CN113231059A - Composite catalyst for electron beam sewage treatment and preparation method and application thereof - Google Patents
Composite catalyst for electron beam sewage treatment and preparation method and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 49
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
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- 229910052738 indium Inorganic materials 0.000 claims description 19
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- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
-
- B01J35/40—
-
- B01J35/613—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/305—Treatment of water, waste water, or sewage by irradiation with electrons
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention relates to the field of catalysts, in particular to a composite catalyst, a preparation method thereof, a method for degrading a high-molecular organic compound by using the composite catalyst, and application of the method in treatment of wastewater and solid waste containing the high-molecular compound. The composite catalyst comprises a catalyst main body and a modification factor loaded on the catalyst main body; wherein the catalyst body comprises In2O3Hollow nanotubes, the modification factor comprising Pd. The composite catalyst can be used for catalyzing and degrading organic polymer with electron beam irradiationThe compound has good degradation effect especially for high-concentration organic compounds and macromolecular organic matters which are difficult to degrade and have long chains, and has low cost, high speed and high efficiency; the method is particularly suitable for sewage treatment and waste treatment, so that the organic pollutants are thoroughly degraded to the discharge standard, and the method has the advantages of good economy, no risk of newly-increased dangerous waste and salinity and the like.
Description
Technical Field
The invention relates to the field of catalysts, and particularly relates to a composite catalyst and a preparation method and application thereof.
Background
High-concentration and difficult-to-degrade macromolecular organic matters exist in sewage and landfill leachate in chemical industrial parks. With the implementation of policies such as 'ten items of water', advanced treatment of difficultly degraded sewage to reach environmental emission standards becomes an important requirement in the industry. At present, a membrane filtration method is adopted, pollutants in sewage are mainly subjected to membrane separation, 40% -60% of clear water after membrane separation reaches the standard and is discharged, and concentrated water formed by enrichment of residual pollutants is difficult to obtain effective treatment and discharge. For example, the landfill leachate membrane treatment process comprises the following steps: the process flow of biochemistry, ultrafiltration, nanofiltration and Reverse Osmosis (RO) is adopted, so that the investment is large, the treatment capacity is small, and the treatment efficiency is low. Particularly, concentrated water generated in the sewage membrane treatment process is usually used as landfill leachate after being recharged to a landfill for secondary adsorption, and the process flow is repeated; after the operation for a period of time, part of the concentrated water in the recharging landfill site loses the secondary adsorption capacity, so that the concentration of the landfill leachate is higher and higher, and the treatment difficulty is higher and higher. And the ultrahigh water inlet concentration causes the membrane system to carry out back washing operation frequently, the service life of the membrane treatment system is shortened, the yield of the produced clear water is gradually reduced, and the operation and maintenance cost is continuously improved.
On the other hand, the traditional processes represented by fenton, catalytic ozonation and biochemical treatment have significant technical bottlenecks: 1. most of the long-chain polluted organic matters are difficult to achieve the degradation target through a sewage biochemical process; 2. long-chain organic pollutants can not be used as nutrient substances of microorganisms in the sewage biochemical process, and a large amount of carbon sources are added to maintain the operation of a biochemical system; 3. the single-stage Fenton and ozone catalytic oxidation have low treatment efficiency on most long-chain polluted organic matters, and in order to achieve the treatment target, a multi-stage treatment unit needs to be built, so that the sewage treatment process has the problems of long flow, high treatment cost, complex operation, poor stability and the like; 4. in the single-stage Fenton and ozone catalytic oxidation process, a large amount of chemical agents are required to be added, a large amount of hazardous waste sludge is generated in the treatment process, the hazardous waste treatment cost is increased, and meanwhile, the risk of environmental hidden danger is increased; 5. dissolved oxidants and the like are used in a large amount in the Fenton and ozone catalytic oxidation process, so that the salinity and other toxic and harmful components in the sewage are increased, the process unit can only be used as a tail end treatment unit, the ecological damage of tail water discharge to a receiving water body is obvious, and the discharge standard is difficult to reach in the environment with salinity requirement on discharge.
It can be seen that one of the major problems facing the current field of wastewater treatment is: when processing high molecular compounds, the method has the difficulties of difficult degradation, high cost, complex process, secondary pollution brought by the processing process and the like. Therefore, it is important to develop a method for treating a polymer compound simply and efficiently.
Disclosure of Invention
The invention aims to overcome the defects of difficult degradation, high cost, complex working procedures, secondary pollution caused by a treatment process and the like of the conventional method for degrading a high molecular compound, and provides a composite catalyst, a preparation method and application thereof. The composite catalyst can be used for catalyzing and degrading high-molecular organic compounds in cooperation with electron beam irradiation, has a good degradation effect especially on high-concentration organic compounds, difficultly-degraded and long-chain high-molecular organic matters, and is low in cost, rapid and efficient; the method is particularly suitable for treating waste water and wastes, so that the organic pollutants are thoroughly degraded to the discharge standard, and the method has the advantages of good economy, no risk of newly-increased dangerous wastes and salinity and the like.
The inventors of the present invention found that In prepared by the prior art2O3Carriers are often non-uniform in size, difficult to control in size, and small in specific surface area; and thus the particles supported thereon are often non-uniform and of larger size, with lower actual loadings. Based on this, the inventors of the present invention have conducted intensive studies and found a technical solution of the present invention; the inventor of the invention further finds that the composite catalyst is particularly suitable for catalysis under the action of electron beam irradiation, can efficiently degrade high molecular compounds, and has wide application in fields of wastewater/solid treatment and the likeHas wide application prospect.
The first aspect of the present invention provides a composite catalyst comprising a catalyst main body and a modification factor supported on the catalyst main body; wherein the catalyst body comprises In2O3Hollow nanotubes, the modification factor comprising Pd.
Preferably, the In2O3The average diameter of the hollow nanotubes is 20nm to 10 μm, preferably 400nm to 1 μm.
Preferably, the In2O3The average length of the hollow nanotubes is between 100nm and 10 μm, preferably between 500nm and 5 μm.
Preferably, the specific surface area of the composite catalyst is 1-100m2A/g, preferably from 20 to 60m2A/g, more preferably 30 to 40m2/g。
Preferably, the particles of Pd have an average diameter of 1 to 10nm, preferably 2 to 4 nm.
Preferably, the loading of Pd in the composite catalyst is 0.1 to 5 wt%, preferably 1.5 to 2.5 wt%. The weight is based on the weight of Pd element.
The form of the Pd present in the composite catalyst is determined according to the specific preparation process, and may include the simple substance of Pb, and various oxides and salts (e.g., carbonate), etc. The presence does not significantly affect the catalytic effect, and preferably 50 mol% or more is present in the elemental form.
The composite catalyst of the present invention can be prepared In accordance with the art2O3The conventional application mode of the catalyst is used for catalysis.
The inventor of the invention further finds that the composite catalyst is particularly suitable for being matched with electron beam irradiation to catalytically degrade macromolecular organic compounds. The composite catalyst of the invention can achieve better effect than the conventional application mode in the novel application mode.
Therefore, preferably, the catalyst is a catalyst for catalytically degrading a high molecular organic compound in cooperation with electron beam irradiation.
For example, the energy of electron beam irradiation is 1-10MeV, and the beam intensity is 80-300 mA.
For example, the energy of electron beam irradiation is 2-3MeV, and the beam intensity is 100-200 mA.
The electron beam irradiation mode can be continuous irradiation or pulse irradiation; for example, pulse irradiation, with a single irradiation time of 0.01 to 2s (more preferably 0.5 to 1s) at intervals of 1 to 60s (preferably 3 to 10 s).
The pulse frequency can be adjusted according to the content of the high molecular organic compound, and under the normal condition, for example, when the sewage of most sewage treatment plants is treated, the pulse frequency is 1-3 times; for the sewage (the content of the high molecular organic compound is not too high) of a common sewage treatment plant, the irradiation is carried out for 1 time.
The actual irradiation time of the electron beam may be 0.1 to 5s, preferably 0.5 to 2 s. The term "actual irradiation time" refers to an interval time when irradiation is not performed (for example, when pulse irradiation is performed) is not calculated.
Under the environment that the electron beam generates free radicals, the material to be treated and the catalyst can be continuously contacted for 2s-10min, preferably 0.5-5 min. Namely, the effect of effectively degrading the high molecular organic compound can be achieved.
The amount of the composite catalyst can be adjusted within a wide range according to a specific degradation object.
For example, the amount of the catalyst used may be 0.1 to 5g, preferably 100-500mg, per L of the wastewater containing 1000mg/L of the high molecular weight organic substance having a molecular weight of more than 5 KDa.
The catalyst is matched with the electron beam under the optimal condition, so that the use effect of degrading the high-molecular organic compound by using the catalyst and electron beam irradiation in a matching way can be further improved, and the high-molecular organic compound with high concentration, difficult degradation and long chain can be more easily degraded.
The application range of the catalyst of the invention is not particularly limited to the range of the 'macromolecular organic compounds', and the catalyst has catalytic degradation effect on various macromolecular organic compounds, such as some organic compounds which are common in wastewater with high COD. The molecular weight of the "polymer" is not particularly limited, but any organic compound which can be degraded or needs to be degraded is understood as a "polymer" from the viewpoint of the function of the catalyst of the present invention, for example, having a molecular weight of 5kDa or more.
In a second aspect, the present invention provides a method for preparing the composite catalyst of the first aspect of the present invention, the method comprising the steps of:
(1) preparing an indium sacrificial template;
(2) calcining the indium sacrificial template to obtain In2O3A hollow nanotube;
(3) putting the In2O3The hollow nanotube, a palladium source and a reducing agent are contacted, and the obtained material is roasted.
In the step (1), the indium sacrificial template may use commercially available MIL-68 (In).
In step (1), preferably, the indium sacrificial template is obtained by a preparation process comprising: the indium salt is used as a raw material and is prepared by a solvothermal method.
In the step (1), preferably, the process of preparing the indium sacrificial template comprises: carrying out hydrothermal reaction on a mixed material of indium salt, phthalic acid and N, N-Dimethylformamide (DMF).
Preferably, the indium salt, phthalic acid and N, N-dimethylformamide are used in a ratio of (0.3g to 0.5 g): (0.15g-0.25 g): (4mL-6mL), more preferably (0.35g-0.45 g): (0.18g-0.22 g): (4.5mL-5.5 mL).
The hydrothermal reaction can be carried out under normal pressure, and therefore the temperature of the hydrothermal reaction is about 100 ℃.
The concentration of the indium salt in the aqueous solution of the hydrothermal reaction is, for example, 0.01 to 0.15 g/mL.
Preferably, the hydrothermal reaction time is 18h to 30h, more preferably 20h to 28 h.
The indium salt may be an inorganic salt of various kinds of indium, for example, indium nitrate.
The phthalic acid is, for example, terephthalic acid and/or isophthalic acid, preferably terephthalic acid.
In the step (2), the calcining process comprises a temperature rising stage and a stabilizing stage; wherein the temperature raising stage comprises: the temperature rising rate is 1-15 ℃/min (preferably 3-8 ℃/min), and the temperature end point is 400-600 ℃ (preferably 450-550 ℃); the stabilization phase comprises: keeping for 1-3h (preferably 1.5-2.5h) at 400-600 deg.C (preferably 450-550 deg.C).
In the step (2), it is further preferable that the temperature raising phase includes a first temperature raising phase, a second temperature raising phase and a third temperature raising phase; wherein, the temperature rising rate of the first temperature rising stage is 1-4 ℃/min (preferably 2-3 ℃/min), and the temperature end point is 150-; the temperature rise rate of the second temperature rise stage is 5-8 ℃/min (preferably 5-6 ℃/min), and the temperature end point is 350-450 ℃ (preferably 400-430 ℃); the temperature rise rate of the third temperature rise stage is 2-6 ℃/min (preferably 4-5 ℃/min), and the temperature end point is 400 ℃ -600 ℃ (preferably 450 ℃ -550 ℃). More preferably, the difference between the temperature increase rates of the adjacent stages is 1 ℃/min or more. The present inventors have conducted extensive studies and found that In can be obtained by such a specific temperature raising process2O3The nano tube has higher specific surface area and can more uniformly load Pd particles; and can make In2O3Hollow nanotubes consist of smaller particles and have a certain roughness on the surface.
Preferably, the method of the present invention further comprises: the indium sacrificial template is pre-fired under vacuum conditions prior to calcination. The inventors of the present invention have found that the operation of this calcination enables In to be obtained2O3The hollow nanotubes have a more uniform size distribution.
Preferably, the burn-in conditions include: the vacuum degree is 100Pa-150Pa, the temperature is 100 ℃ to 150 ℃, and the time is 8h-16 h; more preferably, the burn-in conditions include: the vacuum degree is 110-130Pa, the temperature is 110-130 ℃, and the time is 10-14 h.
In the step (3), the In2O3The weight ratio of the hollow nanotube, the palladium source in Pd and the reducing agent is 100 mg: (10mmol-30 mmol): (50-150mmol), more preferably 100 mg: (12mmol-25 mmol): (80-120 mmol).
In step (3), preferably, the contacting comprises: firstly, In is2O3After the hollow nanotube is contacted with the palladium source for a period, the hollow nanotube is contacted with the reducing agent. Preferably, the In is first introduced2O3The hollow nanotubes are contacted with the palladium source for 0.5 to 3 hours (preferably 0.8 to 1.5 hours).
Preferably, the In is applied before the contacting is performed2O3The hollow nanotubes are first dispersed under ultrasonic conditions.
Preferably, the conditions of the calcination include: the roasting temperature is 300-500 ℃, and the roasting time is 3-5 h; more preferably, the conditions of the calcination include: the roasting temperature is 350-450 ℃, and the roasting time is 3.5-4.5 h.
The palladium source may be selected from Na2PdCl4、PdCl2And Pd (NO)3)2Preferably Na2PdCl4。
Preferably, the reducing agent is selected from NaBH4Tannic acid, tetrabutylammonium borohydride and one or more of the following, preferably NaBH4。
The third aspect of the invention also provides the composite catalyst prepared by the method of the second aspect.
The fourth aspect of the invention also provides the application of the composite catalyst in degrading high molecular organic compounds and/or in sewage treatment in cooperation with electron beams.
The method of the invention can be applied to various fields needing to degrade high molecular organic compounds, such as the recycling of high molecular organic compounds, the preparation of small molecular substances by the high molecular organic compounds, the treatment of wastewater/solid containing high concentration of the high molecular organic compounds, and the like. The method can be further matched with a conventional waste treatment mode, for example, the comprehensive treatment is carried out by combining treatment processes such as Fenton, ozone catalytic oxidation, biochemical treatment and the like, and the better treatment effect can be realized by lower cost and simpler operation. By the treatment of the method, the high molecular organic compound can be degraded into small molecular substances with the molecular weight of below 1000.
Through the technical scheme, compared with the prior art, the invention at least has the following advantages:
(1) in of the composite catalyst of the present invention2O3The size of the nano tube is uniform;
(2) in of the composite catalyst of the present invention2O3The Pd particles loaded on the nanotube have uniform size, high loading amount and uniform distribution;
(3) the composite catalyst is particularly suitable for catalysis under the action of electron beam irradiation, and can degrade high molecular compounds more efficiently compared with a conventional catalysis mode.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Drawings
FIG. 1 shows In prepared In example 12O3Scanning Electron Microscope (SEM) images of hollow nanotubes, wherein fig. 1a, 1b and 1c represent different magnifications.
FIG. 2 shows In prepared In example 12O3Transmission Electron Microscopy (TEM) images of hollow nanotubes, where fig. 2a and 2b represent different magnifications.
Detailed Description
The present invention will be described in detail below by way of examples. The described embodiments of the invention are only some, but not all embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents used in the following examples are all commercially available analytical reagents unless otherwise specified.
The following group a examples are presented to illustrate the composite catalyst of the present invention.
Example A1
(1) Weighing 5ml of DMF solution in a hydrothermal reaction kettle, adding 0.4g of indium nitrate and 0.2g of terephthalic acid, reacting at 100 ℃ for 24 hours, and centrifugally drying to obtain an indium sacrificial template;
(2) carrying out heat treatment on the indium sacrificial template obtained in the step (1) for 12h under the vacuum condition that the vacuum degree is 120Pa and the temperature is 120 ℃; then transferring the mixture into a muffle furnace, raising the temperature to 500 ℃ at the temperature rise rate of 5 ℃/min, and continuing calcining for 2h to obtain In with a hollow structure2O3A nanotube;
(3) 100mg of In was measured2O3Adding 10mL deionized water, performing ultrasonic treatment for 10min, uniformly dispersing the sample, and adding 12mL Na with concentration of 1.6M2PdCl4The solution is stirred for 1h, and then 100mL of NaBH reducing agent with the concentration of 1mol/L is added4(ii) a And placing the obtained material in a roasting furnace at 400 ℃ for roasting and activating for 4 hours to obtain a powdery composite catalyst, which is marked as A1.
For In obtained In the step (2)2O3The hollow nanotubes were observed by Scanning Electron Microscopy (SEM), the results are shown in fig. 1, and they were observed by Transmission Electron Microscopy (TEM), the results are shown in fig. 2. As can be seen from FIGS. 1 and 2, In of the present invention2O3The diameter and length distribution of the hollow nanotubes were very uniform, and it can be seen that In was present2O3The hollow nanotubes have uniform particle size and significant roughness. The specific surface area was found to be 36m by BET instrument (Micromeritics, Tristar II 3020)2/g。
Example A2
(1) Measuring 4.5ml of DMF solution in a hydrothermal reaction kettle, adding 0.35g of indium nitrate and 0.18g of terephthalic acid, reacting at 100 ℃ for 22 hours, and then centrifugally drying to obtain an indium sacrificial template;
(2) carrying out heat treatment on the indium sacrificial template obtained in the step (1) for 11h under the vacuum condition that the vacuum degree is 130Pa and the temperature is 110 ℃; then transferring the mixture into a muffle furnace, and heating the mixture to 480 ℃ at a heating rate of 4 ℃/minAnd continuously calcining for 2.2h to obtain In with a hollow structure2O3A nanotube;
(3) 100mg of In was measured2O3Adding 10mL deionized water, performing ultrasonic treatment for 10min, uniformly dispersing the sample, and adding 7mL Na with concentration of 2M2PdCl4The solution is stirred for 0.8h, and then 100mL of NaBH reducing agent with the concentration of 1.2mol/L is added4(ii) a And placing the obtained material in a roasting furnace at 350 ℃ for roasting and activating for 4.5 hours to obtain a powdery composite catalyst, which is marked as A2. The specific surface area was found to be 35m2/g。
Example A3
(1) Weighing 5.5ml of DMF solution in a hydrothermal reaction kettle, adding 0.45g of indium nitrate and 0.22g of terephthalic acid, reacting at 100 ℃ for 26 hours, and then centrifugally drying to obtain an indium sacrificial template;
(2) carrying out heat treatment on the indium sacrificial template obtained in the step (1) for 14h under the vacuum condition that the vacuum degree is 115Pa and the temperature is 130 ℃; then transferring the mixture to a muffle furnace, heating to 190 ℃ at the speed of 2 ℃/min, heating to 420 ℃ at the speed of 6 ℃/min, heating to 500 ℃ at the speed of 4 ℃/min, and continuously calcining for 2h to obtain In with a hollow structure2O3A nanotube;
(3) 100mg of In was measured2O3Adding 10mL deionized water, performing ultrasonic treatment for 10min, and adding 10mL Na with concentration of 1.6M after the sample is uniformly dispersed2PdCl4The solution is stirred for 1.5h, and 40mL of NaBH reducing agent with the concentration of 2mol/L is added4(ii) a And placing the obtained material in a roasting furnace at 450 ℃ for roasting and activating for 3.5 hours to obtain a powdery composite catalyst, which is marked as A3. The specific surface area was found to be 34m2/g。
Example A4
A composite catalyst was prepared by reference to the procedure of example A1, except that step (1) was not performed, and commercially available MIL-68(In) was used as the sacrificial template for indium.
The composite catalyst was finally obtained and was designated as A4.
Example A5
A composite catalyst was prepared by referring to the method of example A1, except that, in step (1), the hydrothermal reaction was changed to be carried out under pressurized conditions, thereby adjusting the temperature to 140 ℃ and the time to 6 hours.
The composite catalyst was finally obtained and was designated as A5.
Example A6
A composite catalyst was prepared by referring to the method of example A1, except that in step (2), the vacuum heat treatment operation was omitted and the sacrificial indium template obtained in step (1) was directly placed in a muffle furnace for calcination.
The composite catalyst was finally obtained and was designated as A6.
Example A7
A composite catalyst was prepared by reference to the procedure of example A1, except that no reducing agent was added and hydrochloric acid was added instead to adjust the pH of the solution to 3.
The composite catalyst was finally obtained and was designated as A7.
Comparative example AD1
In prepared In step (2) of example 12O3The hollow nanotubes act as a catalyst, and no longer support Pd. Denoted catalyst AD 1.
Comparative example AD2
With reference to example 1, except that In2O3The Pd supported on the hollow nanotubes is replaced by Zn. Specifically, Na is added in step (3)2PdCl4The same molar amount of zinc nitrate was substituted.
The final composite catalyst was obtained and was designated AD 2.
The following group B of application examples are provided to illustrate the method of the present invention for catalytically degrading a high molecular weight organic compound.
In order to illustrate that the catalyst of the invention is not limited to specific compounds, the liquid to be treated adopted by the invention is a high-concentration high-molecular organic compound obtained by primarily treating sewage discharged by a printing and dyeing mill. The following application examples and comparative examples all used the same liquid to be treated.
In 1dm2The stainless steel sieve plate is respectively loaded with the catalysts obtained in the application examples and the comparative examples for standby.
Application example B1
A1 dm X1.5 dm container was charged with a stainless steel mesh plate loaded with 100mg of catalyst A1 at a distance of 0.5dm from the bottom surface, and 1L of the solution to be treated was poured.
The container was irradiated with electron beams of 2.5MeV and 100mA in beam intensity. Irradiating the electron beam for 0.5s, and then irradiating the electron beam for 0.5s again after 30s intervals; and then, continuously contacting the liquid to be treated with the catalyst for 3min, pouring out the liquid, and sampling for detection.
Application examples B2-B7
Reference was made to application example B1, except that application examples B2-B7 replaced the stainless steel screen plates loaded with catalyst a1 with stainless steel screen plates loaded with a2-a7, respectively.
After the treatment, respectively sampling and detecting.
Comparative example BD1
Reference application example B1 was carried out with the exception that the stainless steel sieve plate loaded with catalyst a1 was replaced with a stainless steel sieve plate loaded with AD 1.
And sampling and detecting after the treatment.
Comparative example BD2
Reference application example B1 was carried out with the exception that the stainless steel sieve plate loaded with catalyst a1 was replaced with a stainless steel sieve plate loaded with AD 2.
And sampling and detecting after the treatment.
Comparative example BD3
A1 dm X1.5 dm container was charged with a stainless steel mesh plate loaded with catalyst A1 at a distance of 0.5dm from the bottom surface, and 1L of the liquid to be treated was poured.
The liquid to be treated is not irradiated with an electron beam but is irradiated with light. Specifically, the container was irradiated with a 300W UV lamp for 120 minutes.
And sampling and detecting after the treatment.
Comparative example BD4
The reference application example B1 was carried out, except that no catalyst was used and only electron beam irradiation was carried out.
And sampling and detecting after the treatment.
Test example
The treated solutions obtained in group B of the application examples were checked for the content (mg/L) of high molecular weight organic substances having a molecular weight of more than 5kDa and the average molecular weight (kDa) of the organic substances in the solutions by gel chromatography and mass spectrometry, respectively, and the results are shown in Table 1.
TABLE 1
It can be seen from table 1 that, under the catalysis of the catalyst of the present invention, the high molecular organic compound can be effectively degraded into low molecular organic compound in a short time, and the effect is significantly better than that of the comparative example.
Application example C1
The catalyst and the electron beam irradiation method are used for treating organic sewage.
After the sewage of a certain synthetic leather enterprise is subjected to primary pretreatment, the indexes of the sewage are that the pH is 8.5, the COD is 3000mg/L and NH4The content of N is 100mg/L, the SS is 90mg/L and the chroma is 90 times. The wastewater was subjected to ultra-magnetic separation and then to electron beam irradiation in the manner described in example B1. Then, the sewage enters an A/O biochemical treatment, and a contact oxidation method is adopted in an O tank; the contact oxidation method is preferably combined with filling. Wherein the first-stage A biochemical residence time is 24 hours, the first-stage O biochemical residence time is 24 hours, the second-stage A biochemical residence time is 24 hours, and the second-stage O biochemical residence time is 24 hours.
And finally, the sewage enters an active sand filter to remove residual pollutants, so that the sewage reaches the environmental protection discharge standard of the first class A.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A composite catalyst, characterized in that the composite catalyst comprises a catalyst body and a modification factor supported on the catalyst body; wherein the catalyst body comprises In2O3Hollow nanotubes, the modification factor comprising Pd.
2. The composite catalyst according to claim 1, wherein the loading of the Pd in the composite catalyst is 0.1-5 wt%, preferably 1.5-2.5 wt%.
3. The composite catalyst according to claim 1 or 2, wherein the specific surface area of the composite catalyst is 1 to 100m2/g；
Preferably, the In2O3The average diameter of the hollow nano-tube is 20nm-10 μm, and the average length is 100nm-10 μm;
preferably, the Pd particles have an average diameter of 1-10 nm.
4. The composite catalyst according to claim 1, wherein the catalyst is a catalyst for catalytically degrading a high molecular organic compound in cooperation with electron beam irradiation.
5. A method of preparing the composite catalyst of any one of claims 1-4, comprising the steps of:
(1) preparing an indium sacrificial template;
(2) calcining the indium sacrificial template to obtain In2O3A hollow nanotube;
(3) putting the In2O3The hollow nanotube, a palladium source and a reducing agent are contacted, and the obtained material is roasted.
6. The method of claim 5, wherein in the step (1), the indium sacrificial template preparation process comprises: carrying out hydrothermal reaction on a mixed material of indium salt, phthalic acid and N, N-dimethylformamide;
preferably, the indium salt, phthalic acid and N, N-dimethylformamide are used in a ratio of (0.3g to 0.5 g): (0.15g-0.25 g): (4mL-6 mL);
preferably, the hydrothermal reaction time is 18h-30 h.
7. The method of claim 5, wherein in step (2), the calcining comprises a temperature-raising stage and a stabilizing stage; wherein the temperature raising stage comprises: the temperature rising rate is 1-15 ℃/min, and the temperature end point is 400-600 ℃; the stabilization phase comprises: keeping the temperature at 400-600 ℃ for 1-3 h.
8. The method of claim 5 or 7, wherein the method further comprises: pre-burning the indium sacrificial template under a vacuum condition before calcining;
preferably, the burn-in conditions include: the vacuum degree is 100Pa-150Pa, the temperature is 100 ℃ to 150 ℃, and the time is 8h to 16 h.
9. The method of claim 5, wherein, In step (3), the In2O3The weight ratio of the hollow nanotube, the palladium source in Pd and the reducing agent is 100 mg: (10mmol-30 mmol): (50-150 mmol);
preferably, the conditions of the calcination include: the roasting temperature is 300-500 ℃, and the roasting time is 3-5 h;
preferably, the palladium source is selected from Na2PdCl4、PdCl2And Pd (NO)3)2One or more of (a).
10. A composite catalyst prepared according to the method of any one of claims 5 to 9.
11. Use of the composite catalyst of any one of claims 1 to 4 or 10 in the degradation of high molecular organic compounds in conjunction with electron beam and/or in wastewater treatment.
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| CN113880187A (en) * | 2021-09-03 | 2022-01-04 | 厦门大学 | Treatment process for treating organic sewage by using electron beam irradiation and catalyst |
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