CN106770452B - A method of catalyst is evaluated using thermal analysis system - Google Patents
A method of catalyst is evaluated using thermal analysis system Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002076 thermal analysis method Methods 0.000 title claims abstract description 9
- 238000012360 testing method Methods 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011156 evaluation Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 239000013558 reference substance Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000010926 purge Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000012512 characterization method Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000010429 evolutionary process Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001629 sign test Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/22—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on combustion or catalytic oxidation, e.g. of components of gas mixtures
Abstract
A kind of method using thermal analysis system evaluation catalyst provided by the invention, pass through the differential thermal information of the catalyst of continuous detection temperature programmed reduction in situ and this pair of temperature programmed oxidation during opposite, the TPR-TPO-DTA test result of known catalytic performance sample and unknown catalytic performance sample can be obtained, further according to the relative size of the two difference of the summit temperature of respective initial peak in TPR-DTA and TPO-DTA curve, in conjunction with the catalytic performance of known sample, the catalytic performance of unknown sample under the same reaction conditions is judged.
Description
Technical field
The present invention relates to a kind of methods for evaluating catalyst performance, and in particular to a kind of to evaluate catalyst using thermal analysis system
Method.
Background technique
Various catalyst, especially various metals and metal-modified catalyst are in coal chemical industry, gas chemical industry and C1ization
It learns and is widely used in chemical engineering industry, such as Raney nickel used in methanation, the catalysis of iron used in F- T synthesis
Agent and Co catalysts, modified copper catalyst etc. used in one-step method from syngas preparation of dimethyl ether.Using different process conditions,
It is equally the available multifarious product using synthesis gas as raw material using different catalyst.Some reaction products are more
For hydro carbons, some reactions then tend to generate oxycompound.This is because metal has different redox characteristics, make
At H species and O species, Competition Evolutionary process is multifarious on the surface of different metal catalyst, this spy of different catalysts
Property on difference, be largely fixed them when reacting under synthesizing atmosphere, the whole selectivity of reaction product.Work as catalysis
In the various elementary reactions carried out on agent surface, when elementary reaction relevant to H species is dominant, C species are several in conjunction with O species
Rate is small, and hydro carbons accounts for absolutely leading in product；And if C species have more maximum probability when elementary reaction relevant to O species is dominant
In conjunction with O species, C-O key is formed, generates the oxygen containing compounds such as alcohol, aldehyde, ketone, acid, ester.So can be by online in situ
Oxidation and the reducing property for continuously detecting same catalyst sample quickly judge, screen out substantially urging for unknown catalyst sample
Change performance, realizes the quick screening of catalyst.
In order to analyze the reason of leading to different catalysts performance difference, need to carry out characterization test to catalyst sample,
Different characterizing methods provides some characteristics of the catalyst under various process.In miscellaneous characterization method, some tables
The process of sign means is opposite process, and e.g., in characterization test process first, the state of catalyst sample becomes B from A, and
In characterization test process second, the state of catalyst sample is to become A from B, and such process first and second are just each other with respect to process.
In the analytic process of these existing characterization methods, every kind characterization during parameter setting be all to pass through it is excellent
Change screening, to realize that maximum precision and resolution ratio, such as the amount of sample, the heating rate of sample room handle gas
Concentration, flow etc.；Certain characterization test that different parameter settings will lead to the same sample provides different analyses as a result, example
Such as, in temperature programmed reduction (TPR) characterization test, when heating rate is set as faster parameter, may cover it is some compared with
The reduction peak occurred under slow heating rate.The reason of generating above-mentioned phenomenon be, the direct shadow of the parameter setting in characterization method
Ring dynamic (dynamical) process that tested sample is undergone in the characterization, in other words, the specific power that caltalyst reveals
Learn parameter setting when characteristic is controlled by characterization test.The main purpose of existing characterization method is to compare different catalysts
The series of results that some the best characterization parameter of sample in some characterization method obtains under conditions of setting, judges catalyst
Influence of some feature to catalytic performance.Such representation pattern, for analyzing a large amount of catalyst samples in certain single table
Performance in sign test is largely effective；But due to the difference of the procedure parameter setting in different characterization methods, cause same urge
The connection that comparison can not be established between the result of the different characterization methods of agent sample (as mentioned above, is not excluding
Under the premise of influencing in terms of parameter setting difference bring dynamics, the different characterization results for comparing same sample lack reasonability
And operability.Such situation is particularly evident between the characterization test means of opposite process-type.Due to beginning and end it
Between mutual inversion corresponding relationship also have operability so that the characterization test result of relatively opposite process-type is not only valuable,
As long as establishing the characterization test carried out under same external dynamics feature architecture, result has comparativity.
Summary of the invention
Thermal analysis method is utilized the object of the present invention is to provide a kind of, and will aoxidize and restore this pair of opposite process group
The method of the catalytic performance characterization carried out altogether.In characterization, it will aoxidize and restore this pair of opposite process and combine,
And all parameters (nature parameters and composition parameter in addition to handling gas) setting during making every kind is consistent, is established with this
The phenetic analysis method got up, because, during sample experience, it is only possible to there are the differences of chemical atmosphere, and other
Physical parameter relevant with dynamics, such as starting and finishing temperature, rate of temperature change handle gas velocity, gas pressure
Deng, it is all just the same, so, both can be connected with respect to the data of the characterization result of process and be compared, and from
In obtain more advanced information.From the above mentioned, catalyst performance characterizing method provided by the invention, can compare oxidationreduction
The different performance of same catalyst during opposite, and the result of traditional characterization test can only characterize every kind of evaluation and test
Performance difference in journey between different catalyst samples.
Specifically, the combination for oxidization-reduction type with respect to process, by traditional, individual temperature programmed reduction (TPR)
It is connected with temperature programmed oxidation (TPO) means, cooperates suction/heat release letter during thermal analyzer tracing detection TPR-TPO
Breath forms and carries out follow-on test in situ, that is, TPR-TPO-DTA to same catalyst sample using differential thermal analysis,
In the test process of TPR-TPO-DTA, in addition to the type property of processing gas is different, other all parameters of setting TPR and TPO are protected
It holds unanimously, the DTA curve of the TPR and TPO that obtain on this basis can carry out numerical value comparative analysis, same further to dissect
Sample generates the reason of difference and these differences in TPR and TPO and will cause which type of influence to catalytic performance, can also benefit
The performance difference shown in TPR-TPO-DTA test with different catalyst samples, characterizes the correlated performance of different samples.
Catalyst is tested in the atmosphere of synthesis gas (gaseous mixture of hydrogen and carbon monoxide) using the method for TPR-TPO-DTA
In catalytic performance when, specific process can be as follows, and the catalyst sample of 1mg-10g is put into the sample cell of thermal analyzer
(inertia reference substance, such as corundum are put into the reference cell of thermal analyzer), first with containing O2Inert gas (such as O2/N2、O2/Ar、O2/
He) sample and reference substance are pre-processed in 400 DEG C of warm areas below；Temperature programming is carried out also first after pretreatment
The analysis test of former (TPR), is passed through containing H simultaneously into sample cell and reference substance pond2Reducibility gas (such as H2/N2、H2/
Ar、H2/ He), with the speed of 1K/min-10K/min to sample cell and reference cell temperature programming, thermal analyzer is recorded during this
The temperature signal of sample and reference substance, forming TPR-DTA curve, (using temperature as abscissa, sample and the reference substance temperature difference are vertical sit
Target curve)；After TPR process analysis procedure analysis, be passed through inert purge gas into sample cell and reference cell, cool to 60 DEG C with
Under, hand-off process gas is O2/N2、O2/ Ar or O2/ He etc. contains O2Oxidizing gas, with TPR analyze in identical parameter setting
The analysis test for carrying out TPO, obtains TPO-DTA curve；Last inert gas purge cooling, terminates TPR-TPO-DTA test.
Carry out that detailed process is as follows when catalyst performance judges with the TPR-TPO-DTA test data of acquisition, if sample A
For the catalyst sample of known catalytic performance, B is the catalyst sample of unknown performance, THAAnd TOARespectively A sample TPR-DTA
The summit temperature (abscissa in curve at summit) of initial peak, T in curve and TPO-DTA curveHBAnd TOBRespectively B sample
The summit temperature of initial peak in TPR-DTA curve and TPO-DTA curve.In conjunction with the summit of initial peak in each sample test curve
The relative size of difference between temperature, and referring to the performance of known sample A, judge the catalytic performance trend of unknown sample B.
Judging rules are as follows: work as TOB-THB≥TOA-THA>=0, and when the catalytic selectivity of A is to generate hydro carbons as trend, it is unknown
The selectivity of the reaction product of sample B is also more generation hydro carbons；Work as THB-TOB≥THA-TOA>=0, and the catalytic selectivity of A with
When generation oxygenatedchemicals is trend, the selectivity of the reaction product of unknown sample B is also more generation oxygenatedchemicals.It can not
Strictly meet in other situations of above-mentioned rule, method provided by the invention cannot be used to determine the performance of catalyst.
A kind of method using thermal analysis system evaluation catalyst provided by the invention passes through continuous detection catalyst sample in situ
Differential thermal signal (TPR-TPO-DTA) of product during temperature programmed reduction and temperature programmed oxidation, in conjunction with provided by the invention
Judging rules, can be with performance trend of Fast Evaluation catalyst when containing using in synthesis gas atmosphere.
Specific embodiment
The present invention is further detailed below in conjunction with embodiment, the following examples are only used for explaining in detail
Illustrate the present invention, does not limit the scope of the invention in any way.
Embodiment 1
The A of known catalytic performance is HTB-1H hydrogenation catalyst (Liaoning Haitai development in science and technology Co., Ltd), it is known that A passes through
290 DEG C, H2After handling activation in 4 hours, in H2/ CO=3, pressure 2.1MPa, when reacting at 285 DEG C of temperature, CH in product4Selection
Property be 79%, i.e. A be under the above-described reaction conditions it is a kind of tend to selection generate hydro carbons catalyst.
Unknown catalytic performance B's the preparation method comprises the following steps: weigh through 600 DEG C roast 4 hours after 100 grams of alumina support,
By 126 grams of nickel nitrate [Ni (NO3)2·6H2O], 1.7 grams of ammonium metatungstate [(NH4)6H2W12O40·xH2O] and 2.7 grams of yttrium nitrates
[YNO3·6H2O] with deionized water altogether it is molten after be impregnated on alumina support；It is each at being dried 5 hours, 300 DEG C and 450 DEG C at 110 DEG C
It decomposes 2 hours, being formed (weight %) is nickeliferous 20%, tungsten 1.0%, the B of yttrium 0.5%.
Carry out continuous TPR-TPO-DTA test in situ, the differential thermal signal limited public affairs of capital instrument high-tech instrument respectively to A and B
Department's ZCR-A differential thermal analyzer provides.The testing procedure and parameter of A and B is to weigh the sample (20-30 mesh) of 0.5g to be put into differential thermal
The sample cell of analyzer is put into the corundum in granules of same mesh number in reference cell, while into sample cell and reference cell with 5L/min
Flow be passed through O2/N2The gas of=1mol/19mol, temperature programming (rise to 120 DEG C at room temperature with 20K/min, after being kept for 1 hour
200 DEG C are risen to the rate of 10K/min, is warming up to 300 DEG C again after being kept for 1 hour with the rate of 5K/min, after being kept for 1.5 hours
Be warming up to 400 DEG C with the rate of 5K/min) to 400 DEG C keep 0.5 hour after, stop heating, when temperature is down to 120 DEG C or less
Afterwards, N is switched to2Purging, system, which continues to cool in 60 DEG C of backward sample cells and reference cell, is passed through H2/N2=1mol/9mol's is mixed
Gas is closed, flow 2L/min starts simultaneously at temperature programming, from 60 DEG C, stops adding after rising to 820 DEG C with the rate of 10K/min
Heat, thermal analyzer record differential thermal signal forms TPR-DTA curve therebetween (the above are TPR-DTA test process)；System is through course
After sequence heating reduction process, then use N2Purging cools to 60 DEG C, the TPO-DTA test of start program heating and oxidation, to sample cell
O is passed through with the flow of 2L/min in reference cell2/N2The gas of=1mol/9mol, starts simultaneously at temperature programming, from 60 DEG C,
Stop heating (it can be seen that being consistent in parameter setting and TPR in TPO) after rising to 820 DEG C with the rate of 10K/min,
Between thermal analyzer record differential thermal signal formed TPO-DTA curve.
TPR-TPO-DTA test result shows, THA=249 DEG C, TOA=271 DEG C, THB=258 DEG C, TOB=293℃.Because of TOB-
THB(35) > TOA-THA(22) 0 >, and the catalytic selectivity of A with generate hydro carbons be it is leading, therefore, it is determined that the catalysis of unknown B sample
It reacts more more options and generates hydro carbons.As verifying, B passes through 290 DEG C, H2After handling activation in 4 hours, in H2/ CO=3, pressure
2.1MPa, when reacting at 285 DEG C of temperature, CH in product4Selectivity be 69%, be not detected as alcohols, ethers etc. containing oxidation
Object.
Embodiment 2
Commercially available MS-2 methanol synthesis catalyst (Liaoning Haitai development in science and technology Co., Ltd) is as known catalytic performance
Sample A, commercially available TMF-95 furfural hydrogenation dimethyl furan catalyst (Liaoning Haitai development in science and technology Co., Ltd) is not as
Know the sample B of catalytic performance.
Known A passes through 268 DEG C, H2After handling activation in 4 hours, in H2/ CO=2, pressure 3.5MPa react at 260 DEG C of temperature
When, CH in product3The selectivity of OH is 84%, i.e. A is a kind of trend selection generation oxycompound (alcohol under the above-described reaction conditions
Class) catalyst.
Carry out continuous TPR-TPO-DTA test in situ, the differential thermal signal limited public affairs of capital instrument high-tech instrument respectively to A and B
Department's ZCR-A differential thermal analyzer provides.The testing procedure and parameter of A and B is to weigh the sample (20-30 mesh) of 1g to be put into differential thermal point
The sample cell of analyzer is put into the corundum in granules of same mesh number in reference cell, while into sample cell and reference cell with 10L/min's
Flow is passed through O2/N2The gas of=1mol/9mol, temperature programming (rise to 120 DEG C at room temperature with 20K/min, after being kept for 1 hour with
The rate of 10K/min rises to 200 DEG C, is warming up to 300 DEG C again after being kept for 1 hour with the rate of 5K/min, after being kept for 1.5 hours with
The rate of 5K/min is warming up to 350 DEG C) to 350 DEG C keep 0.5 hour after, stop heating, after temperature is down to 120 DEG C or less,
Switch to N2Purging, system, which continues to cool in 60 DEG C of backward sample cells and reference cell, is passed through H2/N2The mixing of=1mol/19mol
Gas, flow 1.5L/min, starts simultaneously at temperature programming, from 60 DEG C, stops adding after rising to 770 DEG C with the rate of 10K/min
Heat, thermal analyzer record differential thermal signal forms TPR-DTA curve therebetween (the above are TPR-DTA test process)；System is through course
After sequence heating reduction process, then use N2Purging cools to 60 DEG C, the TPO-DTA test of start program heating and oxidation, to sample cell
O is passed through with the flow of 1.5L/min in reference cell2/N2The gas of=1mol/19mol, starts simultaneously at temperature programming, goes out from 60 DEG C
Hair stops heating (it can be seen that keeping one in parameter setting and TPR in TPO after rising to 770 DEG C with the rate of 10K/min
Cause), thermal analyzer record differential thermal signal forms TPO-DTA curve therebetween.
The test result of TPR-TPO-DTA shows, THA=251 DEG C, TOA=236 DEG C, THB=270 DEG C, TOB=246℃.Because
THB - TOB(24) > THA - TOA(15) 0 >, and the catalytic selectivity of A is leading to generate oxycompound, therefore, it is determined that not
Know that the catalysis reaction more more options of B sample generate oxycompound.As verifying, B passes through 268 DEG C, H2After handling activation in 4 hours,
In H2/ CO=2, pressure 3.5MPa, when reacting at 260 DEG C of temperature, CH in product3The selectivity of OH is 64%, that is to say, that in product
It is more oxygen-containing class.
Claims (3)
1. a kind of method using thermal analysis system evaluation catalyst, for quickly judging that unknown catalyst is containing synthesis gas atmosphere
The selective trend of product when middle use, which is characterized in that pass through continuous detection temperature programmed reduction in situ and temperature programming oxygen
The differential thermal information of catalyst during changing this pair relatively, can obtain known catalytic performance sample and unknown catalytic performance sample
The TPR-TPO-DTA test result of product, further according to the summit of the two respective initial peak in TPR-DTA and TPO-DTA curve
The relative size of the difference of temperature judges unknown sample under the same reaction conditions in conjunction with the catalytic performance of known sample
Catalytic performance；Detailed process is as follows, if sample A is the catalyst sample of known catalytic performance, B is the catalyst of unknown performance
Sample, THAAnd TOAThe summit temperature of initial peak respectively in A sample TPR-DTA curve and TPO-DTA curve, that is, curve
Abscissa at middle summit, THBAnd TOBThe summit temperature of initial peak respectively in B sample TPR-DTA curve and TPO-DTA curve
Degree；Work as TOB-THB≥TOA-THA>=0, and when the catalytic selectivity of A is to generate hydro carbons as trend, the reaction product of unknown sample B
Selectivity also generates hydro carbons to be more；Work as THB-TOB≥THA-TOA>=0, and the catalytic selectivity of A is to become to generate oxygenatedchemicals
When gesture, the selectivity of the reaction product of unknown sample B is also more generation oxygenatedchemicals.
2. a kind of method using thermal analysis system evaluation catalyst according to claim 1, it is characterised in that carry out TPR-
When TPO-DTA analysis test, in addition to the type property of processing gas is different, other all parameters are kept during TPR and TPO is arranged
Unanimously.
3. a kind of method using thermal analysis system evaluation catalyst according to claim 1, it is characterised in that TPR-TPO-
DTA analysis test the specific steps are, the catalyst sample of 1mg-10g is put into the sample cell of thermal analyzer, and heat point
It is put into inertia reference substance corundum in the reference cell of analyzer, first uses O2/N2、O2/ Ar or O2/ He is right in 400 DEG C of warm areas below
Sample and reference substance are pre-processed；The analysis test for carrying out temperature programmed reduction (TPR) after pretreatment first, to sample
H is passed through in pond and reference substance pond simultaneously2/N2、H2/ Ar or H2/ He, with the speed of 1K/min-10K/min to sample cell and reference
Pond temperature programming, thermal analyzer record the temperature signal of sample and reference substance during this, form TPR-DTA curve, the curve
Using temperature as abscissa, using sample and the reference substance temperature difference as ordinate；After TPR process analysis procedure analysis, to sample cell and reference cell
In be passed through inert purge gas, cool to 60 DEG C hereinafter, hand-off process gas be O2/N2、O2/ Ar or O2/ He, in analyzing with TPR
Identical parameter setting carries out the analysis test of TPO, obtains TPO-DTA curve；Last inert gas purge cooling, terminates TPR-
TPO-DTA test.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710056828.2A CN106770452B (en) | 2017-01-26 | 2017-01-26 | A method of catalyst is evaluated using thermal analysis system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710056828.2A CN106770452B (en) | 2017-01-26 | 2017-01-26 | A method of catalyst is evaluated using thermal analysis system |
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| Publication Number | Publication Date |
|---|---|
| CN106770452A CN106770452A (en) | 2017-05-31 |
| CN106770452B true CN106770452B (en) | 2019-05-28 |
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Citations (4)
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| CN1490620A (en) * | 2003-08-26 | 2004-04-21 | 上海师范大学 | Catalyst surface-characteristic comprehensive measuring device and application thereof |
| CN104020261A (en) * | 2014-06-19 | 2014-09-03 | 赵锦玲 | Method for testing selectivity of catalyst |
| CN204314248U (en) * | 2014-12-10 | 2015-05-06 | 中国石油天然气股份有限公司 | A kind of temperature programme adsorption/desorption system and reaction unit thereof |
| CN106018664A (en) * | 2016-08-16 | 2016-10-12 | 王宏铭 | Method for evaluating inactivation performance of nickel catalyst in laboratory |
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| CN1490620A (en) * | 2003-08-26 | 2004-04-21 | 上海师范大学 | Catalyst surface-characteristic comprehensive measuring device and application thereof |
| CN104020261A (en) * | 2014-06-19 | 2014-09-03 | 赵锦玲 | Method for testing selectivity of catalyst |
| CN204314248U (en) * | 2014-12-10 | 2015-05-06 | 中国石油天然气股份有限公司 | A kind of temperature programme adsorption/desorption system and reaction unit thereof |
| CN106018664A (en) * | 2016-08-16 | 2016-10-12 | 王宏铭 | Method for evaluating inactivation performance of nickel catalyst in laboratory |
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