CN1214247C - Catalyst surface-characteristic comprehensive measuring device and application thereof - Google Patents
Catalyst surface-characteristic comprehensive measuring device and application thereof Download PDFInfo
- Publication number
- CN1214247C CN1214247C CN 03150580 CN03150580A CN1214247C CN 1214247 C CN1214247 C CN 1214247C CN 03150580 CN03150580 CN 03150580 CN 03150580 A CN03150580 A CN 03150580A CN 1214247 C CN1214247 C CN 1214247C
- Authority
- CN
- China
- Prior art keywords
- interface
- way valve
- gas
- flow
- valve
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention provides a comprehensive instrument for measuring the surface property of catalysts and an application thereof. The instrument of the present invention at least comprises a carrier gas supply inlet, a work gas supply inlet, an other gas supply inlet, a gas flowmeter, a mixer, a first four-way valve, a second four-way valve, a first six-way valve, a second six-way valve, a saturator, a program temperature-controlling heating furnace, a sample pipe where a thermocouple is inserted, a thermal conductivity cell, a cold trap, a chromatographic column, a hydrogen flame detector and a sampling, display and spectrogram printing system of a computer. The instrument in the structure can test the surface property of catalysts through the technologies of temperature programmed reduction, temperature programmed desorption, H-2-O-2 titration, temperature programmed surface reaction, temperature programmed oxidation or temperature programmed decomposition, etc., and various performance spectrograms of catalysts can be obtained. The present invention has the advantages of simple structure, convenient operation, collection of various testing technologies into a whole, time saving, strength saving and few error, and the properties of catalysts under an actual work condition can be measured practically.
Description
Technical field
The present invention relates to a kind of testing tool, particularly a kind of catalyst surface character comprehensive tester and application thereof.
Technical background
In heterogeneous catalyst research, because the complicacy of the composition of catalyzer own, structure and relevant with it reaction kinetics system, make to run into very big difficulty explaining on catalytic activity and the mechanism, thereby hindered selection particular chemical process optimum catalyst.
Though the characterizing method at catalyzer has much at present, as X-ray powder diffraction, Electronic Speculum, photoelectron spectroscopy, infrared spectrum, heat analysis etc., these technology all can not provide the character of catalyzer under practical working situation.
The general physical method except the restriction of each comfortable instrument and theoretical side, as combining with adsorption process, often can profoundly be set forth the problem of the aspects such as absorption property, surface structure, surface nature and dynamics of catalyzer.So chemisorption (desorption) is widely used in the research of variety of catalyst types as a kind of mainly and effectively means.
Temperature programmed desorption (TPD) technology, a progress as flash desorption (FD) technology, at first proposed by Y.Amenomiya and R.J.Cvetanovic in 1963, people enlarge rapidly in research practice and have improved this The Application of Technology and theoretical analysis subsequently.
B.D.McNicol and Hirosh Miura etc. have developed temperature programmed reduction (TPR) technology on the temperature programmed desorption technical foundation.
J.G.McCarty and A.Brenner etc. have then developed temperature programmed surface reaction (TPSR) and temperature Programmed Decomposition (TPDE) technology respectively.
Numerous researchers has been developed temperature programmed oxidation (TPO) technology, H again later on
2-O
2The titrimetry technology.These methods are further investigation catalyzer and disclose the essence of catalytic action, and many high-effect, high sensitivity, technological means fast are provided.
Shortcoming and urgent problem that present instrument and method of testing exist:
Above-mentioned measuring technology all realizes on the self-made Instrument of function singleness and complicated operation.Up to now, the still comprehensive instrument that is integrated in one of the multiple technologies of above-mentioned sign catalyzer of no-trump and catalytic reaction and the method for testing that on this instrument, realizes.Traditional method of testing is time-consuming, effort, error are big, especially does quantitative test, and difficulty just more seems.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of catalyst surface character comprehensive tester, and the method that adopts this instrument test catalyst surface character, to overcome the above-mentioned defective that prior art exists, satisfy the needs of scientific research and engineering design.
Technical scheme of the present invention:
Instrument of the present invention comprises at least: sample hose, thermal conductivity cell detector (abbreviation conductance cell), cold-trap and the chromatographic column of carrier gas air source inlet, work air source inlet, other air source inlet, gas meter, mixer, first four-way valve, second four-way valve, first six-way valve, second six-way valve, saturator, temperature programmed control heating furnace, interpolation thermopair and hydrogen flame detector, computer sampling and demonstration, spectrogram print system.
Said carrier gas air source inlet is connected by pipeline with mixer through gas meter, and mixer is connected with first interface of first four-way valve;
Said work air source inlet is connected through first interface of gas meter with the mixer and first four-way valve; Or behind gas meter, directly be connected with the 4th interface of first four-way valve, the 3rd interface of first four-way valve is connected with the 3rd interface of second four-way valve.
Said other air source inlet is connected with second interface of second four-way valve through gas meter, and first interface of second four-way valve is a drain;
Second interface of first four-way valve is connected with the gas access of conductance cell reference arm, and the gas vent of conductance cell reference arm is connected with the 3rd interface of first six-way valve;
The 4th interface of second four-way valve is connected with first interface of first six-way valve; Second interface of first six-way valve is connected with the 5th interface through quantity tube, and the 6th interface is connected with the gas access of saturator, and the 4th interface is connected with second interface of second six-way valve through first cold-trap;
First interface of second six-way valve is connected with the gas access of said sample hose, the 3rd interface and second cold-trap link, the second cold-trap other end is connected with hydrogen flame detector with the gas access of conductance cell gage beam or through chromatographic column, the 4th interface is connected with the gas vent of sample hose, the 5th interface is a drain, and the 6th interface is connected with the gas vent of saturator.
Said sample hose is arranged in the heating furnace.
Conductance cell (or hydrogen flame) detecting device shows with computer sampling, spectrogram with the thermopair electrical signal, print system links to each other with lead.
The instrument of said structure can adopt temperature programmed reduction (TPR), temperature programmed desorption (TPD), H
2-O
2Titration (HOT), temperature programmed surface reaction (TPSR), temperature programmed oxidation (TPO) or temperature Programmed Decomposition technology such as (TPDE) are tested the surface property of catalyzer, and can obtain the above-mentioned various performance spectrograms of catalyzer.
Instrument of the present invention, simple in structure, easy to operate, can integrate various measuring technologies, can the character of practical measurement catalyzer under practical working situation, save time, laborsaving, error is little.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is for containing Cu houghite catalyzer TPR spectrogram.
Fig. 3 is the TPR spectrogram of CuO.
Fig. 4 is the H of ferric oxide catalyzer
2Desorption TPD spectrogram.
Fig. 5 is the NH that contains the molybdenum molecular sieve catalyst
3Desorption TPD spectrogram.
Figure 6 Wei Palladium catalyzer (Pd/Al
2O
3) the HOT spectrogram.
Fig. 7 is the TPSR spectrogram that contains Cu houghite catalyzer.
Fig. 8 is the TPO spectrogram that contains the Zn catalyzer.
Fig. 9 is the TPDE spectrogram of CuZnAlCe houghite catalyzer.
Embodiment
Referring to Fig. 1, instrument of the present invention comprises:
Instrument of the present invention comprises at least: carrier gas air source inlet 18, work air source inlet 19, other air source inlet 20, gas meter 4, mixer 5, first four-way valve 6, second four-way valve 7, first six-way valve 8, second six-way valve 11, saturator 10, temperature programmed control heating furnace 14, sample hose 13, conductance cell 16, cold- trap 12,14, chromatographic column and hydrogen flame detector 17, computer sampling and the demonstration of interpolation thermopair, spectrogram print system.
Said carrier gas air source inlet 18 is connected by pipeline through pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4 and mixer 5, and the outlet of mixer 5 is connected with first interface 601 of first four-way valve 6;
Said work air source inlet 19 is connected with first interface 601 of the mixer 5 and first four-way valve 6 through pressure maintaining valve 1, drying tube 2, flow stabilizing valve 31, gas meter 4; Or behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 32, gas meter 4, directly be connected with the 4th interface 604 of first four-way valve 6, the 3rd interface 603 of first four-way valve 6 is connected with the 3rd interface 703 of second four-way valve 7;
Said other air source inlet 20 is connected with second interface 702 of second four-way valve 7 through pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, and first interface 701 of second four-way valve 7 is a drain;
The 4th interface 704 of second four-way valve 7 is connected with first interface 801 of first six-way valve 8; Second interface 802 of first six-way valve 8 is connected with the 5th interface 805 through quantity tube 9, and the 6th interface 806 is connected with the gas access of saturator 10, and the 4th interface 804 is connected with second interface 1102 of second six-way valve 11 through first cold-trap 12;
Said sample hose 13 is arranged in the heating furnace 14.
Conductance cell (or hydrogen flame) detecting device shows with computer sampling, spectrogram with the thermopair electrical signal, print system links to each other with lead.
Adopt above-mentioned instrument by temperature programmed reduction (TPR) method the surface nature of catalyzer to be tested, ultimate principle is such:
TPR is meant in the temperature programme process, and catalyzer is reduced.It can provide load type metal catalyst in reduction process, interactional information between the metal oxide or between metal oxide and the carrier.A kind of pure metal oxide has specific reduction temperature, can utilize this reduction temperature to characterize the character of this oxide.If introduce another kind of oxide in the oxide, two kinds of oxides mix, if each oxide still keeps the reduction temperature of self constant in the TPR process, then do not have an effect each other; Otherwise if solid phase reaction has taken place two kinds of oxides, variation has taken place in the character of oxide, and then original reduction temperature also will change.Can observe this variation with the TPR method.
Hydrogen-consuming volume when utilizing the TPR spectrogram can see certain oxide reduction of load effectively, the complexity during reduction, and interaction between metal oxide and the carrier is provided, and metal is in information such as carrier surface dispersivenesses.In addition, during to the heating and decomposition of bi-component metallic catalyst in the preparation of its oxide precursor, if two kinds of oxides are had an effect (or part is had an effect) mutually, then the reducing property of active component oxide will change, and can observe this variation with the TPR method.Its fundamental equation is:
2lnT
m-lnβ+ln[H
2]
m＝E
R/RT
m+ln(E
R/AR)
[H in the formula
2]
m------density of hydrogen when-rate of reduction reaches maximum value;
E
R-------reduction reaction energy of activation;
β-------rate of heat addition;
The A-------pre-exponential factor;
T
m--the temperature under-----peak maximum;
The R-------gas law constant.
(2lnT
m-ln β+ln[H
2]
m) to 1/T
mMapping is a straight line, can ask E by the slope of straight line
RThe change of hydrogen concentration and flow velocity causes T
mVariation and equation obtain dry straight consistent.This method sensitivity is high, and reducing action is as long as the consumption of hydrogen is that 1 μ mol just can be detected.
Described method comprises the steps:
(1) get 20～80 purpose catalyst samples, 0.2～0.3g, the sample hose 13 of packing into, two ends add a small amount of silica sand of handling, and at a small amount of beyond the Great Wall glass wool of port pine loose ground;
(2) sample pretreatment.With He (or N
2) be carrier gas, switch first four-way valve 6, make first interface 601 of first four-way valve 6 be in the position that communicates with second interface 602; Switch first six-way valve 8, make the 3rd interface 803 of first six-way valve 8 be in the position that communicates with the 4th interface 804; Switch second six-way valve 11, make first interface 1101 of second six-way valve 11 be in the position that communicates with second interface 1102, the 3rd interface 1103 is in the position that communicates (the TPR operation does not relate to second four-way valve 7) with the 4th interface 1104;
At this moment, He enters from carrier gas air source inlet 18, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, mixer 5, first interface, 601 places by first four-way valve 6 flow into, flow out at second interface, 602 places, place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and flow out, then flow into the place, gas access of sample hose 13 and flow out by its exit by first interface, 1101 places; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Second cold-trap 15 of flowing through subsequently flows into the place, gas access of conductance cell 16 gage beams 1602 and flows out and emptying from its exit.
Make He pass through sample hose 13 with the flow velocity of 30～90ml/min, the speed with 3～20 ℃/min heats up heating furnace 14 simultaneously, rises to 100～800 ℃ by room temperature, and constant temperature still dropped to room temperature at logical He after 1～3 hour, closed the He source;
(3) with H
2Be reducing gas, enter the pressure maintaining valve 1 of flowing through, drying tube 2, flow stabilizing valve 31, gas meter 4, mixer 5 from work air source inlet 19.Regulate H
2Flow, and then open He source of the gas, H
2-He mixes in mixer 5, and the control total flow obtains 5～10%H at 30～90ml/min
2-He combination gas;
The position of each four-way valve, six-way valve all remains unchanged at this moment, and the air-flow approach when promptly mixed gas is flowed through approach and sample pretreatment is identical.
Open detecting device and computer sampling system, treat baseline stability after, start the temperature controller program, heating furnace 14 is heated up with 5～25 ℃/min speed, temperature rises to 400～800 ℃ by room temperature.Begin to carry out the temperature programme surface reduction.
(4) voltage signal exported of thermopair in the sample hose 13 and conductance cell 16 through A/D (analog/digital) conversion back input computing machine show, printing, can obtain the TPR spectrogram of catalyzer.
Adopt above-mentioned instrument by temperature programmed desorption (TPD) method the surface nature of catalyzer to be tested, ultimate principle is such:
The TPD technology is a kind of flow method, be applicable to practical Application of Catalyst fundamental research, though constantly occur advanced experimental apparatus and research method now, wait surface nature and the active sites order of studying catalyzer as photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), ion scattering (ISS), paramagnetic resonance method (ESR), but very complicated.We can say that the TPD technology is more superior, and suitable room for development is arranged.
For uniform outer surface, there is not the thermal desorption fundamental equation that absorption again takes place:
2logT
m-logβ＝E
d/2.303RT
m+logE
d/ARnθ
m n-1
The one-level desorption process can be reduced to:
2logT
m-logβ＝E
d/2.303RT
m+logE
d/AR
In the formula
β--------heating rate;
T
m--------temperature when the peak occurring;
E
d--------energy of activation during desorption;
The A--------pre-exponential factor;
N--------desorption progression;
θ
m-------T=T
mThe time coverage;
The R--------gas law constant.
Change heating rate β and can obtain corresponding T
mWith (2logT
m-log β) to 1/T
mMap a straight line, can try to achieve E by the slope and the intercept of straight line
dAnd A, by E
dWith the A situation of activated centre energy distribution as can be known.Further can try to achieve the desorption rate constant K by the Arrhenius equation
dTemperature dependency.Described method comprises the steps:
(1) catalyzer is packed into sample hose 13, two ends add the silica sand of handling on a small quantity, and at a small amount of beyond the Great Wall glass wool of port pine loose ground;
(2) catalyst sample is done activation or cleaning surfaces processing;
(3) catalyzer is to the absorption of adsorbate
The I adsorbate is liquid operation
With He gas is other gas, and He gas is introduced by other air source inlet 20 places.Switch second four-way valve 7, make second interface 702 of second four-way valve 7 and the 4th interface 704 be in the position that communicates; Switch first six-way valve 8, make first interface 801 of first six-way valve 8 and second interface 802 be in the position that communicates, the 5th interface 805 and the 6th interface 806 are in the position that communicates; Switch second six-way valve 11, make first interface 1101 of second six-way valve 11 and the 6th interface 1106 be in the position that communicates, the 4th interface 1104 and the 5th interface 1105 are in the position that communicates (catalyzer does not relate to first four-way valve to the adsorption operations of adsorbate);
At this moment, He gas is introduced by other air source inlet 20 places, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, flows out by second interface, the 702 places inflow of second four-way valve 7 and by the 4th interface 704 places; Then flow into first interface 801 of first six-way valve 8 and by flowing out at second interface, 802 places, flow into the 5th interface 805 of these six-way valves 8 and flow out through quantity tube 9 again by the 6th interface 806 places; Flow into then and the place, liquid adsorbate saturator 10 gas accesses that accounts for its volume 1/5～1/3 has been housed and the adsorbate steam is taken out of from the exit; This combination gas (He and adsorbate steam) flows out by the 6th interface 1106 inflows of second six-way valve 11 and from first interface 1101, flow into the air intake opening of sample hose 13 again, the sample absorption of flowing in the pipe, residual air flow to the 4th interface 1104 of second six-way valve 11 from the gas outlet of sample hose 13 and by 1105 emptying of the 5th interface.
Make He gas pass through saturator, bring the adsorbate steam into sample hose, the absorption regular hour with the flow velocity of 10～60ml/min.
The II adsorbate is the operation of gaseous state
Only need adsorbate gas is directly replaced above-mentioned He gas (need not to adorn adsorbate in the saturator), gas flow rate and flow process are all the same.
Purging before the III TPD
Making He gas is that carrier gas enters from carrier gas air source inlet 18, and switch valve makes first interface 601 of first four-way valve 6 be in the position that communicates with second interface 602; The 3rd interface 803 of first six-way valve 8 is in the position that communicates with the 4th interface 804; First interface 1101 of second six-way valve 11 is in the position that communicates with second interface 1102, throws off the 4th interface 1104 junction of sample hose 13 outlets and second six-way valve 11 again.
This time, He gas enters from carrier gas air source inlet 18, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, mixer 5, first interface, 601 places by first four-way valve 6 flow into, flow out at second interface, 602 places, 1601 places, reference arm gas access by conductance cell 16 flow into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and, then flow into the place, gas access and the emptying of sample hose 13 by direct outflow the in its exit by the outflow of first interface, 1101 places.
He gas is by above-mentioned gas circuit, and at room temperature scavenging pipeline and sample are 1～3 hour, and the flow velocity of He is 10～60ml/min, wait to purge finish after, again sample hose 13 outlets are connect mutually with the 4th interface 1104 of second six-way valve 11;
At this moment, He gas enters from carrier gas air source inlet 18, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, mixer 5, first interface, 601 places by first four-way valve 6 flow into, flow out at second interface, 602 places, place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and flow out, then flow into the place, gas access of sample hose 13 and flow out by the exit by first interface, 1101 places; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Flow through behind second cold-trap 15, the gas access of inflow conductance cell 16 gage beams 1602 is located and is flowed out and emptying from the exit again.
No matter adsorbate is liquid or gas, and the purge operations before the temperature programmed desorption is all identical.
(4) open detecting device and computer sampling system, treat baseline stability after, start heating furnace temperature controller program, heating furnace 14 is heated up with 5～25 ℃/min speed, temperature rises to 400～800 ℃ by room temperature, begins to carry out temperature programmed desorption.
(5) voltage signal exported of thermopair in the sample hose 13 and conductance cell 16 through A/D (analog/digital) conversion back input computing machine show, printing, can obtain the TPD spectrogram of catalyzer.
Adopt above-mentioned instrument to pass through H
2-O
2Titration technique (HOT) method is tested the surface nature of catalyzer, and ultimate principle is such:
If by chemisorption, then there is a simple relation in adsorbate with the form of individual layer between by the metallic atom number of saturated adsorption gas molecule number and catalyst surface.Therefore, just can directly obtain the atom number of surface metal by measuring adsorption molecule in the chemisorption amount of adsorbent surface, and then obtain the dispersion situation of surface metal.
If the sectional area of a metallic atom is known, then can calculate the specific surface of metal.Atomic model as surface metal also is known, then also can calculate the average crystal grain size of metal.
Described method comprises the steps:
Get 20～80 purpose dry catalysts 0.2～1.0 gram sample hose 13 of packing into, two ends add a small amount of silica sand of handling, and at port pine loose ground plug with a small amount of glass wool.
(1) with H
2Gas is working gas, and stream valve 31 cuts out, and flow stabilizing valve 32 is in open mode; Switch valve makes first interface 601 of first four-way valve 6 and second interface 602 be in the position that communicates, and the 3rd interface 603 and the 4th interface 604 are in the position that communicates; The 3rd interface 703 and the 4th interface 704 of second four-way valve 7 are in the position that communicates; First interface 801 of first six-way valve 8 is in the position that communicates with second interface 802, and the 5th interface 805 and the 6th interface 806 are in the position that communicates; First interface 1101 and the 6th interface 1106 of second six-way valve 11 are in the position that communicates, and the 4th interface 1104 and the 5th interface 1105 are in the position that communicates.
At this moment, H
2Gas is introduced from work air source inlet 19, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 32, gas meter 4, flows out by the 4th interface 604 places inflow of first four-way valve 6 and by the 3rd interface 603 places; Then flow into the 3rd interface 703 places of second four-way valve 7 and flow out by the 4th interface 704 places; Flow into first interface 803 of first six-way valve 8 subsequently and by flowing out at second interface, 802 places, flow into the 5th interface 805 of these six-way valves 8 and flow out through quantity tube 9 again by the 6th interface 806 places; Flow into the air intake opening of saturator 10 then and flow out by the gas outlet; Flow into the 6th interface 1106 of second six-way valve 11 again and flow out from first interface 1101; Then flow into the air intake opening of sample hose 13, flow to the 4th interface 1104 of second six-way valve 11 from the gas outlet of sample hose 13 again and by 1105 emptying of the 5th interface.
Make H
2Gas passes through sample hose 13 with the flow velocity of 10～30ml/min, the heating rate of heating furnace 14 is 5～20 ℃/min, be warming up to after a certain temperature between 200～700 ℃ the constant temperature reduction 1～4 hour by room temperature, and then it is be cooled to constant temperature after a certain temperature between room temperature～400 ℃, and constant in this temperature in follow-up " chemisorption of oxygen ", " hydrogen titration " experimentation.With He (or N
2) gas is that carrier gas enters from carrier gas source inlet 18, by sample hose 13, closes H with the flow velocity of 10～60ml/min simultaneously
2Gas.Logical He (or N
2) purpose of gas is to remove H remaining in the pipeline
2Gas, He (or N
2) air-blowing swept 0.5～2 hour.
He (or N
2) when air-blowing was swept, first interface 601 and the 3rd interface 603 of first four-way valve 6 were in the position that communicates; The 3rd interface 703 and the 4th interface 704 of second four-way valve 7 are in the position that communicates; First interface 801 and second interface 802 of first six-way valve 8 are in the position that communicates, and the 5th interface 805 and the 6th interface 806 are in the position that communicates; The first and the 6th interface 1101,1106 of second six-way valve 11 is in the position that communicates, and the 4th interface 1104 and the 5th interface 1105 are in the position that communicates.
This time, He (or N
2) gas enters from carrier gas air source inlet 18, behind flow through corresponding pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, the mixer 5, flow into and flow out by the 3rd interface 603 places by first interface, 601 places of first four-way valve 6; Then flow into the 3rd interface 703 places of second four-way valve 7 and flow out by the 4th interface 704 places; Flow into first interface 801 of first six-way valve 8 subsequently and by flowing out at second interface, 802 places, flow into the 5th interface 805 of these six-way valves 8 and flow out through quantity tube 9 again by the 6th interface 806 places; Flow into the air intake opening of saturator 10 then and flow out by the gas outlet; Flow into the 6th interface 1106 of second six-way valve 11 again and flow out from first interface 1101; Then flow into the air intake opening of sample hose 13, flow to the 4th interface 1104 of second six-way valve 11 from the gas outlet of sample hose 11 again and by 1105 emptying of the 5th interface.
He (or N
2) when end is swept in air-blowing, switch valve, first and second interfaces 601 with first four-way valve 6,602 are in the position that communicates, third and fourth interface 703 of second four-way valve 7,704 are in the position that communicates, third and fourth interface 803 of first six-way valve 8,804 are in the position that communicates, first and second interfaces 1101,1102 of second six-way valve 11 are in the position that communicates, and the 3rd interface 1103 and the 4th interface 1104 are in the position that communicates, the 5th interface 1105 and the 6th interface 1106 are in the position that communicates, and open conductance cell 16 and computer sampling system then.
After purging end, He (or N
2) gas still enters from carrier gas source inlet 18, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, mixer 5, flow into and flow out by second interface, 602 places by first interface, 601 places of first four-way valve 6; Place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and flow out, then flow into the place, gas access of sample hose 13 and flow out by its exit by first interface, 1101 places; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Second cold-trap 15 of flowing through subsequently flows into the place, gas access of conductance cell 16 gage beams 1602 and flows out and emptying from the exit.
(2) chemisorption of oxygen
With O
2Gas is other work gas, only switches second four-way valve 7, makes second interface 702 of second four-way valve 7 and the 4th interface 704 be in the position that communicates, and all the other valve locations all remain unchanged, O
2Gas velocity is 10～60ml/min.
This time, O
2Gas enters from other air source inlet 20, behind flow through corresponding pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, the gas meter 4, flows into second interface, 702 places of second four-way valve 7 and is flowed out by the 4th interface 704 places; Flow into first interface 801 of first six-way valve 8 subsequently and by flowing out at second interface, 802 places, flow into the 5th interface 805 of these six-way valves 8 and flow out through quantity tube 9 again by the 6th interface 806 places; Flow into the air intake opening of saturator 10 then and flow out by the gas outlet; Flow into the 6th interface 1106 of second six-way valve 11 again and from 1105 emptying of the 5th interface.
As seen, two-way gas (He gas and O are arranged simultaneously in the instrument
2Gas) along separately gas circuit, mutual irrelevant ground constant speed is flowing.
Then, keep the invariant position of all the other valves, only switch first six-way valve 8.Make first interface 801 and the 6th interface 806 of first six-way valve 8 be in the position that communicates, second interface 802 and the 3rd interface 803 are in the position that communicates, and the 4th interface 804 and the 5th interface 805 are in the position that communicates.
This moment O
2Gas flows out at the 4th interface 704 places of second four-way valve 7, flows into first interface 801 of first six-way valve 8 again and flows out (quantity tube 9 of no longer flowing through) by the 6th interface 806 places, flows into the air intake opening of saturator 10 then and is flowed out by the gas outlet; Flow into the 6th interface 1106 of second six-way valve 11 again and from 1105 emptying of the 5th interface.
And He gas is flowed out by conductance cell 16 reference arms 1601 gas outlets this moment, flows into the 3rd interface 803 of first six-way valve 8 and by the outflow of second interface, 802 places, flows into quantity tube 9 subsequently, with the O in the quantity tube 9
2The band of gas is gone into the 5th interface 805 of first six-way valve 8 and is flowed out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 again and flow out the O in this quantity tube 9 by first interface, 1101 places
2Gas in sample surfaces generation chemisorption, consumes part of O along with He gas flows into sample hose 13 again
2Gas, residual gas is flowed out by sample hose 13 exits; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Second cold-trap 15 of flowing through subsequently flows into the place, gas access of conductance cell 16 gage beams 1602 and flows out and emptying from the exit.Obviously, the gas componant of conductance cell 16 reference arms 1601 of flowing through is different with the gas componant of conductance cell 16 gage beams 1602 of flowing through, thereby causes the variation of the voltage signal that conductance cell 16 exported.
After 2～10 seconds, make first six-way valve 8 switch go back to the origin-location again, even first interface 801 of first six-way valve 8 and second interface 802 are in the position that communicates, the 3rd interface 803 and the 4th interface 804 are in the position that communicates, and the 5th interface 805 and the 6th interface 806 are in the position that communicates.At this moment, He gas and O
2Along separately gas circuit, mutual irrelevant ground constant speed is flowing gas again.
Once switching back and forth of above-mentioned first six-way valve 8 promptly claims pulse to advance O
2Once (with the O in the quantity tube
2Mode with pulse is brought sample hose into by He).Along with the number of times increase of pulse sample introduction, O
2In the sample surfaces chemisorption that reaches capacity gradually.O is advanced in pulse
2Repeatedly, measure the O in the effluent gases after each pulse
2The spectrum peak area, in sample hose sample no longer with O
2Till the effect (this time O
2The spectrum peak area will remain unchanged).The time interval of two subpulses is 2～10min.
(3) hydrogen titration
With H
2Be work gas, H
2Gas velocity is 10～60ml/min.Switch valve makes third and fourth interface 603,604 of first four-way valve 6 be in the position that communicates, and first and second interfaces 601,602 are in the position that communicates; Third and fourth interface 703,704 of second four-way valve 7 is in the position that communicates; First and second interfaces 801,802 of first six-way valve 8 are in the position that communicates, and third and fourth interface 803,804 is in the position that communicates, and the 5th and the 6th interface 805,806 is in the position that communicates; First and second interfaces 1101,1102 of second six-way valve 11 are in the position that communicates, and third and fourth interface 1103,1104 is in the position that communicates, and the 5th and the 6th interface 1105,1106 is in the position that communicates.
This time, H
2Gas enters from work air source inlet 19, behind the corresponding pressure maintaining valve 1 of flowing through, drying tube 2, flow stabilizing valve 32 (flow stabilizing valve 31 is in closed condition), the gas meter 4, flows out by the 4th interface 604 places inflow of first four-way valve 6 and by the 3rd interface 603 places; Then flow into the 3rd interface 703 of second four-way valve 7 and flow out by the 4th interface 704 places; Flow into first interface 801 of first six-way valve 8 subsequently and by flowing out at second interface, 802 places, flow into the 5th interface 805 of these six-way valves 8 and flow out through quantity tube 9 again by the 6th interface 806 places; Flow into the air intake opening of saturator 10 then and flow out by the gas outlet; Flow into the 6th interface 1106 of second six-way valve 11 again and flow out and emptying from the 5th interface 1105.
He gas still enters from carrier gas source inlet 18, and its flow velocity and flow process all remain unchanged.
At this moment, two-way gas (He gas and H are arranged simultaneously in the instrument
2Gas) along separately gas circuit, mutual irrelevant ground constant speed is flowing.
Then, H is advanced in pulse
2(advance O as pulse
2Equally operate), i.e. H
2Gas is brought into sample hose 13 with impulse form by carrier gas He, with the O of sample surfaces chemisorption
2Reaction claims H
2Titration.The time interval of two subpulses is 2～10min.Measure after each pulse H in the effluent gases
2The spectrum peak area; H in effluent gases
2Peak area constant till.
The voltage signal that thermopair in the sample hose 13 and conductance cell 16 are exported changes input computing machine demonstration after A/D (analog/digital) conversion respectively, prints, and can obtain the HOT spectrogram.
(4) advance H by each subpulse
2Peak area, by following various calculating, can try to achieve dispersion degree, specific surface and the grain size etc. of sample:
In the formula: A
iAdvance H the i time
2The time peak area
A
sBase peak area (during titration, last invariable peak area)
V
sThe pulse sample size (the quantity tube volume, ml)
V
aH
2Adsorbance (ml)
II is with V
aVolume when being converted into standard state by following formula
In the formula: T is room temperature (K); P is atmospheric pressure (mmHg)
III dispersion degree dispersion degree is the oxygen atomicity [O] or the surfactivity metallic atom number [M of chemisorption
*] with catalyzer on the ratio of total metallic atom number [M].Oxygen absorption is undertaken by following form with the hydrogen titration:
When being chemisorption, oxygen atom of a Pt atomic adsorption;
When titration, the oxygen atom of chemisorption on Pt consumes two hydrogen atoms, react, generate water, be adsorbed on the carrier, simultaneously because the Pt atom itself will adsorb a hydrogen atom after deoxidation, so, titration is adsorbed on the used hydrogen amount of oxygen atom itself on the Pt, only is 2/3 of total hydrogen-consuming volume, i.e. Biao Mian Pt atomicity (Pt
*) be the H that consumes
22/3 of molecular number.So be calculated as follows dispersion degree:
In the formula: M is the atomic weight of carried metal; W is catalyst quality (g); P% is the percent by weight of carried metal in the catalyzer; V
a 0(H
2) H when being the mark attitude
2Adsorbance (ml).
The IV specific surface
In the formula: N
ABe the A Fujiadeluo constant; σ is the cross-sectional area (cm of metallic atom
2).
The V grain size also is the average crystal grain size.It calculates based on Hughes[] on the model based.The basic assumption of Hughes is: all Pt crystal grain all is desirable, cube of a size, and its face contacts with carrier, and remaining five face is exposing, and cubical one side length d is relevant with surface area S, volume V or density p, that is:
In the formula: S is specific surface area (cm
2/ g); V is specific volume (cm
3/ g); ρ is the density (g/cm of Pt
3).
Adopt above-mentioned instrument by temperature programmed surface reaction (TPSR) method the surface nature of catalyzer to be tested, ultimate principle is such:
In the temperature programme process, surface reaction and desorption take place simultaneously, are called temperature programmed surface reaction.This technology generally has two kinds of ways: the first will be adsorbed under reaction conditions and react through preprocessed catalyst, and the temperature from the room temperature temperature programme to a certain setting is come out each adsorbed on catalyst surface surface species limit border ring desorption again; It two is itself to be exactly reactant as the carrier gas of desorption (or in the carrier gas certain component), in the temperature programme process, and carrier gas (or in the carrier gas certain component) certain adsorbing species that reaction forms on catalyst surface, on one side reaction, desorption on one side.
Consider desirable absorption situation, the desorption thing no longer adsorbs, and the molecule of adsorbing species is attracted on the uniform catalyst surface, then surface reaction speed γ
ROr desorption rate γ
DCan be expressed as general formula
γ
i＝-dθ/dt＝K
iθ
n＝A
iθ
nexp[-(E
i/RT)] (1)
K
i: reaction or desorption rate constant; θ: surface coverage; N: the progression of reaction or desorption; E
i: reaction or desorptive activation energy; T: time; T: absolute temperature.Suppose that herein catalyst surface is even, be about to E
iRegard irrelevant amount as with θ.
Temperature continuously changes during temperature programme, meets following formula
T=T
o+ β t or dT/dt=β (2)
β: heating rate; T
o: begin to react and the temperature during desorption.
When carrying out TPSR, along with the rising of temperature, a maximum value appears in reaction or desorption rate.Carrier gas is taken the desorption thing out of from catalyzer, can obtain to be proportional to the desorption peaks of desorption substrate concentration by pick-up unit.Peak area is represented the size of desorption rate, T
mPeak temperature when reaching maximal value for desorption rate.
When maximum value appears in desorption peaks, d γ
iSo/dt=0 to (1) decline branch and make it equal zero, can get after the arrangement
2LogT
m-Logβ＝E
i/2.303RT
m+Log(E
i/A
iR) (3)
This formula explanation E
iWith β, T
mBetween have definite quantitative relationship.
Said method comprises the steps:
(1) get 20～80 purpose dry catalysts, 0.2～1.0 gram sample, the sample hose 13 of packing into, two ends add a small amount of silica sand of handling, and at a small amount of beyond the Great Wall glass wool of port pine loose ground.In saturator 10, add the liquid reactant that accounts for its volume 1/5～1/3.
(2) sample pretreatment.He gas is introduced by other air source inlet 20 places, switched second four-way valve 7, make second interface 702 of second four-way valve 7 and the 4th interface 704 be in the position that communicates; Switch first six-way valve 8, make first interface 801 of first six-way valve 8 and second interface 802 be in the position that communicates, the 5th interface 805 and the 6th interface 806 are in the position that communicates; Switch second six-way valve 11, make first interface 1101 and the 6th interface 1106 of second six-way valve 11 be in the position that communicates, the 4th interface 1104 and the 5th interface 1105 are in the position that communicates (adsorption operations of catalyzer liquid towards reactant does not relate to first four-way valve 6).
At this moment, He gas is introduced by other air source inlet 20 places, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, flows out by second interface, the 702 places inflow of second four-way valve 7 and by the 4th interface 704 places; Then flow into first interface 801 of first six-way valve 8 and by flowing out at second interface, 802 places, flow into the 5th interface 805 of these six-way valves 8 and flow out through quantity tube 9 again by the 6th interface 806 places; Flowing into saturator 10 gas accesses then locates and reactant vapor is taken out of from the exit; This combination gas (He and reactant vapor) flows out by the 6th interface 1106 inflows of second six-way valve 11 and from first interface 1101, flow into the air intake opening of sample hose 13 again, the sample absorption of flowing in the pipe, residual air flow to the 4th interface 1104 of second six-way valve 11 from 13 gas outlets of sample hose and by 1105 emptying of the 5th interface.
He gas passes through saturator 10 with the flow velocity of 10～60ml/min, and brings reactant vapor into constant sample hose 13 at proper temperature, makes sample absorption 1～3 hour.Absorption finishes, and closes this gas circuit, makes the sample hose temperature revert to room temperature.
As reactant is gaseous state, then can directly this gaseous reactant be replaced He to introduce from other air source inlet and get final product (need not to refill reactant in the saturator).
Then He gas is introduced from carrier gas air source inlet 18, switch valve makes first interface 601 of first four-way valve 6 be in the position that communicates with second interface 602; The 3rd interface 603 of first six-way valve 6 is in the position that communicates with the 4th interface 604; First interface 1101 of second six-way valve 11 is in the position that communicates with second interface 1102, throws off the 4th interface 1104 junction of sample hose 13 outlets and second six-way valve 11 again.
This time, He gas enters from carrier gas air source inlet 18, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, mixer 5, is flowed into by first interface, 601 places of first four-way valve 6, flow out at second interface, 602 places; Place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and, then flow into the place, gas access and the emptying of sample hose 13 by direct outflow the in its exit by the outflow of first interface, 1101 places.
He is by above-mentioned gas circuit, and with the flow velocity of 10～60ml/min, at room temperature scavenging pipeline and sample are 1～3 hour, remove the reactant of reversible adsorption.
After treating that purging finishes, again sample hose 13 outlets are connect mutually with the 4th interface 1104 of second six-way valve 11.At this moment, He gas enters from carrier gas air source inlet 18, behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, mixer 5, first interface, 601 places by first four-way valve 6 flow into, flow out at second interface, 602 places, place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and flow out, then flow into the place, gas access of sample hose 13 and flow out by the exit by first interface, 1101 places; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Flow through behind second cold-trap 15, the gas access of inflow conductance cell 16 gage beams 1602 is located and is flowed out and emptying from the exit again.
Flow velocity when He gas still keeps purging passes through sample.
(3) open detecting device and computer sampling system, treat baseline stability after, start the temperature controller program, heating furnace 14 is heated up with 5～25 ℃/min speed, temperature rises to 400～800 ℃ by room temperature.Begin to carry out temperature programmed surface reaction.
The voltage signal that thermopair in the sample hose 13 and conductance cell 16 (or hydrogen flame detector 17) are exported changes input computing machine demonstration after A/D (analog/digital) conversion respectively, prints, and can obtain the TPSR spectrogram.
(4), can collect the reaction mixture of a certain temperature range by second cold-trap 15 to organic substance.Utilize inert carrier gas (He, N then
2Deng) it is taken out of, detect forming and print the result after the chromatographic column of flowing through by computer sampling systematic analysis reaction mixture by hydrogen flame detector.
Adopt above-mentioned instrument by temperature programmed oxidation (TPO) method the surface nature of catalyzer to be tested, ultimate principle is such:
Work as O
2During the catalyst surface of the mixed gas that is mixed with inert gas He by carbon distribution, for certain specific carbon species, it will be under specific temperature with combination gas in O
2Oxidation reaction takes place, and will consume the O in the combination gas this moment
2In case the gas componant of the conductance cell reference arm of flowing through changes with the gas componant of the gage beam of flowing through, the output electric signal of conductance cell will become thereupon.If with the temperature of certain heating rate change catalyst sample, the O of the sample surfaces of flowing through so
2When certain temperature and the reaction of certain carbon species, when another temperature, react with another carbon species.Can get temperature～time thus, the curve of conductance cell output signal～time, as these two curves are shown in the same coordinate system, the gained spectrogram is the TPO spectrum.
The TPO technology is mainly used in the charcoal regeneration of carbon deposition catalyst and investigates, and also is useful on the reaction in research gas phase oxygen and catalyst surface absorption hydrogen and surperficial oxygen room.
Charcoal regeneration for catalyzer is investigated, and TPO can reflect each the temperature oxygen consumption situation in the carbon overall process of burning continuously, and the speed of carbon is burnt in reflection indirectly.Can show the heterogencity degree of carbon species by oxygen consumption peak number order, shape etc., can carry out related with carbon deposition quantity by TPO oxygen consumption peak area.
Described method comprises the steps:
(1) get the dry carbon deposition catalyst sample 0.2～1.0 of 20～80 purposes and restrain the sample hose 13 of packing into, two ends add a small amount of silica sand of handling, and at a small amount of beyond the Great Wall glass wool of port pine loose ground.
With O
2Enter the pressure maintaining valve 1 of flowing through, drying tube 2, flow stabilizing valve 31, gas meter 4, mixer 5 from work air source inlet 19.He gas enters from carrier gas air source inlet 18, flows through behind corresponding pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, the gas meter 4, also enters mixer 5.Make two-way gas in mixer 5, preparation is mixed into the O that flow velocity is 10～60ml/min
2+ He combination gas (O
2Percent by volume 5～20%).
The position of each valve is: first interface 601 of first four-way valve 6 is in the position that communicates with second interface 602; The 3rd interface 603 of first six-way valve 6 is in the position that communicates with the 4th interface 604; First interface 1101 of second six-way valve 11 is in the position that communicates with second interface 1102, and the 3rd interface 1103 is in the position that communicates (the TPO operation does not relate to second four-way valve) with the 4th interface 1104.
At this moment, combination gas flows out from mixer 5 exits, and first interface, 601 places by first four-way valve 6 flow into again, and flow out at second interface, 602 places; Place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and flow out, then flow into the place, gas access of sample hose 13 and flow out by its exit by first interface, 1101 places; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Second cold-trap 15 of flowing through subsequently flows into the place, gas access of conductance cell 16 gage beams 1602 and flows out and emptying from the exit.
(3) open thermal conductivity cell detector and computer sampling system; The heating rate of heating furnace 14 is set at 5～25 ℃/min, and temperature rises to 400～800 ℃ by room temperature.The voltage signal that thermopair in the sample hose 13 and conductance cell 16 are exported changes input computing machine after A/D (analog/digital) conversion respectively, after treating baseline stability, start heating furnace temperature controller program, show, print the TPO spectrogram of derived sample by computing machine.
Adopt above-mentioned instrument by temperature Programmed Decomposition (TPDE) method the surface nature of catalyzer to be tested, ultimate principle is such:
Temperature Programmed Decomposition is the variation of research catalyzer its character and state in heating process, and this is changed function as temperature or time, studies a kind of technology of its rule.That is under temperature programme, dynamically measure a class technology of catalyst property and temperature relation.When sample is heated in heating furnace, rising gradually along with temperature, the material of some sample surfaces will begin desorption or decompose desorption, and these materials of deviating from are brought into thermal conductivity cell detector (or multi-ion detection of chromatography-mass spectroscopy instrument) by inert carrier gas immediately and detect.
Described method comprises the steps:
(1) get 20～80 purpose dry catalysts 0.2～1.0 and restrain the sample hose 13 of packing into, two ends add a small amount of silica sand of handling, and at a small amount of beyond the Great Wall glass wool of port pine loose ground.
(2) with He (or N
2) gas is from 18 introducings of carrier gas air source inlet, switch valve makes first interface 601 of first four-way valve 6 be in the position that communicates with second interface 602; The 3rd interface 803 of first six-way valve 8 is in the position that communicates with the 4th interface 804; First interface 1101 of second six-way valve 11 is in the position that communicates with second interface 1102, and the 3rd interface 1103 is in the position that communicates with the 4th interface 1104.
At this moment, He (or N
2) gas enters from carrier gas air source inlet 18, flow through behind pressure maintaining valve 1, drying tube 2, flow stabilizing valve 3, gas meter 4, the mixer 5, first interface, 601 places by first four-way valve 6 flow into, flow out at second interface, 602 places, place, reference arm 1601 gas accesses by conductance cell 16 flows into then, and flow out in the exit; Flow into the 3rd interface 803 places of first six-way valve 8 again and flow out by the 4th interface 804 places; Behind first cold-trap 12, flow to second interface, 1102 places of second six-way valve 11 and flow out, then flow into the place, gas access of sample hose 13 and flow out by the exit by first interface, 1101 places; Flow into the 4th interface 1104 places of second six-way valve 11 again and flow out by the 3rd interface 1103 places; Flow through behind second cold-trap 15, the gas access of inflow conductance cell 16 gage beams 1602 is located and is flowed out and emptying from the exit again.Carrier gas He (or N2) flow velocity is 20～60ml/min.
(3) open thermal conductivity cell detector and computer sampling system; The heating rate of heating furnace 14 is set at 5～25 ℃/min, and temperature rises to 400～800 ℃ by room temperature.The voltage signal that thermopair in the sample hose 13 and conductance cell 16 are exported changes input computing machine after A/D (analog/digital) conversion respectively.After treating baseline stability, start heating furnace temperature controller program, show, print the TPDE spectrogram of derived sample by computing machine.
Adopt instrument as shown in Figure 1, carry out the TPR test containing Cu houghite catalyzer.
1). that gets that calcination process crosses contains Cu houghite 0.2g, reducing gas H
2Account for H
25% (combination gas overall flow rate: 50ml/min) of-He combination gas;
2). treat baseline walk steady after, carry out temperature programmed reduction with the heating rate of 10 ℃/min.Its TPR spectrum is Fig. 2.
As a comparison, done the TPR test of CuO again.
1). get dry CuO0.04g, reducing gas H
2Account for H
25% (combination gas overall flow rate: 50ml/min) of-He combination gas;
2). treat baseline walk steady after, carry out temperature programmed reduction with the heating rate of 10 ℃/min.Its TPR spectrum is Fig. 3.
As seen from the figure, the TPR spectrogram that contains Cu houghite catalyzer and CuO all has only a spectrum peak, and the former top temperature is 262, and the latter's top temperature is 310, and the former top temperature has descended 48 by contrast.This explanation contains Cu houghite catalyzer plants the existence of oxide and interaction has taken place because of it, thereby causes the reducing property of active component cupric oxide to change.
Embodiment 2
Adopt instrument as shown in Figure 1, the ferric oxide catalyzer is carried out the TPD test.
1) ferric oxide catalyzer 0.8g, reducing gas H
2Account for H
25% (combination gas overall flow rate: 50ml/min) of-He combination gas; At 450 ℃ of following reductase 12 h; Then, close He, at logical H
2(30ml/min), be chilled to room temperature (27 ℃).
2) close H
2, open He (30ml/min) purging and remove the H of reversible adsorption
2, treat baseline walk steady after, carry out H with 25 ℃/min speed again
2Desorption.
Going out the peak direction can adjust by " positive negative " switch of selecting detecting device.The TPD spectrogram is seen Fig. 4.
As seen from Figure 4, this catalyzer has only the desorption peaks of a broadening, shows that the energy distribution on the catalyst surface is more even; The top temperature is 296 ℃, and this suction H is described
2The activated centre is a medium tenacity.
Embodiment 3
Adopt instrument as shown in Figure 1, carry out the TPD test containing the molybdenum molecular sieve catalyst.
1) get catalyzer 0.2 gram that high-temperature roasting is handled, the sample hose of packing into purges 1h at 400 ℃ of He, is cooled to 120 ℃ again, treat temperature constant after, with He through saturator with NH
3Steam is introduced in the sample hose and is adsorbed.
2) He (40ml/min) does carrier gas, purges to remove the NH of reversible adsorption
3, treat baseline walk steady after, carry out temperature programmed desorption with 10 ℃/min speed again.The TPD spectrogram is seen Fig. 5.
Spectrogram illustrates that there are three kinds of adsorption sites (top temperature: 242 ℃, 325 ℃, 472 ℃) at least in this catalyst surface, and its surperficial energy distribution is uneven, and based on the weak acid center.
Embodiment 4
Adopt instrument ， Dui Palladium catalyzer (Pd/Al as shown in Figure 1
2O
3) carry out HOT test.
1) absorption O
2Afterwards, use H
2The HOT spectrogram of titration is seen Fig. 6.As seen from the figure, the first five subpulse sample introduction does not have peak appearance, the 6th H
2Titration begins to occur the peak.
2) data processing.Each peak area is 157.798; 268.024; 270.976; 273.002; 277.182; 277.658; 277.607; 277.299; 277.361.Substitution corresponding calculated formula calculates V
a(H
2)=0.8488ml; V
a 0(H
2)=0.7571ml.The catalyst quality that takes by weighing during because of measurement is 0.8g, and it is 0.99% that this catalyzer contains the Pd percentage composition; So calculating can get the dispersion degree R=0.303 of this catalyst surface Pd.
Adopt instrument as shown in Figure 1, carry out the TPSR test containing Cu houghite catalyzer.
1) get above-mentioned catalyzer 1.0 grams, reactant is a cyclohexanol, and carrier gas is N
2, carry out pre-service set by step.
2) other end with sample hose links to each other with the 4th interface 1104 of second six-way valve 11, logical N
2(40ml/min), treat baseline walk steady after, carry out temperature programmed surface reaction with 10 ℃/min speed again.The TPSR spectrogram is seen Fig. 7.
As seen from Figure 7, occur two peaks on the TPSR spectrogram, its top temperature is respectively 80 ℃ and 188 ℃; The area of corresponding arbitrary unit is 1449 and 2821.Effluent to each peak correspondence carries out constituent analysis (effluent when collecting different temperatures with the cold-trap of this device detects with hydrogen flame detector), shows that the low temperature peak is a cyclohexanol, and the high temperature peak is mainly the product cyclohexanone except that a spot of cyclohexanol is arranged.Explanation exists two class adsorption reaction centers of cyclohexanol on the surface of this catalyzer, the low temperature peak is weak adsorption reaction center, conversion to the cyclohexanol molecule does not have influence, and the high temperature peak is corresponding to strong adsorption reaction center, and the cyclohexanol of absorption in the heart dehydrogenation reaction can take place in this type of.
From the area at two peaks, this catalyst surface is based on strong adsorption reaction center, and the cyclohexanol translation table is revealed higher activity.
Adopt instrument as shown in Figure 1, carry out the TPO test containing the Zn catalyzer.
1) taking by weighing the 0.3g catalyzer sample hose of packing into, behind the following 300 ℃ of activation 2h of logical He, is that the cyclohexanol steam is brought in carrier gas into He again, and sample is hung burnt the processing.Behind the reaction 4h, He purges 1h;
2) sample hose is inserted the synthesis measuring instrument apparatus, operate by the TPO operation steps.Temperature programme speed is 10 ℃/min.Fig. 8 is the TPO collection of illustrative plates of this catalyzer.
As seen from Figure 8,280 ℃ have begun to burn carbon, and about 600 ℃ are burnt the carbon end.Burning in the carbon overall process continuously, three oxygen consumption peaks appear, its top temperature be respectively 319 ℃ (acromions), 345 ℃ and 453 ℃.From the number at the asymmetry of peak shape and peak as can be known, the carbon distribution species are comparatively complicated.In addition, the area at preceding two peaks is 1.5 times of last peak area, and the carbon distribution species total amount that this explanation catalyst surface is 280-360 ℃ will be more than the total amount of high temperature carbon distribution species.
Adopt instrument as shown in Figure 1, CuZnAlCe houghite catalyzer is carried out the TPDE test.
1) takes by weighing the 0.1g catalyzer sample hose of packing into, logical carrier gas He (40ml/min);
2) sample hose is inserted the synthesis measuring instrument apparatus, operate by the TPDE operation steps.Temperature programme speed is 15 ℃/min.Fig. 9 is the TPDE collection of illustrative plates of this catalyzer.
As shown in Figure 9, this sample just decomposes since 56 ℃, until 469 ℃ of decomposition finish.From figure, to decompose and two mild " tack " peaks occur, the time that the former continues, the latter then continued nearly 9 minutes less than 1 minute, illustrated that the decomposable process of this sample is comparatively complicated.
Claims (6)
1. catalyst surface character comprehensive tester, it is characterized in that, this instrument comprises at least: carrier gas air source inlet (18), work air source inlet (19), other air source inlet (20), gas meter (4), mixer (5), first four-way valve (6), second four-way valve (7), first six-way valve (8), second six-way valve (11), saturator (10), temperature programmed control heating furnace (14), the sample hose of interpolation thermopair (13), conductance cell (16), cold-trap (12,14), chromatographic column and hydrogen flame detector (17) and computer sampling, spectrogram shows, print system links to each other with lead;
Said carrier gas air source inlet (18) is connected by pipeline with mixer (5) through gas meter (4), and the outlet of mixer (5) is connected with first interface (601) of first four-way valve (6);
Said work air source inlet (19) is connected with first interface (601) of mixer (5) and first four-way valve (6) through flow stabilizing valve (31), gas meter (4); Or behind flow stabilizing valve (32), gas meter (4), directly be connected with the 4th interface (604) of first four-way valve (6), the 3rd interface (603) of first four-way valve (6) is connected with the 3rd interface (703) of second four-way valve (7);
Said other air source inlet (20) is connected with second interface (702) of second four-way valve (7) through gas meter (4), and first interface (701) of second four-way valve (7) is a drain;
Second interface (602) of first four-way valve (6) is connected with the gas access of the reference arm (1601) of conductance cell (16), and the gas vent of conductance cell (16) reference arm (1601) is connected with the 3rd interface (803) of first six-way valve (8);
The 4th interface (704) of second four-way valve (7) is connected with first interface (801) of first six-way valve (8); Second interface (802) of first six-way valve (8) is connected with the 5th interface (805) through quantity tube (9), the 6th interface (806) is connected with the gas access of saturator (10), and the 4th interface (804) is connected with second interface (1102) of second six-way valve (11) through first cold-trap (12);
First interface (1101) of second six-way valve (11) is connected with the gas access of said sample hose (13), the 3rd interface (1103) links with second cold-trap (15), second cold-trap (15) other end is connected with hydrogen flame detector (17) with the gas access of conductance cell (16) gage beam (1602) or through chromatographic column, the 4th interface (1104) is connected with the gas vent of sample hose (13), the 5th interface (1105) is a drain, and the 6th interface (1106) is connected with the gas vent of saturator (10);
Said sample hose (13) is arranged in the heating furnace (14);
Conductance cell or hydrogen flame detector show with computer sampling, spectrogram with the thermopair electrical signal, print system links to each other with lead.
2. instrument according to claim 1 is characterized in that, said carrier gas air source inlet (18) is connected with gas meter (4) through pressure maintaining valve (1), drying tube (2), flow stabilizing valve (3).
3. instrument according to claim 1, it is characterized in that said work air source inlet (19) is connected with first interface (601) of mixer (5) and first four-way valve (6) through pressure maintaining valve (1), drying tube (2), flow stabilizing valve (31), gas meter (4); Or behind pressure maintaining valve (1), drying tube (2), flow stabilizing valve (32), gas meter (4), directly be connected with the 4th interface (604) of first four-way valve (6);
4. instrument according to claim 1 is characterized in that, said other air source inlet (20) is connected with gas meter (4) through pressure maintaining valve (1), drying tube (2), flow stabilizing valve (3).
5. each described instrument of claim 1～4 is used for the test of catalyst surface performance.
6. application according to claim 5 is characterized in that, adopts temperature programmed reduction method, temperature programmed desorption method, H
2-O
2A kind of surface property to catalyzer in titration technique, temperature programmed surface reaction method, temperature programmed oxidation method or the temperature programmed decomposition is tested.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150580 CN1214247C (en) | 2003-08-26 | 2003-08-26 | Catalyst surface-characteristic comprehensive measuring device and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03150580 CN1214247C (en) | 2003-08-26 | 2003-08-26 | Catalyst surface-characteristic comprehensive measuring device and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1490620A CN1490620A (en) | 2004-04-21 |
| CN1214247C true CN1214247C (en) | 2005-08-10 |
Family
ID=34156536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03150580 Expired - Fee Related CN1214247C (en) | 2003-08-26 | 2003-08-26 | Catalyst surface-characteristic comprehensive measuring device and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1214247C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101650324B (en) * | 2009-08-21 | 2011-04-06 | 重庆大学 | Device for testing heat map spectra of microbial biochemical reaction |
| CN102359989B (en) * | 2011-07-18 | 2013-06-19 | 上海上计群力分析仪器有限公司 | Multifunctional catalyst reaction evaluation and characterization device and application thereof |
| CN105424875B (en) * | 2014-09-03 | 2019-01-15 | 湖南华思仪器有限公司 | The straight adsorption tube of Dynamic Adsorption instrument |
| CN105445416A (en) * | 2014-09-03 | 2016-03-30 | 湖南华思仪器有限公司 | Dynamic adsorption instrument |
| CN105067752B (en) * | 2015-07-24 | 2017-04-19 | 中国科学院重庆绿色智能技术研究院 | Program heating analysis equipment and method for testing property of its catalyst |
| CN106442851B (en) * | 2016-09-20 | 2018-06-19 | 王宏铭 | Method for evaluating performance of catalyst |
| CN106442850B (en) * | 2016-09-20 | 2018-06-19 | 王宏铭 | Method for evaluating selectivity of catalyst |
| CN106841293B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst is evaluated using difference quotient thermogravimetric |
| CN106770452B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst is evaluated using thermal analysis system |
| CN106872518B (en) * | 2017-01-27 | 2019-05-28 | 王宏铭 | A kind of application method of the differential scanning calorimetric in evaluating catalyst |
| CN108445090A (en) * | 2018-03-29 | 2018-08-24 | 辽宁科技大学 | Realize device, the method for chemisorption amount and chemisorption electric signal simultaneous quantitative characterization |
| CN109030679A (en) * | 2018-07-19 | 2018-12-18 | 浙江赛鹭鑫仪器有限公司 | A kind of second level pyrolysis analysis system |
| CN110220941B (en) * | 2019-06-04 | 2020-08-04 | 江南大学 | Method for measuring carbon deposition content inside and outside microporous molecular sieve |
| CN113049517B (en) * | 2021-02-18 | 2023-02-03 | 天津科技大学 | Temperature programming-infrared spectrum combined device and application thereof in catalyst preparation |
| CN115552216A (en) * | 2021-03-26 | 2022-12-30 | 中国科学院上海微系统与信息技术研究所 | In-situ real-time programmed temperature analysis method |
| CN114216921B (en) * | 2021-05-08 | 2023-11-03 | 中国科学院上海微系统与信息技术研究所 | Method for testing activation energy of catalyst |
-
2003
- 2003-08-26 CN CN 03150580 patent/CN1214247C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1490620A (en) | 2004-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1214247C (en) | Catalyst surface-characteristic comprehensive measuring device and application thereof | |
| CN1028494C (en) | Carbon adsorption made from pyrolysed polymer of pore sulfonation | |
| CN1214849C (en) | Carbon dioxide absorption agent | |
| CN1213804C (en) | Method of activating catalyst for carbon monoxide removal method for removing carbon monoxide, method of operating fuel cell system | |
| CN1200262C (en) | Method and equipment for measuring amount of gas adsorbed by powder | |
| CN86106219A (en) | The sorbent material of Separation and Recovery carbon monoxide and method for making thereof, and with the method for its Separation and Recovery high-purity CO | |
| CN1849501A (en) | Low thermal inerta scanning adiabatic calorimeter | |
| CN1549792A (en) | Method for the selective production of ordered carbon nanotubes in a fluidised bed | |
| CN1656013A (en) | Low-temperature hydrogen production from oxygenated hydrocarbons | |
| Cassinelli et al. | Time-resolved XAS/MS/Raman monitoring of mutual copper self-reduction and ethanol dehydrogenation reactions | |
| Lamberti et al. | Description of a flexible cell for in situ X-ray and far-IR characterization of the surface of powdered materials | |
| CN1878604A (en) | Reactive gas filter | |
| Matusiewicz et al. | Determination of As, Sb, Se, Sn and Hg in beer and wort by direct hydride generation sample introduction− electrothermal AASPresented, in part, at the 1st International IUPAC Symposium on Trace Elements in Food, Warsaw, Poland, October 9–11, 2000. | |
| JP4763624B2 (en) | Analyzer with top-loading reaction tube | |
| CN102004130B (en) | Full-automatic multi-purpose adsorption instrument | |
| CN1135603A (en) | Method for making fifteen kinds of test paper for quickly testing common chemical contamination in food | |
| CN1189386C (en) | Hydrogen producer | |
| CN1844324A (en) | Preparation method of composite carbon carrier noble metal dehydrogenation catalyst | |
| CN1500065A (en) | Carbon monoxide removel method, operating method for fuel reforming system, carbon monoxide remover, fuel reforming system having carbon monoxide remover, and filter | |
| CN100338809C (en) | Method of activating catalyst for carbon monoxide removal, catalyst for removing carbon monoxide, method of removing carbon monoxide, and method of operating fuel cell system | |
| CN1021224C (en) | Process for making tetrahydrofuran and 1,4-butanediol using pd/re hydrogenation catalyst | |
| CN2834691Y (en) | An equipment for preparing metal nitride catalytic material | |
| CN1560317A (en) | Dynamic control system for low-pressure carburating heat treament furnace | |
| CN100345811C (en) | Acrylic acid production from propane in absence of molecular oxygen | |
| CN1267728C (en) | Soft measuring method for yield rate of catalytic cracking reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |