CN107337213B - A kind of Silicate-1 molecular sieve and preparation method thereof containing trace metal ion - Google Patents
A kind of Silicate-1 molecular sieve and preparation method thereof containing trace metal ion Download PDFInfo
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Abstract
The Silicate-1 molecular sieve and preparation method thereof containing trace metal ion that the invention discloses a kind of, the BET specific surface area of the Silicate-1 molecular sieve are 400-500 meters2/ gram, particle size is 0.1-0.2 microns, and the mass ratio of silica and metal ion is (5000-200000): 1, which includes: a, by the mixing of silicon source, metal ion source, organic formwork agent and water, obtains colloid admixture；B, the colloid admixture obtained in step a is subjected to hydrothermal crystallizing.Using the thin Silicate-1 molecular sieve close to neutrality containing trace metal ion of the available high-crystallinity of method provided by the invention, fine grained, metal ion content is in 5-200ppm range, made catalyst applied in the production of caprolactam, the conversion ratio of cyclohexanone oxime can be improved, extend catalyst life, promotes the economy of vapour phase rearrangement novel technique.
Description
Technical field
The Silicate-1 molecular sieve and preparation method thereof containing trace metal ion that the present invention relates to a kind of.
Background technique
In recent decades, more and more zeolite molecular sieves are as catalysis material in petroleum refining and petrochemical industry
It is widely used.Wherein people are most interested and most study is with ZSM-5 type structure (the entitled MFI of geometry
Topology) various molecular sieves, such as sial ZSM-5 molecular sieve, the hetero atom sial ZSM-5 molecular sieve (hetero atom of introducing
Have: germanium, boron, chromium, iron, calcium etc.), the hetero atom ZSM-5 molecular sieve (such as TS-1, CrS-1, MnS-1) without aluminium.But to ZSM-5
Family not yet causes people's extensive concern without aluminium total silicon Silicalite-1 molecular sieve, as new catalytic material still in grinding
The hair stage.
Silicalite-1 molecular sieve is also known as total silicon -1, -1 molecular sieve of pure silicon, in 1978 by U.S. combinating carbide public affairs
The E.M.Flanigen etc. of department is successfully synthesized out for the first time, belongs to one of the member of " Pentasil " family.Silicalite-
1 molecular sieve is a kind of silica zeolite without aluminium with MFI topology, is group in ZSM-5 type structure molecular screen family
At a kind of simplest molecular sieve, skeleton only contains silicon atom and oxygen atom, basic structural unit SiO4Tetrahedron.
Silicalite-1 molecular sieve possesses microcellular structure abundant and regular uniform three-dimensional tubulus, has determining ZSM-5 type
The crystal structure of molecular sieve, higher inner ratio surface area, the performances such as good thermal stability, absorption and desorption ability.
Silicalite-1 molecular sieve can make the material of UF membrane, and acyl in oneself can also be produced as Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement
The catalyst of amine.
The synthetic method of Silicalite-1 molecular sieve generally uses traditional Organic Ingredients hydro-thermal method, and silicon source can be selected solid
Body silica, silica solution, white carbon black, ethyl orthosilicate (abbreviation TEOS) etc., template mostly use tetrapropylammonium hydroxide (referred to as
TPAOH), low-carbon hydro carbons quaternary ammonium salt or both mixture, aminated compounds etc., the crystallization three days at a temperature of 170 DEG C.American Association
The Silicalite-1 molecular sieve relative crystallinity of the synthesis such as carbide company is poor, more containing amorphous silicon oxide, crystal
Grain is larger.
The coesite disclosed in United States Patent (USP) US2876072 is to be aoxidized earliest by the crystal of artificial synthesized molecular sieve type
Silicon, it is to use steam, and strong acid or organic chelating agent handle the crystalline aluminosilicate of molecular sieve type, then extract tetrahedron
What the aluminium in skeleton was formed.
The Silicalite-1 molecular sieve disclosed in United States Patent (USP) US4061724, the crystal structure with MFI, its system
There is no silicon source, only silicon source, alkali source, template and water in standby raw material, the Silicalite- formed different from extracting framework aluminum
1 molecular sieve is the Silicalite-1 molecular sieve directly synthesized.Silicon source used in this Silicalite-1 molecular sieve is that silicon is molten
One of glue, Silica hydrogel or White Carbon black, it is to become 150-700H by mole group2O:13-50SiO2: 0-6.5M2O:Q2O's
Reaction mixture synthesis in hydrothermal crystallizing 50~150 hours under 100~250 DEG C, self-generated pressure, wherein M is alkali metal, and Q is
Molecular formula is R4X+Quaternary cation, R represents hydrogen or has the alkyl of 2-6 carbon atom, and X is phosphorus or nitrogen.
The Silicalite-1 molecular sieve of MFI structure disclosed in Japan Patent JP59164617, is with ethyl orthosilicate
It (TEOS) is silicon source, tetrapropylammonium hydroxide is template preparation.In CATAL.REV.-SCI.ENG., 39 (4), 395~
It is in 424 (1997) studies have shown that the Silicalite-1 molecular sieve BET with higher synthesized using ethyl orthosilicate as silicon source
Total specific surface and external surface area, can respectively reach 400 meters2/ gram and 15-30 meters2/ gram, and the conversion ratio of cyclohexanone oxime and acyl in oneself
The selectivity of amine and the increase of external surface area are directly proportional.
Silicalite-1 molecular sieve disclosed in Chinese patent CN00123576.1 includes two kinds of synthetic methods, method
First is that: after mixing at room temperature with tetrapropylammonium hydroxide by ethyl orthosilicate, stir, hydrolyze, be warming up to 70-75 DEG C, add
Water needs to increase temperature in synthesis process and catches up with alcohol by mixture hydrothermal crystallizing, then closed processes after mixing with organic base.Side
Method second is that ethyl orthosilicate is mixed at room temperature with tetrapropylammonium hydroxide, is stirred, after hydrolysis, Jia Shui plus ethyl alcohol are formed
Molar concentration is TPAOH/SiO2=0.05-0.5, EtOH/SiO2=4-30, H2O/SiO2The mixture of=2-100；It will mixing
Object hydrothermal crystallizing；Product of roasting and organic base closed processes after mixing have added a large amount of ethyl alcohol, former material in synthesis process
Expect at high cost, COD discharge amount is big, and the molecular sieve solid content of synthesis reactor is low.
Silicalite-1 molecular sieve disclosed in Chinese patent CN 102050464A, synthesis process include the following steps:
(1) ethyl orthosilicate mixed at room temperature with tetrapropylammonium hydroxide, stirred, is fully hydrolyzed 3-5 hours, water supplement, formed
Molar concentration is TPAOH/SiO2=0.05-0.5, EtOH/SiO2=4, H2O/SiO2The mixture of=5-100；It (2) will be above-mentioned
Mixture is in closed reactor, and 80-120 DEG C crystallization 0.5-10 days under self-generated pressure are washed out, filter, dry, 400-
600 DEG C roasting 1-10 hours.
But so far there is not yet containing extremely micro or trace metal ion Silicalite-1 Zeolite synthesis
Related report.
Summary of the invention
The object of the present invention is to provide a kind of Silicate-1 molecular sieve and preparation method thereof containing trace metal ion, energy
The performance for effectively changing Silicate-1 molecular sieve, obtains unexpected effect.
To achieve the goals above, the present invention provides a kind of Silicate-1 molecular sieve containing trace metal ion, should
The BET specific surface area of Silicate-1 molecular sieve is 400-500 meters2/ gram, particle size is 0.1-0.2 microns, silica and gold
The mass ratio for belonging to ion is (5000-200000): 1.
Preferably, the metal ion is selected from Co2+、Ni2+、Cu2+、Zn2+、Fe2+、Mn2+、Cr3+、Fe3+、Ga3+、Al3+、
Ti4+、Zr4+、Sn4+、Ge4+、Pb4+、Mn4+、V5+、Sb5+、Mn6+、Mo6+And W6+At least one of.
The preparation method of also a kind of Silicate-1 molecular sieve containing trace metal ion of the present invention, this method comprises: a,
Silicon source, metal ion source, organic formwork agent and water are mixed, colloid admixture is obtained, wherein with molar ratio computing, the colloid
SiO in mixture2: organic formwork agent: H2O=1:(0.05-0.50): the mass ratio of (5-100), silica and metal ion is
(5000-200000): 1；B, the colloid admixture obtained in step a is subjected to hydrothermal crystallizing.
Preferably, the silicon source in step a is selected from least one of silica gel, silica solution and organosilicon acid esters.
Preferably, the silicon source in step a is methyl orthosilicate and/or ethyl orthosilicate.
Preferably, the source metal in step a is the compound containing metal ion.
Preferably, the metal ion is selected from group ib, group iib, group ivb, Group VB, group VIB, Section VII B
At least one of race, group III A, group IVA and ion of V A race metallic element.
Preferably, the metal ion is selected from Co2+、Ni2+、Cu2+、Zn2+、Fe2+、Mn2+、Cr3+、Fe3+、Ga3+、Al3+、
Ti4+、Zr4+、Sn4+、Ge4+、Pb4+、Mn4+、V5+、Sb5+、Mn6+、Mo6+And W6+At least one of.
Preferably, the organic formwork agent in step a is selected from fat amine compound, alcamine compound and quaternary amine
At least one of alkaloid compound.
Preferably, the organic formwork agent in step a is tetraethyl ammonium hydroxide and/or tetrapropylammonium hydroxide.
It preferably, further include low-carbon alcohols in the colloid admixture in step a, the low-carbon alcohols and SiO2Molar ratio
For 1:(4-15).
Preferably, the low-carbon alcohols are methanol and/or ethyl alcohol.
Preferably, it is blended in lower progress under conditions of temperature is 10-50 DEG C described in step a, mixes the time of progress
It is 0.5-10 hours.
Preferably, the condition of hydrothermal crystallizing described in step b are as follows: temperature is 80-120 DEG C, and the time is 0.5-10 days.
Preferably, this method further includes the step that the crystallization product that step b is obtained is washed, filters, dries and roasted
Suddenly.
Through the above technical solutions, extremely micro metal ion energy is added in Silicate-1 sieve synthesis procedure
The performance for effectively changing Silicate-1 molecular sieve, obtains unexpected effect.In cyclohexanone oxime gas phase beckmann rearrangement
In reaction, using existing Silicate-1 sieve peg-raking catalyst, cyclohexanone oxime conversion ratio and caprolactam selectively compare
Height respectively reaches 99.1% and 95.5% in Fast Evaluation the 6th hour, substantially achieves the limit, but with the extension of reaction time,
It is difficult to ensure that catalyst stability and service life.Using the available high-crystallinity of method provided by the invention, fine grained is thin, it is micro- to contain
The Silicate-1 molecular sieve close to neutrality of metal ion is measured, metal ion content is catalyzed in 5-200ppm range
Agent is applied in the production of caprolactam, and the conversion ratio of cyclohexanone oxime can be improved, and extends catalyst life, promotes vapour phase rearrangement
The economy of novel technique.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction of the Silicate-1 molecular sieve containing trace metal ion prepared by the embodiment of the present invention 1
Spectrogram；
Fig. 2 is the transmission electron microscope of the Silicate-1 molecular sieve containing trace metal ion prepared by the embodiment of the present invention 1
Photo.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
First aspect present invention provides a kind of Silicate-1 molecular sieve containing trace metal ion, the Silicate-1
The BET specific surface area of molecular sieve is 400-500 meters2/ gram, particle size is 0.1-0.2 microns, the matter of silica and metal ion
Amount is than being (5000-200000): 1.
According to the first aspect of the invention, the metal ion can be for selected from Co2+、Ni2+、Cu2+、Zn2+、Fe2+、Mn2+、
Cr3+、Fe3+、Ga3+、Al3+、Ti4+、Zr4+、Sn4+、Ge4+、Pb4+、Mn4+、V5+、Sb5+、Mn6+、Mo6+And W6+At least one of.
Second aspect of the present invention provides a kind of preparation method of Silicate-1 molecular sieve containing trace metal ion, should
Method includes: a, by the mixing of silicon source, metal ion source, organic formwork agent and water, obtains colloid admixture, wherein with molar ratio
It counts, SiO in the colloid admixture2: organic formwork agent: H2O=1:(0.05-0.50): (5-100), it is preferable that SiO2: it is organic
Template: H2O=1:(0.15-0.25): (10-50)；The mass ratio of silica and metal ion is (5000-200000): 1,
Preferably, the mass ratio of silica and metal ion is (10000-100000): 1；B, the colloid obtained in step a is mixed
It closes object and carries out hydrothermal crystallizing.
According to the second aspect of the invention, the silicon source in step a can be the conventional selection of this field, such as can be with
For selected from least one of silica gel, silica solution and organosilicon acid esters；Preferably general formula is (OR1)4The organosilicon acid esters of Si,
In, R1For the alkyl of 1-4 carbon atom；Further preferably methyl orthosilicate and/or ethyl orthosilicate.
According to the second aspect of the invention, the metal ion is the metal ion that is easy or can enter framework of molecular sieve,
Such as it can be for selected from group ib, group iib, group ivb, Group VB, group VIB, V Group IIB, group III A, group IVA
With the ion of the metallic element of V A race.Preferably, the metal ion is selected from Co2+、Ni2+、Cu2+、Zn2+、Fe2+、Mn2+、
Cr3+、Fe3+、Ga3+、Al3+、Ti4+、Zr4+、Sn4+、Ge4+、Pb4+、Mn4+、V5+、Sb5+、Mn6+、Mo6+And W6+At least one of.
It is highly preferred that the metal ion is the metal ion that is easy or can enter framework of molecular sieve of trivalent or tetravalence, such as can be with
For selected from Cr3+、Fe3+、Ga3+、Al3+、Ti4+、Zr4+、Sn4+、Ge4+、Pb4+And Mn4+At least one of.It is further preferred that institute
Stating metal ion is selected from Fe3+、Al3+、Ti4+And Zr4+At least one of.
According to the second aspect of the invention, the metal ion source in step a can be to contain above-mentioned metal ion
Compound, such as can be the nitrate containing above-mentioned metal ion, chlorate, acetate, carbonate, or lipid gold
Belong to compound, such as tetraethyl titanate, butyl titanate.The present invention does not have the water soluble compound containing above-mentioned metal ion
There is special requirement, it can be using any water soluble compound material containing above-mentioned metal ion being available commercially on the market
Material, for example, when introducing Al to Silicate-1 molecular sieve3+When, it can be using SB powder, V250 powder, boehmite, C-1 powder etc.
Material.
According to the second aspect of the invention, the organic formwork agent in step a can be the conventional selection of this field, example
It such as can be for selected from least one of fat amine compound, alcamine compound and quaternary amine alkaloid compound.Wherein, described
The general formula of fat amine compound is R2(NH2)n, R2For the alkyl with 1-6 carbon atom, integer of the n between 1-3 is described
Fat amine compound is preferably selected from least one of ethamine, n-butylamine, n-propylamine, ethylenediamine and hexamethylene diamine.Wherein, institute
The general formula for stating alcamine compound is (HOR3)mN, R3For the alkyl with 1-4 carbon atom, integer of the m between 1-3 is described
Alcamine compound is preferably selected from least one of monoethanolamine, diethanol amine and triethanolamine.Wherein, the quaternary amine alkali
Class compound is preferably the alkyl quaternary amine alkali class compound with 1-4 carbon atom, further preferably tetraethyl ammonium hydroxide
And/or tetrapropylammonium hydroxide.
According to the second aspect of the invention, in order to keep sieve particle smaller in favor of carrying out catalysis reaction, in step a
It can also include low-carbon alcohols, the low-carbon alcohols and SiO in the colloid admixture2Molar ratio can be 1:(4-15).Wherein,
The low-carbon alcohols can be methanol and/or ethyl alcohol.
According to the second aspect of the invention, mixing described in step a can temperature be 10-50 DEG C under conditions of under into
Row, the time for mixing progress can be 0.5-10 hours.
According to the second aspect of the invention, the condition of hydrothermal crystallizing described in step b can use the conventional strip of this field
Part, for example, the condition of hydrothermal crystallizing described in step b can be with are as follows: temperature is 80-120 DEG C, and the time is 0.5-10 days.
According to the second aspect of the invention, this method can also include conventional treatment method of this field to molecular sieve, example
Such as, this method can also include the steps that the crystallization product for obtaining step b is washed, filtered, dried and roasted, wherein
The condition of the drying can be with are as follows: temperature is 100-120 DEG C, and the time is 20-30 hour, and the condition of the roasting can be with are as follows: warm
Degree is 400-600 DEG C, and the time is 1-10 hours.
The Silicate-1 molecule that Silicate-1 molecular sieve synthesized by the present invention is synthesized with art methods
Specific surface having the same and Extra specific surface area are sieved, therefore can be applied in the production of caprolactam；Synthesized by the present invention
Silicate-1 molecular sieve contains the metal ion of 5-200ppm, prepares acyl in oneself applied to cyclohexanone oxime gas phase beckmann rearrangement
In the reaction of amine, the conversion ratio of cyclohexanone oxime can be improved, and catalyst stability is good, catalyst life is longer.
Below by embodiment, the present invention will be further described, but content not thereby limiting the invention.
The BET specific surface of Silicate-1 sieve sample in example containing trace metal ion, Extra specific surface area data by
U.S.'s Micromeritics ASAP-2400 type automatic absorbing instrument is made, test condition are as follows: N2Make adsorbate, adsorption temp is-
196.15 DEG C (liquid nitrogen temperature), the constant temperature degassing 6h at 1.3Pa, 300 DEG C；X-ray diffraction spectra data are public by German SIEMENS
The D5005D type diffractometer of department is made, test condition are as follows: Cu target K α radiation, Ni optical filter, tube voltage 40kV, tube current 40mA；
The grain morphology of sample is by FEI Co.'s Tecnai G2F20S-TWIN type determination of transmission electron microscopy, test condition are as follows:
Using suspension method sample preparation, catalyst sample dehydrated alcohol is dispersed, shaken well, draws the dilute black aqueous mixture of water and drip to
On copper mesh, after ethyl alcohol volatilization completely in observing samples crystallite dimension size.Use Baird PS-4 type ICP-AES plasma
Body inductive coupling Atomic Emission Spectrometer AES measures the precious metal ion content of sample, test condition are as follows: with HF acid or aqua regia dissolution
Solid molecular sieves or catalyst make the silica volatility in sample, measure in aqueous solution.
Embodiment 1
By 208 grams of ethyl orthosilicates, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 180 gram of 22.5 weight %, 0.0281
Gram Fe (NO3)3·9H2O and 220 gram of water mixes, and stirs 3 hours under room temperature, forms colloid admixture, and mixture molar ratio is
SiO2: TPAOH:H2O=1:0.2:20, SiO2With Fe3+Mass ratio be 15347:1, will said mixture move into 1000 milliliters in
In the stainless steel cauldron of lining teflon, in 100 DEG C crystallization 3 days, washing, filtering, 120 DEG C drying 24 hours, 550 DEG C roast
It burns 6 hours, obtains Silicate-1 molecular sieve manufactured in the present embodiment.
The iron ion content of Silicate-1 zeolite product manufactured in the present embodiment is 64ppm, and BET specific surface area is
446 meters2/ gram, Extra specific surface area is 61 meters2/ gram, the X-ray diffraction spectrogram of product is as shown in Figure 1, transmission electron microscope photo such as Fig. 2 institute
Show.Its X-ray diffraction (XRD) spectrogram and Microporous Materials, the MFI knot recorded on Vol 22, p637,1998
Structure standard x RD chromatogram characteristic is consistent, this shows that the molecular sieve has MFI crystal structure；From transmission electron microscope photo as can be seen that
Silicate-1 zeolite crystal is uniform in size, and particle size is 0.1-0.2 μm.
Embodiment 2
By 208 grams of ethyl orthosilicates, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 180 gram of 22.5 weight %, 0.118
Gram Al (NO3)3·9H2O and 220 gram of water mixes, and stirs 5 hours under room temperature, forms colloid admixture, and mixture molar ratio is
SiO2: TPAOH:H2O=1:0.2:20, SiO2With Al3+Mass ratio be 7067:1, will said mixture move into 1000 milliliters in
In the stainless steel cauldron of lining teflon, in 100 DEG C crystallization 3 days, washing, filtering, 120 DEG C drying 24 hours, 550 DEG C roast
It burns 6 hours, obtains Silicate-1 molecular sieve manufactured in the present embodiment.
The aluminium composition of Silicate-1 zeolite product manufactured in the present embodiment is 140ppm, and BET specific surface area is
433 meters2/ gram, Extra specific surface area is 51 meters2/ gram, the X-ray diffraction spectrogram of product is similar with Fig. 1, transmission electron microscope photo and Fig. 2 class
Seemingly.
Embodiment 3
By 208 grams of ethyl orthosilicates, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 180 gram of 22.5 weight %, 0.0042
Gram ZrOCl2·8H2O and 220 gram of water mixes, and stirs 4 hours under room temperature, forms colloid admixture, and mixture molar ratio is SiO2:
TPAOH:H2O=1:0.2:20, SiO2With Zr4+Mass ratio be 50596:1, by said mixture immigration 1000 milliliters of liners gather
In the stainless steel cauldron of tetrafluoroethene, in 120 DEG C crystallization 3 days, washing, filtering, 120 DEG C drying 24 hours, 550 DEG C roast 6
Hour, obtain Silicate-1 molecular sieve manufactured in the present embodiment.
The zirconium ion content of Silicate-1 zeolite product manufactured in the present embodiment is 20ppm, and BET specific surface area is
428 meters2/ gram, Extra specific surface area is 48 meters2/ gram, the X-ray diffraction spectrogram of product is similar with Fig. 1, transmission electron microscope photo and Fig. 2 class
Seemingly.
Embodiment 4
The tetrapropylammonium hydroxide of 208 grams of ethyl orthosilicates (being abbreviated as TEOS), 180 gram of 22.5 weight % (are abbreviated as
TPAOH), 0.0252 gram of butyl titanate and 220 grams of water mix, and stir 4 hours under room temperature, form colloid admixture, mixture
Molar ratio is SiO2: TPAOH:H2O=1:0.2:20, SiO2With Ti4+Mass ratio be 16937:1, said mixture is moved into
In the stainless steel cauldron of 1000 milliliters of inner liner polytetrafluoroethylenes, in 120 DEG C crystallization 3 days, washing, filtering, 120 DEG C of dryings 24 are small
When, 550 DEG C roast 6 hours, obtain Silicate-1 molecular sieve manufactured in the present embodiment.
The titanium ion content of Silicate-1 zeolite product manufactured in the present embodiment is 60ppm, and BET specific surface area is
451 meters2/ gram, Extra specific surface area is 58 meters2/ gram, the X-ray diffraction spectrogram of product is similar with Fig. 1, transmission electron microscope photo and Fig. 2 class
Seemingly.
Embodiment 5
By 208 grams of ethyl orthosilicates, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 360 gram of 22.5 weight %, 184 grams
Ethyl alcohol, 0.028 gram of Cr (NO3)3·9H2O and 440 gram of water mixes, and stirs 5 hours under room temperature, forms colloid admixture, mixture
Molar ratio is SiO2: TPAOH:H2O=1:0.4:40, SiO2With Cr3+Mass ratio be 16483:1, ethyl alcohol/SiO2=8, it will be upper
State mixture move into 1000 milliliters of inner liner polytetrafluoroethylenes stainless steel cauldron in, in 100 DEG C crystallization 3 days, washing, filtering,
120 DEG C drying 24 hours, 550 DEG C roast 6 hours, obtain Silicate-1 molecular sieve manufactured in the present embodiment.
The chromium content of Silicate-1 sieve sample manufactured in the present embodiment is 60ppm, BET specific surface area 433
Rice2/ gram, Extra specific surface area is 52 meters2/ gram, the X-ray diffraction spectrogram of sample is similar with Fig. 1, and transmission electron microscope photo is similar with Fig. 2.
Embodiment 6
By tetrapropylammonium hydroxide (being abbreviated as TPAOH), the 276 grams of second of 208 grams of ethyl orthosilicates, 90 gram of 22.5 weight %
Alcohol, 0.056 gram of Fe (NO3)3·9H2O and 110 gram of water mixes, and stirs 4 hours under room temperature, forms colloid admixture, and mixture rubs
You are than being SiO2: TPAOH:H2O=1:0.1:10, SiO2With Fe3+Mass ratio be 7673:1, ethyl alcohol/SiO2=10, it will be above-mentioned
Mixture move into 1000 milliliters of inner liner polytetrafluoroethylenes stainless steel cauldron in, in 120 DEG C crystallization 3 days, washing, filtering, 120
DEG C dry 24 hours, 550 DEG C roasted 6 hours, obtain Silicate-1 molecular sieve manufactured in the present embodiment.
The iron content of Silicate-1 sieve sample manufactured in the present embodiment is 131ppm, BET specific surface area 425
Rice2/ gram, Extra specific surface area is 28 meters2/ gram, the X-ray diffraction spectrogram of sample is similar with Fig. 1, and transmission electron microscope photo is similar with Fig. 2.
Embodiment 7
By 152 grams of methyl orthosilicates, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 180 gram of 22.5 weight %, 192 grams
Methanol, 0.010 gram of boehmite (aluminium weight is 35%) and 130 grams of water mix, and stir 6 hours under room temperature, it is mixed to form colloid
Object is closed, mixture molar ratio is SiO2: TEAOH:H2O=1:0.2:10, SiO2With Al3+Mass ratio be 15884:1, methanol/
SiO2=10, said mixture is moved into the stainless steel cauldron of 1000 milliliters of inner liner polytetrafluoroethylenes, in 120 DEG C of crystallization 3
It, washing, filtering, 120 DEG C drying 24 hours, 550 DEG C roasting 6 hours, obtain Silicate-1 molecule manufactured in the present embodiment
Sieve.
The aluminium content of Silicate-1 sieve sample manufactured in the present embodiment is 62ppm, BET specific surface area 411
Rice2/ gram, Extra specific surface area is 26 meters2/ gram, the X-ray diffraction spectrogram of sample is similar with Fig. 1, and transmission electron microscope photo is similar with Fig. 2.
Comparative example 1
This comparative example illustrates the process that Silicate-1 molecular sieve is synthesized according to the method two of Chinese patent CN1338427A.
139 grams of ethyl orthosilicates are poured into 1000 milliliters of beakers at room temperature, are stirred 30 minutes, 22.5% tetrapropyl hydrogen
In 120 grams of addition TEOS of amine-oxides (being abbreviated as TPAOH) aqueous solution, stirring hydrolysis 5 hours, adds 147 grams of water, adds ethyl alcohol at room temperature
267 grams, it is stirred for colloidal sol, the chemical composition of mixed sols is H at this time2O/SiO2=20, EtOH/SiO2=12.7,
TPAOH/SiO2=0.20,110 DEG C crystallization 2 days, washing, filtering, 120 DEG C drying 24 hours, 550 DEG C roasting 5 hours.
The Silicate-1 zeolite product BET specific surface area of preparation is 441 meters2/ gram, Extra specific surface area is 51 meters2/ gram.It produces
The X-ray diffraction spectrogram of product is similar with Fig. 1, and transmission electron microscope photo is similar with Fig. 2.
Comparative example 2
This comparative example illustrates the process of the method synthesis Silicate-1 molecular sieve according to Chinese patent CN102050464A.
208 grams of ethyl orthosilicates (being abbreviated as TEOS) are poured into 1000 milliliters of beakers at room temperature, are stirred 30 minutes, are used
In 22.5% 180 grams of addition ethyl orthosilicates of tetrapropylammonium hydroxide (being abbreviated as TPAOH) solution, stirring hydrolyzes 3- at room temperature
5 hours, add 220 grams of water, forms colloidal sol, stir evenly, molar concentration TPAOH/SiO2=0.2, EtOH/SiO2=4, H2O/
SiO2=20, said mixture is moved into the stainless steel cauldron of 1000 milliliters of inner liner polytetrafluoroethylenes, in 100 DEG C of crystallization 3
It, washing, filtering, 120 DEG C drying 24 hours, 550 DEG C roasting 5 hours.
The BET specific surface area of the Silicate-1 zeolite product of preparation is 439 meters2/ gram, Extra specific surface area be 60 meters2/ gram,
The X-ray diffraction spectrogram of product is similar with Fig. 1, and transmission electron microscope photo is similar with Fig. 2.
Comparative example 3
This comparative example illustrates to synthesize Silicate-1 molecular sieve according to the method for United States Patent (USP) USP4061724 embodiment 1
Process.
By NaOH solution, SiO2Content is mixed for the hydrosol, 4-propyl bromide (the being abbreviated as TPABr) solution of 30 weight %
It closes, obtaining molar ratio is 4.1Na2O:50SiO2: 691H2The mixture of O:1TPABr, by said mixture in 200 DEG C of crystallization 3
It, washing, filtering, 110 DEG C drying 24 hours, 600 DEG C roasting 4 hours.
The BET specific surface area of the Silicate-1 sieve sample of preparation is 417 meters2/ gram, Extra specific surface area be 36 meters2/ gram,
The X-ray diffraction spectrogram of sample is similar with Fig. 1, and transmission electron microscope photo is similar with Fig. 2.
Testing example
This testing example is for illustrating Silicate-1 molecular sieve synthesized by embodiment 1-7 and comparative example 1-3 in gas
Catalysis reaction result in phase Beckmann rearrangement.According to the nitrogenous compound post-processing approach in CN102233277A patent
The Silicate-1 molecular sieve of embodiment 1-7 and comparative example 1-3 are post-processed.Respectively by 9.5 grams of embodiment 1-7 and comparison
Example 1-3 synthesized by Silicate-1 molecular sieve and 95 grams of ammonium hydroxide and ammonium nitrate composition alkaline buffer solution (wherein, ammonium hydroxide and
The weight ratio of aqueous ammonium nitrate solution is 3:2, pH value 11.35) being added to reaction kettle with pressure, (KCF-100ml type magnetic agitation is high
Press kettle, Yantai high and new technology industrial development zone Ke Li automatic control equipment research institute) in, in 80 DEG C, 2.3kg/cm2It stirs 1 hour under pressure, then washes
It washs, filter, dry, obtain the catalyst of the molecular sieve containing MFI structure.
Experimental condition 1: reaction unit is normal pressure continuous flow fixed bed, and reactor inside diameter is 5 millimeters, the filling of catalyst
0.37 gram of amount, catalyst grain size 20-60 mesh.Catalyst is located in normal pressure, 350 DEG C of nitrogen atmosphere in advance after being packed into reaction tube
Reason 1 hour.The concentration of raw material cyclohexanone oxime is 35%, and weight space velocity (WHSV) is 16h-1, solvent is methanol, and reaction temperature is
380 DEG C, nitrogen flow is 1.8 ls/h, the reaction time 6 hours.
Experimental condition 2: reaction unit is continuous flow fixed bed, and reactor inside diameter is 28 millimeters, reaction pressure:
0.1MPa；Reaction temperature: 360 DEG C -400 DEG C；N2: oxime=12:1 (molar ratio)；Water/oxime mass percent 1.2%m；Vaporizer
175 DEG C of temperature control；Pipeline keeps the temperature 185 DEG C；Industrially prepared catalyst 30g；Bed height: 15.0cm；The concentration of raw material cyclohexanone oxime
It is 35%, weight space velocity (WHSV) 0.5h-1。
Test reaction the 6th hour (experimental condition 1) and the 600th hour (experimental condition 2) cyclohexanone oxime conversion ratio, will be anti-
Answer product by collecting after water circulating cooling.It is formed using capillary gas chromatography product, hydrogen flame detector, test
Condition are as follows: 250 DEG C of temperature of vaporization chamber, detection room temperature is 230 DEG C, and column temperature is temperature programming, 110 DEG C constant temperature 8 minutes, 15 DEG C/
Min is raised to 230 DEG C of constant temperature 14 minutes again.Reaction result is shown in Table 1.
Table 1
| Number | 6h conversion ratio/% | 600h conversion ratio/% |
| Embodiment 1 | 99.68 | 99.61 |
| Embodiment 2 | 99.82 | 99.68 |
| Embodiment 3 | 99.40 | 99.50 |
| Embodiment 4 | 99.55 | 99.56 |
| Embodiment 5 | 99.36 | 99.45 |
| Embodiment 6 | 99.39 | 99.48 |
| Embodiment 7 | 99.42 | 99.53 |
| Comparative example 1 | 97.87 | 99.06 |
| Comparative example 2 | 97.30 | 99.01 |
| Comparative example 3 | 69.7 | 82.55 |
It can be seen that from the result of embodiment 1-7 and comparative example 1-3 using the method system in United States Patent (USP) USP4061724
When standby Silicate-1 sieve peg-raking catalyst, the conversion ratio of cyclohexanone oxime is 69.7%, and is used provided by the invention
The Silicate-1 molecular sieve containing trace metal ion of example 1-7 synthesis, the conversion ratio of cyclohexanone oxime can achieve after 6 hours
Silicate-1 molecular sieve synthesized by method is urged in 99.36% or more, with prior art CN1338427A, CN102050464A
Agent is compared, and the conversion ratio of cyclohexanone oxime can also be improved 1.5% or more.Under the same test conditions, comparative example 1-3
Silicate-1 sieve peg-raking catalyst carries out 600 hours rear catalyst inactivations in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement,
The conversion ratio of cyclohexanone oxime is only only up to 99.06%, and the Silicate-1 containing trace metal ion of example 1-7 synthesis
After molecular sieve is for reacting 600 hours, the conversion ratio of cyclohexanone oxime also can achieve 99.45% or more, and the service life of catalyst is more
It is long.
It is described the prefered embodiments of the present invention in detail above in conjunction with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical solution of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of Silicate-1 molecular sieve containing trace metal ion, the BET specific surface area of the Silicate-1 molecular sieve are
400-500 meters2/ gram, particle size is 0.1-0.2 microns, and the mass ratio of silica and metal ion is (5000-200000):
1。
2. Silicate-1 molecular sieve according to claim 1, wherein the metal ion is selected from Co2+、Ni2+、Cu2 +、Zn2+、Fe2+、Mn2+、Cr3+、Fe3+、Ga3+、Al3+、Ti4+、Zr4+、Sn4+、Ge4+、Pb4+、Mn4+、V5+、Sb5+、Mn6+、Mo6+And W6 +At least one of.
3. a kind of preparation method of the Silicate-1 molecular sieve containing trace metal ion, this method comprises:
A, silicon source, metal ion source, organic formwork agent and water are mixed, obtains colloid admixture, wherein with molar ratio computing, institute
State SiO in colloid admixture2: organic formwork agent: H2O=1:(0.05-0.50): the matter of (5-100), silica and metal ion
Amount is than being (5000-200000): 1；The organic formwork agent is selected from fat amine compound, alcamine compound and quaternary amine alkali
At least one of class compound；
B, the colloid admixture obtained in step a is subjected to hydrothermal crystallizing.
4. according to the method described in claim 3, wherein, the silicon source in step a is selected from silica gel, silica solution and organosilicon
At least one of acid esters.
5. according to the method described in claim 3, wherein, the silicon source in step a is methyl orthosilicate and/or positive silicic acid second
Ester.
6. according to according to the method for claim 3, wherein the metal ion source in step a is to contain metal ion
Compound.
7. the method according to claim 3 or 6, wherein the metal ion is selected from group ib, group iib, Section IV B
Race, Group VB, group VIB, V Group IIB, group III A, group IVA and V A race metallic element ion at least one
Kind.
8. according to the method described in claim 7, wherein, the metal ion is selected from Co2+、Ni2+、Cu2+、Zn2+、Fe2+、Mn2 +、Cr3+、Fe3+、Ga3+、Al3+、Ti4+、Zr4+、Sn4+、Ge4+、Pb4+、Mn4+、V5+、Sb5+、Mn6+、Mo6+And W6+In at least one
Kind.
9. according to the method described in claim 3, wherein, the organic formwork agent in step a be tetraethyl ammonium hydroxide and/
Or tetrapropylammonium hydroxide.
10. according to the method described in claim 3, further include low-carbon alcohols in the colloid admixture in step a wherein, institute
State low-carbon alcohols and SiO2Molar ratio be 1:(4-15).
11. according to the method described in claim 10, wherein, the low-carbon alcohols are methanol and/or ethyl alcohol.
12. according to the method described in claim 3, wherein, it is blended in described in step a under conditions of temperature is 10-50 DEG C
Lower progress, the time for mixing progress is 0.5-10 hours.
13. according to the method described in claim 3, wherein, the condition of hydrothermal crystallizing described in step b are as follows: temperature 80-120
DEG C, the time is 0.5-10 days.
14. according to the method described in claim 3, this method further include the crystallization product that step b is obtained is washed, mistake
The step of filter, dry and roasting.
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| CN109772426B (en) * | 2019-01-23 | 2021-09-21 | 浙江恒澜科技有限公司 | Microspheric MFI topological structure all-silicon-1 molecular sieve catalyst containing trace rare earth ions and spray forming preparation method thereof |
| CN109833898B (en) * | 2019-01-23 | 2021-05-14 | 浙江恒澜科技有限公司 | Preparation method of spherical MFI topological structure all-silicon molecular sieve catalyst containing trace rare earth ions and preparation method of caprolactam |
| CN109775714B (en) * | 2019-01-23 | 2021-05-14 | 浙江恒澜科技有限公司 | MFI topological structure silicon molecular sieve containing trace rare earth ions and preparation method thereof |
| CN112239212B (en) * | 2019-07-19 | 2022-06-07 | 浙江恒逸石化研究院有限公司 | Silicon molecular sieve with MFI topological structure and preparation method and application thereof |
| CN111348659B (en) * | 2020-04-15 | 2022-09-09 | 鞍山师范学院 | Preparation method of spherical B-Silicalite molecular sieve |
| CN111790434A (en) * | 2020-07-03 | 2020-10-20 | 浙江恒澜科技有限公司 | Catalyst containing silicon molecular sieve with MFI topological structure, preparation method and application thereof, and gas phase Beckmann rearrangement reaction method |
| CN111790433A (en) * | 2020-07-03 | 2020-10-20 | 浙江恒澜科技有限公司 | Catalyst containing silicon molecular sieve with MFI topological structure, preparation method and application thereof, and gas phase Beckmann rearrangement reaction method |
| CN111847472A (en) * | 2020-07-03 | 2020-10-30 | 浙江恒澜科技有限公司 | Silicon molecular sieve with MFI topological structure and preparation method and application thereof |
| CN112142670A (en) * | 2020-09-02 | 2020-12-29 | 浙江恒澜科技有限公司 | Preparation method of caprolactam |
| CN115475655B (en) * | 2021-05-31 | 2024-04-05 | 中国石油化工股份有限公司 | Boron-containing Silicate-1 molecular sieve catalyst, preparation method thereof and method for preparing caprolactam |
| CN115475650B (en) * | 2021-05-31 | 2024-04-05 | 中国石油化工股份有限公司 | Niobium-containing Silicate-1 molecular sieve catalyst, preparation method thereof and method for preparing caprolactam |
| CN113477272A (en) * | 2021-07-09 | 2021-10-08 | 武汉工程大学 | Metal-doped MFI type molecular sieve catalyst, and preparation method and application thereof |
| CN114768550B (en) * | 2021-11-26 | 2024-02-20 | 南京工业大学 | Preparation method and application of W-atom doped Silicalite-1 molecular sieve membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840473A (en) * | 2005-03-31 | 2006-10-04 | 中国石油化工股份有限公司 | Vanadium-substituted silicate molecular sieve and its preparing method |
| CN104098106A (en) * | 2014-07-08 | 2014-10-15 | 黄河三角洲京博化工研究院有限公司 | One-step synthesizing method for hollow type multilevel-hole Fe-Silicalite-1 |
| CN104556110A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Tin-silicon molecular sieve as well as synthesis method and application thereof |
| CN105314650A (en) * | 2014-06-23 | 2016-02-10 | 中国石油化工股份有限公司 | Vanadium silicon molecular sieve and preparation method of same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110098491A1 (en) * | 2009-10-28 | 2011-04-28 | Bernard Cooker | Direct epoxidation process using alkanoic acid modifier |
-
2016
- 2016-04-29 CN CN201610282727.2A patent/CN107337213B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1840473A (en) * | 2005-03-31 | 2006-10-04 | 中国石油化工股份有限公司 | Vanadium-substituted silicate molecular sieve and its preparing method |
| CN104556110A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Tin-silicon molecular sieve as well as synthesis method and application thereof |
| CN105314650A (en) * | 2014-06-23 | 2016-02-10 | 中国石油化工股份有限公司 | Vanadium silicon molecular sieve and preparation method of same |
| CN104098106A (en) * | 2014-07-08 | 2014-10-15 | 黄河三角洲京博化工研究院有限公司 | One-step synthesizing method for hollow type multilevel-hole Fe-Silicalite-1 |
Non-Patent Citations (2)
| Title |
|---|
| synthesis and characterization of a chromium silicalite-1;T.Chapus等;《ZEOLITES》;19941231;第14卷;第166-173页 * |
| synthesis and characterization of chromium silicalite;Jose Silvio等;《Chem.Mater.》;19931231;第5卷;第349-355页 * |
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