CN106168584A - Method for measuring relative crystallinity of SAPO-11 molecular sieve - Google Patents
Method for measuring relative crystallinity of SAPO-11 molecular sieve Download PDFInfo
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- CN106168584A CN106168584A CN201510257328.6A CN201510257328A CN106168584A CN 106168584 A CN106168584 A CN 106168584A CN 201510257328 A CN201510257328 A CN 201510257328A CN 106168584 A CN106168584 A CN 106168584A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 238000010812 external standard method Methods 0.000 claims abstract description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 4
- 238000004458 analytical method Methods 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 230000004913 activation Effects 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000001144 powder X-ray diffraction data Methods 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 235000013312 flour Nutrition 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 230000004069 differentiation Effects 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011863 silicon-based powder Substances 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003908 quality control method Methods 0.000 description 5
- 239000012925 reference material Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002447 crystallographic data Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 230000010076 replication Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- Analysing Materials By The Use Of Radiation (AREA)
Abstract
A method for determining the relative crystallinity of SAPO-11 molecular sieve comprises the following steps: a. pretreatment of a sample: grinding, sieving, roasting, activating and temperature-controlled constant-humidity water absorption to obtain a standard sample to be detected and an industrial sample to be detected; b. determination of working conditions of powder X-ray diffractometer: after starting the powder X-ray diffractometer, selecting NIST silicon powder, checking that the angle reproducibility of the goniometer is +/-0.0001 degrees and the stability of the whole machine is less than or equal to 0.1 percent, and determining the parameters of the voltage, the current, the divergence slit, the divergence height limiting slit, the anti-divergence slit, the receiving slit, the optical filter or the monochromator of the diffractometer according to the signal-to-noise ratio S/N of the weakest diffraction peak diffraction signal in the X-ray diffraction spectrogram of the industrial sample to be detected, so as to obtain the optimal powder X-ray diffraction spectrogram of the sample; c. measuring; d. and (4) calculating, namely calculating the relative crystallinity of the industrial sample to be measured by using an external standard method.
Description
Technical field
Patent of the present invention relates to a kind of powder X-ray diffraction method measuring molecular sieve crystallinity, specifically
It it is a kind of powder X-ray diffraction method measuring industrial products SAPO-11 molecular sieve relative crystallinity.
Background technology
Molecular sieve, as catalyst or catalyst carrier, is widely used in the catalytic process of petrochemical industry.Relatively
Degree of crystallinity, cell parameter, silica alumina ratio, purity etc. are to characterize the indispensable basic parameter of molecular sieve performance.
Therefore, the relative crystallinity of Accurate Determining molecular sieve for design preparation of molecular sieve and evaluates associated catalytic
The performance of agent is highly important.Powder X-ray diffractometry sample preparation is simple, minute is short, repeated
Well, reliability is high, expense is low, is widely used in molecular sieve crystallinity, cell parameter, silica alumina ratio, purity
Deng mensuration in.But use powder X-ray diffractometry to measure industrial products SAPO-11 molecular sieve phase in detail
To patent, standard or the research report of degree of crystallinity, there is not been reported.
Relate to SAPO-11 molecular sieve more be synthesis or the report of relevant catalyticing research, but lead to wherein
Often the most simply sketch this mensuration, do not describe concrete assay method or step, such as, Wang Xiaoxiao, Guo
Few green grass or young crops, Zhang Wei, waits the impact [J] on its degree of crystallinity Yu catalytic performance of the .SAPO-11 Zeolite synthesis condition. point
Muonic catalysis, 2013,27 (4): 295～305.In this paper, king etc. measures SAPO-11 and relatively ties
Crystalline substance degree uses: sample compares with the characteristic peak diffracted intensity of reference HZSM-5, this employing
Different formula, there is the biggest shortcoming as reference in different molecular sieves, because degree of crystallinity and relatively
Degree of crystallinity investigate crystallization situation when being and carry out Study on Crystallization in Zeolite synthesis research and development one is extremely important
Parameter.Same recipe, the molecular sieve of same molecular sieve, especially industrial mass manufacture, carry out the right of degree of crystallinity
Bizet is meaningful, and this is often referred to two aspect contents: in technique and on analysis science.Solve this problem difficult
Degree is the biggest: first, will do the synthesis of substantial amounts of technique and analysis and characterization is tested, and its quantity can reach respectively
Up to a hundred or hundreds of time, then could solve preferably to go out the SAPO-11 molecular sieve problem of a high-crystallinity,
In the process, need to solve the quantitative analysis problems such as its purity, stray crystal, element, pattern, this problem
Do not solve, it is impossible to solve the problem analysis of relative crystallinity, that is: during relative crystallinity measures, reference material
Synthesis, the first step that preferred, quantitatively characterizing is key, be all same molecular sieves and industry's enlarging production thereof
Product in degree of crystallinity the highest.Otherwise, data are nonsensical maybe cannot explain that data are the highest and (be more than
100%) or the lowest (less than 100%).It is known that the degree of crystallinity of perfect cystal material is 100
%, the relative crystallinity of any common crystallization material should not surpass 100%, and its numerical value is high or low to be shown: its work
Do not resolve reference material select permeability.
" powder polycrystal X ray diffractive technology principle and application ", publishing house of Zhengzhou University, Zhang Haijun etc.
Chief editor, when mentioning XRD test, the pre-treatment to sample is to grind, " powder polycrystal X ray diffractive technology
Principle and application " in sample grind after powder size be about 1-5 μm, there is serious drawback in this grinding,
It cannot be guaranteed that the problem producing electrostatic during solution particle screening.It is known that: less than 10 micron granularities
Granule how to obtain？The most also require the granule having certain particle size scope, necessarily need sieve.It is smaller than
The standard sieve of 10 microns, does not the most sell, even if spending a large amount of foreign exchange, and special order, outward
Business replies: it cannot be guaranteed that the problem producing electrostatic during solving particle screening.
To sum up, there is a lot of drawback in prior art, and system with molecular sieve for preparing for patent emphasize it is important that synthesis condition
Selection, be wherein not related to or relate to less XRD characterize problem.The all SAPO-11 related to divide
Sub-sieve series is for patent, when relating to crystallinity analysis problem, mostly just list instrument XRD or its
Contrast between XRD spectra and spectrogram thereof, crystallinity data etc., detailed analysis process or method do not have.
Patent of the present invention can contribute to the product Analysis of quality control of specification industrial products SAPO-11 molecular sieve
The commercial introduction of SAPO-11 molecular sieve and subsequent catalyst is applied and is carried out outer committee and analyzes work.Due to domestic
There is no outward disclosed industrial products SAPO-11 molecular sieve relative crystallinity and analyze the standard of test method, because of
This, patent of the present invention is combined point with many laboratorys of industrial products SAPO-11 molecular sieve relative crystallinity
Analysis result of study is foundation, determines the method precision of patent of invention.
Summary of the invention
It is an object of the invention to, first solve the select permeability of reference substance, reference substance selects SAPO-11 to divide
How son sieve reference material, select and carry out Exact Analysis sign, is that we analyze, at hundreds of times, the basis tested
On propose first, at present, do not have any document to report.
It is another object of the present invention to, through lot of experiments, be screening equally, our this patent has only to do
Being ground to 35-45 μm to by SAPO-11 molecular sieve, do so obtains benefit and is: save time, laborsaving,
Because granule is the most tiny, it is also less prone to produce electrostatic, and, also it is most critical: its analysis precision can meet
Commercial production requirement efficient, quick.
The present invention provides the powder X-ray of a kind of Accurate Determining industrial products SAPO-11 molecular sieve relative crystallinity
Diffraction, provides reliable skill for the synthesis of molecular sieve or the preparation of associated catalysts and commercial Application
Art is supported.A kind of method measuring SAPO-11 molecular sieve relative crystallinity, comprises the steps:
A, the pre-treatment of sample
By SAPO-11 zeolites sample and production piece to be measured through grinding, sieving, calcination activation
Standard specimen to be measured and Industrial sample to be measured is prepared with four steps of temperature control constant humidity water suction；
B, the determination of powder x-ray diffraction working condition
After starting powder x-ray diffraction, selecting NIST silica flour, the angle repeatability verifying clinometer is
± 0.0001 °, complete machine degree of stability is≤0.1%, according in Industrial sample X-ray diffraction spectrogram to be measured
The signal to noise ratio S/N ＞ 10 of weak diffraction maximum diffracted signal, determine diffractometer voltage, electric current, divergent slit,
Dissipate limitation in height slit, antiscatter slits, reception slit, optical filter or the parameter of monochromator, it is thus achieved that examination
The optimal powder X-ray diffraction spectrogram of sample；
C, mensuration
Under identical powder x-ray diffraction working condition, standard to be measured for SAPO-11 molecular sieve is tried
Sample and Industrial sample to be measured are loaded in corresponding powder x-ray diffraction glass or aluminum quality sample frame respectively,
Carry out Specimen Determination and collect its powder X-ray diffraction data；
D, calculating
Use the Chemical Measurement swarming method of powder X-ray diffraction data processing system software, measure examination
The integrating peak areas intensitometer numerical value of sample (002) crystallographic plane diffraction peak, calculates production piece to be measured by external standard method
Relative crystallinity.On the basis of lot of experiments, it is thus achieved that SAPO-11 molecular sieve (002) crystal face diffraction
The integrating peak areas intensitometer numerical value at peak is directly related with the catalytic performance of this molecular sieve and associated catalysts thereof,
Propose first to select this peak to carry out relative crystallinity mensuration.
Open powder x-ray diffraction and carry out SAPO-11 zeolites sample and Industrial sample to be measured
Measure, under the same test conditions, collect SAPO-11 molecule in the range of 2 θ angle 7 °～30 ° respectively
Sieve standard specimen and the copper K of Industrial sample to be measuredαX ray diffracting data, uses powder X-ray diffraction number
According to the Chemical Measurement swarming method (selecting Pearson-VII method) of processing system software, measure each respectively
The integrating peak areas intensitometer numerical value of individual sample (002) crystallographic plane diffraction peak, calculates the phase of sample by external standard method
To degree of crystallinity.
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, wherein, in step a
The relative crystallinity of described SAPO-11 molecular sieve production piece to be measured ranges preferably from 68%～98%；
The degree of crystallinity of SAPO-11 zeolites sample is preferably 99%, and its stray crystal content is preferably smaller than 0.5%,
Purity is preferably superior to 99%, and when synthesizing with production piece to be measured, has identical proportioning raw materials and synthesis
Method.
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, these, it is preferred to,
In step a before described SAPO-11 sieve sample calcination activation is processed, to described SAPO-11
Sieve sample carries out removed template method process.
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, these, it is preferred to,
SAPO-11 sieve sample described in step a carries out the step of removed template method process:
First carry out the heat analysis of described SAPO-11 sieve sample, by its thermogravimetric curve or one
Subdifferential curve, it is thus achieved that the minimum temperature of removed template method completely, and take off under this minimum temperature
Template agent removing.
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, wherein, in step a
Described grinding, sieve after, the Task-size Controlling of powder ranges preferably from 10 μm～50 μm, more preferably 35
μm～45 μm.
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, wherein, in step a
Described calcination activation condition is preferably: Muffle furnace roasting 2～6h, calcination activation temperature is preferably 250～450
℃。
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, wherein, in step c,
In climatic chamber, specimen holder and standard specimen to be measured and Industrial sample to be measured are carried out identical temperature control permanent
Wet process, described temperature-control range is preferably 35～65 DEG C, more preferably 45～55 DEG C, and temperature control constant humidity is inhaled
The water time is preferably 3～7h.
The method of mensuration SAPO-11 molecular sieve relative crystallinity of the present invention, wherein, in step d,
Use the Chemical Measurement swarming method of powder X-ray diffraction data processing system software, measure sample
(002) the integrating peak areas intensitometer numerical value of crystallographic plane diffraction peak.
The present invention also can details are as follows:
First by SAPO-11 zeolites sample and production piece to be measured through grinding, sieving, roasting
Activation, temperature control constant humidity water suction process and obtain sample to be tested, at identical powder x-ray diffraction work bar
Under part, SAPO-11 zeolites sample and Industrial sample to be measured are respectively pressed into corresponding X-ray and spread out
Penetrate in instrument specimen holder, carry out Specimen Determination and collect powder X-ray diffraction data respectively.Use powder X-ray
The Chemical Measurement swarming method of ray diffraction data processing system software, measures each sample (002) brilliant
The peak area of face diffraction maximum, calculates the relative crystallinity of sample by external standard method.It is characterized in that sample is ground
Sieve particle size range controls to be less than 10 μm in 35 μm～45 μm, i.e. particle size deviation；At sample calcination activation
Using Muffle furnace during reason, temperature controls at 250～450 DEG C, and roasting time 2～6h obtains clean surface
Sample to be tested, then carry out saturated water suction process, standard specimen to be measured and Industrial sample be respectively pressed into phase
In the specimen holder answered, carry out Specimen Determination and collect its powder X-ray diffraction data；The sample of filling sample
Product frame is also carried out identical constant humidity and processes；After opening powder x-ray diffraction, verify powder X-ray with silica flour
The angle repeatability (± 0.0001 °) of x ray diffractometer x clinometer and complete machine degree of stability (≤0.1%) meet
Measure requirement.
Using said method, industry SAPO-11 sample relative crystallinity measurement range is 68%～98%；
The degree of crystallinity of SAPO-11 molecular sieve pure phase standard sample is 99%, as outer standard specimen.SAPO-11 molecule
Sieve standard sample to use high-power (such as, 18kW) powder x-ray diffraction to carry out purity check,
To ensure that stray crystal contained by it is better than 99% less than 0.5% i.e. purity, amorphous does not detects.
Using said method, owing to sample is after grinding, sieving, particle size range controls in 35 μm～45
μm, i.e. Control granularity deviation are less than 10 μm, improve the accuracy and more that powder diffraction data measures
Save time, laborsaving, sample is ground to 1 μm～10 μm or narrower particle size range can also, but the most time-consuming,
Laborious and difficulty of sieving is very big, because sample powder easily produces electrostatic, therefore the operation that makes to sieve becomes difficulty；Separately
Outward, sieve needs special customized to foreign trader, and buying sieve needs many foreign exchanges, and foreign trader claims simultaneously and can not protect
Demonstrate,prove such fine powder to sieve the problem easily producing electrostatic.
Use said method, carry out using Muffle furnace roasting 2～6h, sintering temperature during sample activating pretreatment
250～450 DEG C, effectively the SAPO-11 molecular sieve adsorption of removed template method can be included that water etc. is each
Plant inorganic and Organic substance removing, obtain the sample of clean outer surface.If sample contains template, then need elder generation
Carry out SAPO-11 molecular sieve heat analysis, by its TG curve and DTG (differential) curve, found
The minimum temperature of full removed template method, then carry out thorough removed template method at such a temperature and prevent molecular sieve to tie
Structure is destroyed.Before SAPO-11 molecular sieve calcination activation, need first to guarantee removed template method.
Using said method, the specimen holder used by test is also required to carry out at identical temperature control constant humidity with sample
Reason.
Use said method, with silica flour verify powder x-ray diffraction clinometer angle repeatability (±
0.0001 °) and complete machine degree of stability (complete machine Stabilily parameter method: METHOD FOR CONTINUOUS DETERMINATION Si powdered sample (111)
Crystallographic plane diffraction peak integrating peak areas intensitometer numerical value n reaches more than 10 times, then carries out the relative standard of data
Variance analysis, it is desirable to≤0.1%) meet mensuration requirement, to ensure that the precision of inventive method meets its Quality Control
The requirement analyzed.
Beneficial effects of the present invention:
When the most clearly proposing the analysis of crystalline material relative crystallinity, the selection principle of crystallization reference material and selection
Method；
Having only to accomplish SAPO-11 molecular sieve is ground to 35-45 micron, do so obtains benefit and is:
Save time, laborsaving, because granule is the most tiny, be also less prone to produce electrostatic, and, be also most critical: its point
Analysis precision can meet commercial production requirement efficient, quick；
Meanwhile, about calcination activation: the most clearly propose first to carry out the heat analysis of molecular sieve, minimum to determine
Activation temperature, and under this minimum temperature, carry out the roasting of molecular sieve to activate it, ensureing not saboteur
On the premise of sieve structure, it is thus achieved that the molecular sieve of clean surface, in order to carry out subsequent analysis；
Temperature control constant humidity absorbs water: proposes temperature control first and properly increases water suction temperature, can ensure saturated water suction
Under the conditions of, make water absorption course shorten, this is conducive to accelerating to analyze speed；
About instrumental calibration to determine that the scheme of accuracy of instrument is to propose first in this patent；
Problem about obtaining optimal spectrogram: through lot of experiments, as long as this patent obtains guarantee
In SAPO-11 molecular sieve, the signal to noise ratio of the most weak spectral peak is more than 10, can meet XRD relative crystallinity analysis
The new ideas required；
On the basis of lot of experiments, it is thus achieved that the peak area of SAPO-11 molecular sieve (002) crystallographic plane diffraction peak
Integrated intensity count value is directly related with the catalytic performance of this molecular sieve and associated catalysts thereof, proposes choosing first
Select this peak and carry out relative crystallinity mensuration.
The X-ray powder providing a kind of Accurate Determining industrial products SAPO-11 molecular sieve relative crystallinity spreads out
Shooting method, provides reliable technology to prop up for the synthesis of molecular sieve or the preparation of associated catalysts and commercial Application
Hold.
Accompanying drawing explanation
Fig. 1: a kind of industry SAPO-11 typical x-ray diffractogram of powder of molecular sieve sample；
Fig. 2: a kind of industry SAPO-11 molecular sieve sample typical Chemical Measurement swarming fitted figure.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
The signal to noise ratio of the most weak diffraction maximum diffracted signal in Industrial sample X-ray diffraction spectrogram to be measured:
In the present invention, to the most weak diffraction maximum diffracted signal in Industrial sample X-ray diffraction spectrogram to be measured
Signal to noise ratio is not particularly limited, the most weak diffraction maximum diffraction in usual Industrial sample X-ray diffraction spectrogram to be measured
The signal to noise ratio S/N ＞ 10 of signal, determines diffractometer voltage, electric current, divergent slit, dissipates limitation in height
Slit, antiscatter slits, reception slit, optical filter or the parameter of monochromator, it is thus achieved that the optimal powder of sample
X-ray diffraction spectrogram；
If S/N≤10, due to the most weak diffraction maximum diffraction letter in Industrial sample X-ray diffraction spectrogram to be measured
Number signal to noise ratio too small, cause relative crystallinity analytical data can not meet its commercial production Analysis of quality control logarithm
According to the requirement of accuracy, there is no other beneficial effects.
The relative crystallinity scope of the production piece to be measured of SAPO-11 molecular sieve described in step a:
In the present invention, the relative crystallization of production piece to be measured to SAPO-11 molecular sieve described in step a
Degree scope is not particularly limited, the phase of SAPO-11 molecular sieve production piece to be measured described in usual step a
It is 68%～98% to crystallinity range；
If the relative crystallinity of SAPO-11 molecular sieve production piece to be measured is less than 68%, due to
The relative crystallinity of SAPO-11 molecular sieve production piece to be measured is too small, causes this batch molecular sieve quality degradation
And it cannot be guaranteed that it can be used for the preparation of subsequent catalyst；And SAPO-11 molecular sieve production piece to be measured
Relative crystallinity more than 98%, due to the relative crystallinity mistake of SAPO-11 molecular sieve production piece to be measured
Greatly, causing this batch molecular sieve for time prepared by subsequent catalyst, the catalytic performance of catalyst is the most bad, and
Without other beneficial effects.
SAPO-11 zeolites sample:
In the present invention, SAPO-11 zeolites sample is not particularly limited, usual SAPO-11
The degree of crystallinity of zeolites sample is 99%, and its stray crystal content is less than 0.5%, and purity is better than 99%,
And when synthesizing by identical method with production piece to be measured, there is identical proportioning raw materials；
If stray crystal content >=0.5%, due to stray crystal too high levels, it is possible to also without a kind of stray crystal, sometimes
Containing two kinds of stray crystals, and considering in the case of stray crystal content analysis error, causing it cannot be guaranteed that selected standard
Thing degree of crystallinity is better than 99%, there is no other beneficial effects；
If purity≤99%, owing to purity is too low, cause it cannot be guaranteed that selected reference material degree of crystallinity is better than 99
%, there is no other beneficial effects.
The Task-size Controlling scope of powder:
In the present invention, the Task-size Controlling scope of powder is not particularly limited, the Task-size Controlling of usual powder
Scope is 10 μm～50 μm, preferably 35 μm～45 μm；
If the Task-size Controlling scope of powder is less than 10 μm, cause ground sample time-consuming, laborious；Sieve aperture is more
Little, sieve is the most expensive, as selected the sieve of too small sieve aperture will to increase the cost buying sifter device；Further, sieve aperture
The least, granule is the most tiny, the most easily plays electrostatic when sieving, and the generation of electrostatic can not be normal by impact screening operation
Carry out, and the Task-size Controlling scope of powder is more than 50 μm, causes diffraction data Quality Down, it is impossible to ensure
The data precision needed for commercial production Analysis of quality control, there is no other beneficial effects.
Calcination activation condition described in step a:
In the present invention, calcination activation condition described in step a is not particularly limited, in usual step a
Described calcination activation condition is: Muffle furnace roasting 2～6h, and calcination activation temperature is 250～450 DEG C；
If Muffle furnace roasting is less than 2h, owing to roasting time is too short, cause activation not exclusively, it is impossible to protect
Card obtains the molecular sieve of clean surface；And Muffle furnace roasting is more than 6h, owing to roasting time is long, cause
Time is wasted, and the waste energy, there is no other beneficial effects；
If calcination activation temperature is less than 250 DEG C, owing to sintering temperature is too small, cause the wave of roasting time
Take, and activation is not exclusively, it is impossible to ensure to obtain the molecular sieve of clean surface；And calcination activation temperature exceedes
450 DEG C, owing to sintering temperature is excessive, cause the waste energy, and be likely to result in framework of molecular sieve excess shrinkage,
Partially or completely the structure of saboteur's sieve, there is no other beneficial effects.
Temperature control constant humidity processes:
In the present invention, the process of temperature control constant humidity is not particularly limited, in usual step c, in constant temperature and humidity
Case carries out identical temperature control constant humidity to specimen holder and standard specimen to be measured and Industrial sample to be measured process, described
Temperature-control range is 35～65 DEG C, and the temperature range of optimization is 45～55 DEG C；Temperature control constant humidity absorbent time is
3～7h；
If temperature control is less than 35 DEG C, owing to temperature is too low, cause absorbent time long, close to diel,
Commercial production Analysis of quality control requirement efficient, quick, and too low temperature can not be met, as close to room temperature,
Climatic chamber control the most bad to humiture；And temperature control is more than 65 DEG C, owing to temperature is too high, cause case
Interior water vapour content is the highest, is not easy to form uniform moisture film final impact analysis number at molecular sieve outer surface
According to preci-sion and accuracy, there is no other beneficial effects；
If temperature control constant humidity absorbent time is less than 3h, owing to the time is too short, cause at molecular sieve outer surface
One layer of uniform moisture film, the preci-sion and accuracy of impact analysis data, and temperature control constant humidity can not be formed completely
Absorbent time is more than 7h, due to overlong time, causes the time to waste, there is no other beneficial effects.
1, sample pre-treatments
Take each about 1g of SAPO-11 zeolites sample and production piece to be measured respectively, finely ground, sieve,
Collect 35 μm～the sample powder of 45 μm, then take 0.2g screening respectively, be placed in the non-reactive crucible such as pottery,
Put into activation 4h in 350 DEG C of Muffle furnaces, when muffle furnace is down to about 125 DEG C, will with crucible pliers
Crucible is transferred to fill in the climatic chamber of magnesium chloride saturated solution, and the temperature inside the box is not less than 45 DEG C of conditions
Under, temperature control constant humidity accelerates water suction 5h.The specimen holder of filling sample is also carried out identical temperature control constant humidity and processes.
2, instrument working condition
The analysis of industry SAPO-11 molecular sieve sample is shown by powder x-ray diffraction: spreading out of diffraction maximum
Penetrate intensity to increase along with divergent slit, the increase of reception slit；Scanning step increases, the point-point of curve
Distribution becomes dredges；Scanning speed is the slowest, and curve is the most smooth；Along with voltage, the increase of electric current, product diffraction maximum
Diffracted intensity the most linearly increasing.According to above-mentioned experiment, consider intensity, the peak back of the body ratio, resolution, song
The factors such as linear light slippery, peak shape symmetry, preferably go out to be suitable for industry SAPO-11 molecular sieve sample analysis
Powder x-ray diffraction working condition is shown in Table 1.Analysis of spectra is quantified as: Industrial sample X-ray diffraction
The signal to noise ratio S/N ＞ 10 of the most weak diffraction maximum diffracted signal in spectrogram.
Table 1 instrument working condition
Start powder x-ray diffraction, after instrument stabilizer, verify the angle of instrument clinometer with silica flour
Repeatability (± 0.0001 °) and complete machine degree of stability (≤0.1%) meet the requirement that subsequent sample measures.Right
Powder x-ray diffraction is set, and maybe can obtain with the typical instrument working condition reached listed by table 1
Other suitable condition of equal signal to noise ratio (S/N) is (as the industrial SAPO-11 that powder x-ray diffraction measures
When in molecular sieve diffraction spectrogram, the S/N of smallest peaks is not less than 10:1, X-ray diffractometer working condition
Meet to analyze and require).Utilize optimal SAPO-11 molecular sieve powder X-ray diffraction curve (see Fig. 1),
Chemo metric software procedure of peak decomposing is used to obtain the relative crystallization of industry SAPO-11 molecular sieve with external standard method
Degree (see Fig. 2).
3, Specimen Determination
SAPO-11 zeolites sample to be measured and the Industrial sample of saturated water suction are respectively pressed into accordingly
In specimen holder, powder x-ray diffraction is debug specimen holder.At the powder x-ray diffraction recommended
Under working condition, respectively SAPO-11 zeolites sample to be measured and Industrial sample are measured and receive
Collection powder X-ray diffraction data.Use the stoichiometry of powder X-ray diffraction data processing system software
Learn procedure of peak decomposing, respectively bioassay standard sample and the integrating peak areas of sample to be tested (002) crystallographic plane diffraction peak
Intensitometer numerical value.Standard specimen replication twice, takes the integrating peak areas of its (002) crystallographic plane diffraction peak
The meansigma methods of intensitometer numerical value is for quantitative Analysis.The Exemplary chemical meterological of industry SAPO-11 molecular sieve
Swarming fitted figure is shown in Fig. 2.
4, data process
The relative crystallinity RCi of industry SAPO-11 molecular sieve is calculated by formula (1), and numerical value represents with %:
In formula (1):
The integrating peak areas intensitometer of Ai industry SAPO-11 molecular sieve sample (002) crystallographic plane diffraction peak
Numerical value；
The integrating peak areas intensitometer of As SAPO-11 zeolites sample (002) crystallographic plane diffraction peak
Numerical value；
The degree of crystallinity of Cs SAPO-11 zeolites sample, 99% (mass fraction).
According to above-mentioned testing program, respectively the relative of 4 selected horizontal samples is tied at 12 laboratorys
Crystalline substance degree is measured, and gained test data is shown in Table 2, table 3, table 4, table 5.Between 12 laboratorys
The precision that draws of result of the test statistical analysis be shown in Table 6.Require each sample replication twice, survey
Determine result and take one decimal place.
The original analysis data (%) of table 2 industry SAPO-11 molecular sieve sample relative crystallinity
The original analysis data (%) of table 3 industry SAPO-11 molecular sieve sample relative crystallinity
The original analysis data (%) of table 4 industry SAPO-11 molecular sieve sample relative crystallinity
The original analysis data (%) of table 5 industry SAPO-11 molecular sieve sample relative crystallinity
Table 6 method precision (%)
| Relative crystallinity scope | Repeatability | Repeatability |
| 68～98 | 3 | 4 |
Claims (9)
1. the method measuring SAPO-11 molecular sieve relative crystallinity, comprises the steps:
A, the pre-treatment of sample
By SAPO-11 zeolites sample and production piece to be measured through grinding, sieving, calcination activation and temperature control constant humidity four steps that absorb water prepare standard specimen to be measured and Industrial sample to be measured；
B, the determination of powder x-ray diffraction working condition
After starting powder x-ray diffraction, select NIST silica flour, the angle repeatability verifying clinometer is ± 0.0001 °, complete machine degree of stability is≤0.1%, according to the signal to noise ratio S/N ＞ 10 of the most weak diffraction maximum diffracted signal in Industrial sample X-ray diffraction spectrogram to be measured, determine diffractometer voltage, electric current, divergent slit, dissipate limitation in height slit, antiscatter slits, reception slit, optical filter or the parameter of monochromator, it is thus achieved that the optimal powder X-ray diffraction spectrogram of sample；
C, mensuration
Under identical powder x-ray diffraction working condition, standard specimen to be measured for SAPO-11 molecular sieve and Industrial sample to be measured are loaded into respectively in corresponding powder x-ray diffraction glass or aluminum quality sample frame, carry out Specimen Determination and collect its powder X-ray diffraction data；
D, calculating
Use the Chemical Measurement swarming method of powder X-ray diffraction data processing system software, measure the integrating peak areas intensitometer numerical value of sample (002) crystallographic plane diffraction peak, calculate the relative crystallinity of production piece to be measured by external standard method.
The method of mensuration SAPO-11 molecular sieve relative crystallinity the most according to claim 1, it is characterised in that the relative crystallinity scope of the production piece to be measured of SAPO-11 molecular sieve described in step a is 68%～98%；The degree of crystallinity of SAPO-11 zeolites sample is 99%, and its stray crystal content is less than 0.5%, and purity is better than 99%, and when synthesizing with production piece to be measured, has identical proportioning raw materials.
The method of mensuration SAPO-11 molecular sieve relative crystallinity the most according to claim 1, it is characterised in that in step a before described SAPO-11 sieve sample calcination activation is processed, described SAPO-11 sieve sample is carried out removed template method process.
The method of mensuration SAPO-11 molecular sieve relative crystallinity the most according to claim 3, it is characterised in that SAPO-11 sieve sample described in step a carries out the step of removed template method process and is:
First carry out the heat analysis of described SAPO-11 sieve sample, by its thermogravimetric curve or its once differentiation curve, it is thus achieved that the minimum temperature of removed template method completely, and under this minimum temperature, carry out removed template method.
5. according to the method for the mensuration SAPO-11 molecular sieve relative crystallinity described in any one of Claims 1 to 4, it is characterised in that after grinding described in step a, sieving, the Task-size Controlling scope of powder is 10 μm～50 μm.
The method of mensuration SAPO-11 molecular sieve relative crystallinity the most according to claim 5, it is characterised in that after grinding described in step a, sieving, the Task-size Controlling scope of powder is 35 μm～45 μm.
7., according to the method for the mensuration SAPO-11 molecular sieve relative crystallinity described in any one of Claims 1 to 4, it is characterised in that calcination activation condition described in step a is: Muffle furnace roasting 2～6h, calcination activation temperature is 250～450 DEG C.
8. according to the method for the mensuration SAPO-11 molecular sieve relative crystallinity described in any one of Claims 1 to 4, it is characterized in that, in step c, in climatic chamber, specimen holder and standard specimen to be measured and Industrial sample to be measured are carried out identical temperature control constant humidity to process, described temperature-control range is 35～65 DEG C, and temperature control constant humidity absorbent time is 3～7h.
The method of mensuration SAPO-11 molecular sieve relative crystallinity the most according to claim 8, it is characterized in that, in step c, in climatic chamber, specimen holder and standard specimen to be measured and Industrial sample to be measured being carried out identical temperature control constant humidity and process, described temperature-control range is 45～55 DEG C.
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| CN108275693A (en) * | 2016-12-30 | 2018-07-13 | 中国石油天然气股份有限公司 | Method for preparing SAPO-11 molecular sieve amorphous substance |
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| EP0103117A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
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| EP0103117A1 (en) * | 1982-07-26 | 1984-03-21 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
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| CN108275693A (en) * | 2016-12-30 | 2018-07-13 | 中国石油天然气股份有限公司 | Method for preparing SAPO-11 molecular sieve amorphous substance |
| CN108275693B (en) * | 2016-12-30 | 2020-04-10 | 中国石油天然气股份有限公司 | Method for preparing SAPO-11 molecular sieve amorphous substance |
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