Japan

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APPLIED CATALYSIS A:GENERAL

ELSEVIER

Applied Catalysis A: General 145 (1996) 419-428

Global Overview of Catalysis Japan

1. M a j o r academic societies There are several academic societies relating to catalysis in Japan. The scientists working for homogeneous catalysis such as metal complex catalysis, organic synthesis, catalytic chiral reaction, and polymerization have not formed their own societies; therefore it is mostly the societies in the field of heterogeneous catalysis that will be introduced here. The numerical values in the text are mainly those as of December 31 st, 1994.

I. 1. The Catalysis Society of Japan Founded: 1958. Members: 1895 regular members, 256 student members, 22 honorary members, and 146 companies. The distribution of the ages of members (as shown in Fig. 1) is clearly wellbalanced: young researchers are continuously joining the society. (1.6O/o)

(5.7'/,,) 21-30

(20.1"/,)

[ ] 31-40

q

[] 41-50 [ ] 514~0 [ ] 61-70 [] 71-90

(2o.4%)

~z,4.,*voI Fig, 1. Distribution of members' ages of the Catalysis Society of Japan. 0926-860X/96/$15.00 Copyright © 1996 Elsevier Science B.V. All rights reserved. P I I S0926-860X(96)00140-8

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N. Nojiri and M. Iwamoto/Applied Catalysis A: General 145 (1996) 419-428

Publications: 8 issues of Shokubai (Catalysis) which include reviews and long abstracts of annual debates. One yearbook. Many proceedings of meetings. Divisions: 14 forums of reference catalysts, fine chemicals, chemical sensors, practical catalysts, catalytic combustion, electro- and photo-catalysis, metal complex catalysis, computer-aided catalysis, etc. Meetings: Spring and Autumn meetings with 300-350 presentations and 450-550 attendees in each. Bi- or tri-lateral meetings with China and USA, France, Germany, Korea, Russia, Taiwan, United Kingdom. Many meetings of the above divisions. The total number of attendees to these meetings was 5704 in 1994, which was approximately three times the number of regular members, suggesting a high level of activity of the society.

1.2. The Japan Petroleum Institute Founded: 1958 Members: 4681 regular and student members, and 377 companies. Publications: 12 issues of Petrotech that include reviews and 6 issues of the Journal of the Japan Petroleum Institute. Many proceedings of the meetings. Divisions: 6 divisions such as natural resources development, refining, petrochemicals, energy and environment. Meeting: Spring and Autumn meetings. One annual meeting of the Petrochemical Division.

1.3. The Japan Association of Zeolites Founded: 1984 Members: 367 regular members, 33 student members, and 54 companies. Publications: 4 issues of newsletter and one proceedings of the annual meeting. Meeting: One annual meeting.

1.4. The Society of Chemical Engineers, Japan Founded: 1936 Members: 8060 regular members, 1297 student members, 74 honorary members, and 567 companies. Publications: 12 issues of Kagaku Kougaku which include reviews. 6 issues of Kagaku Kougaku Ronbunshuu which cover original papers in Japanese and 6 issues of Journal of Chemical Engineering of Japan in English. Many symposium series and proceedings. Divisions: 22 forums of catalysis, chemical vapor deposition, separation, environmental engineering, etc. Meetings: Spring and Autumn meetings.

1.5. The Electrochemical Society of Japan Founded: 1933. Members: 3176 regular, student, and honorary members, and 213 companies. Publications: 12 issues of Denki Kagaku which include original papers and reviews. 7 books such as 'New Electrochemistry' and 'Electrochemical Handbook'.

N. Nojiri and M. Iwamoto/Applied Catalysis A: General 145 (1996) 419-428

421

Divisions: 7 divisions including chemical sensors, etc. 18 forums such as electro-organic chemistry, new materials, and solid state chemistry. Meetings: Spring and Autumn meetings. Several workshops and seminars. Many meetings of the above divisions.

2. Research trends in Japan The Catalysis Society of Japan has annually published a yearbook. On the basis of the 1995 version, 245 laboratories (typically one professor, one associate professor or assistant professor, and one research associate in a laboratory) are working for catalytic research in universities, 50 in national institutes, and 8 in colleges of technology. The number of papers published in international journals and domestic journals from these laboratories is approximately 1200 in 1994. It is very difficult for us to introduce and/or summarize the research areas or trends in Japan based on these papers. To clarify them, the research areas of 355 presentations at the 1995 autumn meeting of the Catalysis Society of Japan (October 1995) are therefore listed (see Table 1). Note that most of the studies on homogeneous catalysis, metal complex catalysis, and organic synthesis with catalysts are presented in other meetings in Japan. Table 1 Research areas in the 1995 autumn meeting of the Catalysis Society of Japan Oxidation and catalytic combustion Hydrogenation and dehydrogenation Organic synthesis, acid-base catalysis, and polymerization Environmental catalysis for removal of nitrogen oxides for desulfurization for fluorocarbon chemistry Reaction of CO 2 with hydrogen or organic compounds Electrocatalysis on metal or semiconductor electrodes Photocatalysis such as water decomposition and oxidation of hydrocarbons Application of various oxides and metals as chemical sensors Preparation of new materials or development of novel preparation methods Characterization of catalysts and surface sciences Computer-aided chemistry Others

29 39 29 46 6 7 24 19 21 9 28 70 19 9

It is reasonable that research on catalysis has partly been dependent on the demands of the period. For example, the research on environmental catalysis has recently become one of the most popular fields in the world and of course in Japan, since it has been recognized as an important and essential one. In particular, the research on novel deNOx systems, i.e., the catalytic decomposition and the selective catalytic reduction by hydrocarbons in the presence of excess oxygen, has been widely studied on oxides, metals, and zeolites. At present major efforts are being devoted to revealing the reaction mechanism of the latter reaction. The characteristic topic in the above list is the catalytic reaction of CO2. In Japan, the government is financially assisting research towards the prevention of global warming due to carbon dioxide, which is one of the reasons for the high number of studies on it.

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N. NojM and M. Iwamoto/Applied Catalysis A: General 145 (1996) 419-428

The other major topic in recent research is the preparation and application of mesoporous materials. The invention of a new family of mesoporous silica materials has dramatically expanded the range of crystallographically defined pore sizes from the micropore to the mesopore regime. The synthesis uses ordered arrays of surfactant molecules as a template. The resulting new materials exhibit several remarkable features: (1) well-defined pore sizes and shape, (2) fine adjustability of the pore size, (3) high thermal and hydrolytic stability, (4) a very high degree of pore ordering over micrometer length scales. If the synthetic approach can be generalized to transition metal oxide mesostructures, the resulting nano-composite materials might find applications in high-surface-area redox catalysts, adsorption-desorption phenomena, new active phase/support composites, etc.

3. Government support The Japanese government supports catalytic research through three financial systems. Three ministries are involved: The Ministry of Education, Science, and Culture (Mombusho), The Ministry of International Trade and Industry (MITI), and The Science and Technology Agency (Kagichou). In principle, the universities are supported by Mombusho and the national institutes and laboratories by the latter two Ministries. At present, however, many projects have been suggested from the researchers of academic positions and supported by the latter. A typical example of the support from Mombusho is summarized in Table 2. One can clearly see that the amount of grant-in-aid has increased year by year. The drastic increase of the budget in 1995 is due to a new three-year project on fundamental research on catalysis. Table 2 Grants-in-Aid" for catalytic research (field no. 463)" from the Ministry of Education, Science and Culture (Mombusho) of Japan (in million yen) Classification of the

1993

Grants-in-Aid

No. of Projects

Sum of Grants

No. of Projects

Scientific Research on Priority Areas

0

0

0

Co-operative Research

0

0

Scientific Research

27

Encouragement of Young Scientists Developmental Scientific Research Total

1994

1995 Sum of Grants

No. of Projects

Sum of Grants

0

78

351

0

0

2

3.1

82.1

32

86.5

39

105.8

12

11.5

16

15.1

16

15.2

5

13.3

6

48.7

12

58.8

44

106.9

54

150.3

147

533.9

Stipends of employees and students are not included. h Many research projects in catalysis, which are not included in this table, are also supported in the other research fields such as chemistry, industrial organic chemistry, advanced materials, environmental sciences.

N. Nojiri and M. IwamotoPtpplied Catalysis A: General 145 (1996) 419-428

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4. Activities in companies working in catalysis New processes commercialized after the publication of two reviews [1,2] and those under developement mainly on a pilot scale are listed in Table 3, although not fully covered because of the difficulty of gathering all the information on them. In general, development of new processes and catalysts for refining are remarkable. Several companies have disclosed various new processes for deep desulfurization of gas oil and for aromatization of LPG fraction or C4 raffinate. Table 3 Recent new processes and catalysts #

Companies

Process

Comments

1

Nippon Oil

Deep desulfurization of gas oil to decrease the S content to <0.05%

Two-step process; lst/deep desulfurization, 2nd/decolorization (Co-Mo catalyst). Plant completion; 1994.8.

2

Japan Energy

Deep desulfurization of gas oil

An active and long-life catalyst (Co-Mo/A1203) with high surface area and acid amount. Already used commercially.

Mitsubishi Oil Chiyoda Corp.

Aromatization of LPG or light naphtha (Z-forming)

Metallosilicate catalyst alternately regenerated in two reactors. Demonstration test (200 bbl/D); 1990.11-1991.12.

4

Asahi Chemical Ind.; Sanyo Petrochemical

Aromatization of C4, C5 raffinate or LPG/C4, C5 fraction of FCC gasoline (Alpha-process)

Simple one-step process based on the use of olefin containing feedstocks by modified ZSM-5 zeolite catalyst in swing reactors. Commercial operation (3500 bbl/D); 1993.7.

5

NEC

A catalyst producing a high caloric butene reforming gas without CO

A Pd-Rh catalyst useful for changing shift gas enriched with CH~ without harmful CO. Under development.

6

Osaka Gas

hnproved steam reforming process

Improved by the installation of high-desulfurization unit at the upstream. Commercial Op.; Town gas production (100 MM M3/D) 1987-.

7

Nippon Shokubai

Vapor-phase synthesis of ethylene sulfide

Heterogeneous catalytic process of a 3-membered heterocyclic compound following ethylene imine process. Pilot test; 1994.7.

8

Idemitsu Petrochemical

c~-Olefin manufacturing by ethylene oligomerization

ZrCl:EtA1C12-Et3Al-organic P/S ligand catalyst. Commercial plant (50 kilotons); 1989.4-.

9

Idemitsu Petrochemical

Syndiotactic polystyrene manufacturing

Metallocene-based catalyst developed by joint R and D with Dow. Semi-commercial plant (5 kilotons) completion; 1996.8.

10

Mitsui Petrochemical

Cycloolefin copolymer manufacturing

Semi-commercial production; 4000 t/y. Metallocene catalyst; 1995-.

ll

Mitsubishi Gas Chemical

Methyl formate process for MMA

New acetonecyanhydrin process using acetone, CH3OH and NH 3 as raw materials. Plant (41000 t/y) completion; 1996/E.

12

Mitsubishi Gas Chemical

o-Xylene process for 2,6-NDCA

A process including addition of o-xylene and butadiene, cyclization, dehydrogenation, isom. and separation Commercial plant (1000 t/y) completion; 1995/E. (continued on next page)

N. Nojiri and M. Iwamoto/Applied Catalysis A: General 145 (1996) 419-428

424

Table 3 (continued) #

Companies

Process

Comments

13

Mitsubishi Chemical

New "~:-butyrolactone process from MAH

Ru-based homogeneous catalytic process with a high yield from maleic anhydride. Commercialization (I0000 fly); 1997.3rd Q.

14

Mitsubishi Chemical

Biphenyltetracarboxylic acid process through dehalogenating dimerization

New process via chloro-o-phthalic acid obtained from o-phthalic acid and chlorine. Already commercialized by Pd-based catalyst in aq. NaOH.

15

Showa Denko

Ethylene process for acetic acid

Pd-heteropoly catalyst. The plant (100 kilotons) completion; 1997.8.

16

Kao

Unsaturated amine manufacturing

Dioleildimethylammoniumchloride through oleonitrile hydrogenation by a Cu-Zn-Ru catalyst. Commercial use; 1989.3-.

17

Asahi Chemical Ind.

Non-phosgene process for polycarbonate via diphenylcarbonate

Diphenylcarbonate obtained from dimethylcarbonate reacts with bisphenol A to produce polycarbonate. Pilot plant (10 t/y) stage.

18

Nippon Kokan

Gas-phase toluene process for phenol

Two step gas phase process; lst/oxidn of toluene to benzoic acid, 2nd/oxidn of benzoic acid to phenol by NiO-Fe203-Na,eO-V205.

19

Nissan Motor Toyota Motor

A three-way automotive catalyst comprising Pd as the main component

A 5-component catalyst including Pd, AI203, CeO 2 and others. Commercial use; 1993.11.

20

Toyota Motor Toyota Chuuken Cataler Ind.

A new concept automotive emission control system for lean-bum engines using a 3-way catalyst containing alkaline materials as NOx storage.

An alkaline materials added 3-way catalyst which stores NOx in lean operating conditions and reduces stored NOx in very short rich operation without HC and CO emission deterioration with fuel consumption increase within only 1%.

21

Matsuda Motor

Waste plastics decomposition catalyst

Waste plastics (from a motor vehicle etc.) can be converted to fuels by a 10-time cheaper catalyst than zeolite-base cat.

22

Matsushita Electric Ind.

Catalysts for living circumstances

Various catalysts used in wide variety of electric appliances.

23

Kuraray

Catalysts for household use

Active catalysts at low temperatures used for keeping freshness of vegetables and deodorizing in a refrigerator etc.

24

Mitsubishi Paper

Photocatalytic deodorant sheets

Non-woven sheets containing TiO2-based catalyst.

25

TOTO

Various photocatalytic-sterilized products

Tiles and sanitary ceramics containing TiO 2 catalyst effective for germiciding.

T h e m o s t n o t e w o r t h y e x a m p l e in n e w c h e m i c a l p r o c e s s e s a p p r o a c h i n g i n d u s t r i a l i z a t i o n w o u l d b e S h o w a D e n k o ' s direct acetic acid p r o d u c t i o n f r o m e t h y l e n e . T h e e s t a b l i s h m e n t o f an e c o n o m i c a l p r o c e s s o t h e r t h a n M o n s a n t o ' s acetic acid p r o c e s s w h i c h h a s b e e n c a l l e d the u l t i m a t e process, is really a surprise. It is also n o t a b l e that a c e r t a i n h e t e r o p o l y catalyst, w h i c h is one o f J a p a n ' s s p e c i a l t y catalysts, m i g h t b e u s e d in

N. Nojiri and M. IwamotoPlpplied CatalysisA: General 145 (1996) 419-428

425

this process. Mitsubishi Gas Chemical developed a new acetoncyanhydrin (ACH) process which uses methyl formate instead of HCN as a raw material. The revived ACH process uses no HCN and discharges no ammonium sulfate. In the polymer manufacturing field, a syndiotactic polystyrene catalyst of Idemitsu Petrochemical is famous. The semi-commercial plant is reported to start shortly. Commercial plans of polyolefin manufacturing by metallocene-based catalysts have also been announced by many Japanese companies, which are not listed in Table 3. Several new chemical processes other than the above have been commercialized but the numbers are not so large. In pilot stage developments, NKK's gas-phase phenol process from toluene is noteworthy in that it intends to develop a gas-phase process which has not been realized before. Asahi Chemical's diphenylcarbonate process may be environmentally favourable because it is without phosgene. In other fields, catalysts relating to environment preservation are steadily expanding. Palladium-containing three-way catalysts for automotive use developed independently by Nissan Motor and Toyota Motor are very important from an economical view point because they use no Rhodium. And a new concept catalyst created by Toyota Motor and others is epoch-making in that it can be used for automotive emission control for lean burn engines. Amenity has recently become one of the key words in Japan and catalysts for deodorization for instance have been used extensively even in articles for domestic use and many chemical companies have rushed to this field. In conclusion, recent activity in process and catalyst development in Japan has been very high but activity in the development of big processes like energy-related ones appears lower than that in EC and USA.

5. Catalysis impact 5.1. Production of catalysts The amount of catalyst delivered in Japan has increased steadily and doubled from 1985 to 1994 as shown in Table 4. Because of the sharp price drop of catalysts, the money involved has not increased so much, however, it is still ranked the second in the world. Table 5 and Figs. 2 and 3 show the breakdown. Petroleum refining and auto exhaust catalysts are the top in quantity and in value, respectively. The Catalyst Manufacturers' Association (Japan) founded in 1965 has 63 member companies at present, 22 formal members and 41 supporting ones. Table 4 Statistics of industrial catalyst in Japan (quantity in tons; value in million yen) Fiscal year

1984

1986

1988

1990

1992

1994

Shipment

quantity value

35 160 78 212

42 619 87 901

43 321 86 967

51 308 113 871

55 314 111 072

68 374 97 786

Export

quantity value

7 605 14 205

9 047 15 748

12 801 23 477

16 495 25 685

16 704 30 495

30 993 25 412

Import

quantity value

11 309 34 849

8 918 29 903

11 491 23 532

16 424 41 456

19 985 44 764

24 598 28 948

Domestic demand

quantity value

38 864 98 856

42 490 102 056

42 001 87 022

51 237 129 642

58 595 125 341

61 979 101 322

L26

N. NojM and M. Iwamoto/Applied Catalysis A: General 145 (1996) 419-428

Fable 5 2atalyst Production in 1994 (quantity in 1000 tons; value in 100 million yen) Jsage

Quantity

Value

~etroleum Refining rleavy Oil 9etrochemical )olymerization 3as Production ~uto Exhaust 3thers rotal

26.5 14.2 11 5.5 3 5.6 2.7 68.4

90.1 118.5 222.7 60.1 44.9 326.6 95.1 958

(4%) O t h e r s (8%) A u t o [- "

(4%) (;as P r o d u c t i o (3.%)

(8%) l'olymevizaCiCm

l'o c i-o 1 {~l.lln I¢ef'in

(16%) P e t r o c h e m i c a l

(21%) lleavy 0 i l Fig. 2. Catalyst production in 1994.

(9. q0~,~

nt

ho,-<

(9. 4%) I'etl'oleuln Re['iui n,<

2. ,1%) Ileavy 0 i l

(34. 1%) Auto E x h a u s t 23.2%) P e t r o c h e ~ n i c a l

(4.7%) (;as P r o d u c t i o n

(6.3%)

P(~lymc'vization

Fig. 3. Value of catalyst production in 1994.

N. Nojiri and M. IwarnotolApplied CatalysisA: General 145 (1996) 419-428

427

5.2. Trade in catalysts The quantity and the value of catalysts imported and exported are also shown in Table 4. They have a large influence on domestic production of catalysts since their volumes are so large.

5.3. Chemical and petrochemical industry As most chemicals, especially petrochemicals, are catalytically produced, the growth of the catalyst industry is a good indicator for the growth of the chemical industry as a whole. The total output of the Japanese chemical industry in 1993 was worth US$ 232 billion, which was the 5th place in Japanese industry (7.5% of total turnover) and 2nd in the world chemical industry. Table 6 shows the increase in capacity and numbers of companies producing important petrochemicals. Table 6 Growth of the petrochemical industry in Japan Product

1965 #a

Ethylene Benzene Toluene Xylene p -Xylene Cyclohexane Styrene monomer (SM) Vinyl chloride monomer (VCM) Propylene oxide (PO) Ethylene oxide (EO) Low-density polyethylene (LDPE) High-density polyethylene (HDPE) Polypropylene (PP) Polystyrene (PS) Polyvinyl chloride (PVC) Acrylonitrile-butadiene-styrene resins Acrylonitrile (AN) Caprolactam Terephthalic acid (TPA) Dimethyl terephthalate (DMT) Styrene-butadiene rubber (SBR) Butadiene rubber (BR) Acetaldehyde Phthalic anhydride (PA) Maleic anhydride (MA) Polypropylene glycol (PPG) Propylene glycol (PG) Phenol Acetone Octanol Acetic acid

1975 cap.b

9 6 6 6 2 3 5 6 6 4 6 3 4 5 14 6 6 5 4 3 2 2 5

4 5 4 4 7

"Number of companies, b Unit: 1000 tons/year.

#

1985 cap.

#

1994 cap.

942 203 189 120 31 66 248 139 68 79 300 112 74 157 585 23 160 201 102 74 191 20 238

14 22 17 18 7 7 8 17 6 4 10 10 9 8 18 9 7 4 5 6 6 5 7

5460 2513 1221 1569 575 591 1345 2330 241 525 1393 888 965 758 1842 345 738 486 231 734 684 215 711

11 21 18 20 6 7 7 18 5 6 12 10 12 8 18 10 6 4 6 2 7 5 6

4327 3081 1317 1860 736 551 1459 1954 277 621 1194 748 1332 928 1557 552 647 466 945 335 652 227 613

16 111 74 70 201

5 9 5 2 6 4 7

80 213 69 280 295 185 611

4 13 5 4 7 4 7

64 304 74 380 391 306 558

# 12 23 17 24 10 7 1(1 11 5 6 11 10 15 9 17 11 6 4 4 2 6 5 5 7 6 9 5 5 5 4 3

cap. 7078 4976 1685 4511 2200 806 2976 2603 381 924 2258 1286 2581 1371 2458 751 655 562 1530 380 625 302 424 312 141 367 87 890 438 336 565

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N. NojM and M. Iwamoto/Applied CatalysisA: General 145 (1996) 419-428

R and D expenditure of the chemical industry in 1993 was approximately US$ 15 billion, amounting to 17.2% of all of Japanese industry research spending. The ratio to sales was 5.45% which is the 3rd heighest in Japanese manufacturing industry.

References [1] M. Misono and N. Nojiri, Appl. Catal., 64 (1990) 1-30. [2] N. Nojiri and M. Misono, Appl. Catal. A, 93 (1993) 103o122.

Naohiro Nojiri Chemical Science Laboratories Mitubishi Chemical Corporation Yokkaichi Research Center 1 Toho-cho, Yokkaichi Mie 510 Japan

Masakazu Iwamoto Catalysis Research Center Hokkaido University Sapporo 060 Japan