CN104098106B - The method of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 a kind of - Google Patents

The method of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 a kind of Download PDF

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CN104098106B
CN104098106B CN201410322589.7A CN201410322589A CN104098106B CN 104098106 B CN104098106 B CN 104098106B CN 201410322589 A CN201410322589 A CN 201410322589A CN 104098106 B CN104098106 B CN 104098106B
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silicalite
source
zeolite
iron
hollow type
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CN104098106A (en
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牟庆平
郭新闻
侯晓峰
代成义
栾波
刘民
张安峰
姚刚
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Dalian University of Technology
Chambroad Chemical Industry Research Institute Co Ltd
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Chambroad Chemical Industry Research Institute Co Ltd
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Abstract

The invention provides a kind of method and application of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite, adopting silicon source, organic source of iron, alkali source, template and water is raw material, crystallization in crystallizing kettle, centrifugation, washing, dry, roasting, prepares the hollow type Fe-Silicalite-1 zeolite that simultaneously has micropore and mesoporous distribution. Synthesis technique of the present invention is simple, does not need multistep operation, also without additionally adding expensive additive; By regulating source of iron kind, can effectively regulate pattern and the pore-size distribution of Fe-Silicalite-1 zeolite; The Fe-Silicalite-1 zeolite of synthesized of the present invention, for catalysis methanol propylene reaction processed, is had to higher Propylene Selectivity, methanol conversion and catalyst life.

Description

The method of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 a kind of
Technical field
The invention belongs to inorganic chemical synthesis technical field, relate to a kind of preparation method of Fe-silicalite and answerWith, be specifically related to a kind of method and application of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite.
Background technology
Propylene, as a kind of important industrial chemicals, is widely used in polypropylene, expoxy propane, acrylonitrile etc.In the production process of chemical products. Propylene is mainly obtained through steam cracking or catalytic cracking by petroleum at present,But China is the serious deficient countries of petroleum resources, this just makes to develop new production of propylene techniqueIt is essential to become. Preparing propylene from methanol (MTP) technology can be utilized the abundant coal of reserves or natural gas via Methanol third because of itAlkene, receives increasing concern.
ZSM-5 zeolite molecular sieve is because of its good hydrothermal stability, higher Propylene Selectivity and strongerCarbon accumulation resisting ability, becomes the main catalyst that catalysis methanol propylene processed reacts. Research shows, weak acid is strongDegree and preferably duct diffusivity are favourable to improving Propylene Selectivity and extending catalyst life-span. Summer Tsing-Hua University etc.People adopts the Fe-ZSM-5 zeolite with weaker acid intensity as catalyst, after hydrothermal treatment consists for catalysisThe reaction of preparing light olefins from methanol, has obtained higher selectivity of light olefin. The people such as Mei adopt after aqueous slkaliFacture has obtained mesoporous H-ZSM-5 molecular sieve, has improved Propylene Selectivity and P/E than (propylene in productMol ratio with ethene). Therefore, the synthetic multi-stage porous Fe-Silicalite-1 zeolite with weaker acid intensity, rightThe Propylene Selectivity and the catalyst stability that improve preparing propylene from methanol reaction have very important significance.
The report of at present synthetic multi-stage porous Fe-Silicalite-1 zeolite is few, mainly adopts alkali treatment method or soft or hardTemplate, not only complex procedures, and cost is higher. In the situation that not adding the soft template such as organosilicon, oneThe method of the synthetic hollow type multi-stage porous Fe-Silicalite-1 zeolite of step there is not yet report.
Summary of the invention
In order to solve the deficiencies in the prior art part, the technical solution used in the present invention is:
A method for one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite, comprises the steps:
Under room temperature, silicon source is joined in the mixed solution of template, alkali source and water, stir 3h, add and haveMachine source of iron and water, continue to pack in crystallizing kettle after stirring 2h, through crystallization, centrifugation, and washing, dry,Roasting, obtains Fe-Silicalite-1 zeolite;
Described, silicon source is ethyl orthosilicate or Ludox;
Described, template is TPAOH or 4-propyl bromide;
Described, alkali source is TPAOH or NaOH;
Described, source of iron be ferrocene or ferric acetyl acetonade or ironic citrate or ferric citrate or ferric oxalate orFerrous gluconate;
Described, with the molar ratio computing of pure material, SiO in silicon source2: Fe in source of iron2O3: in templateTPA+: the OH in alkali source-∶H2O＝1∶0.003-0.03∶0.1-0.6∶0.1-0.6∶10-100；
Described, crystallization temperature is 80-200 DEG C, crystallization time is 1-5d.
Preferred silicon source is ethyl orthosilicate, and ethyl orthosilicate can complete hydrolysis be silicic acid, is conducive to iron thingPlant and silicon species combination.
Preferred template is TPAOH, and TPAOH plays alkali source and template simultaneouslyEffect, do not introduce again other anion or cation, can make positive silicic acid complete hydrolysis.
Preferred alkali source is TPAOH, and TPAOH plays alkali source and template simultaneouslyEffect, does not introduce again other anion or cation, can make positive silicic acid complete hydrolysis.
Preferred source of iron is ironic citrate, and ironic citrate can slow down iron ion hydrolytic polymerization in alkaline systemGenerate oxide or precipitation of hydroxide.
The preferred molar ratio computing with pure material, SiO in silicon source2: Fe in source of iron2O3: the TPA in template+∶OH in alkali source-∶H2O=1: 0.021: 0.27: 0.27: 37, under this material ratio, be conducive to colloidal solGel process, and crystallization afterwards.
A purposes for Fe-Silicalite-1 zeolite, uses it for catalysis methanol propylene reaction processed, wherein, and willSynthetic Fe-Silicalite-1 zeolite uses aluminium oxide extruded moulding, hands over through 0.4M aqueous ammonium nitrate solution room temperatureChange 3 times, use after 2M inorganic pickling for preparing propylene from methanol reaction, described inorganic acid be hydrochloric acid or sulfuric acid orNitric acid or phosphoric acid.
The Fe-Silicalite-1 of hollow type multi-stage porous yet there are no bibliographical information, and the hollow type of synthetic other typesZeolite molecular sieve also uses multistep processes mostly, and the present invention has utilized one-step method synthetic, and synthesis technique is simple, noNeed multistep operation, also without additionally adding expensive additive;
By regulating source of iron kind, can effectively regulate pattern and the pore-size distribution of Fe-Silicalite-1 zeolite, exampleIf use Organic Iron as source of iron, due to the complexing of part, suppressed iron ion in alkaline solutionHydrolysis, meanwhile, different types of part likely can interact with template, to the life of zeoliteLength has played the effect of " cut-off ", has reduced the particle diameter of zeolite, has produced a large amount of multi-stage porous;
The Fe-Silicalite-1 zeolite of synthesized of the present invention, for catalysis methanol propylene reaction processed, is had higherPropylene Selectivity, methanol conversion and catalyst life.
In sum, advantage of the present invention is: synthesis technique is simple, does not need multistep operation, also without volumeAdd expensive additive outward; By regulating source of iron kind, can effectively regulate Fe-Silicalite-1 zeolitePattern and pore-size distribution; With common zeolite facies ratio, there is hollow pattern, pore-size distribution is except common zeoliteMicropore canals also there is mesoporous distribution outward. The Fe-Silicalite-1 zeolite of synthesized of the present invention is used for to catalysisPreparing propylene from methanol reaction, compared with ZSM-5, Fe-Silicalite-1 has more weak acid center, in catalysisIn preparing propylene from methanol reaction, be conducive to slow down propylene side reaction further occurs on acid site, with common shapeThe Fe-Silicalite-1 of looks compares, and the sample in the present invention has more mesoporous distribution, has larger appearanceCarbon ability. There is higher Propylene Selectivity, methanol conversion and catalyst life.
Brief description of the drawings
Fig. 1 is the XRD collection of illustrative plates of the synthetic Fe-Silicalite-1 zeolite of embodiment 1;
Fig. 2 is the SEM picture of embodiment 1 sample;
Fig. 3 is the TEM picture of embodiment 1 sample;
Fig. 4 is the nitrogen physisorption desorption curve of embodiment 1 sample;
Fig. 5 is pore-size distribution and the BET specific area of embodiment 1 sample;
Fig. 6 is the result of embodiment 1 sample catalysis methanol propylene reaction processed, and its reaction condition is: reaction temperatureDegree: 500 DEG C, reaction pressure: normal pressure, methanol quality air speed: 1h-1, in reactant water and methyl alcohol moleRatio: 5: 1.
Detailed description of the invention
Embodiment 1
15.4mL ethyl orthosilicate is joined in the aqueous solution of 16.5mL TPAOH to (1.14Mol/L), under room temperature, stir 3h, add 0.71g ironic citrate and 33mL water, continue to fill after stirring 2hEnter in crystallizing kettle 170 DEG C of crystallization 3d, centrifugation, washing, 100 DEG C of dried overnight, 540 DEG C of roasting 6hAfter obtain Fe-Silicalite-1. Raw materials used, with the molar ratio computing of pure material, SiO in silicon source2: in source of ironFe2O3: the TPA in template+: the OH in alkali source-∶H2O＝1∶0.021∶0.27∶0.27∶37；
Fig. 1 is the XRD collection of illustrative plates of sample, and as can be seen from the figure sample has MFI structure;
Fig. 2 is the SEM picture of sample, and as can be seen from the figure sample particle size homogeneous is 400nmThe little grain colony aggressiveness of left and right;
Fig. 3 is the TEM picture of sample, and as can be seen from the figure, sample is reunited and formed by little crystal grain, little crystalline substanceBetween grain, exist intergranular mesoporous, and whole aggregate particle have hollow structure;
Fig. 4 is the nitrogen physisorption desorption curve of sample, and sample is at P/P0Absorption within the scope of=0.2-0.9 canTo be summed up as the capillary condensation of nitrogen in mesoporous, this with tem observation to result conform to;
Fig. 5 is pore-size distribution and the BET specific area of sample, and result shows that sample has larger BET ratioSurface area, and there is micropore and mesoporous distribution simultaneously.
Embodiment 2
15.4mL ethyl orthosilicate is joined in the aqueous solution of 16.5mL TPAOH to (1.14Mol/L), under room temperature, stir 3h, add 1.01g ironic citrate and 33mL water, continue to fill after stirring 2hEnter in crystallizing kettle, 80 DEG C of crystallization 5d, centrifugation, washing, 100 DEG C of dried overnight, after 540 DEG C of roasting 6hObtain Fe-Silicalite-1. Raw materials used, with the molar ratio computing of pure material, SiO in silicon source2: Fe in source of iron2O3∶TPA in template+: the OH in alkali source-∶H2O＝1∶0.03∶0.27∶0.27∶37。
Embodiment 3
15.4mL ethyl orthosilicate is joined in the aqueous solution of 16.5mL TPAOH to (1.14Mol/L), under room temperature, stir 3h, add 0.10g ironic citrate and 33mL water, continue to fill after stirring 2hEnter in crystallizing kettle 200 DEG C of crystallization 1d, centrifugation, washing, 100 DEG C of dried overnight, 540 DEG C of roasting 6hAfter obtain Fe-Silicalite-1. Raw materials used, with the molar ratio computing of pure material, SiO in silicon source2: in source of ironFe2O3: the TPA in template+: the OH in alkali source-∶H2O＝1∶0.003∶0.27∶0.27∶37。
Embodiment 4
Choosing ferric citrate is source of iron, and addition is 0.81g, and all the other are identical with embodiment 1.
Embodiment 5
Choosing ferric acetyl acetonade is source of iron, and addition is 1.02g, and all the other are identical with embodiment 1.
Embodiment 6
Choosing ferric oxalate is source of iron, and addition is 0.52g, and all the other are identical with embodiment 1.
Embodiment 7
Choosing ferrous gluconate is source of iron, and addition is 1.39g, and all the other are identical with embodiment 1.
Embodiment 8
Choosing ferrocene is source of iron, and addition is 0.54g, and all the other are identical with embodiment 1.
Embodiment 9
13.8g Ludox (30wt%) is joined to 4.96g 4-propyl bromide, 0.75g NaOHIn the mixed solution of 20mL water, under room temperature, stir 3h, add 0.71g ironic citrate and 16.3mL water,After continuing to stir 2h, pack in crystallizing kettle, 170 DEG C of crystallization 3d, centrifugation, washing, 100 DEG C were driedAt night, after 540 DEG C of roasting 6h, obtain Fe-Silicalite-1. Raw materials used, with the molar ratio computing of pure material, silicon sourceMiddle SiO2: Fe in source of iron2O3: the TPA in template+: the OH in alkali source-∶H2O＝1∶0.021∶0.27∶0.27∶37。
Embodiment 10
By 6.2g Ludox (30wt%) join 4.96g 4-propyl bromide, 0.75g NaOH andIn the mixed solution of 20mL water, under room temperature, stir 3h, add 0.32g ironic citrate and 31.6mL water,After continuing to stir 2h, pack in crystallizing kettle, 170 DEG C of crystallization 3d, centrifugation, washing, 100 DEG C were driedAt night, after 540 DEG C of roasting 6h, obtain Fe-Silicalite-1. Raw materials used, with the molar ratio computing of pure material, silicon sourceMiddle SiO2: Fe in source of iron2O3: the TPA in template+: the OH in alkali source-∶H2O＝1∶0.021∶0.6∶0.6∶100。
Embodiment 11
37.3g Ludox (30wt%) is joined to 4.96g 4-propyl bromide, 0.75g NaOHIn the mixed solution of 7mL water, under room temperature, stir 3h, add 1.92g ironic citrate and 0.5mL water,After continuing to stir 2h, pack in crystallizing kettle, 170 DEG C of crystallization 5d, centrifugation, washing, 100 DEG C were driedAt night, after 540 DEG C of roasting 6h, obtain Fe-Silicalite-1. Raw materials used, with the molar ratio computing of pure material, silicon sourceMiddle SiO2: Fe in source of iron2O3: the TPA in template+: the OH in alkali source-∶H2O＝1∶0.021∶0.1∶0.1∶10。
Experimental example 1
The Fe-Silicalite-1 zeolite of embodiment 1 synthesized is used to aluminium oxide extruded moulding, through 0.4M nitreAcid aqueous ammonium room temperature exchange 3 times, reacts for preparing propylene from methanol after the pickling of use 2M salt.
Fig. 6 is the result of embodiment 1 sample catalysis methanol propylene reaction processed, and result shows hollow type multi-stage porousFe-Silicalite-1 catalyst has good catalyst stability, higher Propylene Selectivity and P/E ratio.

Claims (7)

1. a method for one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite, is characterized in that comprisingFollowing steps:
Under room temperature, silicon source is joined in the mixed solution of template, alkali source and water, stir 3h, add and haveMachine source of iron and water, continue to pack in crystallizing kettle after stirring 2h, through crystallization, centrifugation, and washing, dry,Roasting, obtains Fe-Silicalite-1 zeolite;
Described, silicon source is ethyl orthosilicate or Ludox;
Described, template is TPAOH or 4-propyl bromide;
Described, alkali source is TPAOH or NaOH;
Described, source of iron be ferrocene or ferric acetyl acetonade or ironic citrate or ferric citrate or ferric oxalate orFerrous gluconate;
Described, with the molar ratio computing of pure material, SiO in silicon source2: Fe in source of iron2O3: in templateTPA+: the OH in alkali source-：H2O=1：0.003-0.03：0.1-0.6：0.1-0.6：10-100；
Described, crystallization temperature is 80-200 DEG C, crystallization time is 1-5d.
2. the method for a kind of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite as claimed in claim 1,It is characterized in that, described silicon source is ethyl orthosilicate.
3. the side of a kind of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite as claimed in claim 1 or 2Method, is characterized in that, described template is TPAOH.
4. the side of a kind of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite as claimed in claim 1 or 2Method, is characterized in that, described alkali source is TPAOH.
5. the method for a kind of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite as claimed in claim 1,It is characterized in that, described source of iron is ironic citrate.
6. the method for a kind of one-step synthesis hollow type multi-stage porous Fe-Silicalite-1 zeolite as claimed in claim 1,It is characterized in that the described molar ratio computing with pure material, SiO in silicon source2: Fe in source of iron2O3: templateIn TPA+: the OH in alkali source-：H2O=1：0.021：0.27：0.27：37。
7. a purposes for Fe-Silicalite-1 zeolite described in claim 1, uses it for catalysis methanol propylene processed anti-Should, wherein, synthetic Fe-Silicalite-1 zeolite is used to aluminium oxide extruded moulding, through 0.4M ammonium nitrateAqueous solution room temperature exchange 3 times, after the inorganic pickling of use 2M, for preparing propylene from methanol reaction, described inorganic acid isHydrochloric acid or sulfuric acid or nitric acid or phosphoric acid.
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