CN1077549C

CN1077549C - Electric multiphase catalyzed reaction process disposing industrial waste water containing dinitrophenol

Info

Publication number: CN1077549C
Application number: CN 96115545
Authority: CN
Inventors: 谢茂松; 王学林
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 1996-08-20
Filing date: 1996-08-20
Publication date: 2002-01-09
Anticipated expiration: 2016-08-20
Also published as: CN1174175A

Abstract

The present invention relates to an electric multiphase catalyzed reaction method for disposing industrial waste water containing dinitrophenol. M-R/SiO2, Al2O3 or active carbon is used as a catalyst, wherein the M is one of transition metal elements Fe, Co, Ni, Ti, V, Mn, W or P or the oxide of a plurality of elements, the R is Zr or a rare-earth element, the weight content of a metal group is from 0.4% to 8%, the R is from 0.1% to 2%, and the rest is a carrier; in a flat plate-shaped or cylindrical electric multiphase catalytic reactor, the catalyst is filled between electrode plates, direct-current voltage of 2 to 10V is additional added, and then the reaction is carried out at normal temperature and pressure. The present invention has the advantages of simple equipment, convenient operation and long service life of the catalyst. The present invention can be used for effectively disposing industrial waste water containing dinitrophenol without secondary pollution.

Description

Electricity consumption---heterogeneous catalytic reaction is handled the method for dinitrophenol(DNP) trade effluent

The present invention relates to a kind of method of Industrial Wastewater Treatment, specifically provide a kind of adopt---heterogeneous catalytic reaction is handled the method that contains dinitrophenol(DNP) waste water that industrial dye factory discharges.

Along with development of human society, more and more Duo high product innovation is satisfying the growing material demand of people.Also produce a large amount of objectionable impuritiess on the other hand simultaneously, contaminate environment, harm humans space from bottom to top, this is recognized by increasing people that therefore, the protection environment is preserved our planet, decontamination is to face the problem that presses for solution.Trade effluent has a large capacity and a wide range, and polluted source destroys ecotope.Biological degradation the chances are the most frequently used process for the treatment of waste water.But some trade effluent is difficult to administer with biodegradable method, and as the improvement of dinitrophenol(DNP), because its tinting strength is extremely strong, complicated component in the waste water is (as also containing Na ₂SO ₄Reach compositions such as NaCl), the pH value is 1～2, and acidity and corrodibility are strong, and toxicity is big, and the toxic content height just can not be handled with biochemical process.Multi-phase catalysis action is the strong means that material is transformed, but the reaction conditions of generally wanting is higher, has not yet to see to utilize heterogeneous catalytic method to administer the report that contains this trade effluent of dinitrophenol(DNP) effectively.It is a kind of that present inventors once provided in early days---heterogeneous catalytic reaction process (CN1078171A), this technology is that chemical catalysis and electrocatalysis process are combined, utilize catalyst activity component and electric activated acting in conjunction, make reaction molecular activation, can be than carrying out single reaction that can not take place under the mild reaction conditions with catalyzer.Utilize this method can handle the waste water of brew-house, and receive satisfied effect.

The purpose of this invention is to provide a kind of electricity consumption---heterogeneous catalytic reaction is handled the method for dinitrophenol(DNP) trade effluent.Utilize this method the dye processing plant waste discharge that contains dinitrophenol(DNP) of utmost point refractory reason can be handled, and non-secondary pollution, make this waste water reach emission standard.

In electricity consumption---heterogeneous catalytic reaction is handled and is contained in the organism trade effluent process, and organic matter degradation is actually organism and is decomposed by catalyzed oxidation.Its reaction process is, on the one hand under the activation of extra electric field, can in the aqueous solution, cause the free radical that produces based on OH, because the OH free radical that generates has very strong oxidisability and to the non-selectivity of organism reaction, making the organism catalyzed oxidation at normal temperatures and pressures of bio-refractory fall can become possibility.On the other hand, processed organic pollutant can selectively be carried out catalyzed oxidation at catalyst surface.Therefore, select suitably to contain the catalyzer of active ingredient and the processing that current field condition just can realize containing the organism trade effluent expeditiously.The present invention on the basis of present inventor's previous work, selects suitable catalyzer and reaction conditions that the trade effluent that contains dinitrophenol(DNP) is handled just.Specifically of the present invention---the heterogeneous catalyst method is handled the method for dinitrophenol(DNP) trade effluent, carries out under normal temperature and pressure under the following conditions.

1. with M/SiO ₂, Al ₂O ₃Or gac is catalyzer, and wherein M is the oxide compound of one or more elements among transition metal Fe, Co, Ni, Ti, V, Mn, W or the Pd, SiO ₂, Al ₂O ₃Or gac is carrier, and the content of metal component (weight) is 0.4～8.0%, and surplus is carrier.

The Preparation of catalysts method can adopt pickling process, with soluble chloride that contains metal ion or nitrate aqueous solution, behind the impregnated carrier, placed 1～30 hour down in 25～60 ℃, be 80～110 ℃ of oven dry, under 300～450 ℃, carry out roasting 1～10 hour again, can obtain finished catalyst.When being carrier with the activated carbon, roasting is to carry out under nitrogen protection.

2. in flat or round tube type electro multiphase catalysis reactor, catalyzer is filled between two-plate or between electrode, being added in two interpolar volts DSs is 2～10V, and electric current is advisable to be not less than 20mA.Because adopting the electro multiphase catalysis method handles in the waste water, composition difference with waste water, the scope that working current changes will be greatly, when strength of current is lower than 20mA, the electric field-activate effect weakens, to influence wastewater treatment speed, but too high strength of current can not improve activation effectively, will consume bigger electric energy again.

In above-mentioned reaction,, can in catalyzer, add rare earth element or Zr as auxiliary agent for improving activity of such catalysts.The activity of such catalysts component is M-R, and wherein R is Zr, rare earth or mixed rare-earth elements.Catalyzer consist of M:0.4～8%, R:0.1～2%, surplus is carrier.Catalyzer consists of M:2～4% preferably, R:0.5～1%, and surplus is carrier.

Below by example technology of the present invention is given to illustrate further.

Embodiment 1 M/SiO ₂Preparation of catalysts

Get Fe (NO ₃) ₃And Ti (NO ₃) ₃Aqueous solution is mixed with steeping fluid, strength of solution and usage quantity by the carrier amount and the preparation catalyzer in metal content routinely technology carry out.With 40～60 order SiO ₂Powder is done in 110 ℃ and was dried 2 hours to going into to stir placement 12 hours in the steeping fluid, in 350 ℃ of following roastings 5 hours, naturally cools to room temperature and makes catalyzer again.The weight of metal component is in the catalyzer: Fe:2%, Ti:0.5%; All the other are SiO ₂By the M/SiO that can make the different metal component with quadrat method ₂Catalyzer, the composition representation of its catalyzer is identical.

Example 2 M-R/SiO ₂Preparation of catalysts

Get Mn (NO ₃) ₄, Ti (NO ₃) ₃And LaCl ₃Aqueous solution is mixed with steeping fluid, makes the catalyzer that contains auxiliary agent R by the method for example 1, and the metal component weight content is in the catalyzer: Mn:4%, Ti:1%, La:0.5%.Can make the M-R/SiO of different metal component by same procedure ₂Catalyzer, the composition representation of its catalyzer is identical.Carrier can be SiO in the preparation ₂, Al ₂O ₃Or gac.When being carrier with the gac, roasting is carried out under nitrogen atmosphere.

Example 3---heterogeneous catalyst method is handled and is contained the dinitrophenol(DNP) aqueous solution

In the cylindric glass reactor of 60 millimeters of internal diameters, place two same internal diameter stainless steel electrodes of being with meshes in reactor two ends equality, adorn the Fe-Ti/SiOs of 140 grams between electrode by example 1 preparation ₂Catalyzer, the dinitrophenol(DNP) that adds 400 milliliters of outfits is the 900ml/l aqueous solution, under different impressed voltages, handled respectively 2 hours, as seen its reaction result shows photometer measurement absorbancy (colorimetric pool 1cm with 723 types that Shanghai the 3rd analytical instrument factory produces, wavelength 420nm) analyze, measuring result is listed in table 1.30 ℃ of temperature of reaction, normal pressure, result after 2 hours reaction times.

Table 1 voltage, electric current is to---the influence of heterogeneous catalytic reaction

Electric current and voltage colourity

0 0 ?0.400

1 10 ?0.380

2 20 0.272

4 50 ?0.261

6 95 ?0.236

8 105 ?0.235

10 150 0.211

12 190 ?0.209

14 205 ?0.209

16 220 ?0.205

20 300 0.201

30 510 ?0.201

Example 4---heterogeneous catalyst method is handled and is contained the dinitrophenol(DNP) aqueous solution

Press the reactor of example 3, test conditions and measuring method select for use example 1 or 2 controlling catalysts to replace example 3 catalyzer, and its measuring result is listed in table 2.

The performance of table 2 M-R catalyzer (only represent metal content %, surplus is carrier)

Catalyzer is formed colourity

4%Fe 1.0%La carrier S iO ₂ 0.250

3%Co 0.5%Ni 0.1%V carrier S iO ₂ 0.249

1%Mn 1.0%Ti 0.5%La+Ce carrier A l ₂O ₃ 0.210

4%Mn 1.0%Ti 0.5%La+Ce carrier active carbon 0.209

6%Mn 1.0%Ti 0.5%La+Ce carrier S iO ₂ 0.220

10%Mn 1.0%Ti 0.5%La+Ce carrier S iO ₂ 0.305

Example 5---heterogeneous catalyst method is handled and is contained the dinitrophenol(DNP) trade effluent

Catalyzer (the 4%Mn of the about 10l example 1 of dress between 330mm * 165mm two cube electrode electrodes is housed in the plastic containers of 20l, 1%Ti, 0.5%La+Ce), apply 6 volts of voltages, 500～800 milliamperes in electric current, (Dalian Dye Factory provides the 15l trade effluent, and wherein dinitrophenol(DNP) content is about 900mg/l, Ma ₂SO ₄Impurity such as about 10g/l and NaCl) at normal temperature, the above-mentioned refining plant of flowing through under the normal pressure is pressed example 3 method amount absorbancys, and it the results are shown in table 3.

Table 3---heterogeneous catalyst method is handled trade effluent

Treatment time (hour) 12345

Colourity (1cm colorimetric pool, 420nm wavelength) 0.774 0.187 0.127 0.104 0.104

Dinitrophenol(DNP) concentration (PPm) 30.34 9.72 4.87 4.00 3.04

Example 6 life of catalyst

Utilize the reactor and the measuring method of example 3, handle example 5 described trade effluents continuously, treatment condition are with waste water air speed 1.4mlg ^-1H ^-1, 6 volts of voltages, 650 milliamperes in electric current, normal pressure, normal temperature reaction down utilized this device to add 400ml waste water measurement processing again and the results are shown in table 4 after 200 day.

The test of table 4 life of catalyst

Treatment time (hour) 123

Colourity (1cm colorimetric pool, 420nm wavelength) 0.228 0.143 0.116

Of the present invention by above-mentioned example---heterogeneous catalytic reaction is handled the method that contains the dinitrophenol(DNP) trade effluent, has following major advantage:

(1) need use the activated at catalyzer different with common heterogeneous catalysis process, this process is that electricity consumption plays activated catalyst.

(2) different with surface electrode reaction, in---heterogeneous catalysis process, the inversion quantity of the organic waste electric weight of getting along well is directly proportional little power consumption.

(3) can operate at normal temperatures and pressures.

(4) organic waste of needs degraded or oxidation can be multiple, the kind of waste water broad that can administer.

(5) acid-basicity to waste water does not have particular requirement.

(6) waste water the solid acrobatics in filtering out waste water, does not need that waste water is done more early stage and handles before entering reactor.

(7) it is few to remove the required time of organic waste, the efficient height.

(8) equipment is simple, and is easy to operate, and investment and working cost are cheap.

(9) non-secondary pollution.

Claims

1. employing---heterogeneous catalytic reaction is handled the method for dinitrophenol(DNP) trade effluent, it is characterized in that it being to be undertaken by following condition:

1) with SiO ₂, Al ₂O ₃Or gac is carrier, makes M/SiO ₂, Al ₂O ₃Or the catalyzer of gac, wherein M is transition metal Fe, Co, and Ni, Ti, V, Mn, the oxide compound of one or more elements among W or the Pd, the weight content of metal component are 0.4～8%, surplus is carrier;

2) in flat board or garden cartridge type electro multiphase catalysis reactor, catalyzer is filled between battery lead plate, 2～10 volts of impressed DC voltages, reacts under normal temperature and pressure.

2. in accordance with the method for claim 1, it is characterized in that adding in the catalyzer auxiliary agent Zr, rare earth or mixed rare-earth elements, the weight content of metal component M-R is in the catalyzer: M:0.4～8%, auxiliary agent R:0.1～2%.