Recent progress in catalytic technology in Japan – II (1994–2009)

Applied Catalysis A: General 389 (2010) 27–45

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Applied Catalysis A: General journal homepage: www.elsevier.com/locate/apcata

Recent progress in catalytic technology in Japan – II (1994–2009) Takashiro Muroi ∗ , Naohiro Nojiri, Takashi Deguchi The Catalysis Society of Japan, Kanda-Surugadai 1-5, Chiyoda-ku, Tokyo 101-0062, Japan

a r t i c l e

i n f o

Article history: Received 20 April 2010 Received in revised form 30 August 2010 Accepted 30 August 2010 Available online 6 September 2010 Keywords: Catalytic technologies Petroleum and energy Bulk chemicals Polymers Fine chemicals Auto exhaust catalysts Environmental catalysts Green sustainable chemistry

a b s t r a c t Catalytic processes developed and commercialized in Japan during 1994–2009 are reviewed and classified into 6 industrial areas: petroleum and energy, bulk chemicals, polymers, fine chemicals, auto exhaust catalysts, and environmental catalysts. They have contributed to overcome a rise in oil price as well as to promote Green Sustainable Chemistry. While these technologies made significant contributions to respond to social issues or commercial demands, continuous efforts for development of these processes greatly promoted the catalytic science and technologies including catalytic materials, concepts, mechanism and surface science of catalysis. © 2010 Elsevier B.V. All rights reserved.

1. Introduction The first review and its supplement under this title by Misono and Nojiri were published in 1990 and in 1993, respectively [1,2]. This is the second review describing the new catalytic technologies developed in Japan and commercialized during the past 16 years, from 1994 to 2009. A wide variety of catalysts and catalytic processes have been successfully developed to overcome a rise in oil price and/or environmental problems. 2. Background Since the first review and its supplement were issued in the early 1990s, the world economic circumstances have been changing drastically. The main concerns in chemical industry have been the following three items: (1) Steep rise and drastic fluctuation of oil price; (2) Remarkable growth of Asian chemical industry; (3) Strong social demands for green and sustainable chemistry (GSC). Although the oil price was about USD 20/bbl in the 1990s, it went up beyond USD 130/bbl in 2008 and suddenly dropped to USD 40/bbl and is now about USD 80/bbl. This situation turned people’s eyes to the use of natural gas and even coal. In the petrochemical field, the developments of the technologies not only for energy

∗ Corresponding author at: Kariya 5-8-5, Ushiku, Ibakaki 300-1235, Japan. Tel.: +81 29 8738844; fax: +81 29 8738844. E-mail address: takashiro [email protected] (T. Muroi). 0926-860X/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2010.08.061

and material-saving but also for the usage of inexpensive starting materials such as alkanes were accelerated. The production capacity of ethylene has increased in Taiwan, Korea, Singapore and China to meet the strong and growing demands. Construction of ethylene crackers is still continuing in China. In contrast, the ethylene production in Japan has been almost flat at 7.5 million t/y since the last construction of an ethylene cracker in 1993. Chemical companies in Japan were forced to move their production sites outside the country and some technologies newly developed in Japan have been commercialized in the Asian area. The demand for GSC has become crucial. “The Presidential Green Chemistry Award” and “Annual Green Chemistry & Engineering Conference” were started in the USA in 1996. GSC has been promoted also in Europe. In Japan, “Green & Sustainable Chemistry Network (GSCN)” was established in 2000. The mission of GSCN is to promote research and development for human health and safety through the innovation of chemical technology. These movements have stimulated the motivation to develop new chemical processes and pollution controlling technologies and also to generate biomass based chemistry. 3. Catalytic technologies developed New catalytic technologies commercialized in 1994–2009 are classified under business sectors and are listed in Table 1. Several cases which attained to pilot test stage are also included. Technologies which draw special attention in each sector are commented on

28

Table 1 New catalytic technologies developed in Japan (1994–2009); Ex.: reaction conditions adopted from open literature or patents. No.

Product

Statement

Key reaction

Catalyst

Company

Ref.

Co–Mo–P/HY-Al2 O3

Cosmo Oil Co., Ltd.

[3,4]

Ni–Mo–TiO2 /Al2 O3

Idemitsu Kosan Co., Ltd.

[5]

Co-Mo/Al2 O3 Ni–(Co)–Mo/Al2 O3

Nippon Ketjen Co., Ltd. Albemarle Corp.

[6]

1. Petroleum and energy

1

2

Diesel oil

Diesel oil

Nano-scale Co–Mo cluster catalysts prepared with phosphorus and citric acid. Used for ultra-deep desulfurization of diesel fractions. Many plants have been commercialized since 2003.

Ex. 350 ºC, 5 MPa.

3

Sulfur-free kerosene and gas oil

Hydrotreating catalyst (STARS catalyst) for producing sulfur-free kerosene and gas oil. Commercialized in 1998.

4

Middle distillate

Hydrocracking of residue for producing high yield of middle distillate.

Residue + H2 → Middle distillate

Ni–Mo/Al2 O3

Cosmo Oil Co., Ltd.

[7,8]

5

Middle distillate

Hydrocracking by USY with controlled acidity.Reduced octahedral Al in USY. Installed at a refinery in 2001.

VGO + H2 → Middle distillate

US-Y zeolite

Nippon Oil Corp.

[9]

6

Gasoline

Deep desulfurization of FCC gasoline (ROK-Fine) by catalyst of controlled Co/(Co + Mo) ratio to suppress hydrogenation of olefins. Started at Nippon Oil from 2004.

RS + 2 H2 → RH2 + H2 S

Co–Mo/Al2 O3

Nippon Oil Corp.

[10,11]

7

Gasoline

High octane FCC gasoline. The improved catalyst has low acid density by controlling rare earth metal content and suppresses hydrogen transfer reactions.

VGO + Residue → High RON gasoline

Low RE FCC catalyst

Cosmo Oil Co., Ltd.

[12]

8

Gasoline and propylene

FCC process (HS-FCC) to produce high yields of propylene. Hydrogen transfer reaction is controlled by the acidity of catalyst. Down flow reactor. 30B/D of pilot plant in Saudi Arabia. 3,000B/D semi-commercial plant will start at the end of 2010.

VGO → Gasoline + CH3 CH CH2

FCC catalyst with controlled acidity.

Nippon Oil Corp.

[13,14]

Pt–SO4 2− /ZrO2

Cosmo Oil Co., Ltd. Mitsubishi Heavy Industries, Ltd.

[15,16]

␥-Al2 O3 with controlled pores distribution and impurity

Toyo Engineering Corp.

[17,18]

9

10

Gasoline

DME (Dimethyl ether)

Ex. 600 ◦ C, contact time = 0.5 s, Cat/Oil = 15–30.

Isomerization of light naphtha (Par-Isom process). Many plants since1996. Licensed to UOP.

Ex. approx. 200 ºC, 3 MPa, LHSV = 2-3 h-1.

Dehydration of methanol.

2CH3 OH → CH3 OCH3 + H2 O

30 t/d plant started in 2003 and 340 t/d plant started in 2006 in China. The other plants using coal-derived methanol in China since 2007.

Ex. 300 ◦ C, 1.1 MPaG, MeOH GHSV = 1700 h−1 .

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

Catalyst for deep desulfurization. Interaction between Mo and Al2 O3 is weakened by addition of TiO2 . Commercialized in 2002. 3 plants in Idemitsu Kosan.

Ex. 340-350 ºC, 4.9 MPa.

11

Hydrogen

Highly active steam reforming catalyst, named ISOP catalyst, has bi-modal structure. Catalyst has been supplied to Japan, Germany, Bangladesh, Indonesia since 1997.

12

Hydrogen

Steam reforming to produce hydrogen from kerosene for fuel cell and hydrogen station. Low carbon deposition. Ni-based sulfur adsorbent was also developed. Demonstration fuel cell facility is running.

13

Hydrogen

Sulfur removal of naphtha by Ni–Mo/Al2 O3 and CuO–ZnO followed by steam reforming with Ru-Al2 O3 catalyst at low steam ratio. Commercialized in 2000 for fuel cell hydrogen.

CH4 + H2 O → CO + 3 H2

Ni/bimodal Al2 O3

Toyo Engineering Corp.

[19,20]

Ru/ZrO2

Idemitsu Kosan Co., Ltd.

[21,22]

H2 S + MeO → MeS + H2 O

HDS: Ni–Mo/Al2 O3

Osaka Gas Co., Ltd.

[23]

CH4 + H2 O → CO + 3H2 CO + H2 O → CO2 + 2H2

Adsorption: CuO–ZnO Reforming: Ru/Al2 O3

Asahi Kasei Chemicals Corp.

[24]

Nippon Oil Corp.

[25]

CO + H2 O → CO2 + 2H2 Ex. 20-30 ◦ C lower than conventional catalysts. Kerosene + H2 O → H2 + CO Ex. 730 ◦ C, S/C = 3, life > 25,000 h

2. Bulk chemicals 14 Aromatics

15

16

17

18

19

Aromatics

Benzene

Methanol

Acetic acid

Acetic acid

Production of aromatics from light naphtha (␣-process). Stable steam-treated ZSM-5. Commercialized in 1993. Aromatics from light naphtha (Z-former) with metallosilicate catalyst using swing reactor. Pilot plant was operated for one year from 1991.

Light Naphtha → Aromatics Fixed bed. Ex. 500 ◦ C, 0.1 MPa, WHSV = 4 h−1 . Light Naphtha → Aromatics

Ga-silicate

Chiyoda Corp. Fixed bed. Ex. 538 ◦ C, 0.1 MPa, LHSV = 2 h−1 .

+

Pt/KL-zeolite catalyst modified with F for dehydroaromatization of n-hexane. Applied in Aromax process developed by CPChem in 1999. Used in 4 plants in the world.

Fixed bed

CO2 and H2 are used as feed. 100 t/y pilot plant started in 2009.

CO2 + 3H2 → CH3 OH + H2 O

Catalyst developed by RITE.

Fixed bed. Ex. CO2 /CO/H2 = 22/3/75, 273 ◦ C, 5 MPa, SV = 10,000 h−1 .

First commercial process for acetic acid production by direct oxidation of ethylene. 13,000 t/y plant was commercially operated from 1997 to 2008.

C2 H4 + O2 → CH3 COOH

First fixed bed process for acetic acid production by methanol carbonylation (Acetica process). Rh complex immobilized by pyridine resin. Plant is under construction in China.

Modified ZSM-5

4 H2

Pt/F-modified KL zeolite

Idemitsu Kosan Co., Ltd.

[26–28]

Cu/ZnO/ZrO2 /Al2 O3 /Ga2 O3

Mitsui Chemicals, Inc. Research Institute of Innovative Technology for the Earth

[29,30]

Pd–H4 SiW12 O40 /SiO2

Showa Denko K.K.

[31]

([RhI2 (CO)]- )-pyridine resin

Chiyoda Corp.

[32,33]

Ex. 480 ◦ C, 0.5 MPa, WHSV = 2 h−1 .

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

Ex. hydrodesulfurization: 380 ◦ C, 1 MPa, LHSV = 2 h−1 , H2 /Naphtha = 0.1 mol/mol. Adsorption: 350 ◦ C, 0.8 MPaG. S < 0.1 ppb. Reforming: 490 ◦ C, 0.8 MPa, steam/carbon = 1.7.

H2 /HC = 5 mol/mol

Fixed bed. Ex. 150 ◦ C, 0.5 MPaG, GHSV = 3000 h−1 . CH3 OH + CO → CH3 COOH Fluidized bed. Ex. 190 ◦ C, 4.0 MPaG.

29

30

Table 1 (Continued ) No.

Product

Statement

Key reaction

Catalyst

Company

Ref.

20

Ethyl acetate

First direct process for ethyl acetate production from ethylene and acetic acid. 50,000 t/y plant started in Indonesia in 1999.

C2 H4 + CH3 COOH → CH3 COOC2 H5

H4 SiW12 O40 /SiO2

Showa Denko K.K.

[34,35]

Production of propylene from light naphtha using swing reactor (␻-process). First commercial plant started in 2006.

Light Naphtha (C4 ’) → Propylene

Modified ZSM-5

Asahi Kasei Chemicals Corp.

[36]

Phosphonium salt

Mitsubishi Chemical Corp.

[37,38]

Supported precious metal

Nippon Oil Corp.

[39]

Zeolite

Toray Industries, Inc.

[40]

Pd–Pb/SiO2

Asahi Kasei Chemicals Corp.

[41–43]

Supported Pd

Ube Industries, Ltd.

[44,45]

Supported Pd

Ube Industries, Ltd.

[44,45]

21

22

Propylene

Ethylene glycol

Fixed bed, Swing reactor. Ex. 600 ◦ C, 0.1 MPa, WHSV = 41.7 h−1 .

(Ri)4 P+ XRi: Alkyl, Aryl X: Halogen

Homogeneous continuous process. MEG selectivity 99.3–99.4%.

Hydration: continuous the same catalyst at atmospheric press.

23

Aromtics-free solvent

60,000 kl/y plant was commercialized in 2006.

24

Cumene

Transalkylation of C9 + and benzene.

Highly active and long-lived catalyst. Commercialized in 1996.

25

26

27

Methyl methacrylate (MMA)

Dimethyl oxalate

Dimethyl carbonate

+ 3H2

Hydrogenation and hydrodesulfurization of hydrotreated gas oil.

R-SH + H2 → RH + H2 S Aromatics <1 vol ppm, S < 1 mass ppm.

+

2

Ex. 400 ◦ C, 4 MPa, WHSV = 2.5 h−1 , H2 /Feeds = 4 mol/mol.

MMA production by direct oxidative esterification of methacrolein by methanol. First 100,000 t/y commercial plant started in 1998.

Slurry bed, bubbling reactor. Ex. 80 ◦ C, 0.4 MPa

Oxidative coupling of CO. Gas phase process using MeONO instead of slurry process using BuONO. NO is recycled producing methyl nitrite (non-catalytic). Started in 2006

2CO + 2CH3 ONO → (COOCH3 )2 + 2 NO 2NO + 2CH3 OH + 1/2O2 → 2CH3 ONO + H2 O

Produced from CO and methanol using CH3 ONO. NO is recycled producing methyl nitrite (non-catalytic). 15,000 t/y of continuous gas phase plant was commercialized in 1993.

CO + 2CH3 ONO → (CH3 O)2 CO + 2NO 2NO + 2CH3 OH + 1/2O2 → 2CH3 ONO + H2 O

Fixed bed. Ex. 100–130 ◦ C, 0.1–0.4 MPa.

Fixed bed. Ex. 100–130 ◦ C, 0.1–0.4 MPa.

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

Selective ethylene glycol production from ethylene oxide. First 15,000 t/y plant started in 2001. Licensed to Shell as OMEGA process.

Fixed bed, Sel. >98%, life >10,000 h. Ex. 165 ◦ C, 0.8 MpaG.

28

Diethanolamine

Selective diethanolamine production from ethylene oxide and ammonia. Regeneration using liquid NH3 . 50,000 t/y plant was commercialized in 2003.

2EO + NH3 → (HOCH2 CH2 )2 NH Fixed bed. Ex.182–199 ◦ C, 14 MPa, NH3 /EO = 10–17 mol/mol, WHSV = 5–15 h−1 .

N 29

␧-Caprolactam

Adipic acid

[46,47]

HN

High silica MFI

Sumitomo Chemical Co., Ltd.

[48–50]

N-hydroxyphthalimide with Mn or Co complex.

Daicel Chemical Industries, Ltd.

[51,52]

Ion exchange resin

Zeon Corp.

[53]

Epoxidation: Mesoporous TiO2 -SiO2 Hydrogenolysis of cumyl alcohol: Pd/Al2 O3

Sumitomo Chemical Co., Ltd

[54]

Ru complex

Mitsubishi Chemical Corp.

[55]

Ru complex

Mitsubishi Chemical Corp.

[56]

Fluidized bed. Ex. 370 ◦ C, WHSV = 8 h−1 .

Air oxidation of cyclohexane using N-hydroxyphthalimide (NHPI) and Mn or Co complex as catalyst. Pilot plant started in 2009.

O2

COOH

NHPI

COOH

Homogeneous. Ex. 100 ◦ C, 10 h.

31

Cyclopentyl-methylether

+

Gas phase alkylation by ion exchange resin. New solvent for general use.

OCH3

CH3OH

Fixed bed, gas phase. Ex. 90 ◦ C.

O

32

Propylene oxide

OOH

Cumene hydroperoxide is used as epoxidizing agent for propylene to propylene oxide. Cumyl alcohol is recycled to cumene by hydrogenolysis.

OH

H2

200,000 ton/y plants were commercialized in Japan in 2003 and in Saudi Arabia in 2009

O2

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

30

Nippon Shokubai Co., Ltd.

O

OH

Vapor phase Beckmann rearrangement. Fluid bed catalyst.

60,000 t/y plant started in 2003.

Rare earth-ZSM-5 (Binderless)

Epoxydation: Fixed bed. Ex. 60 ◦ C. H

33

34

␥-Butyrolactone

␥-Butyrolactone

Hydrogenation of succinic anhydride in homogeneous system following hydrogenation of maleic anhydride. 15,000 t/y plant was commercialized in 1997.

O

O O

O

Homogeneous. Ex. 200 ◦ C, 1 MPa.

Dehydrogenative ring closure of 1,4-butanediol. First commercial homogeneous catalyst for dehydrogenation.

O

Homogeneous. Ex. 203 ◦ C, 4.5 h, Conv. 100%, Sel. 96.6%. 31

32

Table 1 (Continued ) No. 35

Product Acrylonitrile

Statement Ammoxidation of propane using fluidized bed reactor. 70,000 t/y revamped plant started in Korea in 2007. New plant in Thailand is under construction.

Key reaction O2

CH3 CH2 CH3 + NH3 −→CH2 CHCN

Catalyst

Company

Ref.

Multi-component molybdate catalyst

Asahi Kasei Chemicals Corp.

[57]

Fe–K oxide with additives

Süd-Chemie Catalyst Japan, Inc.

[58,59]

Pt-Nb2 O5 /Al2 O3

Mitsubishi Chemical Corp.

[60]

Supported Ni

Kuraray Co., Ltd.

[61]

Nitrogen containing compound

Mitsubishi Chemical Corp.

[62,63]

Ion exchange resin promoted by sulfur compounds.

Mitsubishi Chemical Corp.

[64]

RuO2 /TiO2

Sumitomo Chemical Co., Ltd.

[65–67]

Pt/granular carbon

Asahi Glass Co., Ltd.

[68,69]

Fluidized bed. Ex. 440 ◦ C, contact time 1.0 s g/cc.

H2 36

Styrene

Improved catalyst for dehydrogenation of ethylbenzene. Commercially supplied to many plants from 1999. Fixed bed. Ex. 620 ◦ C, LHSV = 1.0 h−1 .

38

Styrene

1,9-Nonane diamine

Hydrogen removal in dehydrogenation of ethylbenzene. 370,000 t/y plant commercialized at Kashima in 2003. Licensed to Shell.

H2 + 1/2O2 → H2 O in reaction gas stream Fixed bed. Ex. 550–640 ◦ C.

Reductive amination of 1,9-nonanedial in slurry bed. 3000 t/y plant started in 1998.

(SMSI effect)

Slurry bed.

39

Diphenyl carbonate

Diphenyl carbonate from phenol and phosgene with nitrogen containing compound recycle system. 17,000 t/y of commercial plant started in 2000. Homogeneous. Ex. 150 ◦ C.

40

Bisphenol-A

Modified ion exchange resin catalyst. 100,000 t/y plant started in 2002.

Fixed bed. Ex. 70 ◦ C, PhOH/Acetone = 10/1, LHSV = 1 h−1 . 41

42

Chlorine

Chloroform

2HCl + 1/2O2 → H2 O + Cl2

Recovery of chlorine from hydrogen chloride. First fixed bed process. Commercial plant started in 2002. Two plants are running in Japan.

Fixed bed. Ex. 360–300 ◦ C.

First commercial plant using Pt- granular carbon.

CCl4 + H2 → CHCl3 + HCl Fixed bed. Ex. 160 ◦ C.

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

37

Newly developed metallocene catalyst.

xCH2 CH2 + yCH2 CHR → LLDPE

Single site catalyst

Sumitomo Chemical Co., Ltd.

[70–72]

44

Linear low density polyethylene (LLDPE)

Newly developed metallocene catalyst.

xCH2 CH2 + yCH2 CHR → LLDPE

Single site catalyst

Mitsubishi Chemical Corp. Japan Polychem Corp.

[73–76]

45

Linear low density polyethylene (LLDPE)

Double bridged metallocene catalyst.

xCH2 CH2 + yCH2 CHR → LLDPE

Single site catalyst

Idemitsu Kosan Co., Ltd.

[77–80]

46

Linear low density polyethylene (LLDPE)

Supported metallocene catalyst and activators were developed for gas phase process to produce LLDPE. Started in 1995.

xCH2 CH2 + yCH2 CHR → LLDPE

Supported single site catalyst

Mitsui Chemicals, Inc.

[81]

47

Polyethylene wax

Metallocene catalyst for functional polyethylene wax. 9000 t/y in 2004.

nCH2 CH2 → PE Wax

Single site catalyst

Mitsui Chemicals, Inc.

[82]

48

Liquid higher olefin

New functional liquid polymer by polymerization of ␣-olefins. Commercialized in 1989.

nCH2 CH2 → ␣-Olefin

Single site catalyst

Idemitsu Kosan Co., Ltd.

[83]

49

Polypropylene

Metallocene on clay mineral which is support and promoter. Commercialized in 2000.

Single site catalyst on montmorillonite

Japan Polypropylene Corp.

[84,85]

Mitsubishi Chemical Corp.

Single site catalyst

Japan Polypropylene Corp.

[86]

Single site Ti catalyst

Idemitsu Kosan Co., Ltd.

[87]

Base catalyst

Mitsubishi Chemical Corp.

[63,88]

ZrO2 /SiO2

Mitsubishi Chemical Corp.

[89]

50

High molecular weight polypropylene

Soft polypropylene produced with metallocene catalyst in gas phase process. Commercialized in 2009.

51

Syndiospecific polystyrene

First process of syndiotactic polymerization of styrene. 5000 t/y plant was commercialized in 1997.

n n

n n

n n/2

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

3. Polymers 43 Linear low density polyethylene (LLDPE)

O

n HO

52

Polycarbonate

Melt-polymerization process for polycarbonate. 20,000 t/y plant was commercialized in 2000.

OH

+ n

PhO

OPh

O O

O

C

n

+ 2n

PhOH

Homogeneous. Ac O

53

Polyoxytetra methylene glycol

Ring opening polymerization with fixed bed solid acid catalyst. 25,000 t/y of commercial plant started in 2000.

O

AcO

O ROH - AcOH

Fixed bed. Ex. 40 ◦ C, 5 h.

AcO

H

n

O

H

n

[90]

33

34

Table 1 (Continued ) No.

Product

Statement

Key reaction 1)

2)

+

CO

O

54

Polycarbonate

First commercial polycarbonate plant using CO2 . Diphenyl carbonate from phenol CO2 via ethylene carbonate and dimethyl carbonate. Ethylene glycol is co-produced. 65,000 t/y plant started in 2002, and 75,000 t/y plant was also commercialized at Chimei Asahi Co. in Taiwan in 2006, and also in Russia, Korea and Saudi Arabia.

Phenol resin

2 MeOH

1) metal salt (e.g. KI) 2) alkali (e.g. KOH) 3) metal compound (e.g. Pb(OPh)2 ) 4) base (very small amount)

Asahi Kasei Chemicals Corp.

[91–95]

Organic phosphoric acid.

Sumitomo Bakelite Co., Ltd.

[96]

Alkaline earth metal oxides, metal hydrides and metal alkoxides.

Mitsui Chemicals, Inc.

[97–102]

Phosphazene catalysts. PZN: [(Me2 N)3 P = N]4 P+ XPZO: [(Me2 N)3 P = N]3 P = O

Mitsui Chemicals, Inc.

[103,104]

O MeO

OMe

+

OH

HO

O

O

MeO

OMe

+

PhOH

PhO

2 PhO

OMe

+

MeOH

O OMe

PhO

n HO

OH

+

2 MeOH O

PhO

OPh

O Ph

+ n

O O

O

C

n

+ 2n

PhOH

Ethylene carbonate: homogeneous, 90 ◦ C, 9.5 MPa., Transesterification: homogeneous, 1st reactor: 198 ◦ C, 0.65 MPaG (top), 2nd reactor: 198 ◦ C, 280 mmHg (top).

Novolac-type phenolic resin with narrow molecular weight distribution is produced by organic phosphoric acid catalyst. 300 t/y plant was commercialized in 2001.

Ref.

O O

O

4)

Company

Homogeneous. SiH +

56

Organo silicon polymer

Heat resistant organosilicon polymer, poly[(phenylsilylene)ethynylene-1,3phenyleneethylene], was prepared by dehydrogenative coupling polymerization with base catalysts.

Si

Si

H X

Y

0.5 > Y > 0.01, X + Y = 1. Slurry bed. Ex. 25 ◦ C, 2 h + 80 ◦ C, 26 h, 0.1 MPa.

57

Poly (oxypropylene)polyol

Ring opening polymerization of polyol and propylene oxide by organic compound catalyst. 10,000 t/y plant was commercialized in 2002. Homogeneous. Ex. 80 ◦ C, polymerization activity : 450 g/mol min.

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

55

3)

+

O O

O

O

Catalyst

4. Fine chemicals

58

N-vinyl-2-pyrrolidone

Dehydration of N-(2-hydroxyethyl)-2-pyrrolidone. Highly active and selective, weak acid-base bi-functional catalyst. Commercial 3000 t/y plant started in 2001.

4-Acetoxy azetizinone

Nippon Shokubai Co., Ltd.

[105]

[RuCl(p-cymene){(R)dtbm-segphos}]Cl

Takasago International Corp.

[106]

H4 SiW12 O40 /SiO2

Showa Denko K.K.

[107]

Pd compound-P(t-Bu)3

Tosoh Corp.

[108]

Pd-Pt/carbon.

N.E. Chemcat Corp.

[109]

Transition metal modified ZSM-5.

Koei Chemical Co., Ltd.

[110]

Pd complex.

Nihon Nohyaku Co., Ltd.

[111]

Fixed bed. Ex. 400 ◦ C, GHSV = 200 h−1 . O

59

Alkali metal oxide-modified SiO2

OH

O

H

O

OMe

Asymmetric hydrogenation yield is improved to 98%. 120 t/y plant is running.

OMe

NHCOPh

NHCOPh

Homogenous. O

O

60

Tetralone

+

Tetralone synthesis from p-xylene and ␥-butyrolactone.

O

R

61

Arylamine

Br

+

HN

NH

Amination of arylhalide by Pd complex. NH

N R

Homogeneous. Ex. 120 ◦ C, 0.1 MPa, 3 h.

62

Debenzylation

Highly active Pd-Pt bimetal catalyst for hydrogenolysis of benzyl ether or amine compounds for deprotection. Slurry bed. Ex. r.t., 0.1 MPa.

CH 3CHO / HCHO / NH 3

63

Pyridine

Pyridine synthesis by Chichibabin reaction. Catalyst is regenerated using methanol.

+ N

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

Slurry bed. Ex. 200 ◦ C, 5 h.

N

Fixed bed. Ex. 450 ◦ C, CH3 CHO/HCHO/NH3 = 2/1/4 (mol), SV = 1,000 h−1 .

64

Flutolanil

Heck carbonylation to produce flutolanil, a pesticide for brown rice disease.

35

Homogeneous. Ex. 200 ◦ C.

36

Table 1 (Continued ) No.

Product

Statement

Key reaction H

65

Adamantane

Isomerization of tetrahydrodicyclopentadiene to adamantane. First fixed bed process. 300 t/y plant was commercialized in 2008.

Adamantanol

New oxidation process of adamantane using N-hydroxyphthalimide as catalyst. Commercialized.

OH

Asymmetric oxidation of indene by NaClO. Indene epoxide is introduced to optically active amino-indanol, an intermediate of HIV protease inhibitor. Production started in 1997.

Pt-rare earth/Y-zeolite.

Idemitsu Kosan Co., Ltd. JGC C&C

[112,113]

OH

Homogeneous. Ex. 75 ◦ C, air, 1 h.

N-hydroxyphthalimidetransition metal.

Daicel Chemical Industries, Ltd.

[114,115]

Mn-salen complex.

Nissan Chemical Industries, Ltd.

[116–118]

Pd/carbon.

Koei Chemical Co., Ltd.

[119]

Ru-(R)-BINAP complex.

Nissan Chemical Industries, Ltd.

[120]

Propargyl cinchonaalkaloids with propagyl.

Daiso Co., Ltd.

[121]

O

Homogeneous. R X

+

(HO) 2B

N

68

Phenyl pyridine derivatives

Production of arylpyridines and arylquinolines by Suzuki-Miyaura coupling.

R

N

Slurry bed. Ex. 80 ◦ C, with NaCO3 , over night.

69

Anti-␤-hydroxy-␣amino acid

Production of anti-HIV medicine by anti selective hydrogenation. 0.5–1 t/y plant started in 2005. Homogeneous.

70

Cinchona alkaloid derivatives

Asymmetric desymmetrization by alcoholysis of meso cyclic anhydrides. Unreacted amino acid anhydride and catalysts are separated only by extraction after hydration. Hundreds kg/y production started in 2003.

P: Protection agent Homogeneous. Ex. −60 ◦ C, 30 h.

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

Optically active indene epoxide

Ref.

OH +

NaOCl

67

Company

Isomerization: fixed bed. Ex. 325 ◦ C, 5 MPa, WHSV = 0.6 h−1 . O

66

Catalyst Isomerization

O

O NaClO N+

O

71

2-Hydroxy-1,4naphthoquinone

Synthesis from naphthoquinone by phase transfer catalyst. The product is an intermediate of tickcide, dodecyl-2-hydroxy-1,4-naphtoquinone.

O O O

Tetrabutylammonium bromide.

Kawasaki Kasei Chemicals Ltd.

[122]

Tertiary amine.

Nippon Shokubai Co., Ltd.

[123]

Pt, Rh on ACZ.

Toyota Motor Corp.

[124–126]

(ACZ: CeO2 –ZrO2 dispersed alumina particles)

Toyota Central R&D Labs., Inc.

Pd-perovskite.

Daihatsu Motor Co., Ltd. Japan Atomic Energy Agency

NaOH HO O ◦

Ex. 40 C, NaClO aq. soln. dropping 60 min. ␣-Hydroxy methylacrylate

Hydroxymethylation of methyl acrylate.

CH2 CH + COOCH3

HCHO

CH2 CCH2OH COOCH3

Homogeneous. Ex. 50 ◦ C, 8 h. 5. Auto exhaust gas treatment 73 Three-way catalysts for gasoline engine

74

75

76

Three-way catalysts for gasoline engine

Three-way catalysts for gasoline engine

Three-way catalysts for gasoline engine

Three-way catalysts containing ceria-zirconia solid solutions with high oxygen storage/release capacity. Fluorite structure is formed by dissolving zirconia in ceria. Sintering of CeO2 -ZrO2 is suppressed by alumina particles. Installed in USA, Japan, and other countries since 2001.

HC (Hydrocarbon) + O2 → H2 O + CO2 CO + 1/2O2 → CO2 NOx + reducing gases (HC, CO and H2 ) → N2 + H2 O + CO2

“Intelligent catalyst”. Pd-Perovskite is coated inside of Pt/Rh layer. Self-regeneration due to Pd dissolving in perovskite in oxidative atmosphere and its deposition on the surface in reductive atmosphere. 2.7million pieces were installed from 2002 to Aug. 2007.

HC (Hydrocarbon) + O2 → H2 O + CO2 CO + 1/2O2 → CO2 NOx + reducing gases (HC, CO and H2 ) → N2 + H2 O + CO2

Self-generative catalysts named Super Intelligent catalyst. Perovskite was applied to Pt and Rh in addition to Pd. 530,000 pieces were installed (2005–August 2007) in Japan and Europe.

High heat resistant catalyst. Reduction of Pt loading can be realized using CeO2 –ZrO2 –Y2 O3 (CZY) supports where Pt forms Pt–O–Ce bonds, preventing aggregation of Pt particles at high temperature. Commercialized since 2005.

[127,128]

Cataler Corp. Hokko Chemical Industry Co., Ltd.

HC (Hydrocarbon) + O2 → H2 O + CO2 CO + 1/2O2 → CO2 NOx + reducing gases (HC, CO and H2 ) → N2 + H2 O + CO2

HC (Hydrocarbon) + O2 → H2 O + CO2 CO + 1/O2 → CO2 NOx + reducing gases (HC, CO and H2 ) → N2 + H2 O + CO2

(Pd-Perovskite) + (PtPerovskite) + (RhPerovskite).

Daihatsu Motor Co., Ltd. Japan Atomic Energy Agency

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

72

[129,130]

Cataler Corp. Hokko Chemical Industry Co., Ltd. Mixture of Pt/CZY catalysts and Rh/CeO2 -doped ZrO2 catalysts.

Toyota Motor Corp.

[131–134]

Toyota Central R&D Labs., Inc. Cataler Corp.

(CZY: CeO2 –ZrO2 –Y2 O3 ) Alumina support.

37

38

Table 1 (Continued ) No.

Product

Statement

Key reaction

Catalyst

Company

Ref.

77

Three-way catalysts for gasoline engine

High heat- resistant catalyst. Pt is supported on CeO2 , anchor material, and dispersed in wall material to avoid cohering. Amount of Pt loading was reduced.

HC (Hydrocarbon) + O2 → H2 O + CO2

Pt/CeO2 .

Nissan Motor Co., Ltd.

[135,136]

PM/M/(Al2 O3 + TiO2 + ZrO2 ). (PM = Pt or Rh, M = alkali or alkaline earth metal) TiO2 improves sulfur resistance and Rh/ZrO2 is effective for H2 formation to decompose sulfate.

Toyota Motor Corp. Toyota Central R&D Labs., Inc.

[137,138]

Cataler Corp.

78

NOx storage/ reduction catalyst

NSR catalyst (NOx Storage/Reduction catalyst) for lean-burn and direct injection gasoline engines. NOx interacts with NOx storage material (Ba, K, Li etc) via Pt or Rh particles: Commercialized in Japan from August 1995 to 2002

CO + 1/2O2 → CO2 NOx + reducing gases (HC, CO and H2 ) → N2 + H2 O + CO2 Lean burn condition NO + 1/2O2 → NO2 NO2 + 1/2O2 + MOx → M(NO3 )x Rich burn condition M(NO3 )x + HC (Hydrocarbon) + CO → MOx + N2 + H2 O + CO2 (M: Ba, K, Li)

Hydrocarbon adsorption for three-way catalyst

HC (hydrocarbon) emission at cold start is adsorbed on undercoated zeolite. 970,000 pieces (October 1998–April. 2007)

HC → Adsorption HCads + O2 → CO2 + H2 O

Zeolite.

Nissan Motor Co., Ltd.

[139,140]

80

Diesel exaust gas DeNOx

Urea SCR (Selective Catalytic Reduction system). 8,000 pieces/y were installed from2007

CO(NH2 )2 + H2 O → 2NH3 + CO2 4NO + 4NH3 → 4N2 + 6H2 O 6NO2 + 8NH3 → 7N2 + 12H2 O NO + NO2 + 2NH3 → 2N2 + 3H2 O

Urea SCR catalyst.

Mitsubishi Fuso Truck and Bus Corp.

[141]

81

Diesel exhaust soot and NOx removal

NO is oxidized to NO2 at first converter and the resulting NO2 oxidizes soot which is trapped on honeycomb wall. 40,000 pieces/y have been installed since 2006.

1st coverter NO + 1/2O2 → NO2 2nd converter NO2 + C → NO + CO2

1st: PM/honeycomb. 2nd:

Mitsubishi Fuso Truck and Bus Corp.

[141]

PM/SiC wall through honeycomb.

82

Diesel exhaust soot and NOx removal

DPNR (Diesel Particulate – NOx Reduction) system. Short rich burn operation is inserted in every 50–60 s of lean burn operation. NOx and soot are removed simultaneously. Commercialized in Europe and Japan since 2003

Lean burn conditions NO + 1/2O2 → NO2 NO2 + C → NO + CO2 NO2 + O2 + MOx → M(NO3 )y Rich burn conditions M(NO3 )y + HC + CO → MOx + N2 + H2 O + CO2 (M: Ba, K, Li)

NOx storage/reduction catalysts.

Toyota Motor Corp. Hino Motors, Ltd.

[142–144]

83

Diesel exhaust NOx removal

Urea SCR system. NOx is reduced by NH3 formed from urea using zeolite catalyst Commercialized in Japan since 2004

CO(NH2 )2 + H2 O → 2NH3 + CO2 4NO + 4NH3 + O2 → 4N2 + 6H2 O 6NO2 + 8NH3 → 7N2 + 12H2 O NO + NO2 + 2NH3 → 2N2 + 3H2 O

Zeolite materials.

Nissan Diesel Motor Co., Ltd. Tokyo Roki Co., Ltd.

[145–147]

84

Diesel exhaust soot removal

Soot on diesel particulate filter is oxidized on ZrO2 -based catalyst. Oxygen ion conduction is supposedly involved in the high performance. Introduced to the market in 2008.

C + O2 → CO2

ZrO2 materials.

Mazda Motor Corp.

[148]

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

79

6. Pollution Control 85 H.C.,bacteria, NO, SO2 removal.

86

88

SOx removal

Dioxine removal

(1) SO2 and SO3 from power plant are adsorbed and oxidized into H2 SO4 . H2 SO4 is washed out continuously by water. Thermal regeneration of ACF is unnecessary. (2) NOx in the atmosphere is adsorbed and oxidized into HNO3 which is occasionally washed out with water. sprinkler or rainfall at the road side. Desulfurization of plant waste gas.. Conversion of SO2 to SO3 which reacts with water. Formed H2 SO4 is removed automatically. Regeneration is not necessary. Applied to coal power plant (CASOX process). Commercialized in 2003.

(1) HCHO + 3/2O2 → H2 O + CO2 Bacteria + O2 → H2 O + CO2

TiO2 (anatase). V-BiOx (Visible light).

TOTO Ltd. and many companies.

[149–151]

Activated Carbon Fibers (ACF). Honeycomb or molding.

Kyushu Univ. Osaka Gas Co., Ltd.

[152–155]

Carbon honeycomb.

Chiyoda Corp.

[156]

TiO2 –V2 O5 honeycomb.

Nippon Shokubai Co., Ltd.

[157]

TiO2 –V2 O5 honeycomb.

Mitsubishi Heavy Industries, Ltd.

[158]

Pt/Na-mordenite.

Tosoh Corp.

[159]

AlPO4 .

Ohita Univ. Showa Denko K.K. Kankyosoken Co., Ltd.

[160]

(2) NO + 1/2O2 + H2 O → HNO3 SO2 + 1/2O2 + H2 O → H2 SO4

(1) SO2 + 1/2O2 → SO3 SO3 + H2 O → H2 SO4 2) NO + 1/2O2 + H2 O → HNO3 Fixed bed.

SO2 + 1/2 O2 → SO3 SO3 + H2 O → H2 SO4 Fixed bed, trickle bed.

Decomposition of dioxins in incinerator off gas. Catalyst is installed in front of NH3 SCR reactor. Fixed bed. Ex. 200–230 ◦ C.

89

Dioxine removal

Decomposition of dioxins in incinerator off gas. Catalyst is installed in front of NH3 SCR reactor.

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

87

SOx , NO removal

(1) Formaldehyde vapor from walls in a room, odor components and bacteria are decomposed with OH radical produced by photocatalyst. Used in construction materials. (2) NOx or SOx is oxidized and removed as acids with rain water by catalyst coated on highway guard rails.

Fixed bed. Ex. 150 ◦ C, SV = 3,000 h−1 . 90

91

Combustion of chlorinated VOC

Decomposition of flon

Decomposition of organic chlorides. Mordenite decomposes chlorides and Pt combusts organic compounds. Commercialized in 2001. Decomposition of perchloro compounds leaked from etching and dry cleaning equipment.

C2 H4 Cl2 + 5/2O2 → 2CO2 + H2 O + 2HCl Fixed bed. Ex. 200–240 ◦ C. CCl2 F2 + O2 → CO2 + Cl2 + F2 CCl2 F2 + 2H2 O → CO2 + 2HCl + 2HF Fixed bed. Ex. 700 ◦ C, with steam, GHSV = 3000 h−1 .

39

40

Table 1 (Continued ) Product

Statement

Key reaction

Catalyst

Company

Ref.

92

Decomposition of perfluoro compounds

Decomposition of perchloro compounds leaked from etching and dry cleaning equipment..

CCl2 F2 + O2 → CO2 + Cl2 + F2 CCl2 F2 + 2H2 O → CO2 + 2HCl + 2HF

WO3 -coated TiO2 /SiO2 .

Hitachi, Ltd.

[161,162]

93

Hypochlorite removal

Hypochlorite decomposition in waste water.

2NaClO → 2NaCl + O2

[163,164]

Fixed bed. Ex. r.t., 0.1 MPa.

Supported Ni on fluorinated polymer membrane.

Tosoh Corp.

Commercialized in 1996. Ammonium ion in waste water is removed by nitrite ion and hydrogen peroxide in two steps. Applied to waste water from power plant.

NH4 + + NO2 − → N2 + 2H2 O

Pt/TiO2 .

Kurita Water Industries Ltd.

[165]

Ru/TiO2 .

Teijin Fibers Ltd.

[166]

Precious metal/TiO2 ·Fe2 O3 .

Nippon Shokubai Co., Ltd.

[167,168]

Fixed bed.

94

Ammonium ion removal

2NH4 + + 3H2 O2 → N2 + 6H2 O + 2H+ Fixed bed. Ex. 160 ◦ C, 0.8 MPa.

95

96

Acetic acid recovery

Waste water treatment

HCOOH, HCHO + O2 → CO2 + H2 O

Selective oxidation of formic acid and formaldehyde in waste water containing acetic acid which is recovered. Commercialized in 1996.

Fixed bed. Ex. 190 ◦ C, 2.0 MPa, WHSV = 2 h−1 .

Waste water containing sulfur compounds like Na2 S from ethylene plant. Several plants were commercialized.

Na2 S + 2O2 → Na2 SO4 NaSH + 2O2 + NaOH → Na2 SO4 + H2 O Na2 S2 O3 + 2O2 + 2NaOH → 2Na2 SO4 + H2 O Fixed bed. Ex. 200 ◦ C, 4.0 MPa, air, WHSV = 2 h−1 .

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

No.

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

below (the figures at the end of sentences refer to the numbers in the Table 1). 3.1. Petroleum and energy Though the environment has been improved year by year in Japan, suspended particle matter (SPM) in the atmosphere is still beyond the environmental standard, this is a serious problem especially in large cities. The main source of SPM is soot contained in diesel engine exhaust gas; the sulfur in diesel oil is one of the important causes to generate soot. Although development of technologies to remove SPM in diesel engine exhaust gas has been advanced as will be described later, it is also required to depress the generation of SPM itself. Thus the sulfur content in diesel oil was regulated to be less than 10 ppm in 2009 and development of deep hydrodesulfurization (HDS) catalysts was quickly required. The nano-technology was successfully applied to the preparation of the catalysts with the aid of academic characterization techniques [1–3]. The developed Co–Mo–P/HY-Al2 O3 catalyst had three times higher HDS activity than the conventional one. The catalyst has multiple layers of MoS2 slabs and the edges of MoS2 are mainly occupied by active Co–Mo–S phases. Sulfur-free gasoline was introduced to reduce the work load of three-way NOx storage-type catalysts for auto exhaust catalyst. Invention of the catalysts which could desulfurize high sulfur FCC gasoline without hydrogenation of olefins was based on the discovery of a proper Co/(Mo + Co) ratio [6]. High yield propylene production from FCC process gas was realized by adopting downflow reactors called downers together with proper zeolite catalysts [8]. Because of short residence time due to higher catalyst/oil ratio and adoption of the downers to prevent back-mixing, thermal decomposition of the products could be depressed, resulting in the high selectivity. Dimethyl ether is a big concern in China as a new energy source. Large scale plants that can dehydrate methanol derived from natural gas or coal were built in China based on Japanese technologies [10]. The high performance catalyst is ␥-Al2 O3 , whose pore distribution and impurity contents are adequately controlled to achieve high activity as well as high stability. The hydrogen production system for fuel cells should be compact. Ni catalysts supported on bimodal Al2 O3 and Ru/ZrO2 were developed [11,12]. These catalysts are highly active and do not require high steam ratio owing to the low carbon formation characteristic. 3.2. Bulk chemicals In the field of hydrocarbon processing, the demand for aromatics is increasing in East Asia. In the current situation of limited aromatic sources, two types of new technology have emerged; One is aromatics obtained from light naphtha by a modified zeolite catalyst [14,15] and the other is aromatics obtained from C6 paraffin in naphtha by Pt/F-modified KL zeolite, which has higher activity, selectivity and stability than ordinary Pt/KL zeolite and conventional Pt/Al2 O3 catalysts [16]. These effects were attributed to high Pt dispersion and to the electron-rich state of Pt. A new type of modified ZSM-5 was developed and commercialized to produce propylene from C3 and C4 raffinate [21]. These 3 technologies show that zeolites remain in an important position in hydrocarbon conversion. Highly selective processes were found for the production of ethylene oxide derivatives. A new selective monoethylene glycol process through ethylene carbonate was commercialized [22]. Here, ethylene carbonate is produced from ethylene oxide and carbon dioxide by phosphonium salt catalyst and then hydrated to form ethylene glycol. Higher yield of monoethylene glycol and

41

much smaller amounts of higher glycols compared to conventional processes were attained. The shape selectivity of zeolite is utilized to produce diethanolamine from ethylene oxide and ammonia. [28]. The process can be controlled to form diethanolamine in high selectivity using La-modified ZSM-5. It is expected that monoethanolamine reacts with ethylene oxide to form diethanolamine in the narrow micropores, whereas dietanolamine cannot react to form triethanolamine due to the shape selectivity of modified ZSM-5. The regeneration of the catalyst is carried out using liquid ammonia in the reactor. Elimination of co-products has been an important target of catalytic technologies. Conventional Beckmann rearrangement of cyclohexanone oxime to produce ␧-caprolactam using fuming sulfuric acid co-produces a large amount of ammonium sulfate. High silica ZSM-5 zeolite was found to show Beckmann rearrangement activity in vapor phase, the active sites being silanols on the surface of the zeolite [29]. The process using a fluidized bed reactor was commercialized together with ammoximation process (introducing EniChem’s technology) for the oxime production from cyclohexanone to realize an ␧-caprolactam process free from ammonium sulfate co-production. Propylene oxide process with no co-products was commercialized using cumene hydroperoxide as epoxidation agent. Mesoporous titanosilicate catalyst gives a very high yield of propylene oxide [32]. Cumyl alcohol formed in the epoxidation is hydrogenated to cumene which is recycled to generate cumene hydroperoxide in the system. Shortening of reaction steps is often realized by catalyst innovation. A direct oxidation process of ethylene to acetic acid was commercialized, the catalyst being Pd-heteropoly acid on SiO2 in gas phase reaction [18], although this process recently ceased its operation for economical reasons. Direct ethyl acetate production from ethylene and acetic acid also using heteropoly acid/SiO2 has started [20]. Both processes are of interest as the examples of applications of supported heteropoly acid catalysts to gas phase reactions. Bimetallic Pd-Pb/SiO2 catalyst was applied to one-step methyl methacrylate production by oxy-esterification from methacrolein and methanol in slurry phase [25]. Conventional gas phase process for isobutylene-based MMA production developed in Japan [1] is composed of (1) oxidation of isobutylene to methacrolein by Mo–Bi–O based composite oxide catalyst; (2) oxidation of methacrolein to methacrylic acid by Mo–P–O heteropoly acid catalyst and (3) esterification of methacrylic acid with methanol by ion exchange resin catalyst. The oxy-esterification technology improved the process by displacing steps (2) and (3) at the same time. The processes using alkanes as a raw material instead of alkenes have been promoted. Although alkanes are less expensive than their corresponding alkenes because of their lower degree of processing, it is more difficult to convert them selectively to the products. The revamped acrylonitrile plant that employs ammoxidation of propane by a multi-metal molybdate catalyst has started up [35]. A pilot plant for adipic acid production from cyclohexane by liquid phase oxidation catalyzed by homogeneous Mn complex using N-hydroxyphthalimide as co-catalyst has started [30]. Several other unique technologies were developed in the field of oxidation. HCl oxidation by a fixed bed RuO2 /TiO2 catalyst has been developed and commercialized [41]. This compact process is for the recovery of chlorine and is applicable to many plants producing HCl as a byproduct. On the other hand, a HCl oxidation process using Cr2 O3 /SiO2 fluidized bed catalyst had been developed earlier also in Japan [1]. To increase styrene yield in dehydrogenation of ethylbenzene, researchers developed a high performance novel catalyst to oxidize

42

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

produced hydrogen selectively in the reactor to shift the reaction equilibrium [37]. Pt/Nb2 O5 –Al2 O3 catalyst was designed based on strong metal-support interaction (SMSI) concept to improve selectivity for H2 oxidation by depressing styrene oxidation. This is an interesting example that utilizes a positive aspect of SMSI. In the field of C1 chemistry, a pilot plant for methanol production from CO2 using a highly active methanol synthesis catalyst, Cu/ZnO/ZrO2 /Al2 O3 /Ga2 O3 has started [17]. A fixed bed acetic acid process by carbonylation of methanol using Rh complex immobilized on pyridine resin was developed [19]. Such a plant is now under construction in China. Dimethyl oxalate and dimethyl carbonate processes from carbon monoxide and methanol were developed and commercialized [26,27]. CO and methyl nitrite react over a supported Pd catalyst in gas phase to produce dimethyl oxalate or dimethyl carbonate. NO formed is separated and used for its reactions with methanol and O2 in a separate process regenerating methyl nitrite. Interestingly, Cl containing (oxidized) Pd produces the carbonate and Cl-free (metallic) Pd produces the oxalate, both selectively. Homogeneous catalytic technologies also have shown great advances including oxidation using N-hydroxyphthalimide as co-catalyst mentioned above. Two processes to produce ␥butylolactone were developed using Ru complexes under mild conditions; one is by hydrogenation of maleic anhydride [33] and the other is by dehydrogenative ring closure of 1,4-butanediol [34]. Homogeneous catalyses are more favorably used for fine chemical production, as will be described later. 3.3. Polymers In the field of polyolefins, polymerizations with single site catalysts were extensively studied and the commercializations of the processes using them were achieved. Single site catalysts for LLDPE have been commercialized by several companies [43–46]. Various types of catalysts with novel metallocene structures and/or ligands were developed, although the catalysts in practice are not disclosed. Supported single site catalysts and the activators were developed for gas phase process [46]. A single site catalyst supported on clay mineral is used for polypropylene [49]. The first syndiotactic polymerization process of styrene in the world was commercialized [51] using a Ti compound combined with methylaluminoxane (MAO) as catalyst. Besides the processes listed in Table 1, unique post-metallocene catalysts like phenoxy imine compound are found [169]. And the developments of Ziegler-Natta catalysts by modification with internal and external donors are still continuing in polypropylene field. The research on new functional polymers has also been conducted using half-metallocene catalysts [170–173]. The first multi-step commercial polycarbonate (PC) plant using CO2 was started in 2002 [54]. Each step uses its own catalyst: (1) CO2 and ethylene oxide produce quantitatively ethylene carbonate by a salt catalyst such as KI; (2) ethylene carbonate reacts with methanol to co-produce dimethyl carbonate and monoethylene glycol by an alkaline catalyst such as KOH; (3) dimethyl carbonate reacts with phenol to yield diphenyl carbonate (DPC) by metal compound catalyst such as Pb(OPh)2 ; (4) the final step is transesterification polymerization of DPC and bisphenol-A using a gravity-utilized, non-agitation polymerization reactor using a very small amount of OH- as catalyst. Another new PC process was commercialized, in which DPC is produced from phenol and carbonyl dichloride using a new nitrogen containing catalyst [39,52]. Carbonyl dichloride is completely consumed and the HCl generated can be effectively utilized for regeneration of Cl2 by oxidation or for hydrochloric acid production. In the conventional PC process, Cl in carbonyl dichloride is treated by NaOH to form NaCl-containing waste water. Transester-

ification of DPC and bisphenol-A to produce PC is performed in the presence of an alkali metal compound catalyst. The plant for polytetramethylene glycol by ring opening polymerization using a fixed bed solid acid catalyst (ZrO2 /SiO2 ) was started [53]. Novolac-type phenolic resin with a narrow molecular weight distribution is produced by an organic phosphoric acid catalyst [55]. Highly heat resistant organsilicon polymer, poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene], is prepared by dehydrogenative coupling polymerization between phenylsilane and 1,3-diethynylbenzene with base catalysts [56]. Phosphazene catalysts were developed for ring opening polymerization of propylene oxide with polyol to produce very pure and high molecular weight polypropylene glycols [57]. Phosphazenium ion is very effective as a countercation to anionic species to accelerate the anionic reaction and can be removed efficiently from the reaction mixture using solid acid adsorbents with appropriate pore size and specific surface area. It is the first commercial application of organo-catalysis to polymerization. 3.4. Fine chemicals Acid–base catalysts play important roles in reactions such as dehydration and isomerization. The vapor phase dehydration process of N-(2-hydroxyethyl)-2-pyrrolidone to produce N-vinyl2-pyrrolidone was commercialized with alkali (or alkaline earth) metal oxides modified SiO2 catalysts [58]. The catalyst, having both weakly acidic and weakly basic sites, is highly active and selective and researchers suppose that the isolated silanol of the catalyst surface plays an important role. Tetralone is produced from p-xylene and ␥-butylolactone by heteropoly acid supported on SiO2 [60]. Modified ZSM-5 was successfully introduced to pyridine synthesis through the Chichibabin reaction [63]. Regeneration with methanol was found to give the catalyst long life. Current synthesis of adamantane is based on the isomerization of hydrogenated dicyclopentadiene with AlCl3 . This is a batch process and needs waste water treatment. A fixed bed process by modified Y-zeolite catalyst was developed and commercialized [65]. Selevtive oxidation processes have been developed using various oxidation agents. Oxidation process of adamantane to produce adamantanol was developed using air as an oxidizing agent and Mn or Co complex together with N-hydroxyphthalimide as catalyst [66]. A phase transfer catalyst in NaClO oxidation was applied to obtain 1,4-naphthoquinone 2-oxide, an intermediate of an insecticide (tickcide) [71]. The oxidation with H2 O2 by heteropoly acid or Na2 WO4 catalysts to produce epoxides from olefins has been vigorously studied [174–176]. For asymmetric synthesis to produce intermediates of medicines, many metal complexes with unique chiral ligands such as [RuCl(p-cymene){(R)-dtbm-segphos}Cl have been developed. 4-Acetoxyazetizinone has been produced commercially [59]. Asymmetric synthesis is developed not only for hydrogenation but also for oxidation. Asymmetric oxidation of indene by NaClO using a Mn salen complex catalyst produces optically active indene epoxide, which is transformed to optically active amino indanol, an intermediate of HIV protease inhibitor [67]. Pd catalysts are conveniently applied to various fine chemical processes. Aryl amine derivatives are produced by amination of aryl halides by a Pd complex [61]. Flutolanil, a pesticide for brown rice disease, is produced by Heck carbonylation by a Pd complex [64]. Production of aryl pyridine derivatives is the first successful application of the Suzuki–Miyaura reaction to pyridine derivatives by Pd/carbon [68]. Benzyl group, a protecting group for hydroxy or amino compounds, is easily eliminated by hydrogenolysis using highly active Pd(99)Pt(1)/carbon bimetal catalyst [62].

T. Muroi et al. / Applied Catalysis A: General 389 (2010) 27–45

It is highly plausible that a lot more catalysts have been utilized for fine chemicals production, because catalytic technologies tend to be kept undisclosed as know-how in this field.

43

tion of formic acid and formaldehyde in the recovery of acetic acid from terephthalic acid waste water [95]. A Ni/fluorinated polymer membrane catalyst is developed for hypochlorite decomposition [93].

3.5. Auto exhaust catalysts To reduce the loading amount of platinum group metals, heat resistant catalyst for prevention of sintering was developed [74,75]. The stability of the Pd or Rh/perovskite catalyst was explained as follows: the Pd or Rh metal moves into the lattice of peroveskite at high temperature oxidative atmosphere and comes out from the lattice at reductive atmosphere. This was evidenced by EXAFS. A technology to prevent sintering using strong interaction or anchor effect of Pt with the carriers such as CeOx was also developed and commercialized [76,77]. In response to more strict regulation, researchers developed Pt or Pd/zeolite catalysts which reduce generation of harmful gas at cold start. It adsorbs hydrocarbons at start up and combusts them after warming up [79]. Diesel engines are widely used for large vehicles such as buses and trucks in Japan. For soot removal, wall-through honeycomb was developed as a soot trap filter; as for the material, SiC was found to have the highest heat resistance among ceramics. It was also found that NO2 is a more effective oxidation gas of soot on Pt catalysts than O2 . Especially the NO2 /NO ratio of 1/1 gave the highest conversion of soot on Pt catalysts. Thus the system composed of oxidation of NO to a proper concentration of NO2 (1st step) and fast oxidation of soot by NO2 (2nd step) was developed [81,82]. NO + 1/2O2 → NO2 (1st) 2NO2 + C → CO2 + 2NO(2nd) As the third step, DeNOx system by metal modified zeolite using SCR (Selective Catalytic Reduction) by NH3 evolved from a urea solution was adopted. ZrO2 -based new catalysts were developed and commercialized. These catalysts exhibit high carbon-burning performance and superior thermal stability in diesel particulate filters [84]. Presumably they promote the carbon burning by a mechanism where oxygen ions in the lattice of the oxide are transferred to the active sites by oxygen-ion conduction. 3.6. Environmental catalysts Photo-catalysis based on TiO2 has become very popular. Photocatalysts have been widely used in construction materials such as housing walls, bath and sanitary room wall to keep air and surfaces clean, in air conditioners to remove smell or bacteria, and in wrapping films for keeping flowers and vegetables fresh [85]. They are applied to even high-way guard rails and pavement as DeNOx device by oxidation to nitric acid. Sulfur removal system of waste gas has been developed [86]. Carbon honeycomb catalysts convert SO2 to SO3, which is then removed with water continuously as H2 SO4 . The system is applied to coal power plants. Dioxins decomposition catalysts were found and installed in incinerators [88,89]. Organic chlorides as VOC (volatile organic compound) are decomposed by Pt/mordenite [90]. Perchloro compounds left over from etching and dry cleaning equipment are decomposed by AlPO4 or WO3 -coated TiO2 /SiO2 catalysts [91,92]. Waste water treatment catalysts have been developed. A Pt–TiO2 catalyst is used for oxidative treatment of waste water from chemical plants containing sulfur compounds [96]. Ammonium ions in waste water from power plants are oxidized to nitrogen with nitrite ion and hydrogen peroxide by a Pt–TiO2 catalyst in 2 steps [94]. A Ru–TiO2 catalyst has been applied to selective oxida-

4. Conclusion Overall 96 catalytic technologies in 6 industrial areas were introduced above and in Table 1. About 1/3 of those are related to the area of bulk chemicals and the remaining 2/3 spread almost equally over the other 5 areas. About 3/4 of the developed catalysts are heterogeneous and the remaining 1/4 are homogeneous. About 1/3 of the catalysts are based on precious metals, another 1/3 are based on transition metals other than precious metals and the final 1/3 is composed of main group elements, including acid-base catalysts, zeolites, ion exchange resins and organic catalysts. Among these, the contribution of zeolites is outstanding. Many processes for producing chemicals such as aromatics, propylene, ␧-caprolactam, pyridine, diethnolamine and adamantane were commercialized using zeolites. Although zeolites have been applied to refinery processes including FCC and hydrocracking, the technologies have been successively improved. Zeolites are also applied to exhaust gas treatment for gasoline engine and diesel engine. Precious metals are widely utilized except for polymerization area. Pd and Pt are most frequently used not only for hydrogenation, but also for selective oxidation. Several unique chemical processes were developed using Ru both in homogeneous catalysis (for asymmetric syntheses and ␥-butyrolactone syntheses) and in heterogeneous catalysis (for Cl2 regeneration and steam reforming to produce hydrogen for fuel cells). Rh is used for auto exhaust gas treatment. It is also used in a chemical process as immobilized complexes for fixed bed catalysis. Catalysts based on transition metals other than precious metals are widely spread to various fields. For example, Ti is used as metallocene catalysts for olefin polymerization, as TiO2 for photocatalysts, dioxin removal and catalyst carriers, as titanosilicate for epoxidation and so on. In addition, transition metals such as V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo and W are used in the forms of oxide, composite oxide, heteropolyacid, metal or homogeneous catalysts. Contribution of catalyst makers should not be neglected for developing useful industrial catalysts described in Table 1. In many cases, they have supported the R&D of new catalytic processes from the basic stage like catalyst screening to the final stage of its commercial usage. Conventional commercial catalysts have also shown great improvements. Lastly it should be noted that collaboration between industry and academia has effectively promoted the technology development. Some of the important technologies were developed based on academic seeds, while the cooperative works of academia and industry led to innovation in many cases. Acknowledgements The article could be completed thanks to the kind advice of Profs. Makoto Misono, Yoshio Ono and Eiichi Kikuchi from the start to completion. The authors are also very grateful for the thoughtful support of the following researchers; Akinobu Shiga, Masahiro Sugiura, Masazumi Chono, Michio Ueshima, Naoshi Imaki, Norio Tanaka, Takashi Fujikawa, Takeshige Takahashi, and Tatsuya Miyatake. References [1] M. Misono, N. Nojiri, Appl. Catal. 64 (1990) 1–30. [2] N. Nojiri, M. Misono, Appl. Catal. A 93 (1993) 103–122.

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