CN107337213A - A kind of Silicate-1 molecular sieves containing trace metal ion and preparation method thereof - Google Patents
A kind of Silicate-1 molecular sieves containing trace metal ion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of molecular sieves of Silicate 1 containing trace metal ion and preparation method thereof, the BET specific surface area of the molecular sieves of Silicate 1 is 400 500 meters2/ gram, particle size is 0.1 0.2 microns, and the mass ratio of silica and metal ion is (5,000 200000)：1, the preparation method includes：A, silicon source, metal ion source, organic formwork agent and water are mixed, obtains colloid admixture；B, the colloid admixture obtained in step a is subjected to hydrothermal crystallizing.The molecular sieves of Silicate 1 of thin, containing trace metal ion the close neutrality of high-crystallinity, fine grained can be obtained using method provided by the invention, metal ion content is in 5 200ppm scopes, made catalyst applied in the production of caprolactam, the conversion ratio of cyclohexanone oxime can be improved, extend catalyst life, lift the economy of vapour phase rearrangement novel technique.
Description
Technical field
The present invention relates to a kind of Silicate-1 molecular sieves containing trace metal ion and preparation method thereof.
Background technology
In recent decades, increasing zeolite molecular sieve as catalysis material in petroleum refining and oil
Work is widely used in field.Wherein people are most interested and most study is with ZSM-5
The various molecular sieves of type structure (the entitled MFI topologies of geometry), such as sial ZSM-5 molecules
Sieve, (hetero atom of introducing has hetero atom sial ZSM-5 molecular sieve：Germanium, boron, chromium, iron, calcium etc.),
Hetero atom ZSM-5 molecular sieve (such as TS-1, CrS-1, MnS-1) without aluminium.But to ZSM-5 family
Race not yet causes people's extensive concern without aluminium total silicon Silicalite-1 molecular sieves, as new catalytic material
Still in development.
Silicalite-1 molecular sieves are also known as total silicon -1, the molecular sieve of pure silicon -1, in 1978 by American Association carbon
E.M.Flanigen of compound company etc. is successfully synthesized out first, belongs to " Pentasil " family
One of member.Silicalite-1 molecular sieves are a kind of total silicon molecules without aluminium with MFI topologies
Sieve, is to form a kind of simplest molecular sieve in ZSM-5 type structure molecular screens family, its skeleton only contains
There are silicon atom and oxygen atom, basic structural unit SiO4Tetrahedron.Silicalite-1 molecular sieves possess rich
Rich microcellular structure and regular uniform three-dimensional tubulus, there is the crystalline substance of the type ZSM 5 molecular sieve determined
The performances such as body structure, higher inner ratio surface area, good heat endurance, absorption and desorption ability.
Silicalite-1 molecular sieves can make the material of UF membrane, can also make Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement
Produce the catalyst of caprolactam.
The synthetic method of Silicalite-1 molecular sieves typically uses traditional Organic Ingredients hydro-thermal method, and silicon source can
From solid oxidation silicon, Ludox, white carbon, tetraethyl orthosilicate (abbreviation TEOS) etc., template
More using TPAOH (abbreviation TPAOH), low-carbon hydro carbons quaternary ammonium salt or both mixture, amine
Class compound etc., crystallization three days at a temperature of 170 DEG C.The synthesis such as U.S. combinating carbide company
Silicalite-1 molecular sieve relative crystallinities are poor, more containing amorphous silicon oxide, and crystal grain is larger.
The coesite disclosed in United States Patent (USP) US2876072 is earliest by artificial synthesized molecular sieve type
Crystalline silica, it is to use the crystalline aluminosilicate of steam, strong acid or organic chelating agent to molecular sieve type
Handled, then extract what aluminium in tetrahedral framework was formed.
The Silicalite-1 molecular sieves disclosed in United States Patent (USP) US4061724, there is MFI crystal knot
Structure, there is no silicon source, only silicon source, alkali source, template and water in its preparing raw material, different from extracting
Framework aluminum and the Silicalite-1 molecular sieves formed, are the Silicalite-1 molecular sieves directly synthesized.It is this
Silicon source used in Silicalite-1 molecular sieves is one kind in Ludox, Silica hydrogel or White Carbon black, and it is by rubbing
Your composition is 150-700H2O：13-50SiO2：0-6.5M2O：Q2O reactant mixture 100~
250 DEG C, hydrothermal crystallizing synthesis in 50~150 hours under self-generated pressure, wherein, M is alkali metal, Q
It is that molecular formula is R4X+Quaternary cation, R represents hydrogen or has the alkyl of 2-6 carbon atom, X be phosphorus or
Nitrogen.
The Silicalite-1 molecular sieves of MFI structure disclosed in Japan Patent JP59164617, are with just
Silester (TEOS) is silicon source, and TPAOH is prepared by template.
CATAL.REV.-SCI.ENG., 39 (4), the research in 395~424 (1997) shows, with positive silicon
Acetoacetic ester is that the Silicalite-1 molecular sieves of silicon source synthesis have higher BET always than surface and outer surface
Product, can respectively reach 400 meters2/ gram and 15-30 rice2/ gram, and the conversion ratio of cyclohexanone oxime and acyl in oneself
The selectivity of amine is directly proportional to the increase of external surface area.
Silicalite-1 molecular sieves disclosed in Chinese patent CN00123576.1, include two kinds of synthesis sides
One of method, method is：Tetraethyl orthosilicate is mixed at room temperature with TPAOH, stirred, water
Xie Hou, 70-75 DEG C is warming up to, adds water, it is closed by mixture hydrothermal crystallizing, then after being mixed with organic base
Handle, need rise temperature to catch up with alcohol in its building-up process.The two of method are by tetraethyl orthosilicate and tetrapropyl
Ammonium hydroxide is mixed, stirred at room temperature, and after hydrolysis, Jia Shui plus ethanol, forming molar concentration is
TPAOH/SiO2=0.05-0.5, EtOH/SiO2=4-30, H2O/SiO2=2-100 mixture；Will be mixed
Compound hydrothermal crystallizing；Product of roasting is well mixed rear closed processes with organic base, is added in its building-up process
A large amount of ethanol, the cost of raw material is high, and COD discharge capacitys are big, the molecular sieve solid content of synthesis reactor is low.
Silicalite-1 molecular sieves disclosed in Chinese patent CN 102050464A, building-up process include following
Step：(1) tetraethyl orthosilicate is mixed at room temperature with TPAOH, stirred, be fully hydrolyzed
3-5 hours, water is added, it is TPAOH/SiO to form molar concentration2=0.05-0.5, EtOH/SiO2=4,
H2O/SiO2=5-100 mixture；(2) by said mixture in closed reactor, under self-generated pressure
80-120 DEG C of crystallization 0.5-10 days, it is washed out, filters, drying, 400-600 DEG C of roasting 1-10 hour.
But so far there is not yet being closed containing extremely micro or trace metal ion Silicalite-1 molecular sieves
Into relevant report.
The content of the invention
It is an object of the invention to provide a kind of Silicate-1 molecular sieves containing trace metal ion and its preparation
Method, it can effectively change the performance of Silicate-1 molecular sieves, obtain unexpected effect.
To achieve these goals, the present invention provides a kind of Silicate-1 molecules containing trace metal ion
Sieve, the BET specific surface area of the Silicate-1 molecular sieves is 400-500 rice2/ gram, particle size 0.1-0.2
The mass ratio of micron, silica and metal 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 sieves containing trace metal ion of the present invention, this method
Including：A, silicon source, metal ion source, organic formwork agent and water are mixed, obtain colloid admixture,
Wherein, with molar ratio computing, SiO in the colloid admixture2：Organic formwork agent：H2O=1：(0.05-0.50)：
The mass ratio of (5-100), silica and metal ion is (5000-200000)：1；B, by step a
In the obtained colloid admixture carry out hydrothermal crystallizing.
Preferably, the silicon source in step a be in silica gel, Ludox and organosilicon acid esters extremely
Few one kind.
Preferably, the silicon source in step a is methyl silicate and/or tetraethyl 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, V B
Race, vib, V Group IIB, group III A, group IVA and V A races metallic element from
At least one of son.
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, alcamines
At least one of compound and quaternary amine alkaloid compound.
Preferably, the organic formwork agent in step a is tetraethyl ammonium hydroxide and/or tetrapropyl hydrogen-oxygen
Change ammonium.
Preferably, low-carbon alcohols, the low-carbon alcohols and SiO are also included in the colloid admixture in step a2
Mol ratio be 1：(4-15).
Preferably, the low-carbon alcohols are methanol and/or ethanol.
Preferably, lower progress under conditions of temperature is 10-50 DEG C, mixing are blended in described in step a
The time of progress is 0.5-10 hours.
Preferably, the condition of hydrothermal crystallizing is described in step b：Temperature is 80-120 DEG C, and the time is
0.5-10 days.
Preferably, this method also includes washing the obtained crystallization products of step b, filtering, drying
The step of with roasting.
Pass through above-mentioned technical proposal, extremely micro gold is added in Silicate-1 sieve synthesis procedures
Category ion can effectively change the performance of Silicate-1 molecular sieves, obtain unexpected effect.In ring
On hexanone oxime vapor phase beckmann rearrangement reaction, using existing Silicate-1 sieve peg-raking catalysts, hexamethylene
Ketoxime conversion ratio and caprolactam selectivity are higher, and Fast Evaluation respectively reaches 99.1% on the 6th hour
With 95.5%, the limit is substantially achieved, but with the extension in reaction time, it is difficult to ensure that catalyst stabilization
Property and life-span.Using method provided by the invention can obtain high-crystallinity, fine grained it is thin, containing micro gold
Belong to the neutral Silicate-1 molecular sieves that approach of ion, metal ion content is in 5-200ppm scopes, general
It makees catalyst applied in the production of caprolactam, can improve the conversion ratio of cyclohexanone oxime, extension is urged
In the agent life-span, lift the economy of vapour phase rearrangement novel technique.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing be for providing a further understanding of the present invention, and a part for constitution instruction, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the X of the Silicate-1 molecular sieves containing trace metal ion prepared by the embodiment of the present invention 1
X ray diffraction spectrogram；
Fig. 2 is the Silicate-1 molecular sieves containing trace metal ion prepared by the embodiment of the present invention 1
Transmission electron microscope photo.
Embodiment
The embodiment of the present invention is described in detail below in conjunction with accompanying drawing.It should be appreciated that
Embodiment described herein is merely to illustrate and explain the present invention, and is not limited to this hair
It is bright.
First aspect present invention, there is provided a kind of Silicate-1 molecular sieves containing trace metal ion, should
The BET specific surface area of Silicate-1 molecular sieves is 400-500 rice2/ gram, particle size is that 0.1-0.2 is micro-
The mass ratio of rice, silica and metal ion is (5000-200000)：1.
According to the first aspect of the invention, the metal ion can be 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.
A kind of second aspect of the present invention, there is provided preparation of the Silicate-1 molecular sieves containing trace metal ion
Method, this method include：A, silicon source, metal ion source, organic formwork agent and water are mixed, obtained
Colloid admixture, wherein, with molar ratio computing, SiO in the colloid admixture2：Organic formwork agent：
H2O=1：(0.05-0.50)：(5-100), it is preferable that SiO2：Organic formwork agent：H2O=1：(0.15-0.25)：
(10-50)；The mass ratio of silica and metal ion is (5000-200000)：1, it is preferable that oxidation
The mass ratio of silicon and metal ion is (10000-100000)：1；B, the glue that will be obtained in step a
Body mixture 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 area,
Such as can be selected from least one of silica gel, Ludox and organosilicon acid esters；Preferably formula is
(OR1)4Si organosilicon acid esters, wherein, R1For the alkyl of 1-4 carbon atom；More preferably
Methyl silicate and/or tetraethyl orthosilicate.
According to the second aspect of the invention, the metal ion is easily or can be into the gold of framework of molecular sieve
Belong to ion, such as can be selected from group ib, group iib, group ivb, Group VB, VI B
Race, V Group IIB, group III A, group IVA and V A races metallic element ion.It is preferred that
For 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 easy of trivalent or tetravalence or can entered
Enter the metal ion of framework of molecular sieve, such as can be selected from Cr3+、Fe3+、Ga3+、Al3+、Ti4+、
Zr4+、Sn4+、Ge4+、Pb4+And Mn4+At least one of.It is further preferred that the metal ion
For 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 gold
Belong to ion compound, such as can be the nitrate containing above-mentioned metal ion, chlorate, acetate,
Carbonate, or lipid metallic compound, such as tetraethyl titanate, butyl titanate.The present invention for
The water soluble compound containing above-mentioned metal ion does not have special requirement, can use and on the market may be used
Any water soluble compound material containing above-mentioned metal ion being commercially available, for example, when to
Silicate-1 molecular sieves introduce Al3+When, SB powder, V250 powder, boehmite, C-1 can be used
The materials such as powder.
According to the second aspect of the invention, the organic formwork agent in step a can be the normal of this area
Rule selection, such as can be selected from fat amine compound, alcamine compound and quaternary amine alkaloid compound
At least one of.Wherein, the formula of the fat amine compound is R2(NH2)n, R2For tool
There are the alkyl of 1-6 carbon atom, integers of the n between 1-3, the fat amine compound is preferably
Selected from least one of ethamine, n-butylamine, n-propylamine, ethylenediamine and hexamethylene diamine.Wherein, the alcohol
The formula of aminated compounds is (HOR3)mN, R3For the alkyl with 1-4 carbon atom, m be 1-3 it
Between integer, the alcamine compound is preferably selected from MEA, diethanol amine and triethanolamine
At least one.Wherein, the quaternary amine alkaloid compound is preferably the alkyl quaternary with 1-4 carbon atom
Amine alkaloid compound, more preferably tetraethyl ammonium hydroxide and/or TPAOH.
According to the second aspect of the invention, in order that sieve particle is smaller in favor of carrying out catalytic reaction,
Low-carbon alcohols, the low-carbon alcohols and SiO can also be included in the colloid admixture in step a2Mole
Than that can be 1：(4-15).Wherein, the low-carbon alcohols can be methanol and/or ethanol.
According to the second aspect of the invention, the mixing described in step a can be 10-50 DEG C in temperature
Under the conditions of it is lower carry out, 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 this area
Normal condition, for example, the condition of hydrothermal crystallizing described in step b can be：Temperature is 80-120 DEG C,
Time is 0.5-10 days.
According to the second aspect of the invention, this method can also include conventional treatment of this area to molecular sieve
Method, for example, this method can also include the obtained crystallization products of step b are washed, filtered,
The step of drying and being calcined, wherein, the condition of the drying can be：Temperature is 100-120 DEG C, when
Between be 20-30 hours, the condition of the roasting can be：Temperature is 400-600 DEG C, time 1-10
Hour.
Silicate-1 molecular sieves synthesized by the present invention synthesize obtained Silicate-1 with art methods
Molecular sieve has identical than surface and Extra specific surface area, therefore can be applied in the production of caprolactam；This
The synthesized Silicate-1 molecular sieves of invention contain 5-200ppm metal ion, applied to cyclohexanone oxime
Gas phase beckmann rearrangement is prepared in the reaction of caprolactam, can improve the conversion ratio of cyclohexanone oxime, and be catalyzed
Agent stability is good, and catalyst life is longer.
Below by embodiment, the present invention will be further described, but not thereby limiting the invention interior
Hold.
In example the BET of the Silicate-1 sieve samples containing trace metal ion than surface, outer compare table
Face data are made by U.S.'s Micromeritics ASAP-2400 type automatic absorbing instrument, and test condition is：
N2Make adsorbate, adsorption temp is -196.15 DEG C (liquid nitrogen temperatures), and constant temperature takes off at 1.3Pa, 300 DEG C
Gas 6h；X-ray diffraction spectra data are made by the D5005D type diffractometers of German SIEMENS companies,
Test condition is：Cu target K α radiations, Ni optical filters, tube voltage 40kV, tube current 40mA；Sample
The grain morphology of product by FEI Co.'s Tecnai G2F20S-TWIN type determination of transmission electron microscopy,
Test condition is：Using suspension method sample preparation, catalyst sample is disperseed with absolute ethyl alcohol, shaken well,
Draw the dilute black aqueous mixture of water to drip on copper mesh, the crystal grain chi in observing samples after ethanol volatilization completely
Very little size.Surveyed using Baird PS-4 type ICP-AES plasma inductives Atomic Emission Spectrometer AES
The precious metal ion content of random sample product, test condition are：With HF acid or aqua regia dissolution solid molecular sieves or
Catalyst, make the silica volatility in sample, determined in the aqueous solution.
Embodiment 1
208 grams of tetraethyl orthosilicates, 180 gram of 22.5 weight % TPAOH (are abbreviated as
TPAOH), 0.0281 gram of Fe (NO3)3·9H2O and 220 gram of water mixes, and stirring 3 is small under normal temperature
When, colloid admixture is formed, mixture mol ratio is SiO2：TPAOH：H2O=1：0.2：20,
SiO2With Fe3+Mass ratio be 15347：1, said mixture is moved into 1000 milliliters of liner polytetrafluoros
It is small in 100 DEG C of crystallization 3 days, washing, filtering, 120 DEG C of dryings 24 in the stainless steel cauldron of ethene
When, 550 DEG C are calcined 6 hours, obtain Silicate-1 molecular sieves manufactured in the present embodiment.
The iron ion content of Silicate-1 zeolite products manufactured in the present embodiment is 64ppm, BET ratios
Surface area is 446 meters2/ gram, Extra specific surface area is 61 meters2/ gram, X-ray diffraction spectrogram such as Fig. 1 of product
Shown, transmission electron microscope photo is as shown in Figure 2.Its X-ray diffraction (XRD) spectrogram and Microporous
The MFI structure standard x RD chromatogram characteristics recorded on Materials, Vol 22, p637,1998 are consistent,
This shows that the molecular sieve has MFI crystal structures；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
208 grams of tetraethyl orthosilicates, 180 gram of 22.5 weight % TPAOH (are abbreviated as
TPAOH), 0.118 gram of Al (NO3)3·9H2O and 220 gram of water mixes, and is stirred 5 hours under normal temperature,
Colloid admixture is formed, mixture mol ratio is SiO2：TPAOH：H2O=1：0.2：20, SiO2
With Al3+Mass ratio be 7067：1, by said mixture 1000 milliliters of inner liner polytetrafluoroethylenes of immigration
In stainless steel cauldron, in 100 DEG C of crystallization 3 days, washing, filtering, 120 DEG C of dryings 24 hours, 550 DEG C
Roasting 6 hours, obtains Silicate-1 molecular sieves manufactured in the present embodiment.
The aluminium composition of Silicate-1 zeolite products manufactured in the present embodiment is 140ppm, BET ratios
Surface area is 433 meters2/ gram, Extra specific surface area is 51 meters2/ gram, the X-ray diffraction spectrogram and Fig. 1 of product
Similar, transmission electron microscope photo is similar with Fig. 2.
Embodiment 3
208 grams of tetraethyl orthosilicates, 180 gram of 22.5 weight % TPAOH (are abbreviated as
TPAOH), 0.0042 gram of ZrOCl2·8H2O and 220 gram of water mixes, and is stirred 4 hours under normal temperature,
Colloid admixture is formed, mixture mol ratio is SiO2：TPAOH：H2O=1：0.2：20, SiO2
With Zr4+Mass ratio be 50596：1, said mixture is moved into 1000 milliliters of inner liner polytetrafluoroethylenes
Stainless steel cauldron in, in 120 DEG C of crystallization 3 days, washing, filtering, 120 DEG C of dryings 24 hours,
550 DEG C are calcined 6 hours, obtain Silicate-1 molecular sieves manufactured in the present embodiment.
The zirconium ion content of Silicate-1 zeolite products manufactured in the present embodiment is 20ppm, BET ratios
Surface area is 428 meters2/ gram, Extra specific surface area is 48 meters2/ gram, the X-ray diffraction spectrogram and Fig. 1 of product
Similar, transmission electron microscope photo is similar with Fig. 2.
Embodiment 4
By 208 grams of tetraethyl orthosilicates (being abbreviated as TEOS), 180 gram of 22.5 weight % tetrapropyl hydrogen-oxygen
Change ammonium (being abbreviated as TPAOH), 0.0252 gram of butyl titanate and 220 grams of water mixing, stirred under normal temperature
4 hours, colloid admixture is formed, mixture mol ratio is SiO2：TPAOH：H2O=1：0.2：20,
SiO2With Ti4+Mass ratio be 16937：1, said mixture is moved into 1000 milliliters of liner polytetrafluoros
It is small in 120 DEG C of crystallization 3 days, washing, filtering, 120 DEG C of dryings 24 in the stainless steel cauldron of ethene
When, 550 DEG C are calcined 6 hours, obtain Silicate-1 molecular sieves manufactured in the present embodiment.
The titanium ion content of Silicate-1 zeolite products manufactured in the present embodiment is 60ppm, BET ratios
Surface area is 451 meters2/ gram, Extra specific surface area is 58 meters2/ gram, the X-ray diffraction spectrogram and Fig. 1 of product
Similar, transmission electron microscope photo is similar with Fig. 2.
Embodiment 5
208 grams of tetraethyl orthosilicates, 360 gram of 22.5 weight % TPAOH (are abbreviated as
TPAOH), 184 grams of ethanol, 0.028 gram of Cr (NO3)3·9H2O and 440 gram of water mixing, normal temperature
Lower stirring 5 hours, forms colloid admixture, mixture mol ratio is SiO2：TPAOH：H2O=1：
0.4：40, SiO2With Cr3+Mass ratio be 16483：1, ethanol/SiO2=8, said mixture is moved
In the stainless steel cauldron for entering 1000 milliliters of inner liner polytetrafluoroethylenes, in 100 DEG C of crystallization 3 days, washing,
Filtering, 120 DEG C of drying 24 hours, 550 DEG C of roastings 6 hours, obtain Silicate-1 manufactured in the present embodiment
Molecular sieve.
The chromium content of Silicate-1 sieve samples manufactured in the present embodiment is 60ppm, and BET compares surface
Product is 433 meters2/ gram, Extra specific surface area is 52 meters2/ gram, X-ray diffraction spectrogram and Fig. 1 classes of sample
Seemingly, transmission electron microscope photo is similar with Fig. 2.
Embodiment 6
208 grams of tetraethyl orthosilicates, 90 gram of 22.5 weight % TPAOH (are abbreviated as
TPAOH), 276 grams of ethanol, 0.056 gram of Fe (NO3)3·9H2O and 110 gram of water mixing, normal temperature
Lower stirring 4 hours, forms colloid admixture, mixture mol ratio is SiO2：TPAOH：H2O=1：
0.1：10, SiO2With Fe3+Mass ratio be 7673：1, ethanol/SiO2=10, said mixture is moved
In the stainless steel cauldron for entering 1000 milliliters of inner liner polytetrafluoroethylenes, in 120 DEG C of crystallization 3 days, washing,
Filtering, 120 DEG C of drying 24 hours, 550 DEG C of roastings 6 hours, obtain Silicate-1 manufactured in the present embodiment
Molecular sieve.
The iron content of Silicate-1 sieve samples manufactured in the present embodiment is 131ppm, and BET compares surface
Product is 425 meters2/ gram, Extra specific surface area is 28 meters2/ gram, X-ray diffraction spectrogram and Fig. 1 classes of sample
Seemingly, transmission electron microscope photo is similar with Fig. 2.
Embodiment 7
152 grams of methyl silicates, 180 gram of 22.5 weight % TPAOH (are abbreviated as
TPAOH), 192 grams of methanol, 0.010 gram of boehmite (aluminium weight is 35%) and 130 grams of water mix
Close, stirred 6 hours under normal temperature, form colloid admixture, mixture mol ratio is SiO2：TEAOH：
H2O=1：0.2：10, SiO2With Al3+Mass ratio be 15884：1, methanol/SiO2=10, will be above-mentioned
Mixture is moved into the stainless steel cauldron of 1000 milliliters of inner liner polytetrafluoroethylenes, in 120 DEG C of crystallization 3
My god, washing, filtering, 120 DEG C of drying 24 hours, 550 DEG C of roastings 6 hours, obtain the present embodiment system
Standby Silicate-1 molecular sieves.
The aluminium content of Silicate-1 sieve samples manufactured in the present embodiment is 62ppm, and BET compares surface
Product is 411 meters2/ gram, Extra specific surface area is 26 meters2/ gram, X-ray diffraction spectrogram and Fig. 1 classes of sample
Seemingly, transmission electron microscope photo is similar with Fig. 2.
Comparative example 1
This comparative example illustrates to synthesize Silicate-1 molecules according to Chinese patent CN1338427A method two
The process of sieve.
139 grams of tetraethyl orthosilicates are poured into 1000 milliliters of beakers at room temperature, stirred 30 minutes,
120 grams of 22.5% TPAOH (being abbreviated as TPAOH) aqueous solution is added in TEOS, room temperature
Lower stirring hydrolysis 5 hours, adds 147 grams of water, adds 267 grams of ethanol, be stirred for colloidal sol, now mix
The chemical composition for closing colloidal sol is H2O/SiO2=20, EtOH/SiO2=12.7, TPAOH/SiO2=0.20,
110 DEG C of crystallization 2 days, washing, filtering, 120 DEG C of drying 24 hours, 550 DEG C of roastings 5 hours.
The Silicate-1 zeolite products BET specific surface area of preparation is 441 meters2/ gram, Extra specific surface area is
51 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 2
This comparative example illustrates to synthesize Silicate-1 molecules according to Chinese patent CN102050464A method
The process of sieve.
208 grams of tetraethyl orthosilicates (being abbreviated as TEOS) are poured into 1000 milliliters of beakers at room temperature,
Stirring 30 minutes, added with 22.5% 180 grams of TPAOH (being abbreviated as TPAOH) solution
Enter in tetraethyl orthosilicate, at room temperature stirring hydrolysis 3-5 hours, add 220 grams of water, form colloidal sol, stirring
Uniformly, molar concentration TPAOH/SiO2=0.2, EtOH/SiO2=4, H2O/SiO2=20, will be above-mentioned mixed
Compound is moved into the stainless steel cauldron of 1000 milliliters of inner liner polytetrafluoroethylenes, in 100 DEG C of crystallization 3 days,
Washing, filtering, 120 DEG C of drying 24 hours, 550 DEG C of roastings 5 hours.
The BET specific surface area of the Silicate-1 zeolite products of preparation is 439 meters2/ gram, Extra specific surface area
For 60 meters2/ gram, the X-ray diffraction spectrogram of product is similar with Fig. 1, transmission electron microscope photo and Fig. 2 classes
Seemingly.
Comparative example 3
This comparative example illustrates to synthesize Silicate-1 according to the method for United States Patent (USP) USP4061724 embodiments 1
The process of molecular sieve.
By NaOH solution, SiO2Content is the 30 weight % hydrosol, 4-propyl bromide (brief note
For TPABr) solution mixing, it is 4.1Na to obtain mol ratio2O：50SiO2：691H2O：1TPABr
Mixture, said mixture is small in 200 DEG C of crystallization 3 days, washing, filtering, 110 DEG C of dryings 24
When, 600 DEG C are calcined 4 hours.
The BET specific surface area of the Silicate-1 sieve samples of preparation is 417 meters2/ gram, Extra specific surface area
For 36 meters2/ gram, the X-ray diffraction spectrogram of sample is similar with Fig. 1, transmission electron microscope photo and Fig. 2 classes
Seemingly.
Testing example
This testing example is used to illustrate the Silicate-1 molecules synthesized by embodiment 1-7 and comparative example 1-3
Sieve the catalytic reaction result in vapor phase beckmann rearrangement reaction.According in CN102233277A patents
After nitrogen-containing compound post-processing approach is carried out to embodiment 1-7 and comparative example 1-3 Silicate-1 molecular sieves
Processing.Respectively by 9.5 grams of embodiment 1-7 and comparative example 1-3 synthesized by Silicate-1 molecular sieves and 95
Alkaline buffer solution (wherein, the weight of the ammoniacal liquor and aqueous ammonium nitrate solution ratio of gram ammoniacal liquor and ammonium nitrate composition
For 3：2, pH value 11.35) be added to reactor with pressure (KCF-100ml type magnetic agitation autoclaves,
Yantai high and new technology industrial development zone Ke Li automatic control equipments research institute) in, in 80 DEG C, 2.3kg/cm2Stirring 1 is small under pressure
When, it is washed out, filters, drying, obtains the catalyst of the molecular sieve containing MFI structure.
Experimental condition 1：Reaction unit is that normal pressure continuously flows fixed bed, and reactor inside diameter is 5 millimeters,
0.37 gram of the loadings of catalyst, catalyst grain size 20-60 mesh.Catalyst after reaction tube is loaded,
Pre-processed 1 hour in normal pressure, 350 DEG C of nitrogen atmosphere.The concentration of raw material cyclohexanone oxime is 35%, weight
It is 16h to measure air speed (WHSV)-1, solvent is methanol, and reaction temperature is 380 DEG C, nitrogen flow 1.8
L/h, 6 hours reaction time.
Experimental condition 2：Reaction unit is continuous flowing fixed bed, and reactor inside diameter is 28 millimeters, reaction
Pressure：0.1MPa；Reaction temperature：360℃-400℃；N2：Oxime=12：1 (mol ratio)；Water/
Oxime mass percent 1.2%m；175 DEG C of vaporizer temperature control；Pipeline is incubated 185 DEG C；Industrially prepared catalysis
Agent 30g；Bed height：15.0cm；The concentration of raw material cyclohexanone oxime is 35%, weight space velocity (WHSV)
0.5h-1。
The hexamethylene of test reaction the 6th hour (experimental condition 1) and the 600th hour (experimental condition 2)
Ketoxime conversion ratio, collected after reaction product is cooled down by water circulation.Surveyed using capillary gas chromatography
Fixed output quota thing forms, hydrogen flame detector, and test condition is：250 DEG C of temperature of vaporization chamber, detect room temperature
For 230 DEG C, column temperature is temperature programming, and 110 DEG C of constant temperature 8 minutes, 15 DEG C/min is raised to 230 DEG C of constant temperature again
14 minutes.Reaction result is shown in Table 1.
Table 1
| Numbering | 6h conversion ratios/% | 600h conversion ratios/% |
| 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 is can be seen that from embodiment 1-7 and comparative example 1-3 result using United States Patent (USP) USP4061724
In method prepare Silicate-1 sieve peg-raking catalysts when, the conversion ratio of its cyclohexanone oxime is 69.7%,
And the Silicate-1 molecular sieves containing trace metal ion of example 1-7 provided by the invention synthesis are used, 6
The conversion ratio of cyclohexanone oxime can reach more than 99.36% after hour, with prior art CN1338427A,
Silicate-1 molecular sieve catalysts in CN102050464A synthesized by method are compared, and cyclohexanone oxime turns
Rate can also improve more than 1.5%.Under the same test conditions, comparative example 1-3 Silicate-1
Sieve peg-raking catalyst carries out 600 hours rear catalysts in Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement and lost
Living, the conversion ratio of cyclohexanone oxime is only only up to 99.06%, and what example 1-7 was synthesized contains trace meter
The Silicate-1 molecular sieves of ion are used for after reacting 600 hours, and the conversion ratio of cyclohexanone oxime can also reach
To more than 99.45%, the life-span of catalyst is longer.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing, it is still, of the invention and unlimited
Detail in above-mentioned embodiment, can be to the present invention in the range of the technology design of the present invention
Technical scheme carry out a variety of simple variants, these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Sign, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention no longer separately illustrate to various combinations of possible ways.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of Silicate-1 molecular sieves containing trace metal ion, the BET of the Silicate-1 molecular sieves
Specific surface area is 400-500 rice2/ gram, particle size is 0.1-0.2 microns, silica and metal ion
Mass ratio is (5000-200000)：1.
2. Silicate-1 molecular sieves according to claim 1, wherein, the metal ion is choosing
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 sieves containing trace metal ion, this method include：
A, silicon source, metal ion source, organic formwork agent and water are mixed, obtains colloid admixture, its
In, with molar ratio computing, SiO in the colloid admixture2：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.
4. according to the method for claim 3, wherein, the silicon source in step a is selected from silicon
At least one of glue, Ludox and organosilicon acid esters.
5. according to the method for claim 3, wherein, the silicon source in step a is positive silicic acid
Methyl esters and/or tetraethyl orthosilicate.
6. basis is in accordance with the method for claim 3, wherein, the metal ion in step a
Source is the compound containing metal ion.
7. the method according to claim 3 or 6, wherein, the metal ion is selected from I B
Race, group iib, group ivb, Group VB, vib, V Group IIB, group III A,
At least one of ion of group IVA and V A races metallic element.
8. according to the method for 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+At least one of.
9. according to the method for claim 3, wherein, the organic formwork agent in step a is
Selected from least one of fat amine compound, alcamine compound and quaternary amine alkaloid compound.
10. according to the method for claim 3, wherein, the organic formwork agent in step a is
Tetraethyl ammonium hydroxide and/or TPAOH.
11. the method according to claim 11, wherein, in the colloid admixture in step a
Also include low-carbon alcohols, the low-carbon alcohols and SiO2Mol ratio be 1：(4-15).
12. according to the method for claim 11, wherein, the low-carbon alcohols are methanol and/or ethanol.
13. according to the method for claim 3, wherein, the temperature that is blended in described in step a is
Lower under conditions of 10-50 DEG C to carry out, the time for mixing progress is 0.5-10 hours.
14. the method according to claim 11, wherein, the condition of hydrothermal crystallizing described in step b
For：Temperature is 80-120 DEG C, and the time is 0.5-10 days.
15. the crystallization that according to the method for claim 3, this method also includes obtaining step b is produced
The step of thing is washed, filtered, being dried and is calcined.
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