CN103657742B - A kind of iron ion exchanges the preparation method of modified molecular screen - Google Patents
A kind of iron ion exchanges the preparation method of modified molecular screen Download PDFInfo
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- CN103657742B CN103657742B CN201210330903.7A CN201210330903A CN103657742B CN 103657742 B CN103657742 B CN 103657742B CN 201210330903 A CN201210330903 A CN 201210330903A CN 103657742 B CN103657742 B CN 103657742B
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Abstract
The invention provides a kind of iron ion and exchange the preparation method of modified molecular screen, comprise the following steps: in iron salt solutions, 1) add reduced iron powder and parent molecule sieve carries out ion-exchange reactions; 2) Separation of Solid and Liquid is carried out after completion of the reaction; 3) wash to remove residual molysite to gained solid product; 4) drying is carried out to the product after washing; 5) product is placed in magnetic field and carries out Magnetic Isolation, to get rid of iron powder wherein.The present invention exchanges modified molecular screen by once exchanging the iron ion that can obtain high exchange degree; Inert environments protection need not can prevent the oxidation of ferrous ion, what produce in process not exchangedly can be removed to the residue species on molecular sieve, thus obtains comparatively pure exchange product.<!--1-->
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, be specifically related to the preparation method that a kind of iron ion exchanges modified molecular screen.
Background technology
It is a kind of of great value catalysis material that iron ion exchanges modified molecular screen, and it is at NO
xexcellent activity and selectivity is demonstrated in a series of catalytic reaction such as SCR and SCR.Preparing iron ion, to exchange the usual method of modified molecular screen be carry out ion exchange in solution or solid state ion exchange by molecular sieve precursor and iron containing compounds and obtain.
Traditional ion-exchange is the aqueous solution ion-exchange process adopting 1970S to grow up: molecular sieve precursor be suspended in the exchanged metal cation aqueous solution and carry out liquid-solid exchange, its general process can be described as: stirred at a certain temperature by suspension, and then Separation of Solid and Liquid, washing are also dry.Be that the ion-exchange exchanging presoma can represent with following chemical reaction equilibrium equation with hydrogen type molecular sieve:
In chemical reaction equilibrium equation, M is n
+valency cation is (as Fe
2+, Fe
3+deng); A is m
-valency anion; Z is monovalent molecules sieve skeleton shelf structure; A, b, m, x are molecule molal quantity.
From above-mentioned chemical reaction equilibrium equation, the reaction of the ion exchange in solution of molecular sieve also exists following deficiency: (1) according to above-mentioned chemical equilibrium equation formula, along with the carrying out of exchange reaction, M in solution
n+cation concn reduces, H
+concentration increases, and the change of the two is all unfavorable for that ion-exchange reactions forward carries out, and thus a step exchanges and can only obtain very low ion-exchange degree.Therefore whole ion exchange process needs repeatedly to carry out obtaining higher ion-exchange degree, and this directly causes operating process loaded down with trivial details, and need process a large amount of waste liquids.(2) some cation, as ferrous ion, also unstable in aqueous, easy oxidation or reduction and generate precipitation, cause ion-exchange reactions not occur, corresponding ion-exchange reactions must be carried out in inert environments (document Appl.Cata.B, described in 2010,101:649: at inert gas N
2fe is carried out under protection
2+the ion-exchange reactions of ion and molecular sieve), be not thus a kind of easy method of operating.
The method of another kind of ion-exchange is solid state ion exchange method; its basic process is: by molecular sieve and exchanged metallic compound Homogeneous phase mixing; solid-state reaction is carried out under air, vacuum or inert atmosphere; the advantage of this exchanged form is; can by once exchanging and obtaining higher exchange degree; but it is Shortcomings still: (1) many solid-state ion exchanges still must carry out in inert gas shielding even vacuum, to avoid the generation of the side reactions such as such as cationic oxidation.(2) not easily do not removed in subsequent steps to the metallic compound of molecular sieve or the oxide that formed in exchange process by complete exchange, be thus difficult to obtain comparatively pure exchange product.
Summary of the invention
The deficiency that iron ion exchanges modified molecules screen method is prepared for traditional ion exchange in solution and solid state ion exchange, the iron ion that the present invention aims to provide a kind of improvement exchanges modified molecular screen preparation method, overcome common liquid-phase ion exchange exchange degree low, need repeatedly repeatedly carry out, the ferrous ion easily shortcoming such as oxidized in the liquid phase, exchange modified molecular screen by once exchanging the iron ion that can obtain high exchange degree; The method inert environments protection need not can prevent the oxidation of ferrous ion, and what produce in process not exchangedly can be removed to the residue species on molecular sieve, thus obtains comparatively pure exchange product.
Iron ion exchanges a preparation method for modified molecular screen, comprises the following steps:
1) in iron salt solutions, add reduced iron powder and parent molecule sieve, the mixture of molysite, iron powder and parent molecule sieve is stirred to carry out ion-exchange reactions;
2) Separation of Solid and Liquid is carried out after completion of the reaction;
3) wash to remove residual molysite to the solid product after separation;
4) drying is carried out to the product after washing;
5) dried product is placed in magnetic field and carries out Magnetic Isolation, thus obtain pure iron ion exchange modified molecular screen.
The preferred embodiments of the invention are:
In step 1), iron salt concentration is that 0.001mol/L is to saturated concentration, it is 0.1:1 ~ 10:1 that described reduced iron powder addition and described parent molecule sieve mass ratio, the mass volume ratio of the mixture that described parent molecule sieve and iron powder form and described iron salt solutions is 1:5 ~ 1:50g/ml, at 0 DEG C to 100 DEG C temperature, stir 1 ~ 24 hour to carry out ion-exchange reactions to the mixture of molysite, iron powder and parent molecule sieve;
Step 2) described in Separation of Solid and Liquid by filtering, the mode such as centrifugal completes.
Wash to remove residual molysite to gained solid matter with deionized water in step 3);
Washing process can repeatedly carry out reaching good removal effect.
Between 0 ~ 150 DEG C, carry out sufficient drying to the product after washing in step 4), dry run can select air blast at a certain temperature or natural drying, can also carry out vacuum drying under vacuum conditions.
Desciccate is placed in magnetic field and carries out Magnetic Isolation by step 5), to get rid of iron powder wherein, thus obtains pure iron ion exchange modified molecular screen.
The preferred embodiments of the invention are one or more that parent molecule sieves for Hydrogen Si-Al molecular sieve, in preferred BETA, L, MAZ, MFI, FER, MOR, Y zeolite; Described iron salt solutions, one or more in preferred iron chloride, ferric nitrate, ferric sulfate, frerrous chloride, ferrous nitrate, copperas solution.
Reaction principle of the present invention: add reduced iron powder in ion exchange in solution process, react below occurring in switching architecture:
H
++Fe→H
2+Fe
2+
This reaction will consume the H generated in molecular sieve and iron salt solutions ion exchange process
+, meanwhile, the Fe consumed in ion-exchange reactions can be supplemented in time
2+, H in inhibition system
+concentration increases and Fe
2+the reduction of concentration, thus chemical balance is carried out towards the positive direction of ion-exchange reactions.
2) Fe will be suppressed adding of iron powder
2+oxidized.
Beneficial effect of the present invention:
1) iron ion that the present invention obtains exchanges modified molecular screen and has high exchange degree.
2) the present invention is simple to operate, without the need to carrying out external inert environments protection.
3) later separation of the present invention is simple, by Magnetic Isolation, can be easy to remove iron powder, obtain pure iron ion and exchange modified molecular screen.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum before and after the ion-exchange of HY molecular sieve,
This infrared spectrum gathers under the vacuum condition of 500 DEG C, and in Fig. 1, A is the infrared spectrum of parent molecule sieve, and B is the infrared spectrum that iron ion exchanges modified molecular screen;
Fig. 2 is the infrared spectrum before and after the ion-exchange of HZSM-5 molecular sieve,
This infrared spectrum gathers under the vacuum condition of 500 DEG C, and in Fig. 2, C is the infrared spectrum of parent molecule sieve, and D is the infrared spectrum that iron ion exchanges modified molecular screen;
Fig. 3 is the infrared spectrum that different switching method gained iron ion exchanges modified molecular screen,
This infrared spectrum gathers under the vacuum condition of 500 DEG C, and in Fig. 3, E prepares gained iron ion for method described in comparative example 1 and exchanges the infrared spectrum of modified molecular screen, and in Fig. 3, F prepares the infrared spectrum that gained iron ion exchanges modified molecular screen for method described in embodiment 2.
Detailed description of the invention
Embodiment 1
Reduced iron powder and silica alumina ratio be 8 HY parent molecule sieve 1:1 in mass ratio and mix, the mixture that iron powder and parent molecule sieve is added the FeCl of 1mol/L
2in solution, in every 10ml solution, add 1g solid; Stir at 80 DEG C of temperature and carry out ion-exchange in 24 hours; Suction filtration after exchange, and spend deionized water; Sample is 110 DEG C of oven dry; Sample is placed in magnetic field, and Magnetic Isolation goes out iron powder, obtains iron ion and exchanges modified molecular screen.
Embodiment 2
Reduced iron powder and silica alumina ratio be 25 HZSM-5 parent molecule sieve 1:1 in mass ratio and mix, the mixture that iron powder and parent molecule sieve is added the FeCl of 0.5mol/L
2in solution, solid-to-liquid ratio is add 1g solid in every 10ml solution; Stir at 80 DEG C of temperature and carry out ion-exchange in 24 hours; Suction filtration after exchange, and spend deionized water; Sample is 110 DEG C of oven dry; Sample is placed in magnetic field, and Magnetic Isolation goes out iron powder, obtains iron ion and exchanges modified molecular screen.
Embodiment 3
Reduced iron powder and silica alumina ratio be 5 HY parent molecule sieve 1:2 in mass ratio and mix, the mixture that iron powder and parent molecule sieve is added the FeCl of 0.3mol/L
2in solution, solid-liquid ratio is add 1g solid in every 10ml solution; Stir at 80 DEG C of temperature and carry out ion-exchange in 12 hours; Centrifugation after exchange, and spend deionized water; Sample is 150 DEG C of oven dry; Sample is placed in magnetic field, and Magnetic Isolation goes out iron powder, obtains iron ion and exchanges modified molecular screen.
Embodiment 4
Reduced iron powder and silica alumina ratio be 8 HY parent molecule sieve 1:1 in mass ratio and mix, the mixture that iron powder and parent molecule sieve is added the FeCl of 1mol/L
2in solution, solid-to-liquid ratio is add 1g solid in every 10ml solution; Stir at 80 DEG C of temperature and carry out ion-exchange in 24 hours; Suction filtration after exchange, and spend deionized water; Sample is 110 DEG C of oven dry, and the iron ion obtaining mixing iron powder exchanges modified molecular screen.
Embodiment 5
Reduced iron powder and HMOR parent molecule sieve 10:1 in mass ratio and mix, and the mixture that iron powder and parent molecule sieve are added the FeCl of 0.001mol/L
2in solution, in every 50ml solution, add 1g solid; Stir at 0 DEG C of temperature and carry out ion-exchange in 24 hours; Suction filtration after exchange, and spend deionized water; Sample is 25 DEG C of vacuum drying; Sample is placed in magnetic field, and Magnetic Isolation goes out iron powder, obtains iron ion and exchanges modified molecular screen.
Embodiment 6
Reduced iron powder and HBETA parent molecule sieve 1:10 in mass ratio and mix, and the mixture that iron powder and parent molecule sieve is added saturated FeCl
2in solution, in every 5ml solution, add 1g solid; Stir at 100 DEG C of temperature and carry out ion-exchange in 1 hour; Suction filtration after exchange, and spend deionized water; Sample is 100 DEG C of vacuum drying; Sample is placed in magnetic field, and Magnetic Isolation goes out iron powder, obtains iron ion and exchanges modified molecular screen.
Comparative example 1
By silica alumina ratio be 25 HZSM-5 parent molecule sieve add the FeCl of 0.5mol/L
2in solution, solid-to-liquid ratio is add 1g solid in every 10ml solution, and stir at 80 DEG C of temperature and within 24 hours, carry out ion-exchange, suction filtration after exchange, and spend deionized water, sample is 110 DEG C of oven dry; Sample after oven dry is added the FeCl of 0.5mol/L
2in solution, solid-to-liquid ratio is add 1g solid in every 10ml solution, stirs and carry out second time ion-exchange in 24 hours at 80 DEG C of temperature, and after exchange, suction filtration, washing are also dry, obtains iron ion and exchanges modified molecular screen.According to in-situ ft-ir characterization result, this method through the iron ion exchange degree of twice ion-exchange far below the iron ion exchange degree preparing gained sample through embodiment 2.
Beneficial effect of the present invention is by accompanying drawing 1, and the characterization result of accompanying drawing 2 and the in-situ ft-ir shown in accompanying drawing 3 is illustrated
By reduced iron powder, FeCl
2solution and silica alumina ratio are the HY molecular sieve mixing of 8, carry out ion-exchange with the step of method described in embodiment 1 and obtain iron ion exchange modified molecular screen, use the means of in-situ ft-ir to exchange modified molecular screen to parent molecule sieve and iron ion respectively to characterize, infrared spectrum gathers under the vacuum condition of 500 DEG C, the results are shown in accompanying drawing 1.Curve A in accompanying drawing 1 is the infrared spectrum of parent molecule sieve, and the curve B in accompanying drawing 1 is the infrared spectrum that iron ion exchanges modified molecular screen.Result shows, and characteristic infrared vibration peak parent molecule sieve infrared spectrum characterizing acid hydroxy group (is positioned at 3620cm
-1, 3545cm
-1) in weakened after ion-exchange or disappearance, show the H on parent molecule sieve
+be partially or completely exchange; Iron ion exchanges characteristic infrared vibration peak modified molecular screen infrared spectrum characterizing acid hydroxy group and absorbs very weak or without obvious infra-red absorbance signals, shows that gained iron ion exchanges modified molecular screen and has high exchange degree.
By reduced iron powder, FeCl
2solution and silica alumina ratio are the HZSM-5 molecular sieve mixing of 25, carry out ion-exchange with the step of method described in embodiment 2 and obtain iron ion exchange modified molecular screen, use the means of in-situ ft-ir to exchange modified molecular screen to parent molecule sieve and iron ion respectively to characterize, infrared spectrum gathers under the vacuum condition of 500 DEG C, the results are shown in accompanying drawing 2.Curve C in accompanying drawing 2 is the infrared spectrum of parent molecule sieve, and the curve D in accompanying drawing 1 is the infrared spectrum that iron ion exchanges modified molecular screen.Result shows, and characteristic infrared vibration peak parent molecule sieve infrared spectrum characterizing acid hydroxy group (is positioned at 3610cm
-1) in weakened after ion-exchange or disappearance, show the H on parent molecule sieve
+be partially or completely exchange; Iron ion exchanges characteristic infrared vibration peak modified molecular screen infrared spectrum characterizing acid hydroxy group and absorbs very weak or without obvious infra-red absorbance signals, shows that gained iron ion exchanges modified molecular screen and has high exchange degree.
By FeCl
2solution and silica alumina ratio are the HZSM-5 molecular sieve mixing of 25, carry out ion-exchange obtain iron ion exchange modified molecular screen with the step of method described in comparative example 1; By reduced iron powder, FeCl
2solution and silica alumina ratio are the HZSM-5 molecular sieve mixing of 25, carry out ion-exchange obtain iron ion exchange modified molecular screen with the step of method described in embodiment 2.Use the means of in-situ ft-ir to exchange modified molecular screen to the iron ion of two kinds of method gained respectively to characterize, infrared spectrum gathers under the vacuum condition of 500 DEG C, the results are shown in accompanying drawing 3.Curve E in accompanying drawing 3 prepares gained iron ion for method described in comparative example 1 and exchanges the infrared spectrum of modified molecular screen, and the curve F in accompanying drawing 3 prepares the infrared spectrum that gained iron ion exchanges modified molecular screen for method described in embodiment 2.Result shows, and method described in comparative example 1 is prepared gained iron ion and exchanged the characteristic infrared vibration peak that the infrared spectrum of modified molecular screen characterizes acid hydroxy group and (be positioned at 3610cm
-1) relative absorbance intensity higher, method described in embodiment 2 prepares that infrared spectrum that gained iron ion exchanges modified molecular screen characterizes the relative absorbance intensity of the characteristic infrared vibration peak of acid hydroxy group is lower, show that method described in embodiment 2 is prepared gained iron ion and exchanged modified molecular screen and method described in comparative example 1 and prepare gained iron ion and exchange compared with modified molecular screen, there is high exchange degree.
Claims (9)
1. iron ion exchanges a preparation method for modified molecular screen, said method comprising the steps of:
1) in iron salt solutions, add reduced iron powder and parent molecule sieve, the mixture of molysite, iron powder and parent molecule sieve is stirred to carry out ion-exchange reactions;
2) Separation of Solid and Liquid is carried out after completion of the reaction;
3) wash to remove residual molysite to the solid product after separation;
4) drying is carried out to the product after washing;
5) dried product is placed in magnetic field and carries out Magnetic Isolation, thus obtain pure iron ion exchange modified molecular screen;
Wherein, described parent molecule sieve is Hydrogen Si-Al molecular sieve;
Described iron salt solutions is divalent iron salt solution.
2. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, it is characterized in that, step 1) described in the concentration of iron salt solutions be that 0.001mol/L is to saturated concentration, the mass ratio that described reduced iron powder addition and described parent molecule sieve is 0.1:1 ~ 10:1, and the mass volume ratio of the mixture that described parent molecule sieve and iron powder form and described iron salt solutions is 1:5 ~ 1:50g/ml.
3. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, it is characterized in that, step 1) in stir when carrying out ionic reaction, the time is 1 ~ 24 hour, and temperature is 0 DEG C ~ 100 DEG C.
4. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, it is characterized in that, step 2) described in Separation of Solid and Liquid completed by filter type or centrifugation.
5. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, it is characterized in that, step 3) washing of middle use deionized water.
6. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, it is characterized in that, step 3) described in wash and repeatedly carry out.
7. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, it is characterized in that, step 4) in dry temperature be 25 ~ 150 DEG C, drying mode adopts forced air drying, natural drying or vacuum drying.
8. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, and it is characterized in that, described Hydrogen Si-Al molecular sieve is one or more in BETA, L, MAZ, MFI, FER, MOR, Y zeolite.
9. iron ion as claimed in claim 1 exchanges the preparation method of modified molecular screen, and it is characterized in that, described iron salt solutions is the mixed liquor of one or more in frerrous chloride, ferrous nitrate, copperas solution.
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| BR112022001106A2 (en) * | 2019-08-29 | 2022-05-03 | Basf Corp | Method for forming a selective catalytic reduction (scr) catalyst, iron-promoted zeolite, selective catalytic reduction (scr) catalyst composition, engine exhaust gas treatment system, and nitrogen oxides removal method |
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| CN101024194A (en) * | 2007-03-29 | 2007-08-29 | 南京工业大学 | Composite modified molecular sieve catalyst and preparation method and application thereof |
| CN101837988A (en) * | 2010-03-12 | 2010-09-22 | 重庆理工大学 | Method for preparing iron modified SBA-15 mesoporous molecular sieve |
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| AU687582B2 (en) * | 1994-07-07 | 1998-02-26 | Mobil Oil Corporation | Catalytic system for the reduction of nitrogen oxides |
| WO2000072965A1 (en) * | 1999-05-27 | 2000-12-07 | The Regents Of The University Of Michigan | Zeolite catalysts for selective catalytic reduction of nitric oxide by ammonia and method of making |
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|---|---|---|---|---|
| CN101024194A (en) * | 2007-03-29 | 2007-08-29 | 南京工业大学 | Composite modified molecular sieve catalyst and preparation method and application thereof |
| CN101837988A (en) * | 2010-03-12 | 2010-09-22 | 重庆理工大学 | Method for preparing iron modified SBA-15 mesoporous molecular sieve |
Non-Patent Citations (1)
| Title |
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| "Fe-ZSM-5 for selective catalytic reduction of NO with NH3: a comparative study of different preparation techniques";R.Q.Long,et al;《Catalysis Letters》;20010701;第74卷(第3-4期);第202页左栏第2段 * |
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