CN106841293B - A method of catalyst is evaluated using difference quotient thermogravimetric - Google Patents
A method of catalyst is evaluated using difference quotient thermogravimetric Download PDFInfo
- Publication number
- CN106841293B CN106841293B CN201710056836.7A CN201710056836A CN106841293B CN 106841293 B CN106841293 B CN 106841293B CN 201710056836 A CN201710056836 A CN 201710056836A CN 106841293 B CN106841293 B CN 106841293B
- Authority
- CN
- China
- Prior art keywords
- sample
- tpr
- tpo
- dtg
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000012360 testing method Methods 0.000 claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000011156 evaluation Methods 0.000 claims abstract description 6
- 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 20
- 238000004458 analytical method Methods 0.000 claims description 13
- 239000000047 product 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 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application 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 8
- 230000004913 activation Effects 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
- 238000011161 development 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
- 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
- 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
- 238000002411 thermogravimetry 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
- 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
- 150000001875 compounds Chemical class 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
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000010429 evolutionary process 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
A kind of method using difference quotient thermogravimetric evaluation catalyst provided by the invention, pass through the weight rate of the catalyst sample of continuous detection temperature programmed reduction in situ and this pair of temperature programmed oxidation during opposite, the TPR-TPO-DTG 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-DTG and TPO-DTG 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 difference quotient thermogravimetric
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
Difference quotient thermogravimetric analysis means (DTG) is utilized the object of the present invention is to provide a kind of, and will aoxidize and restore this
To opposite process combine progress catalytic performance characterization method.In characterization, this pair of opposite mistake will be aoxidized and restored
Journey is combined, and all parameters (nature parameters and composition parameter in addition to handling gas) setting during making two kinds is kept
Unanimously, the phenetic analysis method set up with this, because, during sample experience, it is only possible to which there are chemical atmospheres
Difference, and other physical parameters relevant with dynamics, such as starting and finishing temperature, rate of temperature change handle gas
Flow velocity, gas pressure etc. is all just the same, so, both can be connected with respect to the data of the characterization result of process
It compares, and therefrom obtains more advanced information.From the above mentioned, catalyst performance characterizing method provided by the invention, can be with
The different performance of same catalyst during comparing oxidationreduction relatively, and the result of traditional characterization test can only characterize
Evaluate the performance difference in every kind of test process 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 the example weight during DTG analyzer tracing detection TPR-TPO
Change rate forms and carries out follow-on test in situ, that is, TPR-TPO- to same catalyst sample using difference quotient thermogravimetry
DTG, in the test process of TPR-TPO-DTG, in addition to the type property of processing gas is different, setting TPR's and TPO is other all
Parameter is consistent, and the DTG curve of the TPR and TPO that obtain on this basis can carry out numerical value comparative analysis, further to cut open
Which type of the reason of analysis same sample generates difference in TPR and TPO and these differences, which will cause to catalytic performance, influences,
It can use the performance difference that different catalyst samples are shown in TPR-TPO-DTG test, characterize the phase of different samples
Close performance.
Catalyst is tested in the atmosphere of synthesis gas (gaseous mixture of hydrogen and carbon monoxide) using the method for TPR-TPO-DTG
In catalytic performance when, specific process can be as follows, and the catalyst sample of 1mg-10g 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 400 DEG C of warm areas below；
The analysis test for carrying out temperature programmed reduction (TPR) after pretreatment first, is passed through into sample cell containing H2Reproducibility
Gas (such as H2/N2、H2/Ar、H2/ He), with the speed of 1K/min-10K/min to sample cell temperature programming, thermogravimetric analyzer note
The weight rate of sample during this is recorded, forming TPR-DTG curve, (using temperature as abscissa, example weight change rate is vertical
The curve of coordinate)；After TPR process analysis procedure analysis, it is passed through inert purge gas to sample cell, cools to 60 DEG C hereinafter, at switching
Qi-regulating is O2/N2、O2/ Ar or O2/ He etc. contains O2Oxidizing gas, with TPR analyze in identical parameter setting carry out TPO's
Analysis test, obtains TPO-DTG curve；Last inert gas purge cooling, terminates TPR-TPO-DTG test.
Carry out that detailed process is as follows when catalyst performance judges with the TPR-TPO-DTG 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-DTG
The summit temperature (abscissa at summit) of initial peak, T in curve and TPO-DTG curveHBAnd TOBRespectively B sample TPR-DTG
The summit temperature of initial peak in curve and TPO-DTG curve.Between summit temperature in conjunction with initial peak in each sample test curve
The relative size of difference judge the catalytic performance trend of unknown sample B and referring to the performance of known sample A.
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 difference quotient thermogravimetric evaluation catalyst provided by the invention passes through continuous detection catalyst sample in situ
Weight rate (TPR-TPO-DTG) of product during temperature programmed reduction and temperature programmed oxidation is provided in conjunction with the present invention
Judging rules, can with Fast Evaluation catalyst containing in synthesis gas atmosphere use when performance trend.
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-DTG test in situ respectively to A and B, weight rate is limited with capital instrument high-tech instrument
Company's ZRT-A thermogravimetric 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 sample
Product pond is passed through O with the flow of 5L/min2/N2The gas of=1mol/19mol, temperature programming (rise to 120 at room temperature with 20K/min
DEG C, 200 DEG C are risen to the rate of 10K/min after being kept for 1 hour, is warming up to 300 again after being kept for 1 hour with the rate of 5K/min
DEG C, with the rate of 5K/min be warming up to 400 DEG C after being kept for 1.5 hours) kept for 0.5 hour to 400 DEG C after, stop heating, work as temperature
After degree is down to 120 DEG C or less, N is switched to2Purging, system, which continues to cool to 60 DEG C of backward sample cells, is passed through H2/N2=1mol/9mol
Gaseous mixture, flow 2L/min starts simultaneously at temperature programming, from 60 DEG C, stops after rising to 820 DEG C with the rate of 10K/min
It only heats, thermogravimetric analyzer records example weight change rate therebetween, and forming TPR-DTG curve, (the above are TPR-DTG to test
Journey)；After system undergoes temperature programmed reduction process, then use N2Purging cools to 60 DEG C, the TPO-DTG of start program heating and oxidation
Test, is passed through O to sample cell with the flow of 2L/min2/N2The gas of=1mol/9mol, 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 820 DEG C with the rate of 10K/min
Cause), thermogravimetric analyzer records example weight change rate therebetween, forms TPO-DTG curve.
TPR-TPO-DTG test result shows, THA=234 DEG C, TOA=257 DEG C, THB=243 DEG C, TOB=277℃.Because of TOB-
THB(34) > TOA-THA(23) 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-DTG test in situ respectively to A and B, weight rate is limited with capital instrument high-tech instrument
Company's ZRT-A thermogravimetric 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 thermogravimetric
The sample cell of analyzer is passed through O with the flow of 10L/min2/N2The gas of=1mol/9mol, temperature programming is (at room temperature with 20K/
Min rises to 120 DEG C, rises to 200 DEG C after being kept for 1 hour with the rate of 10K/min, again with the rate of 5K/min after being kept for 1 hour
Be warming up to 300 DEG C, be warming up to 350 DEG C after being kept for 1.5 hours with the rate of 5K/min) kept for 0.5 hour to 350 DEG C after, stop
Heating, after temperature is down to 120 DEG C or less, switches to N2Purging, system, which continues to cool in 60 DEG C of backward sample cells, is passed through H2/
N2The gaseous mixture of=1mol/19mol, flow 1.5L/min, starts simultaneously at temperature programming, from 60 DEG C, with the speed of 10K/min
Rate stops heating after rising to 770 DEG C, therebetween thermogravimetric analyzer record example weight change rate, formation TPR-DTG curve (the above are
TPR-DTG test process)；After system undergoes temperature programmed reduction process, then use N2Purging cools to 60 DEG C, start program heating
The TPO-DTG of oxidation is tested, and is passed through O into sample cell with the flow of 1.5L/min2/N2The gas of=1mol/19mol, is opened simultaneously
Beginning temperature programming stops heating from 60 DEG C, after rising to 770 DEG C with the rate of 10K/min (it can be seen that the parameter in TPO
It is consistent in setting and TPR), thermogravimetric analyzer records example weight change rate therebetween, forms TPO-DTG curve.
The test result of TPR-TPO-DTG shows, THA=238 DEG C, TOA=221 DEG C, THB=257 DEG C, TOB=233℃.Because
THB - TOB(24) > THA - TOA(17) 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 difference quotient thermogravimetric 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 weight rate of catalyst during changing this pair relatively, can obtain known catalytic performance sample and unknown catalytic performance
The TPR-TPO-DTG test result of sample, further according to the peak of the two respective initial peak in TPR- DTG and TPO-DTG curve
The relative size for pushing up the difference of temperature judges unknown sample in same reaction condition in conjunction with the catalytic performance of known sample
Under catalytic performance；Detailed process is as follows, if sample A is the catalyst sample of known catalytic performance, B is the catalysis of unknown performance
Agent sample, THAAnd TOAThe summit temperature of initial peak respectively in A sample TPR-DTG curve and TPO-DTG curve, that is, peak
Abscissa at top, THBAnd TOBThe summit temperature of initial peak respectively in B sample TPR-DTG curve and TPO-DTG curve；When
TOB-THB≥TOA-THA>=0, and when the catalytic selectivity of A is to generate hydro carbons as trend, the selection of the reaction product of unknown sample B
Property be also more to generate hydro carbons；Work as THB-TOB≥THA-TOA>=0, and the catalytic selectivity of A is to generate oxygenatedchemicals as trend
When, the selectivity of the reaction product of unknown sample B is also more generation oxygenatedchemicals.
2. a kind of method using difference quotient thermogravimetric evaluation catalyst according to claim 1, it is characterised in that carry out TPR-
When TPO-DTG 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 difference quotient thermogravimetric evaluation catalyst according to claim 1, it is characterised in that TPR-TPO-
DTG analysis test the specific steps are be put into the catalyst sample of 1mg-10g in the sample cell of thermogravimetric analyzer, first use O2/
N2、O2/ Ar or O2/ He pre-processes sample in 400 DEG C of warm areas below；Program liter is carried out after pretreatment first
The analysis test of temperature reduction (TPR), H is passed through into sample cell2/N2、H2/ Ar or H2/ He, with the speed of 1K/min-10K/min
To sample cell temperature programming, thermogravimetric analyzer records the weight rate of sample during this, forms TPR-DTG curve, the song
For line using temperature as abscissa, example weight change rate is ordinate；After TPR process analysis procedure analysis, inertia is passed through into sample cell
Purge gas cools to 60 DEG C hereinafter, hand-off process gas is O2/N2、O2/ Ar or O2/ He, with TPR analyze in identical parameter
The analysis test for carrying out TPO is set, TPO-DTG curve is obtained；Last inert gas purge cooling, terminates TPR-TPO-DTG and surveys
Examination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710056836.7A CN106841293B (en) | 2017-01-26 | 2017-01-26 | A method of catalyst is evaluated using difference quotient thermogravimetric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710056836.7A CN106841293B (en) | 2017-01-26 | 2017-01-26 | A method of catalyst is evaluated using difference quotient thermogravimetric |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106841293A CN106841293A (en) | 2017-06-13 |
| CN106841293B true CN106841293B (en) | 2019-05-28 |
Family
ID=59122388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710056836.7A Active CN106841293B (en) | 2017-01-26 | 2017-01-26 | A method of catalyst is evaluated using difference quotient thermogravimetric |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106841293B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106226190A (en) * | 2016-08-16 | 2016-12-14 | 王宏铭 | A kind of system of laboratory evaluation Raney nickel inactivation performance |
-
2017
- 2017-01-26 CN CN201710056836.7A patent/CN106841293B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106226190A (en) * | 2016-08-16 | 2016-12-14 | 王宏铭 | A kind of system of laboratory evaluation Raney nickel inactivation performance |
Non-Patent Citations (2)
| Title |
|---|
| Comments on the characterisation of oxidation catalysts using TPR/TPO;Nianxue Song;《Catalysis Letters 》;20050831;第271-279页 |
| Ni、Zn 改性 CuO / SiO2催化剂的TPR-TPO循环表征;赵小贞等;《工业催化》;20130331;第39-44页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106841293A (en) | 2017-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106872518B (en) | A kind of application method of the differential scanning calorimetric in evaluating catalyst | |
| Ming et al. | Characterization of cobalt Fischer-Tropsch catalysts I. Unpromoted cobalt-silica gel catalysts | |
| CN106841295B (en) | A method of catalyst is evaluated using differential scanning calorimetry | |
| Smith et al. | The partial oxidation of methane to formaldehyde: role of different crystal planes of MoO3 | |
| Wörner et al. | Development of a novel Ru-based catalyst system for the selective oxidation of CO in hydrogen rich gas mixtures | |
| Fadoni et al. | Temperature programmed desorption, reduction, oxidation and flow chemisorption for the characterisation of heterogeneous catalysts. Theoretical aspects, instrumentation and applications | |
| CN106841294B (en) | A kind of method of differential thermal analysis evaluation catalytic performance | |
| Huang et al. | The effect of catalyst preparation on catalytic activity: I. The catalytic activity of Ni/Al2O3 catalysts prepared by wet impregnation | |
| Mirzaei et al. | Kinetics modeling of Fischer–Tropsch synthesis on the unsupported Fe-Co-Ni (ternary) catalyst prepared using co-precipitation procedure | |
| CN106802262B (en) | A method of catalyst performance is tested using thermogravimetry | |
| Veselovskyi et al. | A high efficient two phase CuO/Cu2 (OH) 3NO3 (Co2+/Fe3+) composite catalyst for CO-PROX reaction | |
| CN106841293B (en) | A method of catalyst is evaluated using difference quotient thermogravimetric | |
| CN106770452B (en) | A method of catalyst is evaluated using thermal analysis system | |
| CN106442851B (en) | A kind of method for evaluating catalyst performance | |
| Bachelier et al. | Oxygen uptake by sulfided nickel-aluminum oxide catalysts. Correlation with activity | |
| CN106442850B (en) | A kind of method for evaluating catalyst choice | |
| Williams et al. | Determination of carbon dioxide in the parts-per-million range with gas chromatography | |
| Guczi et al. | Highly dispersed FeRu CO-conversion catalysts prepared from H2FeRu3 (CO) 13 and Fe2Ru (CO) 12 bimetallic clusters on silicagel | |
| Fichtl et al. | On the temperature programmed desorption of hydrogen from polycrystalline copper | |
| Beecroft et al. | The use of differential scanning calorimetry in catalyst studies. The methanation of carbon monoxide over nickel/alumina catalysts | |
| Abdouss et al. | Effect of drying conditions on the catalytic performance, structure, and reaction rates over the Fe-Co-Mn/MgO catalyst for production of light olefins | |
| Liu et al. | Effect of metal loading sequence on the activity of Sn-Ni/C for methanol carbonylation | |
| Kaleńczuk | Study on the properties of iron–cobalt alumina supported catalyst for ammonia | |
| Belokon et al. | The Physical And Mechanical Properties Of Intermetallic Catalysts For The Neutralization Of Carbon-Containing Components Of Emission Gases | |
| Abdollahi et al. | Fischer–Tropsch study over impregnated silica-supported cobalt–iron nanocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20181205 Address after: 242300 Fuhua International Community, Ningguo City, Xuancheng City, Anhui Province, 13-2-401 Applicant after: Wang Hongming Address before: 241000 New Riyton Mansion, Jinghu Century City, Jinghu District, Wuhu City, Anhui Province, 23-1-3102 Applicant before: WUHU NIUTAI INTELLECTUAL PROPERTY INFORMATION CONSULTING CO.,LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240419 Address after: 528000, First Floor, No. 85 Beihe Comprehensive Community, Lvdi Community, Xingtan Town, Shunde District, Foshan City, Guangdong Province (Residence Declaration) Patentee after: Foshan Jinghang Metal Products Co.,Ltd. Country or region after: China Address before: 242300 Fuhua International Community, Ningguo City, Xuancheng City, Anhui Province, 13-2-401 Patentee before: Wang Hongming Country or region before: China |