Lloyd L. Handbook of Industrial Catalysts

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258 Chapter 6

Butane can also be isomerized with platinum on chlorided alumina cata-

lysts, under the same conditions, to produce isobutane for use as feedstock in

alkylation processes and more recently for the production of MTBE .

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5. K. G, Mackenzie, Refinery Nat Gasoline Mfr, (Nov 1939) 494.

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Book, Nijgh and Van Ditmar NV, The Hague, 1950, p. 83.

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Refinery Catalysts 259

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Turner, and B. M. Moyse, Oil Gas J., (May 17 1999) 41.

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Rhone, France; Tricat Inc, MacAlester, Oklahoma, 1995–1996.

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W. Ward, Fuel Proc. Tech. 35 (1993) 55; J. W. Ward, Prep. Catalysts III,

Ed. by Poncelet, Elsevier, Amsterdam, 1983, p. 587.

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(1968); 3434966 (1969); R. L. Jacobson, H. E. Kluksdahl, C. S. McCoy and

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Catal. 56 (1979) 1.

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3745112 (1973).

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Antonio, AM-93-10 (1993).

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46. D. P. Burke, Catalysts, Chem. Week, (Nov 1, 1972) 27.

47. J. P. Boitiaux, J. M. Deves, B. Didillon, and C. R. Marcilly, Catalytic Naph-

tha Reforming, Ed. by G. J. Antos, A. M. Aitani, and J. M. Parera, Dekker,

New York, 1995, p. 79.

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260 Chapter 6

49. H. E. Robson, G. P. Hammer and W. F. Arey, Molecular Sieve Zeolites II,

in Advances in Chemistry Series, No. 102, Ed. by E. M. Flanigen and L. B.

Sand, 1971, p. 417.

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Antos, A. M. Aitani, and J. M. Parera, Dekker, New York, 1995, p. 492.

54. N. Y. Chen, J. Garwood, and F. G. Dyer, Shape Selective Cracking in In-

dustrial Applications, Dekker, New York, 1989.

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Ed. by J. A. Rabo, 1976, p. 714.

PETROCHEMICAL CATALYSTS

7.1. THE DEVELOPMENT OF PETROCHEMICALS

Organic chemical compounds have been produced on an industrial scale for over

a century. In the early days, the source of carbon was coal, and many of the

compounds were produced via the intermediate manufacture of acetylene and

benzene. The development of crude oil refining and the use of new processes to

satisfy the increase in demand for gasoline has provided refinery off-gases and

other hydrocarbons that are now used as the main source of industrial organic

compounds, and the term petrochemicals arose to describe this evolution of the

chemical industry.

For example, in the early years following the development of the Haber-

Bosch process for the manufacture of ammonia, both ammonia and methanol

were manufactured from synthesis gas derived from coal. This was eventually

replaced by a naphtha-like fraction from the refining of crude oil, and much of

the World capacity for methanol and ammonia is now derived from natural gas.

In general, refinery feeds have now replaced coal for the production of synthesis

gas almost entirely, and both ammonia and methanol can rightly be regarded as

petrochemicals. Such is the scale of modern refining, together with the increased

demand for petrochemical products such as plastics, fibers, and rubber, petro-

chemical complexes are now frequently closely linked to refineries. For exam-

ple, of the 666 million tonnes of naphtha produced in 1997, up to 40% were

used in the steam crackers and aromatics units that provided feeds for petro-

chemical production. Many chemicals are made using continuously operating

refinery-like processes, often with several reaction steps in sequence, and the

L. Lloyd, Handbook of Industrial Catalysts, Fundamental and Applied Catalysis,

DOI 10.1007/978-0-387-49962-8_7, © Springer Science+Business Media, LLC 2011

261

262 Chapter 7

products must be produced to tight chemical specifications. Some of the oxida-

tion, hydrogenation/dehydrogenation reactions developed more than 80 years

ago are still being used, although efficiency and selectivity have been greatly

improved by the use of better catalysts and equipment.

About 1914 the volume of gasoline sold exceeded the demand for kerosene.

Consequently thermal cracking processes were introduced, since these resulted

in an increase in the gasoline yield from crude oil. However, cracking produced

large volumes of low-molecular-weight gases, which at first were used as fuel.

The almost worthless gas did, however, contain significant volumes of olefins,

which were eventually to become the aliphatic building blocks used in produc-

ing high-octane gasoline and, later, petrochemicals.

The Mellon Institute in Pittsburgh was founded in 1911 by a group includ-

ing the Mellon brothers, who were the main shareholders in the Gulf Oil Corpo-

ration. George Curme of the Institute worked with both Prest-O-Lite, which

supplied acetylene lamps, and Union Carbide, the largest supplier of calcium

carbide, on alternative ways to produce acetylene and commercially useful or-

ganic derivatives of both acetylene and ethylene. In a series of experiments, it

was demonstrated that ethylene produced by cracking had potential to be a

cheaper chemical intermediate than acetylene.

Union Carbide and Linde then began to develop the production of ethylene

from the ethane present in natural gas. This led to the purchase of a small gaso-

line plant at Clendenin, West Virginia, where ethane-rich natural gas was avail-

able from the Kanawha Valley. An ethane-cracking unit began operation in 1921

and provided ethylene as well as liquefied petroleum gas that was sold for do-

mestic use.

Following further development work, ethylene glycol became the first pet-

rochemical to be produced at the ethylene plant in South Charleston that began

operating about 1925. Glycol antifreeze was widely used in automobile engines

by 1927. Numerous other organic syntheses were being developed at the same

time for commercial production in the small petrochemical complex. By 1926,

as many as six ethylene and two propylene derivatives were available, and by

1934 the number had increased to 35-ethylene and 15-propylene products.

During the same period Universal Oil Products developed olefin polymeri-

zation and hydrogenation processes and the Shell Chemical Company became

interested in olefin chemistry and petrochemicals. Shell opened its Emeryville,

California, research center in 1928 and developed methods for the production of

alcohols, ketones, and esters from propylene and butylenes, as well as synthetic

chlorohydrins, glycols, and glycerol. Many of these petroleum chemicals were

produced in Martinez, California, from 1933 and the use of petrochemical cata-

lysts became established.

By 1940, after the start of World War II, the production of petroleum chem-

icals, as they were still known, and the use of catalysts were common practice in

the United States. Subsequently, the 1930s became known as the miracle dec-

Petrochemical Catalysts 263

ade, because the catalysts petrochemical processes that had been introduced

began to provide artificial fibers, polymers, and synthetic rubbers. The use and

development of these processes and the associated technology were accelerated

as demand caused by the war required plants to be built to produce large quanti-

ties of polyvinyl chloride, butadiene–styrene rubber, polyethylene, and nylon.

Until 1945, most developments in the petrochemical industry arose in the

United States, where refinery processes were advanced and feedstocks were

readily available. There were no similar refineries in Europe and chemical pro-

duction was still firmly based on coal. Petrochemicals could not be produced in

Europe until the late 1950s, when the first large refineries were built and cheap

naphtha was used in steam crackers and for ammonia production. Estimates of

petrochemical production in both the United States and Europe from 1935 to

1965 demonstrate the difference as shown in Table 7.1.

More than 90% of today’s petrochemicals are produced from refinery prod-

ucts. Most are based on the use of C

–C

olefins and aromatics from hydrocar-

bon steam cracking units, which are even more closely linked to refineries. In

North America, the feedstock for steam cracker units have generally been

ethane, propane, or LPG. As a result, most of the propylene and aromatics have

been provided by FCC units and catalytic reformers. In many other parts of the

world where naphtha feed has been more readily available, supplies of propyl-

ene and aromatics have been produced directly by steam cracking. When neces-

sary, the catalytic dehydrogenation of paraffins or dealkylation of toluene can

balance the supply of olefins or benzene. In Table 7.2 some of the catalytic pro-

cesses that convert olefins and benzene from a steam cracker into basic petro-

chemicals for the modern chemical industry are shown.

Before 1965, the production of petrochemicals as a new branch of the

chemical industry does not seem to have been widely mentioned in textbooks

and little general information was available.

Industry, however, well aware of

the potential demand for the new products, was developing large new plants to

take advantage of the economies possible from large-scale operation. ICI, for

example, opened its Petrochemical and Polymer Laboratory⎯later to become its

Corporate Laboratory⎯about this time. Since then many new processes and

TABLE 7.1. Petroleum Chemicals Production 1935–1965 (Million Tonnes)

United States Europe

1935 0.5 –

1940 1.1 –

1945 4.5 –

1950 7.2 < 0.1

1955 14.4 0.4

1960 24.7 1.7

1965 42.3 ~ 5

264 Chapter 7

petrochemical products have been introduced. Generally the processes have used

catalysts and include development of the hydrogenation and oxidation proce-

dures first used in the 1920s and 1930s. Many new reactions and syntheses have

now evolved and the range of catalysts has undergone continuous improvement.

The industry has moved a long way from the time when DuPont claimed it had

made a fiber—Nylon—from coal-air-water! Fully detailed information is not

usually provided, but the importance of petrochemical processes has now been

recognized and is described in many reviews and books.

Annual meetings and

conferences are organized by chemical societies, chemical engineering societies

and catalyst companies to review the latest processes, catalyst science and cata-

lyst developments.

TABLE 7.2. Petrochemicals From Naphtha Steam Cracking.

Feed Primary products Main secondary derivatives

Fuel gas 270,000 tonnes/year (16.9%) Fuel, ammonia/methanol

Propane cracking, etc.

Ethylene 500,000 tonnes/year (31.2%) Polyethylene (58%)

Ethylene oxide (10%)

Styrene (7%)

Vinyl chloride (15%)

Ethanol (2%)

Naphtha 1.6 million

tes.year−1

Propylene 250,000 tonnes/year (15.6%) Polypropylene (50%)

Acrylonitrile (11%)

Cumene (7%)

Oxoalcohols (10%)

Propylene oxide (10%)

Isopropylalcohol (4%)

Butenes 40,000 tonnes/year (2.5%)

Polymers

MTBE

Butadiene 50,000 tonnes/year Rubber

Pyrolysis gasoline 450,000 tonnes/year

(28%)

Benzene/styrene (46%)

Cyclohexane (13%)

Toluene

Benzene

Solvents

Xylenes-polyester

Gasoline

Fuel oil 40,000 tonnes/year (2.5%)

About 80% of petrochemicals are produced with the oleﬁns and aromatics from steam crackers. A

typical 500,000 tes/year

ethylene plant would crack up to 1.6 million tes/year

of naphtha, giving the

fractions shown. Uses of individual products are listed.

Petrochemical Catalysts 265

7.1.1. Isopropyl Alcohol

Isopropanol was one of the first petrochemicals to be produced on a large scale

and is still widely used as a solvent and chemical intermediate. Originally, pro-

duction was by direct catalytic hydration of propylene in the liquid phase:

+ H

O → C

OH (7.1)

Concentrated 70–98% sulfuric acid was used as the catalyst at a low pressure

and temperature. The reaction mechanism involved the sulfate monoester inter-

mediate, which was then hydrolyzed to isopropanol. The process is similar to the

production of ethanol from ethylene, although the hydration step becomes easier

as the carbon number of the olefin increases. The acid strength required for ef-

fective operation decreases from more than 90% for ethylene hydration to about

70% for propylene hydration.

The homogeneous sulfuric acid process has since been replaced by phos-

phoric acid–impregnated silica and tungstic oxide catalysts. The tungstic acid

catalyst operated at pressures as high as 250 atm and at 250

–290

C, whereas

phosphoric acid was active at 25–50 atm and 170

–190

C. A high wa-

ter/propylene ratio of about 2–5 was required in order to avoid polymer for-

mation. Although selectivity was as high as 97%, the propylene conversion was

only about 6%.

A trickle phase process using strong acid-ion exchangers has now been de-

veloped by Deutsche Texaco. The process operates with a high water/propylene

ratio of 12–15 at 80–100 atm and 130

–160

C to give 75% propylene conversion

at up to 95% selectivity. The ion exchange resin loses activity after about 8

months as the acid groups on the resin are hydrolyzed. Other olefins, ranging

from ethylene to butylenes can also be hydrated with acid-ion exchange resins.

7.1.1.1. Acetone

Until about 1970 most of the acetone used was produced in the gas phase from

the azeotropic mixture of isopropanol and water by a dehydrogenation process:

OH → CH

COCH

+ H

(7.2)

A copper oxide/zinc oxide catalyst (1 CuO / 2 ZnO) was operated in the tem-

perature range 220

–340

C to give a 95% yield at about 90% conversion. The

reaction was endothermic and took place in 20-ft long, 2-in diameter tubes with

the operating temperature limited by the maximum allowable flue gas tempera-

ture. At 325

C, the equilibrium conversion was about 97% at 5 atm. At higher

temperatures, however, increasing byproducts formation decreased selectivity to

less than 90–95% more than offsetting any advantage from increased conver-

266 Chapter 7

sion. Activity was greater with low impurity levels in the catalyst, such as the

residual sodium remaining from the precipitation stage of preparation, and high

physical strength was needed. Spent catalyst was removed from the narrow

tubes by drilling, as polymeric by-products tended to gum up the reactor tubes.

Another gas phase dehydrogenation process was used to prepare methyl

ethyl ketone (MEK) from secondary butanol with a similar copper oxide/zinc

oxide catalyst:

CH(OH)CH

→ C

COCH

+ H

(7.3)

However, a liquid phase dehydrogenation process, using Raney nickel or Raney

copper catalysts in a high-boiling solvent at about 150

C, gave 80–95% second-

ary butanol conversion to MEK at more than 95% selectivity.

With the introduction of the cumene–phenol process, which provides large

volumes of acetone by-product, the older dehydrogenation process is now rarely

used.

7.1.1.2. Bisphenol-A

Bisphenol-A is produced at 500

C by the condensation of acetone with phenol in

the presence of an acid catalyst. In early processes sulfuric acid or dry hydro-

chloric acid was promoted with methyl mercaptans. More recently acid ion ex-

change resins have been used:

2 C

OH + CH

COCH

→ C

(OH)C(CH

)

(OH) + H

O (7.4)

Bisphenol-A is used in the manufacture of epoxy resins, plastics such as poly-

carbonates, and polysulfones.

7.1.1.3. Cumene

It was realized during World War II that alkylated benzene molecules could be

used to increase the octane level of aviation gasoline. The Petroleum Admin-

istration for War had asked for a high-octane synthetic aromatic component in

1941 and propyl benzene, also known as cumene, and butyl benzene were pro-

duced in the United States and the United Kingdom, respectively. In 1944, the

Hock and Lang process,

which produced phenol and acetone from cumene was

introduced, and this industrial process became the basis of the major source of

phenol throughout the world:

+ C

→ C

(7.5)

+ O

→ C

(OOH) (7.6)

Petrochemical Catalysts 267

(OOH) → C

OH + CH

COCH

(7.7)

More recently, new processes for phenol which do not produce acetone by prod-

ucts have been described.

As in all alkylation reactions the catalyst used to produce cumene from pro-

pylene and benzene is a strong acid and a number of processes have been intro-

duced. The first were developed by Distillers and Hercules in 1953:

• Sulfuric acid or aluminum trichloride in the liquid phase at 35

–40

C and

7 atm.

• Hydrofluoric acid in the liquid phase at 50

–70

C and 7 atm.

• Phosphoric acid supported on kieselguhr promoted with HF in the gas

phase at 200

–300

C and 20–40 atm.

Phosphoric acid/kieselguhr with added steam or aluminum trichloride have

been the most widely used catalytic processes. Excess benzene is usually added

to the reaction mixture to limit the formation of di- and tri-propylbenzene and to

maximize the selectivity of propylene to cumene. Pure propylene must be used

to avoid the production of ethyl benzene.

Typical acid catalysts are not regenerable and particularly in the case of

aluminium trichloride can lead to disposal problems, so zeolites are now increas-

ingly used as active catalysts. Early problems were encountered with relatively

fast deactivation or the formation of ethyl benzene and butyl benzene from me-

tathesis (disproportionation) reactions. These were overcome when Dow intro-

duced a dealuminated mordenite catalyst (3DDM—three-dimensional dealumi-

nated mordenite) that was both stable over 18 months of testing and regenera-

ble.

Yields with the mordenite catalyst are greater than 99% and purity is al-

most 100%. ENI in Italy used a selective ß-zeolite catalyst and process im-

provements led to an increased plant capacity of 30–40%.

Cumene is converted by a two-step, noncatalytic process into phenol and

acetone. It is first oxidized to hydroperoxide with air at 5–10 atm in an alkaline

solution at pH 8.5–10 and 90

–130

C. The hydroperoxide is then converted to

phenol and acetone in either a homogeneous 0.1–2% sulfuric acid solution at

–65

C or a two-phase liquid mixture with 40% sulfuric acid at 50

7.1.2. Vinyl Chloride

Vinyl chloride was first prepared by Regnier in 1835

when working with Lie-

big. He chlorinated ethylene, or olefiant gas, as it was then known, and convert-

ed the ethylene dichloride, or oil of Dutch chemists (1795), to vinyl chloride by

reaction with caustic potash solution:

+ Cl

→ C

(7.8)