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

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

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 MTBE3i-CH4 Others Total 18 15 13 10 9 8 7 7 6 5 4 4 3 2 1 15 127

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).

 K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434 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 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 SO2 aZrO2 , Fe, Mn, SO2 aZrO2 4 4 Metallosilicate Nb2O5nH2O Hydrotalcite Others 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 Ion-exchange resins Solid acids (not specified) Clays Kaolin, pillared clay, bentonite, montmorillonite Immobilized enzymes Asparatase, nitrilase, amylase Sulfate and carbonate Al2(SO4)3/SiO2, CF3SO3H/SiO2, Na/K2CO3 Sulfonated polysiloxanes 74 31 28 7 4 2 2 54 11 9 7 6 4 3 3 2 2 2 1 1 3 16 7 4 2 1 1 1 16 7 4 3 3 3

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 Total 103 10 14 127

``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/

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

402

Table 5 Alkylation processes S.No. Process 1 Catalyst H-ZSM-5 vapor phase Company MobilBadger Year, scale 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

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

Dilute ethylene sourced from FCC off-gas or steam cracker

High silica zeolite vapor phase 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 2 Solid phosphoric acid (SPA)

ABB Lummus/Unocal/UOP Most of the cumene producer

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

High silica zeolite

MobilBadger/Raytheon

-zeolite Acid zeolite catalytic distillation Mordenite Y-zeolite Acid zeolite catalytic distillation Three-dimensional dealuminated mordenite

Enichem CDTECH DOW Chemicals Lummus CDTECH Catstill-technology DOW/Kellog 3-DDM technology

Diluted mixture of propylene and ethylene sourced from FCC off-gas

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

Table 5 (Continued ) S.No. Process Transalkylation reactor diisopropylbenzenebenzene Catalyst Dealuminated mordenite Company DOW/Kellog UOP Q-Max technology Year, scale 1992 [69], at Terneuzen, Belgium 1996, 145 MIL lb/y [70], BTL Speciality Resins at Blue Island, IL 45 000 t/y [71], Chevron Chemicals at Port Arthur, TX K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

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 Catalytica Kureha/NKK/Chiyoda 1992 (p) [8,103] 1994, 1000 t/y [24,101], at Fukuyama, Japan

H-mordenite Shape selective zeolite combined with separation

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

Table 5 (Continued ) S.No. 9 Process Catalyst MgO Company General Electric BASF AG Year, scale 1970, several units in commercial scale licensed [32] 1985, at Ludwigshafen, Germany K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

10

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] 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]

BF3/g-Al2O3 SbF5/SiO2 Sulfated ZrO2 Solid acid (alkylene catalyst) fluidized bed

Catalytica/Conoco/Neste Oy Chevron/CDTECH Orient Catalyst UOP

Table 6 Isomerization processes S.No. 1 Process Xylene isomerization3p-xylene Catalyst H-ZSM-5 Company Mobil Oil Year, Scale 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 1990, 2000 t/y [2,6]

C8 aromatic mixture3p-xylene

Pentasil zeolite Acid zeolite 1-210 Zeolite

Xyclofining-process UOP ISOMAR technology JFP/Chevron ELUXYL-process Toray

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

High silica zeolite

n-C4 3 i-C4

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 IFP Shell/Layondell/CDTECH/Zeolyst SNAM Nippon Petrochemical/Nippon Oil Mobil/BP/Kellog ISOFIN-process Mobil/Raytheon MOI-process Lyondell Petrochemical, ISOM Plus-process

>35 units licensed [118] 1992, 30 000 BPD [119], Enterprice Products [120] [121] [122] [123] [124] 1991, pilot [5] 1994, 40 000 t/y [125] 1997 (d) [37] 1992, 9000 t/y [126], at Kawasaki, Japan 1994 (p) [12,127] Pilot 4 BPD [128], 100 BPD 1992, 3000 BPSD [129], at Channelview

n-C4 H 3 i-C4 H

SiO2 modified Al2O3 Ferrierite B2O3/Al2O3 Acid catalyst H-ZSM-5 H-ZSM-5 fluidized bed Zeolite

C4 H Y C5 H 3 i-C4 H Y i-C5 H

405

406

Table 6 (Continued ) S.No. Process Catalyst Zeolite Zeolite Zeolite Zeolite 6 7 Light naphtha isomerization Heavy olefins isomerization Zeolite LPI-100TM Acid solid H ion-exchange resin Company Phillips Petrochemical/Texas Olefins SKIP-process UOP, PENTESOM-process, BUTESOM-process PEMEX JFP ISO-4-process UOP PAR-ISOM-process Shell Exxon Year, Scale 1991, 2700 BPD [130,131] 1991 [133], 1992 1994, 27 000 BPD [132], at Minatitlan, Mexico, 1994, 2700 BPD [132], at Cedercyta, Mexico 1984, pilot [130], 160 000 t/y Cosmo Oil [13], Mitsubishi Heavy Ind. 850 000 t/y part of SHOP-process [135,136] 1986 [3]

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

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]

Table 6 (Continued ) S.No. 13 Process Catalyst Pentasil zeolite Company BASF AG Year, Scale 1982, demonstrated [5,138,139] K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

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]

407

408

Table 7 Dehydration and condensation processes S.No. 1 2 3 Process EtOH 3 C2 H4 t-BuOH 3H2 O i-CH4
H2 O

Catalyst Al2O3 Sulfonic acid resin Ion exchange resin

Company Petrobrass UOP DavyMcKee

Year, scale 1980 [19,31] 1981 [3] 1985, 20 000 t/y [5] K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

4 5

CsBaPO/SiO2 ZrO2NaOH

Nippon Shokubai Sumitomo

1991, 2000 t/y [1,6,46,47] 1986 [33,34]

Nb2O5nH2O

Sumitomo

1987 [35,36]

ZrO2KOH

Koei Chemical

1992, (p) [25]

H3PO4aniline salt/SiO2

Nippon Shokubai

1995, 6000 t/y [17]

Table 7 (Continued ) S.No. 9 Process Catalyst Mercapto-functionalized sulfonated polysiloxane Ion-exchange resin Ion-exchange resin Ion-exchange resin Company Degussa AG Chiyoda Bayer AG DOW/Kellog Year, scale 1996, (p) [26] 1994, (p) [24] Commercialized [142] Commercialized [143], Texas and Germany

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

10

Shape selective zeolite, e.g. mordenite fluidized bed Acid ion-exchange resin, e.g. Amberlyst 15 Strongly acidic inorganic and organic ion-exchange resin, e.g. Deloxan-ASP

DSM-Stamicarbon

1997, (p) [105], at Geleen, Netherlands

11 12

Degussa AG Degussa AG

[144] [145,146,150]

13 14 15 16

** Isobutyraldehyde3diisopropyl ketone ** Isobutanol3diisopropyl ketone ** n-Butanoln-butyraldehyde 3di-n-propyl ketone

ZrO2 ZrO2, ZrO2K2O ZrO2MgO

Chisso Chisso Chisso Air Products

1974, 2000 t/y [22] 1974, 2000 t/y [22] 1974, 2000 t/y [22] 1987 [3,6]

17

Pt/H-ion exchange resins trickle bed reactor. H2CO aqueous 3 trioxane Pentasil zeolite

Bayer AG Deutsche Texaco Asahi Chemical

[147] [148] [149] 409

18

410

Table 8 Amination processes S.No. 1 Process 2MeOHNH33Me2NH, MeNH2 Catalyst Modified ion-exchange mordenite RHO-ZK5 zeolite Chabasite Cu, Ni/SiO2Al2O3 Company Nitto Du Pont Air Products Kao Year, scale 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] 1989 [1]

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

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]

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

Table 8 (Continued ) S.No. 7 Modified SiO2Al2O3modified ZSM-5 8 Modified SiO2Al2O3modified ZSM-5 Pentasil zeolite fixed bed H-ZSM-5 fluidized bed Al2O3HF fluidized bed 9 Pentasil zeolite Koei Chem. 1990, 9000 t/y [25] Process Catalyst Company Year, scale

Koei Chem. Armor polymer Nepera Degussa AG BASF AG

1990, 9000 t/y [25] India [6] USA [6] Germany [6] 1986, 6000 t/y [5,6,138], Antwerp, Belgium, 1994, 8000 t/y, Antwerp, Belgium

411

412

Table 9 Cracking processes S.No. 1 Process FCC-processes Catalyst e.g. SiO2Al2O3/US-Y Partially dealuminated Y type zeolite in SiO2Al2O3 Novel Y/SiO2Al2O3 Ultrastable Y containing RE oxides and SiO2 MgOAl2O3-zeolite Magna-Cat Calcined kaolin Ultrastable Y treated with RE dispersed in SiO2Al2O3, cogel/kaolin matrix Pentasil zeolite Ultrastable US-Y zeolite Company Cat. & Chem. UOP Cosmo China Petro Year, scale 1985, a lot of units [1] 1986, 1 MM lb/y [3] 1990 [2] 1993 [4] K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

Heavy oil

Nippon Oil Valero/Kellog Engelhard/Ashland Ashland/Davison

1990 [2] Corpus Christi, TX [152] 1993, 55 000 BPD [3] 1983, 40 000 BPD [3]

3 4

Heavy fractions Cracking above 6508F

5 6

Deep cracking of vacuum gas oil Middle and light distillate from cracking feed Middle distillate catalytic dewaxing Selective cracking of straight chain paraffins and olefins to produce C3 H and C4 H

China Petro Total/IFP

1990, 60 000 t/y [4], 1993, 400 000 t/y 1982, 60 000 t/y [4]

7 8

Proprietary H-ZSM-5

China Petro Mobil

1984, 20 000 t/y [4] 1986 [3]

Table 10 Etherification processes S.No. 1 Process i-CH4 MeOH 3 MTBE Catalyst Ion-exchange resin Company IFP ARCO SNAM/Ecofuel Chevron/Neste Oy (Alberta Envirofuels) Sabic/Shell (SADAT) Lummus Crest CDTECH 2 3 4 i-CH4 MeOH 3 MTBE isooctane i-CH4 EtOH 3 ETBE i-CH5 MeOH 3 TAME Ion-exchange resin Ion-exchange resin Ion-exchange resin SNAM SNAM/Ecofuel IFP/ELF ANIC/SNAM Exxon Neste Oy/Bechtel DavyMcKee Erdoelchemie/Lurgi Mobil Ube Year, scale 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] K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434 1996, 700 000 t/y [155] 1992, 12 500 BPD [156], at Deer Park, Texas Licensing [157] 1996 [29] 1993 [38] 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 1980 (p) [5] 1985, 14 000 BPD [3] 1978 [2]

5 6 7

Olefins MeOH 3 MTBE/TAME 2MeOH 3 MeOMeH2O

Ion-exchange resin Al2O3 AlBPO

8 9

Pillared clay or smectic (bentonite, montmorillonite) Hydrotalcite Mg6Al2O8(OH)2, ROHfatty alcohols, nnarrow molecular weight range Ba or Ca salt/phosphate LaPO4

BP Henkel UCC Shell

(p) [5] 1994 (p) [163] 1985, 60 MMIL lb/y [3] 1995, 500 000 t/y [164]

10

413

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

414

Table 11 Catalyst (a) Aromatization processes 1 CH3 Y CH4 3 alkylaromatics paraffins 2 C3, C43aromatics, particular p-xylenes LPE or refinery light end paraffins and olefins LPG (mainly C3, C4)3BTX LPG or light naphta3aromatics C4, C5 raffinate or C4, C5 fraction of FCC3aromatics C6, C7, naphthanes3aromatics C6, C73preferably benzene ZSM-5 Ga-modified ZSM-5, Zn-modified ZSM-5 Company Mobil BPUOP Cyclar-process Year, scale [3] 1990, 5000 t/y [5], at Grangemouth, Scotland 1995 [165], Ibn Rushd at Yanbu, Saudi Arabia

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3 4 5

Zeolitepromoter Metallosilicate Metal oxide modified ZSM-5

UOP Mitsubishi Oil Chiyoda Asahi Chem. Sanyo Petrochem., ALPHA-process Platforming, Rheniforming, e.g. Chevron UOP

1983 [3] 1991, 200 BPD [22] 1993, 40 000 t/y [22,168170], at Mizushima, Japan

Pt-zeolites Al2O3SiO2, PtRe zeolites Al2O3SiO2

>500 units [171] e.g. 1997, 230 000 t/y [172], CEPSA at Algeciras, Spain 1992, 9 units of 34 [174] 1992/1993, 2 units [173] 1982 [1] 1990 [3]

Naphtha3aromatics

R-132 catalyst Pt L-zeolite Fe-VIb/zeolite Amorphous SiO2Al2O3 with zeolite

UOP LLR-platforming Chevron Chem. AROMAX-process Idemitsu

(b) Hydrocracking process 1 Fixed-bed residual hydrocracking 2 Hydrocracking of heavy oil distillates into gasoline and middle distillates Hydrocracking of gas oils WaxH23gasoline Lub dewaxing Wax oilsH23lower molecular wt. hydrocarbons

ZSM-5

Mobil

[3]

ZSM-5 Zeolite

Mobil BASF

1981, 150015 000 BPD [3] [3]

Table 12 Hydration processes S.No. 1 2 Process C=CH2O 3 EtOH i-C4' 3 t-BuOH Catalyst Solid phosphoric acid Ion-exchange resin Sulfonic acid resin Novel highly siliceous H-ZSM-5, <1 mm Acidbasic catalyst based on TiO2/H3PO4 Company Shell, BP, many others Mitsui Petrochem. UOP/huels Asahi Chem. [1] 1981 [3] 1990, 80 000 t/y [1,6,41,42] Year, scale K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434

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]

415

416

Table 13 Esterification processes Process (a) Esterification processes 1 Ion-exchange resin DavyMcKee 1985, 20 000 t/y [178], 1,4-butanediol-production K. Tanabe, W.F. Holderich / Applied Catalysis A: General 181 (1999) 399434 Catalyst Company Year, scale

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/DME3gasoline 2 3 4 5 MeOH 3 CH3 CH4 some gasoline MeOH 3 CH2 CH3 Olefins of MTO3jet fuel, diesel Olefins of MTO3gasoline

ZSM-5 Modified ZSM-5 SAPO-34 in FCC-catalyst matrix Zeolite Zeolite

Mobil MTG-process Mobil MTO-process UOP Mobil MOGD-process Mobil MOG-process Tonen China Petro

1985, 14 000 BPD [3], New Zealand 1985, 160 BPD [3], UK-Wesseling, Germany 1988 [3] [179] [180] 1988 [2] 1993 [4]

(c) Oligomerization and polymerization processes 1 i-CH4 butenes 3 codimer High SiO2 mordenite 2 CH3 3 polypropylene TiO2MgO

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Table 13 (Continued ) Process 3 4 CH3 3 C9 C12 , diesel Catalyst Pentasil zeolite Cyclodimerization Zn powder/Fe(NO)2Cl liquid phase, slurry Dehydrogenation Pd/MgO gasphase, fixed bed Cyclodimerization Cu-ZSM-5 zeolite CH2 3 1-buteneY 1-hexene CH4 3 linear octenes Ni on Al2O3 (ALON) H3PO4/SiO2 Ni-heterogeneous Ziegler-type catalyst UOP Catpoly-process HULS/UOP Octol-process Company Mossgas Refinery/Sudchemie DSM Chiyoda, BEB-process Year, scale 1992 [181], Mosselbay, South Africa 100 000 t/y [182], economically feasible [183]

DOW Chemicals

(p) [184]

5 6

[185] [186]

417

418

Table 14 Disproportionation processes Process (a) Disproportionation processes 1 Catalyst Zeolite SiO2-modified ZSM-5 ZSM-5 Company UOP Taiwan Styrene Mobil MSTDP process Year, scale 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 1988 [3]

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Zeolite

UOP

(b) Hydrogenation processes 1 COH23gasoline 2 COH23middle distillates

Zeolite Acid catalyst

BP Shell Oil Mitsubishi, Oil-Petronces SMDS-process Mitsubishi Chem. Crossfield-Unilever

1990, (p) [5] 1990, 12 000 BPD [189] 50 000 BPD in Bintulu, Malaysia 1988, 2000 t/y [1,6,48,49] In Unilever plant [190]

ZrO2Cr2O3 Zeolite

White oil hydrogenation (c) MTBE 3 i CH4 1. MTBE 3 i-CH4 MeOH

Zeolite Al2(SO4)3/SiO2 Boron pentasil zeolite Heterogeneous acid catalyst Solid acid SiO2Al2O3

Crossfield-Unilever Sumitomo ANIC/SNAM/ENI UOP IFP SNAM

In Unilever plant [190] 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]

Table 15 Miscellaneous processes S.No. 1 Process Catalyst Company Year, scale 1988 t/y [3]

Strong acid ion-exchangeReilly resin

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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]

4 5 6

CH3OH HCl 3 CH3Cl CH3Cl 3 gasoline NO NH3 3 N2 H2O

Al2O3 ZSM-5 type (Si/Al12) Zeolite Aluminosilicate zeolite WVTiO2 Cs-zeolite

Tokuyama Soda BP-chemicals Engelhard Degussa AG/Lurgi/Lentjes DeNOx-processes Merck

1978, 52 000 t/y [2] 1985 [5] Early 1980 [3], 510 units 1989 (p), 100 MW [5] All over the world 1996 [27,144]

n-alcohols H2S 3 mercaptans CH3OH H2S 3 CH3SH, (CH3)2S

Alkali-oxide on alumina, Elf-Atochem transition metal oxides Alkali on g-Al2O3 IKT-31-1 Orgsintez-Volga Industrial catalyst Conglomerate Zeolites, ion-exchange resinsElf-Atochem Philips Petroleum

Commercialized [9193], 100030 000 t/y, e.g. LACQ, France Commercialized [199] Commercialized [9193], 100030 000 t/y, e.g. LACQ, France 1997, 100 MIL lb/y [192], at Borger, TX

olefins H2S 3 mercaptans

419

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Table 15 (Continued ) S.No. 10 11 12 13 14 15 Process Catalyst Solid acid Cu-catalyst Fe-ZSM-5 Pt/Zn-ZSM-5 FePO4 Immobilized amylase H-beta-zeolite Company DSM Monsanto-Boreskov Institut BP/Mobil TIT Kirin Brewery/Nippon Shokuhin/ Yokokawa Elect./Chiyoda Corp. Rhone-Poulenc Year, scale (p) [193] Pilot plant [197], 1999 commerical plant [198] Pilot [195] [196] 1988 [2] 1996, multi tons [16,194], at Lyon, France

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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. 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].

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.

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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

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needed linear -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

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

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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.

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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

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

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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.)

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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:

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

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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

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4. Future trends 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 aZrO2 and its mod4 ied ones) have been reported since 1990. Nevertheless, not much industrial processes have been developed yet mainly due to catalyst deactivation (leaching or decomposition of SO2 or coking) or 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 aZrO2 4 catalyst in the presence of hydrogen. Although not

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.

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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)

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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. References
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