Phenol process technology

U.S. consumption pattern 1999, 3 619t U.S. producers, 3 610t vapor-phase nitration of, 17 257 vinyl chloride reactions with, 25 632 world production by country, 3 611-612t Benzene-based catalyst technology, 15 500 Benzene-based fixed-bed process technology, 15 505-506 Benzene chlorination process, of phenol manufacture, 18 751 m-Benzenedisulfonic acid, 3 602 p-Benzenedisulfonic acid, 3 602 Benzene feedstock, 23 329 Benzene hexachloride, 3 602 Benzene manufacture, toluene in, 25 180-181... 

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. 

Novolac and resol cold hardening oligomers habe been used 19-75-99). In the case of resol foams the process technology is not different from that used for epoxy foams. Glass, phenolic resins, carbon, polystyrene, polyacrylonitrile and poly(vinylidene chloride) microspheres have been used as fillers ... 

Cumene capacity topped 9.5 million metric tons in 1998 and is projected to reach 10.4 million metric tons by the end of 2003 (19). Like ethylbenzene, cumene is used almost exclusively as a chemical intermediate. Its primary use is in the coproduction of phenol and acetone through cumene peroxidation. Phenolic resins and bisphenol A are the main end uses for phenol. Bisphenol A, which is produced from phenol and acetone, has been the main driver behind increased phenol demand. Its end use applications are in polycarbonate and epoxy resins. The growth rate of cumene is closely related to that of phenol and is expected to be approximately 5.1% per year worldwide over the next five years. Process technologies for both chemicals have been moving away from conventional aluminum chloride and phosphoric acid catalyzed Friedel-Crafts alkylation of benzene, toward zeolite-based processes. 

With over 40 years of continuous technological development, the Kellogg Brown Root (KBR) phenol process features low cumene and energy consumptions, coupled with unsurpassed safety and environmental systems. 

Kvaerner Process Technology Cyclohexanone/cydohexanol Phenol/hydrogen Synthesis of KA oil with high selectivity to cyclohexanone 2 1998... 

Friedel-Crafts technology and zeolite- or other solid catalyst-based processes are currently used for other aromatic alkylations, in particular for the manufacture of linear alkylbenzenes (LABs) made from C10-C14 olefins (Equation 8), or from the corresponding chloroparaffins and benzene, and also to make m- and p-cymene (isopropyltoluene Equation 9). LABs are used for the production of sulfonate detergents, while cymenes lead to m- and p-cresols through a procedure analogous to that used for the cumene-to-phenol process. 

Acetophenone (phenyl methyl ketone) has a wide range of applications in perfumery. It can be recovered from the heavy byproduct stream of a phenol process (which otherwise has fuel value) using the process described in U.S. 4,559,110 assigned to Dow Chemical. It can be made by oxidation of ethylbenzene using the process described in U.S. 4,950,794 (to Arco Chemical Technology). It can also be produced as a natural product by fermentation of cinnamic acid using the process described in U.S. 6,482,794 (to International Elavors Fragrances). Estimate the cost of production via each route. 

UOP is offering the technology for conversion of cumene to phenol and acetone based on UOP/Allied (Now Mobil) phenol process. Similarly, Kellog is offering the technology of Hercules and lately Dow-Mousanto Process. 

With AMS hydrogenation, 1.31 tons of cumene will produce 1 ton of phenol and 0.616 tons of acetone. This high-yield process produces very high-quality phenol and acetone products with very little heavy and light-end byproducts. With over 40 years of continuous technological development, the Kellogg Brown Root (KBR) phenol process features low cumene and energy consumptions, coupled with unsurpassed safety and environmental systems. 

Note Reagents for TM 2.15a and 2.15b are available aromatic compounds, products of the petrochemical industry. Para-nitrobenzoic acid is produced by nitration of toluene to para-isomer as the prevailing product, followed by oxidation of methyl to the carboxylic group. Orf/m-dimethoxybenzene is produced from ort/to-diphenol, which in turn is available by oxidation of phenol. One technological process uses hydrogen peroxide as oxidant [25], and annual production of ort/io-diphenol reaches 20,000 tons/year, mainly intended for the production of pesticides and perfumes. 

Kozlowska H, Naczk M, Shahidi F, Zademowski R 1990. Phenolic acids and tannins in rapeseed and canola. In Canola and Rapeseed. Production, Chemistry, Nutrition and Processing Technology. Shahidi F (Ed.). Van Nostrand Reinhold, United States of America, pp. 193-210. 

Phenol produced by the cumene-phenol process is relatively expensive but Solutia has recently claimed a new process developed in Russia.Benzene is oxidized directly to phenol using nitrous oxide. Phenol is then converted to adipic acid by oxidature procedures. Nitrous oxide from the final nitric acid oxidation to adipic acid is recycled to the first stage. This has been reported as the first new commercial technology since DuPont introduced the direct hydrocya-nation of butadiene to adiponitrile in 1971. 

Sales demand for acetophenone is largely satisfied through distikative by-product recovery from residues produced in the Hock process for phenol (qv) manufacture. Acetophenone is produced in the Hock process by decomposition of cumene hydroperoxide. A more selective synthesis of acetophenone, by cleavage of cumene hydroperoxide over a cupric catalyst, has been patented (341). Acetophenone can also be produced by oxidizing the methylphenylcarbinol intermediate which is formed in styrene (qv) production processes using ethylbenzene oxidation, such as the ARCO and Halcon process and older technologies (342,343). 

Benzene SuIfona.tion. In the benzene sulfonation process, benzene reacts with concentrated sulfuric acid to form benzenesulfonic acid at about 150°C. The benzenesulfonic acid is neutralized with sodium sulfate to produce sodium benzenesulfonate, which is then fused with caustic soda to yield sodium phenate. The sodium phenate is acidified with sulfur dioxide and a small amount of sulfuric acid to release the phenol from the sodium salt. The phenol yield by this process can be as high as 88 mol % to that of the theoretical value based on benzene. Plants employing this technology have been shut down for environmental and economic reasons. 

The hydroxyl group of the resulting phenol is situated immediately adjacent to where the carboxyl group was previously located. This same Hquid-phase copper oxidation process chemistry has been suggested for the production of cresols by the oxidation of toluic acids. y -Cresol would be formed by the oxidation of either ortho or para toluic acids a mixture of 0- and -cresols would be produced from y -toluic acid (6). A process involving the vapor-phase catalytic oxidation of benzoic acid to phenol has been proposed, but no plants have ever been built utilizing this technology (27). 

The reasons for the long-term, commercial robustness of phenolic technology include low cost, versatility, heat and flame resistance, durability, strength and stiffness, low toxicity, and ease of processing. Some key factors are discussed in detail below. 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

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