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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 )
S.No. Process Catalyst Company Year, scale
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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403
Table 5 (Continued )
S.No. Process Catalyst Company Year, scale
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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Table 6 (Continued )
S.No. Process Catalyst Company Year, Scale
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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Table 6 (Continued )
S.No. Process Catalyst Company Year, Scale
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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407
Table 7
Dehydration and condensation processes
S.No. Process Catalyst Company Year, scale
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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Table 7 (Continued )
S.No. Process Catalyst Company Year, scale
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
S.No. Process Catalyst Company Year, scale
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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Table 8 (Continued )
S.No. Process Catalyst Company Year, scale
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
S.No. Process Catalyst Company Year, scale
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
S.No. Process Catalyst Company Year, scale
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.
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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
S.No. Process Catalyst Company Year, scale
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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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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Table 13 (Continued )
Process Catalyst Company Year, scale
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
Process Catalyst Company Year, scale
(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
S.No. Process Catalyst Company Year, scale
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
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Table 15 (Continued )
S.No. Process Catalyst Company Year, scale
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.
K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434 421
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
422 K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434
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
K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434 423
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.
424 K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434
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.
K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434 425
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.)
426 K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434
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
K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434 427
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).
428 K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434
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).
K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434 429
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)
430 K. Tanabe, W.F. HoÈlderich / Applied Catalysis A: General 181 (1999) 399±434
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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Recommended