CN104759288B - A kind of heterogeneous Cu Mn Ce type Fenton catalysts and its production and use - Google Patents
A kind of heterogeneous Cu Mn Ce type Fenton catalysts and its production and use Download PDFInfo
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- CN104759288B CN104759288B CN201410002596.9A CN201410002596A CN104759288B CN 104759288 B CN104759288 B CN 104759288B CN 201410002596 A CN201410002596 A CN 201410002596A CN 104759288 B CN104759288 B CN 104759288B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000975 dye Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011282 treatment Methods 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides a kind of preparation method and application of the heterogeneous type Fenton catalyst of high-performance.Its preparation method comprises the following steps：（1）Configure copper nitrate, cerous nitrate and manganese nitrate mixed solution；（2）The meso pore silicon oxide material of high-sequential is impregnated in step repeatedly（1）In the mixed solution of gained, filtering, washing, dry；（3）By step（2）Obtained material, which is placed in Muffle furnace, to be calcined, and obtains heterogeneous Cu Mn Ce type Fenton catalysts.The embryonic stem-like cells system that the catalyst is formed with hydrogen peroxide, can under conditions of low temperature, normal pressure efficiently catalytic degradation dye wastewater with high concentration, have that manufacture craft is simple, cost is relatively low, specific surface area is big, pore-size distribution is narrow, the advantages that catalytic activity is high, and the pH scope of applications are wide.
Description
Technical field
The invention belongs to catalyst preparation and application field, be related to a kind of heterogeneous Cu-Mn-Ce type Fenton catalysts and
Preparation method and use.
Background technology
Waste water from dyestuff has had resulted in serious problem of environmental pollution, and the health to the mankind brings great threat, though
So traditional homogeneous Fenton catalyst also has considerable catalytic activity for waste water from dyestuff, but its pH scope of application is narrower.Cause
This, prepares one kind efficiently, the wide heterogeneous catalysis of the pH scope of applications has highly important practical meaning in engineering.In recent years
Come, some are also reported for the heterogeneous catalysis of waste water from dyestuff.Wherein, researcher has found the catalysis of bimetallic mixed oxide
Agent, such as MOFe2O3(M:Fe, Co, Cu, Mn), generally there is higher catalytic activity, and CuOFe than Fe2O3 catalyst2O3
And CoOFe2O3Also there is broader pH tolerance ranges（Applied Catalysis B:Environmental2006,66,
(3-4),258-264.）, but this kind of metal oxide catalyst is not dispersed through, is unable to reach nanoscale, and contact surface is smaller, limit
Its catalytic activity is made.Also there are some researchers that active component Cu is dispersed on ZSM-5 molecular sieve（Journal of
hazardous materials2007,144,(3),663-667）, but the duct of ZSM-5 molecular sieve belongs to micropore, it is difficult to it is applicable
In macromolecular substances.Also some researchers have selected some mesoporous supports to be disperseed, its heterogeneous catalysis prepared
The catalytic activity higher than the catalyst not being dispersed through is illustrated, but the active component of this kind of catalyst is due to no addition point
Powder and be prone to reunite, so as to influence its catalytic activity（catalysis communications2006,7,(7),478-
483）.In terms of document and patent results, the existing usual catalytic activity of heterogeneous Fenton catalyst for waste water from dyestuff is not high,
Active component disperse it is uneven, and easily reunite.Therefore, good dispersion degree is prepared and with high performance heterogeneous Fenton-like catalysis
Agent turns into one of study hotspot of waste water from dyestuff.
The content of the invention
It is an object of the invention to provide a kind of heterogeneous Cu-Mn-Ce type Fenton catalysts and preparation method thereof and use
On the way.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of heterogeneous Cu-Mn-Ce type Fenton catalysts, is comprised the following steps：
（1）Configure copper nitrate, cerous nitrate and manganese nitrate mixed solution；
（2）The meso pore silicon oxide material of high-sequential is impregnated in step repeatedly（1）In the mixed solution of gained, filtering,
Washing, dry；
（3）Then, by step（2）Obtained material, which is placed in Muffle furnace, to be calcined, and obtains heterogeneous Cu-Mn-Ce classes
Fenton catalyst（That is Cu-Mn-Ce/ mesopore silicon oxides, Cu-Mn-Ce/OMS）.
Described step（1）In copper nitrate, cerous nitrate, in manganese nitrate mixed solution the concentration of each material be 0.1~
1mol/L。
Described step（2）The dosage of the meso pore silicon oxide material of middle high-sequential is 10~40g/L, and dip time is
4~8h.
The meso pore silicon oxide material of described high-sequential is MCM-41 or SBA-15.
Described step（3）In calcining heat be 300~500 DEG C, calcination time 6h.
Heterogeneous Cu-Mn-Ce type Fenton catalysts made from a kind of above method（That is Cu-Mn-Ce/OMS）.
Described Cu-Mn-Ce type Fenton catalysts belong to new construction high-performance porous catalyst, and its duct is two dimension six
Square structure and uniform and ordered, aperture is larger, and distribution is typically generally 200-600m in 2-10nm, specific surface area2/ g, pore volume
Scope is 0.2-0.6cm3/g.In addition, catalyst activity component is uniformly dispersed, catalytic capability is stronger.
A kind of purposes of above-mentioned heterogeneous Cu-Mn-Ce catalyst treatments waste water from dyestuff, comprises the following steps：
Hydrogen peroxide is added in waste water from dyestuff and heterogeneous Cu-Mn-Ce catalyst composition Fenton-like obtained above is anti-
System is answered to be reacted.In course of reaction, heterogeneous Cu-Mn-Ce catalysts hydrogen peroxide produces free radical degradation of dye point
Son.
Described dyestuff is the one or more in rhodamine B or azogeramine etc., and dye strength is 1~2000mg/
L。
The dosage of the heterogeneous Cu-Mn-Ce catalyst is 0.1~0.4g/L.
The dosage of the hydrogen peroxide is 0.2~0.8mol/L.
Described reaction temperature is 70~90 DEG C.
PH value is 3~7 in described reaction.
The described reaction time is 50-210min.
The invention has the advantages that：
The invention provides a kind of methods for making and using same of heterogeneous Cu-Mn-Ce type Fenton catalysts.The catalyst
Manufacture craft is simple, and cost is relatively low, duct uniform and ordered, and pH is applied widely.The Fenton reaction systems formed with hydrogen peroxide
To dye wastewater with high concentration under conditions of low temperature, normal pressure（Rhodamine B, azogeramine etc.）With higher catalytic activity, even if
In neutral conditions, the catalyst still can keep higher degradation efficiency.
Brief description of the drawings
Fig. 1 is the TEM photos of catalyst in the embodiment of the present invention 1.The catalyst dip time is 6h, is forged at 300 DEG C
6h is burnt to obtain.Dash area is as successfully supported on the reactive metal oxides on mesopore silicon oxide in figure.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
（1）First, mixed solution (copper nitrate, manganese nitrate and the nitre of 1mol/L copper nitrate, manganese nitrate and cerous nitrate are configured
Sour cerium concentration is respectively 1mol/L mixed solution) it is stand-by；
（2）Secondly, 1g SBA-15 are impregnated into the mixed solution of the above-mentioned copper nitrates of 50mL, manganese nitrate and cerous nitrate repeatedly
In（20g/L）8h is stirred, is then filtered, is dried；
（3）Then, by step（2）Middle gained sample is placed in Muffle furnace, and calcining 6h can obtain heterogeneous at 300 DEG C
Cu-Mn-Ce type Fenton catalysts, its TEM picture are as shown in Figure 1.As seen from Figure 1, the catalyst is in edge [110] direction
Show large-scale ordered arrangement strip structure, dash area is as successfully supported on the activity gold on mesopore silicon oxide in figure
Belong to oxide.Its structural parameters is as shown in table 1；
（4）Then, the heterogeneous Cu-Mn-Ce Fenton-likes of 0.2g/L are added to 1000mg/L high concentration rhodamine B solution
Catalyst and 0.4mol/L hydrogen peroxide, regulation pH are heated to 70 DEG C to 3, while by solution, allow the system to react 210min.
Decolorizing effect is notable, and degradation efficiency reaches more than 99%, as shown in table 2.
Embodiment 2
（1）First, 0.1mol/L copper nitrate, the mixed solution of manganese nitrate and cerous nitrate stand-by (copper nitrate, nitric acid is configured
Manganese and nitric acid cerium concentration are respectively 0.1mol/L mixed solution)；
（2）Secondly, 0.5g MCM-41 are impregnated into the mixed of the above-mentioned copper nitrates of above-mentioned 50mL, manganese nitrate and cerous nitrate repeatedly
Close in solution（10g/L）4h is stirred, is then filtered, is dried；
（3）Then, by step（2）Middle gained sample is placed in Muffle furnace, and calcining 6h can obtain heterogeneous at 500 DEG C
Cu-Mn-Ce type Fenton catalysts；
（4）Then, the heterogeneous Cu-Mn-Ce Fenton-likes of 0.1g/L are added to 2000mg/L red 1 solution of high-concentration acidic wastewater
Catalyst and 0.2mol/L hydrogen peroxide, regulation pH are heated to 70 DEG C to 3, while by solution, allow the system to react 210min, as a result
It is shown in Table 2.
Embodiment 3
（1）First, configure 0.5mol/L copper nitrate, manganese nitrate and cerous nitrate mixed solution (copper nitrate, manganese nitrate and
Nitric acid cerium concentration is respectively 0.5mol/L mixed solution) it is stand-by；
（2）Secondly, 2g MCM-41 are impregnated into repeatedly in the mixed solution of 50mL copper nitrates, manganese nitrate and cerous nitrate
（40g/L）6h is stirred, is then filtered, is dried；
（3）Then, by step（2）Middle gained sample is placed in Muffle furnace, and calcining 6h can obtain heterogeneous at 400 DEG C
Cu-Mn-Ce type Fenton catalysts；
（4）Then, the heterogeneous Cu-Mn-Ce Fenton-likes of 0.4g/L are added to 1500mg/L high concentration rhodamine B solution
Catalyst and 0.8mol/L hydrogen peroxide, regulation pH are heated to 80 DEG C to 5, while by solution, allow the system to react 210min, as a result
It is shown in Table 2.
Embodiment 4
（1）First, the mixed solution for configuring 0.5mol/L copper nitrate, manganese nitrate and cerous nitrate is stand-by；
（2）Secondly, 1g SBA-15 are impregnated into repeatedly in the mixed solution of 50mL copper nitrates, manganese nitrate and cerous nitrate
（20g/L）6h is stirred, is then filtered, is dried；
（3）Then, by step（2）Middle gained sample is placed in Muffle furnace, and calcining 6h can obtain heterogeneous at 300 DEG C
Cu-Mn-Ce type Fenton catalysts；
（4）Then, the heterogeneous Cu-Mn-Ce Fenton-likes of 0.2g/L are added to 1mg/L high concentration rhodamine B solution to urge
Agent and 0.4mol/L hydrogen peroxide, regulation pH are heated to 90 DEG C to 3, while by solution, allow the system to react 50min, as a result see
Table 2.
Embodiment 5
（1）First, configure 0.5mol/L copper nitrate, manganese nitrate and cerous nitrate mixed solution (copper nitrate, manganese nitrate and
Nitric acid cerium concentration is respectively 0.5mol/L mixed solution) it is stand-by；
（2）Secondly, 1g SBA-15 are impregnated into repeatedly in the mixed solution of 50mL copper nitrates, manganese nitrate and cerous nitrate
（20g/L）6h is stirred, is then filtered, is dried；
（3）Then, by step（2）Middle gained sample is placed in Muffle furnace, and calcining 6h can obtain heterogeneous at 300 DEG C
Cu-Mn-Ce type Fenton catalysts；
（4）Then, the heterogeneous Cu-Mn-Ce Fenton-likes of 0.2g/L are added to 2000mg/L red 1 solution of high-concentration acidic wastewater
Catalyst and 0.4mol/L hydrogen peroxide, regulation pH are heated to 70 DEG C to 7, while by solution, allow the system to react 210min, as a result
It is shown in Table 2.
Table 1 is the structural parameters of heterogeneous Cu-Mn-Ce type Fenton catalysts in embodiment 1.
Table 1
Table 2 is the decolorizing efficiency of embryonic stem-like cells system in embodiment 1-5.
Table 2
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Decolorizing efficiency | ＞ 99% | ＞ 65% | ＞ 85% | ＞ 99% | ＞ 65% |
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of heterogeneous Cu-Mn-Ce type Fenton catalysts, it is characterised in that comprise the following steps：
(1) copper nitrate, cerous nitrate and manganese nitrate mixed solution are configured；It is and each in sour copper, cerous nitrate and manganese nitrate mixed solution
The concentration of material is 0.1-1mol/L；
(2) meso pore silicon oxide material of high-sequential is impregnated in the mixed solution obtained by step (1) repeatedly, filter, wash,
Dry；The dosage of the meso pore silicon oxide material of wherein described high-sequential is 10-40g/L, dip time 4-8h；And institute
The meso pore silicon oxide material for stating high-sequential is MCM-41 or SBA-15；
(3) obtained material in step (2) is placed in Muffle furnace and calcined, obtain heterogeneous Cu-Mn-Ce Fenton-likes catalysis
Agent；Wherein calcining heat is 300-500 DEG C, calcination time 6h.
2. heterogeneous Cu-Mn-Ce type Fenton catalysts made from the preparation method described in a kind of claim 1.
3. heterogeneous Cu-Mn-Ce type Fenton catalysts according to claim 2, it is characterised in that described is heterogeneous
The pore size distribution range of Cu-Mn-Ce type Fenton catalysts is 2-10nm, specific surface area 200-600m2/ g, pore volume 0.2-
0.6cm3/g。
A kind of 4. purposes of the heterogeneous Cu-Mn-Ce catalyst treatments waste water from dyestuff described in claim 2, it is characterised in that
Comprise the following steps：Hydrogen peroxide is added in waste water from dyestuff and heterogeneous Cu-Mn-Ce catalyst forms embryonic stem-like cells system
Reacted.
5. purposes according to claim 4, it is characterised in that described dyestuff is one kind in rhodamine B or azogeramine
Or more than one, dye strength 1-2000mg/L.
6. purposes according to claim 4, it is characterised in that the dosage of the heterogeneous Cu-Mn-Ce catalyst is
0.1~0.4g/L；
Or the dosage of the hydrogen peroxide is 0.2-0.8mol/L；
Or described reaction temperature is 70-90 DEG C；PH value is 3-7 in described reaction；The reaction time is 50-210min.
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| CN106630102B (en) * | 2017-01-17 | 2020-04-14 | 武汉纺织大学 | Application and method for degrading organic wastewater by using Ce-OMS-2 catalyst |
| CN108273516B (en) * | 2017-10-12 | 2020-10-27 | 北京森泉伟业科技有限公司 | Method for preparing efficient catalyst by electrolytic manganese slag and catalyzing hydrogen peroxide to oxidize and degrade methylene blue |
| CN109046373B (en) * | 2018-07-24 | 2021-02-05 | 成都信息工程大学 | Magnetically separable heterogeneous Fenton-like catalyst CeO2Preparation method and application of/MZFS |
| CN111151289B (en) * | 2019-12-25 | 2022-12-06 | 浙江工商大学 | Manganese-based bimetallic oxide mesoporous material and preparation and application thereof |
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