CN106872518B - A kind of application method of the differential scanning calorimetric in evaluating catalyst - Google Patents
A kind of application method of the differential scanning calorimetric in evaluating catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000012360 testing method Methods 0.000 claims abstract description 31
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 230000008859 change Effects 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000013558 reference substance Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 description 24
- 230000000875 corresponding effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004455 differential thermal analysis 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
- 238000011156 evaluation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 238000002076 thermal analysis method 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
- 239000004215 Carbon black (E152) Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000002596 correlated effect Effects 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
- 238000007689 inspection Methods 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
- 230000009257 reactivity Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000000646 scanning calorimetry Methods 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
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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)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of application method of the differential scanning calorimetric provided by the invention in evaluating catalyst, pass through the heat content change rate of the catalyst of continuous detection temperature programmed reduction in situ and this pair of temperature programmed oxidation during opposite, the TPR-TPO-DSC 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 ratio of the total mark area of respective initial peak area and all peaks in TPR-DSC and TPO-DSC curve, in conjunction with the catalytic performance of known sample, judge the catalytic performance of unknown sample under the same reaction conditions.
Description
Technical field
The present invention relates to a kind of applications of differential scanning amount thermal analysis system, and in particular to a kind of to utilize differential scanning calorimetry
The method for evaluating catalyst reactivity worth in synthesis gas atmosphere.
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
Differential scanning amount thermal analysis method is utilized the object of the present invention is to provide a kind of, and will aoxidize and restore this pair
Opposite process combine progress catalytic performance characterization method.In characterization, this pair of opposite process will be aoxidized and restored
It combines, and all parameters (nature parameters and composition parameter in addition to handling gas) setting during making every kind keeps one
It causes, 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 air-flow
Speed, gas pressure etc. is all just the same, so, can both with respect to processes characterization results data connect into
Row comparison, and therefrom obtain more advanced information.From the above mentioned, catalyst performance characterizing method provided by the invention, can be right
Than the different performance of same catalyst of the oxidationreduction during opposite, and the result of traditional characterization test can only be characterized and be commented
Performance difference in every kind of test process of valence between different catalyst samples.
Specifically, the combination for oxidization-reduction type with respect to process, by traditional, individual temperature programmed reduction (TPR)
It is connected with temperature programmed oxidation (TPO) means, cooperates suction/heat release letter during thermal analyzer tracing detection TPR-TPO
Breath, because in differential thermal analysis (DTA), exothermic peak and endothermic peak on DTA curve have no determining physical meaning, and differential scanning amount
In thermal method (DSC), the peak on DSC curve represents releasing/absorption heat, so, TPR-TPO is detected with differential scanning calorimetry
Suction/exotherm information of sample is more direct effective in the process, that is, forms so-called TPR-TPO-DSC method in the present invention,
In the test process of TPR-TPO-DSC, in addition to the type property of processing gas is different, other all parameters of setting TPR and TPO are protected
It holds unanimously, the DSC curve of the TPR and TPO that obtain on this basis can carry out numerical value comparative analysis, same further to dissect
Sample generates the reason of difference and these differences in TPR and TPO and will cause which type of influence to catalytic performance, can also benefit
The performance difference shown in TPR-TPO-DSC test with different catalyst samples, characterizes the correlated performance of different samples.
Catalyst is tested in the atmosphere of synthesis gas (gaseous mixture of hydrogen and carbon monoxide) using the method for TPR-TPO-DSC
In catalytic performance when, specific process can be as follows, and the catalyst sample of 5mg-5g is put into the sample cell of thermal analyzer
(inertia reference substance, such as corundum are put into the reference cell of thermal analyzer), first with containing O2Inert gas (such as O2/N2、O2/Ar、O2/
He) sample and reference substance are pre-processed in 400 DEG C of warm areas below；Temperature programming is carried out also first after pretreatment
The analysis test of former (TPR), is passed through containing H simultaneously into sample cell and reference substance pond2Reducibility gas (such as H2/N2、H2/
Ar、H2/ He), with the speed of 1K/min-10K/min to sample cell and reference cell temperature programming, thermal analyzer is recorded during this
The heat content change rate (dH/dt) of sample, forming TPR-DSC curve, (using temperature as abscissa, sample dH/dt is the song of ordinate
Line)；After TPR process analysis procedure analysis, it is passed through inert purge gas into sample cell and reference cell, cools to 60 DEG C hereinafter, switching
Processing gas is O2/N2、O2/ Ar or O2/ He etc. contains O2Oxidizing gas, with TPR analyze in identical parameter setting carry out TPO
Analysis test, obtain TPO-DSC curve；Last inert gas purge cooling, terminates TPR-TPO-DSC test.
Detailed process when catalyst performance judges is carried out with the TPR-TPO-DSC test data of acquisition and rule is as follows,
If sample A is the catalyst sample of known catalytic performance, B is the catalyst sample of unknown performance, RHA=ΔHHAi/ΔHHA(Δ
HHAiFor the corresponding integral area of initial peak in the TPR-DSC curve of sample A, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHHAFor
The total mark area at all peaks, i.e., total enthalpy change in the TPR-DSC curve of sample A), ROA=ΔHOAi/ΔHOA(ΔHOAiFor sample
The corresponding integral area of initial peak in the TPO-DSC curve of A, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHOAFor for sample A's
The total mark area at all peaks in TPO-DSC curve, i.e., total enthalpy change), RHB=ΔHHBi/ΔHHB(ΔHHBiFor the TPR- of sample B
The corresponding integral area of initial peak in DSC curve, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHHBIt is bent for the TPR-DSC of sample B
The total mark area at all peaks in line, i.e., total enthalpy change), ROB=ΔHOBi/ΔHOB(ΔHOBiFor in the TPO-DSC curve of sample B
The corresponding integral area of initial peak, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHOBTo own in the TPO-DSC curve of sample B
The total mark area at peak, i.e., total enthalpy change).If RHB-ROB≥RHA-ROA>=0, and the catalytic selectivity of A is to become to generate oxygen-containing class
When gesture, then the selectivity of the reaction product of unknown sample B is also more to generate oxygen-containing class compound；If ROB-RHB≥ROA-RHA≥
0, and when the catalytic selectivity of A is to generate hydro carbons as trend, then the selectivity of the reaction product of unknown sample B is also more towards hydrocarbon
Class.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 differentia scanning calorimetry evaluation catalyst provided by the invention, passes through continuous inspection in situ
The heat content change rate dH/dt of sample of catalyst sample during temperature programmed reduction and temperature programmed oxidation is surveyed, is formed
Application of the TPR-TPO-DSC in evaluating catalyst can be existed in conjunction with judging rules provided by the invention with Fast Evaluation catalyst
Contain performance trend when using in synthesis gas atmosphere.
Specific embodiment
The present invention is further detailed below in conjunction with embodiment, the following examples are only used for explaining in detail
Illustrate the present invention, does not limit the scope of the invention in any way.
Embodiment 1
The A of known catalytic performance is HTB-1H hydrogenation catalyst (Liaoning Haitai development in science and technology Co., Ltd), it is known that A passes through
290 DEG C, H2After handling activation in 4 hours, in H2/ CO=3, pressure 2.1MPa, when reacting at 285 DEG C of temperature, CH in product4Selection
Property be 79%, i.e. A be under the above-described reaction conditions it is a kind of tend to selection generate hydro carbons catalyst.
Unknown catalytic performance B's the preparation method comprises the following steps: weigh through 600 DEG C roast 4 hours after 100 grams of alumina support,
By 126 grams of nickel nitrate [Ni (NO3)2·6H2O], 1.7 grams of ammonium metatungstate [(NH4)6H2W12O40·xH2O] and 2.7 grams of yttrium nitrates
[YNO3·6H2O] with deionized water altogether it is molten after be impregnated on alumina support；It is each at being dried 5 hours, 300 DEG C and 450 DEG C at 110 DEG C
It decomposes 2 hours, being formed (weight %) is nickeliferous 20%, tungsten 1.0%, the B of yttrium 0.5%.
Carry out continuous TPR-TPO-DSC test in situ, thermal signal PerkinElmer company respectively to A and B
DSC4000 differential scanning calorimeter 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
The sample cell of differential thermal analyzer, is put into the corundum in granules of same mesh number and weight in reference cell, while to sample cell and reference cell
In O is passed through with the flow of 5L/min2/N2The gas of=1mol/19mol, temperature programming (120 DEG C are risen to 20K/min at room temperature,
200 DEG C are risen to the rate of 10K/min after being kept for 1 hour, is warming up to 300 DEG C again after being kept for 1 hour with the rate of 5K/min, is protected
Be warming up to 400 DEG C after holding 1.5 hours with the rate of 5K/min) to 400 DEG C keep 0.5 hour after, stop heating, when temperature is down to
After 120 DEG C or less, N is switched to2Purging, system, which continues to cool in 60 DEG C of backward sample cells and reference cell, is passed through H2/N2=1mol/
The gaseous mixture of 9mol, flow 2L/min, starts simultaneously at temperature programming, from 60 DEG C, rises to 820 DEG C with the rate of 10K/min
Stop heating afterwards, therebetween the dH/dt of thermal analyzer record sample, forming TPR-DSC curve, (the above are TPR-DSC to test
Journey)；After system undergoes temperature programmed reduction process, then use N2Purging cools to 60 DEG C, the TPO-DSC of start program heating and oxidation
Test, is passed through O into sample cell and reference cell with the flow of 2L/min2/N2The gas of=1mol/9mol starts simultaneously at program liter
Temperature stops heating from 60 DEG C, after rising to 820 DEG C with the rate of 10K/min (it can be seen that parameter setting and TPR in TPO
In be consistent), therebetween thermal analyzer record sample dH/dt, formed TPO-DSC curve.
TPR-TPO-DSC test result shows, RHA=0.24, ROA=0.31, RHB=0.26, ROB=0.35, because of ROB-RHB
(0.09) > ROA-RHA(0.07) 0 >, and the catalytic selectivity of A with generate hydro carbons be it is leading, therefore, it is determined that unknown B sample
Catalysis reaction more more options generate 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-DSC test in situ, thermal signal PerkinElmer company respectively to A and B
DSC4000 differential scanning calorimeter provides.The testing procedure and parameter of A and B is to weigh the sample (20-30 mesh) of 1g to be put into heat
The sample cell of analyzer is put into the corundum in granules of same mesh number and weight in reference cell, at the same into sample cell and reference cell with
The flow of 10L/min is passed through O2/N2The gas of=1mol/9mol, temperature programming (rise to 120 DEG C at room temperature with 20K/min, keep 1
200 DEG C are risen to the rate of 10K/min after hour, is warming up to 300 DEG C again after being kept for 1 hour with the rate of 5K/min, keeps 1.5
With the rate of 5K/min be warming up to 350 DEG C after hour) kept for 0.5 hour to 350 DEG C after, stop heating, when temperature is down to 120 DEG C
After below, N is switched to2Purging, system, which continues to cool in 60 DEG C of backward sample cells and reference cell, is passed through H2/N2=1mol/19mol
Gaseous mixture, flow 1.5L/min starts simultaneously at temperature programming, from 60 DEG C, after rising to 770 DEG C with the rate of 10K/min
Stop heating, the dH/dt of thermal analyzer record sample, forms TPR-DSC curve therebetween (the above are TPR-DSC test process)；
After system undergoes temperature programmed reduction process, then use N2Purging cools to 60 DEG C, and the TPO-DSC of start program heating and oxidation is surveyed
Examination, is passed through O into sample cell and reference cell with the flow of 1.5L/min2/N2The gas of=1mol/19mol starts simultaneously at program liter
Temperature stops heating from 60 DEG C, after rising to 770 DEG C with the rate of 10K/min (it can be seen that parameter setting and TPR in TPO
In be consistent), therebetween thermal analyzer record sample dH/dt, formed TPO-DSC curve.
The test result of TPR-TPO-DSC shows, RHA=0.39, ROA=0.33, RHB=0.46, ROB=0.38.Because of RHB-ROB
(0.08) > RHA-ROA(0.06) 0 >, and the catalytic selectivity of A with generate oxycompound be it is leading, therefore, it is determined that unknown B sample
The catalysis reaction more more options of product 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 is more in product
Oxygen-containing class.
Claims (3)
1. application method of a kind of differential scanning calorimetric in evaluating catalyst, for quickly judging unknown catalyst containing conjunction
At the selective trend of product when being used in gas atmosphere, which is characterized in that pass through continuous detection temperature programmed reduction in situ and journey
The heat content change rate dH/dt of catalyst during this pair of sequence heating and oxidation is opposite can obtain known catalytic performance sample
It is each in TPR- DSC and TPO-DSC curve further according to the two with the TPR-TPO-DSC test result of unknown catalytic performance sample
From initial peak area and all peaks total mark area ratio difference relative size, in conjunction with the catalytic of known sample
Can, judge the catalytic performance of unknown sample under the same reaction conditions；Detailed process and rule are as follows, if sample A is
Know that the catalyst sample of catalytic performance, B are the catalyst sample of unknown performance, RHA=ΔHHAi/ΔHHA, in this formula, Δ HHAiFor
The corresponding integral area of initial peak in the TPR-DSC curve of sample A, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHHAFor sample A
TPR-DSC curve in all peaks total mark area, i.e., total enthalpy change；ROA=ΔHOAi/ΔHOA, in this formula, Δ HOAiFor sample
The corresponding integral area of initial peak in the TPO-DSC curve of product A, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHOAFor for sample A
TPO-DSC curve in all peaks total mark area, i.e., total enthalpy change；RHB=ΔHHBi/ΔHHB, in this formula, Δ HHBiFor sample
The corresponding integral area of initial peak in the TPR-DSC curve of product B, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHHBFor sample B's
The total mark area at all peaks in TPR-DSC curve, i.e., total enthalpy change；ROB=ΔHOBi/ΔHOB, in this formula, Δ HOBiFor sample B
TPO-DSC curve in the corresponding integral area of initial peak, the i.e. enthalpy change of the corresponding sample of initial peak；ΔHOBFor sample B's
The total mark area at all peaks in TPO-DSC curve, i.e., total enthalpy change；If RHB-ROB≥RHA-ROA>=0, and the catalytic selectivity of A
When generating oxygen-containing class as trend, then the selectivity of the reaction product of unknown sample B is also more to generate oxygen-containing class compound；If
ROB-RHB≥ROA-RHA>=0, and when the catalytic selectivity of A is to generate hydro carbons as trend, then the choosing of the reaction product of unknown sample B
Selecting property is also more towards hydro carbons.
2. a kind of application method of the differential scanning calorimetric according to claim 1 in evaluating catalyst, it is characterised in that
It is other all during setting TPR and TPO in addition to the type property of processing gas is different when progress TPR-TPO-DSC analysis test
Parameter is consistent.
3. a kind of application method of the differential scanning calorimetric according to claim 1 in evaluating catalyst, it is characterised in that
TPR-TPO-DSC analysis test the specific steps are, the catalyst sample of 5mg-5g is put into the sample cell of thermal analyzer, and
It is put into inertia reference substance corundum in the reference cell of analyzer, first uses O2/N2、O2/ Ar or O2/ He, in 400 DEG C of warm areas below
It is interior that sample and reference substance are pre-processed；The analysis test for carrying out temperature programmed reduction (TPR) after pretreatment first, to
H is passed through in sample cell and reference substance pond simultaneously2/N2、H2/ Ar or H2/ He, with the speed of 1K/min-10K/min to sample cell and
Reference cell temperature programming, thermal analyzer record the heat content change rate dH/dt of sample during this, form TPR-DSC curve, the song
Line is using temperature as abscissa, and the dH/dt of sample is the curve of ordinate；After TPR process analysis procedure analysis, to sample cell and reference
It is passed through inert purge gas in pond, cools to 60 DEG C hereinafter, hand-off process gas is O2/N2、O2/ Ar or O2/ He, to be analyzed with TPR
In identical parameter setting carry out the analysis test of TPO, obtain TPO-DSC curve；Last inert gas purge cooling, terminates
TPR-TPO-DSC test.
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| CN110927208A (en) * | 2019-12-03 | 2020-03-27 | 中广核三角洲（太仓）检测技术有限公司 | Method for measuring PP content in HDPE by differential scanning calorimetry |
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