CN106802262A - A kind of method that utilization DTG tests catalyst performance - Google Patents
A kind of method that utilization DTG tests catalyst performance Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000012360 testing method Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 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 21
- 239000007789 gas Substances 0.000 claims description 19
- 238000004458 analytical method Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 244000148755 species properties Species 0.000 claims description 2
- 239000013558 reference substance Substances 0.000 claims 1
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000002411 thermogravimetry Methods 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
- 238000011156 evaluation Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000630 rising effect Effects 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
- 150000001875 compounds Chemical class 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 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
- 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
- 238000003556 assay Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 150000001879 copper Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 230000010429 evolutionary process Effects 0.000 description 1
- 230000007717 exclusion Effects 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
- 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The method that a kind of utilization DTG that the present invention is provided tests catalyst performance, by continuous detection temperature programmed reduction in situ and the weight rate of this pair catalyst with respect to during of temperature programmed oxidation, the TPR TPO DTG test results of known catalytic performance sample and unknown catalytic performance sample can be obtained, further according to the relative size of both respective initial peak area and the differences of the ratio of the total mark area at all peaks in TPR DTG and TPO DTG curves, with reference to the catalytic performance of known sample, judge unknown sample catalytic performance under the same reaction conditions.
Description
Technical field
The present invention relates to a kind of method of assay catalyst performance, and in particular to one kind utilizes thermogravimetry evaluation
The method of catalyst reactivity worth in synthesis gas atmosphere.
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
It is an object of the invention to provide a kind of means of utilization thermogravimetric analysis, and will aoxidize and reduce this pair relative mistakes
Journey combines the method that the catalytic performance that carries out is characterized.In sign, will aoxidize and reduce this pair relative processes and combine
Together, and make it is every kind of during all parameters (except locate qi-regulating nature parameters and composition parameter) set be consistent, with
The phenetic analysis method that this sets up, because, during sample experiences, it is only possible to there are the difference of chemical atmosphere,
And other physical parameters related to dynamics, such as starting and finishing temperature, rate of temperature change, process gas velocity, gas
Body pressure etc., it is all just the same, so, can both with respect to processes characterization results data connect carry out it is right
Than, and therefrom obtain the information of higher level.From the above mentioned, the catalyst performance characterizing method that the present invention is provided, can contrast oxygen
The different performance of the same catalyst during changing-reducing relatively, and the result of traditional characterization test can only characterize evaluation often
Performance difference in kind test process 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 weight of sample during thermogravimetric analyzer tracing detection TPR-TPO
Rate of change, formation carries out follow-on test in situ, that is, TPR-TPO-DTG to same catalyst sample using thermogravimetry,
In the test process of TPR-TPO-DTG, except the species property for locating qi-regulating is different, other all parameters of TPR and TPO are set
It is consistent, the TPR and the DTG curves of TPO for obtaining on this basis can carry out numerical value comparative analysis, further to dissect same
Which type of the reason for one sample produces difference in TPR and TPO and these differences can cause influence on catalytic performance, it is also possible to
The performance difference shown in TPR-TPO-DTG tests using different catalysts sample, characterizes the correlation of different samples
Energy.
Atmosphere of the catalyst in synthesis gas (gaseous mixture of hydrogen and carbon monoxide) is tested using the method for TPR-TPO-DTG
In catalytic performance when, specific process can be as follows, and the catalyst sample of 5mg-5g is put into the sample cell of thermogravimetric analyzer
In, first with containing O2Inert gas (such as O2/N2、O2/Ar、O2/ He) sample is pre-processed in warm area below 400 DEG C;
Pretreatment carries out the analysis test of temperature programmed reduction (TPR) first after terminating, H is contained to being passed through in sample cell2Reproducibility
Gas (such as H2/N2、H2/Ar、H2/ He), with the speed of 1K/min-10Kmin to sample cell temperature programming, thermogravimetric analyzer record
The weight rate of sample during this, (with temperature as abscissa, the weight rate of sample is vertical to form TPR-DTG curves
The curve of coordinate);After TPR process analysis procedure analyses terminate, to inert purge gas are passed through in sample cell, less than 60 DEG C, switching are cooled to
Place's qi-regulating is O2/N2、O2/ Ar or O2/ He etc. contains O2Oxidizing gas, TPO is carried out with identical parameter setting in being analyzed with TPR
Analysis test, obtain TPO-DTG curves;Last inert gas purge cooling, terminates TPR-TPO-DTG tests.
The detailed process and rule carried out when catalyst performance judges with the TPR-TPO-DTG test datas for obtaining are as follows,
If sample A is the catalyst sample of known catalytic performance, B is the catalyst sample of unknown performance, RHA=SHAi/SHA(SHAiIt is sample
The corresponding integral area of initial peak, S in the TPR-DTG curves of product AHAIt is the total mark at all peaks in the TPR-DTG curves of sample A
Area), ROA=SOAi/SOA(SOAiIt is the corresponding integral area of initial peak, S in the TPO-DTG curves of sample AOAIt is sample A's
The total mark area at all peaks in TPO-DTG curves), RHB=SHBi/SHB(SHBiIt is initial peak pair in the TPR-DTG curves of sample B
The integral area answered, SHBIt is the total mark area at all peaks in the TPR-DTG curves of sample B), ROB=SOBi/SOB(SOBiIt is sample
The corresponding integral area of initial peak, S in the TPO-DTG curves of BOBIt is the total mark face at all peaks in the TPO-DTG curves of sample B
Product).If RHB-ROB≥RHA-ROA>=0, and A catalytic selectivity to generate oxygen-containing class as trend when, then the reaction of unknown sample B
The selectivity of product is also more oxygen-containing class compounds of generation;If ROB-RHB≥ROA-RHA>=0, and A catalytic selectivity generating
When hydro carbons is trend, then the selectivity of the product of unknown sample B is also more towards hydro carbons.Above-mentioned rule cannot strictly be met
In the case of other, it is impossible to which the method provided using the present invention judges the performance of catalyst.
The method that a kind of utilization thermogravimetry that the present invention is provided evaluates catalyst, by continuous detection catalyst in situ
The weight rate (TPR-TPO-DTG) of sample sample during temperature programmed reduction and temperature programmed oxidation, with reference to this hair
The judging rules of bright offer, 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-DTG tests in situ, the weight rate capital instrument tech high of sample respectively to A and B
Device Co., Ltd ZRT-A thermogravimetric analyzers are given.The testing procedure and parameter of A and B are the sample (20-30 mesh) for weighing 0.5g
The sample cell of thermogravimetric analyzer is put into, O is passed through with the flow of 5L/min2/N2The gas of=1mol/19mol, temperature programming (room temperature
Under rise to 120 DEG C with 20K/min, 200 DEG C are risen to the speed of 10K/min after being kept for 1 hour, again with 5K/ after being kept for 1 hour
The speed of min is warmed up to 300 DEG C, and 400 DEG C are warmed up to the speed of 5K/min after being kept for 1.5 hours) it is small to 400 DEG C of holdings 0.5
Shi Hou, stops heating, after temperature is down to below 120 DEG C, switches to N2Purging, system continues to cool to 60 DEG C of backward sample cells
In be passed through H2/N2The gaseous mixture of=1mol/9mol, flow 2L/min, starts simultaneously at temperature programming, from 60 DEG C, with 10K/min
Speed rise to 820 DEG C after stop heating, therebetween thermogravimetric analyzer record sample weight rate, formed TPR-DTG curves
(being above TPR-DTG test process);After system experience temperature programmed reduction process, then use N2Purging cools to 60 DEG C, starts
The TPO-DTG tests of temperature programmed oxidation, O is passed through to the flow in sample cell with 2L/min2/N2The gas of=1mol/9mol, together
When start program heat up, from 60 DEG C, after rising to 820 DEG C with the speed of 10K/min stop heating (it can be seen that in TPO
It is consistent in parameter setting and TPR), thermogravimetric analyzer records the weight rate of sample therebetween, forms TPO-DTG curves.
TPR-TPO-DTG test results show, RHA=0.41, ROA=0.45, RHB=0.40, ROB=0.49, because ROB-RHB
(0.09) > ROA-RHA(0.04) > 0, and the catalytic selectivity of A is leading to generate hydro carbons, therefore, it is determined that unknown B samples
Catalytic reaction more more options generate 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-DTG tests in situ, the weight rate capital instrument tech high of sample respectively to A and B
Device Co., Ltd ZRT-A thermogravimetric analyzers are given.The testing procedure and parameter of A and B are that the sample (20-30 mesh) for weighing 1g is put
Enter the sample cell of differential thermal analyzer, O is passed through with the flow of 10L/min2/N2The gas of=1mol/9mol, temperature programming is (at room temperature
120 DEG C are risen to 20K/min, 200 DEG C are risen to the speed of 10K/min after being kept for 1 hour, again with 5K/min after being kept for 1 hour
Speed be warmed up to 300 DEG C, be warmed up to 350 DEG C with the speed of 5K/min after being kept for 1.5 hours) kept for 0.5 hour to 350 DEG C
Afterwards, stop heating, after temperature is down to below 120 DEG C, switch to N2Purging, system continues to cool in 60 DEG C of backward sample cells
It is passed through H2/N2The gaseous mixture of=1mol/19mol, flow 1.5L/min, starts simultaneously at temperature programming, from 60 DEG C, with 10K/
The speed of min stops heating after rising to 770 DEG C, and thermogravimetric analyzer records the weight rate of sample therebetween, forms TPR-DTG bent
Line (being above TPR-DTG test process);After system experience temperature programmed reduction process, then use N2Purging cools to 60 DEG C, opens
The TPO-DTG tests of beginning temperature programmed oxidation, O is passed through to the flow in sample cell with 1.5L/min2/N2The gas of=1mol/19mol
Body, starts simultaneously at temperature programming, and heating is stopped from 60 DEG C, after rising to 770 DEG C with the speed of 10K/min (it can be seen that TPO
In parameter setting and TPR in be consistent), thermogravimetric analyzer records the weight rate of sample therebetween, forms TPO-DTG bent
Line.
The test result of TPR-TPO-DTG shows, RHA=0.52, ROA=0.47, RHB=0.60, ROB=0.54.Because RHB-ROB
(0.06) > RHA-ROA(0.05) > 0, and the catalytic selectivity of A is leading to generate oxycompound, therefore, it is determined that unknown B samples
The catalytic reaction of product more more options generate oxycompound.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 more in product to be
Oxygen-containing class.
Claims (3)
1. a kind of method that utilization DTG tests catalyst performance, for quickly judging that unknown catalyst is containing synthesis gas gas
The selective trend of product when being used in atmosphere, it is characterised in that by continuous detection temperature programmed reduction and temperature programming in situ
The weight rate of the catalyst during aoxidizing this pair relatively, can obtain known catalytic performance sample and unknown catalytic
The TPR-TPO-DTG test results of energy sample, further according to both respective initial peak faces in TPR- DTG and TPO-DTG curves
Product and the relative size of the difference of the ratio of the total mark area at all peaks, with reference to the catalytic performance of known sample, judge unknown
Sample catalytic performance under the same reaction conditions.
2. the method that a kind of utilization DTG according to claim 1 tests catalyst performance, it is characterised in that carry out
During TPR-TPO-DTG analysis tests, except the species property for locating qi-regulating is different, other all parameters during TPR and TPO are set
It is consistent.
3. the method that a kind of utilization DTG according to claim 1 tests catalyst performance, it is characterised in that TPR-
Concretely comprising the following steps for TPO-DTG analysis tests, the catalyst sample of 5mg-5g is put into the sample cell of differential thermal analyzer, is first used
Containing O2Inert gas (such as O2/N2、O2/Ar、O2/ He) sample and reference substance are pre-processed in warm area below 400 DEG C;
Pretreatment carries out the analysis test of temperature programmed reduction (TPR) first after terminating, H is contained to being passed through in sample cell2Reproducibility
Gas (such as H2/N2、H2/Ar、H2/ He), with the speed of 1K/min-10Kmin to sample cell temperature programming, thermogravimetric analyzer record
The weight rate of sample during this, (with temperature as abscissa, the weight rate of sample is vertical to form TPR-DTG curves
The curve of coordinate);After TPR process analysis procedure analyses terminate, to inert purge gas are passed through in sample cell, less than 60 DEG C, switching are cooled to
Place's qi-regulating is O2/N2、O2/ Ar or O2/ He etc. contains O2Oxidizing gas, TPO is carried out with identical parameter setting in being analyzed with TPR
Analysis test, obtain TPO-DTG curves;Last inert gas purge cooling, terminates TPR-TPO-DTG tests.
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