CN106770452A - A kind of method that utilization thermal analysis system evaluates catalyst - Google Patents
A kind of method that utilization thermal analysis system evaluates catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 41
- 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 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000001514 detection method Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 238000004458 analytical method Methods 0.000 claims description 13
- 239000013558 reference substance Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 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
- 239000011261 inert gas Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 244000148755 species properties Species 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 20
- 238000010438 heat treatment Methods 0.000 description 9
- 241000894007 species Species 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 230000004913 activation Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 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
- 230000000630 rising effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical class 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
- -1 C-O keys Chemical class 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 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
- 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
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000010429 evolutionary process Effects 0.000 description 1
- 230000007717 exclusion 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The method that a kind of utilization thermal analysis system that the present invention is provided evaluates catalyst, by continuous detection temperature programmed reduction in situ and the differential thermal information of this pair catalyst with respect to during of temperature programmed oxidation, the TPR TPO DTA test results of known catalytic performance sample and unknown catalytic performance sample can be obtained, further according to the relative size of the difference of the summit temperature of both respective initial peaks in TPR DTA and TPO DTA curves, with reference to the catalytic performance of known sample, unknown sample catalytic performance under the same reaction conditions is judged.
Description
Technical field
The present invention relates to a kind of method for evaluating catalyst performance, and in particular to one kind evaluates catalyst using thermal analysis system
Method.
Background technology
Various catalyst, especially various metals and metal-modified catalyst are in Coal Chemical Industry, gas chemical industry and C1ization
It is widely used in chemical engineering industry, such as the Raney nickel used in methanation, the iron used in F- T synthesis is catalyzed
Agent and Co catalysts, the modified copper catalyst used in one-step method from syngas preparation of dimethyl ether etc..Using different process conditions,
Equally it is the product that can be but varied with synthesis gas as raw material using different catalyst.Some product are more
It is hydro carbons, some reactions then tend to generate oxycompound.This is, because metal has different redox characteristics, to make
Into H species and O species, Competition Evolutionary process varies on the surface of different metal catalyst, this spy of different catalysts
Property on difference, be largely fixed them when being reacted under synthesizing atmosphere, the overall selectivity of product.Work as catalysis
In the various elementary reactions carried out on agent surface, when the elementary reaction related to H species is dominant, C species are several with what O species were combined
Rate is small, and hydro carbons accounts for definitely leading in product；And if when the elementary reaction related to O species is dominant, C species have more maximum probability
Combined with O species, formed the oxygen containing compounds such as C-O keys, generation alcohol, aldehyde, ketone, acid, ester.So, can be by online in situ
Oxidation and the reducing property of same catalyst sample are continuously detected, quickly judged, screened out substantially urging for unknown catalyst sample
Change performance, realize the quick screening of catalyst.
In order to analyze the reason for causing different catalysts performance difference, it is necessary to carry out characterization test to catalyst sample,
Different characterizing methods provides some characteristics of catalyst under various process.In miscellaneous characterization method, some tables
The process for levying means is relative process, and e.g., in characterization test process first, the state of catalyst sample is changed into B from A, and
In characterization test process second, the state of catalyst sample is to be changed into A from B, and such process first and second are just each other with respect to process.
During the analysis of existing these characterization methods, the parameter setting during every kind of sign is all will be by excellent
Change screening, to realize maximum precision and resolution ratio, the amount of such as sample, the heating rate of sample room locates qi-regulating
Concentration, flow etc.；Different parameter settings can cause certain characterization test of same sample to provide different analysis results, example
Such as, in temperature programmed reduction (TPR) characterization test, when heating rate is set to parameter faster, may cover some compared with
The reduction peak occurred under slow heating rate.The reason for producing above-mentioned phenomenon be, the direct shadow of the parameter setting in characterization method
Sound is test for dynamic (dynamical) process that sample experiences in the sign, in other words, the specific power that caltalyst reveals
Characteristic is controlled by parameter setting during characterization test.The main purpose of existing characterization method is to compare different catalysts
The series of results that the optimal characterization parameter of certain of sample in certain characterization method is obtained under conditions of setting, judges catalyst
Influence of certain feature to catalytic performance.Such representation pattern, for analyzing a large amount of catalyst samples in certain single table
The performance levied in test is largely effective；But, due to the difference that the procedure parameter in different characterization methods is set, cause same urging
Cannot be set up between the result of the different characterization method of agent sample contrast contact (because that, without exclusion
On the premise of the dynamics aspect influence that parameter setting different band is come, the different characterization results for comparing same sample lack reasonability
And operability.Such situation is particularly evident between the characterization test means of relative process-type.Due to beginning and end it
Between mutual inversion corresponding relation so that the characterization test result of relatively relative process-type is not only valuable, also there is operability,
As long as the characterization test that foundation is carried out under same external dynamics feature architecture, its result just has comparativity.
The content of the invention
Thermal analysis method is utilized it is an object of the invention to provide one kind, and will be aoxidized and reduced this pair relative process groups
The method that the catalytic performance for carrying out altogether is characterized.In sign, will aoxidize and reduce this pair relative processes and combine,
And make it is every kind of during all parameters (except locate qi-regulating nature parameters and composition parameter) set be consistent, set up with this
The phenetic analysis method got up, because, during sample experiences, it is only possible to there are the difference of chemical atmosphere, and other
The physical parameter related to dynamics, such as starting and finishing temperature, rate of temperature change process gas velocity, gas pressure
Deng, it is all just the same, so, the data of both characterization results with respect to process can be connected and be contrasted, and from
In obtain the information of higher level.From the above mentioned, the catalyst performance characterizing method that the present invention is provided, can contrast oxidationreduction
The different performance of the same catalyst during relative, and the result of traditional characterization test can only be characterized and evaluate every kind of test
Performance difference in journey between different catalysts sample.
Specifically, the combination for oxidization-reduction type with respect to process, by traditional, single temperature programmed reduction (TPR)
Coupled together with temperature programmed oxidation (TPO) means, coordinate the suction/heat release letter during thermal analyzer tracing detection TPR-TPO
Breath, formation 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, except the species property for locating qi-regulating is different, other all parameters for setting TPR and TPO are protected
Hold consistent, the TPR and the DTA curve of TPO for obtaining on this basis can carry out numerical value comparative analysis, further to dissect same
Which type of the reason for sample produces difference in TPR and TPO and these differences can cause influence on catalytic performance, it is also possible to profit
The performance difference shown in TPR-TPO-DTA is tested with different catalysts sample, characterizes the correlated performance of different samples.
Atmosphere of the catalyst in synthesis gas (gaseous mixture of hydrogen and carbon monoxide) is tested 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 the warm area below 400 DEG C)；Pretreatment carries out temperature programming also first after terminating
The analysis test of former (TPR), H is contained to being passed through in sample cell and reference substance pond simultaneously2Reducibility gas (such as H2/N2、H2/
Ar、H2/ He), with the speed of 1K/min-10Kmin to sample cell and reference cell temperature programming, thermal analyzer is recorded during this
The temperature signal of sample and reference substance, (with temperature as abscissa, sample and the reference substance temperature difference are vertical seat to form TPR-DTA curves
Target curve)；After TPR process analysis procedure analyses terminate, to inert purge gas are passed through in 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 identical parameter setting in being analyzed with TPR
The analysis test of TPO is carried out, TPO-DTA curves are obtained；Last inert gas purge cooling, terminates TPR-TPO-DTA tests.
The detailed process carried out when catalyst performance judges with the TPR-TPO-DTA test datas for obtaining is as follows, if sample A
It is the catalyst sample of known catalytic performance, B is the catalyst sample of unknown performance, THAAnd TOARespectively A samples TPR-DTA
The summit temperature (abscissa in curve at summit) of initial peak, T in curve and TPO-DTA curvesHBAnd TOBRespectively B samples
The summit temperature of initial peak in TPR-DTA curve and TPO-DTA curves.With reference to the summit of initial peak in each sample test curve
The relative size of the difference between temperature, and with reference to the performance of known sample A, judge the catalytic performance trend of unknown sample B.
Judging rules are：Work as TOB-THB≥TOA-THA>=0, and A catalytic selectivity to generate hydro carbons as trend when, it is unknown
The selectivity of the product of sample B is also more generation hydro carbons；Work as THB-TOB≥THA-TOA>=0, and A catalytic selectivity with
When generation oxygenatedchemicals is trend, the selectivity of the product of unknown sample B is also more generation oxygenatedchemicals.Cannot
In the case of strictly meeting other of above-mentioned rule, it is impossible to which the method provided using the present invention judges the performance of catalyst.
The method that a kind of utilization thermal analysis system that the present invention is provided evaluates catalyst, by continuous detection catalyst sample in situ
Differential thermal signal (TPR-TPO-DTA) of the product during temperature programmed reduction and temperature programmed oxidation, provides with reference to the present invention
Judging rules, performance trend that can be with Fast Evaluation catalyst when being used in containing 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
The present invention is illustrated, the scope of the present invention is limited never in any form.
Embodiment 1
The A of known catalytic performance is HTB-1H hydrogenation catalysts (Liaoning Haitai development in science and technology Co., Ltd), it is known that A is by 290
DEG C, H2After treatment activation in 4 hours, in H2/ CO=3, pressure 2.1MPa, when being reacted at 285 DEG C of temperature, CH in product4Selectivity
It is 79%, i.e. A is under the above-described reaction conditions a kind of catalyst for tending to selection generation hydro carbons.
The preparation method of the B of unknown catalytic performance is：100 grams of alumina support after being calcined 4 hours through 600 DEG C is weighed,
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
Decompose 2 hours, it is nickeliferous 20%, tungsten 1.0%, the B of yttrium 0.5% to be constituted (weight %).
Carry out continuous TPR-TPO-DTA tests in situ, the differential thermal signal capital instrument limited public affairs of high-tech instrument respectively to A and B
Department's ZCR-A differential thermal analyzers are given.The testing procedure and parameter of A and B are that the sample (20-30 mesh) for weighing 0.5g is put into differential thermal
The sample cell of analyzer, is put into the corundum in granules of same mesh number in reference cell, at the same in sample cell and reference cell with 5L/min
Flow be passed through O2/N2The gas of=1mol/19mol, temperature programming (rises to 120 DEG C, after being kept for 1 hour with 20K/min at room temperature
200 DEG C are risen to the speed of 10K/min, 300 DEG C are warmed up to the speed of 5K/min again after being kept for 1 hour, after being kept for 1.5 hours
Be warmed up to 400 DEG C with the speed of 5K/min) to 400 DEG C keep 0.5 hour after, stop heating, when temperature is down to less than 120 DEG C
Afterwards, N is switched to2Purging, system is passed through H in continuing to cool to 60 DEG C of backward sample cells and reference cell2/N2=1mol/9mol's is mixed
Gas is closed, flow 2L/min starts simultaneously at temperature programming, stop adding from 60 DEG C, after rising to 820 DEG C with the speed of 10K/min
Heat, therebetween thermal analyzer record differential thermal signal form TPR-DTA curves (being above TPR-DTA test process)；System is through course
After sequence heating reduction process, then use N2Purging cools to 60 DEG C, the TPO-DTA tests of start program heating and oxidation, to sample cell
O is passed through with the flow in reference cell with 2L/min2/N2The gas of=1mol/9mol, starts simultaneously at temperature programming, from 60 DEG C,
Risen to the speed of 10K/min and stop after 820 DEG C heating (it can be seen that being consistent in parameter setting in TPO and TPR), its
Between thermal analyzer record differential thermal signal form TPO-DTA curves.
TPR-TPO-DTA test results show, THA=249 DEG C, TOA=271 DEG C, THB=258 DEG C, TOB=293℃.Because TOB-
THB(35) ＞ TOA-THA(22) ＞ 0, and the catalytic selectivity of A is leading to generate hydro carbons, therefore, it is determined that the catalysis of unknown B samples
Reaction more more options generation hydro carbons.Used as checking, B is by 290 DEG C, H2After treatment activation in 4 hours, in H2/ CO=3, pressure
2.1MPa, when being reacted at 285 DEG C of temperature, CH in product4Selectivity be 69%, be not detected as alcohols, ethers etc. containing oxidation
Thing.
Embodiment 2
The sample of commercially available MS-2 methanol synthesis catalysts (Liaoning Haitai development in science and technology Co., Ltd) catalytic performance known to
A, commercially available TMF-95 furfural hydrogenation dimethyl furans catalyst (Liaoning Haitai development in science and technology Co., Ltd) is urged as unknown
Change the sample B of performance.
Known A is by 268 DEG C, H2After treatment 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 under the above-described reaction conditions a kind of trend selection generation oxycompound (alcohol for 84%, i.e. A
Class) catalyst.
Carry out continuous TPR-TPO-DTA tests in situ, the differential thermal signal capital instrument limited public affairs of high-tech instrument respectively to A and B
Department's ZCR-A differential thermal analyzers are given.The testing procedure and parameter of A and B are that the sample (20-30 mesh) for weighing 1g is put into differential thermal point
The sample cell of analyzer, is put into the corundum in granules of same mesh number in reference cell, at the same in 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 with 20K/min at room temperature, after being kept for 1 hour with
The speed of 10K/min rises to 200 DEG C, and 300 DEG C are warmed up to the speed of 5K/min again after being kept for 1 hour, after being kept for 1.5 hours with
The speed of 5K/min is warmed up to 350 DEG C) to 350 DEG C keep 0.5 hour after, stop heating, after temperature is down to below 120 DEG C,
Switch to N2Purging, system is passed through H in continuing to cool to 60 DEG C of backward sample cells and reference cell2/N2The mixing of=1mol/19mol
Gas, flow 1.5L/min, starts simultaneously at temperature programming, stops adding from 60 DEG C, after rising to 770 DEG C with the speed of 10K/min
Heat, therebetween thermal analyzer record differential thermal signal form TPR-DTA curves (being above TPR-DTA test process)；System is through course
After sequence heating reduction process, then use N2Purging cools to 60 DEG C, the TPO-DTA tests of start program heating and oxidation, to sample cell
O is passed through with the flow in reference cell with 1.5L/min2/N2The gas of=1mol/19mol, starts simultaneously at temperature programming, goes out from 60 DEG C
Hair, is risen to the speed of 10K/min and stop after 770 DEG C heating (it can be seen that keeping one in parameter setting in TPO and TPR
Cause), thermal analyzer record differential thermal signal forms TPO-DTA curves 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 the catalytic reaction more more options generation oxycompound of B samples.Used as checking, B is by 268 DEG C, H2After treatment activation in 4 hours,
In H2/ CO=2, pressure 3.5MPa, when being reacted at 260 DEG C of temperature, CH in product3The selectivity of OH is 64%, that is to say, that in product
More is oxygen-containing class.
Claims (3)
1. a kind of method that utilization thermal analysis system evaluates catalyst, for quickly judging that unknown catalyst is containing synthesis gas atmosphere
The selective trend of middle product when using, it is characterised in that by continuous detection temperature programmed reduction and temperature programming oxygen in situ
The differential thermal information of the catalyst during changing this pair relatively, can obtain known catalytic performance sample and unknown catalytic performance sample
The TPR-TPO-DTA test results of product, further according to the summit of both respective initial peaks in TPR- DTA and TPO-DTA curves
The relative size of the difference of temperature, with reference to the catalytic performance of known sample, judges unknown sample under the same reaction conditions
Catalytic performance.
2. the method that a kind of utilization thermal analysis system according to claim 1 evaluates catalyst, it is characterised in that carry out TPR-
During TPO-DTA analysis tests, except the species property for locating qi-regulating is different, other all parameters keep during setting TPR and TPO
Unanimously.
3. the method that a kind of utilization thermal analysis system according to claim 1 evaluates catalyst, it is characterised in that TPR-TPO-
Concretely comprising the following steps for DTA analysis tests, (thermal analyzer in the sample cell of thermal analyzer is put into by the catalyst sample of 1mg-10g
Reference cell in be put into inertia reference substance, such as corundum), first with contain O2Inert gas (such as O2/N2、O2/Ar、O2/ He) at 400 DEG C
Sample and reference substance are pre-processed in following warm area；Pretreatment carries out temperature programmed reduction (TPR) first after terminating
Analysis test, H is contained to being passed through in sample cell and reference substance pond simultaneously2Reducibility gas (such as H2/N2、H2/Ar、H2/ He), with
To sample cell and reference cell temperature programming, thermal analyzer records sample and reference substance during this to the speed of 1K/min-10Kmin
Temperature signal, form TPR-DTA curves (with temperature as abscissa, sample and the reference substance temperature difference are the curve of ordinate)；TPR
After process analysis procedure analysis terminates, to inert purge gas are passed through in sample cell and reference cell, less than 60 DEG C are cooled to, hand-off process gas is
O2/N2、O2/ Ar or O2/ He etc. contains O2Oxidizing gas, with identical parameter setting in being analyzed with TPR carry out TPO analysis survey
Examination, obtains TPO-DTA curves；Last inert gas purge cooling, terminates TPR-TPO-DTA tests.
Priority Applications (1)
| 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 |
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