Merchant market

The heat of hydration is approximately —70 kj /mol (—17 kcal/mol). This process usually produces no waste streams, but if the acrylonitrile feed contains other nitrile impurities, they will be converted to the corresponding amides. Another reaction that is prone to take place is the hydrolysis of acrylamide to acryhc acid and ammonia. However, this impurity can usually be kept at very low concentrations. American Cyanamid uses a similar process ia both the United States and Europe, which provides for their own needs and for sales to the merchant market. 

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. 

The largest production of acrylamide is in Japan the United States and Europe also have large production faciUties. Some production is carried out in the Eastern Bloc countries, but details concerning quantities or processes are difficult to obtain. The principal producers in North America are The Dow Chemical Company, American Cyanamid Company, and Nalco Chemical Company (internal use) Dow sells only aqueous product and American Cyanamid sells both Hquid and sohd monomer. In Europe, Chemische Eabrik Stockhausen Cie, Ahied CoUoids, The Dow Chemical Company, and Cyanamid BV are producers Dow and American Cyanamid are the only suppHers to the merchant market, and crystalline monomer is available from American Cyanamid. Eor Japan, producers are Mitsubishi Chemical Industries, Mitsui Toatsu, and Nitto Chemical Industries Company (captive market). Crystals and solutions are available from Mitsui Toatsu and Mitsubishi, whereas only solution monomer is available from Nitto. 

About 85% of U.S. adipic acid production is used captively by the producer, almost totally ia the manufacture of nylon-6,6 (194). The remaining 15% is sold ia the merchant market for a large number of appHcations. These have been developed as a result of the large scale availabihty of this synthetic petrochemical commodity. Prices for 1960—1989 for standard resia-grade material have parahed raw material and energy costs (petroleum and natural gas)... 

Most manufacturers sell a portion of their alcohol product on the merchant market, retaining a portion for internal use, typically for the manufacture of plasticizers. Sterling Chemicals linear alcohol of 7, 9, and 11 carbons is all used captively. Plasticizer range linear alcohols derived from natural fats and oils, for instance, octanol and decanol derived from coconut oil and 2-octanol derived from castor oil, are of only minor importance in the marketplace. 

The sales brochures of the manufacturers describe the plasticizer range alcohols available on the merchant market (18). Typical properties of several commercial plasticizer range alcohols are presented in Table 8. Because in most cases these ate mixtures of isomers or alcohols with several carbon chains, the properties of a particular material can vary somewhat from manufacturer to manufacturer. Both odd and even carbon chain alcohols are available, in both linear and highly branched versions. Examples of the composition of several mixtures are given in Table 9. 

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. 

Rhc ne-Poulenc (RP), producing both in Europe and the United States, is the only producer of sahcylaldehyde worldwide, for merchant sales. A large portion of it is used captively in the manufacture of coumarin. The remainder is available for the merchant market. 

Economic Aspects. AH diketene production is used captively and, therefore, production figures can only be estimated by the volume of derivatives output on the merchant market. World production of diketene is probably close to 100,000 metric tons, approximately 20% of that production in the United States. Before the discontinuation of aH shipment in the United States, diketene was sold for less than 2.20/kg. 

If two or three of the principal customers are unavailable to a new suppHer, the problem of selling becomes more acute. In fact, if a significant portion of the so-called merchant market is unavailable to a new producer, entry into the field could be disastrous. Special arrangements can arise because of the proximity of suppHer plant to user plant, taw matetial avadabiHty from one firm to the other, common financial ownership to some degree, toU arrangements, etc. 

Table 5. Merchant Market Prices/ /t Nitric Acid, 100% Basis...

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. 

The commodity nature of the product and the easy access to the Hcensed processes enable new producers, particularly in developing countries, to enter the global styrene merchant market with Htde experience in styrene technology. Access to ethylene, which caimot be easily transported by means other than pipelines, is a key factor in considering new styrene faciHties. Timing, or luck, is even more important because the supply and demand of styrene are seldom in balance and the price fluctuates broadly and rapidly as a result. Most of the time, the producers either suffer losses (1981—1985, 1991—1993) or enjoy handsome profits (1987—1990, 1994—mid-1995). Investments in styrene plants are known to have been recovered in less than a year, but prosperity encourages over-investment and lean years may foUow. 

Styrene is manufactured from ethylbenzene. Ethylbenzene [100-41-4] is produced by alkylation of benzene with ethylene, except for a very small fraction that is recovered from mixed Cg aromatics by superfractionation. Ethylbenzene and styrene units are almost always installed together with matching capacities because nearly all of the ethylbenzene produced commercially is converted to styrene. Alkylation is exothermic and dehydrogenation is endothermic. In a typical ethylbenzene—styrene complex, energy economy is realized by advantageously integrating the energy flows of the two units. A plant intended to produce ethylbenzene exclusively or mostly for the merchant market is also not considered viable because the merchant market is small and sporadic. 

In 1991, over 1 x 10 t sulfonic acids were produced in the United States (24). The materials, for the most part, were used as intermediates for the manufacture of sulfonates in the detergent market, dye manufacture, dispersing agents, catalysts, polymers, etc. Production of dodecjlbenzenesulfonic acids derivatives dominated the sulfonic acid market (Table 2). These had a 38% overall share. The differences between the production tons and the tons sold is accounted for by in-plant use by various manufacturers verses merchant market production. 

Uses. The dominant use of sulfur dioxide is as a captive intermediate for production of sulfuric acid. There is also substantial captive production in the pulp and paper industry for sulfite pulping, and it is used as an intermediate for on-site production of bleaches, eg, chlorine dioxide or sodium hydrosulfite (see Bleaching agents). There is a substantial merchant market for sulfur dioxide in the paper and pulp industry. Sulfur dioxide is used for the production of chlorine dioxide at the paper (qv) mill site by reduction of sodium chlorate in sulfuric acid solution and also for production of sodium dithionite by the reaction of sodium borohydride with sulfur dioxide (315). This last appHcation was growing rapidly in North America as of the late 1990s. 

Solution Polymerization. Solution polymerization of vinyl acetate is carried out mainly as an intermediate step to the manufacture of poly(vinyl alcohol). A small amount of solution-polymerized vinyl acetate is prepared for the merchant market. When solution polymerization is carried out, the solvent acts as a chain-transfer agent, and depending on its transfer constant, has an effect on the molecular weight of the product. The rate of polymerization is also affected by the solvent but not in the same way as the degree of polymerization. The reactivity of the solvent-derived radical plays an important part. Chain-transfer constants for solvents in vinyl acetate polymerizations have been tabulated (13). Continuous solution polymers of poly(vinyl acetate) in tubular reactors have been prepared at high yield and throughput (73,74). 

The total 1988 woddwide volumes of n- and isobutyraldehyde were 4.3-4.4 x 10 t and 7.7 x 10 t, respectively. The merchant market for the two aldehydes is relatively insignificant, most of the production being employed captively. The principal U.S. producers of butanals are given in Table 4. The principal producers in Western Europe and Asia are given in Table 5. 

Production figures are not pubHshed by these producers, so precise production amounts are not available however, it is roughly estimated that global production in 1989—1990 was 500,000—600,000 t/yr. Approximately 90% of this aHyl chloride production is used captively to synthesize epichlorohydrin. The remainder is sold on the merchant market with bulk Hst U.S. prices in 1989—1990 of 1.63/kg. Some of the producers Hsted above and several additional companies have announced their intentions to expand or build aHyl chloride capacity. 

The merchant market for chi orohydrin s is small, primarily for specialty appHcations. Ethylene chlorohydrin is sold ia the United States by BASF Corp., Parsippany, N.J., available ia 230 kg net lined steel dmms. Glycerol monochlorohydrin (3-chloro-l,2-propanediol) is available from Dixie Chemical Co., Houston, Tex., in lined steel dmms (227.3 kg net) from Raschig Corp., Richmond, Va. and from Henley Chemicals, Inc., Montvale, N.J., ia steel dmms (240 kg net). Glycerol dichi orohydrin (l,3-dichloro-2-propanol) is not currentiy being produced for the U.S. merchant market but has been available ia the past at a selling price of 5—6/kg. 

Uses of Ghlorohydrins From a volume standpoint almost all of the chlorohydrins produced are immediately converted into epoxides such as propylene oxide and epicblorobydrin. The small quantity of various chlorohydrins sold in the merchant market are used in specialty appHcations. 

Manufacture By distillation of liquid air, the same as nitrogen. Most oxygen is used captively, less than 20% of production being sold on the merchant market. 

Phosgene is manufactured by reacting chlorine gas and carbon monoxide in the presence of activated carbon. Much of the market is captive. The merchant market is small. 

Breakdown of diethylene glycol use is as follows unsaturated polyester resins (20%), polyester polyols (15%), antifreeze blending (12%), triethylene and tetraethylene glycol (9%), solvents (9%) morpholine (7%), and natural gas dehydration (4%). Much of the market is captive. The merchant market is small. 

In Table 9.2, the approximately 75 billion fine-chemical market is subdivided into major applications according to their relevance, namely, fine chemicals for pharmaceuticals, agrochemicals, and specialty chemicals outside life sciences. Furthermore, a distinction is made between captive (in-house) production and merchant market. 

As the leading specialty chemical companies, Degussa, Dow, Chemtura and Rohm Haas, are backward-integrated, the share of in-house production is estimated at 75-80%, leaving a merchant market of approximately 5 billion (see Table 9.2). 

The new production capacity that has come onstream in Asia since the mid-1990s has allowed the fine-chemical companies in these countries to capture a close to 50% share of the global merchant market for API-for-generics, the only segment of the industry where demand has developed favorably lately (see text below). The pharmaceutical industry itself, plagued by underutilized capacity, has gone more aggressively after third-party business. 

Flavors account for the largest share, approximately 40% of the market, followed by fragrances, 35% aroma chemicals, 13% and essential oils, respectively natural extracts (see text above), 12%. Aroma chemicals, that is, the fine chemicals used in the F F formulations, are produced both for captive use and for the merchant market (see Table 11.13). 

Walker, Bingham, A. The Snake-Oil Syndrome Patent Medicine Advertising. Hanover, Mass. Christopher Publishing House, 1994. With reprints of the words and images from patent medicine ads, this book illustrates the excessive claims made by merchants, marketers, and manufacturers during the 1800s and early 1900s. 

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