BEL-CAT Application note

CAT-APP-003

TPR measurement
2 July, 2003 Kazuyuki Nakai Kaori Nakamura TPR is the abbreviation of Temperature Programmed Reduction(Reaction), and it is used as a method to evaluate reduction of catalyst by hydrogen. There are a number of applications such as supported copper catalyst 1), heteropoly acid 2), nickel catalyst 3), oxide such as Bi-Mo or Fe-Sb 4), supported V2O5 5) or Re catalyst 6). It seems that TPR is influenced by experimental condition, especially active gas (H2) concentration, gas flow rate and catalyst volume more easily than TPD is. Therefore, these have to be carefully looked at.

[Introduction]
Experiment involves recording hydrogen concentration change or reaction product amount in carrier gas during temperature up as a function of time or temperature. TPD instrument can be used, but if TCD is used as the detector, it is necessary to mount H2O trap before the detector. The following equation is suggested for calculating energy of activation from TPR curve.

TP2 E ln + p ln[G ]m + (q 1) ln[S ]m = r + const. RTP

(1)

Here, [G]m and [S]m mean hydrogen gas concentration and element concentration of catalyst at peak temperature respectively, and p and q indicate reaction order for each concentration respectively. In general, p and q cannot be determined accurately, thus it is often set as p=q=1. 7) Iwamoto et al carried out TPR measurement of copper ion exchange Y-type zeolite (CuNaY) in the range of 273~1123K (Fig.1) 8).

Fig.1: TPR curve of CuNaY

BEL-CAT Application note

CAT-APP-003

4 reduction peaks appear at 473(I), 593(II), 803(III) and 1123(IV). Hydrogen consumption amount is approx. 0.5mol(H2)/mol(Cu) in each range, 273~773K and 773~1273K. Whole ESR spectrum of Cu2+ disappears by 775K reduction. The color of the sample changes from blue-green (273K) to white (nearly=773K) then to chestnut (>800K). Strong IR adsorption of Cu+-CO can be identified in 773K reduction sample, but Cu+-CO cannot be identified in 1173K sample. TPD peak 9) that attributes to Cu-O-Cu can be obtained by measuring TPD curve of CuNaY that is reduced at 473K. Considering the above results etc., Iwamoto et al attribute 4 reduction peaks to the following reduction process. 2Cu2++H22Cu++2H+ Cu2+-O2--Cu2++H22Cu++H2O 2Cu++H22Cu0+2H+ (peak I) (peak II) (peak III, IV)

This experimental method is extended to apply for mordenite or Cu2+ exchanger of ZSM-5 10), and it has become an important method for studying the characteristics of metal ion in zeolite framework. Also, there is a case that whole reduction amount is determined by chemisorption measurement by oxygen pulse at room temperature cooled down after TPR measurement. In this case, poor reproducibility of TPR and linearity problem can be covered by oxygen pulse method.

[Experiment and Result]

In TPR measurement, it is necessary to detect hydrogen concentration change. In BEL-CAT, TCD is used as the detector, and with He carrier gas that is often used for ammonia TPD it is difficult to detect it due to small specific thermal conductivity difference from H2. Therefore, in case of detection by TCD, H2 carrier gas diluted with Ar is often used. Also, it is necessary to trap the water that is produced by reduction reaction before TCD detector. In BEL-CAT, zeolite 4A is filled in the sample cell for pulse measurement (until the lower part of the cell is filled up), and high temperature pretreatment (400 degree C in carrier gas) is carried out in the reaction section, and then it is advised to remove moisture in the trap section.
G

R1

AV1

PA 1 TA 1

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PV6 PG6 FM1

(0.4ml) (1.2ml)

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TCD MFC Ref INJ

FL 6WAV1 6WAV2

4WMV1

TCD Sen VENT

PV1 PG1 3WAV4 FL EV1

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PV3 PG3
G

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Fig.2: BEL-CAT flow diagram and example of TPR measurement setting

BEL-CAT Application note

CAT-APP-003

Instrument S/N Detector Sample Gas Heating rate

: BEL-CAT-2 : TCD (Half-diffusion type 4 element) : CuO (Wako Pure Chemicals Industries, Ltd. : 5% H2/Ar : 10 degree C/min.

Lot No.APJ4311)

Pretreatment program: Gas 1: H2/Ar Measurement program: Waiting time for TCD stabilization Target temperature Heating rate Target temperature holding time 20 min 1000 degree C 10 degree C/min 30 min in 60 Target temperature 30

1500000

1200000

0.14730 g 0.03370 g 0.01174 g

TCD [V]

900000

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0 100 150 200 250 300 350 400 450 T [] 500 550 600 650 700

Fig.3: CuO TPR spectrum Fig.3 shows that shape of peak significantly changes only as sample mass changes. Also, shape of the peak of sample weight 0.14g indicates that hydrogen concentration is saturated as the introduced hydrogen is completely consumed. When such spectrum is obtained it is better to decrease sample amount or to increase hydrogen concentration in carrier gas.

BEL-CAT Application note

CAT-APP-003

Reference:
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