CN106168583B - Method for determining relative crystallinity of ZSM-23 molecular sieve - Google Patents
Method for determining relative crystallinity of ZSM-23 molecular sieve Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 66
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 38
- 239000002808 molecular sieve Substances 0.000 title abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000012545 processing Methods 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000001144 powder X-ray diffraction data Methods 0.000 claims abstract description 11
- 238000010812 external standard method Methods 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims description 35
- 238000005259 measurement Methods 0.000 claims description 34
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 30
- 230000004913 activation Effects 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000011863 silicon-based powder Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002447 crystallographic data Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 230000004069 differentiation Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000007873 sieving Methods 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 90
- 235000019580 granularity Nutrition 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 230000009286 beneficial effect Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000013558 reference substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000009776 industrial production Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000003908 quality control method Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000010457 zeolite 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002178 crystalline material 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
- 230000035699 permeability Effects 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- 230000000116 mitigating effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 238000010200 validation analysis 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 a ZSM-23 molecular sieve, comprising the steps of: a. pretreatment of a sample: preparing a standard sample to be detected and an industrial sample to be detected by grinding, sieving, roasting, activating and temperature-controlling, constant-humidity and water-absorbing a ZSM-23 molecular sieve standard sample and the industrial sample to be detected; b. determining the working condition of the powder X-ray diffractometer; c. and (3) determination: measuring and collecting powder X-ray diffraction data; d. and (3) calculating: and (3) measuring peak area integral intensity counting values of 8 crystal face diffraction peaks of the samples (111), (121), (042), (003), (112), (060), (122) and (052) by adopting a chemometrics peak separation method of powder X-ray diffraction data processing system software, summing the peak area integral intensity counting values, and calculating the relative crystallinity of the industrial sample to be measured by using an external standard method.
Description
Technical field
The invention patent relates to a kind of powder x-ray diffraction methods for measuring molecular sieve crystallinity, are especially a kind of survey
Determine the powder x-ray diffraction method of industrial products ZSM-23 molecular screen relative crystallinity.
Background technique
Zeolite molecular sieve is widely used in the catalytic process of petrochemical industry as catalyst or catalyst carrier.Opposite knot
Brilliant degree, cell parameter, silica alumina ratio, purity etc. are the characterization indispensable basic parameters of molecular sieve performance.Therefore, Accurate Determining point
Crystallinity of son sieve etc. is highly important for the performance of design preparation of molecular sieve and evaluation associated catalysts.Powder X-ray
Ray diffraction method sample preparation is simple, minute is short, reproducible, high reliablity, expense are low, is widely used in crystallization of molecular sieves
In the measurement of degree, cell parameter, silica alumina ratio and purity etc..
Crystallinity is the important quality Con trolling index of compound probability ZSM-23 molecular screen, actual industry ZSM-23 molecular screen
Be synthesized by and measure its crystallinity to determine crystallization condition, and it be also related to industrial products quality good or not and whether
It can be used for the preparation of subsequent catalyst.But it is opposite to measure industrial products ZSM-23 molecular screen in detail using powder X-ray diffractometry
There is not been reported for patent, standard or the research report of crystallinity.It is related to that ZSM-23 molecular screen is more to be synthesis or relevant urge
Change research report, but generally also only sketch the measurement wherein, does not describe specific determination step (for example, Wang Bin, high
By force, Gao Jiandong waits synthesis and characterization [J] Journal of Molecular Catalysis of high-silica zeolite ZSM-23,2004,18 (4): 253~256.).
" Chinese excellent MA theses full-text database engineering science and technology I is collected ", the 07th phase in 2013, Xing Weijing, " ZSM-
The preparation of 5 molecular sieves and its granularity, crystallinity research ", disclose a kind of XRD measurement ZSM-5 crystallization on July 25th, 2013
The method of degree, it is not that it is disclosed that calculating its relative crystallinity by XRD, ZSM-5 structure is different from ZSM-23 molecular screen
Same substance, ZSM is the Si-Al molecular sieve trade mark of Mobil Corporation.Its analysis method of the different material of different structure is naturally different；
In the series of studies data, zeolites object is not solved the problems, such as, use commercial goods ZSM-5 molecular sieve sample for reference
Sample, therefore do not researched and developed in reference substance selection, to make its relative crystallinity data (percentage) from tens of to more than 100
Differ；Additionally, it is well known that whatsoever crystalline material, the sample of perfection crystallization, crystallinity are likely to be 100%；This
Outside, ZSM-5 is small crystal grain molecular sieve, and the particle size range of product is usually located at 5-7 μm, and some grain sizes are not present down to 2 μm
It is ground up, sieved the problem of being analyzed after acquisition is sieved；Furthermore crystallization temperature is when preparing molecular sieve, in raw material reaction solution
The reaction solution parameter that middle molecular sieve is formed and controlled during growing into big crystal grain, or perhaps reaction temperature also or is said
Temperature of reactor, be in order to prepare the optimal molecular sieve of crystallinity, need to investigate different crystallization (or reaction) temperature and when
Between influence to crystallinity or sample spectral peak with respect to peak height, peak area.It crystallization temperature and time and is obtained by filtration from solution point
Storage is in case of industrial application after son sieves and then washed and be dehydrated, dried, before the XRD analysis for carrying out relative crystallinity,
It needs to roast it, be activated, to obtain the outer surface of complete cleaning, they are two entirely different concepts or mistake
Journey.
" powder polycrystal X ray diffractive technology principle and application ", publishing house, Zhengzhou University, the chief editor such as Zhang Haijun mention XRD
It is grinding to the pre-treatment of sample when test, powder after sample grinding in " powder polycrystal X ray diffractive technology principle and application "
Granularity is about 1-5 μm, and there are serious drawbacks for this grinding, it cannot be guaranteed that generating asking for electrostatic during solving particle screening
Topic.It is known that how the particle of: less than 10 micron granularities obtains? the particle for having certain particle size range is especially also required, centainly
It need sieve.It is smaller than 10 microns of standard sieve, is not all sold both at home and abroad, even if spending a large amount of foreign exchanges, special order, outside
Quotient replies: it cannot be guaranteed that generating electrostatic during solving the problems, such as particle screening.
To sum up, there are many drawbacks for the prior art, and system with molecular sieve for preparing is detailed synthesis condition for the emphasis that patent is emphasized
Selection, wherein not being involved in the problems, such as or being very related to less XRD characterization.All ZSM-23 molecular screens prepare patent, are being related to crystallinity
When problem analysis, comparison, the crystallinity data etc. between instrument XRD or its XRD spectra and its spectrogram are mostly just listed,
Detailed analytic process or method do not have.
In short, in view of the crystallinity of any sample is impossible to be more than perfect 100% crystallinity crystallized, so,
When carrying out relative crystallinity analysis, it is necessary first to solve homology raw material, the same synthesis technology, same point of a highest crystallinity
Son sieve select permeability, this only in molecular sieve industry amplification or high-volume industrial production, just there is great practice significance.It is excellent
It selects a reference substance and is characterized, need for a long time time, and make up to a hundred times (synthesis) or hundreds of times (analysis and characterization) tests, relate to
And XRD, electron microscope, BET, elemental analysis etc..Preferred standard object problem does not solve, and subsequent a series of problems will be unable to solve
Certainly.
The present invention can specification industrial products ZSM-23 molecular screen product Analysis of quality control, facilitate ZSM-23 molecular screen and
Outer committee's analysis work is applied and carried out to the commercial introduction of subsequent catalyst.Due to there is no disclosed industrial products ZSM-23 both at home and abroad
Molecular sieve relative crystallinity analyzes the standard of test method, and therefore, the invention patent is opposite with industrial products ZSM-23 molecular screen
The laboratory the Duo Jia Conjoint Analysis result of study of crystallinity is foundation, determines the method precision of patent of invention.
Summary of the invention
The object of the present invention is to solve the select permeability of reference substance first, reference substance selects ZSM-23 molecular screen reference substance,
Exact Analysis characterization how is selected and carried out, is that we are put forward for the first time on the basis of hundreds of analysis tests, currently, not having
Any document report.
It is another object of the present invention to equally be screening by a large number of experiments, our this patents only need to accomplish ZSM-
23 molecular sieves are ground to 35-45 μm, do so benefit is: it is time saving, laborsaving, because particle is less tiny, be also less prone to generate
Electrostatic, moreover, and most critical: its analysis precision is able to satisfy industrial production and efficiently, quickly requires.
The present invention provides a kind of powder x-ray diffraction side of Accurate Determining industrial products ZSM-23 molecular screen relative crystallinity
Method provides reliable technical support for the synthesis of molecular sieve or the preparation of associated catalysts and industrial application.
The present invention provides a kind of method for measuring ZSM-23 molecular screen relative crystallinity, includes the following steps:
A, the pre-treatment of sample
By ZSM-23 molecular screen standard sample and production piece to be measured by being ground up, sieved, calcination activation and temperature control constant humidity
Four steps that absorb water prepare standard sample to be measured and Industrial sample to be measured；
B, the determination of powder x-ray diffraction operating condition
After starting powder x-ray diffraction, selecting NIST silicon powder to verify the angle reproducibility of angular instrument is ± 0.0001 °,
Complete machine stability is≤0.1%, according to the signal-to-noise ratio of diffraction maximum diffracted signal most weak in Industrial sample X-ray diffraction spectrogram to be measured
S/N > 10 determines powder x-ray diffraction voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, connects
The parameter for receiving slit, optical filter or monochromator, obtains the best powder x-ray diffraction spectrogram of sample；
C, it measures
Under identical powder x-ray diffraction operating condition, by ZSM-23 molecular screen standard sample to be measured and work to be measured
Industry sample is loaded into respectively in corresponding powder x-ray diffraction glass or aluminum specimen holder, is carried out Specimen Determination and is collected it
Powder x-ray diffraction data；
D, it calculates
Using the Chemical Measurement swarming method of powder x-ray diffraction data processing system software, measure sample (111),
(121), (042), (003), (112), (060), (122), (052) 8 crystallographic plane diffraction peak integrating peak areas intensity count value
And sum, the relative crystallinity of Industrial sample to be measured is calculated with external standard method.
It opens powder x-ray diffraction and carries out ZSM-23 molecular screen standard sample and Industrial sample measurement, in identical examination
Under the conditions of testing, the copper K of ZSM-23 molecular screen standard sample and Industrial sample within the scope of 6 °~35 ° of 2 θ angle is collected respectivelyαX-ray
Diffraction data, using the Chemical Measurement swarming method of powder x-ray diffraction data processing system software, measure sample (111),
(121), (042), (003), (112), (060), (122), (052) 8 crystallographic plane diffraction peak integrating peak areas intensity count value
And sum, the relative crystallinity of sample is calculated with external standard method.There are many Chemical Measurement swarming methods, and this patent is through numerical value point
On the basis of analysing a large amount of sampling test data, VII method of Pearson- is selected.
The method of measurement ZSM-23 molecular screen relative crystallinity of the present invention, wherein ZSM-23 described in step a points
The relative crystallinity that son sieves production piece to be measured ranges preferably from 85%~97%；The crystallinity of ZSM-23 molecular screen standard sample
Preferably 99%, stray crystal content is preferably smaller than 0.5%, and purity is preferably superior to 99%, and when synthesizing with production piece to be measured, tool
There are identical raw material proportioning and synthetic method.
It is of the present invention measurement ZSM-23 molecular screen relative crystallinity method, wherein preferably, in step a
Before ZSM-23 molecular screen sample calcination activation processing, the ZSM-23 molecular screen sample is carried out at removed template method
Reason.
The method of measurement ZSM-23 molecular screen relative crystallinity of the present invention, wherein preferably, institute in step a
Stating the step of ZSM-23 molecular screen sample carries out removed template method processing is:
The heat analysis for first carrying out the ZSM-23 molecular screen sample, by its thermogravimetric curve or its once differentiation curve,
The minimum temperature of complete removed template method is obtained, and carries out removed template method under the minimum temperature.
The method of measurement ZSM-23 molecular screen relative crystallinity of the present invention, wherein grinding, mistake described in step a
After sieve, the granularity control range of powder is preferably 10 μm~50 μm, more preferably 35 μm~45 μm.
The method of measurement ZSM-23 molecular screen relative crystallinity of the present invention, wherein calcination activation described in step a
Condition are as follows: calcination activation temperature is preferably 250~450 DEG C, and the calcination activation time is preferably 2~6h.
The method of measurement ZSM-23 molecular screen relative crystallinity of the present invention, wherein in step c, in constant temperature and humidity
It carries out identical temperature control constant humidity to specimen holder and standard sample to be measured and Industrial sample to be measured in case to handle, the temperature-control range is
35~65 DEG C, preferably 45~55 DEG C, temperature control constant humidity absorbent time is preferably 3~7h.
The present invention can also details are as follows:
First by ZSM-23 molecular screen standard sample and production piece by being ground up, sieved, calcination activation, temperature control constant humidity with
Accelerate water suction processing, sample to be tested is obtained, under identical powder x-ray diffraction operating condition, by ZSM-23 molecular screen mark
Quasi- sample and Industrial sample are respectively pressed into corresponding X-ray diffractometer specimen holder, are carried out Specimen Determination and are collected powder X-ray respectively
Ray diffraction data, after starting powder x-ray diffraction, with the angle reproducibility of silicon powder validation instrument angular instrument (±
0.0001 °) and complete machine stability (≤0.1%) meet measurement require；Using powder x-ray diffraction data processing system software
Chemical Measurement swarming method (VII method of Pearson-), measurement (111), (121), (042), (003), (112), (060),
(122), it the integrating peak areas intensity count value of (052) 8 crystallographic plane diffraction peak and sums, the opposite knot of sample is calculated with external standard method
Brilliant degree.It is characterized in that sample is ground up, sieved particle size range control at 35 μm~45 μm, i.e., particle size deviation is less than 10 μm；It is maximum
Limit prepares the powder mull workload of sample when mitigating measurement, and sample powder is avoided easily to generate quiet because granularity is too small
Electricity needs to spend asking for a large amount of foreign exchanges to the special order sieve of foreign manufacturer when also solving very fine particle size powder sieving
Topic, while more there is no concern that foreign trader claims it cannot be guaranteed that solve the problems, such as that such fine powder is sieved easy to produce static electricity；Sample roasting
It burns and uses Muffle furnace when being activated, temperature controls at 250~450 DEG C, obtains the sample to be tested on pure surface, then controlled
Standard sample and Industrial sample are respectively pressed into corresponding specimen holder to accelerate to be saturated water suction processing, carry out sample by temperature, constant humidity
It measures and collects powder x-ray diffraction data.
Using the above method, industrial ZSM-23 sample relative crystallinity measurement range is 85%~97%, and work is completely covered
Basic, normal, high 3 Value levels of industry production ZSM-23 sample relative crystallinity.The knot of ZSM-23 molecular screen pure phase standard sample
Brilliant degree is 99%, is used as outer standard specimen.
Using the above method, ZSM-23 molecular screen pure phase standard sample will use high-power (for example, 18kW) X-ray powder
Diffractometer carries out purity check, and to guarantee that stray crystal is less than 0.5% contained by it, i.e., purity is better than 99%, and amorphous is not detected；And and work
When industry ZSM-23 molecular screen synthesizes, raw material proportioning and synthetic method having the same.
Using the above method, after screening due to sample, the granularity control range of powder is 35 μm~45 μm, that is, is controlled
Granularity partial size deviation improves the accuracy of powder diffraction data measurement less than 10 μm, and more time saving, laborsaving and can avoid
When sieving, because of powder particle is excessively tiny problem extremely easy to produce static electricity.
Using the above method, when carrying out sample activating pretreatment using Muffle furnace roast 2~6h, maturing temperature 250~
450 DEG C, the difference according to its synthetic method includes the difference of raw material proportioning, and when calcination activation needs to avoid temperature is excessively high to cause point
Son sieve crystal structure, which destroys, or temperature is too low causes molecular sieve that cannot sufficiently be activated i.e. the surface that cannot form complete cleaning,
Subsequent water absorption course is influenced, and then influences the relative crystallinity determination data of the molecular sieve.The above method will can effectively take off
The various inorganic and organic impurities such as including water of the ZSM-23 molecular screen absorption of template agent removing is desorbed completely, obtains pure surface
Sample, 110 DEG C of the pretreatment temperature and pre-processing device of this and Y molecular sieve using baking oven be it is completely different, be detailed in industry mark
Quasi- SH/T 0339-1992.
If sample contains template, needs first to carry out the heat analysis of ZSM-23 molecular screen, pass through its TG curve and DTG
(differential) curve finds the minimum temperature for capableing of complete removed template method, then carries out thoroughly removing template under the minimum temperature
Agent avoids molecular sieve structure from being destroyed and furnace temperature is too low and not can be completely removed template because the furnace temperature of removed template method is excessively high
Agent or removing time drag too long.Concrete operations can be placed it in respectively lazy by taking a series of industrial molecular to sieve sample
In the crucibles such as property ceramics, then it is respectively placed in Muffle furnace, after the different time is heated under the minimum temperature of removed template method,
It is drawn off heating furnace respectively and is cooled to room temperature in drier, is then to claim on a ten thousandth gram assay balance in sensibility reciprocal
Amount, finishes if template has removed, and the percentage weightless due to removed template method of sample at this time and later should be constant,
The shortest time of complete removed template method can be found out in this way, and with energy saving, especially in the industrial production, energy-saving benefit is more
It is significant.Before ZSM-23 molecular screen calcination activation, need first to ensure removed template method.
Using the above method, tests specimen holder used and be also required to carry out identical temperature control constant humidity processing with sample.
Using the above method, with NIST silicon powder verify powder x-ray diffraction angular instrument angle reproducibility (±
0.0001 °) and complete machine stability (complete machine stability test method: METHOD FOR CONTINUOUS DETERMINATION Si powder highest peak i.e. its (111) crystal face diffraction
Then peak integrating peak areas intensity count value n carries out the relative standard deviation analysis of data up to 10 times or more, it is desirable that≤0.1%)
Meet measurement to require, to guarantee that the precision of inventive method meets the requirement of its industrial products Analysis of quality control.
After starting powder x-ray diffraction, according to diffraction maximum diffracted signal most weak in Industrial sample X-ray diffraction spectrogram
Signal-to-noise ratio (S/N > 10), determine the other running parameters of diffractometer: voltage, divergent slit, diverging height limitation slit, is prevented electric current
Scatter slit receives slit, optical filter or monochromator, to obtain the best X-ray diffraction spectrogram of sample；
Beneficial effects of the present invention:
When clearly proposing the analysis of crystalline material relative crystallinity for the first time, the selection principle and selection method of reference substance are crystallized；
Only need accomplish for ZSM-23 molecular screen to be ground to 35-45 microns, do so benefit is: it is time saving, laborsaving,
Because particle is less tiny, be also less prone to generate electrostatic, moreover, and most critical: its analysis precision be able to satisfy industrial production efficiently,
Quickly require；
Meanwhile about calcination activation: proposing the heat analysis for first carrying out molecular sieve, clearly for the first time with the minimum activation temperature of determination
Degree, and under this minimum temperature carry out molecular sieve roasting to activate it, guarantee do not destroy molecular sieve structure under the premise of, obtain
The molecular sieve of clean surface is obtained, to carry out subsequent analysis；
Temperature control constant humidity water suction: be put forward for the first time temperature control and properly increase water suction temperature, can guarantee saturation water suction under conditions of,
Shorten water absorption course, this is conducive to accelerate analysis speed；
It with the scheme for determining accuracy of instrument is in this patent to be put forward for the first time about instrumental calibration；
The problem of about best spectrogram is obtained: passing through a large number of experiments, as long as this patent, which obtains, guarantees ZSM-23 molecular screen
In most weak spectral peak signal-to-noise ratio be greater than 10, can meet XRD relative crystallinity analysis require new concept；
A kind of powder x-ray diffraction method of Accurate Determining industrial products ZSM-23 molecular screen relative crystallinity is provided, is
The synthesis of molecular sieve or the preparation of associated catalysts and industrial application provide reliable technical support.
Detailed description of the invention
Fig. 1: the industrial typical x-ray diffractogram of powder of ZSM-23 molecular screen sample；
Fig. 2: the industrial typical Chemical Measurement swarming fitted figure of ZSM-23 molecular screen sample (selects VII side of Pearson-
Method).
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The signal-to-noise ratio of most weak diffraction maximum diffracted signal in Industrial sample X-ray diffraction spectrogram to be measured:
In the present invention, simultaneously to the signal-to-noise ratio of diffraction maximum diffracted signal most weak in Industrial sample X-ray diffraction spectrogram to be measured
It is not particularly limited, the signal-to-noise ratio S/N > 10 of most weak diffraction maximum diffracted signal in usual Industrial sample X-ray diffraction spectrogram to be measured,
It determines powder x-ray diffraction voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, receive slit, filter
The parameter of mating plate or monochromator obtains the best powder x-ray diffraction spectrogram of sample；
If S/N≤10, due to the signal-to-noise ratio of diffraction maximum diffracted signal most weak in Industrial sample X-ray diffraction spectrogram to be measured
It is too small, it causes relative crystallinity analysis data not to be able to satisfy its industrial production Analysis of quality control and data preci-sion and accuracy is wanted
It asks, has no other beneficial effects.
The relative crystallinity range of the production piece to be measured of ZSM-23 molecular screen described in step a:
In the present invention, the relative crystallinity range of the production piece to be measured of ZSM-23 molecular screen described in step a is had no
It is particularly limited to, the relative crystallinity range of ZSM-23 molecular screen production piece to be measured described in usual step a is 85%~97%；
If the relative crystallinity of the production piece to be measured of ZSM-23 molecular screen described in step a is less than 85%, due to ZSM-
The relative crystallinity of 23 molecular sieves production piece to be measured is too small, causes batch molecular sieve quality drop etc. and cannot be guaranteed that it can
Preparation for subsequent catalyst；And the relative crystallinity of the production piece to be measured of ZSM-23 molecular screen described in step a is greater than
97%, since the relative crystallinity of ZSM-23 molecular screen production piece to be measured is excessive, the batch molecular sieve is caused to urge for subsequent
When prepared by agent, the catalytic performance of catalyst might not be got well, and have no other beneficial effects.
ZSM-23 molecular screen standard sample:
In the present invention, ZSM-23 molecular screen standard sample is not particularly limited, usual ZSM-23 molecular screen standard sample
The crystallinity of product is 99%, and for stray crystal content less than 0.5%, purity is better than 99%, and when synthesizing with production piece to be measured, has
Identical raw material proportioning；
If stray crystal content >=0.5%, due to stray crystal too high levels, it is possible to also be free of a kind of stray crystal, contain two kinds sometimes
Stray crystal, and in the case where considering stray crystal content analysis error, it causes to cannot be guaranteed that selected reference substance crystallinity is better than 99%,
Have no other beneficial effects；
If purity≤99%, since purity is too low, cause it cannot be guaranteed that selected reference substance crystallinity has no better than 99%
Other beneficial effects.
The granularity control range of powder:
In the present invention, the granularity control range of powder is not particularly limited, the granularity control range of usual powder is excellent
It is selected as 10 μm~50 μm, more preferably 35 μm~45 μm；
If the granularity control range of powder less than 10 μm, causes ground sample time-consuming, laborious；Sieve pore is smaller, and sieve is got over
Valuableness such as selects the sieve of too small sieve pore that will increase the cost of purchase sifter device；Also, sieve pore is smaller, and particle is more tiny, when sieving
Easier electrostatic, the generation of electrostatic will affect screening operation and cannot proceed normally, and the granularity control range of powder is greater than 50 μ
M causes diffraction data quality to decline, it cannot be guaranteed that data preci-sion and accuracy needed for industrial production Analysis of quality control, has 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, is roasted described in usual step a
Activation condition are as follows: calcination activation temperature is 250~450 DEG C, and the calcination activation time is 2~6h；
If calcination activation temperature is, since maturing temperature is too small, to lead to the waste of calcining time, and living less than 250 DEG C
Change not exclusively, it cannot be guaranteed that obtaining the molecular sieve of clean surface；And calcination activation temperature is more than 450 DEG C, due to maturing temperature mistake
Greatly, the structure for causing waste of energy, and may cause framework of molecular sieve excess shrinkage, partially or completely destroying molecular sieve, has no
Other beneficial effects；
If Muffle furnace roasting is less than 2h, since calcining time is too short, activation is caused not exclusively, it cannot be guaranteed that obtaining cleaning
The molecular sieve on surface；And Muffle furnace roasting since calcining time is too long, causes the time to waste, and waste of energy, has no more than 6h
Other beneficial effects.
The processing of temperature control constant humidity:
In the present invention, the processing of temperature control constant humidity is not particularly limited, in usual step c, to sample in climatic chamber
Product frame and standard sample to be measured and Industrial sample to be measured carry out identical temperature control constant humidity and handle, and the temperature-control range is 35~65
DEG C, the temperature range of optimization is 45~55 DEG C, and temperature control constant humidity absorbent time is 3~7h；
If temperature control is less than 35 DEG C, since temperature is too low, causes absorbent time too long, close to diel, be not able to satisfy work
Industry production is efficient, the requirement of quick Analysis of quality control, and too low temperature, such as close to room temperature, climatic chamber to temperature and humidity not yet
Good control；And temperature control is greater than 65 DEG C, since temperature is excessively high, causes water vapour content in case too high, part water suction is excessively violent,
It is not easy to form the preci-sion and accuracy of uniform moisture film and final impact analysis data in the entire outer surface of molecular sieve, has no it
His beneficial effect.
If temperature control constant humidity absorbent time is less than 3h, since the time is too short, causing cannot complete shape in molecular sieve outer surface
At one layer of uniform moisture film, the preci-sion and accuracy of impact analysis data, and temperature control constant humidity absorbent time is greater than 7h, due to when
Between it is too long, cause the time to waste, have no other beneficial effects.
1, sample pre-treatments
ZSM-23 molecular screen standard sample and production piece respectively about 1g are taken, finely ground respectively, sieving collects 35 μm~45 μm
About 0.2g is sieved, then is respectively placed in the non-reactive crucibles such as ceramics, is put into 350 DEG C of Muffle furnaces and activates 5h, is dropped to muffle furnace
To about 125 DEG C, crucible is transferred in the climatic chamber for filling magnesium chloride saturated solution with crucible pliers, the temperature inside the box is not low
Under the conditions of 45 DEG C, accelerate water suction 5h.The specimen holder of filling sample also carries out identical constant humidity processing.
2, instrument operating condition
Powder x-ray diffraction to industrial ZSM-23 molecular screen sample analysis shows: the diffracted intensity of diffraction maximum with
Divergent slit receives the increase of slit and increases；Scanning step increases, and the point-distribution of curve, which becomes, dredges；Scanning speed is slower,
Curve is more smooth；With the increase of voltage, electric current, the diffracted intensity of product diffraction maximum is also linearly increasing.It is comprehensive according to above-mentioned experiment
It closes and considers the factors such as intensity, peak back ratio, resolution ratio, line smoothing degree, peak shape symmetry, preferably go out to be suitble to industry ZSM-23 molecule
The powder x-ray diffraction operating condition of sieve sample analysis is shown in Table 1.Analysis of spectra quantization are as follows: Industrial sample X-ray diffraction spectrogram
In most weak diffraction maximum diffracted signal signal-to-noise ratio S/N > 10.
1 instrument operating condition of table
Start powder x-ray diffraction, after instrument stabilizer, with silicon powder verify instrument angular instrument angle reproducibility (±
0.0001 °) and complete machine stability (≤0.1%) meet the requirement of measurement.Powder x-ray diffraction is set, institute is reached
The instrument operating condition (being shown in Table 1) of recommendation can obtain other suitable conditions of same signal-to-noise ratio (S/N) (when X-ray powder spreads out
When penetrating the S/N of smallest peaks in the industrial ZSM-23 molecular screen diffraction spectrogram of instrument measurement not less than 10:1, X-ray diffractometer work item
Part can meet analysis and require).Using its best powder x-ray diffraction curve (see Fig. 1), using powder x-ray diffraction data
The Chemical Measurement procedure of peak decomposing (selecting VII method of Pearson-) and external standard method of processing system software obtain industry ZSM-23 points
The relative crystallinity of son sieve.
3, Specimen Determination
The ZSM-23 molecular screen standard sample of saturation water suction and Industrial sample are respectively pressed into corresponding specimen holder, in powder
Adjustment specimen holder on last X-ray diffractometer.Under suitable powder x-ray diffraction operating condition, respectively to ZSM-23 molecule
Sieve standard sample and Industrial sample are measured and collect its powder x-ray diffraction data.At powder x-ray diffraction data
The Chemical Measurement procedure of peak decomposing (selection VII method of Pearson-) for managing system software, measures standard sample and Industrial sample respectively
(111), (121), (042), (003), (112), (060), (122), (052) 8 crystallographic plane diffraction peak integrating peak areas intensity
Count value is simultaneously summed.Standard sample replication twice, take its (111), (121), (042), (003), (112), (060),
(122), the arithmetic mean of instantaneous value of the sum of integrating peak areas intensity count value of (052) 8 crystallographic plane diffraction peak is calculated for quantitative.Work
The typical Chemical Measurement swarming fitted figure of industry ZSM-23 molecular screen (selecting VII method of Pearson-) is shown in Fig. 2.
4, data processing
The relative crystallinity RCi of industrial ZSM-23 molecular screen is calculated by formula (1), and numerical value is indicated with %:
... ... ... ... ... ... ... (formula 1)
In formula (1):
Ai --- industrial ZSM-23 molecular screen sample (111), (121), (042), (003), (112), (060), (122),
The sum of the peak area of (052) 8 crystallographic plane diffraction peak；
As --- ZSM-23 molecular screen standard sample (111), (121), (042), (003), (112), (060), (122),
The sum of the peak area of (052) 8 crystallographic plane diffraction peak；
Cs --- the crystallinity of ZSM-23 molecular screen standard sample, 99% (mass fraction)；
RCi --- the relative crystallinity of industrial ZSM-23 molecular screen, % (mass fraction).
According to above-mentioned testing program, the relative crystallinity of 3 selected horizontal samples is carried out respectively in 12 laboratories
Measurement, gained test data are shown in Table 2, table 3, table 4.The essence obtained by the test result statistical analysis between 12 laboratories
Density is shown in Table 5.It is required that each sample replication twice and asks its arithmetic mean of instantaneous value, measurement result round numbers.
The original analysis data (%) of the industrial ZSM-23 molecular screen sample relative crystallinity of table 2
The original analysis data (%) of the industrial ZSM-23 molecular screen sample relative crystallinity of table 3
The original analysis data (%) of the industrial ZSM-23 molecular screen sample relative crystallinity of table 4
5 method precision of table (%)
| Relative crystallinity range | Repeatability | Reproducibility |
| 85~97 | 3 | 4 |
Claims (6)
1. a kind of method for measuring ZSM-23 molecular screen relative crystallinity, includes the following steps:
A, the pre-treatment of sample
ZSM-23 molecular screen standard sample and production piece to be measured process are ground up, sieved, the water suction of calcination activation and temperature control constant humidity
Four steps prepare standard sample to be measured and Industrial sample to be measured；
B, the determination of powder x-ray diffraction operating condition
After starting powder x-ray diffraction, selecting NIST silicon powder to verify the angle reproducibility of angular instrument is ± 0.0001 °, complete machine
Stability is≤0.1%, according to the signal-to-noise ratio S/N of diffraction maximum diffracted signal most weak in Industrial sample X-ray diffraction spectrogram to be measured
> 10 determines that powder x-ray diffraction voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, reception are narrow
The parameter of seam, optical filter or monochromator, obtains the best powder x-ray diffraction spectrogram of sample；
C, it measures
Under identical powder x-ray diffraction operating condition, ZSM-23 molecular screen standard sample to be measured and industry to be measured are tried
Sample is loaded into respectively in corresponding powder x-ray diffraction glass or aluminum specimen holder, is carried out Specimen Determination and is collected its powder X-ray
Ray diffraction data；
D, it calculates
Using the Chemical Measurement swarming method of powder x-ray diffraction data processing system software, measure sample (111),
(121), (042), (003), (112), (060), (122), (052) 8 crystallographic plane diffraction peak integrating peak areas intensity count value
And sum, the relative crystallinity of Industrial sample to be measured is calculated with external standard method；
After being ground up, sieved described in step a, the granularity control range of powder is 10 μm~50 μm；
Calcination activation condition described in step a are as follows: calcination activation temperature is 250~450 DEG C, and the calcination activation time is 2~6h；
In step a, identical temperature control is carried out to specimen holder and standard sample to be measured and Industrial sample to be measured in climatic chamber
Constant humidity processing, the temperature-control range are 35~65 DEG C, and temperature control constant humidity absorbent time is 3~7h.
2. the method for measurement ZSM-23 molecular screen relative crystallinity according to claim 1, which is characterized in that in step a
The relative crystallinity range of the ZSM-23 molecular screen production piece to be measured is 85%~97%；ZSM-23 molecular screen standard sample
Crystallinity be 99%, stray crystal content is less than 0.5%, and purity is better than 99%, and when synthesize with production piece to be measured, with phase
Same raw material proportioning.
3. the method for measurement ZSM-23 molecular screen relative crystallinity according to claim 1, which is characterized in that in step a
Before to ZSM-23 molecular screen sample calcination activation processing, the ZSM-23 molecular screen sample is carried out at removed template method
Reason.
4. the method for measurement ZSM-23 molecular screen relative crystallinity according to claim 3, which is characterized in that in step a
The step of ZSM-23 molecular screen sample progress removed template method processing, is:
The heat analysis for first carrying out the ZSM-23 molecular screen sample is obtained by its thermogravimetric curve or its once differentiation curve
The minimum temperature of complete removed template method, and removed template method is carried out under the minimum temperature.
5. the method for measurement ZSM-23 molecular screen relative crystallinity according to claim 1, which is characterized in that in step a
It is described be ground up, sieved after, the granularity control range of powder is 35 μm~45 μm.
6. the method for measurement ZSM-23 molecular screen relative crystallinity according to claim 1, which is characterized in that in step c,
Identical temperature control constant humidity is carried out to specimen holder and standard sample to be measured and Industrial sample to be measured in climatic chamber to handle, it is described
Temperature-control range is 45~55 DEG C.
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