CN1517148A - Method of synthesizing iron isomorphous for substituting molecular sieve - Google Patents

Method of synthesizing iron isomorphous for substituting molecular sieve Download PDF

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CN1517148A
CN1517148A CNA03101531XA CN03101531A CN1517148A CN 1517148 A CN1517148 A CN 1517148A CN A03101531X A CNA03101531X A CN A03101531XA CN 03101531 A CN03101531 A CN 03101531A CN 1517148 A CN1517148 A CN 1517148A
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solution
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iron
molecular sieve
water
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CN1265880C (en
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徐龙伢
彭建彪
谢素娟
王清遐
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

A process for synthesizing an iron isomorphously substituting MCM-22 molecular sieve includes such steps as proportionally mixing SiO2, Al2O3, Fe2O3, Na2O, HMI and H2O, hydrothermal crystallizing in sealed reactor, filter, washing, baking and calcining to obtain the Fe-MCM-22 molecular sieve and [Fe, Al]-MCM-22 molecular sieve.

Description

A kind of iron isomorphous replaces the method for molecular sieve
Technical field
The invention belongs to synthesis method of zeolite molecular sieve, specifically relate to the synthetic method that heteroatoms iron replaces the MCM-22 molecular sieve in various degree.
Background technology
Molecular sieve catalyst is the basis in petroleum refining and petrochemical technology field, especially more obtained extensive use by 10 yuan of ZSM-5 molecular sieves that encircle the three dimensional intersection duct of forming, but its shape selective catalysis capabilities limits is aspect some size molecule.(USP 4 by the MCM-22 of the new structure of Mobil report for the nineties, 954,325) molecular sieve belongs to the molecular sieve that has two kinds not intersect the duct system type, it contains 12 yuan of rings and two kinds of channel system of 10 yuan of rings, gives the synthetic of molecular sieve and uses the new prospect of having brought.
The hetero atom isomorphous replaces the element of T position in the molecular sieve can adjustment of acidity, shape selectivity, has also had the character of other element simultaneously, thereby has further widened the range of application of molecular sieve.Utilize other elements that the ordinary silicon aluminum molecular screen is replaced, the ZSM-5 that replaces as B, Fe can make its L acid, B acid and L acid descend respectively, thereby makes molecular sieve needing be suitable for the acid catalyzed reaction of dissimilar and intensity.And other metallic element is introduced the preparation method of molecular sieve, as Fe 2O 3Be supported on the molecular sieve, may cause the skewness of iron.If adopt direct hydro-thermal synthetic silicon iron hetero-atom molecular-sieve, can make the distribution of iron in molecular sieve more even, state is more single.The MFI structural molecule sieve ratio Fe that Fe replaces 3+Iron oxide exchange or that support has better choice in the alkanes oxidative dehydrogenation reaction, all present the selectivity higher than ZSM-5 as Fe-ZSM-5 in isomerisation of olefin, alkylation, high-knock rating gasoline production.The molecular sieve of Fe replacement simultaneously also can be applicable to fields such as gating catalytic oxidation reduction, as alkanes oxidative dehydrogenation, NO xEliminate and wait in the reaction.
Fe replaces MCM-22 synthetic two pieces of reports that P.Wu etc. and F.Testa etc. are only arranged, be in the article of " Synthesis of ferrisilicate with the MCM-22 structure (P.Wu; H.Lin; T.Komatsu; Chem.Commun.1997; 663) " at exercise question, the author is dynamically synthesizing the MCM-22 that Fe replaces with the white carbon black of vapor phase method (fumed silica) under the synthesis condition, and its XRD figure spectrum is similar to MCM-22's; Another piece exercise question is in the article of " synthesis and characterization of Fe-and [Fe; Al]-MCM-22 zeolites (F.Testa; F.Creta; G.D.Diodati; MicroporousMesoporous Mater.1999; 187) ", also is under dynamic synthesis condition, has synthesized the MCM-22 that contains aluminium and do not contain aluminium with white carbon black (fumed silica) and aluminium hydroxide.The source of iron of the two usefulness is a ferric nitrate, all be to add in the initial gel of preparation before the molecular sieve crystallization, and crystallization forms the MCM-22 molecular sieve that Fe replaces in the time more than 7 days.
Summary of the invention
The purpose of this invention is to provide the method that a kind of iron isomorphous replaces molecular sieve, this cheap and easy-operating silicon source of method employing, the synthetic MCM-22 molecular sieve of isomorphous replacement in various degree that taps a blast furnace in short crystallization time.
Its key step of synthetic method of the MCM-22 that the complete iron isomorphous provided by the invention replaces is as follows:
1) sodium metasilicate is dissolved in water, adds acid and promote its dissolving, stir and form solution A;
2) source of iron is mixed with solution B, and regulates the pH value of this solution with nitric acid;
3) stir down with solution A and solution B mixing formation solution C;
4) stir adding template agent and water in solution C down, with the reactor sealing, self-generated pressure, program temperature is raised to crystallization temperature under the dynamic condition.Crystallization temperature and crystallization time are bigger to the influence of crystallization product, when crystallization temperature is higher, can cause occurring oxide in the crystallization product, as SiO 2And Fe 2O 3Deng; When crystallization temperature is low then crystallization time can prolong.Especially to not containing aluminium, the Fe-MCM-22 molecular sieve of an iron content, silicon is more obvious.Therefore crystallization temperature of the present invention is 130-170 ℃, and crystallization time is 50-160 hour;
5) after crystallization was finished, filtration product was washed to pH=7-8, oven dry, and roasting obtains the molecular sieve (Fe-MCM-22 molecular sieve) that the complete iron isomorphous replaces.
The mole proportioning of each raw material should meet in the solution of above-mentioned steps 1 to 4 each step preparation:
SiO 2: Fe 2O 3: Na 2O: template agent: H 2O=20-50: 1: 1.6-4.6: 7.5-13.5: 950-1350.
Wherein, with the pH value of nitric acid regulator solution B, be to make in this acid solution and the alkali source and the remaining Na in back in the step 2 2O meets above-mentioned mole proportioning.
The part iron isomorphous provided by the invention replaces the synthetic method of MCM-22 molecular sieve, and its key step is as follows:
1) Ludox, aluminium source and alkali source are dissolved in the water, stir and form solution A;
2) source of iron is mixed with solution B;
3) stir down with solution A and solution B mixing formation solution C;
4) stir adding template agent and water in solution C down, with the reactor sealing, self-generated pressure, program temperature is raised to crystallization temperature 130-170 ℃ under the dynamic condition, and crystallization time is 30-160 hour;
5) after crystallization was finished, filtration product was washed to pH=7-8, oven dry, and roasting obtains the molecular sieve ([Fe, Al]-MCM-22 molecular sieve) that the part iron isomorphous replaces;
The mole of each raw material is joined and should be met SiO in the solution of each step preparation of above-mentioned steps a to d 2: Al 2O 3: Fe 2O 3: Na 2O: template agent: H 2O=20-50: 0.1-1: 0.01-1: 1.6-4.6: 7.5-13.5: 950-1350.
Wherein, this step 1 is if adopt sodium metasilicate, and during as SODIUM METASILICATE PENTAHYDRATE or nine water sodium metasilicate, then this step is with sodium metasilicate, aluminium source and acid source, as sulfuric acid or nitric acid dissolve in water.
When adopting sodium metasilicate among the step b, need pH value, make in this acid solution and the alkali source and the remaining Na in back with nitric acid regulator solution B 2O meets above-mentioned mole proportioning.
The silicon source of being adopted in the synthetic method provided by the invention, aluminium source, source of iron, acid source, alkali source and template agent etc. determine that according to prior art the present invention is not particularly limited it.But the preferred feedstock of invention is to be the silicon source with Ludox, SODIUM METASILICATE PENTAHYDRATE, nine water sodium metasilicate; With the sodium aluminate is the aluminium source; With the ferric nitrate is source of iron; With sulfuric acid, nitric acid and NaOH as acid source, alkali source; Hexamethylene imine (HMI) is the template agent; The water that adopts is deionized water.
Advantage of the present invention is to adopt Ludox or sodium metasilicate to synthesize the Fe-MCM-22 molecular sieve of the complete iron isomorphous replacement of the high Fe content that pure Fe-Si that [Fe, Al]-MCM-22 molecular sieve that the part iron isomorphous replaces and no aluminium are arranged forms for the silicon source.
Description of drawings
Fig. 1 is the X-ray spectrogram of embodiment 1;
Fig. 2 is the X-ray spectrogram of embodiment 2;
Fig. 3 is the X-ray spectrogram of embodiment 3;
Fig. 4 is the X-ray spectrogram of embodiment 4;
Fig. 5 is the X-ray spectrogram of embodiment 5.
The specific embodiment
The following examples will the present invention is further illustrated.
Embodiment 1
The present embodiment explanation is synthesized Fe with Ludox 2O 3/ Al 2O 3(mol ratio) is the method for 1/4 MCM-22 molecular sieve.
1.45g sodium aluminate (Al 2O 3=16.8wt.%, H 2O=52.0wt.%, Na 2O=31.2wt.%) and 55mL H 2O, 2.98mL NaOH solution (0.1g/mL), 20.3g Ludox (SiO 2Be 26.6wt.%) in reactor, mix the back and stir certain hour, add 2.24mL iron nitrate solution (0.2g/mL) and 3.12g hexamethylene imine then, still is sealed after stirring certain hour again.At 138 ℃ of following dynamic crystallization 48h, stop reaction, product gets [Fe-Al]-MCM-22 molecular sieve after cooling, filtration, washing, drying and roasting.Its XRD spectra is seen Fig. 1.
Embodiment 2
The present embodiment explanation is synthesized Fe with Ludox 2O 3/ Al 2O 3It is the method for 1/1 MCM-22 molecular sieve.
0.91g sodium aluminate (Al 2O 3=16.8wt.%, H 2O=52.0wt.%, Na 2O=31.2wt.%) and 45mL H 2O, 4.71mL NaOH solution (0.1g/mL), 27.1g Ludox (SiO 2Be 26.6wt.%) in reactor, mix the back and stir certain hour, add 6.06mL iron nitrate solution (0.2g/mL) and 3.12g hexamethylene imine then, still is sealed after stirring certain hour again.At 138 ℃ of following dynamic crystallization 88h, stop reaction, product gets [Fe-Al]-MCM-22 molecular sieve after cooling, filtration, washing, drying and roasting.Its XRD spectra is seen Fig. 2.The x-ray fluorescence spectrometry instrument carries out elementary analysis and records e 2O 3Content and Al 2O 3The mol ratio of content is 1.
Embodiment 3
Present embodiment explanation Ludox Fe 2O 3/ Al 2O 3It is the method for 4/1 MCM-22 molecular sieve.
0.36g sodium aluminate (Al 2O 3=16.8wt.%, H 2O=52.0wt.%, Na 2O=31.2wt.%) and 45mL H2O, 2.13mL NaOH solution (0.3g/mL), 20.3g Ludox (SiO 2Be 26.6wt.%) in reactor, mix the back and stir certain hour, add 9.84mL iron nitrate solution (0.2g/mL) and 3.12g hexamethylene imine then, still is sealed after stirring certain hour again.At 138 ℃ of following dynamic crystallization 157h, stop reaction, product gets [Fe-Al]-MCM-22 molecular sieve after cooling, filtration, washing, drying and roasting.Its XRD spectra is seen Fig. 3.
Embodiment 4
The present embodiment explanation is synthesized Fe with sodium metasilicate 2O 3/ Al 2O 3It is the method for 4/1 MCM-22 molecular sieve.
24.21mL H 2SO 4Solution (0.3g/mL), 1.94g nine water ferric nitrates (analyze pure, content＞98.5%) and 35.5mL H 2O adds 0.14g sodium aluminate (Al successively under condition of stirring after mixing in the reactor 2O 3=43.0%, H 2O=5.5%, Na 2O=51.5%), 34.1g nine water sodium metasilicate and 3.12g hexamethylene imine.After stirring certain hour again still is sealed.At 150 ℃ of following dynamic crystallization 90h, stop reaction, product gets [Fe-Al]-MCM-22 molecular sieve after cooling, filtration, washing, drying and roasting.Its XRD spectra is seen Fig. 4.
Embodiment 5
The method of no aluminium Fe-MCM-22 molecular sieve is synthesized in the present embodiment explanation with sodium metasilicate.
23.23mL H 2SO 4Solution (0.3g/mL), 2.42g nine water ferric nitrates (analyze pure, content＞98.5%) and 38.0mL H 2O adds 25.6g nine water sodium metasilicate and 3.12g hexamethylene imine under condition of stirring after mixing in the reactor.After stirring certain hour again still is sealed.At 138 ℃ of following dynamic crystallization 110h, stop reaction, product gets the Fe-MCM-22 molecular sieve after cooling, filtration, washing, drying and roasting.Its XRD spectra is seen Fig. 5.

Claims (9)

1, the synthetic method of a kind of MCM-22 of iron isomorphous replacement, its key step is as follows:
A) sodium metasilicate is dissolved in the water, stirs and form solution A;
B) source of iron is mixed with solution B, and regulates the pH value of this solution with acid;
C) stir down with solution A and solution B mixing formation solution C;
D) stir adding template agent and water in solution C down, with the reactor sealing, self-generated pressure, program temperature is raised to crystallization temperature under the dynamic condition;
E) after crystallization was finished, filtration product was washed to pH=7-8, oven dry, and roasting obtains the molecular sieve that the complete iron isomorphous replaces;
The mole proportioning of each raw material should meet in the solution of each step preparation of above-mentioned steps a to d:
SiO 2: Fe 2O 3: Na 2O: template agent: H 2O=20-50: 1: 1.6-4.6: 7.5-13.5: 950-1350;
Crystallization temperature among the above-mentioned steps d is 130-170 ℃, and crystallization time is 50-160 hour.
2, a kind of iron isomorphous replaces the method for molecular sieve, and its key step is as follows:
A) Ludox, alkali source and aluminium source are dissolved in the water, stir and form solution A;
B) source of iron is mixed with solution B;
C) stir down with solution A and solution B mixing formation solution C;
D) stir adding template agent and water in solution C down, with the reactor sealing, self-generated pressure, program temperature is raised to crystallization temperature under the dynamic condition;
E) after crystallization was finished, filtration product was washed to pH=7-8, oven dry, and roasting obtains the molecular sieve that the part iron isomorphous replaces;
The mole proportioning of each raw material is SiO in the solution of each step preparation of above-mentioned steps a to d 2: Al 2O 3: Fe 2O 3: Na 2O: template agent: H 2O=20-50: 0.1-1: 0.01-1: 1.6-4.6: 7.5-13.5: 950-1350;
Crystallization temperature among the above-mentioned steps d is 130-170 ℃, and crystallization time is 50-160 hour.
3, method as claimed in claim 2 is characterized in that, described step a is dissolved in sodium metasilicate, aluminium source and acid source in the water, stirs to form solution A; Step b regulates the pH value of source of iron solution B with acid.
As each described method among the claim 1-3, it is characterized in that 4, described source of iron is a ferric nitrate.
As each described method among the claim 1-3, it is characterized in that 5, described water is deionized water.
As claim 1 or 3 described methods, it is characterized in that 6, described acid source is sulfuric acid or nitric acid.
7, the method for stating as claim 1 or 2 is characterized in that, described template agent is a hexamethylene imine.
8, method as claimed in claim 2 is characterized in that, described alkali source is a NaOH.
As claim 1 or 3 described methods, it is characterized in that 9, described sodium metasilicate is SODIUM METASILICATE PENTAHYDRATE or nine water sodium metasilicate; The aluminium source is a sodium aluminate.
CN 03101531 2003-01-16 2003-01-16 Method of synthesizing iron isomorphous for substituting molecular sieve Expired - Fee Related CN1265880C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040229B (en) * 2009-10-21 2012-11-21 中国石油化工股份有限公司 Synthetic method of MCM-22 (Multiple Chip Module 22) molecular sieve
CN110947416A (en) * 2019-12-18 2020-04-03 武汉科技大学 For NH3-SCR iron/molecular sieve catalyst, preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040229B (en) * 2009-10-21 2012-11-21 中国石油化工股份有限公司 Synthetic method of MCM-22 (Multiple Chip Module 22) molecular sieve
CN110947416A (en) * 2019-12-18 2020-04-03 武汉科技大学 For NH3-SCR iron/molecular sieve catalyst, preparation method and application thereof
CN110947416B (en) * 2019-12-18 2023-06-13 武汉科技大学 For NH 3 Iron/molecular sieve catalyst of SCR (selective catalytic reduction), and preparation method and application thereof

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