CN103529077A - Home position calorimetric pool - Google Patents
Home position calorimetric pool Download PDFInfo
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- CN103529077A CN103529077A CN201210234046.0A CN201210234046A CN103529077A CN 103529077 A CN103529077 A CN 103529077A CN 201210234046 A CN201210234046 A CN 201210234046A CN 103529077 A CN103529077 A CN 103529077A
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Abstract
The invention relates to a home position calorimetric pool which comprises a sample cup and a reference cup, wherein the two cups are made of Inconel 600TM passive stainless steel of which the structure is not changed in a high-temperature oxidation or reducing atmosphere. The sample cup is used for putting a sample, and the reference cup is empty or is used for putting an inert material, such as quartz sand. The top of the calorimetric pool is provided with a four-way valve, by virtue of switching the four-way valve, different gases are introduced so as to pretreat the sample or react with the sample, after pretreating or reacting is finished, the valve is switched so as to enable the sample to be insolated from outside gas impurities, and the four-way valve, a heat flow calorimeter and an impulse reaction system are combined to perform calorimetric measurement. The home position calorimetric pool provided by the invention can be used for performing quantitative measurement on the quantity, intensity and distribution of catalyst activity centers at different reaction stages, and taking the study on the variance of the catalyst activity centers during a reaction process.
Description
Technical field
The present invention relates to a kind of measurement mechanism applicable to high temperature gas-solid phase reaction process polity's sample surfaces activated centre in-situ characterization and research, in particular to a kind of original position calorimetric measurement pond.
Background technology
In heterogeneous catalytic reaction chemistry, catalytic reaction is carried out on catalyst surface active center, and therefore, the sign of catalyst active center is very important.Although have many modern physicses and chemical characterization method, such as XRD and TEM etc., in many cases, the activated centre of catalyzer is still difficult to determine.Before there is no the suitable quantitative description of effects on surface activated centre number, it is difficult that the reactivity worth in activated centre in different catalysts is compared, and this makes catalytic reaction data often not possess epitaxy.On the other hand, heterogeneous catalyst has comprised interaction special between activated centre and reactant, and this interaction strength research contributes to understand the essence of catalyst active center.The adsorption capacity heat technology that hot-fluid calorimeter combines with vacuum system is the effective means of quantitative examination catalyst active center.By selecting suitable reactant as probe molecule, adsorption capacity heat technology can provide quantity, intensity and the distribution thereof of catalyst active center quantitatively.
Yet, adsorption capacity heat technology is based upon on the basis of vacuum Static Adsorption, can not study the activated centre of catalyzer under reaction conditions, many researchs show, the activated centre of catalyzer can change under reaction conditions, the variation in this activated centre and reactivity associated not clear.In addition, how (for example: under prerequisite catalyst exposure air), the sign activated centre of original position is also very important not change activated centre essence.
Summary of the invention
The object of the present invention is to provide a kind of new original position calorimetric pond, it can be measured in catalytic reaction process on the one hand in situ, the variation of the quantity in activated centre, intensity and distribution thereof; On the other hand, by pulse reaction mode, the absorption of catalyst active center, course of reaction are carried out to calorimetric research, determine the variation of activated centre under reaction conditions.
For achieving the above object, original position calorimetric provided by the invention pond, it comprises:
A calorimetric pond, it comprises:
Four-way valve, sample cup and reference cup, two sleeve pipes, sleeve pipe is comprised of the inner and outer tubes of two end openings, and inner tube is set in outer tube, and the external diameter of inner tube is less than the internal diameter of outer tube;
Sample cup and reference cup are respectively the airtight cavity that upper end is provided with opening;
First interface of four-way valve is connected with inner tube one end of two sleeve pipes respectively by pipeline, and second interface of four-way valve is connected with outer tube one end of two sleeve pipes respectively by pipeline;
The other end of the outer tube of two sleeve pipes is connected with the openend of reference cup with sample cup respectively, and the other end of the inner tube of two sleeve pipes inserts respectively the bottom of sample cup and reference cup.
Described original position calorimetric pond, sample cup is by Inconel600
tMpassive stainless steel build.
Described original position calorimetric pond, sample cup and reference cup are by straight coupling and the outer seal of tube and removably connect.
Described original position calorimetric pond, sample cup is arranged with electric furnace outward, realizes temperature program(me) and controls.
By original position calorimetric provided by the invention pond, can be exposed under the condition of ambient atmos impurity, original position passes into different gas and sample is processed or reacted, and processing and reacted calorimetric pond are inserted calorimeter and linked pulse reaction system (comprising gas chromatography) calorimetric and the measurement of gas absorption/reacting dose are carried out in catalyst activity position.Applying this calorimetric pond can proceed to different phase catalyst active center quantity, intensity and distribution and carry out quantitative measurment reaction, also can study the variation of catalyst active center in course of reaction.
Accompanying drawing explanation
Fig. 1 a is the one-piece construction figure in original position calorimetric of the present invention pond;
Fig. 1 b is calorimetric of the present invention pond pretreatment sample process schematic diagram;
The CO adsorption capacity heat curve comparison of Fig. 2 for adopting original position calorimetric pond of the present invention and known technology to measure;
Fig. 3 is for adopting the CO reactivity of original position calorimetric pond of the present invention and conventional reaction evaluating measurement device;
Fig. 4 is for adopting the contrast of the differential responses stage active sites adsorption property of original position calorimetric of the present invention pond measurement;
Fig. 5 is for adopting original position calorimetric of the present invention pond to measure CO-O
2the variation of circular response condition Xia， catalyst active center, (a) CO or O
2reacting dose; (b) CO
2growing amount; (c) reaction heat.
Main mark explanation in accompanying drawing: 1. four-way valve, 2. straight coupling, 3. sample cup, 4. sample, 5. silica sand, 6. reference cup, 7. sleeve pipe.
Embodiment
Fig. 1 (a, b) is one-piece construction and the sample pretreatment process schematic diagram in original position calorimetric of the present invention pond.
A calorimetric pond, it comprises: four-way valve, sample cup and reference cup, two sleeve pipes, sleeve pipe is comprised of the inner and outer tubes of two end openings, and inner tube is set in outer tube, and the external diameter of inner tube is less than the internal diameter of outer tube;
Sample cup and reference cup are respectively the airtight cavity that upper end is provided with opening; First interface of four-way valve is connected with inner tube one end of two sleeve pipes respectively by pipeline, and second interface of four-way valve is connected with outer tube one end of two sleeve pipes respectively by pipeline; The other end of the outer tube of two sleeve pipes is connected with the openend of reference cup with sample cup respectively, and the other end of the inner tube of two sleeve pipes inserts respectively the bottom of sample cup and reference cup.
Top, calorimetric of the present invention pond is a four-way valve 1, this four-way valve is inserted into respectively the bottom of sample cup 3 and reference cup 6 by the inner tube of sleeve pipe 7, by four-way valve 1, realize the switching of gas with various, gas is by sleeve pipe inner tube process sample, sample cup overcoat electric furnace is realized temperature program(me) and is controlled, and the sample after processing is switched and sealed by four-way valve.Sample cup 3 and reference cup 6 are by Inconel600
tMpassive stainless steel manufacture, under high-temperature oxydation or reducing atmosphere, also can keep stable.Wherein in sample cup 3, place sample, the silica sand of the mid-sky of reference cup or placement inertia.The replacing of sample is undertaken by dismountable straight coupling 2, and the ball face sealing of joint can guarantee in measuring process, the sealing of whole measuring cell.
Fig. 2 is for adopting the CO heat of adsorption of original position calorimetric of the present invention pond measurement to change the result comparison diagram obtaining with conventional adsorption capacity heat device with coverage.
Test condition: 0.1 gram of 5.5%Pt/Al
2o
3under 550 degree, reduce after 30 minutes, be down to room temperature and carry out CO absorption test.
Test result shows that the curve that the heat of adsorption of original position calorimetric of the present invention pond measurement changes with coverage has good accuracy and repeatability.
The comparison diagram of the CO conversion ratio variation with temperature curve that Fig. 3 is the measurement of employing original position calorimetric of the present invention pond and conventional quartz reactor measurement result.
Test condition: 0.1 gram of 5.5%Pt/Al
2o
3under 550 degree, reduce after 30 minutes, be down to room temperature and carry out the test of CO oxidation reaction, CO and O
2gas flow rate be 50ml/min, CO and O
2content be respectively 1%, high-purity He is Balance Air.
Test result show the CO conversion ratio variation with temperature trend in original position of the present invention pond and the result that conventional quartz reactor obtains basically identical, and, empty original position pond does not show that below 200 degree obvious CO transforms, and shows that this calorimetric pond can be used for the character of the different catalytic reaction stages active sites of in situ detection.
Fig. 4 is Pt/Al
2o
3cO heat of adsorption measurement result comparison before and after CO oxidation reaction.Can see after CO oxidation reaction, the heat of adsorption of CO on sample significantly declines, and this illustrates in course of reaction, Pt/Al
2o
3activated centre on catalyzer has occurred to change significantly.
Fig. 5 is CO-O
2the calorimetric result of circulation absorption.
Test condition: 0.02 gram of Au/FeO
x, the lower circulation of 40 degree passes into CO and O
2, measure heat and CO and the O discharging simultaneously
2reacting dose and CO
2growing amount.
Circulation passes into CO and O
2, can see CO
2can repeatedly produce, illustrate in this process, CO can react with carrier surface oxygen and make carrier reduction, and oxygen absorption subsequently can make carrier oxidation again, according to the heat and the Fe that measure
3o
4be oxidized to Fe
2o
3standard heat content unanimously prove that carrier exists oxidation-reduction process in this process.This result show by calorimetric of the present invention pond can be from the angle research course of reaction of calorimetric the variation of catalyst activity position.
Claims (4)
1. an original position calorimetric pond, it comprises:
Four-way valve (1), sample cup (3) and reference cup (6), two sleeve pipes (7), sleeve pipe (7) is comprised of the inner and outer tubes of two end openings, and inner tube is set in outer tube, and the external diameter of inner tube is less than the internal diameter of outer tube;
Sample cup (3) and reference cup (6) are respectively the airtight cavity that upper end is provided with opening;
First interface of four-way valve (1) is connected with inner tube one end of two sleeve pipes (7) respectively by pipeline, and second interface of four-way valve (1) is connected with outer tube one end of two sleeve pipes (7) respectively by pipeline;
The other end of the outer tube of two sleeve pipes (7) is connected with the openend of reference cup (6) with sample cup (3) respectively, and the other end of the inner tube of two sleeve pipes (7) inserts respectively the bottom of sample cup (3) and reference cup (6).
2. original position calorimetric as claimed in claim 1 pond, wherein, sample cup and reference cup are by Inconel600
tMpassive stainless steel build.
3. original position calorimetric as claimed in claim 1 pond, wherein, sample cup and reference cup by straight coupling (2) with the outer seal of tube and removably connect.
4. original position calorimetric as claimed in claim 1 pond, wherein, sample cup is arranged with electric furnace outward, realizes temperature program(me) and controls.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210234046.0A CN103529077B (en) | 2012-07-06 | 2012-07-06 | A kind of original position calorimetric pond |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210234046.0A CN103529077B (en) | 2012-07-06 | 2012-07-06 | A kind of original position calorimetric pond |
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| Publication Number | Publication Date |
|---|---|
| CN103529077A true CN103529077A (en) | 2014-01-22 |
| CN103529077B CN103529077B (en) | 2016-05-11 |
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| CN201210234046.0A Active CN103529077B (en) | 2012-07-06 | 2012-07-06 | A kind of original position calorimetric pond |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108132276A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of measurement gas（Liquid）The device and method of solid phase interaction strength |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3141861U (en) * | 2008-03-07 | 2008-05-22 | 株式会社島津製作所 | Differential scanning calorimeter |
| CN101487806A (en) * | 2009-02-20 | 2009-07-22 | 中山大学 | DSC meter with visualization function |
| CN201926634U (en) * | 2010-11-29 | 2011-08-10 | 陕西科技大学 | Tester for gas specific heat at constant pressure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3141861B2 (en) * | 1998-10-29 | 2001-03-07 | 日本電気株式会社 | Semiconductor storage device and method of manufacturing the same |
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2012
- 2012-07-06 CN CN201210234046.0A patent/CN103529077B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3141861U (en) * | 2008-03-07 | 2008-05-22 | 株式会社島津製作所 | Differential scanning calorimeter |
| CN101487806A (en) * | 2009-02-20 | 2009-07-22 | 中山大学 | DSC meter with visualization function |
| CN201926634U (en) * | 2010-11-29 | 2011-08-10 | 陕西科技大学 | Tester for gas specific heat at constant pressure |
Non-Patent Citations (2)
| Title |
|---|
| GEORGETA POSTOLE ET AL.: ""The poisoning level of Pt/C catalysts used in PEM fuel cells by the hydrogen feed gas impurities: The bonding strength"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 36, no. 11, 31 December 2011 (2011-12-31), pages 6817 - 6825, XP028384864, DOI: 10.1016/j.ijhydene.2011.03.018 * |
| 李林 等: ""高灵敏宽温区吸附热测定装置的建立"", 《催化学报》, vol. 24, no. 11, 30 November 2003 (2003-11-30), pages 872 - 876 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108132276A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of measurement gas（Liquid）The device and method of solid phase interaction strength |
| CN108132276B (en) * | 2016-12-01 | 2020-10-23 | 中国科学院大连化学物理研究所 | Device and method for measuring gas (liquid) -solid phase interaction strength |
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| CN103529077B (en) | 2016-05-11 |
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