CN105618129A - Zeolite Fenton catalyst containing isolated metal species as well as preparation method and application thereof - Google Patents
Zeolite Fenton catalyst containing isolated metal species as well as preparation method and application thereof Download PDFInfo
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- CN105618129A CN105618129A CN201510645926.0A CN201510645926A CN105618129A CN 105618129 A CN105618129 A CN 105618129A CN 201510645926 A CN201510645926 A CN 201510645926A CN 105618129 A CN105618129 A CN 105618129A
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Abstract
The invention belongs to the technical field of wastewater treatment catalyst preparation and particularly relates to a zeolite Fenton catalyst containing an isolated metal species as well as a preparation method and application thereof. The preparation method comprises the following steps: mixing zeolite with a metal chloride precursor solution to prepare a catalyst precursor; and then preparing the Fenton catalyst containing the isolated metal species with a freeze-drying method. According to the zeolite Fenton catalyst containing the isolated metal species prepared with the method, the tetra-coordinated isolated metal species content reaches up to 8.90%; in a process of degrading phenolic waste water, the catalyst has high phenol degradation catalysis efficiency and hydrogen peroxide utilization efficiency as well as low active species leakage amount; and the catalyst is simple in preparation process, low in device requirement and low in cost, can be produced on a large scale and is applied to an actual wastewater treatment process.
Description
Technical field
The invention belongs to wastewater treatment catalyst preparing technical field, be specifically related to a kind of zeolite Fenton Catalysts and its preparation method containing isolated metal species and application. This catalyst is removed for organic quick advanced oxidation in aqueous solution, and this catalyst, while improving organic matter degradation efficiency, also improves the hydrogen peroxide utilization ratio in course of reaction and reduces the amount of leakage of active specy.
Background technology
Bio-refractory class sewage, life and health safety and ecosystem to the mankind all constitute huge potential hazard. In all methods processing bio-refractory class sewage, Fenton method has rapidly and efficiently because of it, simple to operate, to subsequent treatment nonhazardous effect and the advantage such as environmentally friendly, of great interest in processing difficult for biological degradation sewage process.
There is a lot of defects in actual applications in traditional F enton oxidation technology, such as H2O2Utilization rate is low, and Fenton reaction must carry out in acid condition, and COD clearance instability and reaction produce a large amount of iron cement after terminating. In order to solve these difficult problems, a lot of scholars are try to exploitation heterogeneous Fenton catalysis technique to substitute traditional F enton technology. In the process of exploitation heterogeneous Fenton catalyst, many solid matrixs, such as zeolite, activated carbon and silicon dioxide etc., all it is used as the supporter of heterogeneous Fenton catalyst. In these supporters, zeolite has uniform hole dimension because of it, big specific surface area and controlled chemical characteristic etc. and be widely used as the supporter of Fenton catalyst. Generally, prepare the method that zeolite Fenton catalyst adopts and be mainly the post-processing technology of zeolite, namely first zeolite is put in the saline solution containing transition metal, then through obtaining metal oxide supported zeolite catalyst after high-temperature process. These catalyst generally contain only metal-oxide, in actual application, although some defects of conventional homogeneous Fenton technology can be overcome to a certain extent, but it is low to there is also catalytic rate, the defects such as the amount of leakage of active metal species is high and hydrogen peroxide utilization ratio is low.
Isolated metal species are a kind of catalytic site in zeolite with high catalytic activity. But, considerably less (the < 0.50% of content that preparation method containing isolated metal species zeolite catalyst is more complicated and isolated metal species are in zeolite catalyst, mass ratio), therefore, the exploitation simple preparation method just tool containing the isolated metal species zeolite catalyst of high concentration has very great significance. Additionally, zeolite catalyst containing isolated metal species substantially on be all based on the reduction reaction of nitrogen oxides and the research that carries out, there is presently no document and it carried out corresponding applied research in Fenton catalysis.
In sum, simply and efficiently prepare the zeolite catalyst containing the isolated metal species of high concentration, and it is applied in Fenton reaction, to realizing the rapidly and efficiently degraded of difficult for biological degradation sewage, improve the hydrogen peroxide utilization ratio in course of reaction and the recyclable performance of catalyst, there is huge theory value and application prospect.
Summary of the invention
An object of the present invention is to provide a kind of zeolite Fenton catalyst containing isolated metal species, it is characterised in that in described Fenton catalyst, and its composition is containing the isolated metal species of substantial amounts of four-coordination in zeolite supporter.
One of the present invention is containing isolated metal species zeolite Fenton catalyst, it is characterised in that in described catalyst, and the content of isolated metal species is up to 4.10��8.90%.
Transition metal or the multiple hybrid metal elements such as one of the present invention is containing isolated metal species zeolite Fenton catalyst, it is characterised in that in described catalyst, and the metal in isolated metal species generally refers to ferrum, cobalt, copper, nickel, manganese.
One of the present invention is containing isolated metal species zeolite Fenton catalyst, it is characterised in that in described catalyst, selected zeolite is the commercially zeolite such as 4A, 13X, Y, ZSM-5.
The two of the purpose of the present invention are to provide a kind of preparation method containing isolated metal species zeolite Fenton catalyst, its preparation process is as follows: first by the solution blending of zeolite molecular sieve Yu metal chloride presoma, in air bath agitator after vibration, through vacuum filtration, obtain catalyst precursor, prepare catalyst finally by cryodesiccated method.
The preparation method of a kind of zeolite Fenton catalyst containing isolated metal species of the present invention, it is characterised in that include step in detail below:
(1) preparation of catalyst precursor. By zeolite and metal chloride solutions (200��2000mg/L) in mass ratio 1: 5��1: 50 ratio blended, after the 2-5h that vibrates in air bath agitator, through vacuum filtration, it is thus achieved that catalyst precursor.
(2) preparation of catalyst. Being put into by catalyst precursor in freeze dryer, when-10 DEG C��-80 DEG C, freezing 12��48h, is prepared for the zeolite Fenton catalyst containing isolated metal species.
The three of the purpose of the present invention are to provide a kind of application containing isolated metal species zeolite Fenton catalyst, described containing under isolated metal species zeolite Fenton catalyst and the simultaneous condition of hydrogen peroxide, Fenton reaction is carried out, the pollutant in degrading waste water with the waste water containing phenol.
When the volume of waste water is 20��100ml, concentration is 20��200mg/L, pH when being 2.00��7.00, and the quality of the described zeolite Fenton catalyst containing isolated metal species is 0.10g��1.00g, and the consumption of required hydrogen peroxide is 20��100mol/L.
The usefulness of this method is mainly reflected in: (1) is during zeolite with metal precursor solution blending, metal ion in solution can be replaced with the aluminium cations site in zeolite, thus obtaining the zeolite catalyst presoma containing isolated metal species; (2) lyophilization can retain a large amount of isolated metal species in catalyst precursor, thus preparing the zeolite Fenton catalyst containing isolated metal species; (3) the isolated metal species in this catalyst, because it has relatively low ligancy, therefore just there is more empty coordination number of tracks, compared with comparative example, when carrying out the catalytic degradation reaction of phenol under identical condition, this shows higher phenol degrading speed and hydrogen peroxide utilization ratio and less active metal species amount of leakage; (4) the isolated metal species content in this catalyst is up to 8.90%, and the isolated metal species content very little (< 0.50%) in comparative example catalyst, this has very excellent catalytic performance in actual applications by making this catalyst; (5) catalyst preparation process is simple, and cost is low, environmental friendliness, and repeatable utilization, therefore can be mass-produced and is applied in actual sewage processing procedure.
Accompanying drawing explanation
Fig. 1. diffuse spectrogram for the solid UV, visible light of a kind of 4A zeolite Fenton catalyst containing isolated ferrum species of embodiment 1 preparation.
Fig. 2. for the infrared spectrogram of a kind of 4A zeolite Fenton catalyst containing isolated ferrum species of embodiment 1 preparation.
Specific embodiment of the present invention given below, but the present invention should not be limited by the examples:
Detailed description of the invention
Embodiment 1
(1) preparation of catalyst precursor. 10g4A zeolite and 2000mg/LFeCl3Solution mixes according to the ratio of mass ratio 1: 50, and after the 3h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 48h when-55 DEG C, thus being prepared for the 4A zeolite Fenton catalyst containing isolated ferrum species.
The solid UV, visible light of the 4A zeolite Fenton catalyst containing isolated ferrum species diffuses spectrogram as shown in Figure 1, occurring in that sharp-pointed absworption peak containing isolated ferrum species 4A zeolite Fenton catalyst at 209nm place, comparative example catalyst is then then very weak in the absorption at this place; In the scope of wavelength > 300nm, absorption intensity containing isolated ferrum species 4A zeolite Fenton catalyst is then less than comparative example catalyst, these phenomenons illustrate that ferrum species are mainly with ferrum oxygen tetrahedron [FeO containing in isolated ferrum species 4A zeolite Fenton catalyst4] the isolated ferrum species of form exists, and result of calculation show that the content of isolated ferrum species is 8.90%, and in comparative example catalyst, ferrum species are mainly and exist in the form of iron oxides. Accompanying drawing 2 is the infrared spectrum containing isolated ferrum species 4A zeolite Fenton catalyst, and this collection of illustrative plates further demonstrates containing in isolated ferrum species 4A zeolite Fenton catalyst, and ferrum species mainly exist with the tetrahedral isolated ferrum species of ferrum oxygen.
When the pH value of phenol solution is adjusted to 2.00, of the present invention containing isolated ferrum species 4A zeolite Fenton catalyst and comparative example catalyst, degradable phenol required time respectively 13.5min and 110min, the leakage rate of ferrum species and the utilization rate respectively 1.12mg/L of hydrogen peroxide in degradation process, 2.37mg/L and 38.55%, 18.27%.
Embodiment 2
(1) preparation of catalyst precursor. 5g4A zeolite and 2000mg/LFeCl3Solution mixes according to the ratio of 1: 5 (mass ratio), and after the 2h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 34h when-55 DEG C, thus being prepared for containing isolated ferrum species 4A zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 4.00, of the present invention containing isolated ferrum species 4A zeolite Fenton catalyst and comparative example catalyst, degrade 70% phenol required time respectively 8h and 10.3h, the utilization rate of hydrogen peroxide respectively 12.00%, 8.37% in degradation process.
Embodiment 3
(1) preparation of catalyst precursor. 10g4A zeolite and 200mg/LFeCl3Solution mixes according to the ratio of 1: 50, and after the 5h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. Preparation method is with embodiment 1.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated ferrum species 4A zeolite Fenton catalyst, after reaction 12h, the phenol of about 61.69% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Embodiment 4
(1) preparation of catalyst precursor. Preparation method is with embodiment 1.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 24h when-80 DEG C, thus being prepared for containing isolated ferrum species 4A zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated ferrum species 4A zeolite Fenton catalyst, after reaction 12h, the phenol of about 62.45% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Embodiment 5
(1) preparation of catalyst precursor. 10g13X zeolite and 2000mg/LFeCl3Solution mixes according to the ratio of 1: 50, and after the 3h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. Catalyst precursor after freezing 0.5h, is put in freeze dryer in refrigerator, the freezing 24h when-55 DEG C, thus containing isolated ferrum species 13X zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated ferrum species 13X zeolite Fenton catalyst, after reaction 12h, the phenol of about 48.43% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Embodiment 6
(1) preparation of catalyst precursor. Y zeolite and 2000mg/LCuCl2Solution mixes according to the ratio of 1: 50, and after the 3h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 34.5h when-55 DEG C, thus being prepared for containing isolated copper species Y zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated copper species Y zeolite Fenton catalyst, after reaction 12h, the phenol of about 46.24% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Embodiment 7
(1) preparation of catalyst precursor. ZSM-5 zeolite and 2000mg/LCoCl2Solution mixes according to the ratio of 1: 50, and after the 3h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 48h when-55 DEG C, thus being prepared for containing isolated cobalt species ZSM-5 zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated cobalt species ZSM-5 zeolite Fenton catalyst, after reaction 12h, the phenol of about 42.44% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Embodiment 8
(1) preparation of catalyst precursor. 4A zeolite and 2000mg/LFeCl3And CuCl2Solution mixes according to the ratio of 1: 50, and after the 3h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 34.5h when-55 DEG C, thus being prepared for containing isolated ferrum and copper species 4A zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated ferrum with copper species 4A zeolite Fenton catalyst, after reaction 12h, the phenol of about 70.23% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Embodiment 9
(1) preparation of catalyst precursor. 4A zeolite and 2000mg/LFeCl3��CuCl2And CoCl2Solution mixes according to the ratio of 1: 50, and after the 3h that vibrates in air bath agitator, through vacuum filtration, the solid collecting gained is catalyst precursor.
(2) preparation of catalyst. After freezing 0.5h, putting in freeze dryer by catalyst precursor in refrigerator, the freezing 34.5h when-55 DEG C, thus being prepared for simultaneously containing isolated ferrum, copper and cobalt species 4A zeolite Fenton catalyst.
When the pH value of phenol solution is adjusted to 6.30, for of the present invention containing isolated ferrum with cobalt species 4A zeolite Fenton catalyst, after reaction 12h, the phenol of about 78.45% can be degraded, and comparative example catalyst then Pyrogentisinic Acid is without degraded.
Comparative example
By the catalyst precursor of preparation in embodiment 1, under the air conditions of 500 DEG C, high-temperature process 6h, obtain comparative example catalyst, other conditions are all identical.
Claims (7)
1. the zeolite Fenton catalyst containing isolated metal species, it is characterised in that the composition of described Fenton catalyst is containing the isolated metal species of substantial amounts of four-coordination in zeolite supporter.
2. according to claim 1 containing isolated metal species zeolite Fenton catalyst, it is characterised in that in described catalyst, the content of isolated metal species is up to 4.10��8.90%.
3. according to claim 1 containing isolated metal species zeolite Fenton catalyst, it is characterised in that in described catalyst, transition metal or the multiple hybrid metal elements such as metal in isolated metal species generally refers to ferrum, cobalt, copper, nickel, manganese.
4. according to claim 1 containing isolated metal species zeolite Fenton catalyst, it is characterised in that in described catalyst, selected zeolite is the zeolite that 4A, 13X, Y, ZSM-5 etc. have be carried out commercially producing.
5. according to the arbitrary described preparation method containing isolated metal species zeolite Fenton catalyst of right 1��4, it is characterised in that comprise the steps:
(1) preparation of catalyst precursor. By blended according to the ratio of 1: 5��1: 50 (mass ratioes) to zeolite and metal chloride solutions (200��2000mg/L), after the 2-5h that vibrates in air bath agitator, through vacuum filtration, it is thus achieved that catalyst precursor.
(2) preparation of catalyst. Being put into by catalyst precursor in freeze dryer, freezing 12��48h when-10 DEG C��-80 DEG C, thus being prepared for the zeolite Fenton catalyst containing isolated metal species.
6. according to the arbitrary described application containing isolated metal species zeolite Fenton catalyst of right 1��4, described containing under isolated metal species zeolite Fenton catalyst and the simultaneous condition of hydrogen peroxide, Fenton reaction is carried out, the pollutant in degrading waste water with the waste water containing phenol.
7., when the volume of waste water is 20��100ml, concentration is 20��200mg/L, pH when being 2.00��7.00, and the quality of the described zeolite Fenton catalyst containing isolated metal species is 0.10g��1.00g, and the consumption of required hydrogen peroxide is 20��100mol/L.
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Cited By (5)
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| CN106732747A (en) * | 2016-11-28 | 2017-05-31 | 天津工业大学 | A kind of molecular sieve fenton catalyst and high-efficiency synthesis method for eliminating organic dyestuff pollution |
| CN109529868A (en) * | 2018-11-07 | 2019-03-29 | 潍坊职业学院 | A kind of ferrimanganic cobalt codope support type fenton catalyst, preparation method and applications |
| CN109999906A (en) * | 2019-04-12 | 2019-07-12 | 天津工业大学 | Load isolated iron species/polyalcohol stephanoporate Fenton catalytic membrane, preparation method and its application |
| CN110560168A (en) * | 2019-09-30 | 2019-12-13 | 天津工业大学 | Core-shell hierarchical iron/copper bimetallic Fenton catalyst and preparation method and application thereof |
| CN112108185A (en) * | 2019-06-19 | 2020-12-22 | 中国科学院大连化学物理研究所 | Preparation of iron-based catalyst with metal organic framework loaded with isolated sites and application of iron-based catalyst in reaction for preparing methanol by directly converting methane |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732747A (en) * | 2016-11-28 | 2017-05-31 | 天津工业大学 | A kind of molecular sieve fenton catalyst and high-efficiency synthesis method for eliminating organic dyestuff pollution |
| CN109529868A (en) * | 2018-11-07 | 2019-03-29 | 潍坊职业学院 | A kind of ferrimanganic cobalt codope support type fenton catalyst, preparation method and applications |
| CN109999906A (en) * | 2019-04-12 | 2019-07-12 | 天津工业大学 | Load isolated iron species/polyalcohol stephanoporate Fenton catalytic membrane, preparation method and its application |
| CN109999906B (en) * | 2019-04-12 | 2020-12-15 | 天津工业大学 | Isolated iron species/polymer loaded porous Fenton catalytic membrane, and preparation method and application thereof |
| CN112108185A (en) * | 2019-06-19 | 2020-12-22 | 中国科学院大连化学物理研究所 | Preparation of iron-based catalyst with metal organic framework loaded with isolated sites and application of iron-based catalyst in reaction for preparing methanol by directly converting methane |
| CN112108185B (en) * | 2019-06-19 | 2021-08-31 | 中国科学院大连化学物理研究所 | Preparation of iron-based catalyst with metal organic framework loaded with isolated sites and application of iron-based catalyst in reaction for preparing methanol by directly converting methane |
| CN110560168A (en) * | 2019-09-30 | 2019-12-13 | 天津工业大学 | Core-shell hierarchical iron/copper bimetallic Fenton catalyst and preparation method and application thereof |
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Application publication date: 20160601 |