CN108837843A - A kind of Bimetallic Zeolite Catalyst and its preparation and application - Google Patents
A kind of Bimetallic Zeolite Catalyst and its preparation and application Download PDFInfo
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- CN108837843A CN108837843A CN201810670841.1A CN201810670841A CN108837843A CN 108837843 A CN108837843 A CN 108837843A CN 201810670841 A CN201810670841 A CN 201810670841A CN 108837843 A CN108837843 A CN 108837843A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
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Abstract
The present invention proposes a kind of Bimetallic Zeolite Catalyst, is two kinds in Mn, Ce, Co, Ni of the metal with two kinds of metal-modified KIT-6 molecular sieve catalysts, and the molar ratio of Si and each modified metal is 10~60 independently of each other.The present invention also proposes the preparation method and application of the Bimetallic Zeolite Catalyst.Compared with traditional supported catalysts, metal oxide enters in skeleton the present invention, be combined with each other more secured, metal ion is not easy to dissolve out, catalyst performance stabilised.Metallic molecule sieve catalyst prepared by the present invention has unique three-dimensional cubic duct, and hole wall thickness, aperture is big, duct is mutually communicated and the orderly opening substance that is conducive to is spread, and reduces internal mass transfer resistance, is not easy to plug duct.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of catalyst and its preparation with metal-modified modification
And application.
Background technique
PPCPs refers to drug and personal care product, the representative species in the waste water containing PPCPs have antimicrobial,
Antipyretic analgesic anti-inflammatory drug, estrogen and other drugs (such as lipid regulating agent, antiepileptic, tranquillizer, contrast agent) and makeup
Common fragrance in product.Carbamazepine has wide spectrum drug effect, is not only the choice drug of anti-epileptic, is also usually utilized to treatment suppression
The diseases such as strongly fragrant, arrhythmia cordis are widely used because its drug effect is significant.Carbamazepine is entered by pharmaceutical factory waste water and body metabolism
Environment detects the presence of carbamazepine in sewage treatment plant, surface water even drinking water.As research finds Karma
Xiping also has some side effects such as nausea and vomiting, food while having good therapeutic effect to diseases such as epilepsy, depression, arrhythmia cordis
It is intended to change, dysfunction of liver and skin lesion etc., has become one of PPCPs pollutant of greatest concern at present.Research
Personnel point out that this kind of drug is relatively stable, are difficult during sewage treatment and drinking water treatment raw by activated sludge and film
The standard biologics method for treating water such as object reactor is effectively removed.
Ozone is as a kind of novel green clean oxidation technology, because it is with strong oxidizing property and disinfecting power, in water
Process field is widely used.But since independent ozone exists to pollutant oxidation with selective, ozone utilization rate is low, is difficult to
The defects of thorough mineralising pollutant, is restricted the application of this technology to a certain extent.Catalytic ozonation is
Ozone molecule is promoted to decompose the generation stronger hydroxyl radical free radical isoreactivity intermediate of oxidisability using catalyst to strengthen ozone oxygen
Change ability, the hydroxyl radical free radical oxidability that catalysis ozone generates are stronger and to pollutant non-selectivity.O3 catalytic oxidation skill
The key of art is the research and development and preparation of high activated catalyst.
Mesostructured material, SBA-15, KIT-6 etc. are due to specific surface area is high, cellular structure is orderly, hydro-thermal is steady
The advantages that qualitative high, is widely used in absorption, separation and catalytic field.Compared to MCM-41 and SBA-15, KIT-6 has only
Special three-dimensional cubic duct, hole wall thickness, aperture is big, duct is mutually communicated and the orderly opening substance that is conducive to is spread, and reduces internal
Resistance to mass tranfer is not easy to plug duct.But pure KIT-6 is neutral backbone and active site is few.
Summary of the invention
For shortcoming existing for this field, an object of the present invention is to propose a kind of bimetallic molecular sieve catalytic
Agent.
Second object of the present invention is to propose the preparation method of the Bimetallic Zeolite Catalyst.
Third object of the present invention is to propose the application of the Bimetallic Zeolite Catalyst.
The technical solution for realizing above-mentioned purpose of the present invention is：
A kind of Bimetallic Zeolite Catalyst is with two kinds of metal-modified KIT-6 molecular sieve catalysts, the metal choosing
From two kinds in Mn, Ce, Co, Ni, the molar ratio of Si and each modified metal is 10~60 independently of each other.
Pure KIT-6 is neutral backbone and active site is few.Because Mn, Ce, Co, Ni metal oxide have a variety of valence states, tool
There is good redox ability, selects Mn, Ce, Co, Ni to be modified KIT-6, improve the catalytic capability of KIT-6.
Preferably, the Bimetallic Zeolite Catalyst specific surface area is 600~800m2/ g, average pore size be 2~
10nm, total pore volume are 0.5~2.0cm3/g。
It is highly preferred that two kinds of metals are selected from one of the following group：Mn and Ni, Ce and Co, Mn and Co；Si and each
The molar ratio of modified metal is：Si/Mn=Si/Ni=15~25, Si/Ce=Si/Co=15~25, Si/Mn=Si/Co=20
~60.
The preparation method of Bimetallic Zeolite Catalyst of the present invention, including operation：
Template, n-butanol, silicon source, metal salt, which are dissolved in acid solution, is made mixture, at 20~60 DEG C react 20~
30h；
Crystallization is carried out at 95~110 DEG C；
In 500~600 DEG C of temperature lower calcinations.
The metal salt can be selected from nitrate, acetate, sulfate, hydrochloride, oxalates, the phosphoric acid of the modified metal
One of salt.
Wherein, the template is P123, the silicon source is sodium metasilicate or ethyl orthosilicate, sour dense in the acid solution
Degree is 0.1~2mol/L.
Wherein, the template, n-butanol, silicon source mass ratio be (4~6)：(4~6)：(10~12), template
The mass volume ratio example that acid solution is added is 5g：(100~200) mL.
Wherein, 500~600 DEG C are warming up to 1~3 DEG C of heating rate to be calcined.
A preferred technical solution of the present invention is that the preparation method includes step：
(1) by P123It is dissolved in the hydrochloric acid solution that concentration is 0.1~1mol/L；
(2) n-butanol is added into solution, is stirred under the conditions of 30~40 DEG C of temperature；
(3) ethyl orthosilicate and two kinds of metal salts are added, is dissolved in dilute hydrochloric acid solution and forms mixture, at 30~40 DEG C
It is stirred to react under the conditions of temperature 20~30 hours；
(4) step (3) acquired solution is put into hydrothermal reaction kettle, control 95~110 DEG C of reaction crystallization 20~30 of temperature are small
When, crystallized product is filtered, washed；
(5) product after washing is dry at 80~150 DEG C；
(6) product is in 500~600 DEG C of 5~8h of temperature lower calcination after drying.
Application of the Bimetallic Zeolite Catalyst in the processing of the water containing PPCPs.
Further, handled water be in contain carbamazepine, carry out oxidation processes with oxidant, the oxidant is
One of ozone, chlorine, hypochlorous acid, hypochlorite are a variety of；The pH value of the waste water is 2~9；The bimetallic molecular sieve
The dosage of catalyst is 0.1~5g/L.
Another optimal technical scheme of the invention is to carry out oxidation processes with ozone, the pH value of the waste water is 2~9；
Catalyst uses disposable dosing method, and by the way of continuously adding, the Bimetallic Zeolite Catalyst adds ozone
Amount is 1~3g/L.The haptoreaction time of ozone, Bimetallic Zeolite Catalyst and waste water is 1~30min.
Compared with prior art, Bimetallic Zeolite Catalyst of the present invention has the following advantages that：
(1) compared with traditional supported catalysts, metal oxide enters in skeleton the present invention, be combined with each other more firm
Gu metal ion is not easy to dissolve out, catalyst performance stabilised.(2) metallic molecule sieve catalyst prepared by the present invention has unique three
Cube duct is tieed up, hole wall thickness, aperture is big, duct is mutually communicated and the orderly opening substance that is conducive to is spread, and reduces internal mass transfer resistance
Power is not easy to plug duct.(3) metallic molecule sieve catalyst large specific surface area prepared by the present invention, hydrothermal stability height, active group
Divide dispersion degree high, there is certain enrichment to Organic substance in water, pass through surface enrichment organic matter and ozone and promotes ozone
It decomposes and generates more hydroxyl radical free radicals to improve oxidation rate.
Metallic molecule sieve catalyst Mn-Co-KIT-6 effectively increases the efficiency of ozone removal carbamazepine.2.5 points of reaction
Zhong Shi, O3Removal rate to carbamazepine is 25.9%, and catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=20) is to Karma
The removal rate in Xiping is then up to 66%, purer O3Improve 40.1%；O at 10 minutes3Removal rate to carbamazepine is
77.8%, Mn-Co-KIT-6 (Si/Mn=Si/Co=20) are 88.4%, purer O3Improve 10.6%.
Detailed description of the invention
Fig. 1 is the XRD diagram of catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=20) prepared by embodiment 4.
Fig. 2 is the pure O of embodiment 13With embodiment 2, embodiment 3, embodiment 4 prepare catalyst and carbamazepine is gone
Except efficiency chart.
Fig. 3 is the industrial catalyst of catalyst, embodiment 5 and the purchase of embodiment 6 prepared by embodiment 4 to carbamazepine
Removal efficiency figure.
Fig. 4 is removal efficiency figure of the catalyst to carbamazepine of embodiment 4, embodiment 7 and the preparation of embodiment 8.
Fig. 5 be embodiment 4 prepare catalyst in the simulated wastewater of different pH value to the removal efficiency figure of carbamazepine.
Specific embodiment
The present invention is now illustrated with following embodiment, but is not limited to the scope of the present invention.
Means used in embodiment use the means of this field routine unless otherwise instructed.
Embodiment 1：
O3Oxidation test：Simulated wastewater is that (natural ph of waste water is 20mg/L carbamazepine solution 1L when not adjusting pH
6.5) it, is continuously added using ozone as oxidant, gas flow rate 0.25L/min, O3Gas phase concentration 2mg/L.
2~5min sample detection is spaced in 0~15min of haptoreaction time of ozone, molecular sieve catalyst and waste water.
When reacting 2.5 minutes, O3Removal rate to carbamazepine reached for 77.8% (referring to fig. 2) when being 25.9%, 10 minutes.
Embodiment 2：
Catalyst preparation：
5gP123It is dissolved in the dilute hydrochloric acid solution that 175mL concentration is 0.5mol/L, stirs 1h；
5g n-butanol is added, stirs 1h under the conditions of 35 DEG C of water-bath；10.75g ethyl orthosilicate is added, after Si/ in molar ratio
Mn (the NO that 0.634g nickel acetate and 0.93g mass fraction are 50% by Mn=Si/Ni=203)2·4H2Solution dissolution is added in O,
It is stirred for 24 hours under the conditions of 35 DEG C of water-bath；
Solution is put into hydrothermal reaction kettle crystallization in 100 DEG C of baking ovens later and for 24 hours, it is natural to take out reaction kettle after reaction
It is cooled to room temperature, filters, washing.
Obtained product is dried into 6h in 100 DEG C of baking ovens, calcines 6h, the liter of Muffle furnace in 550 DEG C of Muffle furnaces later
Warm rate is 2 DEG C/min, obtains catalyst Mn-Ni-KIT-6 (Si/Mn=Si/Ni=20).It is detected with BET method, gained molecule
The specific surface area of sieve catalyst is 693.1m2/ g, average pore size 5.93nm, total pore volume 1.03cm3/g。
Catalyst activity test：
Simulated wastewater is 20mg/L carbamazepine solution 1L, is continuously added using ozone as oxidant, gas flow rate is
0.25L/min, O3Gas phase concentration 2mg/L, catalyst amount 2g.
When reacting 2.5 minutes, catalyst Mn-Ni-KIT-6 (Si/Mn=Si/Ni=20) is to the removal rate of carbamazepine
Reached for 77.5% (referring to fig. 2) when 44.7%, 10 minutes.
Embodiment 3：
Catalyst preparation：
5g P123It is dissolved in the dilute hydrochloric acid solution that 175mL concentration is 0.5mol/L, stirs 1h；5g n-butanol, water-bath 35 is added
1h is stirred under the conditions of DEG C；10.75g ethyl orthosilicate is added, after in molar ratio Si/Ce=Si/Co=20 by 0.75gCo
(NO3)2·6H2O and 1.12gCe (NO3)2·6H2Solution dissolution is added in O, stirs for 24 hours under the conditions of 35 DEG C of water-bath；Later by solution
It is put into hydrothermal reaction kettle crystallization in 100 DEG C of baking ovens and for 24 hours, takes out reaction kettle cooled to room temperature after reaction, filter, wash
It washs.
Obtained product is dried into 6h in 100 DEG C of baking ovens, calcines 6h, Muffle furnace heating in 550 DEG C of Muffle furnaces later
Rate is 2 DEG C/min, obtains catalyst Ce-Co-KIT-6 (Si/Ce=Si/Co=20).It is detected with BET method, gained molecular sieve
The specific surface area 742m of catalyst2/ g, average pore size 6.51nm, total pore volume 1.21cm3/g。
Catalyst activity test：
Simulated wastewater is 20mg/L carbamazepine solution 1L, is continuously added using ozone as oxidant, gas flow rate is
0.25L/min, O3Gas phase concentration 2mg/L, catalyst amount 2g.When reacting 2.5 minutes, catalyst Ce-Co-KIT-6 (Si/Ce
=Si/Co=20) to reaching for 83.7% (referring to fig. 2) when the removal rate of carbamazepine is 41%, 10 minutes.
Embodiment 4：
Catalyst preparation：
5gP123It is dissolved in the dilute hydrochloric acid solution that 175mL concentration is 0.5mol/L, stirs 1h；Addition 5g n-butanol, 35 DEG C of water-bath
Under the conditions of stir 1h；10.75g ethyl orthosilicate is added, after in molar ratio Si/Mn=Si/Co=20 by 0.75gCo (NO3)2·
6H2Mn (the NO that O and 0.93g mass fraction is 50%3)2·4H2Solution dissolution is added in O, stirs for 24 hours under the conditions of 35 DEG C of water-bath；It
Solution hydrothermal reaction kettle crystallization in 100 DEG C of baking ovens is put into afterwards for 24 hours, to take out reaction kettle after reaction and naturally cool to room
Temperature filters, washing.
Obtained product is dried into 6h in 100 DEG C of baking ovens, calcines 6h, the liter of Muffle furnace in 550 DEG C of Muffle furnaces later
Warm rate is 2 DEG C/min, obtains catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=20).It is detected with BET method, gained molecule
The specific surface area of sieve catalyst is 713.8m2/ g, average pore size 6.02nm, total pore volume 1.07cm3/g。
Fig. 1 is the XRD spectrum of Mn-Co-KIT-6 (Si/Mn=Si/Co=20).XRD diagram shows catalyst Mn-Co-KIT-
6 (Si/Mn=Si/Co=20) tool shows that the catalyst has the three-dimensional of high-sequential vertical there are three apparent characteristic diffraction peak
Square duct.
Catalyst activity test：Simulated wastewater is 20mg/L carbamazepine solution 1L, is continuously added using ozone as oxidant,
Gas flow rate is 0.25L/min, O3Gas phase concentration 2mg/L, catalyst amount 2g.When reacting 2.5 minutes, catalyst Mn-Co-
KIT-6 (Si/Mn=Si/Co=20) reaches 88.4% (referring to figure when being up to 66%, 10 minutes to the removal rate of carbamazepine
2).Compared with Mn-Ni-KIT-6 (Si/Mn=Si/Ni=20) and Ce-Co-KIT-6 (Si/Ce=Si/Co=20), Mn-Co-
The catalytic activity of KIT-6 (Si/Mn=Si/Co=20) is higher, and it is final catalyst that Mn-Co-KIT-6 is selected in research later.
Embodiment 5：
Catalyst activity test：Commercial ozone catalyst 1 and commercial ozone catalyst 2 are ground to powder, take 2g respectively
For reacting, simulated wastewater is 20mg/L carbamazepine solution 1L, and oxidant is ozone, gas flow rate 0.25L/min, O3Gas
Phase concentration 2mg/L.
When reacting 2.5 minutes, commercial ozone catalyst 1 is 23% to the removal rate of carbamazepine, commercial ozone catalyst 2
Removal rate to carbamazepine is 32.5%.Commercialization ozone catalyst 1 reaches 77% to the removal rate of carbamazepine at 10 minutes,
Commercial ozone catalyst 2 reaches 80% (referring to Fig. 3) to the removal rate of carbamazepine.With pure O3Oxidation is compared, and commercial ozone is urged
Agent 1 is to the removal of carbamazepine without facilitation, and commercial ozone catalyst 2 has certain promotion to the removal of carbamazepine
Effect, but facilitation is significantly less than the facilitation of Mn-Co-KIT-6 (Si/Mn=Si/Co=20).
Embodiment 6：
Catalyst preparation：
5gP123It is dissolved in the dilute hydrochloric acid solution that 175mL concentration is 0.5mol/L, stirs 1h；Addition 5g n-butanol, 35 DEG C of water-bath
Under the conditions of stir 1h；10.75g ethyl orthosilicate is added, after in molar ratio Si/Mn=Si/Co=40 by 0.376gCo (NO3)2·
6H2Mn (the NO that O and 0.462g mass fraction is 50%3)2·4H2Solution dissolution is added in O, stirs for 24 hours under the conditions of 35 DEG C of water-bath；
Solution hydrothermal reaction kettle crystallization in 100 DEG C of baking ovens is put into later for 24 hours, to take out reaction kettle after reaction and naturally cool to room
Temperature filters, washing.
Obtained product is dried into 6h in 100 DEG C of baking ovens, calcines 6h, the liter of Muffle furnace in 550 DEG C of Muffle furnaces later
Warm rate is 2 DEG C/min, obtains catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=40), and Mn-Co-KIT-6 is similarly made
(Si/Mn=Si/Co=60).
Catalyst activity test：
Simulated wastewater is 20mg/L carbamazepine solution 1L, is continuously added using ozone as oxidant, gas flow rate is
0.25L/min, O3Gas phase concentration 2mg/L, catalyst amount 2g.
Referring to fig. 4, when reacting 2.5 minutes, catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=40) is to carbamazepine
Removal rate reaches 86.5% when being 61.1%, 10 minutes；When reacting 2.5 minutes, catalyst Mn-Co-KIT-6 (Si/Mn=Si/
Co=60) to the removal rate of carbamazepine be 58.9%, 10 minutes when reach 84.9%.
Embodiment 7：
Catalyst activity test：Simulated wastewater is 20mg/L carbamazepine solution 1L, with hydrochloric acid by the pH tune of simulated wastewater
It is 3, is continuously added using ozone as oxidant, gas flow rate 0.25L/min, O3Gas phase concentration 2mg/L, catalyst Mn-Co-
KIT-6 (Si/Mn=Si/Co=20) dosage 2g.When reacting 2.5 minutes, catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=
20) to the removal rate of carbamazepine be 61%, 10 minutes when reach 91.1%, show acidic environment to Mn-Co-KIT-6 (Si/
Mn=Si/Co=20 activity) has slight facilitation without influence instead (referring to Fig. 5).
Embodiment 8：
Catalyst activity test：Simulated wastewater is 20mg/L carbamazepine solution 1L, with sodium hydroxide solution that simulation is useless
The pH of water is adjusted to 9, gas flow rate 0.25L/min, O3Gas phase concentration 2mg/L, catalyst Mn-Co-KIT-6 (Si/Mn=Si/
Co=20) dosage 2g.When reacting 2.5 minutes, catalyst Mn-Co-KIT-6 (Si/Mn=Si/Co=20) removes carbamazepine
Except rate be 51.5%, 10 minutes when reach 84%, show the alkaline environment to Mn-Co-KIT-6's (Si/Mn=Si/Co=20)
Activity has slight inhibiting effect (referring to Fig. 5).
By embodiment 7-8 it is found that the metallic molecule sieve catalyst has well in the wider pH application range 3-9 of solution
Catalytic activity, the scope of application is wider.
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of Bimetallic Zeolite Catalyst, which is characterized in that be with two kinds of metal-modified KIT-6 molecular sieve catalysts,
The molar ratio of two kinds in Mn, Ce, Co, Ni of the metal, Si and each modified metal is 10~60 independently of each other.
2. Bimetallic Zeolite Catalyst according to claim 1, which is characterized in that the Bimetallic Zeolite Catalyst
Specific surface area is 600~800m2/ g, average pore size are 2~10nm, and total pore volume is 0.5~2.0cm3/g。
3. Bimetallic Zeolite Catalyst according to claim 1 or 2, which is characterized in that two kinds of metals are selected from
With one of the following group：Mn and Ni, Ce and Co, Mn and Co；The molar ratio of Si and each modified metal is：Si/Mn=Si/Ni=15
~25, Si/Ce=Si/Co=15~25, Si/Mn=Si/Co=20~60.
4. the preparation method of the described in any item Bimetallic Zeolite Catalysts of claims 1 to 3, which is characterized in that including behaviour
Make：
Template, n-butanol, silicon source, metal salt, which are dissolved in acid solution, is made mixture, and 20~30h is reacted at 20~60 DEG C；
Crystallization is carried out at 95~110 DEG C；
In 500~600 DEG C of temperature lower calcinations.
5. the preparation method according to claim 4, which is characterized in that the template is P123, the silicon source is sodium metasilicate
Or ethyl orthosilicate, sour concentration is 0.1~2mol/L in the acid solution.
6. the preparation method according to claim 4, which is characterized in that the template, n-butanol, silicon source mass ratio
For (4~6)：(4~6)：(10~12), the mass volume ratio example that acid solution is added in template is 5g：(100~200) mL.
7. the preparation method according to claim 4, which is characterized in that be warming up to 500~600 with 1~3 DEG C of heating rate
It DEG C is calcined.
8. the preparation method according to claim 4, which is characterized in that including step：
(1) by P123It is dissolved in the hydrochloric acid solution that concentration is 0.1~1mol/L；
(2) n-butanol is added into solution, is stirred under the conditions of 30~40 DEG C of temperature；
(3) ethyl orthosilicate and two kinds of metal salts are added, is dissolved in dilute hydrochloric acid solution and forms mixture, in 30~40 DEG C of temperature
Under the conditions of be stirred to react 20~30 hours；
(4) step (3) acquired solution is put into hydrothermal reaction kettle, controls reaction crystallization 20~30 hours of 95~110 DEG C of temperature, it will
Crystallized product is filtered, washed；
(5) product after washing is dry at 80~150 DEG C；
(6) product is in 500~600 DEG C of 5~8h of temperature lower calcination after drying.
9. application of any one of claims 1 to 3 Bimetallic Zeolite Catalyst in the processing of the water containing PPCPs.
10. the method for any one of the application claims 1 to 3 Bimetallic Zeolite Catalyst processing waste water, which is characterized in that
Contain carbamazepine in handled water, carry out oxidation processes with oxidant, the oxidant is ozone, chlorine, hypochlorous acid, secondary
One of chlorate is a variety of；The pH value of the waste water is 2~9；The dosage of the Bimetallic Zeolite Catalyst is 0.1
~5g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112316972A (en) * | 2020-10-16 | 2021-02-05 | 河北莫兰斯环境科技股份有限公司 | Preparation method and application of mesoporous-microporous ZSM-5-based ozone catalyst |
| CN115254176A (en) * | 2022-07-17 | 2022-11-01 | 江苏科技大学 | Nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316972A (en) * | 2020-10-16 | 2021-02-05 | 河北莫兰斯环境科技股份有限公司 | Preparation method and application of mesoporous-microporous ZSM-5-based ozone catalyst |
| CN115254176A (en) * | 2022-07-17 | 2022-11-01 | 江苏科技大学 | Nano-zeolite-coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof |
| CN115254176B (en) * | 2022-07-17 | 2024-03-15 | 江苏科技大学 | Nano zeolite coated heavy metal cluster catalytic wet oxidation catalyst and preparation method and application thereof |
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| CN108837843B (en) | 2021-01-26 |
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