CN106323770A - Method for testing strength of solid particles - Google Patents
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- CN106323770A CN106323770A CN201510386949.4A CN201510386949A CN106323770A CN 106323770 A CN106323770 A CN 106323770A CN 201510386949 A CN201510386949 A CN 201510386949A CN 106323770 A CN106323770 A CN 106323770A
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Abstract
The invention discloses a method for testing strength of solid particles. The solid particles are catalyst carrier particles or catalyst particles. The method comprises the following steps: (1) solid particles are solvents are mixed, in order to obtain a mixture containing solid particles; (2) ultrasonic treatment is carried out for the mixture containing solid particles which is obtained in the step (1), after the ultrasonic treatment is carried out for t1, t2 and t3, particle size detection is carried out for the solid particles, the particle size D(t1), D(t2) and D(t3) are obtained, and D(t1), D(t2) and D(t3) employ the same cumulative particle size distribution percent; (3) strength index L of solid particles is calculated, and the strength index L of solid particles is calculated according to the following formula; wherein the ultrasonic treatment time satisfies t1<t3<t2. The method for testing strength of solid particles has good repeatability and high precision, and effective monitoring for catalyst carrier strength or catalyst strength is carried out.
Description
Technical field
The present invention relates to the method for testing of a kind of solid particle intensity, in particular it relates to a kind of catalyst carries
Body or the method for testing of catalyst strength.
Background technology
Polypropylene catalyst slurry process, substance law (Spheripol technique, Hypol technique etc.) and
During vapor phase method (Novolen technique, Innovene technique etc.) technique uses, prepared by catalyst
Polymer is easily generated fine powder especially micropowder due to many reasons.It is known that fine powder crosses multipair device
Polymer transfer lines, drying system etc. impact, and this is that puzzlement polypropylene industrial device long period makes
One of factor.
Polypropylene catalyst fine powder Producing reason in the course of the polymerization process is extremely complex, has generally believed at present
Following three points: 1) catalyst catalyst carrier intensity deficiency used in preparation process, cause urging
Agent bulk strength is low.In the course of the polymerization process due to operating conditions such as the diffusion of propylene monomer, stir speed (S.S.)s
Impact make catalyst breakage, produce catalyst fines and secondary granule, these catalyst fines and time
Grade particles all has certain activity, just creates fine polymer powder after polymerization process.2) catalyst is defeated
Due to interparticle friction during sending, the catalyst unstable operation during using configuration, aggravation
Crushing of catalyst, produces fine polymer powder after polymerization process.3) catalyst uses in commercial plant
Time due to the difference (such as substance law and vapor phase method) of polymerization technique, the environment residing for catalyst is different, instead
The severity answered is different, when device high load capacity and higher polymerizing condition (as polymerization temperature reach 80～
90 DEG C, most commonly 70 DEG C), catalyst breakage aggravates.Owing to polymer is substantially answering of catalyst
System, so polymeric articles the most just creates fine powder and crushes.
In a word, catalyst carrier intensity determines catalyst body intensity, catalyst body intensity effect substantially
The fine powder of polymer.
The mean diameter of catalyst carrier and catalyst is many below 50 μm, and broken in test process
The most easily cause reunion so that the quantitative test of catalyst carrier and catalyst body intensity is the most tired
Difficult.The method of testing that there is presently no a kind of catalyst carrier and catalyst strength can be used in catalyst load
Body and the evaluation of catalyst strength.
Therefore, this area is needed badly and is developed the method for testing of a kind of catalyst carrier or catalyst strength for commenting
Valency catalyst carrier and catalyst, the production for stably catalyzed agent carrier and catalyst provides support.
Summary of the invention
It is an object of the invention to provide a kind of catalyst carrier intensity or the method for testing of catalyst strength.
Existing catalyst carrier or catalyst breakage are mainly used abrasion of particles Index Instrument and ball mill
Etc. method, however these methods to control difficulty big, be all difficult to control to the degree crushed, and broken after
Catalyst carrier or catalyst granules granularity are difficult to accurately measure owing to the reasons such as reunion exist, strong to carrier
The evaluation of degree cannot be quantitative.The present inventor is found by research, utilizes ultrasonic to catalyst carrier
Or the solution mixture of catalyst processes, prolongation over time, catalyst carrier or catalyst particles
It is more accurate that the granularity of grain changes stable and make granularity because not reuniting measurement.Meanwhile, the present invention
Inventor by research also find, by by ultrasonic t1Rear granularity D (t1) and ultrasonic t2After granularity
D(t2) difference and ultrasonic interlude t3After granularity D (t3) numerical value make than obtain value stabilization,
Reproducible and precision is high, it is possible to represent catalyst carrier or the intensity of catalyst granules well.
To achieve these goals, the present invention provides the method for testing of a kind of solid particle intensity, described solid
Body granule is catalyst carrier particle or catalyst granules, and the method includes:
(1) solid particle is mixed with solvent, obtain the mixture containing solid particle；
(2) mixture containing solid particle that step (1) obtains is carried out supersound process, and to super
Sonication t1、t2、t3Solid particle after time carries out granularity Detection, obtains granularity D (t1)、D(t2)
With D (t3), described D (t1)、D(t2) and D (t3) use identical cumulative particle sizes percentile；
(3) the intensity index L of solid particle, the calculating of the intensity index L of described solid particle are calculated
Carried out by following formula；
Wherein, the time of described supersound process meets t1＜ t3＜ t2。
Catalyst carrier intensity that the present invention provides or the assay method of catalyst strength is reproducible and
Precision is high, it is possible to effectively monitors catalyst carrier intensity or catalyst strength, thus is steady
Determine carrier and offer technical support is provided.It addition, the present invention's is simple to operate, have a wide range of applications popularization
It is worth.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the scanning electron microscope image after magnesium chloride/alcohol adducts Z3 supersound process 10min.
Fig. 2 is the scanning electron microscope image after magnesium chloride/alcohol adducts Z4 supersound process 10min.
Fig. 3 is the scanning electron microscope image after magnesium chloride/alcohol adducts Z3 supersound process 20min.
Fig. 4 is the scanning electron microscope image after magnesium chloride/alcohol adducts Z4 supersound process 20min.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
Term " particle mean size " refers to use Malvern particle size analyzer test sample granularity, when accumulation granularity
Percentile reaches numerical value corresponding when 50%.When " cumulative particle sizes percentile " refers to necessarily measure
The interior size by detector granule, is arranged granular size by computer, accumulation to certain grain
Footpath granule accounts for the percentage composition of overall sample.
The invention provides the method for testing of a kind of solid particle intensity, described solid particle is that catalyst carries
Body granule or catalyst granules, the method includes:
(1) solid particle is mixed with solvent, obtain the mixture containing solid particle；
(2) mixture containing solid particle that step (1) obtains is carried out supersound process, and to super
Sonication t1、t2、t3Solid particle after time carries out granularity Detection, obtains granularity D (t1)、D(t2)
With D (t3), described D (t1)、D(t2) and D (t3) use identical cumulative particle sizes percentile；
(3) the intensity index L of solid particle, the calculating of the intensity index L of described solid particle are calculated
Carried out by following formula；
Wherein, the time of described supersound process meets t1＜ t3＜ t2。
In the present invention, the intensity index L numerical value of described solid particle is the least, represents solid particle the most not
It is easily broken namely the intensity of solid particle is the highest.
In the present invention, for being not particularly limited of consumption of described solvent, the use of described solvent
Amount makes described solid particle be immersed in described solvent.Such as, the described solid relative to 1g
Granule, the usage amount of described solvent can be 50-100mL, under preferable case, described in 1g
Solid particle, the usage amount of described solvent is 100mL.
Owing to minor amount of water easily and in air of catalyst carrier and catalyst granules and oxygen react
Affect the intensity of catalyst carrier and catalyst, therefore, in order to avoid the water in air and oxygen are to test knot
The impact of fruit, under preferable case, described in be blended in airtight container and carry out.Described container can be normal
The sealable container that rule use, such as ampere bottle.
In the present invention, for the process that solid particle mixes with solvent is not particularly limited, example
As this process can be: quantitative solid particle is joined in hermetic container, adds solvent, then
By container closure and mix.So that test result is more accurate, under preferable case, by solid particle
The process mixed with solvent is carried out under isolation air conditions, such as, can carry out in the dry case of glove.Right
Method in described mixing is not particularly limited, such as, can be to use separating apparatus dispersion or manually shake
Shake and disperse.For time of described mixing, also there is no particular limitation, such as 0.2-2 minute.
In the present invention, although the consumption for described solid particle is not particularly limited, but sample
Product be easily caused sample ultrasonic poor effect too much and sample very little without representative, it is therefore preferable that situation
Under, the consumption of described solid particle make it possible to bottom hermetic container formed monolayer of particles, such as,
In the ampere bottle of 50-150mL, the consumption of described solid particle can be 0.5-1g.
In the present invention, can be solvent commonly used in the art for described solvent, the most described molten
Agent can be C6-12Alkane in one or more；Under preferable case, described solvent be hexane, heptane,
One or more in octane, nonane and decane；In the case of Jin Yibuyouxuan, described solvent is hexane.
In the case of in the present invention, it is preferred to, the condition of described supersound process includes: supersonic frequency is
30-80kHz, temperature is 10-50 DEG C.Under preferable case, temperature is 20-30 DEG C.Described supersound process can
To carry out on ultrasonic instrument, so that test result is more accurate and testing efficiency is higher, excellent
In the case of choosing, described ultrasonic instrument is the ultrasonic instrument with multiple ultrasonic transmitter, multiple ultrasonic
Emitter makes the conplane intensity in this instrument identical, it is possible to make measurement result more accurately and
Measure while disclosure satisfy that multiple sample.
The method provided according to the present invention, under preferable case, described t1=0, t3=t2/2.Further preferably
In the case of, t2=10-60min, under most preferred case, t2=20min.Wherein, t1=0 refers to not pass through
Supersound process.
The method provided according to the present invention, D (t1)、D(t2) and D (t3) use identical accumulative grain
Degree percentile, under preferable case, D (t1)、D(t2) and D (t3) it is cumulative particle sizes distribution hundred
Mark is granularity during 10-90%, more preferably in the case of, described D (t1)、D(t2) and D (t3)
It is granularity when 50% for cumulative particle sizes percentile.When cumulative particle sizes percentile is X%,
The granularity of solid particle can represent with DX, such as, when particle size distribution percent is 50%, and solid
The granularity of granule can represent with D50, in like manner, when particle size distribution percent is 10%, and solid
The granularity of grain can represent with D10；When particle size distribution percent is 90%, the granularity of solid particle
Can represent with D90.
In the present invention, the method for described granularity Detection can be method commonly used in the art, such as
Particle size analyzer is used to carry out detecting granularity.Process for described granularity Detection the most particularly limits
Fixed, the process of the most described granularity Detection can be: supersound process t1After time, stop ultrasonic or from super
Sound instrument take out hermetic container and rocks, drawing the mixture containing solid particle with dropper, sending into grain
Degree tester carries out granularity Detection；Then hermetic container is proceeded supersound process, supersound process t2Time
After between, repeat the above steps carries out granularity Detection.Draw the mixture containing solid particle with dropper every time
Amount meet the amount of granularity Detection, can be such as 0.8-1.5mL.
In the present invention, described sonication treatment time refers to the time of accumulative supersound process.
The method provided according to the present invention, described catalyst carrier and described catalyst are spherical or class is spherical
Granule.Mean diameter for described catalyst carrier or described catalyst is not particularly limited,
Such as, the mean diameter of described catalyst carrier or described catalyst can be 10-60 μm.
In the present invention, described catalyst carrier and described catalyst can be commonly used in the art urging
Agent carrier and catalyst, such as, described catalyst carrier can be magnesium halide/alcohol adducts, preferably feelings
Under condition, described catalyst carrier is magnesium chloride/alcohol adducts, and described alcohol can be methanol, ethanol, isopropyl
Alcohol, n-butyl alcohol, isobutanol, isoamyl alcohol, n-octyl alcohol, 2-Ethylhexyl Alcohol, ethylene glycol, propylene glycol, chlorine
At least one in ethanol and ethapon, described magnesium halide/alcohol adducts can be by of the prior art
Prepared by method, such as CN1289542C.Described catalyst can be polyolefin commonly used in the art
Catalyst, described polyolefin catalyst can be prepared by method of the prior art, such as
CN1036011C。
In one embodiment, the strength test method of the solid particle of the present invention may include that
(1) quantitative solid particle is mixed with solvent, use separating apparatus or manually rock dispersion
0.5-2min, obtains the mixture containing solid particle；
(2) it is placed in ultrasonic instrument by the mixture containing solid particle that step (1) obtains
Row supersound process, supersound process t1After time, stop ultrasonic or take out hermetic container also from ultrasonic instrument
Rock, draw the mixture containing solid particle of 0.8-1.5mL with dropper, send into particle size analyzer and enter
Row granularity Detection obtains D (t1)；Then hermetic container is proceeded supersound process, supersound process t3、
t2After time, repeat the above steps carries out granularity Detection and obtains D (t2) and D (t3), described D (t1)、
D(t2) and D (t3) use identical cumulative particle sizes percentile；
(3) the intensity index L of solid particle, the calculating of the intensity index L of described solid particle are calculated
Carried out by following formula；
Wherein, the time of described supersound process meets t1＜ t3＜ t2。
Hereinafter will be described the present invention by embodiment.
In following example
Testing graininess is surveyed by the particle size analyzer of Mastersizer 2000 model of Malvern company of Britain
Fixed.
Scanning electron microscope image is by the Flied emission ring of the XL-30 ESEM-FEG model of FEI Co. of the U.S.
Border scanning electron microscope measures.
Ultrasonic instrument is the ultrasound wave of the P70H model of Elmer-Hans schmidbauer Gmbh company
Processor.
Separating apparatus is the separating apparatus of the small volume dispersion unit model of Malvern company.
Preparation example 1
Magnesium chloride/alcohol adducts Z1 is prepared with reference to the method in CN1289542C embodiment 1.
Preparation example 2
Magnesium chloride/alcohol adducts Z2 is prepared with reference to the method in CN1289542C embodiment 2.
Preparation example 3
Polyolefin is prepared with reference to the step (1) of CN1036011C embodiment 1 and the method for (2)
Catalyst C1, and to record Ti content in catalyst be 2.1 weight %.
According to GB6379 catalyst carrier obtained above and catalyst sample carried out Homogeneity Test:
The catalyst carrier prepared for same batch and catalyst respectively take 5 samples, use Malvern granularity to survey
Examination instrument carry out testing graininess, each sample is tested three times under the same conditions and is averaged, respectively to D10,
D50 and D90 carries out the inspection of F statistic.Use mintab16 software that test data are carried out typically
Linear analysis obtains P and adds up value.Acquired results is as follows:
Magnesium chloride/alcohol adducts Z1:P (D10)=0.228, P (D50)=0.495, P (D90)=0.333
Magnesium chloride/alcohol adducts Z2:P (D10)=0.445, P (D50)=0.470, P (D90)=0.604
Alkene catalyst C1:P (D10)=0.501, P (D50)=0.553, P (D90)=0.682
Conclusion: P > F=0.05, so catalyst carrier and catalyst sample are homogeneity samples in granularity dimension
Product, taken sample is representative.
Embodiment 1
(1) in the dry case of glove, by 0.6g catalyst carrier particle (magnesium chloride/alcohol adducts Z1)
Join in 120mL ampere bottle, add the solvent (hexane) of 60mL, then by airtight for ampere bottle,
Use separating apparatus to disperse 0.5min under 1000rpm, obtain the mixture containing catalyst carrier.
(2) mixture containing catalyst carrier that step (1) obtains is placed in ultrasonic instrument,
(t before supersound process1=0), draw the mixture containing catalyst carrier of 1mL with dropper, send into grain
Degree tester carries out granularity Detection and obtains D (0min), is then turned on ultrasonic instrument and carries out supersound process,
Supersound process t3(10min) after, stop ultrasonic, take out ampere bottle and rock, drawing 1mL with dropper
The mixture containing catalyst carrier, send into particle size analyzer and carry out granularity Detection and obtain D (10min)；
The most again ampere bottle is placed in ultrasonic instrument and proceeds supersound process, supersound process t2(20min)
After, stop ultrasonic and draw 1mL with dropper the mixture repeat the above steps containing catalyst carrier
Carry out granularity Detection and obtain D (20min).Wherein, the condition of described supersound process includes: ultrasonic frequency
Rate is 37KHz, and temperature is 25 DEG C.When granularity Detection detection cumulative particle sizes percentile is 50%
Granularity, acquired results is as shown in table 1.
(3) intensity calculating catalyst carrier particle by following formula according to the granularity of step (2) gained refers to
Number L,
The intensity index L of gained catalyst carrier particle is as shown in table 1.
Embodiment 2
(1) in the dry case of glove, 1g catalyst carrier particle (magnesium chloride/alcohol adducts Z2) is added
Enter in 120mL ampere bottle, add the solvent (hexane) of 50mL, then by airtight for ampere bottle,
Use separating apparatus to disperse 0.5min under 1000rpm, obtain the mixture containing catalyst carrier.
(2) mixture containing catalyst carrier that step (1) obtains is placed in ultrasonic instrument,
(t before supersound process1=0), draw the mixture containing catalyst carrier of 0.8mL with dropper, send into
Particle size analyzer carries out granularity Detection and obtains D (0min), is then turned on ultrasonic instrument and carries out ultrasonic place
Reason, supersound process t3(10min) after, stop ultrasonic, take out ampere bottle and rock, drawing with dropper
The mixture containing catalyst carrier of 0.8mL, feeding particle size analyzer carries out granularity Detection and obtains D
(10min)；The most again ampere bottle is placed in ultrasonic instrument and proceeds supersound process, ultrasonic place
Reason t2(20min), after, ultrasonic and draw 0.8mL with dropper the mixing containing catalyst carrier is stopped
Thing, repeat the above steps carries out granularity Detection and obtains D (20min).Wherein, the bar of described supersound process
Part includes: ultrasonic frequency is 80KHz, and temperature is 30 DEG C.Granularity Detection cumulative particle sizes distribution percentage
Number is granularity when 50%, and acquired results is as shown in table 1.
(3) intensity calculating catalyst carrier particle by following formula according to the granularity of step (2) gained refers to
Number L,
The intensity index L of gained catalyst carrier particle is as shown in table 1.
Embodiment 3
(1) in the dry case of glove, 0.6g catalyst granules (polyolefin catalyst C1) is joined
In 120mL ampere bottle, then the solvent (hexane) of 60mL, then by airtight for ampere bottle, use manually
Rock dispersion 1min, obtain the mixture containing catalyst.
(2) mixture containing catalyst that step (1) obtains is placed in ultrasonic instrument, super
(t before sonication1=0), draw the mixture containing catalyst of 1.5mL with dropper, send into granularity and survey
Examination instrument carries out granularity Detection and obtains D (0min), is then turned on ultrasonic instrument and carries out supersound process, super
Sonication t3(10min) after, stop ultrasonic, take out ampere bottle and rock, drawing 1.5mL with dropper
The mixture containing catalyst, send into particle size analyzer and carry out granularity Detection and obtain D (10min)；So
After ampere bottle is placed in ultrasonic instrument proceeds supersound process again, supersound process t2(20min)
After, stopping ultrasonic and draw 1.5mL with dropper the mixture containing catalyst, repeat the above steps is entered
Row granularity Detection obtains D (20min).Wherein, the condition of described supersound process includes: ultrasonic frequency
For 37KHz, temperature is 20 DEG C.Granularity Detection cumulative particle sizes percentile is granularity when 50%,
Acquired results is as shown in table 1.
(3) pass through following formula according to the granularity of step (2) gained and calculate the intensity index L of catalyst granules,
The intensity index L of gained catalyst granules is as shown in table 1.
Embodiment 4
According to the method for embodiment 1, except that, the addition of solvent (hexane) is 100mL.
In step (2), granularity Detection detection cumulative particle sizes percentile is granularity when 50%, institute
Obtain result as shown in table 1.
Granularity according to step (2) gained calculates the intensity index L of solid particle by following formula,
The intensity index L of gained solid particle is as shown in table 1.
Embodiment 5
According to the method for embodiment 1, except for the difference that, the accumulative grain of granularity Detection detection in step (2)
Degree percentile is granularity when 10%, and acquired results is as shown in table 1.
Granularity according to step (2) gained calculates the intensity index L of solid particle by following formula,
The intensity index L of gained solid particle is as shown in table 1.
Embodiment 6
According to the method for embodiment 1, except for the difference that, the accumulative grain of granularity Detection detection in step (2)
Degree percentile is granularity when 90%, and acquired results is as shown in table 1.
Granularity according to step (2) gained calculates the intensity index L of solid particle by following formula,
The intensity index L of gained solid particle is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| D(t1) | 49.1 | 51.7 | 50.0 | 49.9 | 32.6 | 74.8 |
| D(t2) | 45.5 | 47.7 | 45.9 | 44.9 | 24.7 | 66.3 |
| D(t3) | 47.3 | 48.5 | 46.7 | 47.2 | 26.6 | 70.1 |
| L | 0.076 | 0.082 | 0.088 | 0.105 | 0.297 | 0.121 |
Test case
1, stability checking
Supersound process 0-30min will be carried out, often with a batch of 9 samples with embodiment 1 specimen in use
Carry out primary particle size detection every 5min, and to record cumulative particle sizes percentile be 10%, 50% and 90%
Time granularity, wherein, the condition of supersound process is same as in Example 1.Acquired results such as table 2, table 3
Shown in table 4.
Table 2
Table 3
Table 4
As can be seen from the above table, numerical value is occurred to become with a batch of 9 samples D10 in 20-25min
Change big compared with D50 and D90, and D50 along with ultrasonic time increase and Changing Pattern becomes apparent from, and
And the D50 change of numerical value and precision 2-3 μm of particle size analyzer during 9 reperformance tests
Close.Therefore, D50 data are more stable, use repeated more preferable, the stability of its intensity calculated
Higher.
2, reliability demonstration
Method according to preparation example 1 prepares two batches of magnesium chlorides/alcohol adducts Z3 and magnesium chloride/alcohol adducts
Z4, carries out intensity survey to above-mentioned magnesium chloride/alcohol adducts Z3 and Z4 respectively according to the method for embodiment 1
Examination, and in test process to magnesium chloride/alcohol adducts Z3 and Z4 supersound process 10min, 20min after
It is scanned testing electronic microscope respectively.By calculating, magnesium chloride/alcohol adducts Z3's and Z4 is strong
Degree index is respectively 0.136 and 0.067, and the scanning electron microscope image after supersound process 10min, 20min is such as
Shown in Fig. 1-Fig. 4.
Above-mentioned magnesium chloride/alcohol adducts is used for the synthesis of polyolefin catalyst (with reference to CN1036011C
The synthetic method of catalyst), and the catalyst of magnesium chloride/alcohol adducts Z3 synthesis is designated as sample A and
The catalyst of magnesium chloride/alcohol adducts Z4 synthesis is designated as sample B.By catalyst sample A and sample B
Carry out polyreaction according to following polymerization respectively, and obtained polymer is sieved, institute
Obtain distribution of polymer result as shown in table 5.
Polymerization is: polymerisation in bulk is carried out in 5L stainless steel cauldron, fully puts through propylene steam
After changing, it is sequentially added into 0.5mmol/ml triethyl aluminum hexane solution 3ml, 0.1mmol/ml CHMMDMS
1ml, 15mg catalyst and hydrogen, be subsequently adding propylene liguid 2.3L, is warming up to 70 DEG C, reaction pressure
Power maintains 3.0MPa, reacts 1h, cooling, release, obtains polypropylene.Catalyst activity is with every gram
The polyacrylic quality meter that catalyst obtains.
Under the same terms, the polyreaction that sample A participates in obtains polymer 710g, and catalyst activity is
59167g polymer/g catalyst；The polyreaction that sample B participates in obtains polymer 750g, catalyst
Activity is 62500g polymer/g catalyst.
Table 5
By Fig. 1 Yu Fig. 2, Fig. 3 Yu Fig. 4 contrast it can be seen that through the ultrasonic place of identical time
Magnesium chloride after reason/alcohol adducts Z3 crushes even more serious, namely this sample strength is lower, with the present invention
The intensity index greater strength that strength test draws is the lowest consistent.Further, should from magnesium chloride/alcohol adducts
For synthetic catalyst and for polyreaction acquired results it can be seen that the little magnesium chloride of intensity index/
The catalyst activity that alcohol adducts Z4 obtains is higher, and the polymer degree of crushing that its catalysis obtains is lower.
Therefore, the method for testing of the solid intensity that the present invention provides can reliably represent the intensity of solid particle.
3, the test of precision
Method according to preparation example 1 prepares magnesium chloride/alcohol adducts Z5, according to GB6379.4 with chlorination
Magnesium/alcohol adducts Z5 is the test that sample carries out method precision, and precision represents with relative extreme difference.
Wherein, strength test method and process are same as in Example 1.Repeat test and calculate intensity index L,
Acquired results is as shown in table 6.
Table 6
According to the data of table 6, can be by the essence of the method for testing of sample magnesium chloride/alcohol adducts Z5 intensity
Density is defined as 0.7.
The checking of method precision: prepare 22 batch magnesium chlorides/alcohol adducts according to the method for preparation example 1
Z6-Z27, and the magnesium chloride of 22 batches/alcohol adducts Z6-Z27 is carried out according to the method for embodiment 1
Strength test, acquired results is as shown in table 7, and wherein, each Data duplication is surveyed twice, thus to accrued
Calculate two intensity index L1And L2。
Table 7
| Batch | L1 | L2 | Average | Extreme difference | Extreme difference relatively |
| Z6 | 0.077 | 0.082 | 0.0795 | 0.005 | 0.063 |
| Z7 | 0.067 | 0.065 | 0.066 | 0.002 | 0.030 |
| Z8 | 0.072 | 0.075 | 0.0735 | 0.003 | 0.041 |
| Z9 | 0.026 | 0.045 | 0.0355 | 0.019 | 0.535 |
| Z10 | 0.034 | 0.042 | 0.038 | 0.008 | 0.211 |
| Z11 | 0.114 | 0.12 | 0.117 | 0.006 | 0.051 |
| Z12 | 0.065 | 0.07 | 0.0675 | 0.005 | 0.074 |
| Z13 | 0.049 | 0.05 | 0.0495 | 0.001 | 0.020 |
| Z14 | 0.29 | 0.282 | 0.286 | 0.008 | 0.028 |
| Z15 | 0.136 | 0.124 | 0.13 | 0.012 | 0.092 |
| Z16 | 0.106 | 0.124 | 0.115 | 0.018 | 0.157 |
| Z17 | 0.091 | 0.084 | 0.0875 | 0.007 | 0.080 |
| Z18 | 0.061 | 0.069 | 0.065 | 0.008 | 0.123 |
| Z19 | 0.077 | 0.064 | 0.0705 | 0.013 | 0.184 |
| Z20 | 0.098 | 0.095 | 0.0965 | 0.003 | 0.031 |
| Z21 | 0.048 | 0.066 | 0.057 | 0.018 | 0.316 |
| Z22 | 0.06 | 0.071 | 0.0655 | 0.011 | 0.168 |
| Z23 | 0.105 | 0.097 | 0.101 | 0.008 | 0.079 |
| Z24 | 0.089 | 0.08 | 0.0845 | 0.009 | 0.107 |
| Z25 | 0.138 | 0.121 | 0.1295 | 0.017 | 0.131 |
| Z26 | 0.081 | 0.089 | 0.085 | 0.008 | 0.094 |
| Z27 | 0.116 | 0.114 | 0.115 | 0.002 | 0.017 |
As shown in table 7, the contrast pole difference data of 22 batch strength test index L all < 0.7, thus illustrate
The assay method of the solid particle intensity that the present invention provides has high precision.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a method of testing for solid particle intensity, described solid particle be catalyst carrier particle or
Catalyst granules, the method includes:
(1) solid particle is mixed with solvent, obtain the mixture containing solid particle；
(2) mixture containing solid particle that step (1) obtains is carried out supersound process, and to super
Sonication t1、t2、t3Solid particle after time carries out granularity Detection, obtains granularity D (t1)、D(t2)
With D (t3), described D (t1)、D(t2) and D (t3) use identical cumulative particle sizes percentile；
(3) the intensity index L of solid particle, the calculating of the intensity index L of described solid particle are calculated
Carried out by following formula (1)；
Wherein, the time of described supersound process meets t1＜ t3＜ t2。
Method the most according to claim 1, wherein, the consumption of described solvent makes described solid
Granule is immersed in described solvent.
Method the most according to claim 1 and 2, wherein, described in be blended in airtight container
Carrying out, relative to the described solid particle of 1g, the usage amount of described solvent is 50-100mL.
4. according to the method described in any one in claim 1-3, wherein, described solvent is C6-12
Alkane in one or more；Under preferable case, described solvent is hexane.
Method the most according to claim 1, wherein, the condition of described supersound process includes: super
The frequency of sound is 30-80kHz, and temperature is 20-50 DEG C；Under preferable case, temperature is 20-30 DEG C.
Method the most according to claim 1, wherein, described t1=0, t3=t2/2。
Method the most according to claim 6, wherein, t2=10-60min, under preferable case,
t2=20min.
Method the most according to claim 1, wherein, described D (t1)、D(t2) and D (t3)
Being granularity during 10-90% for cumulative particle sizes percentile, preferably cumulative particle sizes percentile is
Granularity when 50%.
9. wanting the method described in 1 according to right, wherein, described catalyst carrier is magnesium chloride/alcohol adduction
Thing, described catalyst is polyolefin catalyst.
10. according to the method described in claim 1 or 9, wherein, described catalyst carrier or described in urge
The particle mean size of agent is respectively 10-60 μm.
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Citations (1)
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| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
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| CN1718595A (en) * | 2004-07-05 | 2006-01-11 | 中国石油化工股份有限公司 | Globular catalyst component used for olefine polymerization and its catalyst |
Non-Patent Citations (9)
| Title |
|---|
| JIUCHUN YAN, ETC.: "Ultrasonic assisted fabrication of particle reinforced bonds joining aluminum metal matrix composites", 《MATERIALS AND DESIGN》 * |
| 上海科学技术情报研究所: "《国外塑料动态》", 30 April 1974 * |
| 夏洁洁等: "超声波法研究F-T合成铁基催化剂机械强度", 《工业催化》 * |
| 张长森等: "《粉体技术及设备》", 31 January 2007 * |
| 李慧等: "热处理温度对钽粉性能的影响", 《研发与应用》 * |
| 李慧等: "钽粉颗粒强度的研究", 《稀有金属快报》 * |
| 王明德等: "《物理化学实验》", 30 September 2013 * |
| 谢小鹏: "基于实验数据的磨损量计算方法", 《机械科学与技术》 * |
| 马海燕等: "激光粒度仪在测定钽粉粒度分布中的应用", 《宁夏工程技术》 * |
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