CN1265880C - Method of synthesizing iron isomorphous for substituting molecular sieve - Google Patents
Method of synthesizing iron isomorphous for substituting molecular sieve Download PDFInfo
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- CN1265880C CN1265880C CN 03101531 CN03101531A CN1265880C CN 1265880 C CN1265880 C CN 1265880C CN 03101531 CN03101531 CN 03101531 CN 03101531 A CN03101531 A CN 03101531A CN 1265880 C CN1265880 C CN 1265880C
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Abstract
一种铁同晶取代MCM-22分子筛的合成方法，是将硅源、铝源、铁源、碱源或酸源、有机胺模板剂和水按照一定的投料顺序配制成初始反应混合物，其总的摩尔组成为SiO2∶Al2O3∶Fe2O3∶Na2O∶HMI∶H2O＝20-50∶0-1∶0.01-1∶1.6-4.6∶7.5-13.5∶950-1350，然后在密封的反应釜里水热条件下晶化，晶化温度为130-170℃，晶化时间为50-160小时。晶化产物过滤、洗涤、烘干、焙烧得完全铁同晶取代的Fe-MCM-22分子筛和部分铁同晶取代的[Fe，Al]-MCM-22分子筛。A kind of synthesis method of ferroisomorphic replacement MCM-22 molecular sieve is that silicon source, aluminum source, iron source, alkali source or acid source, organic amine templating agent and water are prepared into initial reaction mixture according to certain feeding order, and its total The molar composition of SiO 2 : Al 2 O 3 : Fe 2 O 3 : Na 2 O: HMI: H 2 O = 20-50: 0-1: 0.01-1: 1.6-4.6: 7.5-13.5: 950-1350 , and then crystallize under hydrothermal conditions in a sealed reactor, the crystallization temperature is 130-170°C, and the crystallization time is 50-160 hours. The crystallized product is filtered, washed, dried and roasted to obtain Fe-MCM-22 molecular sieves completely ferroisomorphically substituted and [Fe, Al]-MCM-22 molecular sieves partially ferroisomorphically substituted.
Description
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-22structure (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, stirs and form solution A;
2) source of iron is mixed with solution B, and regulates the pH value of this solution with 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 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, Al]-MCM-22 molecular sieve) that the part iron isomorphous replaces;
The mole of each raw material is joined and should be met in the solution of each step preparation of above-mentioned steps a to d:
SiO
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.
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 H2O, 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.
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 (10)
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, the synthetic method of a kind of MCM-22 of iron isomorphous replacement, 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 in the solution of each step preparation of above-mentioned steps a to d:
SiO
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, method as claimed in 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.
10, method as claimed in claim 3 is characterized in that, described aluminium source is a sodium aluminate.
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| 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 |
| 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 |
| CN120001415A (en) * | 2025-04-21 | 2025-05-16 | 中海油天津化工研究设计院有限公司 | A catalyst for deolefination of reforming oil and preparation method thereof |
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