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Article No : a04_483 Butenes FRITZ OBENAUS, Huls€ AG, Marl, Federal Republic of Germany WILHELM DROSTE, Huls€ AG, Marl, Federal Republic of Germany JOACHIM NEUMEISTER, Huls€ AG, Marl, Federal Republic of Germany 1. Introduction......................... 445 7. Analysis ............................ 452 2. Physical Properties ................... 445 8. Storage and Transportation............. 452 3. Chemical Properties .................. 445 9. Uses and Economic Data ............... 452 4. Resources and Raw Materials ........... 448 10. Toxicology .......................... 454 5. Upgrading of Butenes ................. 449 References .......................... 454 6. Quality Specifications.................. 451 two butane isomers and multiple unsaturated C 1. Introduction 4 hydrocarbons, has been the main barrier for Butenes are unsaturated olefinic hydrocarbons, specific chemical use of the butenes. Until the mid 1980s availability of butene C4H8, Mr 56.1080. There are four isomers: mixtures exceeds by far worldwide the produc- tion of the single butene isomers and their deri- vatives. But during the 1980s the sharp price increase of hydrocarbons accelerated the devel- opment of economic separation processes, which opened for the butenes access to appropriate upgraded use. 2. Physical Properties Butenes are colorless, flammable gases at room temperature and atmospheric pressure. They are completely miscible with alcohols, ethers, and ‘‘Butylenes’’, the older name for ‘‘butenes’’,is hydrocarbons [1]. Butenes are only slightly water still used today; 4 is frequently referred to as soluble and water is only slightly butene soluble ‘‘isobutylene’’. The designation ‘‘n-butenes’’ re- [2]. Important physical properties are summa- fers to mixtures of 1, 2, and 3. rized in Table 1. Other thermodynamic properties All the butenes, which do not exist as natural and transport regulations are reported in [3–5]. products, have been known for more than 100 years, but remained in very limited use and importance. Scarce availability has been for long 3. Chemical Properties the reason. However with the growth of cracking processes in crude oil refining and for ethylene Butenes behave as typical olefins. The main production, butenes have been obtained as reactions are acid-catalyzed addition reactions, coproducts in huge quantities. Since then the isomerization, and polymerization. The four iso- complicated nature of the raw C4 streams, con- mers, including two isomers with nonterminal taining besides the four butene isomers also the double bonds and one branched-chain olefin, Ó 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/14356007.a04_483.pub2 446 Butenes Vol. 6 Table 1. Physical properties of butenes 1-Butene cis-2-Butene trans-2-Butene Isobutene [106-98-9][590-18-1][624-64-6][115-11-7] Melting point (101.3 kPa) C À 185.35 À 138.92 À 105.53 À 140.34 Boiling point (101.3 kPa) C À 6.25 þ 3.72 þ 0.88 À 6.90 Critical temperature C 146.45 162.43 155.48 144.75 Critical pressure MPa 4.02 4.20 4.10 4.00 Critical density g/cm3 0.240 0.234 0.238 0.239 Density of liquid at 25 C g/cm3 0.5888 0.6154 0.5984 0.5879 Density of gas at 0 C, kg/m3 2.582 2.591 2.591 2.582 101.3 kPa Vapor pressure at 0 C kPa 127.3 87.9 98.4 130.3 20 C kPa 252.9 181.2 199.7 257.0 40 C kPa 457.4 337.5 367.8 462.8 60 C kPa 766.7 579.6 626.0 774.3 80 C kPa 1207.8 931.3 999.2 1219.0 100 C kPa 1807.1 1416.4 1512.1 1824.7 Vapor pressure (Antoine equation constants)* temp. range C À 82 to þ 13 À 73.4 to þ 23 À 76 to þ 20 À 82 to þ12 A 6.84290 6.86926 6.86952 6.84134 B 926.10 960.10 960.80 923.20 C 240.00 237.00 240.00 240.00 Heat of vaporization at saturation pressure at 25 C J/g 358.7 394.5 380.3 366.9 at bp J/g 390.6 416.2 405.6 394.2 Isobaric specific heat at 25 C gas in ideal state J kgÀ1 KÀ1 1528 1408 1566 1589 liquid at 101.3 kPa J kgÀ1 KÀ1 2299 2250 2276 2336 0 Enthalpy of formation DHf at 25 C, 101.3 kPa kJ/mol À 0.04 À 6.91 À 11.1 À 16.9 Free enthalpy of formation 0 DGf at 25 C, 101.3 kPa kJ/mol 71.38 65.98 63.10 58.11 Heat of combustion [to H2O (liquid) and CO2 (gas) ] at constant pressure and kJ/mol À 2719.1 À 2712.3 À 2708.1 À 2702.3 25 C Ignition temperature C 384 325 325 465 (DIN 51794) Flammability limits in air at 20 C, 101.3 kPa lower vol % 1.6 1.7 1.7 1.8 higher vol % 9.3 9.7 9.7 8.8 * log10 p¼ AÀB/(tþC), where p is in mm Hg and t in C; to convert mm Hg to kPa, divide by 7.528. show differences in their chemical behavior: are due to different electron densities, polarities, while the 2-butenes as the lowest olefins with and steric effects. nonterminal double bonds generally show a mi- nor chemical activity, isobutene, the lowest Hydration. Acid-catalyzed hydration of branched-chain olefin, exhibits higher reactivity, butenes is one of the commercially most impor- especially in addition and polymerization reac- tant processes. Both gas- and liquid-phase pro- tions. This difference in reactivity permits, e.g., cesses are used. For kinetic and mechanistic the separation of the other isomers through se- studies see references [6], [7] (! Butanols). lective reaction of isobutene. The differences Isobutene yields tert-butyl alcohol (TBA). in activity (isobutene 1-butene > 2-butenes) Sulfuric acid (45 wt %) is commonly used as a Vol. 6 Butenes 447 protonating agent [8]. This process has also While cis/trans-isomerization (Eq. 1) occurs been carried out in the presence of sulfonated at ambient temperatures in the presence of cat- styrene – divinylbenzene ion-exchangers [9]. alysts, carbon rearrangement (Eq. 3) requires The latter liquid-phase process has fewer side temperatures of about 450 C. A large number reactions, such as formation of di- and tri-iso- of catalysts, e.g., Lewis acids, Brønsted acids, butene, less equipment corrosion, and fewer metal oxides, and zeolites, are effective. A re- environmental problems. Hydration is commer- view of catalysts and equilibrium constants as a cially used for separating isobutene from mixed function of temperature is given in [16]. butenes. Hydration of isobutene-free n-butenes to form Polymerization, Oligomerization. The sec-butyl alcohol (SBA) is catalyzed under more two types of reactions depend on the catalyst severe conditions usually by sulfuric acid [10] or system used: more recently by acid ion-exchange resins [11]. a. Coordination catalysts (Ziegler-Natta) Etherification. The acid-catalyzed addition b. Liquid or solid Brønsted and Lewis acids of alcohols to butenes yields alkyl butyl ethers (! Ethers, Aliphatic). Reaction of isobutene For a review see [17]. with methanol, yielding methyl tert-butyl ether Only 1-butene yields high-molecular material (MTB or MTBE), is of technical importance. such as isotactic or atactic poly-1-butene using Liquid phase and ion exchange resins as catalysts Ziegler-Natta catalysts. Isotactic polymers [18] are commonly used [12]. The etherification of n- and copolymers with ethylene or propene are butenes requires more severe conditions and is of produced industrially. no commercial importance. Acidic substances induce poly- or oligomeri- zation by forming carbenium ions [19]. Molecu- Halogenation. 1-Butene reacts with halo- lar mass is dependent on many reaction variables, gens at room temperature to give 1,2-dihalogen- especially temperature: increasing temperature butane and reaction with 2-butenes gives 2,3- generally results in lower molecular masses. dihalogenbutane. Allylic substitution occurs at Polymerization of highly pure isobutene to higher temperatures (> 200 C). This reaction is polyisobutene occurs in an inert solvent at tem- of no practical importance. Isobutene readily peratures between À 10 and À 100 C [20]. reacts with chlorine at low temperatures forming Copolymerization with 1 – 3 % isoprene under methallyl chloride ClCH2C(CH3)¼CH2 [13]. similar conditions yields butyl rubber. Polymer- ization of isobutene in butene mixtures in the Hydroformylation. Hydroformylation of presence of AlCl3 between À 10 and þ 80 C butenes in the presence of cobalt or rhodium yields polybutenes with a few percent n-butene catalysts gives valeric aldehydes and the corre- and isobutane as chain terminators. The molecu- sponding amyl alcohols. n-Pentanol and 2- lar masses lie between 300 and 2500. About 80 – methylbutanol are formed from n-butenes, while 95 % of the isobutene is usually converted to isobutene gives only 3-methylbutanol [14]. polymer [21]. Oligomerization of isobutene to dimers and Hydrocarboxylation. The catalyzed reac- trimers is done by extracting isobutene from tion of butenes with carbon monoxide and water mixed butenes using 65 – 70 wt % sulfuric acid yields carboxylic acids. Particularly isobutene and subsequent heating to 100 C (cold acid readily forms pivalic acid (CH3)3CCOOH in the process). An alternative process uses acid ion- presence of strong acid (Koch reaction [15] ). exchange resins instead of sulfuric acid (Bayer). The resulting isobutene oligomers, mainly 2,2,4- Isomerization. With increasing tempera- trimethylpentenes, contain isomeric n-butene tures the following reactions take place: cooligomers, which increase with higher isobu- tene conversions. A good part of the accompa- cis-2-butene trans-2-butene (1) nying 1-butene is isomerized to 2-butenes [22]. 1-butene 2-butenes (2) n-Butenes are commercially oligomerized n-butenes isobutene (3) by various homogeneous or heterogeneous 448 Butenes Vol.
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