CN106168584B - The method for measuring SAPO-11 molecular sieve relative crystallinity - Google Patents
The method for measuring SAPO-11 molecular sieve relative crystallinity Download PDFInfo
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Abstract
A method of measurement SAPO-11 molecular sieve relative crystallinity includes the following steps: the pre-treatment of a, sample: process is ground up, sieved, calcination activation and temperature control constant humidity absorb water, and standard sample to be measured and Industrial sample to be measured is prepared in four steps；B, the determination of powder x-ray diffraction operating condition: after starting powder x-ray diffraction, select NIST silicon powder, the angle reproducibility for verifying angular instrument is ± 0.0001 °, complete machine stability is≤0.1%, according to the signal-to-noise ratio S/N > 10 of diffraction maximum diffracted signal most weak in Industrial sample X-ray diffraction spectrogram to be measured, it determines diffractometer voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, the parameter for receiving slit, optical filter or monochromator, obtains the best powder x-ray diffraction spectrogram of sample；C, it measures；D, it calculates, the relative crystallinity of production piece to be measured is calculated with 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 SAPO-11 molecular sieve relative crystallinity.
Background technique
Molecular sieve is widely used in the catalytic process of petrochemical industry as catalyst or catalyst carrier.Relative crystallinity,
Cell parameter, silica alumina ratio, purity etc. are the characterization indispensable basic parameters of molecular sieve performance.Therefore, Accurate Determining molecular sieve
Relative crystallinity for design preparation of molecular sieve and evaluate associated catalysts performance be highly important.Powder X-ray is penetrated
Line diffraction approach sample preparation is simple, minute is short, reproducible, high reliablity, expense are low, be widely used in molecular sieve crystallinity,
In the measurement of cell parameter, silica alumina ratio, purity etc..But industrial products SAPO-11 points are measured in detail using powder X-ray diffractometry
There is not been reported for patent, standard or the research report of son sieve relative crystallinity.
Be related to SAPO-11 molecular sieve it is more be synthesis or the report of relevant catalyticing research, but be generally also wherein
The measurement is sketched, does not describe specific measuring method or step, for example, Wang Xiaoxiao, Guo Shaoqing, Zhang Wei, wait .SAPO-11
Influence [J] the Journal of Molecular Catalysis of Zeolite synthesis condition to its crystallinity and catalytic performance, 2013,27 (4): 295~305.At this
In paper, king etc. measure SAPO-11 relative crystallinity using the characteristic peak diffracted intensity of: sample and reference HZSM-5 into
Row compare, it is this using different formulas, different molecular sieves have the shortcomings that as reference it is very big because crystallinity and its
Relative crystallinity is an extremely important parameter for carrying out investigating crystallization situation in Zeolite synthesis research and development when Study on Crystallization.Phase
With formula, same molecular sieve, the especially molecular sieve of industrial mass manufacture, the significant to Bizet of crystallinity is carried out, this is often referred to
Two aspect contents: in technique and on analysis science.It is very big for solving this problem difficulty: firstly, to do a large amount of technique
Synthesis and analysis and characterization test, quantity can reach up to a hundred or hundreds of times respectively, then just can solve and preferably go out a highest knot
The SAPO-11 molecule sieve problem of brilliant degree needs to solve the quantitative analyses such as its purity, stray crystal, element, pattern and asks in the process
Topic, this problem do not solve, and can not solve the problem analysis of relative crystallinity, that is: in relative crystallinity measurement, reference substance is closed
At, preferably, quantitatively characterizing be the crucial first step, be crystallinity in all same molecular sieves and its product of industry's enlarging production
It is highest.Otherwise, data it is nonsensical or without method interpretation data why high (be greater than 100%) or why low (less than 100%).
It is well known that the crystallinity of perfect cystal material is 100%, the relative crystallinity of any common crystallization material should not surpass 100%,
Its numerical value is high or low to be shown: reference substance select permeability is not resolved in its work.
" 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, the prior art is there are many drawbacks, and system with molecular sieve for preparing is the selection of synthesis condition for the emphasis that patent is emphasized,
It is not involved in the problems, such as wherein or is very related to XRD characterization less.All SAPO-11 system with molecular sieve for preparing being related to are being related to tying for patent
When brilliant degree problem analysis, mostly just lists the comparison between instrument XRD or its XRD spectra and its spectrogram, crystallizes degree
According to etc., detailed analytic process or method do not have.
The invention patent can specification industrial products SAPO-11 molecular sieve product Analysis of quality control, facilitate SAPO-11 point
The outer committee's analysis work of the commercial introduction application and development of son sieve and subsequent catalyst.Due to there is no disclosed industrial products both at home and abroad
SAPO-11 molecular sieve relative crystallinity analyzes the standard of test method, and therefore, the invention patent is with industrial products SAPO-11 points
The laboratory the Duo Jia Conjoint Analysis result of study of son sieve relative 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 SAPO-11 zeolites
How object selects and carries out Exact Analysis characterization, and be us is put forward for the first time on the basis of hundreds of analysis tests, currently,
There is no any document report.
It is another object of the present invention to, by a large number of experiments, equally be screening, our this patents only need to accomplish by
SAPO-11 molecular sieve is 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 of Accurate Determining industrial products SAPO-11 molecular sieve relative crystallinity
Method provides reliable technical support for the synthesis of molecular sieve or the preparation of associated catalysts and industrial application.A kind of measurement
The method of SAPO-11 molecular sieve relative crystallinity, includes the following steps:
A, the pre-treatment of sample
By SAPO-11 zeolites sample and production piece to be measured by being ground up, sieved, calcination activation and temperature control constant humidity
Standard sample to be measured and Industrial sample to be measured is prepared in four steps that absorb water；
B, the determination of powder x-ray diffraction operating condition
After starting powder x-ray diffraction, NIST silicon powder is selected, the angle reproducibility for verifying 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 diffractometer voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, receives slit, filter
The parameter of mating plate or monochromator obtains the best powder x-ray diffraction spectrogram of sample；
C, it measures
Under identical powder x-ray diffraction operating condition, by SAPO-11 molecular sieve 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, it is brilliant to measure sample (002)
The integrating peak areas intensity count value of face diffraction maximum, the relative crystallinity of production piece to be measured is calculated with external standard method.Largely trying
On the basis of testing, obtain SAPO-11 molecular sieve (002) crystallographic plane diffraction peak integrating peak areas intensity count value and the molecular sieve and
The catalytic performance of its associated catalysts is directly related, is put forward for the first time and the peak is selected to carry out relative crystallinity measurement.
The measurement that powder x-ray diffraction carries out SAPO-11 zeolites sample and Industrial sample to be measured is opened, in phase
Under same experimental condition, SAPO-11 zeolites sample and Industrial sample to be measured within the scope of 7 °~30 ° of 2 θ angle are collected respectively
Copper KαX ray diffracting data, using the Chemical Measurement swarming method (choosing of powder x-ray diffraction data processing system software
With VII method of Pearson-), the integrating peak areas intensity count value of each sample (002) crystallographic plane diffraction peak is measured respectively, with outer
The relative crystallinity of mark method calculating sample.
The method of measurement SAPO-11 molecular sieve relative crystallinity of the present invention, wherein SAPO-11 described in step a
The relative crystallinity of molecular sieve production piece to be measured ranges preferably from 68%~98%；The knot of SAPO-11 zeolites sample
Brilliant degree is preferably 99%, and stray crystal content is preferably smaller than 0.5%, and purity is preferably superior to 99%, and synthesizes with production piece to be measured
When, raw material proportioning and synthetic method having the same.
It is of the present invention measurement SAPO-11 molecular sieve relative crystallinity method, wherein preferably, in step a
Before SAPO-11 sieve sample calcination activation processing, the SAPO-11 sieve sample is carried out at removed template method
Reason.
The method of measurement SAPO-11 molecular sieve relative crystallinity of the present invention, wherein preferably, institute in step a
Stating the step of SAPO-11 sieve sample carries out removed template method processing is:
The heat analysis for first carrying out the SAPO-11 sieve 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 SAPO-11 molecular sieve 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 SAPO-11 molecular sieve relative crystallinity of the present invention, wherein roast and live described in step a
Change condition is preferred are as follows: Muffle furnace roasts 2~6h, and calcination activation temperature is preferably 250~450 DEG C.
The method of measurement SAPO-11 molecular sieve 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 excellent
35~65 DEG C, more preferably 45~55 DEG C are selected as, temperature control constant humidity absorbent time is preferably 3~7h.
The method of measurement SAPO-11 molecular sieve relative crystallinity of the present invention, wherein in step d, using powder X-ray
The Chemical Measurement swarming method of ray diffraction data processing system software measures the peak area of sample (002) crystallographic plane diffraction peak
Integrated intensity count value.
The present invention can also details are as follows:
SAPO-11 zeolites sample and production piece to be measured process are ground up, sieved first, calcination activation, temperature control
Constant humidity water suction handles to obtain sample to be tested, under identical powder x-ray diffraction operating condition, by SAPO-11 molecular sieve mark
Quasi- sample and Industrial sample to be measured are respectively pressed into corresponding X-ray diffractometer specimen holder, are carried out Specimen Determination and are collected respectively
Powder x-ray diffraction data.Using the Chemical Measurement swarming method of powder x-ray diffraction data processing system software, measurement
The peak area of each sample (002) crystallographic plane diffraction peak calculates the relative crystallinity of sample with external standard method.It is characterized in that sample is ground
Honed sieve particle size range control is at 35 μm~45 μm, i.e., particle size deviation is less than 10 μm；Muffle is used when the processing of sample calcination activation
Furnace, temperature are controlled at 250~450 DEG C, and 2~6h of calcining time obtains the sample to be tested of clean surface, then carries out saturation water suction
Processing, standard sample to be measured and Industrial sample are respectively pressed into corresponding specimen holder, are carried out Specimen Determination and are collected its powder X-ray
Ray diffraction data；The specimen holder of filling sample also carries out identical constant humidity processing；After opening powder x-ray diffraction, silicon is used
Powder verifies the angle reproducibility (± 0.0001 °) of powder x-ray diffraction angular instrument and complete machine stability (≤0.1%) meets survey
Provisioning request.
Using the above method, industrial SAPO-11 sample relative crystallinity measurement range is 68%~98%；SAPO-11 points
The crystallinity of son sieve pure phase standard sample is 99%, is used as outer standard specimen.SAPO-11 zeolites sample will use high-power
(for example, 18kW) powder x-ray diffraction carries out purity check, to guarantee that i.e. purity is better than stray crystal contained by it less than 0.5%
99%, amorphous is not detected.
Using the above method, since sample is after grinding, sieving, particle size range is controlled at 35 μm~45 μm, that is, is controlled
Particle size deviation improves the accuracy and more time saving, laborsaving of powder diffraction data measurement, sample is ground to less than 10 μm
1 μm~10 μm or narrower particle size range can also be with, but more time-consuming, laborious and sieving difficulty is very big, because sample powder easily produces
Raw electrostatic, therefore become difficult sieving operation；In addition, sieve needs, purchase sieve needs many foreign exchanges special customized to foreign trader,
Foreign trader claims simultaneously it cannot be guaranteed that the problem of sieving of such fine powder is easy to produce electrostatic.
Using the above method, 2~6h, maturing temperature 250~450 are roasted using Muffle furnace when carrying out sample activating pretreatment
DEG C, the various inorganic and organic matter such as including water that can effectively adsorb the SAPO-11 molecular sieve of removed template method removes, and obtains
To the sample of clean outer surface.If sample contains template, needs first to carry out SAPO-11 molecular sieve heat analysis, pass through its TG
Curve and DTG (differential) curve, find the minimum temperature of complete removed template method, then carry out thoroughly removing template at such a temperature
Agent simultaneously prevents molecular sieve structure and is destroyed.Before SAPO-11 molecular sieve 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 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 powdered sample (111) crystallographic plane diffraction peak integrating peak areas intensity
Then count value n carries out the relative standard deviation analysis of data up to 10 times or more, it is desirable that and≤0.1%) meet measurement and requires, with
Guarantee that the precision of inventive method meets the requirement of its Analysis of quality control.
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 SAPO-11 molecular sieve being ground to 35-45 micron, do so benefit is: it is time saving, province
Power is also less prone to generate electrostatic because particle is less tiny, moreover, and most critical: its analysis precision is able to satisfy industrial production height
Effect quickly requires；
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 SAPO-11 molecular sieve
In most weak spectral peak signal-to-noise ratio be greater than 10, can meet XRD relative crystallinity analysis require new concept；
On the basis of a large number of experiments, the integrating peak areas intensitometer of SAPO-11 molecular sieve (002) crystallographic plane diffraction peak is obtained
Numerical value is directly related with the catalytic performance of the molecular sieve and its associated catalysts, is put forward for the first time and the peak is selected to carry out relative crystallinity
Measurement.
A kind of powder x-ray diffraction method of Accurate Determining industrial products SAPO-11 molecular sieve 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
A kind of Fig. 1: the typical x-ray diffractogram of powder of industry SAPO-11 molecular sieve sample；
A kind of Fig. 2: the typical Chemical Measurement swarming fitted figure of industry SAPO-11 molecular sieve sample.
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 diffractometer voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, receive slit, optical filter or list
The parameter of color device 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 requirement of industrial production Analysis of quality control to the data precision, has no
Other beneficial effects.
The relative crystallinity range of SAPO-11 molecular sieve production piece to be measured described in step a:
In the present invention, the relative crystallinity range of SAPO-11 molecular sieve production piece to be measured described in step a is had no
Be particularly limited to, the relative crystallinity range of SAPO-11 molecular sieve production piece to be measured described in usual step a be 68%~
98%；
If the relative crystallinity of SAPO-11 molecular sieve production piece to be measured is less than 68%, since SAPO-11 molecular sieve waits for
The relative crystallinity for surveying production piece is too small, causes batch molecular sieve quality drop etc. and cannot be guaranteed that it can be used for subsequent urge
The preparation of agent；And the relative crystallinity of SAPO-11 molecular sieve production piece to be measured is greater than 98%, due to SAPO-11 molecular sieve
The relative crystallinity of production piece to be measured is excessive, and when causing the batch molecular sieve for subsequent catalyst preparation, catalyst is urged
Change performance is simultaneously bad, has no other beneficial effects.
SAPO-11 zeolites sample:
In the present invention, SAPO-11 zeolites sample is not particularly limited, usual SAPO-11 zeolites
The crystallinity of sample is 99%, and stray crystal content is less than 0.5%, and purity is better than 99%, and with production piece to be measured by identical
When method is synthesized, raw material proportioning having the same；
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
10 μm~50 μm, 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 μm,
Diffraction data quality is caused to decline, it cannot be guaranteed that the data precision needed for industrial production Analysis of quality control, has no other beneficial to effect
Fruit.
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: Muffle furnace roasts 2~6h, and calcination activation temperature is 250~450 DEG C；
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；
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.
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；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, is also not easy in molecular sieve appearance
Face forms the preci-sion and accuracy of uniform moisture film and final impact analysis data, has no other beneficial effects；
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
Take SAPO-11 zeolites sample and production piece to be measured respectively about 1g respectively, finely ground, sieving, collect 35 μm~
45 μm of sample powder, then take 0.2g to sieve respectively, it is placed in the non-reactive crucibles such as ceramics, is put into 350 DEG C of Muffle furnaces and activates 4h,
When muffle furnace is down to about 125 DEG C, crucible is transferred to the constant temperature and humidity for filling magnesium chloride saturated solution with crucible pliers
In case, the temperature inside the box is not less than under the conditions of 45 DEG C, and temperature control constant humidity accelerates water suction 5h.The specimen holder of filling sample also carries out identical
The processing of temperature control constant humidity.
2, instrument operating condition
Powder x-ray diffraction to industrial SAPO-11 molecular sieve 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 SAPO-11 points
The powder x-ray diffraction operating condition of son sieve sample analysis is shown in Table 1.Analysis of spectra quantization are as follows: Industrial sample X-ray diffraction spectrum
The signal-to-noise ratio S/N > 10 of most weak diffraction maximum diffracted signal in figure.
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 subsequent sample measurement requirement.Powder x-ray diffraction is set
It is fixed, (work as powder to reach typical instrument operating condition listed by table 1 or other suitable conditions of same signal-to-noise ratio (S/N) can be obtained
When the S/N of smallest peaks is not less than 10:1 in the industrial SAPO-11 molecular sieve diffraction spectrogram of last X-ray diffractometer measurement, X-ray is spread out
Analysis requirement can be met by penetrating instrument operating condition).Using optimal SAPO-11 molecular sieve powder X-ray diffraction curve (see figure
1) relative crystallinity of industrial SAPO-11 molecular sieve, is obtained (see figure using chemo metric software procedure of peak decomposing and external standard method
2)。
3, Specimen Determination
The SAPO-11 zeolites sample and Industrial sample to be measured of saturation water suction are respectively pressed into corresponding specimen holder
In, the adjustment specimen holder on powder x-ray diffraction.Under the powder x-ray diffraction operating condition of recommendation, respectively to be measured
SAPO-11 zeolites sample and Industrial sample are measured and collect powder x-ray diffraction data.Using X-ray powder
The Chemical Measurement procedure of peak decomposing of diffraction data processing system software measures standard sample and sample to be tested (002) crystal face respectively
The integrating peak areas intensity count value of diffraction maximum.Standard sample replication twice, takes the peak area of its (002) crystallographic plane diffraction peak
The average value of integrated intensity count value is calculated for quantitative.The Exemplary chemical meterological swarming of industrial SAPO-11 molecular sieve is fitted
Figure is shown in Fig. 2.
4, data processing
The relative crystallinity RCi of industrial SAPO-11 molecular sieve is calculated by formula (1), and numerical value is indicated with %:
... ... ... ... ... ... ... (formula 1)
In formula (1):
Ai --- the integrating peak areas intensity count value of industrial SAPO-11 molecular sieve sample (002) crystallographic plane diffraction peak；
As --- the integrating peak areas intensity count value of SAPO-11 zeolites sample (002) crystallographic plane diffraction peak；
Cs --- the crystallinity of SAPO-11 zeolites sample, 99% (mass fraction).
According to above-mentioned testing program, the relative crystallinity of 4 selected horizontal samples is carried out respectively in 12 laboratories
Measurement, gained test data are shown in Table 2, table 3, table 4, table 5.It is obtained by the test result statistical analysis between 12 laboratories
Precision is shown in Table 6.It is required that each sample replication is twice, measurement result takes one decimal place.
The original analysis data (%) of 2 industry SAPO-11 molecular sieve sample relative crystallinity of table
The original analysis data (%) of 3 industry SAPO-11 molecular sieve sample relative crystallinity of table
The original analysis data (%) of 4 industry SAPO-11 molecular sieve sample relative crystallinity of table
The original analysis data (%) of 5 industry SAPO-11 molecular sieve sample relative crystallinity of table
6 method precision of table (%)
| Relative crystallinity range | Repeatability | Reproducibility |
| 68~98 | 3 | 4 |
Claims (6)
1. a kind of method for measuring SAPO-11 molecular sieve relative crystallinity, includes the following steps:
A, the pre-treatment of sample
SAPO-11 zeolites sample and production piece to be measured process are ground up, sieved, the water suction of calcination activation and temperature control constant humidity
Standard sample to be measured and Industrial sample to be measured is prepared in four steps；
B, the determination of powder x-ray diffraction operating condition
After starting powder x-ray diffraction, NIST silicon powder is selected, the angle reproducibility for verifying 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 diffractometer voltage, electric current, divergent slit, diverging height limitation slit, antiscatter slits, receives slit, optical filter
Or the parameter of monochromator, obtain the best powder x-ray diffraction spectrogram of sample；
C, it measures
Under identical powder x-ray diffraction operating condition, SAPO-11 molecular sieve 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, measures sample (002) crystal face and spread out
The integrating peak areas intensity count value for penetrating peak, the relative crystallinity of production piece 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: Muffle furnace roasts 2~6h, and calcination activation temperature is 250~450 DEG C；
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 SAPO-11 molecular sieve relative crystallinity according to claim 1, which is characterized in that in step a
The relative crystallinity range of the SAPO-11 molecular sieve production piece to be measured is 68%~98%；SAPO-11 zeolites 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.
3. the method for measurement SAPO-11 molecular sieve relative crystallinity according to claim 1, which is characterized in that in step a
Before to SAPO-11 sieve sample calcination activation processing, removed template method is carried out to the SAPO-11 sieve sample
Processing.
4. the method for measurement SAPO-11 molecular sieve relative crystallinity according to claim 3, which is characterized in that in step a
The step of SAPO-11 sieve sample progress removed template method processing, is:
The heat analysis for first carrying out the SAPO-11 sieve 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 SAPO-11 molecular sieve 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 SAPO-11 molecular sieve relative crystallinity according to claim 1, which is characterized in that step a
In, 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 and is handled,
The temperature-control range is 45~55 DEG C.
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| X射线衍射法测定高岭石合成的NaY分子筛物相组成、结晶度、晶胞参数及硅铝比研究;程群;《冶金标准化与质量》;20060430;第44卷(第2期);第9页左栏 2.2物相分析实验方法，2.3测定结晶度实验方法 |
| ZSM-22分子筛的合成及其催化性能的研究;吴卓;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20091015;论文第6页（2）X射线衍射法 |
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