CN110508276A - A kind of denitration collaboration dechlorination benzene catalyst and preparation method thereof - Google Patents
A kind of denitration collaboration dechlorination benzene catalyst and preparation method thereof Download PDFInfo
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- CN110508276A CN110508276A CN201910851971.XA CN201910851971A CN110508276A CN 110508276 A CN110508276 A CN 110508276A CN 201910851971 A CN201910851971 A CN 201910851971A CN 110508276 A CN110508276 A CN 110508276A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of denitrations to cooperate with dechlorination benzene method for preparing catalyst.The following steps are included: (1) crushes active carbon to obtain the first active carbon powder；(2) the first active carbon powder of nitric acid or dioxygen water process is used, active carbon powder is washed to neutrality by treated, obtains the second active carbon powder after dry；(3) one or more of ferric nitrate, manganese nitrate, cerous nitrate are added in the second active carbon powder, suitable deionized water, ultrasonic disperse is added；(4) moisture in ultrasonic disperse liquid is evaporated off, and in high-temperature process in the presence of an inert gas.Using method of the invention, its catalyst prepared can be in 300 DEG C or less effective cooperation-removal nitrogen oxides and dioxin, and at 250 DEG C, denitration and dechlorination benzene activity can reach 90%, used raw material are nontoxic transition metal element, without secondary pollution to environment.
Description
Technical field
The invention belongs to the nitrogen oxides of environmental protection and control of dioxins technical field, in particular to a kind of denitration collaboration
Dechlorination benzene method for preparing catalyst.
Background technique
Dioxin (Dioxins) is that a kind of highly stable oxygen-containing tricyclic containing chlorine is referred to as, and derives from rubbish
Rubbish burning, insecticide preparation and discharge of vehicle exhaust etc..It is difficult normally hydrolyzed, photodissociation or microorganism in nature
Degradation, therefore it is be easy to cause accumulation in vivo, while dioxin has very strong toxicity, the most toxicity being currently known
Its toxicity of dioxin substance is about 1000 times of the potassium cyanide of equivalent.The improvement of present dioxin still in its infancy, does not have also
There is a mature technology, and the concentration of dioxin is measured less for nitrogen oxides, individually sets up processing equipment meeting
Increase the cost of enterprise.Therefore, more appropriate processing method is using current existing denitrification apparatus, in denitrification process
The removing dioxin of collaboration, had not only improved the utilization rate of equipment in this way, but also reduced costs.
Nitrogen oxides (NOx) is the harmful substance of the main pollution atmosphere of one kind and the master of China's air quality supervision
One of pollutant is wanted, discharge amount drastically influences the air quality in China and the health of the common people.Generally containing dioxin
Can all there be the presence of nitrogen oxides in atmosphere, therefore, it is the hot spot studied at present that the denitration how to cooperate with, which takes off dioxin,.
In numerous control discharged nitrous oxides technologies, SCR technology (SCR) is because its is higher de-
Nitre efficiency and preferable nitrogen selective and be widely used.Wherein, V2O5-WO3/TiO2 catalyst is most common denitration
Catalyst has excellent denitration performance at 350 degree or more, but in the lower situation of temperature, when such as 300 DEG C of <,
Denitration activity but declines obviously, and the removal efficiency of chlorobenzene is lower.How temperature be lower than 300 DEG C when effectively remove nitrogen oxygen
Compound and chlorobenzene are current critical issues urgently to be solved.
Summary of the invention
Technical problems to be solved by the inivention
The object of the present invention is to provide denitrations to cooperate with dechlorination benzene method for preparing catalyst, and the catalyst of preparation can realize collaboration
Denitration takes off dioxin.
Method for solving technical problem
In view of the above-mentioned problems, the invention proposes a kind of denitrations to cooperate with dechlorination benzene method for preparing catalyst comprising following
Step:
(1) active carbon is crushed to obtain the first active carbon powder；
(2) the first active carbon powder of nitric acid or dioxygen water process is used, active carbon powder is washed to neutrality by treated, is done
The second active carbon powder is obtained after dry；
(3) one or more of ferric nitrate, manganese nitrate, cerous nitrate are added in the second active carbon powder, is added appropriate
Deionized water, ultrasonic disperse；
(4) moisture in ultrasonic disperse liquid is evaporated off, and in high-temperature process in the presence of an inert gas.
A kind of embodiment is that moisture is evaporated off using the solution after heating water bath ultrasonic disperse in step (4), steams water
Point, obtained solid is dried；High-temperature process mode in step (4) be solid after drying under atmosphere of inert gases according to
Certain temperature program rises to 400~600 DEG C, and keeps the temperature 3~6h to get catalyst.Preferred 3-15 DEG C/min of heating rate.
A kind of embodiment is that the partial size of the first active carbon is 40~60 mesh；The mass ratio of active carbon and nitric acid be 1:5~
1:20；Concentration of nitric acid is 5-10mol/L, and nitric acid treatment temperature is 60~120 DEG C.
A kind of embodiment is that the ratio (molar ratio) of manganese atom and cerium atom is 0.5:1~5:1, load capacity (quality point
Number) it is 3%~15%, the load capacity (mass fraction) of iron is 3%~15%.
According to another aspect of the present invention, a kind of catalyst being worth according to approach described above is provided.
Beneficial effects of the present invention
1, prepare catalyst can in 300 DEG C or less effective cooperation-removal nitrogen oxides and dioxin, at 250 DEG C,
Its denitration and dechlorination benzene activity can reach 90%.
2, raw material used in the present invention are nontoxic transition metal element, without secondary pollution to environment, are had good
Good application prospect.
From the description of following exemplary embodiment, further characteristic of the invention will become obvious.
Detailed description of the invention
Fig. 1 is denitration collaboration dechlorination benzene catalyst activity test result figure.
Specific embodiment
An embodiment of the disclosure is specifically described below, but the disclosure is not limited to this.
The application provides a kind of denitration collaboration dechlorination benzene catalyst and preparation method thereof, includes the following steps: that (1) will be active
Charcoal crushes to obtain the first active carbon powder；(2) the first active carbon powder of nitric acid or dioxygen water process is used, it will treated active carbon
Powder is washed to neutrality, obtains the second active carbon powder after dry；(3) ferric nitrate, nitric acid are added in the second active carbon powder
Suitable deionized water, ultrasonic disperse is added in one or more of manganese, cerous nitrate；(4) water in ultrasonic disperse liquid is evaporated off
Point, and in high-temperature process in the presence of an inert gas.
Embodiment one
A kind of denitration collaboration dechlorination benzene method for preparing catalyst, includes the following steps:
Step 1: wearing into powdery for column-shaped active carbon, sieving；
Step 2: taking 5g active carbon powder, and 5mol/L nitric acid 35mL processing is added, and filters and washs to neutrality, dry, obtains
To treated active carbon powder；
Step 3: taking the active carbon powder 2g handled well in step 1 in beaker, and 50% manganese nitrate solution is added
0.3mL, is added the deionized water of 10mL, ultrasonic disperse,
Step 4: obtained solid is put into baking oven by solution in heating water bath step 3, stirring until close to being evaporated
120 DEG C of dryings；
Step 5: the solid dry finished being put into tube furnace, 450 DEG C are warming up under N2 atmosphere, keep the temperature 3h to get
Finished catalyst.
Embodiment two
A kind of denitration collaboration dechlorination benzene method for preparing catalyst, includes the following steps:
Step 1: wearing into powdery for column-shaped active carbon, sieving；
Step 2: taking 5g active carbon powder, and 5mol/L nitric acid 50mL processing is added, and filters and washs to neutrality, dry, obtains
To treated active carbon powder；
Step 3: taking the active carbon powder 2g handled well in step 1 in beaker, and 50% manganese nitrate solution is added
0.35mL, six nitric hydrate cerium 0.37g, are added the deionized water of 10mL, ultrasonic disperse,
Step 4: obtained solid is put into baking oven by solution in heating water bath step 3, stirring until close to being evaporated
120 DEG C of dryings；
Step 5: the solid dry finished being put into tube furnace, 500 DEG C are warming up under N2 atmosphere, keep the temperature 5h to get
Finished catalyst.
Embodiment three
A kind of denitration collaboration dechlorination benzene method for preparing catalyst, includes the following steps:
Step 1: wearing into powdery for column-shaped active carbon, sieving；
Step 2: taking 5g active carbon powder, and 5mol/L nitric acid 100mL processing is added, and filters and washs to neutrality, dry,
The active carbon powder that obtains that treated；
Step 3: taking the active carbon powder 2g handled well in step 1 in beaker, and 50% manganese nitrate solution is added
0.5mL, six nitric hydrate cerium 0.52g, Fe(NO3)39H2O 0.7g, are added the deionized water of 10mL, ultrasonic disperse,
Step 4: obtained solid is put into baking oven by solution in heating water bath step 3, stirring until close to being evaporated
120 DEG C of dryings；
Step 5: the solid dry finished being put into tube furnace, 500 DEG C are warming up under N2 atmosphere, keep the temperature 6h to get
Finished catalyst.
Denitration prepared by embodiment one, two, three cooperates with dechlorination benzene catalyst activity, and test results are shown in figure 1.
Fig. 1 denitration cooperates with the reaction condition of dechlorination benzene catalyst activity test:
150 DEG C -300 DEG C of temperature, air speed 25000mL/g h, NO:500ppm, NH3:500ppm, CB:50ppm, O2:
10%, H2O:5%, N2 are Balance Air.As shown in Figure 1, when temperature is 250 DEG C, prepared catalysis by the method for the invention
Its denitration of agent collaboration dechlorination benzene activity can reach 90%.
Embodiment is merely preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto, is appointed
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, all by what those familiar with the art
It is covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of protection of the claims
It is quasi-.
Claims (5)
1. a kind of denitration cooperates with dechlorination benzene method for preparing catalyst, which comprises the following steps:
(1) active carbon is crushed to obtain the first active carbon powder；
(2) the first active carbon powder of nitric acid or dioxygen water process is used, active carbon powder is washed to neutrality by treated, after dry
Obtain the second active carbon powder；
(3) one or more of ferric nitrate, manganese nitrate, cerous nitrate are added in the second active carbon powder, suitable go is added
Ionized water, ultrasonic disperse；
(4) moisture in ultrasonic disperse liquid is evaporated off, and in high-temperature process in the presence of an inert gas.
2. method according to claim 1, wherein moisture is evaporated off using after heating water bath ultrasonic disperse in step (4)
Solution steams moisture, and obtained solid is dried；High-temperature process mode in step (4) is solid after drying in indifferent gas
According to certain temperature program to 400~600 DEG C under body atmosphere, and 3~6h is kept the temperature to get catalyst.
3. any one of -2 the method according to claim 1, wherein the partial size of the first active carbon is 40~60 mesh；Active carbon
Mass ratio with nitric acid is 1:5~1:20；Concentration of nitric acid is 5-10mol/L, and nitric acid treatment temperature is 60~120 DEG C.
4. any one of -3 the method according to claim 1, wherein the ratio (molar ratio) of manganese atom and cerium atom is 0.5:
1~5:1, load capacity (mass fraction) are 3%~15%, and the load capacity (mass fraction) of iron is 3%~15%.
5. catalyst made from a kind of any one of -4 the methods according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198484A (en) * | 2021-05-13 | 2021-08-03 | 昆明理工大学 | Low-temperature CO-SCR denitration Fe-Ce/AC catalyst and preparation method and application thereof |
| CN115105949A (en) * | 2022-07-08 | 2022-09-27 | 潮州市索力德机电设备有限公司 | Method for reducing NOx emission of ceramic gas tunnel kiln |
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2019
- 2019-09-10 CN CN201910851971.XA patent/CN110508276A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105032403A (en) * | 2015-07-07 | 2015-11-11 | 四川大学 | Catalyst used for low temperature desulphurization and denitration of flue gas and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198484A (en) * | 2021-05-13 | 2021-08-03 | 昆明理工大学 | Low-temperature CO-SCR denitration Fe-Ce/AC catalyst and preparation method and application thereof |
| CN115105949A (en) * | 2022-07-08 | 2022-09-27 | 潮州市索力德机电设备有限公司 | Method for reducing NOx emission of ceramic gas tunnel kiln |
| CN115105949B (en) * | 2022-07-08 | 2023-08-11 | 潮州市索力德机电设备有限公司 | Method for reducing NOx discharged by ceramic gas tunnel kiln |
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Application publication date: 20191129 |