Captive use

Mitsui Toatsu Chemical, Inc. disclosed a similar process usiag Raney copper (74) shortiy after the discovery at Dow, and BASF came out with a variation of the copper catalyst ia 1974 (75). Siace 1971 several hundred patents have shown modifications and improvements to this technology, both homogeneous and heterogeneous, and reviews of these processes have been pubHshed (76). Nalco Chemical Company has patented a process based essentially on Raney copper catalyst (77) ia both slurry and fixed-bed reactors and produces acrylamide monomer mainly for internal uses. Other producers ia Europe, besides Dow and American Cyanamid, iaclude AUied CoUoids and Stockhausen, who are beheved to use processes similar to the Raney copper technology of Mitsui Toatsu, and all have captive uses. Acrylamide is also produced ia large quantities ia Japan. Mitsui Toatsu and Mitsubishi are the largest producers, and both are beheved to use Raney copper catalysts ia a fixed bed reactor and to sell iato the merchant market. 

Based on estimates of resin sales for film and sheet. Includes estimate of captive use for photographic film and pressure-sensitive tape. Table 7. U.S. Manufacturers or Distributors of Film and Sheet ... 

Fine chemical companies are generally either small and privately held or divisions of larger companies, such as Eastman Fine Chemicals (United States) and Lonza (Switzerland). Examples of large public fife science companies, which market fine chemicals as a subsidiary activity to their production for captive use, are Hoffmann-La Roche, Sandoz, and Boehringer Ingelheim, which produce and market bulk vitamins and liquid crystal intermediates, dyestuff intermediates, and bulk active ingredients, respectively. Table 3 fists some representative companies having an important fine chemical business. 

Most of the commercial tree plantations that produce wood for captive use as a raw material in manufacturing operations use a portion as fuel. Examples of short-rotation plantations are Hsted in Table 38 (127). Paper companies in the southeastern United States are reported to have short-rotation plantings also, eg, Weyerhaeuser, James River Corp., Buckeye Cellulose, and Lykes Brothers, but the intensity of maintenance is not known (127). 

It is difficult to indicate a representative price for acetylene because it is generally produced either for captive use or on contract. The price seems to be dictated mainly by the price movement of ethylene, often a coproduct as well as an alternative feedstock competing with acetylene. That is, in 1981 when ethylene was 0.55 per kg, acetylene was 1.12 per kg and when in 1987 the price of ethylene dropped to 0.31 per kg, acetylene dropped to 0.68 per kg. 

Most of the HCl produced is consumed captively, ie, at the site of production, either in integrated operations such as ethylenedichloride—vinyl chloride monomer (EDC/VCM) plants and chlorinated methane plants or in separate HCl consuming operations at the same location. Captive use of anhydrous HCl accounted for 80—85% of the total demand in 1989. The combined merchant market for anhydrous and aqueous HCl in that same year was about 9.1 X 10 metric tons on the basis of 100% HCl (see Table 12) (73). 

Aqueous Hydrochloric Acid. Muriatic acid consumption in 1993 was about 1.57 million metric tons (100% basis). The largest captive use of aqueous HCl is for brine acidification prior to electrolysis in chlorine/caustic cells and the largest merchant markets for HCl are steel pickling and oil-well acidizing, which accounted for 25 and 16% of merchant production, respectively, during 1989. 

Uses. The principal use of magnesium hydroxide is in the pulp (qv) and paper (qv) industries (52). The main captive use is in the production of magnesium oxide, chloride, and sulfate. Other uses include ceramics, chemicals, pharmaceuticals, plastics, flame retardants/smoke suppressants, and the expanding environmental markets for wastewater treatment and SO removal from waste gases (87). 

Key contents of a purchase profile report for a specific chemical are identity, location, and capacity of primary vendors expected additions or deletions of capacity and their timing captive use/merchant supply status of each vendor pricing history pricing induences (feedstock, energy, etc) demand by use and anticipated growth and demand in the purchaser company up to five or ten years ahead. 

The only other nitroparaffin manufactured on a large scale was nitrocyclohexane [1122-60-7] made by Hquid-phase nitration of cyclohexane. Nitrocyclohexane was the starting material for S-caprolactam via reduction to cyclohexanone oxime. This process has been superseded by other, more efficient processes (see Caprolactam). Nitrocyclohexane is not being produced ia large quantities for either captive use or sale. 

Production and Sales and Captive Use of Thermosetting and Thermoplastic Resins, Society of the Plastics Industry, Committee on Resiu Statistics, Ernst and... 

Three peroxyacids are produced commercially for the merchant market peroxyacetic acid as a 40 wt % solution in acetic acid, y -chloroperoxybenzoic acid, and magnesium monoperoxyphthalate hexahydrate. Other peroxyacids are produced for captive use, eg, peroxyformic acid generated in situ as an epoxidizing agent. 

Four minerals are the principal commercial sources of potash (Table 2). In all ores, sodium chloride is the principal soluble contaminant. Extraneous water-iasoluble material, eg, clay and siUca, is a significant contaminant ia some of the evaporates being mined from underground deposits. Some European potassium ores contain relatively large amounts of the mineral kieserite, MgS04-H2 0. It is recovered for captive use to produce potassium sulfate compounds or is marketed ia relatively pure form as a water-soluble magnesium fertilizer. 

Consumption of ethanolamines ia the United States has changed dramatically since the 1960s. Consumption ia gas conditioning appHcations has peaked and chemical processing intermediates (captive use for ethyleneamine and surfactant appHcations) has increased significantly. 

The worldwide consumption of 4-dodecylphenol is difficult to estimate since the majority of 4-dodecylphenol produced is captively used. Prices appear in Table 3. Litde growth in the consumption of 4-dodecylphenol is predicted because of the mature nature of the markets of its derivatives. 

The major producers of fatty amine oxides are Jordon Chemical Company, Procter and Gamble, Lonza, Stepan, Sherex Chemicals, and Akzo Chemicals Inc. It is estimated that 13,600 t of amine oxides were purchased for end use ia the Uoited States ia 1987 (68). Of this amouat arouad 80% was coasumed ia various household products, and 10% ia iadustrial, iastitutioaal, and commercial appHcations. These figures do not iaclude the estimated 27,000 —32,000 t of amine oxides produced by Procter and Gamble for captive use. 

Uses. There may be some captive use of carbonyl sulfide for production of certain thiocarbamate herbicides (qv). One patent (38) describes the reaction of diethylamine with carbonyl sulfide to form a thiocarbamate salt which is then alkylated with 4-chloroben2yl haUde to produce 3 -(4-chloroben2yl) A[,A/-diethylthiocarbamate [28249-77-6] ie, benthiocarb [28249-77-6]. Carbonyl sulfide is also reported to be useful for the preparation of abphatic polyureas. In these preparations, potassium thiocyanate and sulfuric acid are used to first generate carbonyl sulfide, COS, which then reacts with a diamine ... 

Economic Aspects. The price of sulfur dichloride was 0.26 /kg bulk ia 1995. Akzo Nobel is the only U.S. producer with merchant sales. Whereas some companies stiH produce sulfur dichloride for captive use (158), Occidental Chemical Company ended sulfur dichloride production ialate 1993. 

Production and Economic Aspects. The 1995 world production of organic titanates is estimated to be 8000—9000 metric tons, some of which is for captive use. Principal producers in the United States are Du Pont, Kenrich Petrochemicals, and Akzo Nobel in the United Kingdom, Tioxide U.K. in Japan, Nippon Soda, Matsumoto Trading, and Mitsubishi Gas Chemicals and in India, Synthochem. 

Brassylic Acid. This acid is commercially available from Nippon Mining Company (Tokyo, Japan). It is made by a fermentation process (76). Several years ago, Emery Group, Henkel Corp. (Cincinnati, Ohio) produced brassyUc acid via ozonization of emcic acid primarily for captive use in making dimethyl brassylate and ethylene brassylate. A pilot-scale preparation based on ozonization of emcic acid has been described in which brassyUc acid yields of 72—82% were obtained in purities of 92—95%. Recrystallization from toluene gave purities of 99% (77). 

Cogeneration is an energy conversion process wherein heat from a fuel is simultaneously converted to useful thermal energy (e.g., process steam) and electric energy. The need for either form can be the primary incentive for cogeneration, but there must be opportunity for economic captive use or sale of the other. In a chemical plant the need for process and other heating steam is hkely to be the primaiy in a pubhc utility plant, electricity is the usual primary produc t. 

The two processors are delivering the product via pipes into one of several tanks in a tank farm. Each tank has parameters such as capacity or cleaning time. From the tanks the product is either delivered to processes on site (captive use) or to customers based on given customer orders. Additionally, it may be stored in two external buffers. In that case there are transportation moves from the tank farm to one of the external buffers (in case of over-production) or from the external buffer to the tank farm (in case of shortages in production) induced. 

Council of European Surfactant Producers (CESIO) statistics [10] indicate a total surfactant production of 2.4 million tons in Europe for 1999, which were distributed in the categories shown in Table 1.5. Other information sources [11] indicate a surfactant consumption of 2.1 million tons in Europe for 1998, which compares very well with the CESIO figure. Europe is a net exporter of surfactants and a precise figure of actual European consumption is thus difficult to estimate, although information from CESIO provides data on total sales and captive use. 

Although the superior properties of PEN have been known for many years, the unavailability of the naphthalate monomer has delayed the development of commercial markets, until relatively recently (1995) when the Amoco Chemical Company offered high purity naphthalene-2,6-dimethyl dicarboxylate (NDC) in amounts of up to 60 million pounds per year. This diester is produced by a five-step synthetic route, starting from the readily available compounds, o-xylene and 1,4-butadiene [3], Prior to this, the NDC diester was obtained by extraction of 2,6-dimethylnaphthalene (DMN) from petroleum streams, where it was present in relatively low abundance. Oxidation of DMN to crude 2,6-naphthalene dixcarboxylic (NDA) is conducted by a similar process to that used for conversion of p-xylcnc to purified terephthalic acid (TA), crude NDA is esterified with methanol, and is then distilled to yield high purity NDC. Other companies (e.g. the Mitsubishi Gas Chemical Company) followed Amoco s introduction with lesser amounts of NDC. Teijin [4] has manufactured PEN for many years for its own captive uses in films. 

The typical size of a Shell process plant described here is 250-350,000 tons per year. The total production of higher olefins via this and similar routes is estimated to be 2 million tons annually. A large part of the alkenes are produced for captive use, i.e. for use by the producing company itself. 

Year Total sales and captive use (kt) 2001 2005 Market shares linked to identified thermoplastic uses (%) AAGR (%/year)... 

As we learned in Chapter 8, the official production of propylene is usually about half that of ethylene, only because a large part of the propylene is used by petroleum refineries internally to alkylate gasolines. This captive use is not reported. Of the propylene used for chemical manufacture, nearly 40% is polymerized to polypropylene, to be discussed in a later chapter. Of the remaining amount of propylene, seven chemicals from the top 50 are manufactured. These are listed in Table 10.1. Their industrial manufacturing methods are summarized in Fig. 10.1. Note that four of these chemicals, cumene, phenol, acetone, and bisphenol A, are also derived from a second basic organic chemical, benzene. 

Chemical reactions enhanced by catalysts or enzymes are an integral part of the manufacturing processes for the majority of chemical products. The total market for catalysts and enzymes amounts to 11.5 billion (2005), of which catalysts account for about 80%. It consists of four main applications environment (e.g., automotive catalysts), 31% polymers (e.g., polyethylene and polypropylene), 24% petroleum processing (e.g., cracking and reforming), 23% and chemicals, 22%. Within the latter, particularly the catalysts and enzymes for chiral synthesis are noteworthy. Within catalysts, BINAPs [i.e., derivatives of 2,2 -bis(diphenylphosphino) -1, l -bis-l,l -binaphthyl) have made a great foray into chiral synthesis. Within enzymes, apart from bread-and-butter products, like lipases, nitrilases, acylases, lactamases, and esterases, there are products tailored for specific processes. These specialty enzymes improve the volumetric productivity 100-fold and more. Fine-chemical companies, which have an important captive use of enzymes, are offering them to third parties. Two examples are described here ... 

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