Liquid-phase carbonization

Property Manufacturer Precursor Product grade Product form Typical range Gas-phase carbons Liquid-phase carbons ... 

On the basis of the phase formed during the carbonization process, the process is mainly classified as gas phase carbonization, liquid phase carbonization, and solid phase carbonization. Liquid phase carbonization is related to the formation of mesophase carbon microbeads (MCMBs), solid phase carbonization... 

Table 3 shows results obtained from a five-component, isothermal flash calculation. In this system there are two condensable components (acetone and benzene) and three noncondensable components (hydrogen, carbon monoxide, and methane). Henry s constants for each of the noncondensables were obtained from Equations (18-22) the simplifying assumption for dilute solutions [Equation (17)] was also used for each of the noncondensables. Activity coefficients for both condensable components were calculated with the UNIQUAC equation. For that calculation, all liquid-phase composition variables are on a solute-free basis the only required binary parameters are those for the acetone-benzene system. While no experimental data are available for comparison, the calculated results are probably reliable because all simplifying assumptions are reasonable the... 

To prepare gas for evacuation it is necessary to separate the gas and liquid phases and extract or inhibit any components in the gas which are likely to cause pipeline corrosion or blockage. Components which can cause difficulties are water vapour (corrosion, hydrates), heavy hydrocarbons (2-phase flow or wax deposition in pipelines), and contaminants such as carbon dioxide (corrosion) and hydrogen sulphide (corrosion, toxicity). In the case of associated gas, if there is no gas market, gas may have to be flared or re-injected. If significant volumes of associated gas are available it may be worthwhile to extract natural gas liquids (NGLs) before flaring or reinjection. Gas may also have to be treated for gas lifting or for use as a fuel. 

Processes rendered obsolete by the propylene ammoxidation process (51) include the ethylene cyanohydrin process (52—54) practiced commercially by American Cyanamid and Union Carbide in the United States and by I. G. Farben in Germany. The process involved the production of ethylene cyanohydrin by the base-cataly2ed addition of HCN to ethylene oxide in the liquid phase at about 60°C. A typical base catalyst used in this step was diethylamine. This was followed by liquid-phase or vapor-phase dehydration of the cyanohydrin. The Hquid-phase dehydration was performed at about 200°C using alkah metal or alkaline earth metal salts of organic acids, primarily formates and magnesium carbonate. Vapor-phase dehydration was accomphshed over alumina at about 250°C. 

Allied-Signal Process. Cyclohexanone [108-94-1] is produced in 98% yield at 95% conversion by liquid-phase catal57tic hydrogenation of phenol. Hydroxylamine sulfate is produced in aqueous solution by the conventional Raschig process, wherein NO from the catalytic air oxidation of ammonia is absorbed in ammonium carbonate solution as ammonium nitrite (eq. 1). The latter is reduced with sulfur dioxide to hydroxylamine disulfonate (eq. 2), which is hydrolyzed to acidic hydroxylamine sulfate solution (eq. 3). 

Activated carbons for use in Hquid-phase appHcations differ from gas-phase carbons primarily in pore size distribution. Liquid-phase carbons have significantly more pore volume in the macropore range, which permits Hquids to diffuse more rapidly into the mesopores and micropores (69). The larger pores also promote greater adsorption of large molecules, either impurities or products, in many Hquid-phase appHcations. Specific-grade choice is based on the isotherm (70,71) and, in some cases, bench or pilot scale evaluations of candidate carbons. 

Table 5. Liquid-Phase Activated Carbon Consumption, 10 t...

Liquid-phase adsorption methods are widely used for quaUty control and specification purposes. The adsorption of iodine from potassium iodide solution is the standard ASTM method D1510-83 (2). The surface area is expressed as the iodine number whose units are milligrams of iodine adsorbed per gram of carbon. It is quite fortuitous that the values of iodine numbers turn out to be about the same as the values for surface areas in square meters per gram by nitrogen adsorption for nonporous carbon blacks. 

The vapor pressure of carbon monoxide has been compiled (11). Liquid-phase vapor pressure is represented by equation 1, where P is the pressure in MPa or atm and Tis the temperature in K (2). 

N sodium hydroxide, 15% Na as carbonate 2-N potassium hydroxide, 15% K as carbonate Hypothetical perfect solvent having no liquid-phase... 

Two complementai y reviews of this subject are by Shah et al. AIChE Journal, 28, 353-379 [1982]) and Deckwer (in de Lasa, ed.. Chemical Reactor Design andTechnology, Martinus Nijhoff, 1985, pp. 411-461). Useful comments are made by Doraiswamy and Sharma (Heterogeneous Reactions, Wiley, 1984). Charpentier (in Gianetto and Silveston, eds.. Multiphase Chemical Reactors, Hemisphere, 1986, pp. 104—151) emphasizes parameters of trickle bed and stirred tank reactors. Recommendations based on the literature are made for several design parameters namely, bubble diameter and velocity of rise, gas holdup, interfacial area, mass-transfer coefficients k a and /cl but not /cg, axial liquid-phase dispersion coefficient, and heat-transfer coefficient to the wall. The effect of vessel diameter on these parameters is insignificant when D > 0.15 m (0.49 ft), except for the dispersion coefficient. Application of these correlations is to (1) chlorination of toluene in the presence of FeCl,3 catalyst, (2) absorption of SO9 in aqueous potassium carbonate with arsenite catalyst, and (3) reaction of butene with sulfuric acid to butanol. 

Adsorption This is the most widely used of the physical-chemical treatment processes. It is used primarily for the removal of soluble organics with activated carbon serving as the adsorbent. Most liquid-phase-activated carbon adsorption reactions follow a Freundlich Isotherm [Eq. (25-21)]. 

Traditionally, active carbons are made in particulate form, either as powders (particle size < 100 pm, with an average diameter of -20 pm) or granules (particle size in the range 100 pm to several mm). The main precursor materials for particulate active carbons, PAC, are wood, coal, lignite, nutshells especially from coconuts, and peat. In 1985, 360 kt of such precursors (including 36 % wood and 28 % coal) were used to make active carbons [10], of which nearly 80 % were used in liquid-phase applications, with the rest being used in gas-phase applications. Important factors in the selection of a precursor material for an active carbon include availability and cost, carbon yield and inorganic (mainly mineral) matter content, and ease of activation. 

Fig. 6. Breakthrough curves for aqueous acetone (10 mg 1" in feed) flowing through exnutshell granular active carbon, GAC, and PAN-based active carbon fibers, ACF, in a continuous flow reactor (see Fig. 5) at 10 ml min" and 293 K [64]. C/Cq is the outlet concentration relative to the feed concentration. Reprinted from Ind. Eng. Chem. Res., Volume 34, Lin, S. H. and Hsu, F. M., Liquid phase adsorption of organic compounds by granular activated carbon and activated carbon fibers, pp. 2110-2116, Copyright 1995, with permission from the American Chemical Society.

Liquid phase applications account for nearly 80% of the total use of activated carbon. Activated carbon used in liquid phase applications typically have a high fraction of pores in the macropore (>50nm) range. This is to permit the liquid phase molecules to diffuse more rapidly into the rest of the pore structure [15]. 

The principal liquid phase applications, the type of carbon used, and 1987 consumption levels are presented in Table 2. 

Table 2. Liquid phase activated carbon consumption [11,16]. copyright 1992 John Willey Sons, Inc., with permission.

The following are some of the typical industrial applications for liquid-phase carbon adsorption. Generally liquid-phase carbon adsorbents are used to decolorize or purify liquids, solutions, and liquefiable materials such as waxes. Specific industrial applications include the decolorization of sugar syrups the removal of sulfurous, phenolic, and hydrocarbon contaminants from wastewater the purification of various aqueous solutions of acids, alkalies, amines, glycols, salts, gelatin, vinegar, fruit juices, pectin, glycerol, and alcoholic spirits dechlorination the removal of... 

In liquid-phase applications, transfer of the adsorbate from the bulk solution to the carbon particle must proceed through two stages first, via transfer of the adsorbate from the bulk liquid to the surface of the carbon particle, and second, by migration... 

---