CN103708498A - Fe-SAPO-34 molecular sieve with high skeleton ion content and preparation method thereof - Google Patents
Fe-SAPO-34 molecular sieve with high skeleton ion content and preparation method thereof Download PDFInfo
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Abstract
The invention provides a Fe-SAPO-34 molecular sieve with high skeleton ion content and a preparation method thereof, overcoming the problems that the prepared metal-modified SAPO-34 molecular sieve reported in literature is low in skeleton metal content and low in catalytic activity when being applied to reaction for preparing olefin by employing methanol. The invention provides a synthetic method of the Fe-SAPO-34 molecular sieve with high skeleton ion content. The method has the characteristics that the prepared SAPO-34 molecular sieve is high in skeleton ion atom content and good in catalytic activity, and has a good industrial application prospect.
Description
Technical field
The invention belongs to a kind of preparation method of molecular sieve, relate in particular to a kind of high skeleton iron level Fe-SAPO-34 molecular sieve and preparation method thereof.
Background technology
SAPO-34 molecular sieve is U.S. UCC company in nineteen eighty-two a member in synthetic SAPO-n Series Molecules sieve first, there is class chabazite structure, there is moderate acid and good thermostability and hydrothermal stability, because it reveals excellent catalytic performance to methanol oxidation preparing low-carbon olefins reaction table and receives much concern.It has CHA structure and moderate acidity, shows excellent catalytic performance and come into one's own in methanol-to-olefins (MTO) technology.CHA includes 8 ring apertures and forms elliposoidal cage and three-dimensional open-framework.Catalytic performance and the structure of SAPO molecular sieve have much relations, in order to expand the applicability energy of SAPO molecular sieve, SAPO molecular sieve are carried out to modification to improve the focus that its catalytic performance is current research.
In building-up process, add a certain metallic element, the Al atom with replacing in skeleton, has just produced strong redox center in skeleton, and the quantity at reduction center increases with the raising of skeleton metal atom.Such character is widely used in multiple catalytic process heteroatoms replacement aluminum phosphate, the people such as Thomas replace aluminum phosphate at heteroatoms and done intensive research aspect catalyzer, and as the application subject study of single-point solid catalyst, have delivered a large amount of articles with regard to MAPO.Bibliographical information claims, adds the SAPO-34 molecular sieve catalytic methanol to olefins reaction of heteroatoms after metal-modified, can effectively improve transformation efficiency and the selectivity to lighter hydrocarbons.By heteroatoms, molecular sieve is carried out to modification and generally comprise two kinds of in-situ synthesis and pickling processes.The molecular sieve of the MeSAPO-34 containing heteroatoms metal that wherein prepared by in-situ synthesis can change at aspects such as catalyst surface acidity, grain size, pore structures.
The report such as Inui and Kang, the SAPO-34 molecular sieve catalytic MTO reaction of Ni modification can obtain very high yield of ethene, and the selectivity of ethene be can reach to 90%.
The reports such as Li, the Fe-MCM-41 molecular sieve that contains high skeleton iron in catalysis of phenol hydrogenation reaction, its catalytic activity than Fe2O3 load catalyst activity be significantly increased, and improve with the increase of skeleton iron content.
CN1704390, by adopting metallic element Zn to carry out modification to SAPO-34, obtains Zn-SAPO-34 molecular sieve, and the catalyzer using it as methanol-to-olefins, and reaction under certain condition generates alkene.The impact that SAPO-34 skeleton structure and pore structure are caused that adds due to metallic element Zn, has improved the selectivity of molecular sieve to low-carbon alkene, and the overall selectivity of light hydrocarbon is greater than 90%, and the reaction times reaches 6 hours.
CN102744102A discloses and a kind ofly by pickling process, SAPO-34 molecular sieve has been carried out to modification, has obtained the catalyzer of area load metal oxide.Use metal-modified SAPO-34 molecular sieve catalyst producing ethylene by ethanol dehydration, have the advantages that ethanol conversion is high, ethylene selectivity good, feed ethanol concentration in reaction is high, air speed ethanol is high and temperature of reaction is low, thereby improved the productive rate of ethene.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of high skeleton iron level Fe-SAPO-34 molecular sieve and preparation method thereof, overcome in the metal-modified SAPO-34 molecular sieve of existing preparation heteroatoms metal content lower, the low problem of catalytic activity while reacting for MTO.
For solving the problems of the technologies described above, the technical scheme that the invention adopts is: a kind of high skeleton iron level Fe-SAPO-34 molecular sieve, the preparation method of this molecular sieve take Complexing Iron directly a large amount of iron atoms to be incorporated in framework of molecular sieve as source of iron, the SAPO-34 molecular sieve of preparing high skeleton iron level, the content of its skeleton iron atom is equal to or higher than 15wt%.
Preferably, the mean pore size of described SAPO-34 molecular sieve is 0.40～0.60nm, is preferably 0.48～0.52nm.
Preferably, the specific surface area of described SAPO-34 molecular sieve is greater than 480m
2/ g.
The present invention also provides a kind of method of preparing high skeleton iron level Fe-SAPO-34 molecular sieve as above, and comprise and be prepared as follows step,
(1), a certain amount of silicon source, phosphorus source, aluminium source, water, source of iron, template are mixed to get to even colloid, wherein Al at 10-70 ℃
2o
3: SiO
2: P
2o
5: H
2o: template: the molar ratio of source of iron is 0.05-2:0.05-2:50-200:2-10:1-20; Be preferably Al
2o
3: SiO
2: P
2o
5: H
2o: template: the molar ratio of source of iron is 0.5-1:0.5-1:100-150:5-8:10-15:5-10;
(2), even colloid that step (1) is obtained, at 10-70 ℃, continue to stir 3 hours, then, under 0-180 ℃ of autogenous pressure hydrothermal condition, crystallization 12-120 hour, obtains the product after crystallization;
(3), by the product after crystallization through product after crystallization is obtained to molecular sieve finished product through suction filtration, washing, oven dry, roasting.
Preferably, described source of iron is a kind of in the Tripotassium iron hexacyanide, yellow prussiate of potash.
Preferably, the template of using is di-n-propylamine, Diisopropylamine, one or more in diethylamine.
Preferably, described silicon source is one or more in aerosil, water glass, tetraethoxy, and described aluminium source is pseudo-boehmite, and described phosphorus source is ortho-phosphoric acid.
Preferably, the oven dry in step (3) is to dry 3-8 hour at 100-130 ℃.
Preferably, described suction filtration, washing process refer to and in suction filtration, add deionized water wash filter cake, to the pH of filtrate be 7.
Preferably, described roasting is ℃ of-700 ℃ insulations of temperature programming to 350 5 hours under the condition of 1 ℃/min.
Advantage and positively effect that the invention has are: SAPO-34 molecular sieve prepared by the present invention, take Complexing Iron as source of iron, a large amount of iron atoms are introduced directly in framework of molecular sieve, improved the content of skeleton iron in Fe-SAPO-34, improve Fe-SAPO-34 molecular sieve catalyst used in methanol to olefins reaction, the acidity that improves catalyzer, strengthens its selectivity and activity.Both the pore passage structure that had kept SAPO-34 molecular sieve rule, the feature of higher specific surface area has again high metal content, given full play to the metallic character that heteroatoms itself has, the catalytic performance of the molecular sieve of further modulation synthesized, expand its range of application, will become the catalytic material of the aspect excellent propertys such as catalytic cracking, catalyzed oxidation, isomerization.Simultaneously, because iron level in the synthetic Fe-SAPO-34 molecular sieve of the present invention is very high, make the corresponding increase in aperture.And the distribution of iron atom is also comparatively even, in the B acid and L acid site that have increased molecular sieve, also make the acid sites of molecular sieve dispersed better, there is very strong potential using value.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the high skeleton iron level Fe-SAPO-34 molecular sieve of embodiment bis-in the present invention.
Fig. 2 is the SEM figure of the high skeleton iron level Fe-SAPO-34 molecular sieve of embodiment bis-in the present invention.
Fig. 3 is the EPR figure of ferro element of the high skeleton iron level Fe-SAPO-34 molecular sieve of embodiment bis-in the present invention.
Embodiment
In the embodiment of the present invention, to take the Tripotassium iron hexacyanide and yellow prussiate of potash be example to source of iron used.Template used be take diethylamine as example, and it is example that aerosil and tetraethoxy be take in silicon source used, and pseudo-boehmite be take as example in aluminium source used; 85% ortho-phosphoric acid be take as example in phosphorus used source; Water used is deionized water; Reagent used all adopts analytical reagent; It is that instrument is Rigaku D/max-RA type X-ray diffractometer, voltage 30kV, electric current 30mA, sweep limit 3-70 ° with the test of powder crystal diffraction that the X-ray diffraction of gained finished product is measured; In gained finished product, the content of iron is measured through X-ray fluorescence spectra, and instrument is Philip Magix-601 fluorescence diffractometer; SEM test is carried out on the JSM-35C of Jeol Ltd. type scanning electron microscope instrument, SEI25Kv, 1.0 * 10-11A; Electron paramagnetic spectrum is tested at Brooker ER041MR, and magneticstrength is 9.44GHz.
Embodiment mono-
10g phosphoric acid and 10g tetraethoxy are joined in 60ml deionized water, stir after 15min, add 11g K
4fe (CN)
6continue to stir after 60min, add 8ml diethylamine, react and after 3 hours, solution is transferred in the autoclave of polytetrafluoro liner, at 160 ℃ of autogenous pressures, crystalline state crystallization is 72 hours.Then by sample suction filtration, with deionized water wash, to neutral, at 100 ℃, be dried 6 hours.With 1 ℃ of min
-1speed temperature programming to 550 ℃, insulation 5h, remove template.
Embodiment bis-
10g phosphoric acid and 12.1g tetraethoxy are joined in 60ml deionized water, stir after 15min, add 11g K
4fe (CN)
6continue to stir after 60min, add 10ml diethylamine, react and after 3 hours, solution is transferred in the autoclave of polytetrafluoro liner, at 160 ℃ of autogenous pressures, crystalline state crystallization is 72 hours.Then by sample suction filtration, with deionized water wash, to neutral, at 100 ℃, be dried 6 hours.With 1 ℃ of min
-1speed temperature programming to 550 ℃, insulation 5h, remove template.
Embodiment tri-
8g phosphoric acid and 12.1g tetraethoxy are joined in 60ml deionized water, stir after 15min, add 11g K
4fe (CN)
6continue to stir after 60min, add 10ml diethylamine, react and after 3 hours, solution is transferred in the autoclave of polytetrafluoro liner, at 180 ℃ of autogenous pressures, crystalline state crystallization is 72 hours.Then by sample suction filtration, with deionized water wash, to neutral, at 100 ℃, be dried 6 hours.With 1 ℃ of min
-1speed temperature programming to 550 ℃, be incubated 5 hours, remove template.
Embodiment tetra-
10g phosphoric acid and 3g silicon-dioxide are joined in 60ml deionized water, stir after 15min, add 11g K
4fe (CN)
6continue to stir after 60min, add 10ml diethylamine, react and after 3 hours, solution is transferred in the autoclave of polytetrafluoro liner, at 160 ℃ of autogenous pressures, crystalline state crystallization is 24 hours.Then by sample suction filtration, with deionized water wash, to neutral, at 100 ℃, be dried 6 hours.With the speed temperature programming to 550 ℃ of 1 ℃ of min-1, insulation 5h, removes template.
Embodiment five
10g phosphoric acid and 12.1g tetraethoxy are joined in 60ml deionized water, stir after 15min, add 11g K
3fe (CN)
6continue to stir after 60min, add 10ml diethylamine, react and after 3 hours, solution is transferred in the autoclave of polytetrafluoro liner, at 160 ℃ of autogenous pressures, crystalline state crystallization is 72 hours.Then by sample suction filtration, with deionized water wash, to neutral, at 100 ℃, be dried 6 hours.With the speed temperature programming to 550 ℃ of 1 ℃ of min-1, insulation 5h, removes template.
Embodiment six
10g phosphoric acid and 2.6g silicon-dioxide are joined in 60ml deionized water, stir after 15min, add 11g K
3fe (CN)
6continue to stir after 60min, add 10ml diethylamine, react and after 3 hours, solution is transferred in the autoclave of polytetrafluoro liner, at 180 ℃ of autogenous pressures, crystalline state crystallization is 72 hours.Then by sample suction filtration, with deionized water wash, to neutral, at 100 ℃, be dried 6 hours.With 1 ℃ of min
-1speed temperature programming to 550 ℃, insulation 5h, remove template.
The high skeleton iron level Fe-SAPO-34 molecular sieve of embodiment bis-preparations is carried out respectively to X-ray diffraction mensuration, SEM test, EPR test, and result as shown in Figure 1, Figure 2, Figure 3 shows.The test result of XRD shows, framework of molecular sieve has still kept good degree of crystallinity after having introduced a large amount of iron atoms.The scanning electron microscope of sample is that SEM result shows, molecular sieve has good crystal morphology, and plane of crystal does not have metal oxide.The EPR data of sample show, the middle iron atom of sample is all that the form with four-coordination exists, and that is to say that the iron in sample has all entered into framework of molecular sieve.
The high skeleton iron level Fe-SAPO-34 molecular sieve of embodiment mono-～embodiment six preparations is carried out respectively to X-ray fluorescence spectra mensuration, measure the content of iron, its iron level is all greater than 15wt%.
Comparative example 1 is set, and this comparative example is for illustrating the catalytic performance of unmodified SAPO-34 molecular sieve.
By unmodified SAPO-34 molecular sieve, for catalysis methanol olefine reaction processed, reaction is carried out on normal pressure continuous fixed bed reactor.In the quartz tube reactor that is 10mm at internal diameter, load 0.2g catalyzer.Reaction conditions is: take air speed as 2.0h
-1pass into methyl alcohol-N
2-H
2o (three's mol ratio is 1:3:5) reaction mixture gas.Concrete grammar is as follows: 80 ℃ of water-baths, in airtight there-necked flask, add the 50ml trimethyl carbinol, 8g pimelinketone, 15g25% ammoniacal liquor, 10g hydrogen peroxide, and the reaction times is 1h.The product that comparative example 1 is obtained, by Agilent 7890 transformation efficiencys of chromatographic determination pimelinketone and the selectivity of cyclohexanone-oxime.
Fe-SAPO-34 molecular sieve after embodiment mono-～embodiment six modifications is substituted to unmodified SAPO-34 molecular sieve according to the method for comparative example 1, for methanol to olefins reaction, Agilent 7890 transformation efficiencys of chromatographic determination methyl alcohol and the selectivity of low-carbon alkene for products therefrom, concrete outcome is in Table 1.
Amount * 100% of the methyl alcohol of methyl alcohol/conversion that wherein, the selectivity of low-carbon alkene=change into low-carbon alkene consumes
Table 1
| Group | Selectivity % |
| Comparative example 1 | 94 |
| Embodiment 1 | 95.2 |
| Embodiment 2 | 97.1 |
| Embodiment 3 | 96.5 |
| Embodiment 4 | 95.7 |
| Embodiment 5 | 95.3 |
| Embodiment 6 | 96.5 |
As seen from the above table, the Fe-SAPO-34 molecular sieve of preparing through the present invention is for methanol to olefins reaction, it, these results suggest that all more than 95% the selectivity of low-carbon alkene, and the high skeleton iron level Fe-SAPO-34 molecular sieve catalytic performance of preparation is improved significantly.
Above the embodiment of the invention is had been described in detail, but described content is only the preferred embodiment of the invention, can not be considered to for limiting practical range of the present invention.All equalization variations of doing according to the invention scope and improvement etc., within all should still belonging to this patent covering scope.
Claims (10)
1. one kind high skeleton iron level Fe-SAPO-34 molecular sieve, it is characterized in that: the preparation method of this molecular sieve take Complexing Iron directly a large amount of iron atoms to be incorporated in framework of molecular sieve as source of iron, the SAPO-34 molecular sieve of preparing high skeleton iron level, the content of its skeleton iron atom is equal to or higher than 15wt%.
2. high skeleton iron level Fe-SAPO-34 molecular sieve as claimed in claim 1, is characterized in that: the mean pore size of described SAPO-34 molecular sieve is 0.40～0.60nm, is preferably 0.48～0.52nm.
3. high skeleton iron level Fe-SAPO-34 molecular sieve as claimed in claim 1 or 2, is characterized in that: the specific surface area of described SAPO-34 molecular sieve is greater than 480m
2/ g.
4. a method of preparing high skeleton iron level Fe-SAPO-34 molecular sieve as claimed in claim 1, is characterized in that: comprises and is prepared as follows step,
(1), a certain amount of silicon source, phosphorus source, aluminium source, water, source of iron, template are mixed to get to even colloid, wherein Al under 10-70oC
2o
3: SiO
2: P
2o
5: H
2o: template: the molar ratio of source of iron is 0.05-2:0.05-2:50-200:2-10:1-20; Be preferably Al2O3:SiO2:P2O5:H
2o: template: the molar ratio of source of iron is 0.5-1:0.5-1:100-150:5-8:10-15:5-10;
(2), even colloid that step (1) is obtained, at 10-70 ℃, continue to stir 3 hours, then, under 0-180 ℃ of autogenous pressure hydrothermal condition, crystallization 12-120 hour, obtains the product after crystallization;
(3), by the product after crystallization through product after crystallization is obtained to molecular sieve finished product through suction filtration, washing, oven dry, roasting.
5. the method for the high skeleton iron level of preparation as claimed in claim 4 Fe-SAPO-34 molecular sieve, is characterized in that: described source of iron is a kind of in the Tripotassium iron hexacyanide, yellow prussiate of potash.
6. the method for the high skeleton iron level of preparation as claimed in claim 4 Fe-SAPO-34 molecular sieve, is characterized in that: the template of using is di-n-propylamine Diisopropylamine, one or more in diethylamine.
7. the method for the high skeleton iron level of preparation as claimed in claim 4 Fe-SAPO-34 molecular sieve, it is characterized in that: described silicon source is one or more in aerosil, water glass, tetraethoxy, described aluminium source is pseudo-boehmite, and described phosphorus source is ortho-phosphoric acid.
8. the method for the high skeleton iron level of preparation as claimed in claim 4 Fe-SAPO-34 molecular sieve, is characterized in that: the oven dry in step (3) is to dry 3-8 hour at 100-130 ℃.
9. the method for the high skeleton iron level of preparation as claimed in claim 4 Fe-SAPO-34 molecular sieve, is characterized in that: described suction filtration, washing process refer to and in suction filtration, add deionized water wash filter cake, to the pH of filtrate be 7.
10. the method for the high skeleton iron level of preparation as claimed in claim 4 Fe-SAPO-34 molecular sieve, is characterized in that: described roasting is ℃ of-700 ℃ insulations of temperature programming to 350 5 hours under the condition of 1 ℃/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754624A (en) * | 2004-09-28 | 2006-04-05 | 中国石油化工股份有限公司 | Metal modified SAPO-34 molecular screen and its uses |
| CN1966149A (en) * | 2005-11-17 | 2007-05-23 | 中国科学院大连化学物理研究所 | Catalyst for chloromethane conversion to produce low carbon olefin and its uses |
| CN101898768A (en) * | 2010-06-24 | 2010-12-01 | 神华集团有限责任公司 | Titanium modified SAPO-34 molecular sieve and preparation method and application thereof |
| CN102198949A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Preparation method of high regularity mesoporous molecular sieve Fe-MCM-41 |
-
2014
- 2014-01-10 CN CN201410013026.XA patent/CN103708498B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754624A (en) * | 2004-09-28 | 2006-04-05 | 中国石油化工股份有限公司 | Metal modified SAPO-34 molecular screen and its uses |
| CN1966149A (en) * | 2005-11-17 | 2007-05-23 | 中国科学院大连化学物理研究所 | Catalyst for chloromethane conversion to produce low carbon olefin and its uses |
| CN102198949A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Preparation method of high regularity mesoporous molecular sieve Fe-MCM-41 |
| CN101898768A (en) * | 2010-06-24 | 2010-12-01 | 神华集团有限责任公司 | Titanium modified SAPO-34 molecular sieve and preparation method and application thereof |
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| CN104709921A (en) * | 2015-03-10 | 2015-06-17 | 中国天辰工程有限公司 | Micro-channel reactor and method applying micro-channel reactor to produce magnetic titanium silicalite |
| CN104709921B (en) * | 2015-03-10 | 2016-08-24 | 中国天辰工程有限公司 | A kind of micro passage reaction and the method using its production Magnetic titanium silicon molecular sieve |
| CN107855132A (en) * | 2017-11-07 | 2018-03-30 | 大连理工大学 | A kind of method and its application using the system with molecular sieve for preparing of SAPO 34 for the catalyst of Fe/SAPO 34 |
| CN107855132B (en) * | 2017-11-07 | 2020-02-18 | 大连理工大学 | Method for preparing Fe/SAPO-34 catalyst by utilizing SAPO-34 molecular sieve and application thereof |
| CN109485068A (en) * | 2018-08-30 | 2019-03-19 | 南京大学 | A kind of two-dimensional ultrathin Me-SAPO-34 molecular sieve sheeting and preparation method thereof |
| CN109485068B (en) * | 2018-08-30 | 2020-11-13 | 南京大学 | Two-dimensional ultrathin Me-SAPO-34 molecular sieve sheet material and preparation method thereof |
| CN109317193A (en) * | 2018-11-12 | 2019-02-12 | 上海第二工业大学 | A kind of application of Fe-SAPO-34 catalyst in methyl stearate synthesis |
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