Industrial Application of Solid Acid Base Catalysts

Applied Catalysis A: General 181 (1999) 399434
Industrial application of solid acidbase catalysts

Kozo Tanabea,*, Wolfgang F. Holderichb,1
a
Research and Development Division, Nippon Shokubai Co., Ltd., 5-8, Nishi Otabi-cho, Suita, Osaka 564-8512, Japan
b
Department 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 acidbase catalysts is presented. The number of processes such as
alkylation, isomerization, amination, cracking, etherication, etc., and the catalysts such as zeolites, oxides, complex oxides,
phosphates, ion-exchange resins, clays, etc., are 127 and 180, respectively. The classication of the types of catalysts into solid
acid, solid base, and solid acidbase bifunctional catalysts gives the numbers as 103, 10 and 14, respectively. Some signicant
examples are described more in detail. On the basis of the survey, the future trend of solid acidbase 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 acidbase 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 claried 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 acidbase
properties for catalytic activities and selectivities
being studied extensively. Now, solid acidbase catalysis is one of the economically and ecologically
important elds in catalysis. The solid acid and base
catalysts have many advantages over liquid Brnstedand Lewis-acid and base catalysts. They are non*Corresponding author.
1
Also corresponding author.
corrosive and environmentally benign, presenting

fewer disposal problems. Their repeated use is possible 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 catalysts 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 acidbase 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
0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00397-4
400
K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434
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 acidbase catalysts.
The larger numbers (188) of the process types are
found for alkylation, isomerization, dehydration and
condensation, amination, cracking and etherication,
and the smaller ones (73) for aromatization, hydration, hydrocracking, MTG/MTO, oligomerization and
polymerization as well as esterication. We accounted
127 different processes. Thereby, we did not differentiate 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 zeolites.
The types of catalysts used in the above industrial
processes are shown in Table 2.
The larger numbers (7416) are seen for zeolites,
oxides, complex oxides, ion-exchange resins and
phosphates, and the smaller ones (73) for clays,
Table 1
Industrial processes using solid acidbase catalysts
Dehydration and condensation
Isomerization
Alkylation
Etherification
Amination
Cracking
Aromatization
Hydration
Oligomerization and polymerization
MTG/MTO-processes
Hydrocracking
Hydrogenation
Esterification
Disproportionation
MTBE!i-C04
Others
Total
18
15
13
10
9
8
7
7
6
5
4
4
3
2
1
15
127
Table 2
Types of catalysts used in industrial processes
Zeolites
Oxides, complex oxides
Ion-exchange resins
Phosphates
Solid acids (not specified)
Clays
Immobilized enzymes
Sulfate, carbonate
Sulfonated polysiloxanes
Total
74
54
16
16
7
4
3
3
3
180
immobilized enzymes, sulfates plus carbonates and

sulfonated polysiloxanes. It is noteworthy that zeolites
occupy about 41% of the acidbase 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 specied,
the number of ZSM-5 plus high silica pentasil zeolites
is the largest among various zeolites. It is also noteworthy that 16 phosphates are used as catalysts in
industrial processes.
2.2. Classification of solid acid, base, and acidbase
bifunctional catalysts
The number of solid acid, base, and acidbase
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
acidbase bifunctional catalysts, the number was estimated 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 acidbase pair sites, since any kind of solid acid (or
solid base) possess more or less base sites (or acid
sites).

Table 3
Detailed kinds of catalysts
Zeolites
ZSM-5, pentasil zeolite, modified ones
Zeolites (not specified), modified ones
Mordenite
Y-zeolite
US-Y
Beta-zeolite
74
31
28
7
4
2
2
Oxides, complex oxides

SiO2Al2O3
Al2O3NaOHNa, Al2O3KOHK, Al2O3HF,
Al2O3BF3, Al2O3K2O
ZrO2, ZrO2Cr2O3, ZrO2MgO, ZrO2NaOH,
ZrO2KOH, ZrO2K2O
Al2O3, Al2O3MgO, Al2O3B2O3, Al2O3NiO
MgO, MgOTiO2, Pd/MgO
SbF5/SiO2, Ta-alkoxide/SiO2, FeV/SiO2
TiO2SiO2, TiO2V2O5WO3, TiO2H3PO4
ReSiO2, ReSiO2Al2O3
2
SO2
4 =ZrO2 , Fe, Mn, SO4 =ZrO2
Metallosilicate
Nb2O5nH2O
Hydrotalcite
Others
54
11
9
Phosphates
SrHPO4, LaHPO4, Li3PO4, AlB phosphate, LaPO4, FePO4
Solid phosphoric acid
SAPO-11, SAPO-34
CsBaPO/SiO2
Ba or Ca salt phosphate
H3PO4aniline salt/SiO2
16
7
4
2
1
1
1
Ion-exchange resins
Solid acids (not specified)
16
7
7
6
4
3
3
2
2
2
1
1
3
Clays
Kaolin, pillared clay, bentonite, montmorillonite
Immobilized enzymes
Asparatase, nitrilase, amylase
Sulfate and carbonate

Al2(SO4)3/SiO2, CF3SO3H/SiO2, Na/K2CO3
Sulfonated polysiloxanes
3
3
2.3. Detailed processes and catalysts

Tables 515, the detailed industrial processes and
catalysts [1,2,3113,114,115119,120,121,122,123,
124128,129,130146,147,148199] together with
the names of companies, the year of industrialization,
and the scales of the products, where (p) denotes
401
Table 4
Number of solid acid, base and acidbase bifunctional catalysts in
industrial processes
Solid acid catalysts
Solid base catalysts
Solid acidbase bifunctional catalysts
103
10
14
Total
127
``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 acidbase bifunctional catalysis.
3. Significant examples
Among the industrial processes given in Tables 5
15, several of the signicant 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 efcient and selective catalysts and the realization of new process
technology is strongly related to environmental compatibility. The goals must be to avoid waste production, 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/
402
Table 5
Alkylation processes
S.No. Process
Catalyst
Company
Year, scale
H-ZSM-5 vapor phase
MobilBadger
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
Diluted mixture of propylene and

ethylene sourced from FCC off-gas
High silica zeolite vapor phase
1992, 10 000 t/y [4], 1 plant, China Petrochemical,

3 licenses [55]
Four licenses [55]
100 000 t/y [57], Supreme Petrochemical at
Nagathone, India
120 000 t/y [58], Angarsk Petrochemical at Angarsk,
Russia
[59]
1995, 260 000 t/y [60], Mitsubishi Chem.,
Yokkaichi, Japan
140 000 t/y [61], Petroquimica, Argentina
100 000 t/y [61], Pemex, Mexico
250 000 t/y [77], Ciba Styrene Monomer
H-ZSM-5 liquid phase

Acidic zeolite liquid phase
MobilRaytheon EB-Max process

ABB Lummus Global
EBZ 500 zeolite liquid phase

Acidic zeolite catalytic distillation
UOP/Lummus
CDTECH
Acidic zeolite liquid phase
ABB Lummus/Unocal/UOP
Solid phosphoric acid (SPA)
Most of the cumene producer
High silica zeolite
MobilBadger/Raytheon
b-zeolite
Acid zeolite catalytic distillation
Enichem
CDTECH
Mordenite
Y-zeolite
Acid zeolite catalytic distillation
DOW Chemicals
Lummus
CDTECH Catstill-technology
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
1996, 265 000 t/y [15]
170 000 t/y [58,60], GP Orgetelko Dzeryinsk at
Nizhny Novgorod, Russia [60]
1994 (p) [11]
1994 (p) [11]
[199]
Three-dimensional dealuminated
mordenite
DOW/Kellog 3-DDM technology
1994, 200 000 t/y [68] at Terneuzen, Belgium

Five projects [68]
Dilute ethylene sourced from

FCC off-gas or steam cracker
Table 5 (Continued )
S.No.
Process
Catalyst
Company
Year, scale
Transalkylation reactor
diisopropylbenzenebenzene
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
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
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
Zeolite
Rutgerswerke AG
(p) [200]
Dealuminated H-mordenite
DOW Chemicals
1989, (p) [104,105]
Pentasil zeolite Encilite 2
Hinduston Polymers Albene

Technology
1989 [108], at Visakhapatnam, India
Pore size regulated ZSM-5
Paschim/IPCL
1997, 1000 t/y [21,30]
403
404
S.No.
9
Process
Catalyst
Company
Year, scale
MgO
General Electric
1970, several units in commercial scale

licensed [32]
1985, at Ludwigshafen, Germany
BASF AG
FeVO/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]
BF3/g-Al2O3
SbF5/SiO2
Sulfated ZrO2
Solid acid (alkylene catalyst)
fluidized bed
Catalytica/Conoco/Neste Oy
Chevron/CDTECH
Orient Catalyst
UOP
57 000 B/y [82,83], Amoco at Yorktown, Virginia

1994, 1 t/d [9,83,88], at Porvoo, Finland
1994, 10 BPD [84,85], at Port Arthur, TX
1020 t/y [86]
(p) [87]
10
Table 6
Isomerization processes
Process
Catalyst
Company
Year, Scale
Xylene isomerization!p-xylene
H-ZSM-5
Mobil Oil
C8 aromatic mixture!p-xylene
Pentasil zeolite
Acid zeolite 1-210
Xyclofining-process
UOP ISOMAR technology
Zeolite
JFP/Chevron ELUXYL-process
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
IIP, India [115]
1996, 40 units [111,112], Reliance Industries [114],
at Jamnagur, India, world largest complex
15 00020 000 t/y [116], demonstration plant [117],
at Pascagoula, MS
High silica zeolite
Toray
1990, 2000 t/y [2,6]
H-mordenite
Fe/Mn/sulfated ZrO2
Zeolite
Zeolite
Zeolite
Zeolite
UOP BUTAMER-process,
PENEX-process
Sun Refining
BP-Chemicals, c4-isomer
Huntsman ISOTEX-process
UCC TIP-process
Shell HYSOMER-process
>35 units licensed [118]

1992, 30 000 BPD [119], Enterprice Products
[120]
[121]
[122]
[123]
[124]
n-C4 ! i-C4
n-C4 0 ! i-C4 0
SiO2 modified Al2O3

Ferrierite
B2O3/Al2O3
Acid catalyst
IFP
Shell/Layondell/CDTECH/Zeolyst
SNAM
Nippon Petrochemical/Nippon Oil
1991, pilot [5]

1994, 40 000 t/y [125]
1997 (d) [37]
1992, 9000 t/y [126], at Kawasaki, Japan
C4 0 ; C5 0 ! i-C4 0 ; i-C5 0
H-ZSM-5
H-ZSM-5 fluidized bed
Zeolite
Mobil/BP/Kellog ISOFIN-process
Mobil/Raytheon MOI-process
Lyondell Petrochemical, ISOM
Plus-process
1994 (p) [12,127]

Pilot 4 BPD [128], 100 BPD
1992, 3000 BPSD [129], at Channelview
405
S.No.
406
S.No.
Process
Catalyst
Company
Year, Scale
Zeolite
1991, 2700 BPD [130,131]
Zeolite
Phillips Petrochemical/Texas
Olefins SKIP-process
UOP, PENTESOM-process,
BUTESOM-process
PEMEX
Zeolite
JFP ISO-4-process
1994, 27 000 BPD [132], at Minatitlan, Mexico,

1994, 2700 BPD [132], at Cedercyta, Mexico
1984, pilot [130], 160 000 t/y
Zeolite LPI-100TM
Acid solid
UOP PAR-ISOM-process
Shell
Cosmo Oil [13], Mitsubishi Heavy Ind.

850 000 t/y part of SHOP-process [135,136]
H ion-exchange resin
Exxon
1986 [3]
Na/NaOH/g-Al2O3
Sumitomo Chemical
[6]
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]
Zeolite
Light naphtha isomerization

Heavy olefins isomerization
1991 [133], 1992
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
IdemitsuKosan
1986, (p) [2,6,138]
S.No.
407
408
Table 7
Dehydration and condensation processes
S.No.
Company
Year, scale
Al2O3
Sulfonic acid resin
Petrobrass
UOP
1980 [19,31]
1981 [3]
Ion exchange resin
DavyMcKee
1985, 20 000 t/y [5]
CsBaPO/SiO2
Nippon Shokubai
1991, 2000 t/y [1,6,46,47]
ZrO2NaOH
Sumitomo
1986 [33,34]
Nb2O5nH2O
Sumitomo
1987 [35,36]
ZrO2KOH
Koei Chemical
1992, (p) [25]
H3PO4aniline salt/SiO2
Nippon Shokubai
1995, 6000 t/y [17]
H2 O
EtOH !
C2 H4
t-BuOH !H2 O i-C04
Catalyst
1
2
Process
S.No.
Process
Company
Year, scale
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]
** Isobutyraldehyde!diisopropyl
ketone
ZrO2
Chisso
1974, 2000 t/y [22]
14
** Isobutanol!diisopropyl ketone
ZrO2, ZrO2K2O
Chisso
1974, 2000 t/y [22]
15
** n-Butanoln-butyraldehyde
!di-n-propyl ketone
ZrO2MgO
Chisso
1974, 2000 t/y [22]
Air Products
1987 [3,6]
Pt/H-ion exchange resins trickle

bed reactor.
Bayer AG
Deutsche Texaco
[147]
[148]
Pentasil zeolite
Asahi Chemical
[149]
16
17
18
H2CO aqueous ! trioxane
409
13
Catalyst
410
Table 8
Amination processes
Process
Catalyst
Company
Year, scale
2MeOHNH3!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

ProductsChemicals
(p) or (d) [6,53]
(p) or (d) [151]
Cu, Ni/SiO2Al2O3
Kao
1989 [1]
SrHPO4, LaHPO4, H3PO4/SiO2
Air Products
1986, 1015 MM lb/y [3,6], Allentown, PA
AlSi zeolite
Berol/Nobel
1984, 50 000 t/y [5], Sweden
MgO, B2O3, Al2O3 or TiO2/SiO2

or Al2O3
USS
1982, 200 MM lb/y [3]
Immobilized asparatase
Tanabe Pharmaceutical,
Mitsubishi Petrochem.
1973, 1000 t/y [1], 1986, 1000 t/y [1]
S.No.
S.No.
Process
Catalyst
Company
Year, scale
Modified SiO2Al2O3modified
ZSM-5
Koei Chem.
1990, 9000 t/y [25]
Modified SiO2Al2O3modified
ZSM-5
Koei Chem.
1990, 9000 t/y [25]
Pentasil zeolite fixed bed

H-ZSM-5 fluidized bed
Al2O3HF fluidized bed
Armor polymer
Nepera
Degussa AG
India [6]
USA [6]
Germany [6]
BASF AG
1986, 6000 t/y [5,6,138], Antwerp, Belgium, 1994,

8000 t/y, Antwerp, Belgium
Pentasil zeolite
411
412
Table 9
Cracking processes
Process
Catalyst
Company
Year, scale
FCC-processes
e.g. SiO2Al2O3/US-Y
Partially dealuminated Y type
zeolite in SiO2Al2O3
Novel Y/SiO2Al2O3
Ultrastable Y containing RE
oxides and SiO2
Cat. & Chem.

UOP
1985, a lot of units [1]

1986, 1 MM lb/y [3]
Cosmo
China Petro
1990 [2]
1993 [4]
Heavy oil
MgOAl2O3-zeolite
Magna-Cat
Nippon Oil
Valero/Kellog
1990 [2]
Corpus Christi, TX [152]
Heavy fractions
Calcined kaolin
Engelhard/Ashland
1993, 55 000 BPD [3]
Cracking above 6508F
Ultrastable Y treated with RE

dispersed in SiO2Al2O3,
cogel/kaolin matrix
Ashland/Davison
1983, 40 000 BPD [3]
Deep cracking of vacuum gas oil
Pentasil zeolite
China Petro
1990, 60 000 t/y [4], 1993, 400 000 t/y
Middle and light distillate from

cracking feed
Ultrastable US-Y zeolite
Total/IFP
1982, 60 000 t/y [4]
Middle distillate catalytic dewaxing
Proprietary
China Petro
1984, 20 000 t/y [4]
Selective cracking of straight

chain paraffins and olefins to
produce C3 0 and C4 0
H-ZSM-5
Mobil
1986 [3]
S.No.
Table 10
Etherification processes
S.No.
Process
Catalyst
Company
Year, scale
i-C04
Ion-exchange resin
IFP
ARCO
SNAM/Ecofuel
19781981, 50 000 t/y11 plants [5]

1986, 320 t/y [3]
1973, 120 000 t/y [38], 1990, 500 000 t/y [153],
Ibn Zahr in Al-Jubail, Saudi-Arabia
1994, 530 000 t/y [154]
MeOH ! MTBE
1996, 700 000 t/y [155]

1992, 12 500 BPD [156], at Deer Park, Texas
Licensing [157]
i-C04 MeOH ! MTBE isooctane
Ion-exchange resin
SNAM
1996 [29]
i-C04 EtOH ! ETBE
Ion-exchange resin
SNAM/Ecofuel
1993 [38]
i-C05 MeOH ! TAME
Ion-exchange resin
IFP/ELF
ANIC/SNAM
Exxon
Neste Oy/Bechtel
DavyMcKee
1984, 8000 t/y [5], 1992, 100 000 t/y [5]

1989, 54 000 t/y [29]
1986 [3]
1995, 116 000 t/y [158], at Porvoo, Finland [159]
1994, 2000 BPD [160], at Shamrock
Olefins MeOH ! MTBE/TAME
Ion-exchange resin
Erdoelchemie/Lurgi
1980 (p) [5]
2MeOH ! MeOMeH2O
Al2O3
Mobil
1985, 14 000 BPD [3]
AlBPO
Ube
1978 [2]
Pillared clay or smectic

(bentonite, montmorillonite)
BP
(p) [5]
Hydrotalcite Mg6Al2O8(OH)2,
ROHfatty alcohols, nnarrow
molecular weight range
Ba or Ca salt/phosphate
Henkel
1994 (p) [163]
UCC
1985, 60 MMIL lb/y [3]
LaPO4
Shell
1995, 500 000 t/y [164]
10
Chevron/Neste Oy (Alberta
Envirofuels)
Sabic/Shell (SADAT)
Lummus Crest
CDTECH
413
MTBE: methyl t-butylether, TAME: t-amyl methylether.
414
Table 11
Company
Year, scale
ZSM-5
Mobil
[3]
C3, C4!aromatics, particular

p-xylenes
LPE or refinery light end paraffins
and olefins
Ga-modified ZSM-5, Zn-modified

ZSM-5
BPUOP Cyclar-process
1990, 5000 t/y [5], at Grangemouth, Scotland
LPG (mainly C3, C4)!BTX
Zeolitepromoter
UOP
1983 [3]
LPG or light naphta!aromatics
Metallosilicate
Mitsubishi Oil Chiyoda
1991, 200 BPD [22]
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 [22,168170], at Mizushima, Japan
C6, C7, naphthanes!aromatics
Pt-zeolites Al2O3SiO2, PtRe

zeolites Al2O3SiO2
Platforming, Rheniforming,
e.g. Chevron
UOP
>500 units [171]
R-132 catalyst
Pt L-zeolite
UOP LLR-platforming
Chevron Chem. AROMAX-process
1992, 9 units of 34 [174]

1992/1993, 2 units [173]
(b) Hydrocracking process

1
Fixed-bed residual hydrocracking
Fe-VIb/zeolite
Idemitsu
1982 [1]
Hydrocracking of heavy oil

distillates into gasoline and
middle distillates
Amorphous SiO2Al2O3 with zeolite
Hydrocracking of gas oils

WaxH2!gasoline
ZSM-5
Mobil
[3]
Lub dewaxing
Wax oilsH2!lower molecular
wt. hydrocarbons
ZSM-5
Zeolite
Mobil
BASF
1981, 150015 000 BPD [3]

[3]
(a) Aromatization processes

1
C03 ; C04 ! alkylaromatics paraffins
2
C6, C7!preferably benzene
Naphtha!aromatics
1995 [165], Ibn Rushd at Yanbu, Saudi Arabia
e.g. 1997, 230 000 t/y [172], CEPSA at Algeciras,

Spain
1990 [3]
Catalyst
Table 12
Hydration processes
Process
Catalyst
Company
Year, scale
C=CH2O ! EtOH
Solid phosphoric acid
Shell, BP, many others
i-C4' ! t-BuOH
Ion-exchange resin
Sulfonic acid resin
Mitsui Petrochem.
UOP/huels
[1]
1981 [3]
Novel highly siliceous H-ZSM-5,

<1 mm
Asahi Chem.
1990, 80 000 t/y [1,6,41,42]
Acidbasic catalyst based on

TiO2/H3PO4
Degussa AG
1997, 10 000 t/y [175], Wesseling, Germany
Acid catalyst
H-ZSM-5
Air Products/DOE
Mobil
(p) [161]
0.5 BPD [162]
MgO
MnO2
Distillers
Reynolds Tobacco
[176]
[177]
Nitrilase immobilized by
polyacrylamide gel into a particle
Nitto
1985, 600020 000 t/y [1,6]
S.No.
415
416
Table 13
Esterification processes
Process
Catalyst
Company
Year, scale
Ion-exchange resin
DavyMcKee
1985, 20 000 t/y [178], 1,4-butanediol-production
Mercapto-functionalized
sulfonated polysiloxane
Degussa AG
1996 (p) [26]
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
(a) Esterification processes
MeOH ! C03 C04 some gasoline
Modified ZSM-5
Mobil MTO-process
1985, 160 BPD [3], UK-Wesseling, Germany
MeOH ! C02 C03
SAPO-34 in FCC-catalyst matrix
UOP
1988 [3]
Olefins of MTO!jet fuel, diesel
Zeolite
Mobil MOGD-process
[179]
Olefins of MTO!gasoline
Zeolite
Mobil MOG-process
[180]
Tonen
1988 [2]
China Petro
1993 [4]
(c) Oligomerization and polymerization processes

1
i-C04 butenes ! codimer
High SiO2 mordenite
2
C03 ! polypropylene
TiO2MgO
Process
3
C03 ! C9 C12 , diesel
Catalyst
Company
Year, scale
Pentasil zeolite
Mossgas Refinery/Sudchemie
1992 [181], Mosselbay, South Africa
Cyclodimerization Zn
powder/Fe(NO)2Cl liquid
phase, slurry
Dehydrogenation Pd/MgO
gasphase, fixed bed
Cyclodimerization Cu-ZSM-5
zeolite
DSM Chiyoda, BEB-process
100 000 t/y [182], economically feasible [183]
DOW Chemicals
(p) [184]
C02 ! 1-butene; 1-hexene
Ni on Al2O3 (ALON)
C04 ! linear octenes
H3PO4/SiO2
Ni-heterogeneous Ziegler-type
catalyst
[185]
UOP Catpoly-process
LS/UOP Octol-process
HU
[186]
417
418
Table 14
Disproportionation processes
Process
Company
Year, scale
Zeolite
SiO2-modified ZSM-5
ZSM-5
UOP
Taiwan Styrene
Mobil MSTDP process
1988 [3]
1987, 3000 t/y [18,23]
1989 [12]
19881990 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
Zeolite
UOP
1988 [3]
(b) Hydrogenation processes

1
COH2!gasoline
Zeolite
BP
1990, (p) [5]
Acid catalyst
Shell Oil Mitsubishi,

Oil-Petronces
SMDS-process
1990, 12 000 BPD [189]

50 000 BPD in Bintulu, Malaysia
ZrO2Cr2O3
Zeolite
Mitsubishi Chem.
Crossfield-Unilever
1988, 2000 t/y [1,6,48,49]

In Unilever plant [190]
Zeolite
Crossfield-Unilever
In Unilever plant [190]
Al2(SO4)3/SiO2
Boron pentasil zeolite
Heterogeneous acid catalyst
Solid acid
SiO2Al2O3
Sumitomo
ANIC/SNAM/ENI
UOP
IFP
SNAM
1984, 50 000 t/y [1]

1984, 1987 [5,6]
1989 [3]
1985 (p) [5]
1987, 500 t/y [29], 1991, 8000 t/y [29], 1993,
62 000 t/y [29]
(a) Disproportionation processes

1
COH2!middle distillates
White oil hydrogenation

(c) MTBE ! i C04
1. MTBE ! i-C04 MeOH
Catalyst
Table 15
Miscellaneous processes
S.No.
Process
Catalyst
Company
Year, scale
Strong acid ion-exchangeReilly

resin
1988 t/y [3]
Ion-exchange resin
TiO2SiO2
TS-1 zeolite
Montedipe
Montedipe
Enichem
1994, 100 000 t/y [5]

1992 (p)
1994, 12 000 t/y [6]
Solid acid
Olin Eiazzi
1994 (p) [11]
CH3OH HCl ! CH3Cl
Al2O3
Tokuyama Soda
1978, 52 000 t/y [2]
CH3Cl ! gasoline
ZSM-5 type (Si/Al12)
BP-chemicals
1985 [5]
NO NH3 ! N2 H2O
Zeolite
Aluminosilicate zeolite
WVTiO2
Engelhard
Degussa AG/Lurgi/Lentjes
DeNOx-processes
Early 1980 [3], 510 units

1989 (p), 100 MW [5]
All over the world
Cs-zeolite
Merck
1996 [27,144]
n-alcohols H2S ! mercaptans

CH3OH H2S ! CH3SH, (CH3)2S
olefins H2S ! mercaptans
Commercialized [9193], 100030 000 t/y, e.g.

LACQ, France
Commercialized [199]
Zeolites, ion-exchange resinsElf-Atochem
Commercialized [9193], 100030 000 t/y, e.g.

LACQ, France
1997, 100 MIL lb/y [192], at Borger, TX
Philips Petroleum
419
Alkali-oxide on alumina,
Elf-Atochem
transition metal oxides
Alkali on g-Al2O3 IKT-31-1 Orgsintez-Volga Industrial
catalyst
Conglomerate
420
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
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. Therefore, 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, formation of oligomers and other impurities.
3.1.1.1. Production of ethylbenzene. The Mobil
Badger vapor phase process was first commercialized 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].
421
CDTECH, a partnership of ABB and Chemical

Research and Licensing, developed a new EB technology 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 ethylene and taking advantage of the reaction heat. Very
clean alkylation and transalkylation units provide EBproduction 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 capacity in Yokkaichi since 1995 [61]. The special proprietary zeolite catalyst exceeded the projected two
year catalyst life before regeneration. A second installation is for Petroquimica Argentina SA with a capacity 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 RD and
offers higher yield and product purity than the existing
commercial processes while eliminating problems
with corrosion, catalyst handling and disposal. Common zeolites such as REY, ZSM-4 or ZSM-5 among
others do not have the combination of activity, selectivity 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
sufciently stable to allow for a long operating cycle
before regeneration. The pilot plant results show a
100% propylene conversion and nearly 100% selectivity in the alkylation reactor over a period of 5000 h
of operation.
422
Ten licensees have chosen the Mobil/Raytheon

cumene technology using renery grade propane/propylene 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. Furthermore, 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 requirements 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 catalyst lifetime, at least.
CDTECHcumene technology [60] is identical to
its ethylbenzene technology. The most difcult 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 Orgetelko-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 CDTECHethylbenzene 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-DDMcumene 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-diisopropylbenzene 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 reactor. 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 introduced as DETAL process [73,74] jointly developed by
UOP and the CEPSA subsidiary Petresa, Petroquimica
Espanola SA. The reaction occurs under mild conditions 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 parafns are
dehydrogenated to olens used for the alkylation of
benzene. UOP also revealed the development of an
ethylene oligomerization process for producing the
needed linear a-olens [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 C3C5 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) process. This rst large scale solid acid alkylation unit
with a daily capacity of 57 000 B will be installed at
Yorktown renery, 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 disclosed a new renery alkylation process jointly developed with Kellog since 1994 [82]. Thereby, triic 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 renery 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 (CRL/Sheridan) runs a 10 BPD
423
pilot plant at Chevron's Port Arthur, Texas, since

1994. The heterogeneous Lewis acid SbF5/silica catalyst 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 1020 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 renery
alkylation. For example, ABB Lummus Global developed 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 Hydrocarbon Technologies developed a non-hazardous,
solid superacid catalyst to convert more than 80%
of low octane olen/isobutane feed into high octane,
multibranched parafns with 95% selectivity at relatively low temperature [90].
It is for certain that the solid acid catalyst technology 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 TopsoeKellog's FBA-process.
3.1.2. Nitto-process for methylamine production
A typical industrially successful example of utilizing 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 modied 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 conventional production, there is no excess of trimethylamine which has to be recycled. According to SRI
International's evaluation [39], the Nitto-process can
increase the capacity by about 3050% and reduce the
energy consumption by 4050% in existing installations (less distillation, no recycling) and can require
about 3040% less capital investment in new
plants. Thus, the product shape selectivity of the
modied mordenite and the possibility of adjusting
its acidity and pore opening and of poisoning the outer
424
surface enables to get a much better composition

of the produced mixture which satises commercial
requirements than in the case of the classical
production over alumina. This Nitto-process is commercially 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 tbutylamine (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 intermediates in this process provides evidently advantages
over the traditional HCN-based Ritter route to t-butylamine starting from isobutene and hydrogen cyanide
where the resulting formamide is saponied. 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
signicant 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/Al2O325)
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 production of adipic acid and caprolactam provides advantages 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 environmentally friendly alternative route. Other companies are also involved in this exciting new
development [6].
3.1.5. Production of thiocompounds
ELF-Atochem [9193] 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 mercaptans, suldes, disuldes, polysuldes, sulfoxides and
thio-acids. For manufacturing mercaptans, alcohols or
olens 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 mercaptans is generally carried out at 3004008C and
<10 bar in the presence of alkali oxides supported on
alumina or transition metal oxides and using an excess
of H2S (1.55 M) and keeping the residence time
535 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-propylmercaptan, 100% conversion of n-propanol and 80%
selectivity are obtained over K2WO4/Al2O3. Similar
results are achieved for the production of n-hexylmercaptan.
Secondary mercaptans are produced from iso-olens and H2S over solid acid catalysts such as ionexchange resins or zeolites. For example, cyclohexylmercaptan is produced from cyclohexene at 2108C,
16 bar, LHSV 0.09 h1 over ion-exchange resin with
9597% selectivity at 92% conversion of the olen.
The service time of the catalyst is more than 1500 h.
For manufacturing 2-butylmercaptan, butene as starting material is better than n-butanol. Using ionexchange resin as catalyst at 1008C and 15 bar,
70% 2-butylmercaptan and 30% butylsulde are
attained at 70% conversion.
For the production of tertiary mercaptans such as
tert-butylmercaptan, tert-octylmercaptan, tert-nonylmercaptan 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 LHSV0.3 h1
using an ion-exchange resin, 100% selectivity for tertdodecylmercaptan 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 zeolite 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 2,6xylenol, 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 olen 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, SiO2Al2O3 [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 SiO2Al2O3, but the benzene ring plane is
parallel to the catalyst surface in the case of an acidic
425
Fig. 1. Adsorbed states of phenol on MgO and SiO2Al2O3.
SiO2Al2O3 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 coefcients 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 olen 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-ethylidenebicyclo [2.2.1] hepta-2-ene (2), a compound for vulcanization 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 308C in the presence of the
superbase catalyst. Thus, after separation of the catalyst, no additional purication 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 2,3dimethylbutene-2, a valuable intermediate for the
production of synthetic pyrethroids. The reaction
reaches an equilibrium at 208C for 3 h, the ratio of
426
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 conversion 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 polyethylenenaphthalate (PEN) and polybutylenenaphthalate (PBN) and of liquid crystal polymers (LCPs). The
polyester PEN is manufactured by transesterication
of NDC with ethylene glycol. PEN has superior
mechanical, thermal and chemical resistance and barrier 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 RD-efforts have been expanded to
develop an economical and ecological route for manufacturing NDC. One interesting procedure (cf.
Table 5, No. 11) was developed by Amoco Chemical
[44,94]. Based on readily available o-xylene as starting 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 butadiene is around 65% and that based on o-xylene is
approximately 93% at 30% conversion of oxylene. 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 carried 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 9294% 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 1,5dimethylnaphthalene. 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
WHSV4.4 h1, 99% conversion and 99% selectivity 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 betazeolite having a low Si/Al ratio and low Na content
are employed in a slurry reactor at a temperature
range of 2403508C 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 isomerization.
Fifth, the oxidation of the 2,6-dimethylnaphthalene occurs via the well established Amoco's MidCentury 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 undergoes an esterification with methanol in the presence 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 cyclization to the desired 2,6-dimethylnaphthalene proceeds
from the alkylate. 81% selectivity based on 32% pxylene conversion and 69% based on 91% butene
conversion [96].
Other routes to provide NDC for PEN production
are based on:
427
Recovery of 2,6-dimethylnaphthalene from refinery 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-methylnaphthalene. 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-commercial 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. However, a shape selective effect is not expected in the
methylation of naphthalene because of the small
size difference of the isomers, particularly of 2,6and 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 reactions disclosed in many patents focus on Y-, USYand -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 produce methyl-2,6-naphthalenedicarboxylate (2,6NDC). 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 polyesters and polyamides:
The alkylation of biphenyl with propylene to form
4,4-diisopropylbiphenyl (DIPB) in the presence of
dealuminated mordenite having SiO2/Al2O3 molar
428
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 sufcient
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. Acidbase 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 selectivity and long life, provided that the acidbase 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 processes have been developed, as shown by double
asterisks in Tables 515. 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 dehydration of 1-cyclohexyl ethanol (cf. Table 7, No. 5), a
ZrO2 catalyst treated with NaOH shows a high conversion 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 acidbase bifunctional
nature of the catalyst is evidenced by the tness of the
distance between an acid site (Zr4) and a base site
(O2) of ZrO2NaOH calcined at 4008C with the
distance between a basic group (COH) 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 important chemicals which are used for the production of
Fig. 3. Synthesis of ethyleneimine (EI) from monoethanolamine

(MEA).
pharmaceuticals and various other amines and for the

production of amine type functional polymer for coatings of paper and textile. As shown in Fig. 3, ethyleneimine 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 acidbase catalysts is more advantageous than the liquid phase
process, provided that the formation of undesirable
by-products such as acetaldehyde, piperidine, ethylamine, acetonitrile, etc., is minimized. For the vapor
phase process, a new efcient catalyst (SiBaCsP
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 h1
[6,7]. The acid and base strengths of the catalyst are
weaker than HO4.8 and H9.4, respectively, and
the reaction is considered to proceed by an acidbase
bifunctional mechanism [46,47]. A plant with a capacity of 2000 t/y is on stream since 1990.
3.3.3. Mitsubishi-process for the production
of aromatic aldehydes
Another example of the acidbase 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
429
4. Future trends
Fig. 4. Acidbase bifunctional mechanism for hydrogenation of

benzoic acid to benzaldehyde over a zirconia catalyst (Zr4: acid
site; O2: base site).
mainly by a halogenation method. However, the

method has disadvantages such as poor yield and
undesirable by-products formation and environmental
inuence. A novel process for synthesizing aromatic
aldehydes by the direct hydrogenation of the corresponding 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 acidbase bifunctional mechanism as
shown in Fig. 4 [49]. Since 1998, Mitsubishi Chemicals has on stream a multi-purpose plant having
2000 t/y capacity for the production of various aromatic aldehydes.
The cost saving by the new process is said to be
about 2030% compared with the conventional route.
Solid acidbase 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 esterication of Table 13a, No. 4 in Table 15) may be
regarded as bifunctional catalysis, though there is
no evidence for acidbase bifunctional mechanism.
Even in the alkylation of phenol with methanol over a
typical base catalyst, MgO, the catalytic function of
MgO is acidbase bifunctional as mentioned in Section 3.2.1. Thus, it is not easy to distinguish between
base- or acid-catalysis and acidbase bifunctional
catalysis. Typical acidbase bifunctional catalysts
are weakly acidic and weakly basic ZrO2 and ZrO2
doped with a small amount of NaOH, Cr2O3, etc. (No.
5, 7, 1315 in Table 7, No. 3 in hydrogenation of
Table 14(b)), and CsBaPO/SiO2 (No. 4 in
Table 7). These almost neutral catalysts which are
similar to some enzymes from a view-point of weak
acidbase 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 deactivation due to coking, they are promising for further
industrial application. Attempt to use weak acidbase
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 acidbase catalysts mentioned above, solid superacids are also one of the
interesting catalysts. More than 200 papers and patents
on solid superacids (mainly, SO2
4 =ZrO2 and its modied ones) have been reported since 1990. Nevertheless, not much industrial processes have been
developed yet mainly due to catalyst deactivation
or coking) or
(leaching or decomposition of SO2
4
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, SO2
4 =ZrO2
catalyst in the presence of hydrogen. Although not
430
much work has been made in the application of

superacid catalysts to organic synthesis, the application will be promising if reactions are carried out at
low temperatures or in liquid phase where catalyst
deactivation and by-products formation can be minimized.
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 mixture of NaXNa2O or CaAK2CO3, rare earth metal/
Al2O3, hybrid solid base (nitrogen compound combined with MCM-41), etc., have been reported to show
pronounced catalytic performance compared with
already known base catalysts [50] for some basecatalyzed reactions [51,52]. Thus, the industrial application 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 zeolites seems to result in the contribution. Zeolites
modied by various ways and methods will make
further contribution to their industrial application.
Mesoporous materials such as SiO2Al2O3, SiO2
TiO2, SiO2, ZrO2, Nb2O5, etc., which are shape selective 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 acidbase
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, signicant
fundamental research on solid acidbase 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 acidbase bifunctional 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
acidbase catalysis provides the fact that a large
number of various solid acidbase catalysts are used
for more than 100 industrial processes. Zeolites, oxides, complex oxides, ion-exchange resins, and phosphates 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 signicance of solid
acidbase bifunctional catalysis and solid base catalysis has been pointed out by explaining several
examples of the industrial processes. On the basis
of the survey, future prospects of solid acidbase
catalysis are speculated.
This survey is not sufcient 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
MIL lb
BIL lb
B (bbl)
BPD
BPSD
BPCD
psig
pound
million pounds
billion pounds
barrel
barrels per day
barrels per steam day
barrels per calendar day
pound per square inch gauge (0.068 atm)
bar
MM
MMM
MW
0.987 atm
million
billion
megawatt
Acknowledgements
We gratefully acknowledge professors and doctors
(cf. [23,2431]) 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 information about processes carried out in their companies.
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Industrial Application of Solid Acid Base Catalysts

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Applied Catalysis A: General 181 (1999) 399434

Industrial application of solid acidbase catalysts

corrosive and environmentally benign, presenting

K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

component of various catalysts. Since, however, the

immobilized enzymes, sulfates plus carbonates and

K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

Oxides, complex oxides

Sulfate and carbonate

2.3. Detailed processes and catalysts

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

H-ZSM-5 vapor phase

1980, 1 MMM lb/y [3,12], 1 plant, Hoechst

Diluted mixture of propylene and

High silica zeolite vapor phase

1992, 10 000 t/y [4], 1 plant, China Petrochemical,

H-ZSM-5 liquid phase

MobilRaytheon EB-Max process

EBZ 500 zeolite liquid phase

Acidic zeolite liquid phase

Solid phosphoric acid (SPA)

Most of the cumene producer

High silica zeolite

Ten licenses [55,62,65]

DOW/Kellog 3-DDM technology

1994, 200 000 t/y [68] at Terneuzen, Belgium

K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

Dilute ethylene sourced from

1992 [69], at Terneuzen, Belgium

UOP Q-Max technology

1996, 145 MIL lb/y [70], BTL Speciality Resins

Solid acid liquid phase

1992 (p) [8,103]

1989, (p) [104,105]

Pentasil zeolite Encilite 2

Hinduston Polymers Albene

1989 [108], at Visakhapatnam, India

Pore size regulated ZSM-5

1997, 1000 t/y [21,30]

K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

1970, several units in commercial scale

1984, 5000 t/y o-cresol [1], 10 000 t/y 2,6-xylenol

Na/K2CO3 basic catalyst

AMOCO Chemical, Teijin

1995, 45 000 t/y [24], at Decatur, Alabama, (p) [95]

1992 [7], demonstration plant

Haldor Topsoe/Kellog FBA-process

1994, 0.5 BPD [13,82]

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

K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

1990, several units [3]

High silica zeolite

1990, 2000 t/y [2,6]

>35 units licensed [118]

SiO2 modified Al2O3

1991, pilot [5]

1994 (p) [12,127]

K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

1991, 2700 BPD [130,131]

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

Cosmo Oil [13], Mitsubishi Heavy Ind.

1986, 2000 t/y [2,6]

1990, 30 000 t/y [3,6]