CN110201708A - A kind of SCR catalyst and preparation method - Google Patents

A kind of SCR catalyst and preparation method Download PDF

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CN110201708A
CN110201708A CN201910509096.7A CN201910509096A CN110201708A CN 110201708 A CN110201708 A CN 110201708A CN 201910509096 A CN201910509096 A CN 201910509096A CN 110201708 A CN110201708 A CN 110201708A
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molecular sieve
preparation
scr catalyst
catalyst
salt
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CN110201708B (en
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冯锡
吴干学
张艳华
杜洪忠
刘志敏
陈耀强
王云
李云
陈启章
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Sinocat Environmental Technology Co Ltd
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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
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • 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

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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention discloses a kind of SCR catalyst and preparation methods.It include: the preparation of modified molecular screen material, material is at powder, a step slurrying, coating roasting；Wherein a step slurrying, which uses that dusty material is dissolved in distilled water and is stirred, is made slurry, it adds soluble copper salt and carries out ion exchange 2-12h, then it is down to room temperature addition soluble ferric iron salt and stirs exchange 0.5-5h, add imported agent and bonding agent stirring, ball milling preparation.The present invention is using cheap mesoporous/large pore molecular sieve as carrier, using alkali metal or alkaline-earth metal to support modification, it prepares alkali metal containing or enters the molecular sieve carrier material of metal ion, then load active component copper and iron by the way of a step slurrying, prepare monoblock type SCR catalyst；This method is easy to operate, and technique and time cost are low, and the catalyst prepared also has good hydrothermally stable performance while with excellent reaction temperature window.

Description

A kind of SCR catalyst and preparation method
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to a kind of SCR catalyst and preparation method.
Background technique
Nitrogen oxides (NOx) in atmosphere is mainly derived from combustion of fossil fuel, is most important atmosphere pollution instantly One of, seriously endanger human health and ecological environment.Currently, ammine selectivity catalytic reduction (NH3- SCR) method be technology the most at The technical method of removal NOx ripe, using mainstream the most a kind of.Its principle is to utilize NH3(or urea) will as reducing agent Toxic NOx selective reduction is nontoxic N2And H2O.In recent years, it has been found that with nontoxic metallic element Cu and Fe be live Property component molecular sieve based catalyst SCR reaction in can show excellent performance.Especially recently this over 10 years with small Porous molecular sieve is that the SCR catalyst of carrier all shows quite apparent advantage in terms of performance and hydrothermal stability, still Its price is also higher by much for comparing common mesoporous/large pore molecular sieve.It can be by molecular sieve SCR catalyst from active component Research field be divided into three classes: the first kind is copper-based SCR catalyst, such catalyst under middle low temperature there is preferable NOx to turn Change efficiency；Second class is iron-based SCR catalyst, such catalyst has excellent catalytic efficiency under high temperature；Third class is Copper and iron composite catalyst, such catalyst low temperature NOx conversion efficiency is slightly below copper-based catalysts and high temperature NOx conversion efficiency is slightly lower In ferrum-based catalyst, but it combines copper-based and ferrum-based catalyst advantage, reaction temperature window in three classes catalyst most It is wide.CN103127951B patent discloses a kind of preparation method of copper and iron composite molecular sieve catalyst, with cheap mesoporous/ Large pore molecular sieve is carrier material, and using copper and iron as active component, which has very wide active temperature windows.But Its cryogenic property decline after hydrothermal aging is also apparent from.For small pore molecular sieve catalyst, hydrothermally stable performance is bright It is aobvious to reduce.And the method for preparing catalyst is complicated, while the preparation process higher cost impregnated.
More and more domestic and foreign scholars wish by adding auxiliary agent come molecular sieves stabilized skeleton or increasing catalyst Acidity, also or the mode of change active component existence improves the amount of active site to further increase copper and iron compound molecule The performance of sieve catalyst, to can exceed that single copper or single iron catalyst.Such as by adding Ce element in Fe/Cu-SSZ-13 Can be improved catalyst low temperature active (Liu Xiaojiao, Li Yonghong, Zhang Ranran.RSC Adv., 2015, 5,85453-85459) hydrothermally stable of copper and iron composite molecular sieve catalyst, or by addition La, Mn, Ce, Ni etc. is improved Property (CN106984357A).
But the above research is substantially through addition rare earth or transition metal element and serves as auxiliary agent, does not have but Perhaps alkaline-earth metal is because while alkali metal to people's alkali metal or alkaline-earth metal is also the very active gold of chemical property Belong to element, but they are easy to cause to be poisoned to SCR catalyst, so that catalyst performance sharply declines.Document report K, Ca, The alkali and alkaline earth metal ions such as Mg, Na can generate obviously poisoning effect to molecular sieve catalyst, can be by active group Divide isolated Cu ion conversion at CuO, the surface acidity of catalyst, or even the collapsing of aggravation framework of molecular sieve is reduced, to reduce The activity (.Chem the Eng J., 2018,334,344-354 such as Fan Chi, Chen Zhen, Pang Lei) of catalyst.It is passing Similarly there is alkali and alkaline earth metal ions poisoning (CN108160087A) on the vanadia-based SCR catalysts of system；Just because of these Reason rarely has in patent and document with alkali metal or alkaline-earth metal the relevant report for the auxiliary agent for doing SCR catalyst, especially It is the auxiliary agent for making copper and iron composite catalyst, is especially used as multiple by the copper and iron of carrier of cheap mesoporous/large pore molecular sieve Close the auxiliary agent of catalyst.
Summary of the invention
Deficiency discloses a kind of SCR catalyst and preparation method to the present invention according to prior art.The invention solves Problem is: further having widened using cheap molecular sieve as the temperature window of the copper and iron composite molecular screen SCR catalyst of carrier；Significantly It improves using cheap molecular sieve as the hydrothermally stable performance of the copper and iron composite molecular screen SCR catalyst of carrier；It develops a kind of new One step slurrying prepares the process flow of molecular sieve SCR catalyst.
The invention is realized by the following technical scheme:
The preparation method of SCR catalyst, it is characterised in that specific preparation process is as follows:
(1) prepared by modified molecular screen material: modified metal salt being dissolved in distilled water, heating stirring is equal to dissolving It is even, then molecular sieve is added in solution and carries out ion exchange, then filtration washing, drying；
(2) material is at powder: by the modified molecular screen material fragmentation after drying and be milled into partial size D50 be 500-3000nm Powder；
(3) one step slurrying: the dusty material in step (2) is dissolved in 50-90 DEG C of distilled water and slurry is made in stirring, is added Add soluble copper salt to carry out ion exchange 2-12h, be then down to room temperature addition soluble ferric iron salt and stir exchange 0.5-5h, then plus Enter imported agent and bonding agent stirring, ball milling；
(4) coating roasting: step (3) slurry is coated on cordierite ceramic or metal beehive carrier, heated-air drying 1-6h is roasted under 450-650 DEG C of air environment afterwards, improved copper and iron composite SCR integral catalyzer is made.
The molecular sieve is sial salt or zeolite molecular sieve with MFI, BEA, MOR or FAU topological structure, SiO2/Al2O Than=10-60；Can be individually has a kind of above-mentioned molecular sieve of topological structure, is also possible to have above-mentioned different topology knot The molecular sieve mixture of structure；It can be with a kind of SiO2/Al2The molecular sieve of O ratio, is also possible to a variety of SiO2/Al2Point of O ratio Son sieve mixture.
The metallic element to support modification is alkali metal or alkaline-earth metal；Modified alkaline metal salt or alkaline earth Metallic salt is: the solubility salt of Li, Na, K, Rb, Cs, Mg, Ca, Ba, Sr, can be it is one such be also possible to it is several Mixture；The concentration of alkali metal or alkaline-earth metal ions in the solution is 0.01-0.5mol/L when modified, and exchange temperature is 50-90 DEG C, swap time 2-12h.
Cu in step (3)2+/ molecular sieve=1-5wt%, Fe3+/ molecular sieve=1-10wt%.
The imported agent be hydroxymethyl cellulose, hydroxyethyl cellulose, triethylamine, ethanol amine, aminoquinoxaline, ammonium hydroxide, The mixture of PVA, PEG or hydration an one or more of boehmite, quality account for the 1-10wt% of slurry total amount.
The bonding agent is the one or several kinds of silica solution, Aluminum sol, zirconium colloidal sol, and bonding agent quality accounts for molecular sieve total amount 1-10wt%.
Slurry pH=5.0-9.0 in the step (3), viscosity=300-3000mPas, ball milling granularity D50=500- 5000nm。
The method of the present invention exchanges to alkali or alkaline earth metal on mesoporous/large pore molecular sieve skeleton, using a step slurrying Method prepares copper and iron composite molecular sieve catalyst.Experiment results proved, alkali or alkaline earth metal improve copper to a certain extent The low-temperature SCR performance of iron composite catalyst, has widened temperature window, while also significantly improving the hydrothermal stability of catalyst Energy；
First heating ion exchange copper in the method for the present invention, then the mode of cooling exchange iron, is guaranteeing that copper ion is preferential Also the speed that iron ion forms floccule in the solution is slowed down while exchanging to framework of molecular sieve to a certain extent, it can be with It is preferably reacted with imported agent, is conducive to the dispersibility on molecular sieve carrier surface；
In the present invention on the one hand imported agent can be reacted with the copper and iron not exchanged on framework of molecular sieve, be improved dried The dispersibility that metallic element adheres in molecular sieve surface in journey, while it being also adjustable slurry, so that the mobility and water conservation of slurry Property in suitable state, be conducive to slurry in the coating on cordierite ceramic or metal beehive carrier surface；
The method that the present invention uses a step slurrying, entire simple process is easy to operate, and time and process costs are lower.
The present invention uses cheap mesoporous/large pore molecular sieve as carrier, using alkali metal or alkaline-earth metal to carrier It is modified, it prepares alkali metal containing or enters the molecular sieve carrier material of metal ion, then loaded by the way of a step slurrying Active ingredient copper and iron prepare monoblock type SCR catalyst.This method is easy to operate, and technique and time cost are low, prepares Catalyst also has good hydrothermally stable performance while with excellent reaction temperature window.
Detailed description of the invention
Fig. 1 is embodiment and comparative example fresh sample NOxTransformation efficiency figure；
Fig. 2 is NO of the embodiment and comparative example after 650 DEG C of 100hrs hydrothermal agingsxTransformation efficiency figure.
In figure, ordinate NOxConversion ratio, unit %；Abscissa is temperature, unit DEG C.
Specific embodiment
The present invention is further described With reference to embodiment, specific embodiment be to the principle of the invention into One step explanation, does not limit the invention in any way, and same or like technology is protected without departing from the present invention with the present invention Range.
The present invention using cheap mesoporous/large pore molecular sieve as the copper and iron composite SCR catalyst of carrier, the preparation method is as follows:
(1) soluble alkali metal or alkali salt the preparation of modified molecular screen carrier material: are dissolved in excessive distillation In water, for heating stirring to being uniformly dissolved, the ionizable metal salt total concentration in solution is 0.01-0.5mol/L, temperature 50-90 ℃；Molecular sieve is added in above-mentioned solution under vigorous stirring and carries out ion exchange, exchange temperature is 50-90 DEG C, when exchange Between be 2-12h, then filtration washing, drying；
(2) carrier material is at powder: by the modified molecular screen material fragmentation of above-mentioned preparation and being milled into partial size in D50=500- The powder of 3000nm range；
(3) one step slurrying: the carrier powder in step (2) is dissolved in a certain amount of distilled water, is heated under stirring 50-90 DEG C, slurry is made；Addition soluble copper salt simultaneously exchanges 2-12h under agitation；It is cooled to room temperature addition soluble iron Salt and stirring and dissolving 0.5-5h；Imported agent is added again, adjusts slurry pH to 5.0-9.0；Then bonding agent stirring, ball milling is added；
(4) coating roasting: step (3) slurry is coated on cordierite or metal beehive carrier, after heated-air drying 1-6h is roasted under 450-650 DEG C of air environment, improved copper and iron composite SCR integral catalyzer is made.
Above-mentioned molecular sieve is sial salt or zeolite molecular sieve with MFI, BEA, MOR and FAU topological structure, SiO2/ Al2O3=10-60；
Molecular sieve, which can be, individually has a kind of above-mentioned molecular sieve of topological structure, is also possible to that there is above-mentioned difference to open up Flutter the molecular sieve mixture of structure；It can be with a kind of SiO2/Al2O3The molecular sieve of weight ratio is also possible to a variety of SiO2/Al2O3The molecular sieve mixture of weight ratio；
Modified alkaline metal salt or alkaline-earth metal salt are: the soluble-salt of Li, Na, K, Rb, Cs, Mg, Ca, Ba, Sr Class, such as its respective nitrate, sulfate or chlorate etc., can be one such can also be several mixtures；
The exchange times of ion exchange can be 1 time, 2 times or repeatedly；
Active ingredient copper is with Cu2+It calculates, accounts for the 1-5wt% of molecular sieve gross mass, iron is with Fe3+It calculates, accounts for the total matter of molecular sieve The 1-10wt% of amount；Soluble copper salt and molysite can be its respective nitrate, acetate, sulfate or chlorate etc.；
The bonding agent is the one or several kinds of silica solution, Aluminum sol, zirconium colloidal sol；
The importing agent composition is also simultaneously slurry form regulator, can not only be reacted with free metal ion, It can also play the role of adjusting slurry pH and improve water-retaining property；It can be hydroxymethyl cellulose, hydroxyethyl cellulose, three second Amine, ethanol amine, aminoquinoxaline, ammonium hydroxide, PVA, PEG and one are hydrated the mixed of one or more of boehmite colloidal sol Close object；
The control of slurry granularity is in D50=500-5000nm, viscosity=300-3000mPas, the solid content of slurry after ball milling =15-60%.
Corresponding catalyst is prepared using the method for the present invention below, and is compared with the catalyst of conventional method preparation.
Embodiment 1
(1) preparation of molecular sieve carrier material: configuration 1.5L concentration is 0.05mol/L potassium nitrate solution, is heated to 70 DEG C Constant temperature is added dry weight 150g ZSM-5 (MFI) molecular sieve in the case where being kept stirring and in isothermal reaction kettle and carries out ion Exchange is modified, swap time 4h；Obtained slurries are filtered, washed, and gained molecular sieve clod is dried, is crushed and is milled into Partial size is in D50The powder of=2000-2500nm range；
(2) slurrying: above-mentioned powder is added in 225g distilled water, and heating stirring is slurried, and tri- water of 16.99g is then added Copper nitrate, constant temperature stir 4h.It is cooled to room temperature and nine water ferric nitrate of 43.29g is added, stir 1h；12g ethylenediamine, 0.48g mono- is added It is hydrated boehmite and 24gPVG solution (20%), pH range is in 7.0-7.5；It is added 32g silica solution (25%), stirs 1h, It is milled to granularity D50=1800-2300；
(3) integral catalyzer prepare: above-mentioned slurry is coated to having a size of 1 ' * 2 ', mesh number be 400cpsi cordierite On carrier, then 120 DEG C of drying, 500 DEG C of roasting 5h, obtain the copper and iron composite SCR catalyst of alkali metals modified, wherein Cu:Fe =3:4；
Comparative example 1
According to patent CN103127951B, the copper and iron for preparing Cu:Fe=3:4 using slurrying coating method after first impregnating is compound Catalyst；
Comparative example 2
The copper and iron composite catalyst of Cu:Fe=3:4 is prepared according to a step pulping process of embodiment 1, difference is used Molecular sieve is the non-modified molecular sieve as comparative example 1；
Comparative example 3
The copper and iron composite catalyst of comparative example 1 is impregnated 3 times repeatedly in the potassium nitrate solution of 0.05mol/L, is soaked every time Drying is taken out after stain 0.5h, is then impregnated again, finally in the lower roasting 1h of 450 DEG C of air gas point；
Embodiment 2
The step of according to embodiment 1, the copper and iron composite SCR catalyst of Cu:Fe=4:3 is prepared, imported agent is 12g second two Amine, 0.32g hydroxymethyl cellulose；
Embodiment 3
The step of according to embodiment 1, prepare the modified copper and iron composite SCR catalyst of calcium nitrate, imported agent be 8g ethylenediamine, 3.6g aminoquinoxaline and 0.32g hydroxymethyl cellulose；
Catalyst in above embodiments and comparative example is subjected to activity rating and hydrothermal aging.
Evaluation condition are as follows: [NO]=500ppm, [NH3]=500ppm, [H2O]=8%, [O2]=10%, N2 are balance Gas, air speed=60000h-1, reaction temperature is 175 DEG C -500 DEG C, and gas component is detected with FT-IR；Aging condition are as follows: 650 DEG C of@ 100hrs。
Evaluation result is as shown in Figure 1 and Figure 2, from figure it follows that (1) utilizes alkali and alkaline earth metal ions elder generation modified molecules Sieve can be improved the cryogenic property of catalyst, widens the reaction temperature window of catalyst and improves the hydrothermal stability of catalyst Can, it not will lead to the poisoning of catalyst chemical element；(2) catalyst can be made to occur in chemical element by way of rear dipping Poison causes activity and hydrothermally stable performance to be decreased obviously；(3) using the catalyst performance of step pulping process preparation and using first The catalyst for the technique preparation that slurrying coats after dipping does not have significant difference in performance.

Claims (8)

1. a kind of preparation method of SCR catalyst, it is characterised in that specific preparation process is as follows:
(1) prepared by modified molecular screen material: modified metal salt being dissolved in distilled water, heating stirring is to being uniformly dissolved, so Molecular sieve is added in solution afterwards and carries out ion exchange, then filtration washing, drying；
(2) material is at powder: by the modified molecular screen material fragmentation after drying and being milled into partial size in the powder that D50 is 500-3000nm End；
(3) one step slurrying: the dusty material in step (2) is dissolved in 50-90 DEG C of distilled water and slurry is made in stirring, addition can Dissolubility mantoquita carries out ion exchange 2-12h, is then down to room temperature addition soluble ferric iron salt and stirs exchange 0.5-5h, adds and lead Enter agent and bonding agent stirring, ball milling；
(4) coating roasting: step (3) slurry is coated on cordierite ceramic or metal beehive carrier, after heated-air drying 1-6h is roasted under 450-650 DEG C of air environment, improved copper and iron composite SCR integral catalyzer is made.
2. the preparation method of SCR catalyst according to claim 1, it is characterised in that: the molecular sieve be with MFI, The sial salt or zeolite molecular sieve of BEA, MOR or FAU topological structure, SiO2/Al2O ratio=10-60；It can be individually with upper The molecular sieve for stating a kind of topological structure is also possible to the molecular sieve mixture with above-mentioned different topology structure；Can be has A kind of SiO2/Al2The molecular sieve of O ratio, is also possible to a variety of SiO2/Al2The molecular sieve mixture of O ratio.
3. the preparation method of SCR catalyst according to claim 1, it is characterised in that: the gold to support modification Belonging to element is alkali metal or alkaline-earth metal；Modified alkaline metal salt or alkaline-earth metal salt are: Li, Na, K, Rb, Cs, Mg, The solubility salt of Ca, Ba, Sr can be and one such is also possible to several mixtures；Alkali metal or alkali when modified The concentration of earthmetal cations in the solution is 0.01-0.5mol/L, and exchange temperature is 50-90 DEG C, swap time 2-12h.
4. the preparation method of SCR catalyst according to claim 1, it is characterised in that: Cu in step (3)2+/ molecular sieve= 1-5wt%, Fe3+/ molecular sieve=1-10wt%.
5. the preparation method of SCR catalyst according to claim 1, it is characterised in that: the imported agent is methylol fibre In dimension element, hydroxyethyl cellulose, triethylamine, ethanol amine, aminoquinoxaline, ammonium hydroxide, PVA, PEG or a hydration boehmite One or more kinds of mixtures, quality account for the 1-10wt% of slurry total amount.
6. the preparation method of SCR catalyst according to claim 1, it is characterised in that: the bonding agent is silica solution, aluminium The one or several kinds of colloidal sol, zirconium colloidal sol, bonding agent quality account for the 1-10wt% of molecular sieve total amount.
7. the preparation method of SCR catalyst according to claim 1, it is characterised in that: slurry pH=in the step (3) 5.0-9.0, viscosity=300-3000mPas, ball milling granularity D50=500-5000nm.
8. a kind of SCR catalyst, it is characterised in that: the catalyst is that any one of claim 1 to 7 the method is prepared Copper and iron composite molecular screen SCR catalyst.
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CN112246275A (en) * 2020-10-23 2021-01-22 大连理工大学 Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof
CN112371166A (en) * 2020-10-19 2021-02-19 江苏大学 Preparation method of secondary modified molecular sieve integrated SCR catalyst
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