CN109985660A - A kind of method and its application of the iron-based molecular sieve catalyst of one-step synthesis method - Google Patents
A kind of method and its application of the iron-based molecular sieve catalyst of one-step synthesis method Download PDFInfo
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Abstract
The present invention provides a kind of methods of the iron-based molecular sieve catalyst of one-step synthesis method: preparing Fe- complex solution and aluminosilicate molecular sieves gel rubber system respectively, Fe- complex solution is slowly added into aluminosilicate molecular sieves gel rubber system again, through still aging after stirring sufficiently, fill kettle crystallization, deionized water washing, filters, dry, roasting obtains solid iron based molecular sieve, then obtains iron-based molecular sieve catalyst through ammonium exchange.This method simple process, it avoids and ammonium nitrate and iron salt solutions ion exchange and calcine technology is used for multiple times, overcome the shortcomings that traditional one-step synthesis must be by later period ion-exchange process load active component, the iron-based molecular sieve catalyst of synthesis has better catalytic activity, Fe species distribution is more uniform, and excellent NH is kept in wider temperature window3- SCR catalytic activity, while there is very excellent high temperature active and N2Selectivity.
Description
Technical field
The invention belongs to chemical field, it is related to the preparation method of iron-based molecular sieve catalyst (Fe-zeolite), and should
The catalyst that method is prepared is for oxynitrides selective catalytic reduction (NH in exhaust gas from diesel vehicle3- SCR) process.
Background technique
Environmental problem becomes the hot issue of present society, and wherein nitrogen oxides endangers increasingly significant caused by environment.
Nitrogen oxides is mainly derived from plant gas and motor-vehicle tail-gas as a kind of main atmosphere pollution.Wherein, the diesel oil tailstock
Gas nitrogen oxides (NOx) pollution have become most one of distinct issues in China's atmosphere pollution.In moving source denitration, ammonia
Selective catalytic reduction (NH3- SCR) eliminate nitrogen oxides (NOx) with its efficiently, low cost advantage become at present it is most potential
With most widely used denitration technology.
Although catalytic component based on vanadium has been widely used for motor vehicle and stationary source denitration, catalytic component based on vanadium hydro-thermal at present
Stability is poor, and active window is narrow, and vanadium is readily volatilized at high temperature to cause loss of active component.And the appearance of molecular sieve catalyst
This defect of catalytic component based on vanadium is compensated for well.Especially Cu modified molecular screen has good fresh activity and hydrothermally stable
Property, this is particularly critical for exhaust gases of internal combustion engines processing.And on the other hand, in diesel vehicle after-treatment system, since SCR processing is single
Member is typically disposed in after DPF, generates amount of heat during after-treatment system initiative regeneration, SCR unit temperature is made to reach 650
DEG C or more.Therefore, to the catalyst requirement of SCR unit its with excellent high temperature active and thermal stability
(Environ.Sci.Technol.2014,48,566-572).Regrettably, Cu base catalyst is at high temperature due to non-selective
NH3Oxidation leads to its N2Selectivity is poor.And it is reported that iron-based molecular sieve catalyst can overcome copper-based molecular sieve catalytic well
This defect of agent, the modified molecular sieve catalyst of iron have activity and N well at high temperature2Selectivity (ACS
Catal.2016,6,2939-2954).It is deposited however, preparing Fe-zeolite molecular sieve catalyst by traditional ion-exchange
In a series of problems: due to being hydrated Fe3+ Ionic radius is much larger than the bore dia of molecular sieve
(Appl.Catal.B:Environ.180(2016)775–787).Based on this, Fe is often used in ion exchange process2+Instead of
Fe3+, while inert gas shielding is used, prevent Fe3+It is oxidized and forms block Fe oxide, Fe species is caused to hardly enter
Molecular sieve pore passage (CN 104624228 A, Catalysis Today 258 (2015) 347-358).Therefore one pot process Fe-
Zeolite had both been avoided that conventional ion exchanged cumbersome step, can also make Fe ion be easier to enter molecular sieve pore passage, while more having
Conducive to the dispersion of Fe species and the stabilization of framework of molecular sieve.However, there are another for one pot process Fe base aluminosilicate molecular sieves
Aspect problem: synthetic aluminosilicate molecules of salt sieve gel rubber system is generally alkaline environment, if Fe salt, which is directly added into gel, to be made
It is formed and is precipitated at Fe salt, in molecular sieve later period ion exchange process, be hardly formed Fe3+Molecular sieve exchange position is entered, Fe is exhausted
Most of is to exist in the form of the oxide, is unfavorable for NH3- SCR reaction.
Summary of the invention
The task of the present invention is a kind of method of iron-based molecular sieve catalyst of one-step synthesis method is provided, technique letter is made it have
It is single, do not need later period ion-exchange process, be environmentally protective, is energy saving, the features such as molecular sieve active component iron content is controllable,
The iron-based molecular sieve catalyst of the method for the present invention preparation can be in NH3Application in-SCR diesel car tail gas refining system, it is main to use
NO is eliminated in selective catalysis.The iron-based molecular sieve catalyst includes Fe-ZSM-5, Fe-Beta, Fe-SSZ-13, Fe-SSZ-
39, Fe-LTA etc..Provided catalyst can efficiently disappear under wider and higher range of reaction temperature (300~600 DEG C)
Except NO (NO conversion ratio is 80%~97%).
Realize the technical scheme is that
The method of the iron-based molecular sieve catalyst of one-step synthesis method provided by the invention is: preparing Fe- complex solution respectively
With aluminosilicate molecular sieves gel rubber system, then Fe- complex solution is slowly added into aluminosilicate molecular sieves gel rubber system,
Through still aging after stirring sufficiently, dress kettle crystallization, deionized water washing is filtered, and dry, roasting obtains iron-based molecular sieve, then passes through
Ammonium exchange obtains iron-based molecular sieve catalyst；
The preparation method of the Fe- complex solution is: a certain amount of complexing agent is dissolved in water, molysite is then added,
Dissolution is sufficiently stirred, iron ion is complexed completely and obtains Fe- complex solution, the complexing agent in following substance one
Kind or it is several: disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, triethanolamine, diethanol amine, citric acid, acetylacetone,2,4-pentanedione,
Ethylenediamine, sulfosalicylic acid, sodium sulfocynanate.
Described is through still aging, dress kettle crystallization, deionized water washing, suction filtration, dry, roasting specific method: warp
After still aging 24 hours, dress kettle is placed in standing crystallization 48h in 170 DEG C of baking ovens, and obtained product is washed with deionized, and takes out
Filter, dry 12h, then roasts 6h at 600 DEG C at 110 DEG C.
The specific method of the ammonium exchange is: gained Fe based molecular sieve is mixed with the ammonium nitrate solution of 1molL-1
Uniformly, wherein solid-to-liquid ratio is 1:100, stirs 12h at 80 DEG C, is washed with deionized, and is filtered, the dry 12h at 110 DEG C,
6h then is roasted at 600 DEG C, obtains iron-based molecular sieve catalyst.
The preparation method of the aluminosilicate molecular sieves gel rubber system is one of following four method:
Method one:
(1) it prepares solution A: a certain amount of sodium hydroxide is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；
The silicon source is sodium metaaluminate, aluminium isopropoxide, boehmite or boehmite；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution；Institute
The silicon source stated is silica solution, waterglass, fumed silica or tetraethyl orthosilicate；The template is tetrapropyl bromination
It is ammonium, tetrapropyl aqua ammonia, ethylenediamine, n-butylamine, diethanol amine, one or more of in triethanolamine；
(3) A is mixed, B solution: to A, after B solution is respectively completely dissolved, slowly B solution is added in solution A, sufficiently
It stirs evenly, obtains aluminosilicate molecular sieves gel rubber system；
The dosage metered dose and its molar ratio of each raw material are successively are as follows:
SiO2: Al2O3: Na2OH:R:H2O:Fe2O3: CA=1~100:1:6:4:1600:0~0.5:0~0.5；
Or
SiO2: Na2O:Al2O3: H2O:R:Fe2O3: CA=1:0.384:0.1~0.025:50:0.3:0~0.5:0~
0.5., wherein: R is template, and CA is complexing agent.
Method two:
(1) it prepares solution A: a certain amount of sodium hydroxide is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；
The silicon source is sodium metaaluminate, aluminium isopropoxide, boehmite or boehmite；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution；Institute
The silicon source stated is silica solution, waterglass, fumed silica or tetraethyl orthosilicate；The template is N, N, N- front three
Base -1- adamantyl ammonium hydroxide；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, is sufficiently stirred
Uniformly, aluminosilicate molecular sieves gel rubber system is obtained；
The dosage metered dose and its molar ratio of each raw material are successively are as follows:
SiO2: Al2O3: Na2O:R:H2O:Fe2O3: CA=1.0:0.1~0.025:0.1:0.2:40:0~0.5:0~
0.5；
Wherein: R is template, and CA is complexing agent.
Method three:
(1) it prepares solution A: a certain amount of sodium hydroxide is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution, institute
The template stated is hydroxide N, N- diethyl-lupetidine or hydroxide N, N- dimethyl -3,5- dimethyl piperazine
Pyridine；
Silicon source described in silicon source described in above-mentioned steps (1) and above-mentioned steps (2) is all from USY molecular sieve；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, is sufficiently stirred
Uniformly, aluminosilicate molecular sieves gel rubber system is obtained；
The dosage metered dose and its molar ratio of each raw material are successively are as follows: SiO2: Al2O3: Na2O:R:H2O:Fe2O3: CA
=1.0:0.1~0.025:0.2:0.2:15:0~0.5:0~0.5；Wherein: R is template, and CA is complexing agent.
Method four:
(1) it prepares solution A: a certain amount of hydrofluoric acid is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；Institute
The silicon source stated is sodium metaaluminate, aluminium isopropoxide, boehmite or boehmite；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution；Institute
The silicon source stated is silica solution, waterglass, fumed silica or tetraethyl orthosilicate；The template is hydroxide 1,2- bis-
Methyl -3- (4- methylbenzyl) imidazoles, hydroxide 1, one of 2- dimethyl -3- (2- luorobenzyl) imidazoles and tetramethyl hydrogen
Amine-oxides；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, is sufficiently stirred
Uniformly, aluminosilicate molecular sieves gel rubber system is obtained；
The dosage metered dose and its molar ratio of each raw material are successively are as follows: SiO2: Al2O3: H2O:R:TMAOH:HF:
Fe2O:CA=1:0.05~0.025:5.0:0.5:0.1~0.05:0.49:0~0.5:0~0.5；Wherein: R is template, CA
For complexing agent.
Iron-based molecular sieve catalyst of the present invention includes Fe-ZSM-5, Fe-Beta, Fe-SSZ-13, Fe-SSZ-39,
Fe-LTA etc., preparation method is as follows:
1) Fe-ZSM-5 system with molecular sieve for preparing is standby:
(1) prepares solution A: a certain amount of alkali (sodium hydroxide) being dissolved in water, is eventually adding silicon source, stirring is abundant to it
Dissolution: sodium metaaluminate, aluminium isopropoxide, boehmite, one of boehmite；
(2) prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution.
Wherein silicon source are as follows: silica solution, waterglass, fumed silica, one of tetraethyl orthosilicate；Template are as follows: tetrapropyl bromine
Change ammonium, tetrapropyl aqua ammonia, ethylenediamine, n-butylamine, diethanol amine, triethanolamine one of which or several；
(3) prepares Fe- complex solution: a certain amount of complexing agent is dissolved in water, molysite is added afterwards, dissolution is sufficiently stirred,
Iron ion is complexed completely and obtains Fe- complex solution.Wherein complexing agent are as follows: disodium ethylene diamine tetraacetate, ethylenediamine tetra-acetic acid
Four sodium, triethanolamine, diethanol amine, citric acid, acetylacetone,2,4-pentanedione, ethylenediamine, sulfosalicylic acid, one of sodium sulfocynanate or several
Kind；
(4) B solution: B solution to A, after B solution is completely dissolved, is slowly added in solution A, is sufficiently stirred by mixing A
Uniformly, Fe- complex solution is slowly added into A, in the mixed solution of B, after stirring sufficiently after still aging 24 hours, fills kettle
Crystallization a couple of days at a certain temperature, raw material proportioning are as follows: (1~100) SiO2: Al2O3: 6Na2O:4R:1600H2O:(0~0.5)
Fe2O3: (0~0.5) CA (wherein R represents template, and CA represents complexing agent).
2) Fe-Beta system with molecular sieve for preparing is standby:
Fe-Beta Zeolite synthesis step and Fe-ZSM-5 system with molecular sieve for preparing are for similar, and wherein gel matches are as follows: SiO2:
0.384Na2O:(0.1~0.025) Al2O3: 50H2O:0.3R:(0~0.5) Fe2O3: (0~0.5) CA.
3) Fe-SSZ-13 system with molecular sieve for preparing is standby:
Fe-SSZ-13 Zeolite synthesis step and Fe-ZSM-5 system with molecular sieve for preparing are for similar, wherein template R are as follows: N, N, N-
Trimethyl -1- adamantyl ammonium hydroxide.Gel proportion are as follows: 1.0SiO2: (0.1~0.025) Al2O3: 0.1Na2O:0.2R:
40H2O:(0~0.5) Fe2O3: (0~0.5) CA.
4) Fe-SSZ-39 system with molecular sieve for preparing is standby:
Fe-SSZ-39 Zeolite synthesis step and Fe-ZSM-5 system with molecular sieve for preparing are for similar, and wherein silicon source and silicon source are all from
USY molecular sieve, wherein template R are as follows: hydroxide N, N- diethyl -2,6- lupetidine, dimethyl -3 hydroxide N, N-,
One of 5- lupetidine.Raw material proportioning are as follows: 1.0SiO2: (0.1~0.025) Al2O3: 0.2Na2O:0.2R:15H2O:
(0~0.5) Fe2O3: (0~0.5) CA.
5) Fe-LTA system with molecular sieve for preparing is standby:
Fe-LTA Zeolite synthesis step and Fe-ZSM-5 system with molecular sieve for preparing are for similar, wherein hydrofluoric acid charging sequence and hydrogen-oxygen
The charging sequence for changing sodium is consistent.Wherein template R are as follows: hydroxide 1,2- dimethyl -3- (4- methylbenzyl) imidazoles, hydroxide 1,
One of 2- dimethyl -3- (2- luorobenzyl) imidazoles and tetramethylammonium hydroxide.Raw material proportioning are as follows: 1.0SiO2: (0.05
~0.025) Al2O3: 5.0H2O:0.5R:(0.1~0.05) TMAOH:0.49HF:(0~0.5) Fe2O3: (0~0.5) CA.
In order to compare the Fe-zeolite difference of one pot process and the preparation of conventional ion exchange process, conventional ion exchange process
The different iron-based molecular sieve preparation methods of preparation are as follows:
The preparation of conventional ion exchange process Fe-zeolite molecular sieve catalyst:
A certain amount of ferrous sulfate is soluble in water, it is prepared into 0.1molL-1Solution, adjust its PH=3 with ammonium hydroxide,
NH is added4(synthesis step is identical as one kettle way, and difference is to be added without Fe- complex compound in gel rubber system molten for type molecular sieve
Liquid), solid-to-liquid ratio 1:100.In N2Under protection, 80 DEG C of stirring 12h are washed with deionized, and are filtered, dry at 110 DEG C
12h then roasts 6h at 600 DEG C, obtains the Fe-zeolite molecular sieve catalyst of conventional ion exchange process preparation.
One of the objects of the present invention is to provide a kind of methods of one-step synthesis method Fe-zeolite molecular sieve catalyst, lead to
The investment ratio regulation copper load capacity for crossing control Fe- complex compound is 0.1~8.00wt.%, while controlling the silicon in gel rubber system
It is 5~40 that aluminium ratio, which reaches control product silica alumina ratio, obtains crystallinity, excellent high-temperature catalytic activity and N with higher2Selection
The Fe-zeolite molecular sieve catalyst of property.
The iron-based molecular sieve catalyst that the method for the present invention is prepared is suitable for diesel vehicle post-processing Urea-SCR system and urges
Change device and stationary source NH3Oxynitrides purification process in-SCR.
In order to overcome the deficiencies of the prior art, prevent in the synthesis process precipitating of the Fe ion under alkaline environment form hydrogen-oxygen
Change iron, the present invention is proposed with a kind of novel synthesis thinking: after first Fe ion is complexed with organic complexing agent, being then added to gel
System.During later period molecular sieve roasts and removes template and organic complexing agent, Fe ion enters ion exchange site.It is this
Method can effectively avoid Fe ion from forming precipitating, mainly exist in the form of an oxide in after baking process.
The method have the advantages that: (1) with the Fe-zeolite of conventional ion exchange process preparation compared with, this synthesis side
Method has simple process, avoids and ammonium nitrate and iron salt solutions ion exchange and calcine technology is used for multiple times, and overcomes tradition one
Walk the shortcomings that synthetic method must be by later period ion-exchange process load active component；(2) it is prepared with conventional ion exchange process
Fe-zeolite is compared, and the Fe-zeolite of this synthetic method synthesis has better catalytic activity, and Fe species distribution is more equal
It is even；(3) excellent NH is kept in wider temperature window using the Fe-zeolite catalyst of this method preparation3- SCR catalysis
Activity, while there is very excellent high temperature active and N2Selectivity.
Detailed description of the invention
Fig. 1 is the XRD diagram of 1,2,3,4,5 and 6 sample of embodiment, and as one-step method and conventional ion exchange process prepare Fe-
The XRD diagram of zeolite, one-step method and two-step method successfully synthesize Fe-zeolite points of crystalline structure indifference as seen from the figure
Sub- sieve catalyst.
Fig. 2 is the NO conversion ratio figure of 1,2,3,4,5 and 6 sample of embodiment, and as one-step method exchanges legal system with conventional ion
The NO conversion ratio figure of standby Fe-zeolite sample, by two figures comparison as it can be seen that one-step method preparation Fe-zeolite it is more traditional from
The standby Fe-zeolite catalytic activity of sub- exchange system is more preferable.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
The synthesis of embodiment 1:Fe-ZSM-5 molecular sieve catalyst
0.9g sodium hydroxide is dissolved in 22g deionized water, sodium metaaluminate 0.51g is added after completely dissolution to it, is stirred
Sufficiently dissolution, obtains solution A.15g silica solution is dissolved in 10g deionized water, 3g tetrapropyl amine bromide is then added, sufficiently stirs
It mixes to obtain solution B, under stiring, solution B is slowly added into solution A.0.33g disodium ethylene diamine tetraacetate is dissolved in 10g
In deionized water, 0.27g ferrous sulfate is added after it is completely dissolved, sufficiently obtains Fe- complex solution after complexing, it will be made
Fe- complex solution is slowly added to A in batches, in the mixed solution of B, stood for 24 hours after stirring 4h.Then dress kettle, is placed in 170
Crystallization 48h at DEG C.Obtained product is washed with deionized, is filtered, dry 12h, then roasts at 600 DEG C at 110 DEG C
6h is burnt, removes organic formwork agent and complexing agent to get Fe-ZSM-5 molecular sieve.To remove the molecular sieve of template and complexing agent with
1mol·L-1Ammonium nitrate solution be uniformly mixed, wherein solid-to-liquid ratio be 1:100, stir 12h at 80 DEG C.It is washed with deionized water
It washs, filters, dry 12h, then roasts 6h at 600 DEG C, obtain Fe-ZSM-5 molecular sieve catalyst at 110 DEG C.
The synthesis of embodiment 2:Fe-Beta molecular sieve catalyst
1.68g sodium hydroxide is dissolved in 24g deionized water, sodium metaaluminate 0.35g is added after completely dissolution to it, is stirred
Sufficiently dissolution, obtains solution A.3.6g fumed silica is dissolved in 10g deionized water, 2.56g tetrapropyl bromine is then added
Change amine, is sufficiently stirred to obtain solution B, under stiring, solution B is slowly added into solution A.By 0.33g ethylenediamine tetra-acetic acid
Disodium is dissolved in 10g deionized water, and 0.27g ferrous sulfate is added after it is completely dissolved, sufficiently obtains Fe- complex compound after complexing
Obtained Fe- complex solution is slowly added to A by solution in batches, in the mixed solution of B, stirs 4h.Then dress kettle, is placed in
Crystallization 144h at 120 DEG C.Obtained product is washed with deionized, is filtered, the dry 12h at 110 DEG C, then at 600 DEG C
Lower roasting 6h removes organic formwork agent and complexing agent to get Fe-Beta molecular sieve.The molecule of template and complexing agent will be removed
Sieve and 1molL-1Ammonium nitrate solution be uniformly mixed, wherein solid-to-liquid ratio be 1:100, stir 12h at 80 DEG C.Use deionized water
Washing filters, and dry 12h, then roasts 6h at 600 DEG C, obtain Fe-Beta molecular sieve catalyst at 110 DEG C.
The synthesis of embodiment 3:Fe-SSZ-13 molecular sieve catalyst
0.81g sodium hydroxide is dissolved in 25.3g deionized water, sodium metaaluminate 2g is added after completely dissolution to it, is stirred
Sufficiently dissolution, obtains solution A.20g silica solution is dissolved in 10g deionized water, 13.55g N, N, N- trimethyl-is then added
1- adamantyl ammonium hydroxide is sufficiently stirred to obtain solution B, under stiring, solution B is slowly added into solution A.It will
0.66g disodium ethylene diamine tetraacetate is dissolved in 10g deionized water, and 0.56g ferrous sulfate, abundant network are added after it is completely dissolved
Fe- complex solution is obtained after conjunction, and obtained Fe- complex solution is slowly added to A in batches, in the mixed solution of B, stirring
4h.Then dress kettle, is placed in crystallization 96h at 150 DEG C.Obtained product is washed with deionized, is filtered, it is dry at 110 DEG C
12h then roasts 6h at 600 DEG C, removes organic formwork agent and complexing agent to get Fe-SSZ-13 molecular sieve.Template will be removed
The molecular sieve and 1molL of agent and complexing agent-1Ammonium nitrate solution be uniformly mixed, wherein solid-to-liquid ratio be 1:100, stirred at 80 DEG C
Mix 12h.It is washed with deionized, filters, dry 12h, then roasts 6h at 600 DEG C, obtain Fe-SSZ-13 at 110 DEG C
Molecular sieve catalyst.
The synthesis of embodiment 4:Fe-SSZ-39 molecular sieve catalyst
0.67g sodium hydroxide is dissolved in 15.6g deionized water, sufficiently dissolution is stirred, obtains solution A.By 12.9g USY
Molecular sieve is added in 10g deionized water and stirs evenly, and 24.6g hydroxide N, N- dimethyl -3,5- lupetidine is then added
, it is sufficiently stirred to obtain solution B, under stiring, solution B is slowly added into solution A.By 0.75g ethylenediamine tetra-acetic acid two
Sodium is dissolved in 10g deionized water, and 0.70g ferrous sulfate is added after it is completely dissolved, and it is molten sufficiently to obtain Fe- complex compound after complexing
Obtained Fe- complex solution is slowly added to A by liquid in batches, in the mixed solution of B, stirs 4h.Then dress kettle, is placed in 135
Crystallization 168h at DEG C.Obtained product is washed with deionized, is filtered, dry 12h, then roasts at 600 DEG C at 110 DEG C
6h is burnt, removes organic formwork agent and complexing agent to get Fe-SSZ-39 molecular sieve.The molecular sieve of template and complexing agent will be removed
With 1molL-1Ammonium nitrate solution be uniformly mixed, wherein solid-to-liquid ratio be 1:100, stir 12h at 80 DEG C.It is washed with deionized water
It washs, filters, dry 12h, then roasts 6h at 600 DEG C, obtain Fe-SSZ-39 molecular sieve catalyst at 110 DEG C.
The synthesis of embodiment 5:Fe-LTA molecular sieve catalyst
0.21g hydrofluoric acid is dissolved in 5.2g deionized water, 1.2g boehmite is then added, sufficiently dissolution is stirred, obtains
Solution A.10g silica solution is added in 5g deionized water and is stirred evenly, 4.62g tetramethylammonium hydroxide and 12.3g is then added
Hydroxide 1,2- dimethyl -3- (4- methylbenzyl) imidazoles, is sufficiently stirred to obtain solution B, and under stiring, solution B is slowly added
Enter into solution A.0.36g disodium ethylene diamine tetraacetate is dissolved in 5g deionized water, 0.30g sulphur is added after it is completely dissolved
It is sour ferrous, Fe- complex solution sufficiently is obtained after complexing, obtained Fe- complex solution is slowly added to A in batches, B's is mixed
It closes in solution, stirs 4h.Then dress kettle, is placed in crystallization 72h at 175 DEG C.Obtained product is washed with deionized, is filtered,
Dry 12h, then roasts 6h at 600 DEG C at 110 DEG C, removes organic formwork agent and complexing agent to get Fe-LTA molecular sieve
Catalyst.
Embodiment 6: conventional ion exchange process Fe-zeolite synthesis
A certain amount of ferrous sulfate is soluble in water, it is prepared into 0.1molL-1Solution, adjust its PH=3 with ammonium hydroxide,
NH is added4(synthesis step is identical as one kettle way, and difference is to be added without Fe- complex compound in gel rubber system molten for type molecular sieve
Liquid), solid-to-liquid ratio 1:100.In N2Under protection, 80 DEG C of stirring 12h are washed with deionized, and are filtered, dry at 110 DEG C
12h then roasts 6h at 600 DEG C, obtains the Fe-zeolite molecular sieve catalyst of conventional ion exchange process preparation.
Wherein the iron-based molecular sieve of direct synthesis is labeled as " Fe-zeolite-one pot ", conventional ion exchange process mark
It is denoted as " Fe-zeolite-IE ".Such as Fe-ZSM-5-one pot represents the iron-based ZSM-5 molecular sieve catalysis of one-step synthesis method
Agent, Fe-ZSM-5-IE represent the iron-based ZSM-5 molecular sieve catalyst of conventional ion exchange process synthesis.
In the present invention, the evaluation of catalyst is with the following method:
By 0.5g Fe-zeolite catalyst fines, the silica solution that 0.4g mass fraction is 30% is mixed with 4g water, is prepared
Slurries are coated on cordierite honeycomb ceramic matrix sample, and catalyst coated weight is about 250gL-1, sample is 100 DEG C dry 2 small
When, 500 DEG C roast 2 hours, and the monoblock type Fe-zeolite catalyst as prepared puts it into fixed bed activity rating device
In, simulated flue gas group becomes 1000ppm NO, 1100ppm NH3, 5%O2And 10%H2O, reaction velocity 30,000h-1。
Attached drawing 1 is the XRD diagram that one-step method and conventional ion exchange process prepare Fe-zeolite, as seen from the figure one-step method and two
Footwork successfully synthesizes the Fe-zeolite molecular sieve catalyst of crystalline structure indifference.
Attached drawing 2 is the NO conversion ratio figure of the Fe-zeolite sample of one-step method and the preparation of conventional ion exchange process, You Liangtu
Comparison is as it can be seen that the Fe-zeolite catalytic activity Fe-zeolite of one-step method preparation standby compared with conventional ion exchange system is more preferable.From
And the simple process of one-step method double template preparation method is further embodied, environmental protection, prepared catalyst catalytic activity is more preferably etc.
Advantage.
The Applicant declares that it should be clear to those skilled in the art, any improvement in the present invention, to the present invention
The equivalence replacement of each raw material of product and the addition of auxiliary element, the selection etc. of concrete mode all fall within protection scope of the present invention
Within the open scope.
Claims (10)
1. a kind of method of the iron-based molecular sieve catalyst of one-step synthesis method, the steps include:
Fe- complex solution and aluminosilicate molecular sieves gel rubber system are prepared respectively, then Fe- complex solution is slowly added into
In gel rubber system, through still aging after stirring sufficiently, dress kettle crystallization, deionized water washing is filtered, and dry, roasting obtains Fe base
Molecular sieve, then Fe based molecular sieve catalyst is obtained through ammonium exchange.
2. according to the method described in claim 1, it is characterized by: the preparation method of the Fe- complex solution is: by one
Quantitative complexing agent is dissolved in water, and molysite is then added, and dissolution is sufficiently stirred, and iron ion is complexed completely, and to obtain Fe- complex compound molten
Liquid, the complexing agent are selected from one or more of following substance: disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate,
Triethanolamine, diethanol amine, citric acid, acetylacetone,2,4-pentanedione, ethylenediamine, sulfosalicylic acid, sodium sulfocynanate；
The preparation method of the aluminosilicate molecular sieves gel rubber system is:
(1) it prepares solution A: a certain amount of sodium hydroxide is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；It is described
Silicon source be sodium metaaluminate, aluminium isopropoxide, boehmite or boehmite；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution；Described
Silicon source is silica solution, waterglass, fumed silica or tetraethyl orthosilicate；The template is 4-propyl bromide, four
It is propyl aqua ammonia, ethylenediamine, n-butylamine, diethanol amine, one or more of in triethanolamine；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, stirs,
Obtain aluminosilicate molecular sieves gel rubber system；
The dosage metered dose and its molar ratio of each raw material are successively are as follows:
SiO2: Al2O3: Na2OH:R:H2O:Fe2O3: CA=1~100:1:6:4:1600:0~0.5:0~0.5；
Or
SiO2: Na2O:Al2O3: H2O:R:Fe2O3: CA=1:0.384:0.1~0.025:50:0.3:0~0.5:0~0.5, its
In: R is template, and CA is complexing agent.
3. according to the method described in claim 1, it is characterized by:
The preparation method of the Fe- complex solution is: a certain amount of complexing agent being dissolved in water, molysite is then added, sufficiently
Stirring and dissolving is complexed iron ion completely and obtains Fe- complex solution, the complexing agent be selected from one of following substance or
It is several: disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, triethanolamine, diethanol amine, citric acid, acetylacetone,2,4-pentanedione, second two
Amine, sulfosalicylic acid, sodium sulfocynanate；
The preparation method of the aluminosilicate molecular sieves gel rubber system is:
(1) it prepares solution A: a certain amount of sodium hydroxide is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；It is described
Silicon source be sodium metaaluminate, aluminium isopropoxide, boehmite or boehmite；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution；Described
Silicon source is silica solution, waterglass, fumed silica or tetraethyl orthosilicate；The template R is N, N, N- trimethyl -1-
Adamantyl ammonium hydroxide；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, stirs,
Obtain aluminosilicate molecular sieves gel rubber system；
The dosage metered dose and its molar ratio of each raw material are successively are as follows:
SiO2: Al2O3: Na2O:R:H2O:Fe2O3: CA=1.0:0.1~0.025:0.1:0.2:40:0~0.5:0~0.5；
Wherein: R is template, and CA is complexing agent.
4. according to the method described in claim 1, it is characterized by:
The preparation method of the Fe- complex solution is: a certain amount of complexing agent being dissolved in water, molysite is then added, sufficiently
Stirring and dissolving is complexed iron ion completely and obtains Fe- complex solution, the complexing agent be selected from one of following substance or
It is several: disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, triethanolamine, diethanol amine, citric acid, acetylacetone,2,4-pentanedione, second two
Amine, sulfosalicylic acid, sodium sulfocynanate；
The preparation method of the aluminosilicate molecular sieves gel rubber system is:
(1) it prepares solution A: a certain amount of sodium hydroxide is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution, it is described
Template R is hydroxide N, N- diethyl-lupetidine or hydroxide N, N- dimethyl -3,5- lupetidine
；
Silicon source described in silicon source described in above-mentioned steps (1) and above-mentioned steps (2) is all from USY molecular sieve；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, stirs,
Obtain aluminosilicate molecular sieves gel rubber system；
The dosage metered dose and its molar ratio of each raw material are successively are as follows: SiO2: Al2O3: Na2O:R:H2O:Fe2O3: CA=
1.0:0.1~0.025:0.2:0.2:15:0~0.5:0~0.5；Wherein: R is template, and CA is complexing agent.
5. according to the method described in claim 1, it is characterized by:
The preparation method of the Fe- complex solution is: a certain amount of complexing agent being dissolved in water, molysite is then added, sufficiently
Stirring and dissolving is complexed iron ion completely and obtains Fe- complex solution, the complexing agent be selected from one of following substance or
It is several: disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, triethanolamine, diethanol amine, citric acid, acetylacetone,2,4-pentanedione, second two
Amine, sulfosalicylic acid, sodium sulfocynanate；
The preparation method of the aluminosilicate molecular sieves gel rubber system is:
(1) it prepares solution A: a certain amount of hydrofluoric acid is dissolved in water, silicon source is then added, stirring is sufficiently dissolved to it；Described
Silicon source is sodium metaaluminate, aluminium isopropoxide, boehmite or boehmite；
(2) it prepares solution B: a certain amount of silicon source being dissolved in water, template is then added, stirs evenly to form B solution；Described
Silicon source is silica solution, waterglass, fumed silica or tetraethyl orthosilicate；The template R is hydroxide 1,2- diformazan
Base -3- (4- methylbenzyl) imidazoles, hydroxide 1, one of 2- dimethyl -3- (2- luorobenzyl) imidazoles and tetramethyl hydrogen-oxygen
Change ammonium；
(3) A is mixed, B solution: to A, after B solution is completely dissolved, slowly B solution is added in solution A, stirs,
Obtain aluminosilicate molecular sieves gel rubber system；
The dosage metered dose and its molar ratio of each raw material are successively are as follows: SiO2: Al2O3: H2O:R:TMAOH:HF:Fe2O:CA
=1:0.05~0.025:5.0:0.5:0.1~0.05:0.49:0~0.5:0~0.5；Wherein: R is template, and CA is complexing
Agent.
6. the method according to any one of claims 1 to 5, it is characterised in that: described through still aging, dress kettle is brilliant
Change, deionized water washing, filter, is dry, roasting specific method is: after still aging 24 hours, dress kettle is placed in 170 DEG C of bakings
Crystallization 48h is stood in case, obtained product is washed with deionized, and is filtered, the dry 12h at 110 DEG C, then at 600 DEG C
Lower roasting 6h.
7. the method according to any one of claims 1 to 5, which is characterized in that the specific method of the ammonium exchange is:
Gained Fe based molecular sieve is uniformly mixed with the ammonium nitrate solution of 1molL-1, wherein solid-to-liquid ratio is 1:100, is stirred at 80 DEG C
12h is mixed, is washed with deionized, is filtered, dry 12h, then roasts 6h at 600 DEG C, obtain Fe based molecular sieve at 110 DEG C
Catalyst.
8. according to the method described in claim 6, it is characterized in that, the specific method that the ammonium exchanges is: by gained Fe base
Molecular sieve is uniformly mixed with the ammonium nitrate solution of 1molL-1, and wherein solid-to-liquid ratio is 1:100, is stirred 12h at 80 DEG C, is spent
Ion water washing filters, and dry 12h, then roasts 6h at 600 DEG C, obtain Fe based molecular sieve catalyst at 110 DEG C.
9. the iron-based molecular sieve catalyst of any one of claims 1 to 8 the method preparation.
10. iron-based molecular sieve catalyst as claimed in claim 9 is for diesel vehicle post-processing Urea-SCR system catalyst and admittedly
Determine source NH3Oxynitrides purification process in-SCR.
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