CN105107522B - A kind of ferro manganese composite oxides catalyst and preparation method thereof - Google Patents
A kind of ferro manganese composite oxides catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of ferro manganese composite oxides catalyst and preparation method thereof, the ferro manganese composite oxides catalyst, for graininess, it is to calcine to be made after the reaction of polyvinyl alcohol, neopelex, ferrous sulfate, sodium carbonate and Natural Manganese iron ore, the paper waste depth degradation that the catalyst is used for after biochemical treatment, the catalyst of the present invention is changed into ferro manganese composite oxides particle from traditional ferrous sulfate, it can be recycled again by calcining, chemical sludge yield is low, save Treatment of Sludge cost, the generation of secondary pollution is reduced, separation of solid and liquid is easily realized.
Description
Technical field
The present invention relates to a kind of ferro manganese composite oxides catalyst and preparation method thereof, belong to water-treatment technology field.
Background technology
Pulp and paper industry is the important component of Chinese national economy, but it also turns into the important water pollution of China
One of source.Wastewater discharge is big, and it contains the lignin and cellulose of high-concentration biological difficult degradation.Fibre suspension contains largely
Organic matter, when these organic matter fermentations decomposition after can consume substantial amounts of dissolved oxygen in water, so that water degradation can be made.Papermaking is given up
Also there is persistent noxious material containing substantial amounts of in water, human health is caused harm.China's processing paper waste is main
Using being method that physical treatment and biochemical treatment are combined, but still there is more benzene ring structure lignin class high in the water after processing
Molecular organic, colourity, COD etc. are still higher.
Fenton treatment technology is one of currently conventional further treatment technique, passes through the strong oxidizing property hydroxyl radical free radical of generation
Can effectively be degraded all kinds of organic pollutions in sewage, while having decolorizing effect.But Fenton process is used, before processing need to be by waste water
PH value is adjusted to 2.5-3, and pH value is adjusted into neutrality after reaction, and acid adjustment, alkali tune add processing cost, and produced substantial amounts of repeatedly
Flocculation sediment, causes the secondary pollution of water body.
The content of the invention
For existing deficiency, the present invention provides a kind of ferro manganese composite oxides catalyst, using the catalyst to slurrying
Paper waste carries out advanced treating, will not produce substantial amounts of flocculation sediment, treatment effeciency is high and cost is low, to paper-making effluent
Reach advanced treating.
Technical scheme is as follows：
A kind of ferro manganese composite oxides catalyst of the present invention, is graininess, and XRD is carried out to material b using Cu-K alpha rays
Characterize, it is 20.8 °, 26.6 °, 36.5 °, 36.5 °, 40 °, 50 °, 60 ° in 2 θ and shows SiO2Characteristic peak；2 θ be 23 °,
33 °, 38.3 °, 55.3 ° show α-Mn2O3Characteristic peak；2 θ be 24 °, 33.1 °, 35.6 °, 49.3 °, 54 ° show α-
Fe2O3Characteristic peak.
Ferro manganese composite oxides catalyst grain diameter is 1-3mm.
The preparation method of the present invention also offer ferro manganese composite oxides catalyst, including step are as follows：
1) polyvinyl alcohol is taken to add distilled water, heating stirring dissolving is cooled to room temperature, poly-vinyl alcohol solution, poly- second is made
The addition of enol and the mass ratio of distilled water are 1：(8-12), unit：100g/L；
2) poly-vinyl alcohol solution is added together with neopelex solution in copperas solution, magnetic agitation
1-2min, then adds sodium carbonate liquor, and mixed solution is made；
The molar concentration of the neopelex solution is (0.1-0.3) mol/L, mole of copperas solution
Concentration is (1.1-1.5) mol/L, and the molar concentration of sodium carbonate liquor is (2-3) mol/L；
Poly-vinyl alcohol solution：Neopelex solution：Copperas solution：Sodium carbonate liquor volume ratio is (3-
7):(15-25):(20-40):(6-10)；
3) take Natural Manganese iron ore to add step 2) made from mixed solution, stirring reaction 3-10h, every liter of mixed solution
Middle addition Natural Manganese iron ore 200-400g；Reaction separates solid particle after terminating, and solid particle is dried, then in 500-
2-4h is calcined at 600 DEG C, cools down, produces product.
Ferro manganese composite oxides class Fenton advanced treating catalyst produced by the present invention be graininess, be by polyvinyl alcohol,
Calcine and be made after neopelex, ferrous sulfate, sodium carbonate and the reaction of Natural Manganese iron ore, polyvinyl alcohol, dodecane
Base benzene sulfonic acid sodium salt, ferrous sulfate, the mass ratio of sodium carbonate and Natural Manganese iron ore are 1:(1~4):(15~25):(3~6):
(35~45).Particle diameter, in 1-3mm, is that iron particle is supported on ferromanganese mineral surface, cost is low, natural environmental-protective, reclaims convenient, with
H2O2Strong oxidizing property hydroxyl radical free radical OH is produced, it is equal to benzene ring structure lignin family macromolecule organic matter, colourity and COD in waste water
There is stronger degradation effect, and substantial amounts of chemical sludge will not be produced.
Above-mentioned steps 1) in, the average degree of polymerization of polyvinyl alcohol is 1700~1800, the addition of polyvinyl alcohol and distillation
The mass ratio of water is 1：5, unit：100g/L.
Above-mentioned steps 2) poly-vinyl alcohol solution：Neopelex solution：Copperas solution：Sodium carbonate liquor body
Product is than being 5:20:30:8.
Above-mentioned steps 3) in calcining heat be 520-580 DEG C, calcination time 2-4h, highly preferred, calcining heat is 550
DEG C, calcination time 3h.
Natural Manganese iron ore is current material, can market buy, the Natural Manganese iron ore that uses of the present invention is purchased from Henan Gong
Certain adopted ore deposit factory.
The present invention also provides a kind of application of ferro manganese composite oxides catalyst, described ferro manganese composite oxides catalyst
For the paper waste depth degradation after biochemical treatment.
It is further preferred that the application of ferro manganese composite oxides catalyst, concrete application method is as follows：
Ferro manganese composite oxides catalyst and hydrogen peroxide are added in pending waste water, pending waste water quality is：CODCr
≤ 500mg/L, SS≤100mg/L, colourity≤100；20-40min is stirred under the conditions of 20-30 DEG C.
Currently preferred, the dosage of catalyst and the mass ratio of waste water are about 1：(10-40), described oxidant is
The volume ratio of mass fraction 20-40% hydrogen peroxide, hydrogen peroxide and waste water is 1：1000-1:3000.
The present invention replaces traditional ferrous salt as catalyst using ferro manganese composite oxides particle, using hydrogen peroxide as oxidant,
To waste water carry out treating technology processing, by hydrogen peroxide catalytic decomposition generation hydroxyl radical free radical (OH) and superoxides from
Son, carbon dioxide, water and inorganic molecules are oxidized to by the organic matter in waste water, bacterium, virus etc., can be in wider pH (3-
8) used in the range of, can efficiently, low cost, the stable such waste water of processing, water outlet is up to GB18918-2002《Integrated wastewater
Discharge standard》In first discharge standard.Cost of the present invention is low, and technological process is simple, easily realizes industrialization.
Beneficial effects of the present invention are as follows：
1st, catalyst cost of the invention is low, sewage treatment technology process and simple to operate, is easy to implement industrialization.
2nd, catalyst applicable pH range of the invention is wide, is not required to be pre-adjusted pH value of waste water, simplifies processing technological flow, drop
Low reagent cost.
3rd, catalyst of the invention is changed into ferro manganese composite oxides particle from traditional ferrous sulfate, and this catalyst is by forging
Burning can be recycled again.Chemical sludge yield is low, saves Treatment of Sludge cost, reduces the generation of secondary pollution.
4th, catalyst of the invention is granular solids, easily realizes separation of solid and liquid.Compared with conventional powder shape catalyst, easily
Recycle and regenerate.Through this catalyst treatment, effluent quality meets GB18918-2002《Integrated wastewater discharge standard》One-level
Discharge standard.
Brief description of the drawings
Fig. 1 is the XRD spectrum of ferro manganese composite oxides particle made from the embodiment of the present invention 2；
Fig. 2 changes to COD treatment effect curve maps for the ferro manganese composite oxides particle of the present invention with pH；
Fig. 3 changes to colourity treatment effect curve map for the ferro manganese composite oxides particle of the present invention with pH；
Fig. 4 changes to ss treatment effect curve maps for the ferro manganese composite oxides particle of the present invention with pH；
Embodiment
Technical scheme is described further with reference to embodiment, but institute's protection domain of the present invention is not limited to
This.
Raw material in embodiment is commercial products, can market buy.
Embodiment 1：
The preparation of ferro manganese composite oxides catalyst
Preparation process：
1) 100g polyvinyl alcohol is taken to add 10L distilled water, heating stirring dissolving is cooled to room temperature, polyvinyl alcohol is made molten
Liquid,
2) poly-vinyl alcohol solution is added mole together with molar concentration 0.2mol/L neopelex solution
In concentration 1.2mol/L copperas solution, magnetic agitation 2min, the sodium carbonate for then adding molar concentration 2.5mol/L is molten
Liquid, is made mixed solution；Poly-vinyl alcohol solution：Neopelex solution：Copperas solution：Sodium carbonate liquor volume
Than for 5:20:30:8；
3) take Natural Manganese iron ore to add step 2) made from mixed solution, stirring reaction 4h, in every liter of mixed solution
Add Natural Manganese iron ore 300g；Reaction separates solid particle after terminating, and solid particle is dried, then in calcining at 450 DEG C
3h, cooling is made ferro manganese composite oxides catalyst, is denoted as material a.
Embodiment 2：
The preparation method of ferro manganese composite oxides catalyst described in be the same as Example 1, difference is：
Step 3), by the solid particle after drying in calcining 3h at 550 DEG C, ferro manganese composite oxides catalyst, note is made
Make material b.
Using Cu-K alpha rays to material b carry out XRD signs, obtained XRD spectrum as shown in figure 1, its 2 θ be 20.8 °,
26.6 °, 36.5 °, 36.5 °, 40 °, 50 °, 60 ° show SiO2Characteristic peak；It is 23 °, 33 °, 38.3 °, 55.3 ° in 2 θ to show
α-Mn2O3Characteristic peak；It is 24 °, 33.1 °, 35.6 °, 49.3 °, 54 ° in 2 θ and shows α-Fe2O3Characteristic peak.
Learnt through spectrofluorimetry, siderochrome composite oxides SiO described above2Content is about 15%, α-Mn2O3Contain
Amount is about 30-50%, α-Fe2O3Content is about 20-40%, trace element about 0.1%.
Embodiment 3：
The preparation method of ferro manganese composite oxides catalyst described in be the same as Example 1, difference is：
Step 3), by the solid particle after drying in calcining 3h at 650 DEG C, ferro manganese composite oxides catalyst, note is made
Make material c.
The catalyst applicable pH range of the present invention is wide, in the range of pH3~8, ferro manganese composite oxides particle of the invention
Shown in changing with pH to COD, colourity and ss treatment effect as Fig. 2-Fig. 4.
Application experiment example 1
Material a made from embodiment 1 is applied to pulp and paper effluent treatment, paper-making effluent COD is 258mg/L,
PH value is 7.6, and paper-making effluent 1L is introduced into class Fenton's reaction system, and the quality for adding above-mentioned material a is 80g, is added
0.6mL30% hydrogen peroxide, reacts 30min.Flocculation, precipitation.The COD of last sewage is that 170mg/L, pH value are 7.5, colourity
40.Specific experiment the results are shown in Table 1.
Application experiment example 2
Material b made from embodiment 2 is applied to pulp and paper effluent treatment, paper-making effluent COD is 258mg/L,
PH value is 7.6, and paper-making effluent 1L is introduced into class Fenton's reaction system, and the quality for adding above-mentioned material b is 80g, add
0.6mL30% hydrogen peroxide, reacts 30min.Flocculation, precipitation.The COD of last sewage is that 42mg/L, pH value are 7.5, colourity 20,
Reach GB18918-2002《Integrated wastewater discharge standard》In first discharge standard.Specific experiment the results are shown in Table 1.
Application experiment example 3
Material c made from embodiment 3 is applied to pulp and paper effluent treatment, paper-making effluent COD is 258mg/L,
PH value is 7.6, and paper-making effluent 1L is introduced into class Fenton's reaction system, and the quality for adding above-mentioned material c is 80g, is added
0.6mL30% hydrogen peroxide, reacts 30min.Flocculation, precipitation.The COD of last sewage is that 205mg/L, pH value are 7.5, colourity
50.Specific experiment the results are shown in Table 1.
Table 1
It the foregoing is only the preferred embodiment of the present invention, it is noted that come for those skilled in the art
Say, under the premise without departing from the principles of the invention, some technical characteristics to the present invention are modified, without departing from skill of the present invention
The connotation of art scheme, these changes all should be covered within the scope of claimed technical scheme of the invention.
Claims (9)
1. a kind of ferro manganese composite oxides catalyst, is graininess, material ferro manganese composite oxides are catalyzed using Cu-K alpha rays
Agent carries out XRD signs, and it is 20.8 °, 26.6 °, 36.5 °, 40 °, 50 °, 60 ° in 2 θ and shows SiO2Characteristic peak；It is in 2 θ
23 °, 33 °, 38.3 °, 55.3 ° show α-Mn2O3Characteristic peak；2 θ be 24 °, 33.1 °, 35.6 °, 49.3 °, 54 ° show α-
Fe2O3Characteristic peak；
The preparation method of described ferro manganese composite oxides catalyst, including step are as follows：
1) polyvinyl alcohol is taken to add distilled water, heating stirring dissolving is cooled to room temperature, poly-vinyl alcohol solution, polyvinyl alcohol is made
Addition and distilled water ratio be 100g：(8-12) L；
2) poly-vinyl alcohol solution is added together with neopelex solution in copperas solution, magnetic agitation 1-
2min, then adds sodium carbonate liquor, and mixed solution is made；The molar concentration of the neopelex solution is
(0.1-0.3) mol/L, the molar concentration of copperas solution is (1.1-1.5) mol/L, and the molar concentration of sodium carbonate liquor is
(2-3)mol/L；Poly-vinyl alcohol solution：Neopelex solution：Copperas solution：Sodium carbonate liquor volume ratio is
(3-7):(15-25):(20-40):(6-10)；
3) take Natural Manganese iron ore to add step 2) made from mixed solution, stirring reaction 3-10h, in every liter of mixed solution plus
Enter Natural Manganese iron ore 200-400g；Reaction separates solid particle after terminating, and solid particle is dried, then in 500-600 DEG C
Lower calcining 2-4h, cooling, produces product.
2. ferro manganese composite oxides catalyst according to claim 1, it is characterised in that ferro manganese composite oxides catalyst
Grain diameter is 1-3mm.
3. ferro manganese composite oxides catalyst according to claim 1, it is characterised in that step 1) in, polyvinyl alcohol
Average degree of polymerization is 1700~1800.
4. ferro manganese composite oxides catalyst according to claim 1, it is characterised in that step 2) poly-vinyl alcohol solution：
Neopelex solution：Copperas solution：Sodium carbonate liquor volume ratio is 5:20:30:8.
5. ferro manganese composite oxides catalyst according to claim 1, it is characterised in that step 3) in calcining heat be
520-580 DEG C, calcination time 2-4h.
6. ferro manganese composite oxides catalyst according to claim 5, it is characterised in that calcining heat is 550 DEG C, calcining
Time 3h.
7. the application of the ferro manganese composite oxides catalyst described in claim 1, described ferro manganese composite oxides catalyst is used
In the paper waste depth degradation after biochemical treatment.
8. the application of ferro manganese composite oxides catalyst according to claim 7, it is characterised in that its concrete application method
It is as follows：Ferro manganese composite oxides catalyst and hydrogen peroxide are added in pending waste water, pending waste water quality is：CODCr≤
500mg/L, SS≤100mg/L, colourity≤100；20-40min is stirred under the conditions of 20-30 DEG C.
9. the application of ferro manganese composite oxides catalyst according to claim 8, it is characterised in that the dosage of catalyst
Mass ratio with waste water is 1：(10-40), the hydrogen peroxide that described hydrogen peroxide is mass fraction 20-40%, hydrogen peroxide and waste water
Volume ratio be 1：1000-1:3000.
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| CN102895980A (en) * | 2012-11-02 | 2013-01-30 | 威水星空（北京）环境技术有限公司 | Ferro-chrome composite oxide and preparation method and application thereof |
| CN104209138A (en) * | 2014-09-04 | 2014-12-17 | 天津大学 | Fe-Mn double-metal heterogeneous Fenton catalyst taking molecular sieve as carrier as well as preparation method and application of catalyst |
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| CN111186896A (en) * | 2019-12-18 | 2020-05-22 | 中国环境科学研究院 | Method for degrading nitrobenzene wastewater by using natural iron-manganese mineral to catalyze double oxidants |
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