 DEG C under keep 1h；Then again with the heating speed of 5 DEG C/min Rate is warming up to 450 DEG C from 150 DEG C, and keeps 3h at 450 DEG C；Then it is down to room temperature naturally from 450 DEG C, is obtained after calcination process Loaded copper oxide (CuO), iron oxide (Fe₂O₃) catalyst.

Supported copper manufactured in the present embodiment, iron catalyst in the load capacity of copper oxide be 2.67%, the load of iron oxide Amount is 1.33%.The ratio between load capacity of catalytic active component copper oxide and iron oxide is 2:1, catalytic active component in the present embodiment Load capacity be 4%.

Embodiment 3A catalyst preparation (double catalytic active components)

Copper nitrate (78.74g) and ferric nitrate (65g) are added to and are gone on a small quantity during in addition to step 3) preparation maceration extract In ionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, copper nitrate-iron is made Maceration extract (182ml), the quality that wherein copper nitrate in maceration extract is converted into copper oxide are converted into the matter of iron oxide with ferric nitrate Amount the ratio between be 2:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (i.e. copper oxide, iron oxide quality with The summation of weighed carrier quality (350g)) 10%；Mixing time is 10min, time of repose 25h in step 4)；Step 5) it is 100 DEG C that temperature is dried in, drying time 5h；With the heating speed of 4.5 DEG C/min during step 6) calcination process Rate from room temperature to 150 DEG C, and under conditions of 150 DEG C under keep 1h；Then again with the heating rate of 4 DEG C/min from 150 DEG C 400 DEG C are warming up to, and keep 4h at 400 DEG C；Then it is down to room temperature naturally from 400 DEG C, load oxygen is obtained after calcination process Change copper (CuO), iron oxide (Fe₂O₃) catalyst except, remaining is same as Example 3.

The load capacity of copper oxide is 6.67% in the catalyst of preparation, and the load capacity of iron oxide is 3.33%.The present embodiment The ratio between load capacity of middle catalytic active component copper oxide and iron oxide is 2:1, and the load capacity of catalytic active component is 10%.

Embodiment 3B catalyst preparation (double catalytic active components)

Copper nitrate (14.46g) and ferric nitrate (12g) are added to and are gone on a small quantity during in addition to step 3) preparation maceration extract In ionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, copper nitrate-iron is made Maceration extract, wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and the mass ratio that ferric nitrate is converted into iron oxide is 2:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (the i.e. quality and weighed load of copper oxide, iron oxide The summation of weight (350g)) 2%；Mixing time is 5min, time of repose 2h in step 4)；It is dried in step 5) Temperature is 120 DEG C, drying time 4.5h；With the heating rate of 4.0 DEG C/min from room temperature liter during step 6) calcination process Temperature to 150 DEG C, and under conditions of 150 DEG C under keep 2h；Then 500 are warming up to from 150 DEG C with the heating rate of 4 DEG C/min again DEG C, and 3h is kept at 500 DEG C；Then it is down to room temperature naturally from 500 DEG C, loaded copper oxide (CuO), oxygen is obtained after calcination process Change iron (Fe₂O₃) catalyst except, remaining is same as Example 3.

The load capacity of copper oxide is 1.33% in the catalyst of preparation, and the load capacity of iron oxide is 0.67%.The present embodiment The ratio between load capacity of middle catalytic active component copper oxide and iron oxide is 2:1, and the load capacity of catalytic active component is 2%.

Embodiment 3C catalyst preparation (double catalytic active components)

Copper nitrate (35.43g) and ferric nitrate (14.76g) are added to less during in addition to step 3) preparation maceration extract It measures in deionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, nitric acid is made Copper-iron maceration extract, the quality that wherein copper nitrate in maceration extract is converted into copper oxide are converted into the quality of iron oxide with ferric nitrate The ratio between be 4:1, the quality of copper oxide and iron oxide after conversion accounts for catalyst total amount (i.e. copper oxide, the quality of iron oxide and title The summation of the carrier quality (350g) taken) 4% except, remaining is same as Example 3.

Embodiment 3D catalyst preparation (double catalytic active components)

Copper nitrate (22.15g) and ferric nitrate (36.9g) are added on a small quantity during in addition to step 3) preparation maceration extract In deionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, copper nitrate-is made Iron maceration extract, the quality that wherein copper nitrate in maceration extract is converted into copper oxide are converted into the mass ratio of iron oxide with ferric nitrate For 1:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (i.e. copper oxide, iron oxide quality with it is weighed The summation of carrier quality (350g)) 4% except, remaining is same as Example 3.

Embodiment 3E catalyst preparation (double catalytic active components)

Ferric nitrate (49.2g) and copper nitrate (14.76g) are added on a small quantity during in addition to step 3) preparation maceration extract In deionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, copper nitrate-is made Iron maceration extract, the quality that wherein ferric nitrate in maceration extract is converted into iron oxide are converted into the mass ratio of copper oxide with copper nitrate For 2:1, the quality of iron oxide and copper oxide after conversion account for catalyst total amount (i.e. iron oxide, copper oxide quality with it is weighed The summation of carrier quality (350g)) 4% except, remaining is same as Example 3.

Embodiment 3F catalyst preparation (double catalytic active components)

Copper nitrate (29.53g) and manganese nitrate (20g) are added to and are gone on a small quantity during in addition to step 3) preparation maceration extract In ionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, copper nitrate-manganese is made Maceration extract, wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and manganese nitrate is converted into manganese oxide (MnO₂) quality The ratio between be 2:1, the quality of copper oxide and manganese oxide after conversion accounts for catalyst total amount (i.e. manganese oxide, the quality of copper oxide and title The summation of the carrier quality (350g) taken) 4% except, remaining is same as Example 3.

Embodiment 3G catalyst preparation (double catalytic active components)

Copper nitrate (29.53g) and nickel nitrate (18.92g) are added to less during in addition to step 3) preparation maceration extract It measures in deionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, nitric acid is made Copper-nickel maceration extract, wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and nickel nitrate is converted into nickel oxide (NiO) Mass ratio is 2:1, and the quality of copper oxide and nickel oxide after conversion accounts for catalyst total amount (the i.e. quality of nickel oxide, copper oxide With the summation of weighed carrier quality (350g)) 4% except, remaining is same as Example 3.

Embodiment 3H catalyst preparation (double catalytic active components)

Manganese nitrate (40g) and ferric nitrate (24.6g) are added to and are gone on a small quantity during in addition to step 3) preparation maceration extract In ionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, ferric nitrate-manganese is made Maceration extract, wherein the manganese nitrate in maceration extract is converted into the quality of manganese oxide and the mass ratio that ferric nitrate is converted into iron oxide is 2:1, the quality of iron oxide and manganese oxide after conversion account for catalyst total amount (the i.e. quality and weighed load of iron oxide, manganese oxide The summation of weight (350g)) 4% except, remaining is same as Example 3.

Embodiment 3I catalyst preparation (double catalytic active components)

Ferric nitrate (36.9g) and nickel nitrate (28.38g) are added on a small quantity during in addition to step 3) preparation maceration extract In deionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, ferric nitrate-is made Nickel maceration extract, the quality that wherein ferric nitrate in maceration extract is converted into copper oxide are converted into the matter of nickel oxide (NiO) with nickel nitrate Amount the ratio between be 1:1, the quality of iron oxide and nickel oxide after conversion account for catalyst total amount (i.e. iron oxide, nickel oxide quality with The summation of weighed carrier quality (350g)) 4% except, remaining is same as Example 3.

Embodiment 3J catalyst preparation (double catalytic active components)

Nickel nitrate (37.84g) and ferric nitrate (24.6g) are added on a small quantity during in addition to step 3) preparation maceration extract In deionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, ferric nitrate-is made Nickel maceration extract, the quality that wherein nickel nitrate in maceration extract is converted into nickel oxide (NiO) are converted into the matter of iron oxide with ferric nitrate Amount the ratio between be 2:1, the quality of nickel oxide and iron oxide after conversion account for catalyst total amount (i.e. iron oxide, nickel oxide quality with The summation of weighed carrier quality (350g)) 4% except, remaining is same as Example 3.

4 catalyst preparation of embodiment (three catalytic active components)

3, maceration extract is prepared

Copper nitrate (29.53g), ferric nitrate (12.3g) manganese nitrate (10g) are added in a small amount of deionized water, stirred, it is molten Deionized water is added after solution, until the total volume of mixed solution is 182ml, maceration extract is made, i.e. copper nitrate-iron-manganese solution (182ml), spare, wherein copper nitrate is converted into the quality of copper oxide in maceration extract, ferric nitrate is converted into the quality of iron oxide, nitre Sour manganese is converted into manganese oxide (MnO₂) mass ratio be 4:1:1, the quality of copper oxide, iron oxide and manganese oxide after conversion accounts for The 4% of catalyst total amount (i.e. the quality and the summation of weighed carrier quality (350g) of copper oxide, iron oxide, manganese oxide).

The oxide precursor object that maceration extract uses in inventive embodiments is illustrated by taking nitrate as an example, in addition to nitrate it Outside, other are suitable for the present invention such as acetate, soluble carbonate salt, formates, lactate.

4, incipient impregnation is handled

The weighed catalyst pretreated carrier of step 1 is poured into copper nitrate-iron-manganese maceration extract (182ml) prepared by step 3 In, carrier is soaked in maceration extract, carries out incipient impregnation processing, and be stirred continuously, shake (so that maceration extract is uniform by carrier Absorption), after stirring, oscillation 10min (usually 5-10min), maceration extract substantially uniformity is adsorbed on carrier；It then will absorption The carrier of maceration extract stands 15h (usually 2-25h is uniformly distributed maceration extract component on carrier), and load maceration extract is made Carrier；

5, it is dried

Load maceration extract carrier is laid in pallet, is put into the baking oven that temperature is 120 DEG C, the dry 5h at 120 DEG C, Every 20min is stirred once in the drying process, and to guarantee that particles by heat is uniform, dry impregnated carrier is made；

6, calcination process

Dry impregnated support particles are placed in Muffle furnace and carry out calcination process, during calcination process with 4.5 DEG C/ The heating rate of min from room temperature to 150 DEG C, and under conditions of 150 DEG C under keep 1h；Then again with the liter of 4 DEG C/min Warm rate is warming up to 500 DEG C from 150 DEG C, and keeps 3h at 500 DEG C；Then room temperature is down to naturally from 500 DEG C, after calcination process Obtain loaded copper oxide (CuO), iron oxide (Fe₂O₃), manganese oxide (MnO₂) catalyst.

Supported copper manufactured in the present embodiment, iron, manganese catalyst in the load capacity of copper oxide be 2.66%, iron oxide it is negative Carrying capacity is 0.67%；The load capacity of manganese oxide is 0.67%.Catalytic active component copper oxide, iron oxide and oxidation in the present embodiment The ratio between load capacity of manganese is 4:1:1, and the load capacity of catalytic active component is 4%.

Embodiment 4A catalyst preparation (three catalytic active components)

By copper nitrate (14.46g), ferric nitrate (6g), manganese nitrate (4.9g) during in addition to step 3) preparation maceration extract It is added in a small amount of deionized water, stirs, add deionized water after dissolution, until the total volume of mixed solution is 182ml, system At copper nitrate-iron-manganese maceration extract, wherein the copper nitrate in maceration extract is converted into the quality of copper oxide, ferric nitrate is converted into oxidation The mass ratio that the quality and manganese nitrate of iron are converted into manganese oxide is 4:1:1, the copper oxide, iron oxide, manganese oxide after conversion Quality sum account for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide quality and weighed carrier quality (350g) it is total With) 2%.

With the heating rate of 5.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and at 150 DEG C Under conditions of lower keep 1h；Then it is warming up to 400 DEG C from 150 DEG C with the heating rate of 5 DEG C/min again, and is kept at 400 DEG C 3h；Then be down to room temperature naturally from 400 DEG C, obtained after calcination process loaded copper oxide, iron oxide, manganese oxide catalyst it Outside, remaining is same as Example 4.

The supported copper of preparation, iron, manganese catalyst in the load capacity of copper oxide be 1.34%, the load capacity of iron oxide is 0.33%；The load capacity of manganese oxide is 0.33%.Catalytic active component copper oxide in the present embodiment, iron oxide and manganese oxide it is negative The ratio between carrying capacity is 4:1:1, and the load capacity of catalytic active component is 2%.

Embodiment 4B catalyst preparation (three catalytic active components)

By copper nitrate (78.74g), ferric nitrate (32.8g), manganese nitrate during in addition to step 3) preparation maceration extract (26.68g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-manganese maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide, ferric nitrate changes The mass ratio that the quality and manganese nitrate for being counted as iron oxide are converted into manganese oxide is 4:1:1, copper oxide, iron oxide after conversion, The quality sum of manganese oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, the quality of manganese oxide and weighed carrier quality The summation of (350g)) 10%.

With the heating rate of 4.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and at 150 DEG C Under conditions of lower keep 1h；Then it is warming up to 450 DEG C from 150 DEG C with the heating rate of 4.5 DEG C/min again, and is protected at 450 DEG C Hold 4h；Then be down to room temperature naturally from 450 DEG C, obtained after calcination process loaded copper oxide, iron oxide, manganese oxide catalyst it Outside, remaining is same as Example 4.

The supported copper of preparation, iron, manganese catalyst in the load capacity of copper oxide be 6.66%, the load capacity of iron oxide is 1.67%；The load capacity of manganese oxide is 1.67%.Catalytic active component copper oxide in the present embodiment, iron oxide and manganese oxide it is negative The ratio between carrying capacity is 4:1:1, and the load capacity of catalytic active component is 10%.

Embodiment 4C catalyst preparation (three catalytic active components)

By copper nitrate (22.145g), ferric nitrate (18.45g), manganese nitrate during in addition to step 3) preparation maceration extract (15g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-manganese maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide, ferric nitrate changes The mass ratio that the quality and manganese nitrate for being counted as iron oxide are converted into manganese oxide is 2:1:1, copper oxide, iron oxide after conversion, The quality sum of manganese oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, the quality of manganese oxide and weighed carrier quality The summation of (350g)) 4%.

With the heating rate of 4.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and at 150 DEG C Under conditions of lower keep 1h；Then it is warming up to 500 DEG C from 150 DEG C with the heating rate of 4.5 DEG C/min again, and is protected at 500 DEG C Hold 5h；Then be down to room temperature naturally from 500 DEG C, obtained after calcination process loaded copper oxide, iron oxide, manganese oxide catalyst it Outside, remaining is same as Example 4.

The supported copper of preparation, iron, manganese catalyst in the load capacity of copper oxide be 2.0%, the load capacity of iron oxide is 1.0%；The load capacity of manganese oxide is 1.0%.The load of catalytic active component copper oxide, iron oxide and manganese oxide in the present embodiment The ratio between amount is 2:1:1, and the load capacity of catalytic active component is 4%.

Embodiment 4D catalyst preparation (three catalytic active components)

By copper nitrate (29.53g), ferric nitrate (16.4g), manganese nitrate during in addition to step 3) preparation maceration extract (6.67g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-manganese maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide, ferric nitrate changes The mass ratio that the quality and manganese nitrate for being counted as iron oxide are converted into manganese oxide is 6:2:1, copper oxide, iron oxide after conversion, The quality sum of manganese oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, the quality of manganese oxide and weighed carrier quality The summation of (350g)) 4%.

With the heating rate of 4.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and at 150 DEG C Under conditions of lower keep 1h；Then it is warming up to 450 DEG C from 150 DEG C with the heating rate of 4.5 DEG C/min again, and is protected at 450 DEG C Hold 5h；Then be down to room temperature naturally from 450 DEG C, obtained after calcination process loaded copper oxide, iron oxide, manganese oxide catalyst it Outside, remaining is same as Example 4.

The supported copper of preparation, iron, manganese catalyst in the load capacity of copper oxide be 2.67%, the load capacity of iron oxide is 0.88%；The load capacity of manganese oxide is 0.44%.Catalytic active component copper oxide in the present embodiment, iron oxide and manganese oxide it is negative The ratio between carrying capacity is 6:2:1, and the load capacity of catalytic active component is 4%.

Embodiment 4E catalyst preparation (three catalytic active components)

By copper nitrate (22.145g), ferric nitrate (24.6g), manganese nitrate during in addition to step 3) preparation maceration extract (10g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-manganese maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide, ferric nitrate changes The mass ratio that the quality and manganese nitrate for being counted as iron oxide are converted into manganese oxide is 3:2:1, copper oxide, iron oxide after conversion, The quality sum of manganese oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, the quality of manganese oxide and weighed carrier quality The summation of (350g)) 4%.

With the heating rate of 5.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and at 150 DEG C Under conditions of lower keep 1h；Then it is warming up to 450 DEG C from 150 DEG C with the heating rate of 4.5 DEG C/min again, and is protected at 450 DEG C Hold 5h；Then be down to room temperature naturally from 450 DEG C, obtained after calcination process loaded copper oxide, iron oxide, manganese oxide catalyst it Outside, remaining is same as Example 4.

The supported copper of preparation, iron, manganese catalyst in the load capacity of copper oxide be 2.01%, the load capacity of iron oxide is 1.33%；The load capacity of manganese oxide is 0.67%.Catalytic active component copper oxide in the present embodiment, iron oxide and manganese oxide it is negative The ratio between carrying capacity is 3:2:1, and the load capacity of catalytic active component is 4%.

5 catalyst preparation of embodiment (double catalytic active component+catalyst aids)

3, maceration extract is prepared

Copper nitrate (22.145g), ferric nitrate (18.45g) cerous nitrate (9.2g) are added in a small amount of deionized water, stirred It mixes, deionized water is added after dissolution, until the total volume of mixed solution is 182ml, maceration extract is made, i.e. copper nitrate-iron-cerium Solution (182ml), spare, the quality that wherein copper nitrate is converted into copper oxide in maceration extract is converted into the matter of iron oxide with ferric nitrate The ratio between amount is 2:1, and the quality of copper oxide and iron oxide after conversion accounts for catalyst total amount (i.e. copper oxide, iron oxide, cerium oxide The summation of quality and weighed carrier quality (350g)) 3%；The quality of cerium oxide accounts for catalyst total amount (i.e. copper oxide, oxidation Iron, cerium oxide quality and weighed carrier quality (350g) summation) 1%.

4, incipient impregnation is handled

5, it is dried

6, calcination process

Dry impregnated support particles are placed in Muffle furnace and carry out calcination process, during calcination process with 4.5 DEG C/ The heating rate of min from room temperature to 150 DEG C, and under conditions of 150 DEG C under keep 1h；Then again with the liter of 4 DEG C/min Warm rate is warming up to 500 DEG C from 150 DEG C, and keeps 3h at 500 DEG C；Then room temperature is down to naturally from 500 DEG C, after calcination process Obtain loaded copper oxide (CuO), iron oxide (Fe₂O₃), cerium oxide (CeO₂) catalyst.

In catalyst preparation process of the present invention, maturing temperature influence catalyst activity component dispersion and catalytic property, For maturing temperature at 400-500 DEG C, catalytic active component precursor, catalyst aid precursor are decomposed into oxide, and dispersion degree is high, One, catalytic activity is improved.When temperature is higher than 400-500 DEG C, the catalytic active component of catalyst, the crystalline substance of adjuvant component are easily caused Grain agglomeration, reduces the specific surface area of catalyst, reduces the contact area of catalyst and reactant, catalytic activity also can It is greatly lowered；Conducive to forming uniform, tiny catalyst when heating rate control is 2.5-5 DEG C/min during calcination process Particle improves the surface area of active component, adjuvant component, improves the catalytic activity of catalyst, if heating rate improves, is more than 5 DEG C/min will lead to the increase of catalyst crystal grain, and surface area is accordingly reduced, and catalytic activity reduces.

The supported copper of preparation, iron, cerium catalyst in the load capacity of copper oxide be 2.0%, the load capacity of iron oxide is 1.0%；The load capacity of cerium oxide is 1%.The ratio between catalytic active component copper oxide and the load capacity of iron oxide are in the present embodiment 2:1, the load capacity of catalytic active component are 3%, and the load capacity of catalyst aid is 1%.

Embodiment 5A catalyst preparation (double catalytic active component+catalyst aids)

By copper nitrate (29.53g), ferric nitrate (16.4g), cerous nitrate during in addition to step 3) preparation maceration extract (4.09g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-cerium maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and ferric nitrate changes Be counted as iron oxide mass ratio be 3:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (i.e. copper oxide, Iron oxide, cerium oxide quality and weighed carrier quality (350g) summation) 3.56%；The quality of cerium oxide accounts for catalyst The 0.44% of total amount (i.e. the quality and the summation of weighed carrier quality (350g) of copper oxide, iron oxide, cerium oxide)；Step 6) With the heating rate of 4.0 DEG C/min from room temperature to 150 DEG C during calcination process, and lower holding under conditions of 150 DEG C 2h；Then it is warming up to 450 DEG C from 150 DEG C with the heating rate of 4 DEG C/min again, and keeps 3h at 450 DEG C；Then from 450 DEG C Naturally it is down to room temperature, except the catalyst that loaded copper oxide, iron oxide, cerium oxide are obtained after calcination process, remaining and embodiment 5 It is identical.

The supported copper of preparation, iron, cerium catalyst in the load capacity of copper oxide be 2.67%, the load capacity of iron oxide is 0.89%；The load capacity of cerium oxide is 0.44%.In the present embodiment the load capacity of catalytic active component copper oxide and iron oxide it Than being 3.56% for the load capacity of 3:1, catalytic active component, the load capacity of catalyst aid is 0.44%.

Embodiment 5B catalyst preparation (double catalytic active component+catalyst aids)

Copper nitrate (14.46g), ferric nitrate (8g), cerous nitrate (2g) are added during in addition to step 3) preparation maceration extract Enter into a small amount of deionized water, stir, add deionized water after dissolution, until the total volume of mixed solution is 182ml, is made Copper nitrate-iron-cerium maceration extract, wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and ferric nitrate is converted into iron oxide Mass ratio be 3:1, the quality of copper oxide and iron oxide after conversion accounts for catalyst total amount (i.e. copper oxide, iron oxide, oxidation The summation of the quality of cerium and weighed carrier quality (350g)) 1.78%；The quality of cerium oxide accounts for catalyst total amount and (aoxidizes Copper, iron oxide, cerium oxide quality and weighed carrier quality (350g) summation) 0.22%；Copper oxide, iron oxide, oxygen The quality for changing cerium accounts for the 2% of catalyst total amount, i.e., copper oxide, iron oxide, cerium oxide total load amount be 2%.Step 6) roasting With the heating rate of 5.0 DEG C/min from room temperature to 150 DEG C in treatment process, and under conditions of 150 DEG C under keep 1h；It connects 500 DEG C are warming up to from 150 DEG C with the heating rate of 5 DEG C/min again, and keep 3h at 500 DEG C；Then it is dropped naturally from 500 DEG C To room temperature, except the catalyst that loaded copper oxide, iron oxide, cerium oxide are obtained after calcination process, remaining is same as Example 5.

The supported copper of preparation, iron, cerium catalyst in the load capacity of copper oxide be 1.33%, the load capacity of iron oxide is 0.45%；The load capacity of cerium oxide is 0.22%.In the present embodiment the load capacity of catalytic active component copper oxide and iron oxide it Than being 1.78% for the load capacity of 3:1, catalytic active component, the load capacity of catalyst aid is 0.22%.

Embodiment 5C catalyst preparation (double catalytic active component+catalyst aids)

By copper nitrate (78.74g), ferric nitrate (43.73g), cerous nitrate during in addition to step 3) preparation maceration extract (10.9g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-cerium maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and ferric nitrate changes Be counted as iron oxide mass ratio be 3:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (i.e. copper oxide, Iron oxide, cerium oxide quality and weighed carrier quality (350g) summation) 8.89%；The quality of cerium oxide accounts for catalyst The 1.11% of total amount (i.e. the quality and the summation of weighed carrier quality (350g) of copper oxide, iron oxide, cerium oxide)；Oxidation Copper, copper oxide, cerium oxide quality account for the 10% of catalyst total amount, i.e., copper oxide, copper oxide, cerium oxide total load amount be 10%.With the heating rate of 5.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and in 150 DEG C of item The lower holding 1h of part；Then it is warming up to 400 DEG C from 150 DEG C with the heating rate of 5 DEG C/min again, and keeps 5h at 400 DEG C；So It is down to room temperature naturally from 400 DEG C afterwards, except the catalyst that loaded copper oxide, iron oxide, cerium oxide are obtained after calcination process, remaining It is same as Example 5.

The supported copper of preparation, iron, cerium catalyst in the load capacity of copper oxide be 6.67%, the load capacity of iron oxide is 2.22%；The load capacity of cerium oxide is 1.11%.In the present embodiment the load capacity of catalytic active component copper oxide and iron oxide it Than being 8.89% for the load capacity of 3:1, catalytic active component, the load capacity of catalyst aid is 1.11%.

Embodiment 5D catalyst preparation (double catalytic active component+catalyst aids)

By copper nitrate (29.53g), ferric nitrate (12.3g), cerous nitrate during in addition to step 3) preparation maceration extract (6.13g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-cerium maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and ferric nitrate changes Be counted as iron oxide mass ratio be 4:1, the quality of copper oxide and iron oxide after conversion account for catalyst total amount (i.e. copper oxide, Iron oxide, cerium oxide quality and weighed carrier quality (350g) summation) 3.33%；The quality of cerium oxide accounts for catalyst The 0.67% of total amount (i.e. the quality and the summation of weighed carrier quality (350g) of copper oxide, iron oxide, cerium oxide)；Oxidation Copper, copper oxide, cerium oxide quality account for the 4% of catalyst total amount, i.e., copper oxide, copper oxide, cerium oxide total load amount be 4%.With the heating rate of 5.0 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and in 150 DEG C of item The lower holding 1h of part；Then it is warming up to 400 DEG C from 150 DEG C with the heating rate of 5 DEG C/min again, and keeps 3h at 400 DEG C；So It is down to room temperature naturally from 400 DEG C afterwards, except the catalyst that loaded copper oxide, iron oxide, cerium oxide are obtained after calcination process, remaining It is same as Example 5.

The supported copper of preparation, iron, cerium catalyst in the load capacity of copper oxide be 2.66%, the load capacity of iron oxide is 0.67%；The load capacity of cerium oxide is 0.67%.In the present embodiment the load capacity of catalytic active component copper oxide and iron oxide it Than being 3.33% for the load capacity of 3:1, catalytic active component, the load capacity of catalyst aid is 0.67%.

Embodiment 5E catalyst preparation (double catalytic active component+catalyst aids)

By copper nitrate (22.145g), ferric nitrate (24.6g), cerous nitrate during in addition to step 3) preparation maceration extract (6.13g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution is Copper nitrate-iron-cerium maceration extract is made in 182ml, and wherein the copper nitrate in maceration extract is converted into the quality of copper oxide and ferric nitrate changes The mass ratio for being counted as iron oxide is 1.5:1, and the quality of copper oxide and iron oxide after conversion accounts for catalyst total amount and (aoxidizes Copper, iron oxide, cerium oxide quality and weighed carrier quality (350g) summation) 3.33%；The quality of cerium oxide, which accounts for, urges The 0.67% of agent total amount (i.e. the quality and the summation of weighed carrier quality (350g) of copper oxide, iron oxide, cerium oxide)；Oxygen Change copper, copper oxide, cerium oxide quality account for the 4% of catalyst total amount, i.e., copper oxide, copper oxide, cerium oxide total load amount be 4%.With the heating rate of 4.5 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and in 150 DEG C of item The lower holding 1h of part；Then it is warming up to 500 DEG C from 150 DEG C with the heating rate of 5 DEG C/min again, and keeps 4h at 500 DEG C；So It is down to room temperature naturally from 500 DEG C afterwards, except the catalyst that loaded copper oxide, iron oxide, cerium oxide are obtained after calcination process, remaining It is same as Example 5.

The supported copper of preparation, iron, cerium catalyst in the load capacity of copper oxide be 2.00%, the load capacity of iron oxide is 1.33%；The load capacity of cerium oxide is 0.67%.In the present embodiment the load capacity of catalytic active component copper oxide and iron oxide it Than being 3.33% for the load capacity of 3:1, catalytic active component, the load capacity of catalyst aid is 0.67%.

Embodiment 6 (three catalytic active components+catalyst aid)

3, maceration extract is prepared

To copper nitrate (19.68g), ferric nitrate (12.3g), manganese nitrate (10g) cerous nitrate (6.13g) be added to and be gone on a small quantity In ionized water, stirring adds deionized water after dissolution, until the total volume of mixed solution is 182ml, maceration extract is made, i.e., Copper nitrate-iron-manganese-cerium solution (182ml), spare, wherein copper nitrate is converted into the quality of copper oxide in maceration extract, ferric nitrate changes The mass ratio that the quality and manganese nitrate for being counted as iron oxide are converted into manganese oxide is 2:1:1, copper oxide, iron oxide after conversion with The quality of manganese oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, the quality of cerium oxide and weighed carrier quality The summation of (350g)) 3.56%；The quality of cerium oxide account for catalyst total amount (i.e. copper oxide, iron oxide, cerium oxide quality with The summation of weighed carrier quality (350g)) 0.44%.

4, incipient impregnation is handled

The weighed catalyst pretreated carrier of step 1 is poured into copper nitrate-iron-manganese-cerium maceration extract prepared by step 3 In (182ml), carrier is soaked in maceration extract, carries out incipient impregnation processing, and be stirred continuously, shake (so that maceration extract quilt Carrier uniform adsorption), after stirring, oscillation 10min (usually 5-10min), maceration extract substantially uniformity is adsorbed on carrier；Then The carrier for having adsorbed maceration extract is stood into 15h (usually 2-25h is uniformly distributed maceration extract component on carrier), is made negative Carry maceration extract carrier；

5, it is dried

6, calcination process

Dry impregnated support particles are placed in Muffle furnace and carry out calcination process, during calcination process with 4.5 DEG C/ The heating rate of min from room temperature to 150 DEG C, and under conditions of 150 DEG C under keep 1h；Then again with the liter of 4 DEG C/min Warm rate is warming up to 500 DEG C from 150 DEG C, and keeps 3h at 500 DEG C；Then room temperature is down to naturally from 500 DEG C, after calcination process Obtain loaded copper oxide (CuO), iron oxide (Fe₂O₃), manganese oxide (MnO₂), cerium oxide (CeO₂) catalyst.

Supported copper manufactured in the present embodiment, iron, manganese, cerium catalyst in the load capacity of copper oxide be 1.78%, iron oxide Load capacity be 0.89%；The load capacity of manganese oxide is 0.89%, and the load capacity of cerium oxide is 0.44%.It is catalyzed in the present embodiment The ratio between load capacity of active constituent copper oxide, iron oxide and manganese oxide is 2:1:1, and the load capacity of catalytic active component is 3.56%, the load capacity of catalyst aid is 0.44%.

Embodiment 6A (three catalytic active components+catalyst aid)

By copper nitrate (22.145g), ferric nitrate (12.3g), manganese nitrate during in addition to step 3) preparation maceration extract (10g), cerous nitrate (6.13g) are added in a small amount of deionized water, and stirring adds deionized water after dissolution, until mixing molten The total volume of liquid is 182ml, copper nitrate-iron-cerium maceration extract is made, wherein the copper nitrate in maceration extract is converted into the matter of copper oxide Amount, ferric nitrate be converted into the quality of iron oxide, manganese nitrate be converted into manganese oxide mass ratio be 3:1:1, the oxidation after conversion Copper, iron oxide, manganese oxide quality account for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, cerium oxide quality with weigh Carrier quality (350g) summation) 3.33%；The quality of cerium oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, oxidation The summation of the quality of cerium and weighed carrier quality (350g)) 0.67%；The matter of copper oxide, copper oxide, manganese oxide, cerium oxide Amount accounts for the 4% of catalyst total amount, i.e., copper oxide, copper oxide, manganese oxide, cerium oxide total load amount be 4%.At step 6) roasting With the heating rate of 5.0 DEG C/min from room temperature to 150 DEG C during reason, and under conditions of 150 DEG C under keep 1h；Then It is warming up to 400 DEG C from 150 DEG C with the heating rate of 5 DEG C/min again, and keeps 4h at 400 DEG C；Then it is down to naturally from 400 DEG C Room temperature obtains except the catalyst of loaded copper oxide, iron oxide, manganese oxide, cerium oxide after calcination process, remaining and embodiment 6 It is identical.

The supported copper of preparation, iron, manganese, cerium catalyst in the load capacity of copper oxide be 2.00%, the load capacity of iron oxide It is 0.67%；The load capacity of manganese oxide is 0.67；The load capacity of cerium oxide is 0.67%.Catalytic active component oxygen in the present embodiment Changing the ratio between load capacity of copper, iron oxide, manganese oxide is 3:1:1, and the load capacity of catalytic active component is 3.33%, catalyst aid Load capacity is 0.67%.

Embodiment 6B (three catalytic active components+catalyst aid)

By copper nitrate (10.85g), ferric nitrate (6g), manganese nitrate (4.9g) during in addition to step 3) preparation maceration extract Cerous nitrate (3g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until the total volume of mixed solution For 182ml, copper nitrate-iron-cerium maceration extract is made, wherein the copper nitrate in maceration extract is converted into the quality of copper oxide, ferric nitrate Be converted into the quality of iron oxide, to be converted into the mass ratio of manganese oxide be 3:1:1 to manganese nitrate, copper oxide, iron oxide after conversion, The quality of manganese oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, the quality of cerium oxide and weighed carrier quality The summation of (350g)) 1.67%；The quality of cerium oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, cerium oxide Quality and weighed carrier quality (350g) summation) 0.33%；The quality of copper oxide, iron oxide, manganese oxide, cerium oxide Account for the 2% of catalyst total amount, i.e., copper oxide, iron oxide, manganese oxide, cerium oxide total load amount be 2%.Step 6) calcination process In the process with the heating rate of 4.5 DEG C/min from room temperature to 150 DEG C, and under conditions of 150 DEG C under keep 1h；Then again It is warming up to 400 DEG C from 150 DEG C with the heating rate of 4 DEG C/min, and keeps 4h at 400 DEG C；Then it is down to room naturally from 400 DEG C Temperature obtains except the catalyst of loaded copper oxide, iron oxide, manganese oxide, cerium oxide after calcination process, remaining and 6 phase of embodiment Together.

The supported copper of preparation, iron, manganese, cerium catalyst in the load capacity of copper oxide be 1.01%, the load capacity of iron oxide It is 0.33%；The load capacity of manganese oxide is 0.33；The load capacity of cerium oxide is 0.33%.Catalytic active component oxygen in the present embodiment Changing the ratio between load capacity of copper, iron oxide, manganese oxide is 3:1:1, and the load capacity of catalytic active component is 1.67%, catalyst aid Load capacity is 0.33%.

Embodiment 6C (three catalytic active components+catalyst aid)

By copper nitrate (59g), ferric nitrate (32.8g), manganese nitrate during in addition to step 3) preparation maceration extract (26.68g) cerous nitrate (16.35g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until mixing The total volume of solution is 182ml, copper nitrate-iron-cerium maceration extract is made, wherein the copper nitrate in maceration extract is converted into copper oxide Quality, ferric nitrate are converted into the quality of iron oxide, manganese nitrate be converted into manganese oxide mass ratio be 3:1:1, the oxygen after conversion Change copper, iron oxide, manganese oxide quality account for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, the quality of cerium oxide and title The summation of the carrier quality (350g) taken) 8.33%；The quality of cerium oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, oxygen Change manganese, cerium oxide quality and weighed carrier quality (350g) summation) 1.67%；Copper oxide, iron oxide, manganese oxide, The quality of cerium oxide accounts for the 10% of catalyst total amount, i.e., copper oxide, iron oxide, manganese oxide, cerium oxide total load amount be 10%. With the heating rate of 5 DEG C/min from room temperature to 150 DEG C during step 6) calcination process, and under conditions of 150 DEG C under Keep 1h；Then it is warming up to 450 DEG C from 150 DEG C with the heating rate of 4.5 DEG C/min again, and keeps 5h at 450 DEG C；Then from 450 DEG C are down to room temperature naturally, except the catalyst that loaded copper oxide, iron oxide, manganese oxide, cerium oxide are obtained after calcination process, Remaining is same as Example 6.

The supported copper of preparation, iron, manganese, cerium catalyst in the load capacity of copper oxide be 5.00%, the load capacity of iron oxide It is 1.67%；The load capacity of manganese oxide is 1.67；The load capacity of cerium oxide is 1.67%.Catalytic active component oxygen in the present embodiment Changing the ratio between load capacity of copper, iron oxide, manganese oxide is 3:1:1, and the load capacity of catalytic active component is 8.33%, catalyst aid Load capacity 1.67%.

Embodiment 6D (three catalytic active components+catalyst aid)

By copper nitrate (22.145g), ferric nitrate (9.22g), manganese nitrate during in addition to step 3) preparation maceration extract (7.5g) cerous nitrate (9.2g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until mixed solution Total volume be 182ml, copper nitrate-iron-cerium maceration extract is made, wherein the copper nitrate in maceration extract is converted into the matter of copper oxide Amount, ferric nitrate be converted into the quality of iron oxide, manganese nitrate be converted into manganese oxide mass ratio be 4:1:1, the oxidation after conversion Copper, iron oxide, manganese oxide quality account for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, cerium oxide quality with weigh Carrier quality (350g) summation) 3%；The quality of cerium oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, cerium oxide Quality and weighed carrier quality (350g) summation) 1%；Copper oxide, copper oxide, manganese oxide, cerium oxide quality account for The 4% of catalyst total amount, i.e. copper oxide, copper oxide, manganese oxide, cerium oxide total load amount be remaining and embodiment except 4% 6 is identical.

The supported copper of preparation, iron, manganese, cerium catalyst in the load capacity of copper oxide be 2%, the load capacity of iron oxide is 0.5%；The load capacity of manganese oxide is 0.5%；The load capacity of cerium oxide is 1%.Catalytic active component copper oxide in the present embodiment, The ratio between load capacity of iron oxide, manganese oxide is 4:1:1, and the load capacity of catalytic active component is 3%, and the load capacity of catalyst aid is 1%.

Embodiment 6E catalyst preparation (three catalytic active components+catalyst aid)

By copper nitrate (16.6g), ferric nitrate (18.45g), manganese nitrate during in addition to step 3) preparation maceration extract (7.5g) cerous nitrate (9.2g) is added in a small amount of deionized water, and stirring adds deionized water after dissolution, until mixed solution Total volume be 182ml, copper nitrate-iron-cerium maceration extract is made, wherein the copper nitrate in maceration extract is converted into the matter of copper oxide Amount, ferric nitrate be converted into the quality of iron oxide, manganese nitrate be converted into manganese oxide mass ratio be 3:2:1, the oxidation after conversion Copper, iron oxide, manganese oxide quality account for catalyst total amount (i.e. copper oxide, iron oxide, manganese oxide, cerium oxide quality with weigh Carrier quality (350g) summation) 3%；The quality of cerium oxide accounts for catalyst total amount (i.e. copper oxide, iron oxide, cerium oxide Quality and weighed carrier quality (350g) summation) 1%；Copper oxide, copper oxide, manganese oxide, cerium oxide quality account for The 4% of catalyst total amount, i.e. copper oxide, copper oxide, manganese oxide, cerium oxide total load amount be remaining and embodiment except 4% 6 is identical.

The supported copper of preparation, iron, manganese, cerium catalyst in the load capacity of copper oxide be 1.5%, the load capacity of iron oxide is 1%；The load capacity of manganese oxide is 0.5%；The load capacity of cerium oxide is 1%.Catalytic active component copper oxide, oxygen in the present embodiment Changing the ratio between load capacity of iron, manganese oxide is 3:2:1, and the load capacity of catalytic active component is 3%, and the load capacity of catalyst aid is 1%.

Comparative example

Certain commercially available commodity ozone catalytic oxidation catalyst embodiment as a comparison is chosen, which is using mixing legal system Standby, carrier is alumina globule, and active component is copper oxide, partial size 3-5mm.

The purified treatment of 1 high-chlorine organic wastewater of test example

The 480mL load that embodiment 2-6E preparation is respectively charged into internal diameter 30mm × height 800mm reactor is a variety of The commercial catalyst of oxide catalyst, reference examples, is then passed through high-chlorine organic wastewater and ozone into reactor, and liquid adverse current connects Touching；Wherein:

The water quality of organic wastewater is as follows: COD 83mg/L, chlorine ion concentration 6000mg/L, conductivity 2.2 × 10⁴μS/ cm；

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.

Water sampling after reaction 3 hours, measurement water outlet COD value.

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.

(1) in water the measuring method of COD content according to national standard " GB/T 31195-2014 high chlorine high-ammonia wastewater chemistry The measurement chloride ion correction method of oxygen demand "；(2) in water the measuring method of chloride ion content according to national standard " GB 11896-89 The measurement silver nitrate titration method of water quality chloride ".

1 catalyst of table aoxidizes high-chlorine organic wastewater Contrast on effect

It is found that the high-chlorine organic wastewater for being 6000mg/L for chloride ion content, influent COD 83mg/ from 1 data of table The catalyst removal efficiency of L, the method for the present invention preparation are high, and COD is reduced significantly in water outlet after wastewater treatment 3h.Comparative example water outlet COD is 61mg/L, can not reach national sewage discharge level-one A standard.

The catalytic efficiency of catalyst of the present invention is stablized, after continuous use 120h, i.e. Continuous Wastewater Treatment 120h, in waste water COD removal efficiency only has slight drop, and reduced rate is lower than 1.2%.

Using multicomponent catalyst of the present invention processing waste water, catalyst prepared by especially embodiment 6C, high-chloride wastewater COD removal rate is up to 45.8% or more, and water outlet COD is 45mg/L, can reach national sewage discharge level-one A standard.

The intensity of the catalyst of the method for the present invention preparation is high, reaches 126N/ or more, catalyst is not fragile in use It is broken；And catalyst stabilization is high, and 120h or more is used continuously, and catalytic activity reduces small, catalyst long service life of the present invention, Reduce cost for wastewater treatment.

The test of 2 catalyst strength of test example

2-6E of embodiment of the present invention system is measured according to chemical industry standard " HG/T 3927-2007 industrial activated alumina " The compression strength of standby catalyst, specific assay method is as follows:

1. taking alumina 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/, and (3) calculating is calculated by formula

In formula: P_i--- the numerical value for the compression strength that each alumina sample is measured, unit N；20 --- sample Grain number.Measurement result is as shown in table 1.

The purified treatment of 3 high-chlorine organic wastewater of test example

The 480mL that embodiment 6A preparation is respectively charged into internal diameter 30mm × height 800mm reactor loads a variety of oxygen Then compound catalyst, commercial catalyst 1,2,3 are respectively passed through 3 kinds of high-chlorine organic wastewaters (water quality such as table respectively into reactor Shown in 2) and ozone, liquid counter current contacting；Wherein:

Water sampling after reaction 3 hours, measurement water outlet COD value, and COD removal rate is calculated, measurement result is as shown in table 2.

2 different catalysts COD removal rate of table

As can be seen from the table, the COD removal rate of 4 kinds of catalyst all reduces, explanation with the increase of chloride ion content Chloride ion is inhibited to catalytic oxidation in water, and chloride ion content is higher, and organic matter degradation difficulty is bigger.Processing is not With the waste water of chlorinity, the catalytic performance of the catalyst of 6A of the embodiment of the present invention is all best.Jilin petrochemical plant waste water chlorine Ion concentration 670mg/L, although the COD removal rate of commercial catalyst 2 is identical with embodiment 6A catalyst, for Tianjin stone Change factory's sewage and the higher waste water of Fushun both chloride ion contents of petrochemical plant waste water, the COD removal rate point of commercial catalyst 2 Not Wei 61% and 40%, decline clearly, be lower than embodiment 6A catalyst removal rate 72% and 54%.Illustrate catalysis of the present invention Agent has good catalytic degradation effect to high-chloride wastewater.

Claims

1. a kind of ozone catalytic oxidation catalyst for degradation of organic waste water, characterized in that including catalytic carrier, catalytic activity Ingredient, wherein the catalytic active component selects metal oxide.

2. catalyst as described in claim 1, characterized in that the catalytic carrier selective oxidation aluminium, silica, activity Charcoal, zeolite, molecular sieve, ceramics, zirconium oxide.

3. catalyst as described in claim 1, characterized in that the metal oxide of the catalytic active component selects metal Copper, iron, manganese, nickel or cobalt oxide at least two.

4. catalyst as described in claim 1, characterized in that the load capacity of the catalytic active component is 1-15%.

5. catalyst as described in claim 1, characterized in that further include catalyst aid, the catalyst aid is lanthanide series metal Oxide.

6. a kind of preparation method of the ozone catalytic oxidation catalyst for degradation of organic waste water, characterized in that including following suitable The step of sequence carries out:

1) water absorption rate (Y, %) of catalytic 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) catalytic active component precursor is added to the water, after dissolution, adds water the catalyst being calculated into step 2) and carry The volume of required maceration extract, is made precursor maceration extract when the processing of body incipient impregnation；

4) catalytic carrier that step 2) weighs is impregnated in the active component precursors maceration extract of step 3) preparation, is carried out isometric Impregnation；

5) carrier after impregnation is subjected to calcination process.

7. preparation method as claimed in claim 6, characterized in that the selection of active component precursors described in step 3) metallic copper, Iron, manganese, nickel or cobalt salt compounds.

8. preparation method as claimed in claim 6, characterized in that impregnation described in step 4) selects at incipient impregnation Reason.

9. preparation method as claimed in claim 6, characterized in that 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 4-5 DEG C/min from room temperature to 150 DEG C, and at 150 DEG C Under the conditions of keep 1-2h；

It 5-2) is warming up to 400-500 DEG C with the rate of 2.5-5 DEG C/min again, and keeps 2-5h under conditions of 400-500 DEG C.

10. a kind of preparation method of the ozone catalytic oxidation catalyst for degradation of organic waste water, characterized in that including following suitable The step of sequence carries out:

1) water absorption rate (Y, %) of catalytic carrier is measured；

3) catalytic active component precursor and catalyst aid precursor are added to the water, after dissolution, add water and calculated into step 2) The volume of required maceration extract, is made precursor maceration extract when obtained catalyst carrier incipient impregnation processing；

4) catalytic carrier that step 2) weighs is impregnated in the precursor maceration extract of step 3) preparation, is carried out at incipient impregnation Reason；

5) carrier after impregnation is subjected to calcination process.