CN105036289A - Method for quickly and efficiently degrading high-concentration unsym-dimethylhydrazine wastewater - Google Patents
Method for quickly and efficiently degrading high-concentration unsym-dimethylhydrazine wastewater Download PDFInfo
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Abstract
The invention discloses a method for quickly and efficiently degrading high-concentration unsym-dimethylhydrazine (UDMH) wastewater. The method comprises the following steps: performing catalytic oxidation on H2O2 by use of a nano sandwich-structured iron-based catalyst and a hydrogen peroxide stabilizer to produce a hydroxyl free radical (.OH); quickly and efficiently degrading UDMH and derivatives thereof. The catalyst is coupled with the free radical for reaction, the practicability is high, COD in UDMH wastewater can be greatly removed at a relatively low temperature and within a relatively wide pH range, and high-toxic UDMH is oxidized into ammonium salt NH4<+>, HCHO, CO2 and the like. The method can efficiently and quickly degrade high-concentration UDMH wastewater, the hydrogen peroxide utilization efficiency can be remarkably improved after the hydrogen peroxide stabilizer is added, the adding amount of hydrogen peroxide is reduced and the treatment effect is improved.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst and catalytic oxidation technique of unsymmetrical dimethyl hydrazine of rapidly and efficiently degrading, that one utilizes catalyzer Wet Catalytic Oxidation Method, coordinate hydrogen peroxide stabilizer, the method for degrading high concentration unsymmetrical dimethyl hydrazine waste water, this technology belongs to nano environmental protection water-treatment technology field.
Background technology:
Unsymmetrical dimethyl hydrazine ((CH
3)
2nNH
2uDMH) generally applied in field of aerospace technology as the efficient fuel of one, but unsymmetrical dimethyl hydrazine possesses the common toxicity of hydrazine class compound, it is produced, transport, store and improper, expiredly scrap discharge etc., all bring serious sewage pollution problem, therefore, the qualified discharge technology of unsymmetrical dimethyl hydrazine receives much concern always.
Prior art is reported, traditional catalyst for chemical bond priming reactions such as C – O, C – N, N – N and N=O mainly comprises the transition metal complexes such as ruthenium (Ru), rhodium (Rh), palladium (Pd), but the price of these complex compounds often costly, and be expendable consumed product.
The Fenton technique of the low cost of waste water industry widespread use, catalyzer is Fe
2+, oxygenant is H
2o
2, degradation process is with Fe
2+oxidation generates Fe
3+, there is following several respects problem in this technique: Fe in the aqueous solution on the one hand
3+bring chroma pollution; In addition on the one hand, once pH value of solution > 5, waste water system can generate cotton-shaped ferric hydroxide precipitate, increases by one flocculation sediment processing step, if keep low pH scope, then pH index does not reach emission request; Moreover catalyst Fe
2+poor stability, stores difficulty large; Catalyst Fe simultaneously
2+autophage oxygenant H
2o
2, make H
2o
2utilization ratio reduces.Therefore, new catalytic material and the catalytic oxidation technique of efficient stable is researched and developed in active demand.
Summary of the invention
Goal of the invention: the object of the present invention is to provide one to utilize nanometer sandwich structure catalyzer Wet Catalytic Oxidation Method, coordinates hydrogen peroxide stabilizer, the method for degrading high concentration unsymmetrical dimethyl hydrazine waste water.
Technical scheme: method of the present invention, comprises and utilizes nanometer sandwich structure ferrum-based catalyst, coordinates hydrogen peroxide stabilizer, catalyzed oxidation H
2o
2, produce hydroxyl radical free radical (OH), rapidly and efficiently degrade unsymmetrical dimethyl hydrazine and derivative thereof.
Wherein, described nanometer sandwich structure ferrum-based catalyst general formula M – O – Fe/SiO
2represent, M represents the one in rhenium, rhodium and cerium, is preferably the nanometer sandwich structure ferrum-based catalyst of rhodium modification; Mass percentage is 1 ~ 5%M – O –, 1 ~ 5%Fe/SiO
2, described mass percentage is M
xo
yburning amount or ferric oxide and SiO
2mass ratio, wherein x=1,2, y=1,2,3.
The preparation method of described nanometer sandwich structure ferrum-based catalyst comprises the steps:
Tetraethoxy, dehydrated alcohol, deionized water are made into mixing solutions, solid nitric acid iron is added stirring and dissolving in described mixing solutions, add dust technology and regulate pH, after diethanolamine condensing reflux 2-8h, be placed in baking oven and dry moisture content formation xerogel, described xerogel is calcined, such as, can be placed in retort furnace and calcine, obtained nanometer iron-based SiO
2, grind described nanometer iron-based SiO
2obtain pulverulent solids; By described nanometer iron-based SiO
2suspension liquid is formed in one in the rhenium (Re) of pulverulent solids immersion anhydrous alcohol solution, rhodium (Rh) and cerium (Ce) salt, dipping stirs 8-12h, rhenium, rhodium, cerium is made to be wrapped in Fe surface, after oven dry, calcining, such as can be placed in retort furnace to calcine, obtained nanometer sandwich structure ferrum-based catalyst.
Wherein, the mass ratio of described tetraethoxy/dehydrated alcohol/deionized water is 1/2 ~ 4/4 ~ 8.
Dust technology regulates described pH to 3 ~ 5, and described calcining temperature is 290 ~ 410 DEG C, and calcination time is 3 ~ 6h.
Aforesaid method comprises and add hydrogen peroxide solution and a small amount of hydrogen peroxide stabilizer in high density unsymmetrical dimethyl hydrazine waste water, and control unsymmetrical dimethyl hydrazine and hydrogen peroxide mol ratio are 1:40 ~ 120, and the volume ratio of hydrogen peroxide and hydrogen peroxide stabilizer is 1 ~ 20:1; System temperature of reaction is 50 ~ 70 DEG C, all can effectively degrade within the scope of this.
The formula of hydrogen peroxide stabilizer is: phytic acid, and substance withdrawl syndrome is 0.0015 ~ 0.3mol/L; Magnesium chloride, substance withdrawl syndrome is 0.005 ~ 0.1mol/L; Water glass, substance withdrawl syndrome is 0.004 ~ 0.08mol/L.
The pH of unsymmetrical dimethyl hydrazine waste water controls 4 ~ 10, and the concentration of unsymmetrical dimethyl hydrazine waste water is 500 ~ 2500mg/L, and the residence time is 8 ~ 20min.The longer reaction of reaction time is more thorough, in this reaction time, all can reach degradation effect.
The invention provides a kind of nanometer sandwich structure Fe catalyst based, low-temperature catalytic oxidation H
2o
2, produce hydroxyl radical free radical (OH).This sandwich structure nano environmental protection material, general formula is M – O – Fe/SiO
2, wherein, M=Re, Rh or Ce, M-O-Fe represents the sandwich structure centered by Sauerstoffatom, SiO that the oxide compound of metal M and ferric oxide are formed
2the sandwich catalyzer of nanometer for support of the catalyst, the cost lower due to it and outstanding catalytic effect, can be widely used in the high-concentration industrial-water having bio-toxicity of difficult degradation.
The performance of catalyzer depends on catalyst activity component, carrier and catalyst aid.Fe based catalyst system, after adding auxiliary agent, changes dispersion and the Electronic Structure of active centre Fe, causes elementary reaction speed generation noticeable change, thus greatly improves activity and the stability of catalyzed oxidation unsymmetrical dimethyl hydrazine.Re, Rh, Ce play electro and structural promoting catalysis to Fe is catalyst based.The interfacial area that one side sandwich structure M – O – Fe close contact is formed is more, electron feedback ability is high, more increase Catalytic active phase M – O – Fe active sites quantity, thus raising catalyst activity, promotor contributes to the high dispersing of Fe at carrier surface on the one hand in addition, also play a part anchor simultaneously and close active centre component Fe, make Fe stably be carried on carrier surface, improve catalyst stability.
In addition, the processing condition of catalyzed degradation process are as pH value, H
2o
2the auxiliary agent of solution dosage, the decomposing hydrogen dioxide solution that slows down speed, i.e. hydrogen peroxide stabilizer etc., all have influence on catalytic degradation efficiency.Hydrogen peroxide stabilizer can be divided into siliceous class and non-silicon class two kinds by its chemical constitution; Adsorption theory and complex Theory two kinds can be divided into by the mechanism of its stabilization function.Wherein H
2o
2the adsorption theory of stablizer mainly refers to by macromolecule glue League membership electrostatic or hydrogen bond, is attached to catalyst surface active position and reaches stable object of decomposing.And complex Theory is by sequestering agent and catalyst surface metal ion generation sequestering action, katalysis of slowing down thus.The two finally effectively can stablize hydroxyl radical free radical (OH) and hydroperoxy-ion [HO
2 –], be beneficial to maintenance high oxidation state, and suppress hydroperoxy radical [HO
2] formation.Make H
2o
2the OH produced can oxidative degradation unsymmetrical dimethyl hydrazine and derivative thereof fully effectively.
Compared with prior art, remarkable advantage of the present invention is: utilize the variation of valence of active ingredient Fe and the electronic compensation of other active metal components in catalyzer to carry out modification to catalyzer, make catalyzer within the scope of lesser temps and wider pH, reactive oxygen species hydroxyl radical free radical OH can be produced by catalysis hydrogen peroxide, by C-N in unsymmetrical dimethyl hydrazine, N-N bond rupture, be degraded to carbonic acid gas, formaldehyde, ammonium salt etc. efficiently, significantly remove the COD in waste water.Use method in the present invention can efficient degrading high concentration unsymmetrical dimethyl hydrazine waste water fast, and can significantly improve hydrogen peroxide utilising efficiency after adding hydrogen peroxide stabilizer, reduce the add-on of hydrogen peroxide, improve treatment effect.
Embodiment:
Below technical scheme of the present invention is described further.
Embodiment 1
Take the tetraethoxy (TEOS) of 35g, 70g dehydrated alcohol, 140g deionized water be made into mixing solutions, TEOS: dehydrated alcohol: deionized water quality is than being 1:2:4, the Iron diacetate solid taking 0.218g adds stirring and dissolving in mixing solutions, adding dust technology regulates pH to be 3, a small amount of diethanolamine condensing reflux is added in above-mentioned solution, afterwards products obtained therefrom is put into baking oven, dry moisture content and form gel, xerogel is put into retort furnace, at 300 DEG C, calcine 3h, obtain nanometer iron-based SiO
2, by nanometer iron-based SiO
2grinding, obtains pulverulent solids, takes 0.22g rhodium acetate, add in dehydrated alcohol, immerses nanometer iron-based SiO after dissolving
2stir in powder solid and form suspension liquid, stir dipping 10h, make Rh be wrapped in Fe surface, after oven dry, put into retort furnace, at 300 DEG C, calcine 3h, obtain nanometer sandwich structure 1%Rh-O-1%Fe/SiO
2catalyzer.
Embodiment 2
Take the tetraethoxy (TEOS) of 35g, 105g dehydrated alcohol, 210g deionized water be made into mixing solutions, TEOS: dehydrated alcohol: deionized water quality is than being 1:3:6, the Iron diacetate solid taking 0.544g adds stirring and dissolving in mixing solutions, adding dust technology regulates pH to be 3, a small amount of diethanolamine condensing reflux is added in above-mentioned solution, afterwards products obtained therefrom is put into baking oven, dry moisture content and form gel, xerogel is put into retort furnace, at 350 DEG C, calcine 4h, obtain nanometer iron-based SiO
2, by nanometer iron-based SiO
2grinding, obtains pulverulent solids, takes 0.55g rhodium acetate, add in dehydrated alcohol, immerses nanometer iron-based SiO after dissolving
2stir in powder solid and form suspension liquid, stir dipping 10h, make Rh be wrapped in Fe surface, after oven dry, put into retort furnace, at 350 DEG C, calcine 4h, obtain sandwich structure 2.5%Rh-O-2.5%Fe/SiO
2catalyzer.
Embodiment 3
Take the tetraethoxy (TEOS) of 35g, 140g dehydrated alcohol, 280g deionized water be made into mixing solutions, TEOS: dehydrated alcohol: deionized water quality is than being 1:4:8, the Iron diacetate solid taking 1.088g adds stirring and dissolving in mixing solutions, adding dust technology regulates pH to be 3, a small amount of diethanolamine condensing reflux is added in above-mentioned solution, afterwards products obtained therefrom is put into baking oven, dry moisture content and form gel, xerogel is put into retort furnace, at 410 DEG C, calcine 6h, obtain nanometer iron-based SiO
2, by nanometer iron-based SiO
2grinding, obtains pulverulent solids, takes 1.1g rhodium acetate, add in dehydrated alcohol, immerses nanometer iron-based SiO after dissolving
2stir in powder solid and form suspension liquid, stir dipping 10h, make Rh be wrapped in Fe surface, after oven dry, put into retort furnace, at 410 DEG C, calcine 6h, obtain sandwich structure 5%Rh-O-5%Fe/SiO
2catalyzer.
Embodiment 4
Take the tetraethoxy (TEOS) of 35g, 105g dehydrated alcohol, 210g deionized water be made into mixing solutions, TEOS: dehydrated alcohol: deionized water quality is than being 1:3:6, the Iron diacetate solid taking 0.544g adds stirring and dissolving in mixing solutions, adding dust technology regulates pH to be 3, a small amount of diethanolamine condensing reflux is added in above-mentioned solution, afterwards products obtained therefrom is put into baking oven, dry moisture content and form gel, xerogel is put into retort furnace, at 350 DEG C, calcine 4h, obtain nanometer iron-based SiO
2, by nanometer iron-based SiO
2grinding, obtains pulverulent solids, takes 0.46g cerous acetate, add in dehydrated alcohol, immerses nanometer iron-based SiO after dissolving
2stir in powder solid and form suspension liquid, stir dipping 10h, make Ce be wrapped in Fe surface, after oven dry, put into retort furnace, at 350 DEG C, calcine 4h, obtain sandwich structure 2.5%Ce-O-2.5%Fe/SiO
2catalyzer.
Embodiment 5
Take the tetraethoxy (TEOS) of 35g, 105g dehydrated alcohol, 210g deionized water be made into mixing solutions, TEOS: dehydrated alcohol: deionized water quality is than being 1:3:6, the Iron diacetate solid taking 0.544g adds stirring and dissolving in mixing solutions, adding dust technology regulates pH to be 3, a small amount of diethanolamine condensing reflux is added in above-mentioned solution, afterwards products obtained therefrom is put into baking oven, dry moisture content and form gel, xerogel is put into retort furnace, at 350 DEG C, calcine 4h, obtain nanometer iron-based SiO
2, by nanometer iron-based SiO
2grinding, obtains pulverulent solids, takes 0.308g ammonium perrhenate, add in dehydrated alcohol, immerses nanometer iron-based SiO after dissolving
2stir in powder solid and form suspension liquid, stir dipping 10h, make Re be wrapped in Fe surface, after oven dry, put into retort furnace, at 350 DEG C, calcine 4h, obtain sandwich structure 2.5%Re-O-2.5%Fe/SiO
2catalyzer.
Embodiment 6
Take the tetraethoxy (TEOS) of 35g, 70g dehydrated alcohol, 140g deionized water be made into mixing solutions, TEOS: dehydrated alcohol: deionized water quality than taking the Iron diacetate of 0.544g for 1:2:4,0.55g rhodium acetate solid adds stirring and dissolving in mixing solutions, the dust technology adding 3% regulates pH to equal 3,2g diethanolamine condensing reflux is added in gained solution, afterwards products obtained therefrom is put into oven for drying moisture content and form gel, finally gained gel is put into retort furnace, at 350 DEG C, calcine 4h, obtain 2.5%Rh-2.5Fe/SiO
2catalyzer.
Embodiment 7
Containing unsymmetrical dimethyl hydrazine starting point concentration at 3 parts of 200mL is 1000mg/L, and initial COD is about in the simulated wastewater of 2100mg/L and adds the hydrogen peroxide that 30mL massfraction is 30% respectively, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:80, is all preheating to 60 DEG C, is added respectively by three parts of simulated wastewaters be respectively filled with a.40g sandwich structure 1%Rh-O-1%Fe/SiO by peristaltic pump
2catalyzer, b.40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO
2catalyzer, c.40g sandwich structure 5%Rh-O-5%Fe/SiO
2catalyzer, in these 3 reaction beds, peristaltic pump continuous charging, start circulating reaction, reaction time is 12min, and it is 60 DEG C that water bath with thermostatic control controls temperature of reaction, detects COD result as following table 1.Embodiment result shows, the degradation effect of b group catalyzer is best, the nanometer iron-based SiO 2 catalyst of sandwich structure described in this patent can process unsymmetrical dimethyl hydrazine waste water effectively efficiently, be anchored on Fe oxide surface when catalyst adjuvant and form M-O-Fe sandwich structure, sandwich structure inhibits active ingredient in the movement of catalyst support surface and gathering, thus improve catalyst performance, but too high auxiliary agent dosage meeting blocking catalyst surfactivity site, reduce catalytic activity.
Table 1 active centre content is on the impact of catalyst effect
Embodiment 8
Containing unsymmetrical dimethyl hydrazine starting point concentration at 3 parts of 200mL is 1000mg/L, and initial COD is about in the simulated wastewater of 2100mg/L and adds the hydrogen peroxide that 30mL massfraction is 30% respectively, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:80, is all preheating to 60 DEG C, is added respectively by three parts of simulated wastewaters be respectively filled with b.40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO by peristaltic pump
2catalyzer, d.40g sandwich structure 2.5%Ce-O-2.5%Fe/SiO
2catalyzer, e.40g sandwich structure 2.5%Re-O-2.5%Fe/SiO
2catalyzer, in these 3 reaction beds, peristaltic pump continuous charging, start circulating reaction, reaction time is 12min, and it is 60 DEG C that water bath with thermostatic control controls temperature of reaction, detects COD result as following table 2.Embodiment result shows, three kinds of catalyzer all can process unsymmetrical dimethyl hydrazine waste water effectively efficiently, and wherein the degradation effect of b group catalyzer is best, and e group catalyzer takes second place, so be that the catalyzer in active centre is more excellent with Rh.
Table 2 active centre kind is on the impact of catalyst effect
Embodiment 9
Containing unsymmetrical dimethyl hydrazine starting point concentration at 200mL is 1000mg/L, and initial COD is about in the simulated wastewater of 2100mg/L and adds 30mL30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:80, is preheated to 60 DEG C, is added be filled with 2.5%Rh-2.5Fe/SiO described in 40g embodiment 6 by peristaltic pump
2in the reaction bed of catalyzer, peristaltic pump continuous charging, start circulating reaction, reaction time is 12min, and it is 60 DEG C that water bath with thermostatic control controls temperature of reaction, and detecting COD result is 280mg/L.Show with the Data Comparison of b group catalyzer in embodiment 7, nanocatalyst prepared by an embodiment 6 step gel method used, compared with sandwich structure nanocatalyst, fail to play the effect of grappling, divided active component Fe, cause catalytic activity good not.
Embodiment 10
Containing unsymmetrical dimethyl hydrazine starting point concentration at 200mL is 500mg/L, and initial COD is about in the simulated wastewater of 1000mg/L and adds 15mL massfraction is 30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is that 1:80 is preheated to 50 DEG C, is added be filled with 40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO by peristaltic pump
2in the reaction bed of catalyzer, peristaltic pump continuous charging, start circulating reaction, reaction time is 8min, and it is 50 DEG C that water bath with thermostatic control controls temperature of reaction, and detection COD is 51mg/L.
Embodiment 11
Containing unsymmetrical dimethyl hydrazine starting point concentration at 200mL is 2500mg/L, and initial COD is about in the simulated wastewater of 5000mg/L and adds 110mL massfraction is 30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:120, is preheated to 70 DEG C, is added be filled with 40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO by peristaltic pump
2in the reaction bed of catalyzer, peristaltic pump continuous charging, start circulating reaction, reaction time is 20min, and it is 70 DEG C that water bath with thermostatic control controls temperature of reaction, detection COD is 96mg/L, the data of 7 to embodiment 11 in conjunction with the embodiments, result shows, the nanometer iron-based SiO 2 catalyst of the sandwich structure described in this patent can concentration for the treatment of be the high density unsymmetrical dimethyl hydrazine waste water of 500 ~ 2500mg/L effectively efficiently, and can by wastewater degradation under each concentration in interval, result COD value is up to standard.
Embodiment 12
Containing unsymmetrical dimethyl hydrazine starting point concentration at 8 parts of 200mL is 1000mg/L, and initial COD is about in the simulated wastewater of 2100mg/L and adds 30mL massfraction is 30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:80, regulates pH to be 3 ~ 10 respectively, be preheated to 60 DEG C, added by gained simulated wastewater be filled with 40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO by peristaltic pump with sodium hydroxide and dilute hydrochloric acid
2in the reaction bed of catalyzer, peristaltic pump continuous charging, start circulating reaction, reaction time is 12min, detect each group of COD, result is as following table 3, and embodiment result shows that unsymmetrical dimethyl hydrazine treatment process described in this patent effectively can process unsymmetrical dimethyl hydrazine waste water in the scope that pH is 4 ~ 10, soda acid scope is large, and the scope of application is wider.
Table 3pH value to be given up water mitigation to processing unsymmetrical dimethyl hydrazine
Embodiment 13
Take 0.0015mol phytic acid, 0.005mol magnesium chloride, 0.004mol water glass adds in the beaker that 1000mL deionized water is housed, and is stirred to and dissolves completely, obtained 1000mL hydrogen peroxide stabilizer a; Take 0.015mol phytic acid, 0.05mol magnesium chloride, 0.04mol water glass adds in the beaker that 1000mL deionized water is housed, and is stirred to and dissolves completely, obtained 1000mL hydrogen peroxide stabilizer b; Take 0.03mol phytic acid, 0.1mol magnesium chloride, 0.08mol water glass adds in the beaker that 1000mL deionized water is housed, and is stirred to and dissolves completely, obtained 1000mL hydrogen peroxide stabilizer c.
Embodiment 14
Containing unsymmetrical dimethyl hydrazine starting point concentration at 4 parts of 200mL is 1000mg/L, initial COD is about in the simulated wastewater of 2100mg/L and adds 1mL hydrogen peroxide stabilizer a respectively, b, c and 1ml distilled water, all adding 30mL massfraction is afterwards 30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:80, is preheated to 60 DEG C, is all added by peristaltic pump by waste water and is filled with 40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO
2in the reaction bed of catalyzer, peristaltic pump continuous charging, start circulating reaction, reaction time is 12min, and detect COD result as following table 4, embodiment result shows,
First three groups experiment and the 4th group of Experimental comparison, hydrogen peroxide stabilizer described in this patent joins the generation effectively stablizing hydroxyl radical free radical in reaction system, increase the utilising efficiency of hydrogen peroxide, improve wastewater degradation effect, and the component concentration optimum value of hydrogen peroxide stabilizer is the proportioning of b group stablizer.
The different hydrogen peroxide stabilizer proportioning of table 4 is on the impact of degradation effect
Embodiment 15
Containing unsymmetrical dimethyl hydrazine starting point concentration at 5 parts of 200mL is 1000mg/L, and initial COD is about in the simulated wastewater of 2100mg/L and adds 1mL respectively, 2mL, 3mL, 4mL, 5mL hydrogen peroxide stabilizer b, all adding 30mL massfraction is afterwards 30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:80, is preheated to 60 DEG C, is all added by peristaltic pump by waste water and is filled with 40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO
2in the reaction bed of catalyzer, peristaltic pump continuous charging, start circulating reaction, reaction time is 12min, and detect COD result as following table 5, embodiment result shows, too much hydrogen peroxide stabilizer adds membership and slows down DeR speed, reduces degradation effect.
Table 5 different volumes hydrogen peroxide stabilizer is on the impact of degradation effect
Embodiment 16
Containing unsymmetrical dimethyl hydrazine starting point concentration at 200mL is 1000mg/L, and initial COD is about in the simulated wastewater of 2100mg/L and adds 1mL hydrogen peroxide stabilizer b, and 15mL massfraction is 30% hydrogen peroxide, described unsymmetrical dimethyl hydrazine and H
2o
2mol ratio is 1:40, is preheated to 60 DEG C, is added by waste water be filled with 40g sandwich structure 2.5%Rh-O-2.5%Fe/SiO by peristaltic pump
2in the reaction bed of catalyzer, peristaltic pump continuous charging, starts circulating reaction, reaction time is 12min, detection COD is 58mg/L, and COD degradation rate reaches 97.2%, and in embodiment result and embodiment 7, the experiment of b group contrasts, the add-on of hydrogen peroxide reduces, degradation effect promotes, so hydrogen peroxide stabilizer of the present invention joins in reaction system, the decomposition that hydrogen peroxide can be made more stable produces hydroxyl radical free radical, improve the utilization ratio of hydrogen peroxide, reduce the waste of hydrogen peroxide.
Claims (7)
1. a method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water, it is characterized in that, described method comprises: utilize nanometer sandwich structure ferrum-based catalyst, coordinates hydrogen peroxide stabilizer, catalyzed oxidation H
2o
2, produce hydroxyl radical free radical (OH), rapidly and efficiently degrade unsymmetrical dimethyl hydrazine and derivative thereof;
Wherein, described nanometer sandwich structure ferrum-based catalyst general formula M – O – Fe/SiO
2represent, M represents the one in rhenium, rhodium and cerium, and mass percentage is 1 ~ 5%M – O –, 1 ~ 5%Fe/SiO
2, described mass percentage is M
xo
yburning amount or ferric oxide and SiO
2mass ratio, wherein x=1,2, y=1,2,3.
2. the method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water according to claim 1, it is characterized in that, the preparation method of described nanometer sandwich structure ferrum-based catalyst comprises the steps:
Tetraethoxy, dehydrated alcohol, deionized water are made into mixing solutions, solid nitric acid iron is added stirring and dissolving in described mixing solutions, add dust technology and regulate pH, after diethanolamine condensing reflux 2 ~ 8h, be placed in baking oven and dry moisture content formation xerogel, calcine described xerogel, obtained nanometer iron-based SiO
2, grind described nanometer iron-based SiO
2obtain pulverulent solids; By described nanometer iron-based SiO
2form suspension liquid in one in the rhenium of pulverulent solids immersion anhydrous alcohol solution, rhodium and cerium salt, dipping stirring 8 ~ 12h, makes rhenium, rhodium, cerium be wrapped in Fe surface, after oven dry, and calcining, obtained nanometer sandwich structure ferrum-based catalyst.
3. the method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water according to claim 2, it is characterized in that, the mass ratio of described tetraethoxy/dehydrated alcohol/deionized water is 1/2 ~ 4/4 ~ 8.
4. the method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water according to claim 2, it is characterized in that, add dust technology and regulate described pH to 3 ~ 5, described calcining temperature is 290 ~ 410 DEG C, and calcination time is 3 ~ 6h.
5. the method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water according to claim 1, it is characterized in that, described method comprises and add hydrogen peroxide and a small amount of hydrogen peroxide stabilizer in high density unsymmetrical dimethyl hydrazine waste water, control unsymmetrical dimethyl hydrazine and hydrogen peroxide mol ratio are 1:40 ~ 120, and the volume ratio of hydrogen peroxide and hydrogen peroxide stabilizer is 1 ~ 20:1; System temperature of reaction is 50 ~ 70 DEG C.
6. the method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water according to claim 5, it is characterized in that, the formula of described hydrogen peroxide stabilizer is: phytic acid, and substance withdrawl syndrome is 0.0015 ~ 0.3mol/L; Magnesium chloride, substance withdrawl syndrome is 0.005 ~ 0.1mol/L; Water glass, substance withdrawl syndrome is 0.004 ~ 0.08mol/L.
7. the method for rapidly and efficiently degrading high concentration unsymmetrical dimethyl hydrazine waste water according to claim 6, it is characterized in that, the pH of described unsymmetrical dimethyl hydrazine waste water controls 4 ~ 10, and the concentration of unsymmetrical dimethyl hydrazine waste water is 500 ~ 2500mg/L, and the residence time is 8 ~ 20min.
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| CN106111200A (en) * | 2016-06-21 | 2016-11-16 | 东南大学 | Many metal corsslinkings for uns-dimethylhydrazine degraded coordinate catalyst and its preparation method and application |
| CN106587456A (en) * | 2017-03-03 | 2017-04-26 | 武汉大学 | Advanced oxidation-flocculation water treatment method based on oxygen molecule activation |
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| CN105617713A (en) * | 2016-03-30 | 2016-06-01 | 中国人民解放军总装备部卫生防疫队 | Unsymmetrical dimethylhydrazine dehydration process |
| CN106111200A (en) * | 2016-06-21 | 2016-11-16 | 东南大学 | Many metal corsslinkings for uns-dimethylhydrazine degraded coordinate catalyst and its preparation method and application |
| CN106111200B (en) * | 2016-06-21 | 2019-03-12 | 东南大学 | More metal corsslinkings cooperation catalyst and its preparation method and application for uns-dimethylhydrazine degradation |
| CN106587456A (en) * | 2017-03-03 | 2017-04-26 | 武汉大学 | Advanced oxidation-flocculation water treatment method based on oxygen molecule activation |
| CN106587456B (en) * | 2017-03-03 | 2019-05-10 | 武汉大学 | A kind of advanced oxidation based on Activation of Molecular Oxygen-flocculation method for treating water |
| CN107151047B (en) * | 2017-05-05 | 2021-11-16 | 周鹏 | Method for treating high-concentration high-chroma or difficult-biochemical organic wastewater and preparing compound oxidant |
| CN107151047A (en) * | 2017-05-05 | 2017-09-12 | 周鹏 | A kind of method that high concentration, high chroma or difficult biochemical treatment of Organic Wastewater and oxidic compound agent are prepared |
| CN110252281A (en) * | 2018-11-21 | 2019-09-20 | 湖北工业大学 | A kind of catalyst and its preparation method and application of energy degradation of dye waste water |
| CN110713247A (en) * | 2019-10-11 | 2020-01-21 | 北京北化汇智能源环境科技有限公司 | Method for treating organic wastewater by catalyzing hydrogen peroxide through solid catalyst |
| CN111389412A (en) * | 2020-03-04 | 2020-07-10 | 华南理工大学 | Supported noble metal catalyst based on carrier morphology modification and preparation and application thereof |
| CN111389412B (en) * | 2020-03-04 | 2021-08-06 | 华南理工大学 | Supported noble metal catalyst based on carrier morphology modification and preparation and application thereof |
| CN111744456A (en) * | 2020-06-03 | 2020-10-09 | 中国人民解放军火箭军工程大学 | Application of hydrogen peroxide modified activated carbon in adsorbing unsymmetrical dimethylhydrazine |
| CN115093004A (en) * | 2022-06-08 | 2022-09-23 | 西南交通大学 | Method for degrading levofloxacin in water body by catalyzing potassium ferrate with ammonium ions |
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