1999 Industrial application of solid acid base catalysts.pdf

Industrial application of solid acid±base catalysts

Kozo Tanabea,*, Wolfgang F. HoÈlderichb,1

aResearch and Development Division, Nippon Shokubai Co., Ltd., 5-8, Nishi Otabi-cho, Suita, Osaka 564-8512, JapanbDepartment of Chemical Technology and Heterogeneous Catalysis, University of Technology, RWTH Aachen,

Worringerweg 1, D-52074, Aachen, Germany

Received 6 July 1998; received in revised form 24 September 1998; accepted 5 November 1998

Abstract

A statistical survey of industrial processes using solid acid±base catalysts is presented. The number of processes such as

alkylation, isomerization, amination, cracking, etheri®cation, etc., and the catalysts such as zeolites, oxides, complex oxides,

phosphates, ion-exchange resins, clays, etc., are 127 and 180, respectively. The classi®cation of the types of catalysts into solid

acid, solid base, and solid acid±base bifunctional catalysts gives the numbers as 103, 10 and 14, respectively. Some signi®cant

examples are described more in detail. On the basis of the survey, the future trend of solid acid±base catalysis and the

fundamental research promising for industrial success are discussed. # 1999 Elsevier Science B.V. All rights reserved.

Keywords: Industrial processes; Solid acid catalyst; Solid base catalyst; Solid acid±base bifunctional catalyst

1. Introduction

More than three hundreds of solid acids and bases

have been developed for the last 40 years. The surface

properties and the structures have been clari®ed by

newly developed measurement methods using modern

instruments and highly sophisticated techniques. The

characterized solid acids and bases have been applied

as catalysts for various reactions, the role of acid±base

properties for catalytic activities and selectivities

being studied extensively. Now, solid acid±base cat-

alysis is one of the economically and ecologically

important ®elds in catalysis. The solid acid and base

catalysts have many advantages over liquid Brùnsted-

and Lewis-acid and base catalysts. They are non-

corrosive and environmentally benign, presenting

fewer disposal problems. Their repeated use is possi-

ble and their separation from liquid products is much

easier. Furthermore, they can be designed to give

higher activity, selectivity, and longer catalyst life.

Therefore, the replacement of the homogeneous cat-

alysts with the heterogeneous ones is becoming even

more important in chemical and life science industry.

Since, however, a question as to how many and what

kinds of industrial processes have been developed by

using solid acid±base catalysts is not clear, we have

made a statistical survey to grasp the tendency of

industrialization and to stimulate further development

of this relevant ®eld of catalysis. On the basis of the

statistical data, the future trend of R&D in solid acid±

base catalysis is speculated.

Solid acids and bases are used also as supports of

catalysts such as metals, oxides, salts, etc., or as one

Applied Catalysis A: General 181 (1999) 399±434

*Corresponding author.1Also corresponding author.

0926-860X/99/$ ± see front matter # 1999 Elsevier Science B.V. All rights reserved.

PII: S0926-860X(98)00397-4

component of various catalysts. Since, however, the

number of uses in such forms is too large to survey,

those cases had to be excluded from this survey, except

the cases where their acidic and basic properties play

vitally important roles for catalytic performance.

2. Results of survey

2.1. Types of industrial processes and catalysts

Table 1 shows the type of industrial processes using

solid acid±base catalysts.

The larger numbers (18±8) of the process types are

found for alkylation, isomerization, dehydration and

condensation, amination, cracking and etheri®cation,

and the smaller ones (7±3) for aromatization, hydra-

tion, hydrocracking, MTG/MTO, oligomerization and

polymerization as well as esteri®cation. We accounted

127 different processes. Thereby, we did not differ-

entiate between the various process developments of

the companies and the types of catalysts used. The

judgement was made by the reaction type. More than

40% of all collected processes are catalyzed by zeo-

lites.

The types of catalysts used in the above industrial

processes are shown in Table 2.

The larger numbers (74±16) are seen for zeolites,

oxides, complex oxides, ion-exchange resins and

phosphates, and the smaller ones (7±3) for clays,

immobilized enzymes, sulfates plus carbonates and

sulfonated polysiloxanes. It is noteworthy that zeolites

occupy about 41% of the acid±base catalysts if the

number of the same kind of zeolite used for one

process is counted as 1. More detailed kinds of

catalysts are given in Table 3.

Although some kinds of zeolites are not speci®ed,

the number of ZSM-5 plus high silica pentasil zeolites

is the largest among various zeolites. It is also note-

worthy that 16 phosphates are used as catalysts in

industrial processes.

2.2. Classification of solid acid, base, and acid±base

bifunctional catalysts

The number of solid acid, base, and acid±base

bifunctional catalysts used in industrial processes

are shown in Table 4.

The number of solid acid catalysts is the largest due

to its demand in the great progress of petroleum and

petrochemical industry for the last 40 years. Although

the study of solid base catalysts which started much

later than that of solid acid catalysts is becoming

interesting and active recently, there are only ten

processes for solid base catalysis at present. As for

acid±base bifunctional catalysts, the number was esti-

mated to be 14, which was limited to those having

some evidence for the bifunctional catalysis. Even for

the reaction which is regarded to be catalyzed simply

by an acid site or a base site, there seems to be a

considerably high possibility of bifunctional catalysis

by acid±base pair sites, since any kind of solid acid (or

solid base) possess more or less base sites (or acid

sites).

Table 1

Industrial processes using solid acid±base catalysts

Dehydration and condensation 18

Isomerization 15

Alkylation 13

Etherification 10

Amination 9

Cracking 8

Aromatization 7

Hydration 7

Oligomerization and polymerization 6

MTG/MTO-processes 5

Hydrocracking 4

Hydrogenation 4

Esterification 3

Disproportionation 2

MTBE!i-C04 1

Others 15

Total 127

Table 2

Types of catalysts used in industrial processes

Zeolites 74

Oxides, complex oxides 54

Ion-exchange resins 16

Phosphates 16

Solid acids (not specified) 7

Clays 4

Immobilized enzymes 3

Sulfate, carbonate 3

Sulfonated polysiloxanes 3

Total 180

400 K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434

2.3. Detailed processes and catalysts

Tables 5±15, the detailed industrial processes and

catalysts [1,2,3±113,114,115±119,120,121,122,123,

124±128,129,130±146,147,148±199] together with

the names of companies, the year of industrialization,

and the scales of the products, where (p) denotes

`̀ under pilot plant'' and (d) `̀ under design'' are shown,

whose inclusions are limited only to those having a

high possibility of industrialization.

A process whose number was marked with an

asterisk is base catalysis and that with double asterisks

is acid±base bifunctional catalysis.

3. Significant examples

Among the industrial processes given in Tables 5±

15, several of the signi®cant examples are described

more in detail.

3.1. Acid catalysis

3.1.1. Alkylation reactions

The environmental concerns and regulations have

been increased in the public, political and economical

world over the last two decades because the quality of

life is strongly connected to a clean environment. The

impulse for developing new, more ef®cient and selec-

tive catalysts and the realization of new process

technology is strongly related to environmental com-

patibility. The goals must be to avoid waste produc-

tion, in particular salt formation, i.e. `̀ 100%

selectivity!'' and `̀ zero emission!'' that implies

`̀ Reactor or Production Integrated Environmental

Protection''.

An excellent example to demonstrate this target is

the alkylation of aromatics. In former days such

processes have been mainly carried out in the presence

of homogeneous Lewis acid catalysts such as AlCl3,

FeCl3, HF, BF3, etc. The well-known drawbacks of

such homogeneously catalyzed processes have to be

overcome by applying heterogeneous catalysis. In this

respect, the discovery of the shape selective acidic

ZSM-5 zeolite and the development of the Mobil/

Table 3

Detailed kinds of catalysts

Zeolites 74

ZSM-5, pentasil zeolite, modified ones 31

Zeolites (not specified), modified ones 28

Mordenite 7

Y-zeolite 4

US-Y 2

Beta-zeolite 2

Oxides, complex oxides 54

SiO2±Al2O3 11

Al2O3±NaOH±Na, Al2O3±KOH±K, Al2O3±HF,

Al2O3±BF3, Al2O3±K2O

9

ZrO2, ZrO2±Cr2O3, ZrO2±MgO, ZrO2±NaOH,

ZrO2±KOH, ZrO2±K2O

7

Al2O3, Al2O3±MgO, Al2O3±B2O3, Al2O3±NiO 6

MgO, MgO±TiO2, Pd/MgO 4

SbF5/SiO2, Ta-alkoxide/SiO2, Fe±V/SiO2 3

TiO2±SiO2, TiO2±V2O5±WO3, TiO2±H3PO4 3

Re±SiO2, Re±SiO2±Al2O3 2

SO2ÿ4 =ZrO2, Fe, Mn, SO2ÿ

4 =ZrO2 2

Metallosilicate 2

Nb2O5�nH2O 1

Hydrotalcite 1

Others 3

Phosphates 16

SrHPO4, LaHPO4, Li3PO4, Al±B phosphate, LaPO4, FePO4 7

Solid phosphoric acid 4

SAPO-11, SAPO-34 2

Cs±Ba±P±O/SiO2 1

Ba or Ca salt phosphate 1

H3PO4�aniline salt/SiO2 1

Ion-exchange resins 16

Solid acids (not specified) 7

Clays 4

Kaolin, pillared clay, bentonite, montmorillonite

Immobilized enzymes 3

Asparatase, nitrilase, amylase

Sulfate and carbonate 3

Al2(SO4)3/SiO2, CF3SO3H/SiO2, Na/K2CO3

Sulfonated polysiloxanes 3

Table 4

Number of solid acid, base and acid±base bifunctional catalysts in

industrial processes

Solid acid catalysts 103

Solid base catalysts 10

Solid acid±base bifunctional catalysts 14

Total 127

K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434 401

Table 5

Alkylation processes

S.No. Process Catalyst Company Year, scale

1 H-ZSM-5 vapor phase Mobil±Badger 1980, 1 MMM lb/y [3,12], 1 plant, Hoechst

AG, 33 licenses [55]

1995, 80 000 t/y [56], China Petrochemical ±

SINOPEC in Daging, China

Dilute ethylene sourced from

FCC off-gas or steam cracker

High silica zeolite vapor phase 1992, 10 000 t/y [4], 1 plant, China Petrochemical,

3 licenses [55]

H-ZSM-5 liquid phase Mobil±Raytheon EB-Max process Four licenses [55]

Acidic zeolite liquid phase ABB Lummus Global 100 000 t/y [57], Supreme Petrochemical at

Nagathone, India

120 000 t/y [58], Angarsk Petrochemical at An-

garsk,

Russia

EBZ 500 ± zeolite liquid phase UOP/Lummus ± [59]

Acidic zeolite catalytic distillation CDTECH 1995, 260 000 t/y [60], Mitsubishi Chem.,

Yokkaichi, Japan

140 000 t/y [61], Petroquimica, Argentina

Acidic zeolite liquid phase ABB Lummus/Unocal/UOP

100 000 t/y [61], Pemex, Mexico

250 000 t/y [77], Ciba Styrene Monomer

2 Solid phosphoric acid (SPA) Most of the cumene producer

High silica zeolite Mobil±Badger/Raytheon Ten licenses [55,62,65]

1.5 BIL lb/y [63,64], Georgia Gulf at

Pasadena, Texas

1996, 1.5 BIL lb/y [65], Citgo Petroleum

1998, 1 BIL lb/y [66], Sun at Philadelphia, PA

1995, 250 000 t/y, Ertisa at Huebla, Spain

b-zeolite Enichem 1996, 265 000 t/y [15]

Acid zeolite catalytic distillation CDTECH 170 000 t/y [58,60], GP ± Orgetelko ± Dzeryinsk at

Nizhny Novgorod, Russia [60]

Mordenite DOW Chemicals 1994 (p) [11]

Y-zeolite Lummus 1994 (p) [11]

Diluted mixture of propylene and

ethylene sourced from FCC off-gas

Acid zeolite catalytic distillation CDTECH Catstill-technology ± [199]

Three-dimensional dealuminated

mordenite

DOW/Kellog 3-DDM technology 1994, 200 000 t/y [68] at Terneuzen, Belgium

Five projects [68]

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Table 5 (Continued )


Transalkylation reactor

diisopropylbenzene�benzene

Dealuminated mordenite DOW/Kellog 1992 [69], at Terneuzen, Belgium

UOP Q-Max technology 1996, 145 MIL lb/y [70], BTL Speciality Resins

at Blue Island, IL

45 000 t/y [71], Chevron Chemicals at Port

Arthur, TX

3 Solid acid liquid phase UOP ± CEPSA, DETAL-technology 1995, 100 000 t/y [73,74], Petresa Petroquimica

at Becancour, Canada 100 000 t/y [76], Quimica

Venoco at Guacara, Venezuela

4 H-mordenite

Shape selective zeolite combined

with separation

Catalytica

Kureha/NKK/Chiyoda

1992 (p) [8,103]

1994, 1000 t/y [24,101], at Fukuyama, Japan

5 Zeolite RuÈtgerswerke AG (p) [200]

6 Dealuminated H-mordenite DOW Chemicals 1989, (p) [104,105]

7 Pentasil zeolite Encilite 2 Hinduston Polymers Albene

Technology

1989 [108], at Visakhapatnam, India

8 Pore size regulated ZSM-5 Paschim/IPCL 1997, 1000 t/y [21,30]

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9 MgO General Electric

BASF AG

1970, several units in commercial scale

licensed [32]

1985, at Ludwigshafen, Germany

10 Fe±V±O/SiO2 Asahi Chem. 1984, 5000 t/y o-cresol [1], 10 000 t/y 2,6-xylenol

[1]

11 Na/K2CO3 basic catalyst AMOCO Chemical, Teijin 1995, 45 000 t/y [24], at Decatur, Alabama, (p) [95]

12 K/KOH/Al2O3 Sumitomo Chemical 1992 [7], demonstration plant

13 CF3SO3H/SiO2 Haldor Topsoe/Kellog FBA-process 1994, 0.5 BPD [13,82]

57 000 B/y [82,83], Amoco at Yorktown, Virginia

BF3/g-Al2O3 Catalytica/Conoco/Neste Oy 1994, 1 t/d [9,83,88], at Porvoo, Finland

SbF5/SiO2 Chevron/CDTECH 1994, 10 BPD [84,85], at Port Arthur, TX

Sulfated ZrO2 Orient Catalyst 10±20 t/y [86]

Solid acid (alkylene catalyst)

fluidized bed

UOP (p) [87]

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Table 6

Isomerization processes

S.No. Process Catalyst Company Year, Scale

1 Xylene isomerization!p-xylene H-ZSM-5 Mobil Oil 1990, several units [3]

1994, 275 000 t/y [109,110]

120 000 t/y Mobil: at Chalmette, Louisiana

30% debottlenecking, Mobil: at Jurong, Singapore

Shell [113] at Godorf, Germany

Pentasil zeolite Xyclofining-process IIP, India [115]

C8 aromatic mixture!p-xylene Acid zeolite 1-210 UOP ISOMAR technology 1996, 40 units [111,112], Reliance Industries [114],

at Jamnagur, India, world largest complex

Zeolite JFP/Chevron ELUXYL-process 15 000±20 000 t/y [116], demonstration plant [117],

at Pascagoula, MS

2 High silica zeolite Toray 1990, 2000 t/y [2,6]

3 n-C4 ! i-C4 H-mordenite UOP BUTAMER-process,

PENEX-process

>35 units licensed [118]

1992, 30 000 BPD [119], Enterprice Products

Fe/Mn/sulfated ZrO2 Sun Refining [120]

Zeolite BP-Chemicals, c4-isomer [121]

Zeolite Huntsman ISOTEX-process [122]

Zeolite UCC TIP-process [123]

Zeolite Shell HYSOMER-process [124]

4 n-C40 ! i-C4

0 SiO2 modified Al2O3 IFP 1991, pilot [5]

Ferrierite Shell/Layondell/CDTECH/Zeolyst 1994, 40 000 t/y [125]

B2O3/Al2O3 SNAM 1997 (d) [37]

Acid catalyst Nippon Petrochemical/Nippon Oil 1992, 9000 t/y [126], at Kawasaki, Japan

5 C40; C5

0 ! i-C40; i-C5

0 H-ZSM-5 Mobil/BP/Kellog ISOFIN-process 1994 (p) [12,127]

H-ZSM-5 fluidized bed Mobil/Raytheon MOI-process Pilot 4 BPD [128], 100 BPD

Zeolite Lyondell Petrochemical, ISOM

Plus-process

1992, 3000 BPSD [129], at Channelview

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Zeolite Phillips Petrochemical/Texas

Olefins SKIP-process

1991, 2700 BPD [130,131]

Zeolite UOP, PENTESOM-process,

BUTESOM-process

1991 [133], 1992

Zeolite PEMEX 1994, 27 000 BPD [132], at Minatitlan, Mexico,

1994, 2700 BPD [132], at Cedercyta, Mexico

Zeolite JFP ISO-4-process 1984, pilot [130], 160 000 t/y

6 Light naphtha isomerization Zeolite LPI-100TM UOP PAR-ISOM-process Cosmo Oil [13], Mitsubishi Heavy Ind.

Heavy olefins isomerization Acid solid Shell 850 000 t/y part of SHOP-process [135,136]

7 H� ion-exchange resin Exxon 1986 [3]

8 Na/NaOH/g-Al2O3 Sumitomo Chemical [6]

9 Na/NaOH/g-Al2O3 Sumitomo Chemical [6]

10 Na/NaOH/Al2O3 Sumitomo Chemical 1986, 2000 t/y [2,6]

11 K2O/Al2O3 Shell [137]

12 Li3PO4 ARCO 1990, 30 000 t/y [3,6]

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13 Pentasil zeolite BASF AG 1982, demonstrated [5,138,139]

14 SAPO 11

High siliceous pentasil zeolite

Ta-alkoxide/SiO2

UCC

Sumitomo Chemical

Mitsubishi Chemical

1992, (p) [8]

1997, (p) [53,140]

1994, (p) [141]

15 Pt/Y-zeolite Idemitsu±Kosan 1986, (p) [2,6,138]

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Table 7

Dehydration and condensation processes


1 EtOH!ÿH2O C2H4 Al2O3 Petrobrass 1980 [19,31]

2 t-BuOH!ÿH2Oi-C04 Sulfonic acid resin UOP 1981 [3]

3 Ion exchange resin Davy±McKee 1985, 20 000 t/y [5]

4 Cs±Ba±P±O/SiO2 Nippon Shokubai 1991, 2000 t/y [1,6,46,47]

5 ZrO2±NaOH Sumitomo 1986 [33,34]

6 Nb2O5�nH2O Sumitomo 1987 [35,36]

7 ZrO2±KOH Koei Chemical 1992, (p) [25]

8 H3PO4±aniline salt/SiO2 Nippon Shokubai 1995, 6000 t/y [17]

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9 Mercapto-functionalized

sulfonated polysiloxane

Ion-exchange resin

Ion-exchange resin

Ion-exchange resin

Degussa AG

Chiyoda

Bayer AG

DOW/Kellog

1996, (p) [26]

1994, (p) [24]

Commercialized [142]

Commercialized [143], Texas and Germany

10 Shape selective zeolite, e.g.

mordenite fluidized bed

DSM-Stamicarbon 1997, (p) [105], at Geleen, Netherlands

11 Acid ion-exchange resin,

e.g. Amberlyst 15

Degussa AG [144]

12 Strongly acidic inorganic and

organic ion-exchange resin,

e.g. Deloxan-ASP

Degussa AG [145,146,150]

13 ** Isobutyraldehyde!diisopropyl

ketone

ZrO2 Chisso 1974, 2000 t/y [22]

14 ** Isobutanol!diisopropyl ketone ZrO2, ZrO2±K2O Chisso 1974, 2000 t/y [22]

15 ** n-Butanol�n-butyraldehyde

!di-n-propyl ketone

ZrO2±MgO Chisso 1974, 2000 t/y [22]

16 Air Products 1987 [3,6]

17 Pt/H-ion exchange resins trickle

bed reactor.

Bayer AG

Deutsche Texaco

[147]

[148]

18 H2CO aqueous ! trioxane Pentasil zeolite Asahi Chemical [149]

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Table 8

Amination processes


1 2MeOH�NH3!Me2NH, MeNH2 Modified ion-exchange mordenite

RHO-ZK5 zeolite

Chabasite

Nitto

Du Pont

Air Products

1985, 40 000 t/y [1,6,138], 1992, 50 000 t/y ICI-Air

Products�Chemicals

(p) or (d) [6,53]

(p) or (d) [151]

2 Cu, Ni/SiO2±Al2O3 Kao 1989 [1]

3 SrHPO4, LaHPO4, H3PO4/SiO2 Air Products 1986, 10±15 MM lb/y [3,6], Allentown, PA

4 Al±Si zeolite Berol/Nobel 1984, 50 000 t/y [5], Sweden

5 MgO, B2O3, Al2O3 or TiO2/SiO2

or Al2O3

USS 1982, 200 MM lb/y [3]

6 Immobilized asparatase Tanabe Pharmaceutical,

Mitsubishi Petrochem.

1973, 1000 t/y [1], 1986, 1000 t/y [1]

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7

Modified SiO2±Al2O3�modified

ZSM-5

Koei Chem. 1990, 9000 t/y [25]

8 Modified SiO2±Al2O3�modified

ZSM-5

Koei Chem. 1990, 9000 t/y [25]

Pentasil zeolite fixed bed Armor polymer India [6]

H-ZSM-5 fluidized bed Nepera USA [6]

Al2O3±HF fluidized bed Degussa AG Germany [6]

9

Pentasil zeolite

BASF AG 1986, 6000 t/y [5,6,138], Antwerp, Belgium, 1994,

8000 t/y, Antwerp, Belgium

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Table 9

Cracking processes


1 FCC-processes e.g. SiO2±Al2O3/US-Y Cat. & Chem. 1985, a lot of units [1]

Partially dealuminated Y type

zeolite in SiO2±Al2O3

UOP 1986, 1 MM lb/y [3]

Novel Y/SiO2±Al2O3 Cosmo 1990 [2]

Ultrastable Y containing RE

oxides and SiO2

China Petro 1993 [4]

2 Heavy oil MgO±Al2O3-zeolite Nippon Oil 1990 [2]

Magna-Cat Valero/Kellog Corpus Christi, TX [152]

3 Heavy fractions Calcined kaolin Engelhard/Ashland 1993, 55 000 BPD [3]

4 Cracking above 6508F Ultrastable Y treated with RE

dispersed in SiO2±Al2O3,

cogel/kaolin matrix

Ashland/Davison 1983, 40 000 BPD [3]

5 Deep cracking of vacuum gas oil Pentasil zeolite China Petro 1990, 60 000 t/y [4], 1993, 400 000 t/y

6 Middle and light distillate from

cracking feed

Ultrastable US-Y zeolite Total/IFP 1982, 60 000 t/y [4]

7 Middle distillate catalytic dewaxing Proprietary China Petro 1984, 20 000 t/y [4]

8 Selective cracking of straight

chain paraffins and olefins to

produce C30 and C4

0

H-ZSM-5 Mobil 1986 [3]

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Table 10

Etherification processes


1 i-C04 �MeOH! MTBE Ion-exchange resin IFP 1978±1981, 50 000 t/y�11 plants [5]

ARCO 1986, 320 t/y [3]

SNAM/Ecofuel 1973, 120 000 t/y [38], 1990, 500 000 t/y [153],

Ibn Zahr in Al-Jubail, Saudi-Arabia

Chevron/Neste Oy (Alberta

Envirofuels)

1994, 530 000 t/y [154]

Sabic/Shell (SADAT) 1996, 700 000 t/y [155]

Lummus Crest 1992, 12 500 BPD [156], at Deer Park, Texas

CDTECH Licensing [157]

2 i-C04 �MeOH! MTBE� isooctane Ion-exchange resin SNAM 1996 [29]

3 i-C04 � EtOH! ETBE Ion-exchange resin SNAM/Ecofuel 1993 [38]

4 i-C05 �MeOH! TAME Ion-exchange resin IFP/ELF 1984, 8000 t/y [5], 1992, 100 000 t/y [5]

ANIC/SNAM 1989, 54 000 t/y [29]

Exxon 1986 [3]

Neste Oy/Bechtel 1995, 116 000 t/y [158], at Porvoo, Finland [159]

Davy±McKee 1994, 2000 BPD [160], at Shamrock

5 Olefins � MeOH ! MTBE/TAME Ion-exchange resin Erdoelchemie/Lurgi 1980 (p) [5]

6 2MeOH ! MeOMe�H2O Al2O3 Mobil 1985, 14 000 BPD [3]

7 Al±B±P±O Ube 1978 [2]

8 Pillared clay or smectic

(bentonite, montmorillonite)

BP (p) [5]

9 Hydrotalcite Mg6Al2O8(OH)2,

ROH�fatty alcohols, n�narrow

molecular weight range

Henkel 1994 (p) [163]

Ba or Ca salt/phosphate UCC 1985, 60 MMIL lb/y [3]

10 LaPO4 Shell 1995, 500 000 t/y [164]

MTBE: methyl t-butylether, TAME: t-amyl methylether.

K.

Tan

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413

Table 11

Catalyst Company Year, scale

(a) Aromatization processes

1 C03; C04 ! alkylaromatics paraffins ZSM-5 Mobil [3]

2 C3, C4!aromatics, particular

p-xylenes

Ga-modified ZSM-5, Zn-modified

ZSM-5

BP±UOP Cyclar-process 1990, 5000 t/y [5], at Grangemouth, Scotland

LPE or refinery light end paraffins

and olefins

1995 [165], Ibn Rushd at Yanbu, Saudi Arabia

3 LPG (mainly C3, C4)!BTX Zeolite�promoter UOP 1983 [3]

4 LPG or light naphta!aromatics Metallosilicate Mitsubishi Oil ± Chiyoda 1991, 200 BPD [22]

5 C4, C5 raffinate or C4, C5 fraction

of FCC!aromatics

Metal oxide modified ZSM-5 Asahi Chem. ± Sanyo Petrochem.,

ALPHA-process

1993, 40 000 t/y [22,168±170], at Mizushima, Japan

6 C6, C7, naphthanes!aromatics Pt-zeolites ± Al2O3±SiO2, Pt±Re

zeolites ± Al2O3±SiO2

Platforming, Rheniforming,

e.g. Chevron

>500 units [171]

C6, C7!preferably benzene UOP e.g. 1997, 230 000 t/y [172], CEPSA at Algeciras,

Spain

7 Naphtha!aromatics R-132 catalyst UOP LLR-platforming 1992, 9 units of 34 [174]

Pt L-zeolite Chevron Chem. AROMAX-process 1992/1993, 2 units [173]

(b) Hydrocracking process

1 Fixed-bed residual hydrocracking Fe-VIb/zeolite Idemitsu 1982 [1]

2 Hydrocracking of heavy oil

distillates into gasoline and

middle distillates

Amorphous SiO2±Al2O3 with zeolite 1990 [3]

3 Hydrocracking of gas oils ZSM-5 Mobil [3]

Wax�H2!gasoline

4 Lub dewaxing ZSM-5 Mobil 1981, 1500±15 000 BPD [3]

Wax oils�H2!lower molecular

wt. hydrocarbons

Zeolite BASF [3]

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Table 12

Hydration processes


1 C=C�H2O ! EtOH Solid phosphoric acid Shell, BP, many others

2 i-C4' ! t-BuOH Ion-exchange resin Mitsui Petrochem. [1]

Sulfonic acid resin UOP/huels 1981 [3]

3 Novel highly siliceous H-ZSM-5,

<1 mm

Asahi Chem. 1990, 80 000 t/y [1,6,41,42]

4 Acid±basic catalyst based on

TiO2/H3PO4

Degussa AG 1997, 10 000 t/y [175], Wesseling, Germany

5 Acid catalyst

H-ZSM-5

Air Products/DOE

Mobil

(p) [161]

0.5 BPD [162]

6 MgO

MnO2

Distillers

Reynolds Tobacco

[176]

[177]

7 Nitrilase immobilized by

polyacrylamide gel into a particle

Nitto 1985, 6000±20 000 t/y [1,6]

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415

Table 13

Esterification processes

Process Catalyst Company Year, scale

(a) Esterification processes

1 Ion-exchange resin Davy±McKee 1985, 20 000 t/y [178], 1,4-butanediol-production

2 Mercapto-functionalized

sulfonated polysiloxane

Degussa AG 1996 (p) [26]

3 Ion-exchange resin Japan Methacryl Monomer

and others

1990, 50 000 t/y [8]

(b) MTG, MTO processes

1 MeOH/DME!gasoline ZSM-5 Mobil MTG-process 1985, 14 000 BPD [3], New Zealand

2 MeOH! C03 � C04 � some gasoline Modified ZSM-5 Mobil MTO-process 1985, 160 BPD [3], UK-Wesseling, Germany

3 MeOH! C02 � C03 SAPO-34 in FCC-catalyst matrix UOP 1988 [3]

4 Olefins of MTO!jet fuel, diesel Zeolite Mobil MOGD-process [179]

5 Olefins of MTO!gasoline Zeolite Mobil MOG-process [180]

(c) Oligomerization and polymerization processes

1 i-C04 � butenes! codimer High SiO2 mordenite Tonen 1988 [2]

2 C03 ! polypropylene TiO2±MgO China Petro 1993 [4]

41

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3 C03 ! C9ÿC12, diesel Pentasil zeolite Mossgas Refinery/SuÈdchemie 1992 [181], Mosselbay, South Africa

4 Cyclodimerization Zn

powder/Fe(NO)2Cl liquid

phase, slurry

DSM ± Chiyoda, BEB-process 100 000 t/y [182], economically feasible [183]

Dehydrogenation Pd/MgO

gasphase, fixed bed

Cyclodimerization Cu-ZSM-5

zeolite

DOW Chemicals (p) [184]

5 C02 ! 1-butene; 1-hexene Ni on Al2O3 (ALON) [185]

6 C04 ! linear octenes H3PO4/SiO2 UOP Catpoly-process [186]

Ni-heterogeneous Ziegler-type

catalyst

HUÈ LS/UOP Octol-process

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417

Table 14

Disproportionation processes


(a) Disproportionation processes

1 Zeolite

SiO2-modified ZSM-5

ZSM-5

UOP

Taiwan Styrene

Mobil MSTDP process

1988 [3]

1987, 3000 t/y [18,23]

1989 [12]

1988±1990 pilot plant [187], Anic-Refinery at

Gela, Italy

Since 1990, >6 units, 1991, 14 000 BPSD [188]

1992, Exxon in Baytown [188], Koch-Refinery

Corpus Christi, Texas

1992 [188], Cepsa at Algericas, Spain

Reliance Industry, India [188]

Mitsubishi Oil [188] at Mizushima, Japan

2 Zeolite UOP 1988 [3]

(b) Hydrogenation processes

1 CO�H2!gasoline Zeolite BP 1990, (p) [5]

2 CO�H2!middle distillates Acid catalyst Shell Oil ± Mitsubishi,

Oil-Petronces

1990, 12 000 BPD [189]

SMDS-process 50 000 BPD in Bintulu, Malaysia

3 ZrO2±Cr2O3

Zeolite

Mitsubishi Chem.

Crossfield-Unilever

1988, 2000 t/y [1,6,48,49]

In Unilever plant [190]

4 White oil hydrogenation Zeolite Crossfield-Unilever In Unilever plant [190]

(c) MTBE! iÿ C041. MTBE! i-C04 �MeOH Al2(SO4)3/SiO2 Sumitomo 1984, 50 000 t/y [1]

Boron pentasil zeolite ANIC/SNAM/ENI 1984, 1987 [5,6]

Heterogeneous acid catalyst UOP 1989 [3]

Solid acid IFP 1985 (p) [5]

SiO2±Al2O3 SNAM 1987, 500 t/y [29], 1991, 8000 t/y [29], 1993,

62 000 t/y [29]

41

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Table 15

Miscellaneous processes


1 Strong acid ion-exchange

resin

Reilly 1988 t/y [3]

2 Ion-exchange resin

TiO2±SiO2

TS-1 zeolite

Montedipe

Montedipe

Enichem

1994, 100 000 t/y [5]

1992 (p)

1994, 12 000 t/y [6]

3 Solid acid Olin Eiazzi 1994 (p) [11]

4 CH3OH � HCl ! CH3Cl Al2O3 Tokuyama Soda 1978, 52 000 t/y [2]

5 CH3Cl ! gasoline ZSM-5 type (Si/Al�12) BP-chemicals 1985 [5]

6 NO � NH3 ! N2 � H2O Zeolite Engelhard Early 1980 [3], 5±10 units

Aluminosilicate zeolite Degussa AG/Lurgi/Lentjes 1989 (p), 100 MW [5]

W±V±TiO2 DeNOx-processes All over the world

7 Cs-zeolite Merck 1996 [27,144]

8 n-alcohols � H2S ! mercaptans Alkali-oxide on alumina,

transition metal oxides

Elf-Atochem Commercialized [91±93], 1000±30 000 t/y, e.g.

LACQ, France

CH3OH � H2S ! CH3SH, (CH3)2S Alkali on g-Al2O3 IKT-31-1

catalyst

Orgsintez-Volga Industrial

Conglomerate

Commercialized [199]

9 olefins � H2S ! mercaptans Zeolites, ion-exchange resinsElf-Atochem Commercialized [91±93], 1000±30 000 t/y, e.g.

LACQ, France

Philips Petroleum 1997, 100 MIL lb/y [192], at Borger, TX

K.

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10 Solid acid Cu-catalyst DSM (p) [193]

11 Fe-ZSM-5 Monsanto-Boreskov Institut Pilot plant [197], 1999 commerical plant [198]

12 Pt/Zn-ZSM-5 BP/Mobil Pilot [195]

13 FePO4 TIT [196]

14 Immobilized amylase Kirin Brewery/Nippon Shokuhin/

Yokokawa Elect./Chiyoda Corp.

1988 [2]

15 H-beta-zeolite Rhone-Poulenc 1996, multi tons [16,194], at Lyon, France

42

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Badger process for the production of ethylbenzene

(EB) from benzene and ethylene have been the base

for breakthrough technology in the ®eld of aromatic

alkylation reactions using solid acid catalysts. There-

fore, much industrial research effort has been invested

to develop alternative solid-acid technologies free of

these drawbacks, such as low yields, environmental

impacts, high investment, corrosive catalysts, forma-

tion of oligomers and other impurities.

3.1.1.1. Production of ethylbenzene. The Mobil±

Badger vapor phase process was first commer-

cialized in a plant with 1 MMM lb/y capacity in

1980 [3]. In the meantime, Mobil has been awarded

33 licenses [55]. This process accounts for 90% of all

new EB-processes installed since 1980. Recently,

strong investments for EB-production using Mobil's

proprietary zeolite-based vapor phase technology

have been made in China, i.e. 60 000 t/y unit (23rd)

of China Petrochemical (SINOPEC) in Daging 1995,

80 000 t/y unit (24th) of Guangzhou Municipal

Ethylene Complex of Guangdong and the 25th unit

of China National Technical [56].

Among these 33 licenses, there are three processes

utilizing dilute ethylene sourced from FCC off-gas

[55] or ethylene/ethane mixtures from ethylene

crackers. A semi-commercial plant with 10 000 t/y

is on stream in a China Petrochemical site since

1992 [4].

Additionally, Mobil Oil in collaboration with

Raytheon Engineers and Constructors licenses the

so-called EB-Max technology. Thereby, the alkylation

is carried out in the liquid phase over a proprietary

zeolite catalyst. Four licenses have signed up for this

new development [55].

ABB Lummus Global developed its own liquid

phase EB-process using an acidic zeolite catalyst.

This technology is licensed to Supreme Petrochemical

running a 100 000 t/y plant in Nagothane, India [57],

and to Angarsk Petrochemical having a 120 000 t/y

unit in Angarsk, Russia [58]. Recently, UOP disclosed

a new alkylation catalyst named EBZ 500 for the

UOP/Lummus liquid phase EB-process using lower

benzene/ethylene ratio and less catalyst volume [59].

Chiba Styrene Monomer has selected ABB Lummus/

Unocal/UOP liquid phase zeolite EB technology for

250 000 t/y [77].

CDTECH, a partnership of ABB and Chemical

Research and Licensing, developed a new EB tech-

nology based on catalytic distillation principles, i.e.

the catalytic reaction is combined with the distillation

in one vessel [60]. The process is carried out in the

presence of an acid zeolite catalyst using dilute ethy-

lene and taking advantage of the reaction heat. Very

clean alkylation and transalkylation units provide EB-

production in extremely high yield and with high

product quality. Mitsubishi Chemical Corp. (MCC)

was the ®rst licensee using this catalytic distillation

technology and running a plant with 260 000 t/y capa-

city in Yokkaichi since 1995 [61]. The special pro-

prietary zeolite catalyst exceeded the projected two

year catalyst life before regeneration. A second instal-

lation is for Petroquimica Argentina SA with a capa-

city of 140 000 t/y and a third one for Pemex, Mexico,

with a capacity of 100 000 t/y [61].

3.1.1.2. Production of cumene. In the case of highly

valuable cumene produced from propylene and

benzene, several companies have been involved in

the development of new zeolite-based processes in

order to avoid the disadvantages of the conventional

processes using solid phosphoric acid (SPA) or

aluminum trichloride as catalysts. The total

worldwide production capacity of cumene is about

6 MIL t/y. The SPA production is still heavily

predominant.

The Mobil/Badger cumene process is offered for

license by the Badger Technology Center of Raytheon

Engineers and Constructors [72]. The process uses a

novel zeolite catalyst developed by Mobil R�D and

offers higher yield and product purity than the existing

commercial processes while eliminating problems

with corrosion, catalyst handling and disposal. Com-

mon zeolites such as REY, ZSM-4 or ZSM-5 among

others do not have the combination of activity, selec-

tivity and stability to form the basis of a successful

commercial process. The suitable zeolite catalyst is

essentially inactive for propylene oligomerization, is

active for the alkylation and transalkylation, and is

suf®ciently stable to allow for a long operating cycle

before regeneration. The pilot plant results show a

100% propylene conversion and nearly 100% selec-

tivity in the alkylation reactor over a period of 5000 h

of operation.


Ten licensees have chosen the Mobil/Raytheon

cumene technology using re®nery grade propane/pro-

pylene feeds after its introduction in 1993 [55,62]. In

the presence of a new high silica ZSM-5 catalyst,

almost stoichiometric yields have been achieved by

avoiding oligomerization reactions and by reducing

the formation of higher alkylated benzene. Further-

more, this process transalkylates heavy aromatics such

as di- and tri-isopropylbenzenes back to cumene; such

a transalkylation which ensures very high process

yields (up to 99.7%), reduces fractionation require-

ments and improves product purity (above 99.97%)

cannot be catalyzed by the conventional SPA-catalyst.

Georgia Gulf expanded its Pasadena, Texas plant up

to 1.5 BIL lb/y using the Mobil/Badger process in

combination with the ISOFIN technology [63,64].

Citgo Petroleum increased its cumene capacity at

Corpus Christi up to 1.5 BIL lb/y by debottlenecking

using Mobil/Badger zeolite catalyst technology since

1996 [65]. Also Sun intends to double the cumene

production at its Philadelphia facility to 1 BIL lb/y

going on stream in 1998 [66]. In Europe, Ertisa will

expand its cumene unit by 225 000 t/y at Huelva,

Spain. This will make it the largest cumene plant in

Europe [67]. Also it was announced to apply MCM 22

as catalyst for this Mobil/Badger cumene process

expecting two years cycle length and ®ve years cat-

alyst lifetime, at least.

CDTECH±cumene technology [60] is identical to

its ethylbenzene technology. The most dif®cult part

has been the service time of the zeolite catalyst. This

problem could be solved by an ideal combination of

the catalytic distillation system and the selection of the

suitable zeolite, thus a catalyst service time of about

2 y is expected. Yields better than 99% are achieved.

This technology was chosen by the Russian GP Orge-

telko-Dzerjinsk which has built a new unit with a

cumene capacity of 170 000 t/y at Nizhny Novgorod

[58]. CDTECH also developed the Catstill-technology

[60]. This is a combination of the CDTECH±ethyl-

benzene and cumene technology. Thereby, the FCC

off-gas as the source of both ethylene and propylene

and the reformate as a source of benzene are employed

to produce EB and cumene simultaneously. The

advantages are to recover gasoline value from the

FCC off-gas which is presently still used as fuel for

burning in boiler and to reduce the benzene content of

the gasoline.

The Dow Chemical commercialized its zeolite

based 3-DDM±cumene process [68]. The process

design includes both liquid phase alkylation and

transalkylation using a novel dealuminated mordenite

with a pseudo-three-dimensional structure (3-DDM).

The alkylation is carried out in a ®xed bed reactor

system containing several catalyst beds. In addition to

the desired main product cumene, preferably p-diiso-

propylbenzene forms due to the shape selectivity of

the catalyst. This isomer is most easily transalkylated

into cumene in a ®xed bed reactor over the 3-DDM

catalyst. Dow has a unit with 200 000 t/y on stream in

Terneuzen, Belgium, since 1994. In 1992, Dow

already installed successfully the transalkylation reac-

tor. They have a licensing agreement with M.W.

Kellogg. The 3-DDM technology is considered for

®ve projects [69].

The Q-Max process based on a new proprietary

zeolite catalyst, too, was developed by UOP for the

production of cumene. The ®rst licensee is BTL

Specialty Resins running a 145 MIL lb/y plant at Blue

Island, Illinois, since 1996 [70]. Also Chevron has

announced to revamp its cumene production facility in

Port Arthur, Texas, using the new Q-Max process. The

capacity of the plant is expected to become 45 000 t/y

[71].

3.1.1.3. Production of linear alkylbenzenes. Linear

alkylbenzenes (LABs) are widely used as raw

materials for detergents by subsequent processing to

alkylarylsulfonates. Because of its rapid and complete

biodegradation, LAB have replaced the branched

chain type BAB. There are two major catalysts for

the industrial production of LAB: HF and AlCl3. The

drawbacks caused by this homogeneous catalysis have

initiated intensive research activity to find an

environmentally benign heterogeneous alternative.

A new detergent alkylation process has been intro-

duced as DETAL process [73,74] jointly developed by

UOP and the CEPSA subsidiary Petresa, Petroquimica

Espanola SA. The reaction occurs under mild condi-

tions in liquid phase in a ®xed bed alkylation reactor

utilizing a solid acid catalyst, probably a zeolite

catalyst. The DETAL process is combined with the

UOP PACOL process in which linear paraf®ns are

dehydrogenated to ole®ns used for the alkylation of

benzene. UOP also revealed the development of an

ethylene oligomerization process for producing the


needed linear a-ole®ns [75]. The erection costs of a

DETAL unit are 30% lower than that of a comparable

HF alkylation unit. The alkylation catalyst is selective

and performs a service time for more than eight

months in the pilot plant test. The expected cycle time

is greater than two years. The product mixture of the

DETAL process is similar to that of a HF-unit.

The ®rst unit with 100 000 t/y is on stream in

Becancour, located between Montreal and Quebec,

since 1995. A second unit with the same capacity is

under construction by Quimica Venoco, Caracas, at

Guacara, Venezuela [76].

3.1.1.4. Production of alkylated gasoline. The US

revised Clean Air Acts Amendments of 1990 listed

HF as a hazardous material. Thus, there are a number

of regulations to limit the storage and use of HF.

Therefore, a lot of research activities came in place

to find an alternative for HF-alkylation in refinery

processes. The first choice is H2SO4 but this

homogeneous catalyst, which suffers from less

efficiency, causes corrosion and disposal of nasty

waste resulting in increasing costs of manufacture.

An overview of HF and H2SO4 catalyzed refinery

alkylation processes for the conversion of isobutane

with butene or mixed C3±C5 olefins is published [78].

Therefore, investigations of solid acid catalysts are

absolutely needed to solve the problem.

It was just announced by Amoco to take the license

for Haldor Topsoe's ®xed bed alkylation (FBA) pro-

cess. This ®rst large scale solid acid alkylation unit

with a daily capacity of 57 000 B will be installed at

Yorktown re®nery, Virginia [79,80].

Several companies started alone or in joint ventures

to develop new solid acid catalysts for isobutane±

alkene alkylation processes [81]. Haldor Topsoe dis-

closed a new re®nery alkylation process jointly devel-

oped with Kellog since 1994 [82]. Thereby, tri¯ic acid

supported on various carriers such as silica, titania,

and zirconia is used in a ®xed bed reactor pilot plant

with 0.5 BPD capacity.

Neste Oy, Conoco and Catalytica had a joint venture

for a re®nery alkylation project. In a pilot plant, slurry

reactor with 1 t/d located at Neste Oys Technology

Center in Porvoo, Finland, a new solid acid proprietary

catalyst BF3/g-Al2O3 developed by Catalytica is

applied since 1994 [83,88]. In a joint venture with

Chevron, CDTECH (CR�L/Sheridan) runs a 10 BPD

pilot plant at Chevron's Port Arthur, Texas, since

1994. The heterogeneous Lewis acid SbF5/silica cat-

alyst is less aggressive than the currently used one and

has a long service time [84,85]. Orient Catalyst, a

subsidiary of Japan Energy, developed a new solid

superstrong acidic catalyst based on sulfated zirconia

which is tested in 10±20 t/y pilot plant [86]. UOP's

solid acid catalyst alkylation (proprietary alkylene

catalyst) is also the pilot plant status using a ¯uidized

bed reactor [87].

A great number of research groups both in industry

and in academic institutions achieved a lot of efforts in

investigating solid acid catalysts for isobutane re®nery

alkylation. For example, ABB Lummus Global devel-

oped in the frame of NIST ATP-project a solid acid

catalyst in which the catalytically active sites are

contained in a thin layer of alumina [89]. Also Hydro-

carbon Technologies developed a non-hazardous,

solid superacid catalyst to convert more than 80%

of low octane ole®n/isobutane feed into high octane,

multibranched paraf®ns with 95% selectivity at rela-

tively low temperature [90].

It is for certain that the solid acid catalyst technol-

ogy will replace the conventional HF or H2SO4 based

isobutane alkylation processes in the near future. The

beginning is made already with Amoco's unit using

Haldor Topsoe±Kellog's FBA-process.

3.1.2. Nitto-process for methylamine production

A typical industrially successful example of utiliz-

ing the shape selectivity of zeolite is the Nitto-process

for the production of di- and monomethylamine

from methanol and ammonia by a gas phase reaction

in the presence of modi®ed ion-exchanged mordenite

preventing the formation of trimethylamine (cf.

Table 8, No. 1). The selectivity for dimethylamine

is about 65% and that for trimethylamine less than 5%

at 3208C [1,6,138]. Therefore, in contrast to the con-

ventional production, there is no excess of trimethy-

lamine which has to be recycled. According to SRI

International's evaluation [39], the Nitto-process can

increase the capacity by about 30±50% and reduce the

energy consumption by 40±50% in existing installa-

tions (less distillation, no recycling) and can require

about 30±40% less capital investment in new

plants. Thus, the product shape selectivity of the

modi®ed mordenite and the possibility of adjusting

its acidity and pore opening and of poisoning the outer


surface enables to get a much better composition

of the produced mixture which satis®es commercial

requirements than in the case of the classical

production over alumina. This Nitto-process is com-

mercially applied by Nitto and ICI [138]. Du Pont as

well as Air Products are in a process to develop

alternative approaches to the Nitto-technology

[53,54].

3.1.3. BASF-process for t-butylamine production

The amination of isobutene with ammonia to t-

butylamine (TBA) takes place over Re-Y-zeolite with

more than 90% selectivity. However, this catalyst

suffers from the disadvantage of rapid deactivation.

BASF has developed the pentasil zeolite which shows

not only more than 99% selectivity, but also affords

commercially acceptable catalyst life (cf. Table 8, No.

9) [5,6,40]. The absence of inorganic coproducts as

well as extremely toxic starting materials and inter-

mediates in this process provides evidently advantages

over the traditional HCN-based Ritter route to t-butyl-

amine starting from isobutene and hydrogen cyanide

where the resulting formamide is saponi®ed. Thus,

this process is worth to be called environmentally safe

and friendly. According to the Ritter-reaction, 4.5 t

starting material are needed to produce 1 t TBA and 3 t

waste are produced per t TBA. In the case of the

BASF-process, 1 t starting material yields almost 1 t

desired product TBA.

3.1.4. Asahi-process for cyclohexanol production

The industrial production of cyclohexanol by the

hydration of cyclohexene over special H-ZSM-5 is a

signi®cant example as a process using a solid acid

other than ion-exchange resin which is catalytically

active in aqueous solution (cf. Table 12, No. 3).

According to Asahi Chem. Ind. which developed

the process for the ®rst time, the catalyst for the

hydration is a high silica H-ZSM-5 (SiO2/Al2O3�25)

having the ratio (0.07/1) of the acid sites on the outer

surface to the total acid sites on the outer and inner

surface and the size of primary crystals of smaller than

0.5 mm [1,6,41]. Using such H-ZSM-5 powders at a

reaction temperature between 1008C and 1208C, the

conversion of cyclohexene between 10% and 15% is

achieved and the selectivity is higher than 98%. The

use of the high silica H-ZSM-5 having hydrophobic

property is one of the key factors, since lower silica

zeolites adsorb water strongly to make the adsorption

of cyclohexene impossible in aqueous solution. The

other factor is the successful recovery of deactivated

catalyst due to coking and dealumination by wet

oxidation and repeated treatment with NaOH/HNO3

[42]. For this hydration, ion-exchange resins which are

less active and lower heat-resistant (above 1008C) than

the zeolitic materials cannot be used as industrial

catalysts.

This new route for manufacturing cyclohexanol

which is a very valuable intermediate for the produc-

tion of adipic acid and caprolactam provides advan-

tages compared with the conventional method: 1 mol

H2 less, one reaction step less and avoidance of the

dangerous oxidation with oxygen. That means an

energetically and economically favorable and envir-

onmentally friendly alternative route. Other compa-

nies are also involved in this exciting new

development [6].

3.1.5. Production of thiocompounds

ELF-Atochem [91±93] is the major producer of

primary, secondary and tertiary mercaptans in Europe

and USA. The capacities for these intermediates are

between 1000 and 30 000 t/y. The sulfur compounds

are used in increasing quantities in agrochemicals,

pharmaceuticals, petrochemicals such as lubricants,

animal food additives, cosmetics and gas odorants.

The product line of ELF-Atochem includes mercap-

tans, sul®des, disul®des, polysul®des, sulfoxides and

thio-acids. For manufacturing mercaptans, alcohols or

ole®ns are used as starting materials and they are

converted with H2S in the presence of heterogeneous

catalysts.

The thiolation of n-alcohols to form primary mer-

captans is generally carried out at 300±4008C and

<10 bar in the presence of alkali oxides supported on

alumina or transition metal oxides and using an excess

of H2S (1.5±5 M) and keeping the residence time

��5±35 s. Methylmercaptan up to dodecylmercaptan

can be produced according to this route. Methanol

reacts with H2S over alkali doped activated alumina to

form CH3SH with around 90% selectivity at 100%

conversion of methanol. In the case of n-propylmer-

captan, 100% conversion of n-propanol and 80%

selectivity are obtained over K2WO4/Al2O3. Similar

results are achieved for the production of n-hexylmer-

captan.


Secondary mercaptans are produced from iso-ole-

®ns and H2S over solid acid catalysts such as ion-

exchange resins or zeolites. For example, cyclohex-

ylmercaptan is produced from cyclohexene at 2108C,

16 bar, LHSV 0.09 hÿ1 over ion-exchange resin with

95±97% selectivity at 92% conversion of the ole®n.

The service time of the catalyst is more than 1500 h.

For manufacturing 2-butylmercaptan, butene as start-

ing material is better than n-butanol. Using ion-

exchange resin as catalyst at 1008C and 15 bar,

70% 2-butylmercaptan and 30% butylsul®de are

attained at 70% conversion.

For the production of tertiary mercaptans such as

tert-butylmercaptan, tert-octylmercaptan, tert-nonyl-

mercaptan and tert-dodecylmercaptan, the starting

materials are isobutene, di-isobutene, tri-propylene,

and tetra-propylene or tri-isobutene. In the case of

tetra-propylene at 608C, 10 bar and LHSV�0.3 hÿ1

using an ion-exchange resin, 100% selectivity for tert-

dodecylmercaptan are achieved at 96% conversion.

Under quite similar conditions, tert-butylmercaptan is

obtained with 100% selectivity at 98% conversion of

isobutene.

It is expected that shape selective regenerable zeo-

lite catalysts which are also applied commercially in

mercaptan syntheses yield even better results.

3.2. Base catalysis

3.2.1. General electric-process for the production

of 2,6-xylenol

The alkylation of phenol with methanol to 2,6-

xylenol, a monomer of PPO resin, over MgO is an

old industrial process developed by General Electrics

(cf. Table 5, No. 9) [32]. Since the alkylation of an

aromatic ring with ole®n or alcohol had been believed

to be catalyzed by acids, the ®nding of the alkylation

over a basic MgO catalyst was surprising and gave a

great impact to catalysis researchers. The selectivity of

MgO for 2,6-xylenol is more than 90%, which is much

higher than that (17%) of solid acid, SiO2±Al2O3 [32].

The reason for the high selectivity is explained by the

difference in the adsorbed state of phenol as shown in

Fig. 1.

According to the IR study, phenol is adsorbed to

dissociate into phenoxide ion and proton in both cases

of MgO and SiO2±Al2O3, but the benzene ring plane is

parallel to the catalyst surface in the case of an acidic

SiO2±Al2O3 which interacts with basic � electron of

the benzene ring, but almost perpendicular in the case

of basic MgO, resulting in the high ortho-selectivity

[32]. This selective alkylation over a basic catalyst is

considered to be applied to other reaction systems if

higher reaction temperature is employed as in the case

of basic catalysts for which catalytic coef®cients for

some reactions are much lower compared to that of

acidic catalysts.

3.2.2. Sumitomo-process for production of

vinylbicycloheptene

Pronounced catalytic activity of solid superbases

for double-bond isomerization of ole®n and side-chain

alkylation of aromatics has resulted in the industrial

application recently. Over a solid superbase, Na/

NaOH/g-Al2O3, 5-vinylbicyclo [2.2.1] hepta-2-ene

(1) is almost completely isomerized to 5-ethylidene-

bicyclo [2.2.1] hepta-2-ene (2), a compound for vul-

canization purposes (cf. Table 6, No. 10), as shown in

the following scheme.

Compound (1) is thermally unstable and tends to

react to tetrahydroindene (3) which can be separated

from the desired product (2) only under extreme and

very costly conditions. However, the isomer (2) is

obtained with very high purity; 99.8% selectivity at

99.7% conversion at ÿ308C in the presence of the

superbase catalyst. Thus, after separation of the cat-

alyst, no additional puri®cation step is necessary

[2,6,7,43]. A 2000 t/y unit is on stream since 1986.

The same catalyst is successfully applied to the

isomerization of 2,3-dimethylbutene-1 to 2,3-

dimethylbutene-2, a valuable intermediate for the

production of synthetic pyrethroids. The reaction

reaches an equilibrium at 208C for 3 h, the ratio of

Fig. 1. Adsorbed states of phenol on MgO and SiO2±Al2O3.


the starting material to the isomerized product being 6/

94 [6,7]. The industrial applications are under design.

3.2.3. Sumitomo-process for production of

t-amylbenzene

The side-chain alkylation of cumene with ethylene

to form t-amylbenzene (cf. Table 5, No. 12) occurs at

408C over a superbase, K/KOH/g-Al2O3. The conver-

sion of cumene and the selectivity for t-amylbenzene

are 99.9% and 99.6%, respectively [6,7]. This process

is commercialized.

3.2.4. Amoco-process for the production of polyester

intermediates

Dimethyl-2,6-naphthalenedicarboxylate (NDC) is a

highly valuable intermediate for the production of

high performance engineering plastics such as poly-

ethylenenaphthalate (PEN) and polybutylenenaphtha-

late (PBN) and of liquid crystal polymers (LCPs). The

polyester PEN is manufactured by transesteri®cation

of NDC with ethylene glycol. PEN has superior

mechanical, thermal and chemical resistance and bar-

rier properties relative to polyethyleneterephthalate

(PET) [107]. Therefore, it is currently applied in

manufacturing magnetic recording tapes as well as

in electronic and speciality ®lms. Other potential

applications are in the ®eld of packaging resins for

¯exible and rigid containers/bottles and of industrial

®bers. For PEN, substantial market potential and

market growth are expected. However, the high cost

of the NDC monomer is the major hindrance for a

wide spread application of PEN.

A lot of R�D-efforts have been expanded to

develop an economical and ecological route for manu-

facturing NDC. One interesting procedure (cf.

Table 5, No. 11) was developed by Amoco Chemical

[44,94]. Based on readily available o-xylene as start-

ing material, NDC is produced in a 45 000 t/y plant at

Decatur site, Alabama, in a sequence of six major acid

and base catalyzed reaction steps (Fig. 2) since 1995.

� First, o-xylene reacts with butadiene in a side

chain alkylation to form 5-(o-tolyl)-2-pentene.

The reaction is carried out in a fixed bed reactor

over a basic catalyst such as K on CaO or Na on

K2CO3 at 1408C. The selectivity based on buta-

diene is around 65% and that based on o-xylene is

approximately 93% at 30% conversion of o-

xylene. Teijin developed also a basic catalyzed

technology for the production of this tolylpentene

[95].

� Second, the acid catalyzed cyclization of the

tolylpentene to form 1,5-dimethyltetralin is car-

ried out either in the vapor phase in a fixed bed

reactor or more preferably in the liquid phase in a

slurry reactor at temperatures between 2008C and

4508C. In the presence of hydrogen at 1508C, a

Fig. 2. Side-chain alkylation of o-xylene with butadiene to form o-tolylpentene catalyzed by a solid superbase, Na/K2CO3, as a step in the

synthesis of 2,6-dimethyl naphthalate (2,6-DMNA). (DMN: dimethylnaphthalene; NDA: Naphthalene dicarboxylic acid.)


yield of 92±94% is obtained over a Cu/Pd doped

ultrastable Y-zeolite. The by-product formation, in

particular, of high boiling C24 dimer alkylate is

reduced by the addition of hydrogen.

� Third, the dehydrogenation of tetralin yields 1,5-

dimethylnaphthalene. This endothermic reaction

occurs between 2208C and 4208C at increased

pressure of up to 20 atm in a fixed bed reactor

over a noble metal catalyst on alumina, silica or

activated carbon as carrier. At 4008C, 200 psig and

WHSV�4.4 hÿ1, 99% conversion and 99% selec-

tivity are achieved. The high pressure is necessary

to keep the feedstock in the liquid phase.

� Fourth, the 1,5-dimethylnaphthalene has to be

isomerized to the desired 1,6-isomer suitable for

PEN and LCP production. For this isomerization,

either an acidic dealuminated Y-zeolite or a beta-

zeolite having a low Si/Al ratio and low Na content

are employed in a slurry reactor at a temperature

range of 240±3508C and a pressure up to 5 atm. A

mixture containing 88% 1,5-isomer is converted in

a fixed bed reactor at 2508C to a product mixture

including about 42% of the 2,6-isomer and around

40% of the 1,6-isomer. The desired 2,6-isomer is

separated either by selective adsorption or by

fractional crystallization to achieve 99% purity.

The other isomers are recycled to the isomeriza-

tion.

� Fifth, the oxidation of the 2,6-dimethylnaphtha-

lene occurs via the well established Amoco's Mid-

Century process as it is applied for the oxidation of

p-xylene to terephthalic acid, i.e. in acetic acid as

solvent, a catalyst system of Co- and Mn-acetate

with hydrogen bromide as promotor in liquid

phase at around 2008C and 300 psig.

� Last, the 2,6-naphthalene dicarboxylic acid under-

goes an esterification with methanol in the pre-

sence of sulfuric acid at 1208C to form NJC. After

crystallization and distillation, NDC is obtained

with 99.9 wt% purity.

More recently, Mitsubishi Oil has disclosed a side

chain alkylation of p-xylene with butene and cycliza-

tion to the desired 2,6-dimethylnaphthalene proceeds

from the alkylate. 81% selectivity based on 32% p-

xylene conversion and 69% based on 91% butene

conversion [96].

Other routes to provide NDC for PEN production

are based on:

� Recovery of 2,6-dimethylnaphthalene from refin-

ery streams. UOP runs a semi-commercial plant

with 4500 t/y capacity in Streveport, Louisiana

[97]. Thereby, the 2,6-isomer is separated from

the other isomers by selective adsorption and acid

catalyzed isomerization [98].

� Acetylation of 2-methylnaphthalene using HF±

BF3 catalyst to form 2-acetyl-6-methylnaphtha-

lene. Mitsubishi Gas Chemical has a 1000 t/y

semi-commercial unit near Okayama running

since 1990 [99] and now most probably also a

10 000 t/y plant [100].

� Alkylation of naphthalene with propylene to form

2,6-diisopropylnaphthalene. This route was jointly

developed by NKK and Chiyoda. A semi-com-

mercial plant with 1000 t/y capacity is installed at

Fukuyama facility [101]. The selective synthesis

of 2,6-dialkylnaphthalenes has focused on solid

acid catalysts providing shape selectivity. How-

ever, a shape selective effect is not expected in the

methylation of naphthalene because of the small

size difference of the isomers, particularly of 2,6-

and 2,7-isomers. Therefore, higher olefins such as

propylene have been used as alkylation reagents.

Furthermore, larger alkyl groups can be easily

oxidized. The alkylation and isomerization reac-

tions disclosed in many patents focus on Y-, USY-

and û-type zeolites. Still a drawback of these

zeolitic catalysts is the deactivation due to the

formation of polymeric by-products. NKK/

Chiyoda uses the alkylation of naphthalene by

propylene in the presence of a zeolitic catalyst

followed by oxidation and esterification to pro-

duce methyl-2,6-naphthalenedicarboxylate (2,6-

NDC). Particularly in Japan some companies have

announced commercial plants for manufacturing

the intermediates of 2,6-NDC. Among them are

Mitsubishi Chemical, Sumikin, Kawasaki Steel,

Nippon Mining, Nippon Steel, Asahi Chemicals,

e.g. Sumikin developed a Pd/Co/Mo-catalyst

[102]. Catalytica showed also strong interest in

the propylation of naphthalene using acidic zeolite

[103].

Other routes to produce precursors for new polye-

sters and polyamides:

� The alkylation of biphenyl with propylene to form

4,4-diisopropylbiphenyl (DIPB) in the presence of

dealuminated mordenite having SiO2/Al2O3 molar


ratio of 2600. This process has been developed by

DOW Chemical [104,105].

� The alkylation of diphenylether as it has been

disclosed by Du Pont de Nemours [11].

PEN consumption is expected to grow from

2.3 MIL lb/y in 1996 to 12 MIL lb/y in 2000 and to

34 MIL lb/y in 2005. In the past, a lack of suf®cient

quantities and high costs of key intermediate NDC has

hindered the production of PEN. Expansion plans are

now in the works by Amoco to expand the facility

between 90 and 110 MIL lb/y by 1999. A second plant

is pledged early next century.

3.3. Acid±base bifunctional catalysis

The simultaneous cooperation of a weak acid site

with a weak base site on a solid surface is surprisingly

powerful to exhibit high catalytic activity and selec-

tivity and long life, provided that the acid±base pair

site is suitably oriented to the basic and acidic groups

of a reactant molecule. The number of these examples

is increasing [45]. For the industrial application of the

bifunctional catalysis, 14 kinds of commercial pro-

cesses have been developed, as shown by double

asterisks in Tables 5±15. A few examples are

described more in detail.

3.3.1. Sumitomo-process for the production of

vinylcyclohexane

In the synthesis of vinylcyclohexane by the dehy-

dration of 1-cyclohexyl ethanol (cf. Table 7, No. 5), a

ZrO2 catalyst treated with NaOH shows a high con-

version of more than 80% and a high selectivity of

about 90%, no catalyst deactivation being observed in

3000 h [33,34]. Polyvinylcyclohexane is a useful

additive to polypropylene. The acid±base bifunctional

nature of the catalyst is evidenced by the ®tness of the

distance between an acid site (Zr4�) and a base site

(O2ÿ) of ZrO2±NaOH calcined at 4008C with the

distance between a basic group (C±OH) and a terminal

acidic group of 1-cyclohexyl ethanol and also by the

values of overlap population calculated according to

the theory of Paired Interacting Orbitals [33].

3.3.2. Nippon Shokubai-process for the production of

ethyleneimine

Ethyleneimine derivatives are commercially impor-

tant chemicals which are used for the production of

pharmaceuticals and various other amines and for the

production of amine type functional polymer for coat-

ings of paper and textile. As shown in Fig. 3, ethyl-

eneimine has been produced by intramolecular

dehydration of monoethanolamine in liquid phase

using sulfuric acid and sodium hydroxide according

to the Wenker-process.

However, the process has some problems such as

low productivity, formation of large amounts of

sodium sulfate (4 t per 1 t ethyleneimine), etc. Thus,

the vapor phase process using solid acid±base cata-

lysts is more advantageous than the liquid phase

process, provided that the formation of undesirable

by-products such as acetaldehyde, piperidine, ethyla-

mine, acetonitrile, etc., is minimized. For the vapor

phase process, a new ef®cient catalyst (Si±Ba±Cs±P±

O) has been developed by Nippon Shokubai (cf.

Table 7, No. 4), the conversion of monoethanolamine

and the selectivity for aziridine being 86% and 81%,

respectively, at 4108C and space velocity of 1500 hÿ1

[6,7]. The acid and base strengths of the catalyst are

weaker than HO��4.8 and Hÿ�9.4, respectively, and

the reaction is considered to proceed by an acid±base

bifunctional mechanism [46,47]. A plant with a capa-

city of 2000 t/y is on stream since 1990.

3.3.3. Mitsubishi-process for the production

of aromatic aldehydes

Another example of the acid±base bifunctional

catalysis is the hydrogenation of aromatic carboxylic

acids to the corresponding aldehydes (cf. Table 14b,

No. 3 of hydrogenation) [1,6]. Aromatic aldehydes are

important intermediates in the production of ®ne

chemicals such as pharmaceuticals, agrochemicals,

and perfumes. These aldehydes have been produced

Fig. 3. Synthesis of ethyleneimine (EI) from monoethanolamine

(MEA).


mainly by a halogenation method. However, the

method has disadvantages such as poor yield and

undesirable by-products formation and environmental

in¯uence. A novel process for synthesizing aromatic

aldehydes by the direct hydrogenation of the corre-

sponding carboxylic acids has been developed using

zirconia-based catalysts by Mitsubishi Kasei. In the

case of the hydrogenation of benzoic acid over ZrO2

doped with a small amount of Cr2O3, the conversion of

benzoic acid and the selectivity for benzaldehyde are

98% and 96%, respectively, at 3508C [48,49]. Even

ZrO2 itself shows a high selectivity of 97%, at the

conversion of 53%. The hydrogenation is considered

to proceed by an acid±base bifunctional mechanism as

shown in Fig. 4 [49]. Since 1998, Mitsubishi Chemi-

cals has on stream a multi-purpose plant having

2000 t/y capacity for the production of various aro-

matic aldehydes.

The cost saving by the new process is said to be

about 20±30% compared with the conventional route.

4. Future trends

Solid acid±base bifunctional catalysis is expected to

become even more important for industrial application

in future. Besides 14 kinds of the processes by the

bifunctional catalysis mentioned in Sections 2.2 and

2.3, seven more processes (No. 8, 9 and 16 in Table 7,

No. 5 in Table 8, No. 6 in Table 10, No. 2 in ester-

i®cation of Table 13a, No. 4 in Table 15) may be

regarded as bifunctional catalysis, though there is

no evidence for acid±base bifunctional mechanism.

Even in the alkylation of phenol with methanol over a

typical base catalyst, MgO, the catalytic function of

MgO is acid±base bifunctional as mentioned in Sec-

tion 3.2.1. Thus, it is not easy to distinguish between

base- or acid-catalysis and acid±base bifunctional

catalysis. Typical acid±base bifunctional catalysts

are weakly acidic and weakly basic ZrO2 and ZrO2

doped with a small amount of NaOH, Cr2O3, etc. (No.

5, 7, 13±15 in Table 7, No. 3 in hydrogenation of

Table 14(b)), and Cs±Ba±P±O/SiO2 (No. 4 in

Table 7). These almost neutral catalysts which are

similar to some enzymes from a view-point of weak

acid±base property exhibit high catalytic performance

for the reactions which have been regarded to be

catalyzed simply by acids or bases, as some examples

are discussed in the foregoing section. In this sense

also, high silica zeolites may be included in this

category. Since weakly acidic and basic catalysts

cause less formation of by-products and less deactiva-

tion due to coking, they are promising for further

industrial application. Attempt to use weak acid±base

bifunctional catalysts for the reactions which are

known to be catalyzed by strong acids or bases

seems to be intriguing as a fundamental research in

this ®eld.

In contrast to the weak acid±base catalysts men-

tioned above, solid superacids are also one of the

interesting catalysts. More than 200 papers and patents

on solid superacids (mainly, SO2ÿ4 =ZrO2 and its mod-

i®ed ones) have been reported since 1990. Never-

theless, not much industrial processes have been

developed yet mainly due to catalyst deactivation

(leaching or decomposition of SO2ÿ4 or coking) or

low selectivity caused by the strong acidity. However,

the skeletal isomerization of n-alkanes to i-alkanes is

said to be commercialized by using a Pt, SO2ÿ4 =ZrO2

catalyst in the presence of hydrogen. Although not

Fig. 4. Acid±base bifunctional mechanism for hydrogenation of

benzoic acid to benzaldehyde over a zirconia catalyst (Zr4�: acid

site; O2ÿ: base site).


much work has been made in the application of

superacid catalysts to organic synthesis, the applica-

tion will be promising if reactions are carried out at

low temperatures or in liquid phase where catalyst

deactivation and by-products formation can be mini-

mized.

As for solid base catalysis, the number of industrial

processes is only 10 at present. However, very

recently, the study of solid base catalysis is becoming

active and new solid bases such as oxynitrides

(AlVOmNn, ZrPOmNn, etc.), KNO3/Al2O3, KF/

Al2O3, meixnerite (anionic clay), a mechanical mix-

ture of NaX�Na2O or CaA�K2CO3, rare earth metal/

Al2O3, hybrid solid base (nitrogen compound com-

bined with MCM-41), etc., have been reported to show

pronounced catalytic performance compared with

already known base catalysts [50] for some base-

catalyzed reactions [51,52]. Thus, the industrial appli-

cation of solid base catalysts is expected to increase in

near future.

Great contribution of various zeolites as catalysts to

industrial processes is worthy of note. Besides the

shape selectivity, the reproducible preparation of zeo-

lites seems to result in the contribution. Zeolites

modi®ed by various ways and methods will make

further contribution to their industrial application.

Mesoporous materials such as SiO2±Al2O3, SiO2±

TiO2, SiO2, ZrO2, Nb2O5, etc., which are shape selec-

tive and have acidic properties and large surface areas

are promising as effective acid catalysts for particular

reactions. Inorganic and organic compounds having

acidic and/or basic property which are incorporated

with mesoporous materials such as MCM-41 will also

become promising as a new type of solid acid±base

catalyst.

On the other hand, the improvement of already

established industrial processes is desired, since, in

most of the processes, the selectivity and life of

catalysts are not necessarily satisfactory, and in

some processes using solid phosphoric acid, etc.,

the catalysts are corrosive and present waste disposal

problems.

On the basis of the present survey, signi®cant

fundamental research on solid acid±base catalysts

which will give an impact to industrial application

in future are considered to be as follows:

1. preparation method of catalysts,

2. deactivation of catalysts,

3. development and utilization of acid±base bifunc-

tional catalysts,

4. development of catalysts other than acidic resins

which can be used in aqueous solution,

5. more application of catalysts to synthesis of fine

and specialty chemicals.

5. Conclusion

The present survey of industrial application of solid

acid±base catalysis provides the fact that a large

number of various solid acid±base catalysts are used

for more than 100 industrial processes. Zeolites, oxi-

des, complex oxides, ion-exchange resins, and phos-

phates occupy large percentage of the catalysts. In

particular, the contribution of various zeolites to

industrial application is realized to be the greatest.

The number of processes using solid acid catalysts is

largest at present. However, the signi®cance of solid

acid±base bifunctional catalysis and solid base cata-

lysis has been pointed out by explaining several

examples of the industrial processes. On the basis

of the survey, future prospects of solid acid±base

catalysis are speculated.

This survey is not suf®cient because some of the

catalysts which are used in new practical processes are

proprietary and secret and some of the companies do

not disclose the scales of production and do not want

their processes to become public. For example, a

major chemical company in Europe carries out 10

processes catalyzed by solid acids or bases. But only

two of them are disclosed. Nevertheless, we hope that

this survey will be useful for the catalysis researchers,

in particular, in universities.

6. Appendix

lb pound

MIL lb million pounds

BIL lb billion pounds

B (bbl) barrel

BPD barrels per day

BPSD barrels per steam day

BPCD barrels per calendar day

psig pound per square inch gauge (0.068 atm)


bar 0.987 atm

MM million

MMM billion

MW megawatt

Acknowledgements

We gratefully acknowledge professors and doctors

(cf. [23,24±31]) for providing new information for this

survey. Also the authors like to express their sincere

thanks to Dr. J. Kervennal (Elf-Atochem), Dr. R.

Vanheertum (Degussa AG), Dr. Irv. W. Potts (DOW

Chemical), Prof. Dr. Rosenkranz (Bayer AG) and Dr.

J.P. Lange (Shell Chemicals) for providing informa-

tion about processes carried out in their companies.

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