Cumene plant/process

A typical phenol plant based on the cumene hydroperoxide process can be divided into two principal areas. In the reaction area, cumene, formed by alkylation of benzene and propylene, is oxidized to form cumene hydroperoxide (CHP). The cumene hydroperoxide is concentrated and cleaved to produce phenol and acetone. By-products of the oxidation reaction are acetophenone and dimethyl benzyl alcohol (DMBA). DMBA is dehydrated in the cleavage reaction to produce alpha-methylstyrene (AMS). 

In the early 1980s Monsanto introduced an A1C13 process based on the same chemistry used in the ethylbenzene process. This process can be operated at lower benzene/propylene ratios than the SPA process because AICI3 can transalkylate the polyalkylated benzenes back to cumene. The process also operates at temperatures lower than the SPA process because the more highly acidic anhydrous AICI3 tends to produce significantly more undesired n-propylbenzene at equivalent temperatures. This technology is currently used in five plants. 

Process features The process allows a substantial increase in capacity for existing SPA, AICl3, or other zeolite cumene plants while improving product purity, feedstock consumption, and utility consumption. The new catalyst is environmentally inert, does not produce byproduct oligomers or coke and can operate at the lowest benzene to propylene ratios of any available technology with proven commercial cycle lengths of over seven years. Expected catalyst life is well over five years. 

Among these processes, only the Hock process and the toluene oxidation are important industrially. The other processes were discarded for economic reasons. In the Hock process acetone is formed as a by-product. This has not, however, hindered the expansion of this process, because there is a market for acetone. New plants predominantly use the cumene process. More than 95% of the 4,691,000 my (m = metric tonnes) consumed is produced by the cumene peroxidation process. Phenol s consumption growth rate of 3% is primarily based on its use in engineering plastics such as polycarbonates, polyetherimide and poly(phenylene oxide), and epoxy resins for the electronic industry. The Mitsui Company is, for instance, the world s second largest producer of phenol. Japan s production... 

Commercial plants The process is used in Polimeri Europe s 400,000 metric tpy cumene plant at Porto Torres, Sardinia. 

In the cumene process, cumene is produced from benzene and propene by Friedel-Crafts alkylation. In modern cumene plants, zeolite catalysts are used with high yields of more than 99.7% at temperatures and pressures of approximately 150 °C and 30 bar, respectively. The reaction heat is 98 kj/mol. 

The cumene oxidation route is the lea ding commercial process of synthetic phenol production, accounting for more than 95% of phenol produced in the world. The remainder of synthetic phenol is produced by the toluene oxidation route via benzoic acid. Other processes including benzene via cyclohexane, benzene sulfonation, benzene chlorination, and benzene oxychl orin ation have also been used in the manufacture of phenol. A Hst of U.S. phenol production plants and their estimated capacities in 1994 are shown in Table 2, and worldwide plants and capacities are shown in Table 3. 

The recovery area of the plant employs fractionation to recover and purify the phenol and acetone products. Also in this section the alpha-methylstyrene is recovered and may be hydrogenated back to cumene or recovered as AMS product. The hydrogenated AMS is recycled as feedstock to the reaction area. The overall yield for the cumene process is 96 mol %. Figure 1 is a simplified process diagram. 

The cumene product is 99.9 wt % pure, and the heavy aromatics, which have a research octane number (RON) of 109, can either be used as high octane gasoline-blending components or combiaed with additional benzene and sent to a transalkylation section of the plant where DIPB is converted to cumene. The overall yields of cumene for this process are typically 97—98 wt % with transalkylation and 94—96 wt % without transalkylation. 

Production of a-methylstyrene (AMS) from cumene by dehydrogenation was practiced commercially by Dow until 1977. It is now produced as a by-product in the production of phenol and acetone from cumene. Cumene is manufactured by alkylation of benzene with propylene. In the phenol—acetone process, cumene is oxidized in the Hquid phase thermally to cumene hydroperoxide. The hydroperoxide is spHt into phenol and acetone by a cleavage reaction catalyzed by sulfur dioxide. Up to 2% of the cumene is converted to a-methylstyrene. Phenol and acetone are large-volume chemicals and the supply of the by-product a-methylstyrene is weU in excess of its demand. Producers are forced to hydrogenate it back to cumene for recycle to the phenol—acetone plant. Estimated plant capacities of the U.S. producers of a-methylstyrene are Hsted in Table 13 (80). 

Vibration from a bad pump bearing caused a pump seal to fail in a cumene section of a phenol acetone unit. The released flammable liquids and vapors ignited. An explosion ruptured other process pipes, adding fuel to the original fire. Damage to the plant exceeded 23 million. 

Cumox [Cumene oxidation] A process for making acetone and phenol by oxidizing cumene, based on the Hock process. This version was further developed and licensed by UOR Three plants were operating in 1986. UOP now licenses the Allied-UOP Phenol process, which combines the best features of Cumox and a related process developed by the Allied Chemical Corporation. 

Other routes. Alternate process technologies for making phenol avoid the cumene route. A few plants have used toluene as a feed, oxidizing it over a cobalt catalyst to give benzoic acid. That is followed by a reduction (removal of oxygen atom) to give phenol and carbon dioxide. 

Treybal, in his book Liquid Extraction [1], works equilibrium material balances with triangular coordinates. The most unique and simple way to show three-phase equilibrium is a triangular diagram (Fig. 7.1), which is used for extraction unit operation in cumene synthesis plants [2], In this process benzene liquid is used as the solvent to extract acetic acid (the solute) from the liquid water phase (the feed-raffinate). The curve D,S,P,F,M is the equilibrium curve. Note that every point inside the triangle has some amount of each of the three components. Points A,... 

Although cyclohexane oxidation dominates the market, because of cheaper raw materials, the hydrogenation of phenol remains competitive, offering better selectivity with fewer environmental and safety problems. In addition, this process allows efficient valorization of phenol-rich wastes from coal industries. Recently built plants make use of this technology, as reported by the engineering group Aker-Kvaerner (www.kvaerner.com, 2004). The availability of low-price phenol is the most important element for profitability. Besides the well-known cumene process, a promising route is the selective oxidation of benzene with N20 on iron-modified ZSM-5 catalyst [12]. In this way, the price of phenol may become independent of the market of acetone. 

This case study deals with the design and simulation of a medium size plant of lOOkton cumene per year. The goal is performing the design by two essentially different methods. The first one is a classical approach, which handles the process synthesis and energy saving with distinct reaction and separation sections. In the second alternative a more innovative technology is applied based on reactive distillation. 

Before 1970, there were five different processes used to make phenol in the United States the sulfonation route, chlorobenzene hydrolysis, the Raschig process, cumene oxidation, and the benzoic acid route. By 1978, the first three processes had essentially disappeared, and 98 percent of the remaining plant capacity was based on cumene oxidation. The oxidation process is shown in Fig. 10.33. 

First commercialized at Georgia Gulfs Pasadena, TX plant in 1994, the Mobil-Badger Cumene process consists of a fixed-bed alkylator, a fixed-bed transalkylator and a separation section (22, 23). Fresh and recycle benzene are combined with liquid propylene in the alkylation reactor where the propylene is completely reacted. Recycled polyisopropylbenzenes are mixed with benzene and sent to the transalkylation unit to produce additional cumene. Trace impurities are removed in the depropanizer column. Byproduct streams consist of LPG (mainly propane contained in the propylene feedstock) and a small residue stream, which can be used as fuel oil. 

Commercial plants The first commercial application of this process came onstream in 1996. At present, there are 12 plants operating with a combined capacity exceeding 5.2 million mtpy. In addition, four grassroots plants and an AICI3 revamp are in the design phase. Fifty percent of the worldwide and 75% of zeolite cumene production are from plants using the Badger process. 

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