Feedstock choice

Agricultural impacts can also be lessened with the use of less intensive agricultural feedstocks that require less fertilizers, chemicals, and energy. Raw materials for PLA production must have certain properties to be competitive on a large scale with petroleum feedstocks. Such desirable characteristics include renewability, cost competitiveness. 

Currently, electricity is obtained mainly from coal, natural gas, and nuclear resources in the United States. Utilizing renewable energy sources for electricity and less intensive agricultural practices could yield a net CO2 sequestration for PLA (approximately 2 kg CO2 sequestered per kg of PLA) and significantly less fossil fuel usage (a savings of up to a factor of 11) compared to petro-polymers [27, 38]. 

CRADLE TO GATE ENVIRONMENTAL FOOTPRINT AND LIFE CYCLE ASSESSMENT OF POLY(LACTIC ACID) 

Bauman and A. M. Tilhnan. The Hitch Hiker s Guide to LCA. Studenthtteratur AB, Lund Sweden 2004. 

Guinee, ed . Handbook on Life Cycle Assessment Operational Guide to the ISO Standards, Kluwer Academic Pubhshers, Amsterdam 2002. 

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A number of conclusions can be drawn from Tables VII and VIII concerning feedstock choice. These are discussed below. 

There is often no single feedstock choice, since feedstock costs frequently vary erratically over a period of several years. A general guide to the influence of feedstock on capital investment of the entire pyrolysis for ethylene production is shown in Fig. 7. Net raw material costs for an ethylene plant often account for about 50-60% of the production costs, depending on whether the feedstock is a light material such as ethane or a heavier material such as naphtha. 

Environmental- and cost-efficiency of the process depend on the feedstock choice. First-pass economic calculations indicate that it will be much more efficient to derive ethanol from sugarcane than from com or sugar beets. 

A detailed study of the properties of the potential products is of prime technical and economic importance, because it allows the refiner to have a choice in selecting feedstocks for his different units for separation, transformation and conversion, to set their operating conditions, in order to satisfy the needs of the marketplace in the best ways possible. 

Since 1960, the Hquid-phase oxidation of ethylene has been the process of choice for the manufacture of acetaldehyde. There is, however, stiU some commercial production by the partial oxidation of ethyl alcohol and hydration of acetylene. The economics of the various processes are strongly dependent on the prices of the feedstocks. Acetaldehyde is also formed as a coproduct in the high temperature oxidation of butane. A more recently developed rhodium catalyzed process produces acetaldehyde from synthesis gas as a coproduct with ethyl alcohol and acetic acid (83—94). 

However, ia some cases, the answer is not clear. A variety of factors need to be taken iato consideration before a clear choice emerges. Eor example, UOP s Molex and IsoSiv processes are used to separate normal paraffins from non-normals and aromatics ia feedstocks containing C —C2Q hydrocarbons, and both processes use molecular sieve adsorbents. However, Molex operates ia simulated moving-bed mode ia Hquid phase, and IsoSiv operates ia gas phase, with temperature swiag desorption by a displacement fluid. The foUowiag comparison of UOP s Molex and IsoSiv processes iadicates some of the primary factors that are often used ia decision making ... 

Olefin Sources. The choice of feedstock depends on the alcohol product properties desired, availabiUty of the olefin, and economics. A given producer may either process different olefins for different products or change feedstock for the same appHcation. Feedstocks beheved to be currentiy available are as follows. 

ElexibiHty allows the operator to pick and choose the most attractive feedstock available at a given point in time. The steam-cracking process produces not only ethylene, but other products as weU, such as propylene, butadiene, butylenes (a mixture of monounsaturated C-4 hydrocarbons), aromatics, etc. With ethane feedstock, only minimal quantities of other products ate produced. As the feedstocks become heavier (ie, as measured by higher molecular weights and boiling points), increasing quantities of other products are produced. The values of these other coproduced products affect the economic attractiveness and hence the choice of feedstock. 

Olefin Feedstock Selection. The selection of feedstock and severity of the cracking process are economic choices, given that the specific plant has flexibiUty to accommodate alternative feedstocks. The feedstock prices are driven primarily by energy markets and secondarily by supply and demand conditions ia the olefins feedstock markets. The prices of iadividual feedstocks vary widely from time to time as shown ia Figure 2, which presents quarterly prices of the various feedstocks ia the United States from 1978 through 1991 ia dollars per metric ton (1000 kg) (4). 

The main difference between gas works and coke oven practice is that, in a gas works, maximum gas yield is a primary consideration whereas in the coke works the quality of the coke is the first consideration. These effects are obtained by choice of a coal feedstock that is suitable to the task. For example, use of lower volatile coals in coke ovens, compared to coals used in gas works, produces lower yields of gas when operating at the same temperatures. In addition, the choice of heating (carbonizing) conditions and the type of retort also play a principal role (10,35). 

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

The equihbrium composition of the product gas can be altered by choice of suitable temperature, pressure, and steam to feedstock ratio to produce a gas mixture consisting largely of methane or largely of hydrogen having varying proportions of carbon monoxide (qv). In each case, some carbon dioxide (qv)... 

Environmental profile has been and will continue to be an important determinant of a market acceptability of surfactants, but will not guarantee its success (111—113). Price and availability have been primary determinants of hydrophobe choice for alcohol-based feedstocks (114). 

Proper choice of feedstocks and use of relatively severe operating conditions ia the reformers produce streams high enough ia toluene to be directiy usable for hydrodemethylation to benzene without the need for extraction. 

Bakers inactive dry yeast is also widely used in the food industry. This yeast may be grown specifically as a food supplement and consequently there is a choice in its composition by varying growth conditions and feedstock makeup. It can possibly produce high levels of nicotinic acid and thiamin, the cmde protein content can be raised to 50—55% and it can be used as a vehicle for the incorporation of micronutrients such as selenium or chromium into the diet. 

Prior to 1975, benzene was catalytically oxidized to produce maleic anhydride, an intermediate in synthesis of polyester resins, lubricant additives, and agricultural chemicals. By 1986 all commercial maleic anhydride was derived from oxidation of / -butane. It is expected that / -butane will remain the feedstock of choice for both economic and environmental reasons. 

The hydroformylation reaction is carried out in the Hquid phase using a metal carbonyl catalyst such as HCo(CO)4 (36), HCo(CO)2[P( -C4H2)] (37), or HRh(CO)2[P(CgH3)2]2 (38,39). The phosphine-substituted rhodium compound is the catalyst of choice for new commercial plants that can operate at 353—383 K and 0.7—2 MPa (7—20 atm) (39). The differences among the catalysts are found in their intrinsic activity, their selectivity to straight-chain product, their abiHty to isomerize the olefin feedstock and hydrogenate the product aldehyde to alcohol, and the ease with which they are separated from the reaction medium (36). 

Catalyst choice is strongly influenced by the nature of the feedstock to be hydrotreated. Thus, whereas nickel-promoted and cobalt—nickel-promoted molybdenum catalysts can be used for desulfurization of certain feedstocks and operating conditions, a cobalt-promoted molybdenum catalyst is generally preferred in this appHcation. For denitrogenation and aromatics saturation, nickel-promoted molybdenum catalysts usually are the better choice. When both desulfurization and denitrogenation of a feedstock are required, the choice of catalyst usually is made so that the more difficult operation is achieved satisfactorily. 

The principal feedstocks used today are the normal paraffin fractions CIO—C13, C12—C14, C14—C17, and C18—C20 together with paraffin wax fractions of C24—C30, precise compositions may vary depending on petroleum oil source. Chlorination extent generally varies from 30 to 70% by weight. The choice of paraffinic feedstock and chlorine content is dependent on the appHcation. 

Catalytic crackings operations have been simulated by mathematical models, with the aid of computers. The computer programs are the end result of a very extensive research effort in pilot and bench scale units. Many sets of calculations are carried out to optimize design of new units, operation of existing plants, choice of feedstocks, and other variables subject to control. A background knowledge of the correlations used in the "black box" helps to make such studies more effective. 

As one would expect, in those cases in which the ionic liquid acts as a co-catalyst, the nature of the ionic liquid becomes very important for the reactivity of the transition metal complex. The opportunity to optimize the ionic medium used, by variation of the halide salt, the Lewis acid, and the ratio of the two components forming the ionic liquid, opens up enormous potential for optimization. However, the choice of these parameters may be restricted by some possible incompatibilities with the feedstock used. Undesired side reactions caused by the Lewis acidity of the ionic liquid or by strong interaction between the Lewis acidic ionic liquid and, for example, some oxygen functionalities in the substrate have to be considered. 

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