Supporting information

Acetaldehyde Production from Ethanol by Eco-Friendly non-Chromium Catalysts

Consisting of Copper and Calcium Silicate

Atsushi Segawa†, ††, Akio Nakashima‡, Ryoichi Nojima‡‡, Naohiro Yoshida††, §, §§ and Masaki
Okamoto*, #

† Central Technical Research Laboratory, JXTG Nippon Oil & Energy Corporation, 8 Chidoricho,
Naka-ku, Yokohama, Kanagawa 231-0815, Japan
††Department of Environmental Chemistry and Engineering, Interdisciplinary Graduate School of

Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama,
Kanagawa 226-8502, Japan
‡Development Section, Production Department, Catalysts Operations Division, Sakai Chemical

Industry Co., Ltd., 5-1, Ebisujima-Cho, Sakai-ku, Sakai, Osaka 590-0985, Japan
‡‡Hofu Plant Chemicals Division, Osaki Industry Co., Ltd., 75, Kohama, Hamakata, Hofu,

Yamaguchi 747-0833, Japan

§Department of Chemical Science and Engineering, School of Materials and Chemical Technology,

Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, Kanagawa 226-8502,

Japan
§ § Earth-life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku,

Tokyo 152-8552, Japan

#Department of Chemical Science and Engineering, School of Materials and Chemical Technology,

Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8552, Japan

* Corresponding author
E-mail: okamoto@cap.mac.titech.ac.jp (M. Okamoto)
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Table S1. Catalytic performance for ethanol dehydrogenation (WHSV = 25 h-1)
Temp. Ethanol Acetaldehyde By-product selectivity Cmol%
Entry oC conv. selectivity
% Cmol% Ethers Ethyl 1-Butanal 2-Butanone 2-Butanol Croton- Crotyl Other
acetate aldehyde alcohol

240 21 93.5 1.3 2.8 0.2 0.8 0.0 0.0 0.2 1.1
CAT-2
260 34 90.6 1.0 4.7 0.4 1.9 0.2 0.0 0.5 0.7

230 19 95.4 0.3 1.6 0.2 0.5 0.6 0.0 0.2 1.3
CAT-3
260 41 92.6 0.2 3.6 0.6 1.4 0.1 0.0 0.5 0.9

230 20 94.8 0.3 1.8 0.2 0.5 0.7 0.0 0.2 1.6

CAT-4 260 44 91.3 0.2 4.0 0.6 1.6 0.1 0.0 0.5 1.6

310 69 86.8 0.2 5.1 1.8 2.0 0.1 1.8 0.5 1.6

S2
Table S2. Catalytic performance for ethanol dehydrogenation (WHSV = 37 h-1)
Temp. Ethanol Acetaldehyde By-product selectivity Cmol%
Entry oC conv. selectivity
% Cmol% Ethers Ethyl 1-Butanal 2-Butanone 2-Butanol Croton- Crotyl Other
acetate aldehyde alcohol

CAT-2 270 39 95.0 0.2 2.2 0.4 0.7 0.0 0.2 0.3 1.0

CAT-3 280 50 93.9 0.1 2.6 0.6 1.0 0.1 0.0 0.4 1.3

CAT-4 290 57 91.1 0.1 3.6 1.0 1.5 0.1 0.9 0.5 1.1

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Table S3. Catalytic performance over commercial CuCr catalyst for ethanol dehydrogenation
Temp. WHSV Ethanol Acetaldehyde By-product selectivity Cmol%
oC h-1 conv. selectivity
% Cmol% Ethers Ethyl 1-Butanal 2-Butanone 2-Butanol Croton- Crotyl Other
acetate aldehyde alcohol

225 11 27 90.2 0.0 5.9 0.4 1.3 0.2 0.0 0.9 1.1

260 11 52 86.3 0.0 6.7 1.1 3.1 0.2 0.0 0.9 1.7

330 14 42 92.2 0.8 2.0 2.1 0.0 0.0 1.3 0.1 1.5

350 7 73 85.7 0.6 3.9 4.7 0.1 0.0 2.1 0.1 2.8

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 250

200
Surface Cu, μmol/g

150

100

50

0
0 10 20 30 40 50 60
Loaded CuO, wt%

Figure S1. The relationship between loaded CuO and surface Cu

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3500
Cu0
3000 Cu0
2500
Intensity, a.u.

2000
(b)
1500
1000
(a)
500 Cu crystallite diameter: 7 nm

0
0 20 40 60 80
2θ, degree

Figure S2. XRD patterns for CAT-2 after:

(a) H2 reduction at 200 oC; (b) Dehydrogenation for 5h at 270 oC

S6