Cyclohexane

M. LARRY CAMPBELL, Exxon Chemical Co., Florham Park, New Jersey, United States 07932

1. 2. 3. 4. 4.1. 4.2. 4.3. 5.

Introduction. . . . . . . . . . . . . . . . . . . Physical Properties . . . . . . . . . . . . . Chemical Properties . . . . . . . . . . . . Production . . . . . . . . . . . . . . . . . . . . Hydrogenation of Benzene . . . . . . . . Separation from Naphtha . . . . . . . . Cost Considerations . . . . . . . . . . . . . Quality Specications and Tests . . .

..... ..... ..... ..... ..... ..... ..... .....

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41 41 41 42 44 46 46 46

6. 7. 7.1. 7.2. 7.3. 8.

Uses, Economic Aspects . . . . . . . . . . . . . . . Homologues . . . . . . . . . . . . . . . . . . . . . . . . Cyclohexene . . . . . . . . . . . . . . . . . . . . . . . . Methylcyclohexane. . . . . . . . . . . . . . . . . . . Methylcyclopentane . . . . . . . . . . . . . . . . . . Toxicology and Occupational Health . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . .

.. .. .. .. .. .. ..

46 47 47 47 47 47 47

1. Introduction
Cyclohexane [110-82-7], C6H12, is a cycloalkane, which was synthesized by BAEYER in 1893 and discovered in Caucasian crude oil by MARKOVNIKOV soon afterward. Its presence in U.S. crude oils was reported in 1931 [1]. Cyclohexane was rst synthesized by hydrogenation of benzene in 1898 [2]. The predominant use of cyclohexane is in the manufacture of nylon.

2. Physical Properties
Like all cycloalkanes and related cycloolens, cyclohexane is a clear liquid with a pungent petroleum-like odor. It is essentially insoluble in water but miscible in most organic liquids, and is noncorrosive, easily ammable, and considered to be much less toxic than benzene. Cyclohexane can exist in two conformations, the chair and boat forms:

Transformation from one isomer to the other involves rotation about carbon carbon single bonds. The energy barriers associated with the transformation are low, but the boat form is estimated to have a potential energy 21 25 kJ/mol higher than the chair form [3]. As a result, cyclohexane is almost exclusively in the chair form at room temperature. Stereochemistry has no inuence on its use as a raw material for nylon manufacture or in other applications. Table 1 lists the important physical properties of cyclohexane; two closely related naphthenes, methylcyclopentane and methylcyclohexane; and the olenic homologue, cyclohexene. Table 2 compares the key properties of some alkylcyclohexanes with cyclohexane. Tables 3, 4, and 5 give boiling points and compositions for azeotropes of cyclohexane with various compounds. Although cyclohexane does not ignite spontaneously at ambient temperature, it must be kept away from an open ame. Information on the explosive limits and ignition properties for cyclohexane and related compounds is given in Table 6.

3. Chemical Properties
Cyclohexane is a relatively stable, nonpolar ring compound. Therefore, with thermal treatment,

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a08_209.pub2

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Table 1. Physical properties of cyclohexane, methylcyclohexane, cyclohexene, and methylcyclopentane Methylcyclohexane [108-87-2] C7H14 98.183 100.934 126.593 0.769 39 1.423 12 6.7550 46.088 35.383 31.150 118.675 83.275 4 568.34 154.870 343.569 27.298 298.97 3.469 0.267 0.732 136.11 329.67 23.70 196.174 146.6 374.1 Methylcyclopentane [96-37-7] C6H12 84.157 71.812 142.455 0.74864 1.40970 6.9333 53.046 31.610 29.098 106.022 84.351 3 940.36 106.76 340.136 35.80 259.58 3.785 0.264 0.505 110.66 267.12 22.19 13.7873 2731.00 47.11

Cyclohexane CAS registry number Formula Mr bp,  C fp,  C r20 , g/cm3 4 nD20 Heat of fusion, kJ/mol Entropy of fusion, J mol1 K1 Heat of vaporization, kJ/mol at 25  C at bp Entropy of vaporization, J mol1 K1 at 25  C at bp Heat of combustiona at 25  C, kJ/mol Heat of formationc, kJ/mol Entropy at 25  C J mol1 K1 D G  , kJ/mol Critical temperature,  C Critical pressure, MPa Critical density, g/cm3 Dynamic viscosity at 20  C, mPa s Kinematic viscosity at 20  C, mm2/s cp at 300 K J mol1 K1 at 800 K J mol1 K1 Surface tension, mN/m Constants for Antoine equationd, kPa [4] A B C Dielectric constant at 20  C and 105 Hz Cryoscopic constante, mole fraction/  C
a b c

Cyclohexene [110-83-8] C6H10 82.141 82.979 103.512 0.810 96 1.446 54 3.2954

[110-82-7] C6H12 84.157 80.738 6.554 0.778 55 1.426 23 2.6787 9.575 33.059 29.977 110.879 84.70 3 922.45 123.22 298.435 31.778 280.3 4.07 0.273 0.977 1.259 107.098 279.51 24.98 13.7377 2766.3 50.50 2.021 0.00411

3 752.92 5.35 106.86 287.4 4.347 0.281 0.980 105.84 249.07 26.56 13.8093 2813.53 49.98

High heating value. At 30  C. Gaseous. d ln p A B/(C T). e For use in calculating mol % purity, p, by using the equation log p 2.00000 (A/2.302 59) (T 0 T) where T 0 is the freezing point of a given sample [5], [6].

little isomerization to methylcyclopentane or ring-opening occurs, but benzene is formed by dehydrogenation. At high temperature (700 800  C) cyclohexane decomposes to butadiene and other products. Aluminum chloride readily isomerizes cyclohexane to methylcyclopentane [7]. The most important commercial reaction of cyclohexane is its liquid-phase oxidation with air in the presence of soluble cobalt or boric acid catalysts to produce a mixture of cyclohexanol and cyclohexanone (KA oil) ( ! Cyclohexanol and Cyclohexanone). Cyclohexanol is oxidized to cyclohexanone, which is used to produce caprolactam, a monomer for nylon-6 production ( ! Caprolactam, Chap. 4.; ! Fibers, 4. Poly-

amide Fibers Alternatively, KA oil can be converted to adipic acid and hexamethylenediamine, the monomers for nylon-66 production ( ! Adipic Acid; ! Hexamethylenediamine) [8].

4. Production
Virtually all cyclohexane is produced commercially by hydrogenation of benzene ( ! Benzene, Chap. 10.). A small amount is produced by superfractionation of the naphtha fraction from crude oil. Naturally occurring cyclohexane can be supplemented by fractionating methylcyclopentane from naphtha and isomerizing it to cyclohexane.

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Table 2. Some physical properties of alkylcyclohexanes Compound, CAS registry number Cyclohexane [110-82-7] Methylcyclohexane [108-87-2] 1,1-Dimethylcyclohexane [590-66-9] cis-1,2-Dimethylcyclohexane [2207-01-4] trans-1,2-Dimethylcyclohexane [6876-23-9] cis-1,3-Dimethylcyclohexane [638-04-0] trans-1,3-Dimethylcyclohexane [2207-03-6] cis-1,4-Dimethylcyclohexane [624-29-3] trans-1,4-Dimethylcyclohexane [2207-04-7] 1,1,3-Trimethylcyclohexane [3073-66-3] 1,1,2-Trimethylcyclohexane [7094-26-0] 1,1,4-Trimethylcyclohexane [7094-27-1] Ethylcyclohexane [1678-91-7] n-Propylcyclohexane [1678-92-8] Isopropylcyclohexane [696-29-7] n-Butylcyclohexane [1678-93-9] Isobutylcyclohexane [1678-98-4] sec-Butylcyclohexane [52993-54-1] tert-Butylcyclohexane [3178-22-1] n-Decylcyclohexane [1795-16-0] cis-1-Methyl-4-isopropylcyclohexane [6069-98-3] trans-1-Methyl-4-isopropylcyclohexane [1678-82-6]
*

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43

bp*,  C 80.738 100.934 119.543 129.728 123.419 120.088 124.450 124.321 119.351 136.626 145.2 135 131.783 156.724 154.762 180.947 171.221 179.335 171.591 297.589 172.7 170.5

fp,  C 6.554 126.593 33.495 50.023 88.194 75.573 90.108 87.436 36.962 65.750 29 111.323 94.900 89.390 74.725 94.785 41.158 1.726 89.80 86.35

20 d4

nD20 1.42623 1.42312 1.42900 1.43596 1.42695 1.42294 1.43085 1.42966 1.42090 1.42955 1.4382 1.4251 1.43304 1.43705 1.44087 1.44075 1.43861 1.44673 1.44694 1.45338

0.77855 0.76939 0.78094 0.79627 0.77601 0.76603 0.78472 0.78285 0.76255 0.77883 0.8000 0.7722 0.78792 0.79360 0.80221 0.79918 0.79521 0.81314 0.81267 0.81858

At 101.3 kPa.

Table 3. Binary azeotropes with cyclohexane Component Cyclohexane, Azeotropic, wt % bp,  C bp,  C 100.0 80.5 80.9 80.1 78.3 97.2 82.3 117.7 97.0 56.3 79.7 91.6 48.6 46.6 48.8 48.1 68.7 81.5 68.0 90.5 42.0 32.5 54.6 56.0 17.0 44.0 37.7 85.0 58.8* 70.0* 73.5* 69.5 80.2 80.0 77.6 77.56 64.8 74.7 69.4 79.8 74.0 53.0 71.6 71.5 54.9 71.6 67.4 77.5 77.9 79.8 69.5

Table 4. Ternary azeotropes with cyclohexane Component A Water Water Water Water Ethanol 1-Propanol 1-Butanol 2-Butanol 2-Methoxyethanol
*

Component, wt % A 4.7 7.0 8.5 5.0 30.4 18.0 4.0 8.0 9.0 B 19.7 17.0 10.0 35.0 10.8 28.0 48.0 42.0 39.1 C* 75.5 76.0 81.5 60.0 58.8 54.0 48.0 50.0 51.9 Azeotropic bp,  C 62.6 62.1 66.6 63.6 63.1 73.8 77.4 76.7 73.0

Component Water 2,4-Dimethylpentane 2,2,3-Trimethylbutane Benzene Ethanol 1-Propanol 2-Propanol 1-Butanol Allyl alcohol Acetone 2-Butanone

B ethanol ethanol 1-propanol 2-butanone benzene benzene benzene benzene benzene

C cyclohexane.

Methyl acetate 57.0 Ethyl acetate 77.1 Vinyl acetate 72.2 2-Methoxyethanol 125.0 Thiophene 84.2 Isopropyl methyl sulde 84.8 Nitromethane 100.8
*

Table 5. Quaternary azeotrope Component, wt % Azeotropic bp,  C 62.19 62.14

Water 7.1 6.1

Ethanol 17.4 19.2

Benzene 21.5 20.4

Cyclohexane 54.0 54.3

vol %.

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Table 6. Explosive limits and ignition properties Explosive limits Lower, vol % Ethylcyclohexane Benzene Cyclohexane Cyclohexene Methylcyclohexane Upper, vol % 0.9 1.2 1.2 1.1 Lower, g/m3 6.6 8.0 8.3 Upper, g/m3 42 39 40 45 310 270 290 Autoignition temp,  C 260 555 260 310 260 Flash point,


21 11 18 < 20 4

4.1. Hydrogenation of Benzene

Benzene can be hydrogenated catalytically to cyclohexane in either the liquid or the vapor phase in the presence of hydrogen. Several cyclohexane processes, which use nickel, platinum, or palladium as the catalyst, have been developed. Usually, the catalyst is supported, e.g., on alumina, but at least one commercial process utilizes Raney nickel. Hydrogenation proceeds readily and is highly exothermic (D H500 K 216.37 kJ/mol). From an equilibrium standpoint, the reaction temperature should not exceed 300  C. Above this, the equilibrium begins to shift in favor of benzene so that high-purity cyclohexane cannot be produced. As a result of these thermodynamic considerations, temperature control of the reaction is critical to obtaining essentially complete conversion of benzene to cyclohexane.

Temperature control requires economic and efcient heat removal. This has been addressed in a number of ways by commercial processes. The earlier vapor-phase processes used multistage reactors with recycle of cyclohexane as a diluent to provide a heat sink, staged injection of benzene feed between reactors, and interstage steam generators to absorb the exothermic heat of hydrogenation [9], [10]. In the 1970s processes have been developed that use only one reactor [11], [12] or a combination of a liquid-and a vaporphase reactor [13]. The objectives of the later processes were to reduce capital cost and improve energy utilization. However, all of the commercial processes have comparably low capital cost and good energy efciency. A generalized ow scheme for a vapor-phase process with multistage reactors in series is shown in Figure 1. Benzene feed is divided and fed to each of the rst two reactors. Recycled

Figure 1. Multistage reactor, vapor-phase process a) Reactors; b) Separator drum; c) Compressor; d) Stabilizer * To hydrogen recovery (optional).

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cyclohexane is introduced to the rst reactor along with hydrogen. The recycled cyclohexane enables higher conversion in the reactors by absorbing part of the heat of hydrogenation. Steam generators between the reactors remove the heat of hydrogenation. The outlet temperature of the last reactor is controlled to achieve essentially 100 % conversion of benzene to cyclohexane. The efuent from the last reactor is cooled, and the vapor and liquid are separated. Part of the hydrogen-rich vapor is recycled to the rst reactor, and the rest is purged to fuel gas or hydrogen recovery facilities. The liquid from the separator goes to a stabilizer where the overhead gas is sent to fuel gas; the remaining material is cyclohexane product, part of which is recycled to the rst reactor. A simplied ow scheme for a process with liquid- and vapor-phase reactors is provided in Figure 2. Benzene and hydrogen are fed to the liquid-phase reactor, which contains a slurry of nely divided Raney nickel. Temperature is maintained at 180 190  C by pumping the slurry through a steam generator and by vaporization in the reactor. Roughly 95 % of the benzene is converted in this reactor. The vapor is fed to a xed-bed reactor where the conversion of benzene is completed. The efuent from the xed-bed reactor is processed as described previously for the vapor-phase process. Benzene hydrogenation is done typically at 20 30 MPa. The maximum reactor temperature

is limited to ca. 300  C so that a typical specication of < 500 mg/kg benzene and < 200 mg/kg methylcyclopentane in the product can be achieved. This is necessary because of the thermodynamic equilibrium between cyclohexane benzene and cyclohexane methylcyclopentane. Actually, equilibrium strongly favors methylcyclopentane, but the isomerization reaction is slow enough with the catalysts employed to avoid a problem if the temperature is controlled. The hydrogen content of the makeup hydrogen has no effect on product purity but it does determine the makeup, recycle, and purge gas rates. Streams with as low as 65 vol % hydrogen can be used. Carbon monoxide and sulfur compounds are catalyst deactivators. Both can be present in the hydrogen from catalytic naphtha reformers or ethylene units, which are typical sources of makeup hydrogen. Therefore, the hydrogencontaining stream is usually passed through a methanator to convert carbon monoxide to methane and water. Prior to methanation, hydrogen-containing gas can be scrubbed with caustic to remove sulfur compounds. Commercial benzene contains less than 1 mg/kg sulfur. In some cases, the recycle gas is also scrubbed with caustic to prevent buildup of hydrogen sulde from the small amount of sulfur in the benzene. With properly treated hydrogen and specication benzene, a catalyst life in excess of three years can be achieved easily in xed-bed

Figure 2. Liquid- and vapor-phase reactor process a) Liquid-phase reactor; b) Vapor-phase reactor; c) Separator drum; d) Compressor; e) Stabilizer * To hydrogen recovery (optional).

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reactors that use noble-metal catalysts supported on a base. The catalyst in the process that uses Raney nickel in suspension is reported to have a typical life of about six months before it must be replaced [14].

The selling price of cyclohexane is tied to the selling price of benzene. In the early 1980s, its price was ca. $ 100 /t above the benzene price.

5. Quality Specications and Tests

The typical purity specication for cyclohexane is 99.9 wt % min. Impurities are unconverted benzene, aliphatic hydrocarbons in the benzene feed to the hydrogenation unit, methylcyclopentane formed by isomerization of cyclohexane, and methylcyclohexane formed by hydrogenation of the small amount of toluene in benzene. Freezing point, relative density, and a distillation range of 1  C, with 80.7  C in the range, are generally specied. A sulfur level of less than 1 mg/kg as measured by ASTM method D-3120 is also specied. In addition, specications of phenol, chloride, and basic nitrogen content exist, but they are of little importance because the levels of these in product cyclohexane are generally less than 0.1 mg/kg. Although these specications, with the appropriate ASTM test method, are used in contractual agreements between cyclohexane producers and their customers, gas chromatography is generally employed for quality control in manufacturing because of its precision and reproducibility.

4.2. Separation from Naphtha

The cyclohexane content of the naphtha fraction of crude oil can vary from 0.5 to 5.0 vol %. However, n-hexane, isohexanes, methylcyclopentane, benzene, and dimethylpentanes have normal boiling points very close to cyclohexane; and the freezing points of cyclohexane and benzene are separated by < 2  C. Consequently, recovery of cyclohexane from naphtha by distillation or crystallization is difcult and uneconomic. Cyclohexane can be separated from benzene by solvent extraction or extractive distillation, but no practical solvent system has been developed for separating cyclohexane from hexanes or methylcyclopentane. Trace quantities of benzene and n-hexane can be removed with zeolite X and zeolite A sieves, respectively. The difculty of separating cyclohexane from naphtha is underscored by the fact that only one company, Phillips Petroleum, produces cyclohexane by distillation (ca. 10 % of U.S. capacity). This route is not used commercially elsewhere in the world.

6. Uses, Economic Aspects

Over 98 % of the cyclohexane produced is used to make nylon intermediates: adipic acid (60 %), caprolactam, and hexamethylenediamine 75 % of the caprolactam produced worldwide is used for nylon 6 manufacture. Minor miscellaneous uses, such as solvents and polymer reaction diluents, consume the remainder of the cyclohexane produced. Cyclohexane consumption dropped signicantly in the early 1980s because of the generally depressed economy. Since then, global demand for cyclohexane had been around 23 % per year. Its growth is limited because nylon is a mature product and other routes to nylon intermediates, which use butadiene, acrylonitrile, or phenol, have been developed. The USA is the most important manufacturer of cyclohexane with ca. 1.5 106 t/a, which accounts for % 34 % of the world production in

4.3. Cost Considerations

The investment for a benzene hydrogenation unit that produces 100 000 t/a of cyclohexane was ca. (5 7) 106 $ for a unit completed in 1985. This excludes investment for hydrogen recovery or manufacture and associated facilities, such as utility systems and tankage. The net operating cost is low because of recovery of the heat of hydrogenation by steam generation and heat integration. The major costs are maintenance expenses, labor, capital recovery charges for the plant and working capital, benzene feedstock, and hydrogen ( ! Hydrogen, 2. Production). The cost of hydrogen can vary widely and can affect cyclohexane manufacturing cost by as much as $ 40 /t.

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2000. Total EU production amounts to % 1000 t/a. The market was severely impacted by the economic downturn; in Europe the overall demand estimately fell by 30 %. Any new investment will be focussed on Asia and the Middle East.

vents, but it is not produced as a pure component in signicant volume.

8. Toxicology and Occupational Health

Cyclohexane is mildly irritating to the skin. Both the TLV TWA and MAKare 200 ppm, 700 mg/ m3 ; the TLV STEL was listed in1986 1987as (375 ppm), (1300 mg/m3), with a note of intention to delete this value [19], [20]. At levels above the TWA, cyclohexane can cause irritation of the eyes and mucous membranes. When high concentrations are inhaled, narcosis may occur. In contrast to benzene, little or no effect on the blood, even after long exposure, has been reported. Methylcyclohexane is somewhat less narcotic than cyclohexane so a higher TLV TWA of 400 ppm, 1600 mg/m3 has been established; the MAK is 200 ppm, 810 mg/m3 ; the TLV STEL was (500 ppm), (2000 mg/m3) in 1986 1987, with the same notation as for cyclohexane. The toxic properties of cyclohexene (TLV TWA and MAK of 300 ppm, 1015 mg/m3) and methylcyclopentane (TLV and MAK have not been established) are thought to be similar to those of cyclohexane.

7. Homologues
7.1. Cyclohexene
Cyclohexene can be used to synthesize many interesting products of potential commercial value. However, no viable process has been developed for producing it in large volume. The reason for this is the difculty in hydrogenating benzene to cyclohexene because the DG  (298 K) for converting benzene to cyclohexene is 22.8 kJ/mol, which is considerably less than that for benzene to cyclohexane [DG  (298 K) 97.9 kJ/mol]. Consequently, the hydrogenation reaction tends to go all the way to cyclohexane. Despite the thermodynamic difculty, considerable work on heterogeneous catalyst systems has been reported [1518]. Ruthenium-based systems appear to be the best, but selectivities for cyclohexene are < 30 %; the rest of the product is cyclohexane.

7.2. Methylcyclohexane
The primary use of methylcyclohexane is as a component in the feed to catalytic naphtha reformers where it is readily dehydrogenated to toluene, a high-octane motor gasoline component. Some methylcyclohexane is used for solvent applications in which it is one component of a narrow boiling range fraction of naphtha. Like cyclohexane, it can be produced easily by hydrogenation of toluene, but no current market exists for large-scale quantities.

References
1 J. H. Bruun, M. M. Hicks-Bruun, J. Res. Natl. Bur. Stand., Sect. A 7 (1931) 607. 2 P. Sabatier, Ind. Eng. Chem. 18 (1926) 1005. 3 W. C. Dauber, K. S. Pitzer in M. S. Newman (ed.): Steric Effects in Organic Chemistry, J. Wiley & Sons, New York 1956, pp. 13 15. 4 R. C. Reid, J. M. Prausnitz, J. K. Sherwood: The Properties of Gases and Liquids, 3rd ed., McGraw-Hill, New York 1977, App. A. 5 Selected Values of Hydrocarbons and Related Compounds, A.P.I. Research Project 44, Carnegie Press, Pittsburgh, Pa. 1960, p. 1. 6 P. R. Dreisbach, Adv. Chem. Ser. 15 (1955) 441. 7 N. I. Shuikin et al., Neftekhimiya 1 (1961) 756; Chem. Abstr. 57 (1962) 8452. 8 G. Nawata, Chem. Econ. Eng. Rev. 4 (1972) no. 5, 47 61. 9 UOP, US 3 054 833, 1962 (G. R. Donaldson, V. Haensel). 10 UOP, US 2 755 317, 1956 (L. S. Kasel). 11 Texaco, US 3 767 719, 1973 (J. H. Colvert, E. F. Jones, H. C. Kaufman, R. Smith).

7.3. Methylcyclopentane
The primary use of methylcyclopentane, like methylcyclohexane, is as a component in the feed to catalytic naphtha reformers where it is isomerized to cyclohexane and, in turn, dehydrogenated to benzene. Methylcyclopentane is a minor component in some light aliphatic sol-

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17 M. M. Johnson, G. P. Nowak, J. Catal. 38 (1975) 518. 18 C. U. I. Oldenbrand, S. T. Lundin, J. Chem. Technol. Biotechnol. 30 (1980) 677 687; 31 (1981) 660 669; 32 (1982) 365 375. 19 ACGIH (ed.): Threshold Limit Values (TLV), ACGIH, Cincinnati, Ohio 1986 1987. 20 DFG (ed.): MAK- und BAT-Werte-Liste 2001, WileyVCH, Weinheim, Germany 2001.

12 S. Field, M. H. Dolson, Hydrocarbon Process. 46 (1967) no. 5, 169 174. 13 Institut Fran ais de Ptrole, US 3 597 489, 1971 (O. D. c e Vu, R. Odello). 14 B. Cha, J. Cosyns, M. Derrien, A. Forge, AIChE Symp. Ser. 70 (1974) no. 142, 128 130. 15 Stamicarbon, US 3 391 206, 1966 (F. Hartog). 16 Du Pont, US 3 767 720, 1973 (W. C. Drinkard).