CN107442104A - It is a kind of suitable for cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas and preparation method thereof - Google Patents

It is a kind of suitable for cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas and preparation method thereof Download PDF

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CN107442104A
CN107442104A CN201710658587.9A CN201710658587A CN107442104A CN 107442104 A CN107442104 A CN 107442104A CN 201710658587 A CN201710658587 A CN 201710658587A CN 107442104 A CN107442104 A CN 107442104A
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catalyst
high temperature
flue gas
pug
denitrating flue
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吴晓东
曹丽
胡建锋
吴新谦
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Longyan Cercis Innovation Research Institute
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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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/10—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • 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]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

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Abstract

The present invention provides a kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, and the coagent of the catalyst is tungsten oxide and cerium oxide, and the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier.Catalyst prepared by the present invention has the following advantages：(1) carrier of the catalyst is titanium dioxide mixing silicon dioxide powder, and occupies most ratios of catalyst quality, and it is low to reduce catalyst cost, and preparation technology is simple, and obtained catalytic mechanical intensity is higher；(2) catalyst has good denitration efficiency and high N at high temperature2Selectivity, accessory substance N2O and NO2Yield it is low, and catalyst has good water resistant sulphur ageing properties.

Description

A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas and its Preparation method
Technical field
The present invention relates to out of stock catalyst field, more particularly to a kind of cerium base high temperature suitable for gas fired-boiler denitrating flue gas Cellular catalyst and preparation method thereof.
Background technology
With increasingly serious as environmental problem caused by main energy resource structure using coal so that natural gas energy resource institute accounting Example increases year by year, at the same time, is needed using natural gas as tail gas clean-up problem caused by the energy urgently to be resolved hurrily.Gas energy institute The pollutant of discharge mainly has NOx, CO2, SO2Deng.In addition, contain substantial amounts of vapor in pollutant, along with combustion gas tail gas takes off Nitre temperature is mainly between 450~600 DEG C so that develops a kind of high temperature denitrating catalyst of good, the high transformation efficiency of water repelling property It is particularly significant.
Current generally use NH in the world3~SCR (ammonia process SCR) technologies remove the NO in tail gasx.With V2O5~WO3/TiO2Denitrating catalyst based on (hereinafter referred to as VWTi) catalyst is widely used in coal-burning power plant, The Temperature Activity window (denitration efficiency more than 80%) of VWTi catalyst is between 250~400 DEG C, the exhaust temperature ten with power plant Split-phase is proper, and has good sulfur resistance.But in plant gas, VWTi catalyst has many limitations using upper Property：On the one hand at higher temperatures, V2O5Highly volatile at high temperature, not only make the activity reduction of catalyst, can also make volatilization The toxicant V gone out2O5Damage the mankind and environment；Denitration effect is bad at high temperature for another aspect VWTi catalyst, while can also Produce N2The problems such as secondary pollutions such as O.In current domestic and international investigative technique, low transition metal is supported on molecular sieve catalyst In there is preferable high temperature denitration performance, but because the cost of molecular sieve is more expensive, and hydrothermal stability is not good enough etc. makes score Sub- sieve catalyst is not utilized industrially well.
Catalyst using cerium base as the active main body of catalyst is mostly applied at medium temperature section (250~450 DEG C), and reason is Cerium base catalyst has stronger oxidation susceptibility at high temperature, has stronger oxidability to the ammonia in atmosphere, makes high temperature Under the conditions of accessory substance NO2And N2O growing amount increase, cause denitration efficiency drastically decline [Appl.Catal.B, 2016,180: 766~774.].Main body of the molecular sieve as catalyst is mostly used in the carrier of current natural gas tai-gas clean-up catalyst, this So that the preparation technology of catalyst is complex, and cost is higher.
The content of the invention
In view of the above-mentioned problems, the present invention improves formula on the basis of existing process, there is provided a kind of honeycomb high temperature denitration The preparation technology of catalyst, the denitrating catalyst for making to produce can adapt to the industry using natural gas as the energy such as plant gas and fill The tail gas feature put：Exhaust temperature window, water content are big.The catalyst of preparation removes denitrification with 90% denitration efficiency, Accessory substance is less, and the cost of honeycomb denitrating catalyst is extremely low.
What the present invention was realized in：
A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, the coagent of the catalyst are Tungsten oxide and cerium oxide, the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier.
Preferably, the catalyst components content is as follows：
It is 85%~95% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 3%~8% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 2%~12% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
A kind of preparation method for preparing the above-mentioned cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, bag Include following steps：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 0.1%~3%, ammonium paratungstate be made into concentration for 1%~ 5% secondary tungsten acid ammonium solution is stand-by；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, will then match somebody with somebody The cerous acetate and secondary tungsten acid ammonium solution put pour into, while add hydroxypropyl methyl cellulose and PEO enters as binding agent Row is mediated, and is remixed, that is, well mixed pug is made；
2) it is old
Old 12h~48h in the cool is placed into the pug sealing being well mixed in step 1)；Old purpose be in order to Remove partial moisture in pug；
3) extrusion molding
Pug after will be old carries out extrusion molding；Pug can be loaded extruder and carry out extrusion molding, passed through first Fine screen mesh filters out bulky grain, and the pug after filtering is passed through into the mould extrusion molding of forming machine again；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology For：One-level dries the procedural heating~wet down method that uses, and heating rate is 0.05 DEG C/h~1 DEG C/h, and highest drying temperature is 50 DEG C~80 DEG C；Secondary drying uses freeze-day with constant temperature, and drying temperature is 40 DEG C~100 DEG C, and drying time is 1h~48h；Wherein Mainly for reducing the humidity of catalyst prod and increasing semi-finished product intensity, secondary drying mainly makes catalyst uniform for one-level drying Dry, be easy to sinter；
5) it is calcined
Dried cellular idiosome is calcined into 3h~24h at 500 DEG C~700 DEG C, then cools to room temperature with the furnace.
Preferably, the mol ratio of cerous acetate and ammonium paratungstate is 0.1 in step 1):10~2:5.
Further, cerous acetate and ammonium paratungstate are added during carrier in step 1), and ammonium paratungstate first adds, cerous acetate After add.It can so make the catalyst activity after calcining more preferable.
Preferably, step 1) can also add the pH value of ammoniacal liquor regulation pug during mixing.Add ammoniacal liquor regulation The pH value of pug can avoid corrosion of the acid pug to machine in extrusion.
Further, the pH value of pug is adjusted to 9~10 with ammoniacal liquor.
Preferably, the auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid.
Further, the sequencing of these three auxiliary agents of glycerine, silica, lactic acid addition is：Glycerine is first, titanium dioxide Silicon takes second place, lactic acid is eventually adding.
Preferably, one-level drying causes temperature often to raise 1 DEG C using procedural heating~wet down method in step 4), and pug is wet Degree declines 2%.
Advantages of the present invention：
(1) carrier of the catalyst is titanium dioxide mixing silicon dioxide powder, and occupies most ratios of catalyst quality Example, selected coagent is tungsten oxide and cerium oxide, and proportion is low, and catalyst cost is low, and preparation technology is simple, obtained Catalytic mechanical intensity it is higher, be adapted to commercial Application.
(2) catalyst has good denitration efficiency and high N at high temperature2Selectivity, accessory substance N2O and NO2Production Raw amount is low, and catalyst has good water resistant sulphur ageing properties.
Brief description of the drawings
Fig. 1 is the NO of different catalystsxConversion ratio；
Fig. 2 is different catalysts NO during water sulphur agingxThe variation tendency of conversion ratio.
Embodiment
To describe the technology contents of the present invention, construction feature, the objects and the effects in detail, below in conjunction with embodiment And accompanying drawing is explained in detail.
Embodiment 1
A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, the coagent of the catalyst are Tungsten oxide and cerium oxide, the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier, and wherein the catalyst components content is such as Under：
It is 85% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 3% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 12% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
The preparation method of the above-mentioned cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, including it is as follows Step：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 0.1%, ammonium paratungstate is made into the para-tungstic acid that concentration is 1% Ammonium salt solution is stand-by；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, then by the cerous acetate of configuration and Secondary tungsten acid ammonium solution pours into, while adds hydroxypropyl methyl cellulose and PEO is mediated as binding agent, then mixes Close, that is, well mixed pug is made；The mol ratio of cerous acetate and ammonium paratungstate is 0.1 in step 1):10, cerous acetate and secondary tungsten Sour ammonium is added during carrier, and ammonium paratungstate first adds, and is added after cerous acetate；Step 1) adds ammoniacal liquor tune during mixing The pH value of pug is saved to 9；Auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid, glycerine, silica, The sequencing that lactic acid these three auxiliary agents add is：Glycerine is formerly, silica takes second place, lactic acid is eventually adding.
2) it is old
Old 12h in the cool is placed into the pug sealing being well mixed in step 1)；
3) extrusion molding
Pug after will be old carries out extrusion molding；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology For：One-level dries the procedural heating~wet down method that uses, and heating rate is 0.05 DEG C/h, and highest drying temperature is 50 DEG C；Two level Drying uses freeze-day with constant temperature, and drying temperature is 40 DEG C, drying time 48h；
5) it is calcined
Dried cellular idiosome is calcined into 24h at 500 DEG C, then cools to room temperature with the furnace.
Embodiment 2
A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, the coagent of the catalyst are Tungsten oxide and cerium oxide, the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier, and wherein the catalyst components content is such as Under：
It is 90% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 8% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 2% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
The preparation method of the above-mentioned cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, including it is as follows Step：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 3%, ammonium paratungstate is made into the ammonium paratungstate that concentration is 5% Solution for later use；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, then by the cerous acetate of configuration and secondary Ammonium tungstate solution pours into, while adds hydroxypropyl methyl cellulose and PEO is mediated as binding agent, remixes, Well mixed pug is made；The mol ratio of cerous acetate and ammonium paratungstate is 2 in step 1):5, cerous acetate and ammonium paratungstate add During entering carrier, ammonium paratungstate first adds, and is added after cerous acetate；Step 1) adds ammoniacal liquor regulation pug during mixing PH value to 10；Auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid, glycerine, silica, lactic acid These three auxiliary agents add sequencing be：Glycerine is formerly, silica takes second place, lactic acid is eventually adding.
2) it is old
Old 48h in the cool is placed into the pug sealing being well mixed in step 1)；
3) extrusion molding
Pug after will be old carries out extrusion molding；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology For：One-level dries the procedural heating~wet down method that uses, and heating rate is 1 DEG C/h, and highest drying temperature is 80 DEG C；Secondary drying Using freeze-day with constant temperature, drying temperature is 100 DEG C, drying time 1h；
5) it is calcined
Dried cellular idiosome is calcined into 3h at 700 DEG C, then cools to room temperature with the furnace.
Embodiment 3
A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, the coagent of the catalyst are Tungsten oxide and cerium oxide, the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier, and wherein the catalyst components content is such as Under：
It is 95% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 3% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 2% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
The preparation method of the above-mentioned cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, including it is as follows Step：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 0.5%, ammonium paratungstate is made into the para-tungstic acid that concentration is 3% Ammonium salt solution is stand-by；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, then by the cerous acetate of configuration and Secondary tungsten acid ammonium solution pours into, while adds hydroxypropyl methyl cellulose and PEO is mediated as binding agent, then mixes Close, that is, well mixed pug is made；The mol ratio of cerous acetate and ammonium paratungstate is 1 in step 1):5, cerous acetate and para-tungstic acid Ammonium is added during carrier, and ammonium paratungstate first adds, and is added after cerous acetate；Step 1) adds ammoniacal liquor regulation during mixing The pH value of pug is to 9.5；Auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid, glycerine, silica, The sequencing that lactic acid these three auxiliary agents add is：Glycerine is formerly, silica takes second place, lactic acid is eventually adding.
2) it is old
Old 24h in the cool is placed into the pug sealing being well mixed in step 1)；
3) extrusion molding
Pug after will be old carries out extrusion molding；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology For：One-level dries the procedural heating~wet down method that uses, and heating rate is 0.1 DEG C/h, and highest drying temperature is 65 DEG C；Two level is done Dry to use freeze-day with constant temperature, drying temperature is 70 DEG C, drying time 24h；
5) it is calcined
Dried cellular idiosome is calcined into 12h at 600 DEG C, then cools to room temperature with the furnace.
Embodiment 4
A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, the coagent of the catalyst are Tungsten oxide and cerium oxide, the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier, and wherein the catalyst components content is such as Under：
It is 87% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 4% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 9% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
The preparation method of the above-mentioned cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, including it is as follows Step：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 2%, ammonium paratungstate is made into the ammonium paratungstate that concentration is 2% Solution for later use；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, then by the cerous acetate of configuration and secondary Ammonium tungstate solution pours into, while adds hydroxypropyl methyl cellulose and PEO is mediated as binding agent, remixes, Well mixed pug is made；The mol ratio of cerous acetate and ammonium paratungstate is 0.1 in step 1):5, cerous acetate and ammonium paratungstate Add during carrier, ammonium paratungstate first adds, and is added after cerous acetate；Step 1) adds ammoniacal liquor regulation mud during mixing The pH value of material is to 10；Auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid, glycerine, silica, breast The sequencing that these three sour auxiliary agents add is：Glycerine is formerly, silica takes second place, lactic acid is eventually adding.
2) it is old
Old 20h in the cool is placed into the pug sealing being well mixed in step 1)；
3) extrusion molding
Pug after will be old carries out extrusion molding；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology For：One-level dries the procedural heating~wet down method that uses, and heating rate is 0.3 DEG C/h, and highest drying temperature is 60 DEG C；Two level is done Dry to use freeze-day with constant temperature, drying temperature is 85 DEG C, drying time 10h；
5) it is calcined
Dried cellular idiosome is calcined into 16h at 550 DEG C, then cools to room temperature with the furnace.
Embodiment 5
A kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, the coagent of the catalyst are Tungsten oxide and cerium oxide, the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier, and wherein the catalyst components content is such as Under：
It is 92% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 5% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 3% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
The preparation method of the above-mentioned cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, including it is as follows Step：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 1.5%, ammonium paratungstate is made into the secondary tungsten that concentration is 2.5% Acid ammonium solution is stand-by；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, then by the cerous acetate of configuration Poured into secondary tungsten acid ammonium solution, while add hydroxypropyl methyl cellulose and PEO is mediated as binding agent, then Mixing, that is, well mixed pug is made；The mol ratio of cerous acetate and ammonium paratungstate is 2 in step 1):15, cerous acetate and secondary tungsten Sour ammonium is added during carrier, and ammonium paratungstate first adds, and is added after cerous acetate；Step 1) adds ammoniacal liquor tune during mixing The pH value of pug is saved to 9；Auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid, glycerine, silica, The sequencing that lactic acid these three auxiliary agents add is：Glycerine is formerly, silica takes second place, lactic acid is eventually adding.
2) it is old
Old 35h in the cool is placed into the pug sealing being well mixed in step 1)；
3) extrusion molding
Pug after will be old carries out extrusion molding；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology For：One-level dries the procedural heating~wet down method that uses, and heating rate is 0.75 DEG C/h, and highest drying temperature is 70 DEG C；Two level Drying uses freeze-day with constant temperature, and drying temperature is 78 DEG C, drying time 28h；
5) it is calcined
Dried cellular idiosome is calcined into 8h at 650 DEG C, then cools to room temperature with the furnace.
Experimental example one
(1) prepare and contain 5%WO3, 5%SiO2, 90%TiO2Cerium base high temperature cellular catalyst (WTiSi)
It is respectively 5%WO in mass ratio3, 5%SiO2, 90%TiO2Weigh ammonium paratungstate 244g, SiO2Powder 200g, TiO2Powder 3.6kg, separately weigh glycerine 200g, lactic acid E50g, glass fibre 500g, hydroxypropyl methyl cellulose 47g, PEO 50g, Ammoniacal liquor 1L, deionized water 3.76L, and 244g ammonium paratungstates are dissolved in 1.5L deionized waters, 40 DEG C of heating stirring 10min.
The first step mixes：Titanium dioxide 3kg, glycerine 200g, lactic acid E50g, ammoniacal liquor 1L are added in blender and mixed And 30min is stirred with 50Hz frequency；
Second step mixes：After the completion of first time mixes, the secondary tungsten acid ammonium solution of configuration is slowly added to, with 20Hz frequency Rate stirs 60min.
3rd step mixes：After the completion of second mixes, by titanium dioxide 600g, SiO2Powder 200g, glass fibre 500g add Enter to continue into batch mixing mixing and with 50Hz frequency stirring 40min stirrings；
4th step mixes：After the completion of third time mixes, then by hydroxypropyl methyl cellulose 47g and PEO 50g Mediated as binding agent, deionized water 2.26L is added in batch mixing mixing and with 50Hz frequency stirring 30min stirrings, Obtain catalyst pug.
Pug sealing is placed into old 24h in the cool by the pug obtained in step 1, after filtered, extrusion, shaping, It is respectively 5%WO to obtain mass ratio after 550 DEG C of 90 DEG C of dry 48h, Muffle furnace roasting 6h in climatic chamber3, 5%SiO2、 90%TiO2WO3-TiO2-SiO2(hereinafter referred to as WTiSi) honeycomb fashion high temperature SCR denitration.
(2) prepare and contain 0.5%CeO2, 5%WO3, 5%SiO2, 89.5%TiO2Cerium base high temperature cellular catalyst (0.5CeWTiSi)
It is respectively 0.5%CeO in mass ratio2, 5%WO3, 5%SiO2, 89.5%TiO2Weigh cerous acetate 36g, para-tungstic acid Ammonium 244g, SiO2Powder 200g, TiO2Powder 3.6kg, separately weigh glycerine 200g, lactic acid E50g, glass fibre 500g, hydroxypropyl methyl Cellulose 47g, PEO 50g, ammoniacal liquor 1L, deionized water 3.76L, and 36g cerous acetates, 244g ammonium paratungstates difference is molten Solution is in 0.5L and 1L deionized waters, 40 DEG C of heating stirring 10min.
The first step mixes：Titanium dioxide 3kg, glycerine 200g, lactic acid E50g, ammoniacal liquor 1L are added in blender and mixed And 30min is stirred with 50Hz frequency；
Second step mixes：After the completion of first time mixes, the cerous acetate solution and secondary tungsten acid ammonium solution of configuration are slowly added Enter, 60min is stirred with 20Hz frequency.
3rd step mixes：After the completion of second mixes, by titanium dioxide 600g, SiO2Powder 200g, glass fibre 500g add Enter to continue into batch mixing mixing and with 50Hz frequency stirring 40min stirrings；
4th step mixes：After the completion of third time mixes, then by hydroxypropyl methyl cellulose 47g and PEO 50g Mediated as binding agent, deionized water 2.26L is added in batch mixing mixing and with 50Hz frequency stirring 30min stirrings, Obtain catalyst pug.
Pug sealing is placed into old 24h in the cool by the pug obtained in step 1, after filtered, extrusion, shaping, It is respectively 0.5%CeO to obtain mass ratio after 550 DEG C of 90 DEG C of dry 48h, Muffle furnace roasting 6h in climatic chamber2, 5%WO3、 5%SiO2, 89.5%TiO2CeO2-WO3-TiO2-SiO2(hereinafter referred to as 0.5CeWTiSi) honeycomb fashion high temperature SCR denitration is catalyzed Agent.
(3) prepare and contain 1%CeO2, 5%WO3, 5%SiO2, 89%TiO2Cerium base high temperature cellular catalyst (1CeWTiSi)
It is identical with the preparation process of experimental example two, it the difference is that only：36g cerous acetate is substituted for 73g acetic acid Cerium, obtained after calcining mass ratio is respectively 1%CeO2, 5%WO3, 5%SiO2, 89%TiO2CeO2-WO3-TiO2-SiO2 (hereinafter referred to as 1CeWTiSi) honeycomb fashion high temperature SCR denitration.
WTiSi, 0.5CeWTiSi and 1CeWTiSi are subjected to catalyst under the conditions of plant gas tail gas is simulated respectively SCR performance test.Specifically test program is：Be 35mm*35mm by sectional dimension, hole count 10*10, aperture Cut into 10cm length for 5mm catalyst and be placed in quartz tube reactor, be passed through the simulation distribution of Natural Gas Power Plant tail gas, Contain NH in the simulation distribution composition3(500ppm)、NO(500ppm)、H2O (10%), O2(5%), N2Balance, air speed 5000h-1, simulation distribution NO after catalyst at 450-600 DEG CxConcentration.With moral figure flue gas analyzer on-line checking, NO is obtainedx Conversion ratio is as shown in Figure 1.Using 550 DEG C, in NH3(500ppm)、NO(500ppm)、H2O (10%), SO2(20ppm), O2 (5%), N2Balance, air speed 5000h-1Under conditions of aging 24h, it is as shown in Figure 2 to obtain aging data curve.
NOxConversion ratio is defined as：
Wherein NOxInclude NO and NO2。
From Fig. 1 and Fig. 2, by adding cerium oxide in coagent, coordinate another coagent tungsten oxide And the carrier by titanium dioxide mixing silicon dioxide powder, out of stock catalyst prepared by the present invention have good performance.
Embodiments of the invention are the foregoing is only, not thereby limit the scope of patent protection of the present invention, every utilization The equivalent structure or equivalent flow conversion that present specification is made with accompanying drawing, or directly or indirectly it is used in other correlations Technical field, be included within the scope of the present invention.

Claims (10)

1. a kind of cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas, it is characterised in that the catalyst Coagent is tungsten oxide and cerium oxide, and the catalyst is using titanium dioxide mixing silicon dioxide powder as carrier.
2. being applied to the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 1, its feature exists In the catalyst components content is as follows：
It is 85%~95% that titanium dioxide, which accounts for the overall mass fraction of catalyst,；
It is 3%~8% that silicon dioxide powder, which accounts for the overall mass fraction of catalyst,；
It is 2%~12% that the summation of tungsten oxide and cerium oxide, which accounts for the overall mass fraction of catalyst,.
3. such as the cerium base high temperature cellular catalyst suitable for gas fired-boiler denitrating flue gas as described in claim 1 to 2 is any Preparation method, comprise the following steps：
1) batch mixing
Cerous acetate is made into the cerous acetate solution for later use that concentration is 0.1%~3%, it is 1%~5% that ammonium paratungstate, which is made into concentration, Secondary tungsten acid ammonium solution is stand-by；After titanium dioxide is mixed with silicon dioxide powder, add auxiliary agent and be well mixed, then by the vinegar of configuration Sour cerium and secondary tungsten acid ammonium solution pour into, while add hydroxypropyl methyl cellulose and PEO is pinched as binding agent Close, remix, that is, well mixed pug is made；
2) it is old
Old 12h~48h in the cool is placed into the pug sealing being well mixed in step 1)；
3) extrusion molding
Pug after will be old carries out extrusion molding；
4) dry
The pug after extrusion molding is dried using secondary drying technology；The parameter of described secondary drying technology is：One Level dries the procedural heating~wet down method that uses, and heating rate is 0.05 DEG C/h~1 DEG C/h, and highest drying temperature is 50 DEG C~80 ℃；Secondary drying uses freeze-day with constant temperature, and drying temperature is 40 DEG C~100 DEG C, and drying time is 1h~48h；
5) it is calcined
Dried cellular idiosome is calcined into 3h~24h at 500 DEG C~700 DEG C, then cools to room temperature with the furnace.
4. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 3 Method, it is characterised in that the mol ratio of cerous acetate and ammonium paratungstate is 0.1 in step 1):10~2:5.
5. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 4 Method, it is characterised in that cerous acetate and ammonium paratungstate are added during carrier in step 1), and ammonium paratungstate first adds, after cerous acetate Add.
6. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 3 Method, it is characterised in that step 1) can also add the pH value of ammoniacal liquor regulation pug during mixing.
7. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 6 Method, it is characterised in that adjusted the pH value of pug to 9~10 with ammoniacal liquor.
8. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 3 Method, it is characterised in that the auxiliary agent described in step 1) comprises at least glycerine, silica, three kinds of lactic acid.
9. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 8 Method, it is characterised in that the sequencing that glycerine, silica, lactic acid these three auxiliary agents add is：Glycerine is first, silica Take second place, lactic acid is eventually adding.
10. it is applied to the preparation side of the cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas as claimed in claim 3 Method, it is characterised in that one-level is dried in step 4) causes temperature often to raise 1 DEG C using procedural heating~wet down method, and pug is wet Degree declines 2%.
CN201710658587.9A 2017-08-04 2017-08-04 It is a kind of suitable for cerium base high temperature cellular catalyst of gas fired-boiler denitrating flue gas and preparation method thereof Pending CN107442104A (en)

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CN112439400A (en) * 2019-08-28 2021-03-05 中国石油化工股份有限公司 Strip-shaped silicon dioxide carrier with grid structure, preparation method thereof, catalyst and application
CN112473694A (en) * 2019-09-12 2021-03-12 国家能源投资集团有限责任公司 Catalyst support composition, catalyst support and preparation method thereof
CN113600179A (en) * 2021-09-16 2021-11-05 山东博霖环保科技发展有限公司 Denitration catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112439400A (en) * 2019-08-28 2021-03-05 中国石油化工股份有限公司 Strip-shaped silicon dioxide carrier with grid structure, preparation method thereof, catalyst and application
CN112473694A (en) * 2019-09-12 2021-03-12 国家能源投资集团有限责任公司 Catalyst support composition, catalyst support and preparation method thereof
CN113600179A (en) * 2021-09-16 2021-11-05 山东博霖环保科技发展有限公司 Denitration catalyst and preparation method thereof

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