CN104549231B - A kind of preparation method of catalyst of catalytic decomposition garbage incinerating tail gas Zhong bioxin - Google Patents

A kind of preparation method of catalyst of catalytic decomposition garbage incinerating tail gas Zhong bioxin Download PDF

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CN104549231B
CN104549231B CN201510053040.7A CN201510053040A CN104549231B CN 104549231 B CN104549231 B CN 104549231B CN 201510053040 A CN201510053040 A CN 201510053040A CN 104549231 B CN104549231 B CN 104549231B
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catalyst
preparation
bioxin
tail gas
honeycomb
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CN104549231A (en
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王国忠
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Wang Guozhong
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Abstract

The invention discloses the Catalysts and its preparation method producing bioxin in a kind of catalytic degradation garbage incinerating tail gas, adopt extrinsion pressing to prepare honeycomb type catalyst, then carry out obtained by drying and activation.Catalyst is main carriers with CNT, with VOx, WOx, MnOx, TiO 2for main active catalytic component, this catalyst is vanadium-tungsten-manganese-titanium catalyst system.This catalyst is applicable to the catalytic cracking reaction of dioxins materials.Catalyst of the present invention, improves the specific area of catalyst effectively, improves the activity of catalyst, and enhances the intensity of catalyst.

Description

A kind of preparation method of catalyst of catalytic decomposition garbage incinerating tail gas Zhong bioxin
Technical field
The present invention relates to the manufacture method producing the catalyst of bioxin in a kind of catalytic decomposition garbage incinerating tail gas.
Background technology
The removal technology of current ， bioxin has following several: high-temperature process (high-temp combustion, motlten metal pyrolytic, molten salt oxidation, pyrolytic etc.); Oxidation non-burning technology (catalytic oxidation, supercritical water oxidation, electrochemical oxidation etc.); Reduction technique (carrier catalysis degradation process, metal and metal oxide oxidation catalyst, ball milling, sodium reduction etc.); Photocatalyst (sunshine is degraded, photochemical degradating, UV degradation, photocatalysis), biodegradation etc.
The method of conventional removal bioxin is as follows: utilize at monoblock reactor and divest N0x catalytic elimination/oxidation; Catalytic elimination and degraded is carried out at catalytic filter; Carbon fibre, compression bed or moving bed use active carbon to remove or fluidization technique; Adsorb comprising on the compression bed detesting water zeolite, sepiolite or carbon micro-nano mitron; Wet-cleaned is carried out with acid or alkali; Carry out half-dried cleaning fluid with pulverized limestone and can remove a part of bioxin.
Utilize catalysis technique process bioxin to be a kind of newer method, allow the flue gas containing bioxin flow in Catalytic Layer, bioxin can be oxidized by oxygen at low temperatures, generate CO 2, the inorganic harmless object such as water and HCl.Catalyst mostly is titanium oxide and carries the noble metal catalyst such as the transition-metal catalysts such as vanadium, tungsten, molybdenum and year gold, palladium, the platinum such as silica gel, active carbon.
Be a technology being proved to be feasible to the catalytic oxidation of the PCDD/Fs in flue gas, the PCDD/Fs concentration in flue gas can be reduced to lower than 0.1 ng TEQ/Nm by it 3, Hagenmaier and people such as grade prove TiO 2for the V of carrier 2o 5/ WO 3it is highly effective at the same temperature that catalyst removes nitrogen oxide (NOx) through SCR (SCR), and main cause is that they can be oxidized PCDD/Fs and become oxycarbide, water and hydrogen chloride.
Summary of the invention
The invention provides a kind of hydrogenation catalyst, compared with prior art in this catalyst, activity component load quantity is low, and has the catalytic activity of catalyst known in the state of the art.
Technical scheme of the present invention realizes by the following method:
A) take the ammonium metavanadate of 125g respectively, the ammonium metatungstate of 250g, the titanium sulfate of 130g, the manganese nitrate of 130g, the Ludox of 800-1200g, constantly stir at the temperature of 25 DEG C, be dissolved in the deionized water of 1000ml;
B) CNT is put in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, maintain 10-15 hour at 120-150 DEG C after, be cooled to room temperature, then take out CNT and spend deionized water filtration, for subsequent use;
C) step b) taking 2000g cleans CNT for subsequent use, the activated clay of 50g and the tung oil of 40g, and add in the solution that step a) configures, import in mixing roll and carry out uniform stirring, mixing time is 0.5-1.5h;
Obtain pottery pureed blank, add in hydraulic press, extruded, obtained aperture is the honeycomb catalyst of 1mm;
D) by step c) obtained honeycomb type catalyst is immersed in 4, in the acetone soln of 4 '-methyl diphenylene diisocyanate, then a small amount of 2 are added, 4-dichlorobenzoperoxide, 1-METHYLPYRROLIDONE, flavonols, trimethylhexamethylenediamine, 50 DEG C are soaked 4-16 hour, then filter out honeycomb type catalyst, replace washing 4 times with deionized water and ethanol;
E) by steps d) clean honeycomb type catalyst is placed in micro-wave oven and heats at air atmosphere, and the moisture making it remove a part is hardening, and the power of micro-wave oven is 1500W;
F) by step e) in obtained dried honeycomb catalyst carry out the cutting of physics, obtain long 10mm, diameter is the small-sized honeycomb catalyst of 20mm, then being placed in internal diameter is 21mm, length is in the quartz reactor of 750mm, quartz reactor is placed in the isothermal reaction stove that internal diameter is 35mm, under oxygen atmosphere, progressively be warming up to 550 DEG C, heating rate need control at 10-20 DEG C/minute, carry out the activation of catalyst, soak time is 0.5h-1h, thus produces the catalyst of bioxin in obtained catalytic degradation garbage incinerating tail gas.
The BET specific surface area of obtained catalyst is 800-1000 m 2/ g.
The pore volume of obtained catalyst is 0.1-0.3cm 3/ g, aperture is 50-150.
Obtained catalyst is at the temperature of 250 DEG C, and 10000h -1air speed under, the catalysis degradation modulus of Dui bioxin is 99.9%.
beneficial effect of the present invention
(1) catalyst of the present invention is vanadium-tungsten-manganese-titanium System Catalyst, is HCl and SO wherein to waste incineration 2there is good anti-toxic effects;
(2) honeycomb catalyst and add carbon nanotube powder, there is good adaptive capacity in the duct of its rule to the impurity in tail gas, increases specific area simultaneously, improves the activity of catalyst, under high-speed, reaction rate is also higher, can reduce the cost of catalyst; Greatly improve the intensity of catalyst, be easier to realize industrialization, advantage is more obvious in actual applications simultaneously.
(3) CNT is immersed in 4, in 4 '-methyl diphenylene diisocyanate, the carrier of catalyst defines one deck overlay film, improve the resistance to elevated temperatures of catalyst carrier and the bulk strength of active component and carrier.2, a small amount of interpolation of 4-dichlorobenzoperoxide, 1-METHYLPYRROLIDONE, flavonols, trimethylhexamethylenediamine, achieve and introduce active function groups in carbon nano tube surface, improve the catalytic activity of catalyst and the selective of Dui bioxin, create synergy simultaneously, improve the ageing resistace of carrier.The absorption property of catalyst significantly promotes simultaneously, and the BET specific surface area of obtained catalyst reaches 800-1000 m 2/ g, is much higher than the absorption property of existing catalyst.
(4) experimental result shows, catalyst of the present invention is at the temperature of 250 DEG C, and 10000h -1air speed (SV) under, the catalysis degradation modulus of its Dui bioxin is 99.9%.
Detailed description of the invention
embodiment 1
A) take the ammonium metavanadate of 125g respectively, the ammonium metatungstate of 250g, the titanium sulfate of 130g, the manganese nitrate of 130g, the Ludox of 800-1200g, constantly stir at the temperature of 25 DEG C, be dissolved in the deionized water of 1000ml;
B) CNT is put in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, maintain 10-15 hour at 120-150 DEG C after, be cooled to room temperature, then take out CNT and spend deionized water filtration, for subsequent use;
C) step b) taking 2000g cleans CNT for subsequent use, the activated clay of 50g and the tung oil of 40g, and add in the solution that step a) configures, import in mixing roll and carry out uniform stirring, mixing time is 0.5-1.5h;
Obtain pottery pureed blank, add in hydraulic press, extruded, obtained aperture is the honeycomb catalyst of 1mm;
D) by step c) obtained honeycomb type catalyst is immersed in 4, in the acetone soln of 4 '-methyl diphenylene diisocyanate, then a small amount of 2 are added, 4-dichlorobenzoperoxide, 1-METHYLPYRROLIDONE, flavonols, trimethylhexamethylenediamine, 50 DEG C are soaked 4-16 hour, then filter out honeycomb type catalyst, replace washing 4 times with deionized water and ethanol;
E) by steps d) clean honeycomb type catalyst is placed in micro-wave oven and heats at air atmosphere, and the moisture making it remove a part is hardening, and the power of micro-wave oven is 1500W;
F) by step e) in obtained dried honeycomb catalyst carry out the cutting of physics, obtain long 10mm, diameter is the small-sized honeycomb catalyst of 20mm, then being placed in internal diameter is 21mm, length is in the quartz reactor of 750mm, quartz reactor is placed in the isothermal reaction stove that internal diameter is 35mm, under oxygen atmosphere, progressively be warming up to 550 DEG C, heating rate need control at 10-20 DEG C/minute, carry out the activation of catalyst, soak time is 0.5h-1h, thus produces the catalyst of bioxin in obtained catalytic degradation garbage incinerating tail gas.
comparative example 1
A) take the ammonium metavanadate of 125g respectively, the ammonium metatungstate of 250g, the titanium sulfate of 130g, the manganese nitrate of 130g, the Ludox of 800-1200g, constantly stir at the temperature of 25 DEG C, be dissolved in the deionized water of 1000ml;
B) take the aluminium oxide of 2000g, the activated clay of 50g and the tung oil of 40g, add in the solution that step a) configures, import in mixing roll and carry out uniform stirring, mixing time is 0.5-1.5h; Obtain pottery pureed blank, add in hydraulic press, extruded, obtained aperture is the honeycomb catalyst of 1mm;
C) by step b) honeycomb type catalyst be placed in micro-wave oven and heat at air atmosphere, the moisture making it remove a part is hardening, and the power of micro-wave oven is 1500W;
D) by step c) in obtained dried honeycomb catalyst carry out the cutting of physics, obtain long 10mm, diameter is the small-sized honeycomb catalyst of 20mm, then being placed in internal diameter is 21mm, length is in the quartz reactor of 750mm, quartz reactor is placed in the isothermal reaction stove that internal diameter is 35mm, under oxygen atmosphere, progressively be warming up to 550 DEG C, heating rate need control at 10-20 DEG C/minute, carry out the activation of catalyst, soak time is 0.5h-1h, thus produces the catalyst of bioxin in obtained catalytic degradation garbage incinerating tail gas.
comparative example 2
A) take the ammonium metavanadate of 125g respectively, the ammonium metatungstate of 250g, the titanium sulfate of 130g, the manganese nitrate of 130g, the Ludox of 800-1200g, constantly stir at the temperature of 25 DEG C, be dissolved in the deionized water of 1000ml;
B) take the silica of 2000g, the activated clay of 50g and the tung oil of 40g, add in the solution that step a) configures, import in mixing roll and carry out uniform stirring, mixing time is 0.5-1.5h; Obtain pottery pureed blank, add in hydraulic press, extruded, obtained aperture is the honeycomb catalyst of 1mm;
C) by step b) honeycomb type catalyst be placed in micro-wave oven and heat at air atmosphere, the moisture making it remove a part is hardening, and the power of micro-wave oven is 1500W;
D) by steps d) in obtained dried honeycomb catalyst carry out the cutting of physics, obtain long 10mm, diameter is the small-sized honeycomb catalyst of 20mm, then being placed in internal diameter is 21mm, length is in the quartz reactor of 750mm, quartz reactor is placed in the isothermal reaction stove that internal diameter is 35mm, under oxygen atmosphere, progressively be warming up to 550 DEG C, heating rate need control at 10-20 DEG C/minute, carry out the activation of catalyst, soak time is 0.5h-1h, thus produces the catalyst of bioxin in obtained catalytic degradation garbage incinerating tail gas.
Produce in the reaction of bioxin by the catalyst application that embodiment 1 and comparative example 1,2 obtain in catalytic degradation garbage incinerating tail gas, catalyst loading amount is 500ml.Be 250 DEG C in reaction temperature, the gas space velocity containing bioxin is 10000h -1, the reaction time is 4h, sample analysis.Result is as table 1.
The test result of bioxin is produced in table 1 catalytic degradation garbage incinerating tail gas
Sample Reaction temperature (DEG C) Reaction time (dividing) Bioxin clearance (%)
Embodiment 1 250 240 99.9
Comparative example 1 250 240 58.9
Comparative example 2 250 240 54.6

Claims (4)

1. the preparation method of the catalyst of bioxin in catalytic degradation garbage incinerating tail gas, it is characterized in that, concrete preparation process is as follows:
A) take the ammonium metavanadate of 125g respectively, the ammonium metatungstate of 250g, the titanium sulfate of 130g, the manganese nitrate of 130g, the Ludox of 800-1200g, constantly stir at the temperature of 25 DEG C, be dissolved in the deionized water of 1000ml;
B) CNT is put in the mixed solution of red fuming nitric acid (RFNA) and hydrofluoric acid, high pressure hydration under ar gas environment, maintain 10-15 hour at about 120-150 DEG C after, be cooled to room temperature, then take out CNT and spend deionized water filtration, for subsequent use;
C) take 2000g step b) and clean CNT for subsequent use, the activated clay of 50g and the tung oil of 40g, add in the solution that step a) configures, import in mixing roll and carry out uniform stirring, mixing time is 0.5-1.5h,
Obtain pottery pureed blank, add in hydraulic press, extruded, obtained aperture is the honeycomb catalyst of 1mm;
D) by step c) obtained honeycomb type catalyst is immersed in 4, in the acetone soln of 4 '-methyl diphenylene diisocyanate, then a small amount of 2 are added, 4-dichlorobenzoperoxide, 1-METHYLPYRROLIDONE, flavonols, trimethylhexamethylenediamine, 50 DEG C are soaked 4-16 hour, then filter out honeycomb type catalyst, replace washing 4 times with deionized water and absolute ethyl alcohol;
E) by steps d) clean honeycomb type catalyst is placed in micro-wave oven and heats at air atmosphere, and the moisture making it remove a part is hardening, and the power of micro-wave oven is 1500W;
F) by step e) in obtained dried honeycomb catalyst carry out the cutting of physics, obtain long 10mm, diameter is the small-sized honeycomb catalyst of 20mm, then being placed in internal diameter is 21mm, length is in the quartz reactor of 750mm, quartz reactor is placed in the isothermal reaction stove that internal diameter is 35mm, under oxygen atmosphere, progressively be warming up to 550 DEG C, heating rate need control at 10-20 DEG C/minute, carry out the activation of catalyst, soak time is 0.5h-1h, thus produces the catalyst of bioxin in obtained catalytic degradation garbage incinerating tail gas.
2. preparation method as claimed in claim 1, is characterized in that: the BET specific surface area of obtained catalyst is 800-1000 m 2/ g.
3. preparation method as claimed in claim 1, is characterized in that: the pore volume of obtained catalyst is 0.1-0.3cm 3/ g, aperture is 50-150.
4. preparation method as claimed in claim 1, is characterized in that: obtained catalyst is at the temperature of 250 DEG C, and 10000h -1air speed under, the catalysis degradation modulus of Dui bioxin is 99.9%.
CN201510053040.7A 2015-02-02 2015-02-02 A kind of preparation method of catalyst of catalytic decomposition garbage incinerating tail gas Zhong bioxin Expired - Fee Related CN104549231B (en)

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CN111185200B (en) * 2020-03-12 2022-08-02 青岛理工大学 Preparation method of hydrogenation catalyst for treating dioxin in garbage gasification tail gas
CN112902193B (en) * 2021-02-23 2022-05-17 山东大学 Garbage incinerator system and catalytic removal method for garbage incineration flue gas purification hearth

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CN101607203A (en) * 2009-07-16 2009-12-23 浙江大学 Be used to remove the Catalysts and its preparation method of dioxin-type halogenated aromatic compounds

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