Residence time carbonization

Another hydrogenation process utilizes internally generated hydrogen for hydroconversion in a single-stage, noncatalytic, fluidized-bed reactor (41). Biomass is converted in the reactor, which is operated at about 2.1 kPa, 800°C, and residence times of a few minutes with steam-oxygen injection. About 95% carbon conversion is anticipated to produce a medium heat value (MHV) gas which is subjected to the shift reaction, scmbbing, and methanation to form SNG. The cold gas thermal efficiencies are estimated to be about 60%. 

At still higher temperatures, when sufficient oxygen is present, combustion and "hot" flames are observed the principal products are carbon oxides and water. Key variables that determine the reaction characteristics are fuel-to-oxidant ratio, pressure, reactor configuration and residence time, and the nature of the surface exposed to the reaction 2one. The chemistry of hot flames, which occur in the high temperature region, has been extensively discussed (60-62) (see Col ustion science and technology). 

Manufacture and Processing. The largest volume of coal is carbonized in batch coke ovens to produce a hard coke suitable for blast furnaces for the reduction of iron ore. Oven temperatures, as measured in the flues, are between 1250 and 1350° and residence time varies between 17 and 30 h. The gas made in this process is mainly used as fuel and other appHcations in the steel works (see Fuels, synthetic). 

One patent describes a continuous process involving an aqueous alkah metal hydroxide, carbon disulfide, and an alcohol (82). The reported reaction time is 0.5—10 min before the mixture is fed to the dryer. The usual residence time is on the order of hours. A study ia the former USSR reported the use of the water—alcohol azeotrope for water removal from isobutyl or isoamyl alcohol and the appropriate alkah hydroxide to form the alkoxide prior to the addition of carbon disulfide (83). 

A typical reactor operates at 600—900°C with no catalyst and a residence time of 10—12 s. It produces a 92—93% yield of carbon tetrachloride and tetrachloroethylene, based on the chlorine input. The principal steps in the process include (/) chlorination of the hydrocarbon (2) quenching of reactor effluents 3) separation of hydrogen chloride and chlorine (4) recycling of chlorine to the reactor and (i) distillation to separate reaction products from the hydrogen chloride by-product. Advantages of this process include the use of cheap raw materials, flexibiUty of the ratios of carbon tetrachloride and tetrachloroethylene produced, and utilization of waste chlorinated residues that are used as a feedstock to the reactor. The hydrogen chloride by-product can be recycled to an oxychlorination unit (30) or sold as anhydrous or aqueous hydrogen chloride. 

Pressure and residence time have relatively Htde effect on reaction selectivity, at least within the ranges normally encountered. Poor mixing and excessive residence time result in increased carbonization of the reactor. 

The calcium cyanamide feed is weU mixed with the recycled slurry and filtrate ia a feed vessel. The calcium cyanamide is added at a rate to maintain a pH of 6.0—6.5 ia the cooling tank. The carbonation step can be conducted ia a turbiae absorber with a residence time of 1—2 min. After the carbonation step, the slurry is held at 30—40°C to complete the formation of calcium carbonate, after which the slurry is cooled and filtered. AH equipment for the process is preferably of stainless steel. The resulting solution is used directiy for conversion to dicyandiamide. 

In AFBC units, heat is removed from the flue gas by a convection-pass tube bank. The particulates leaving the boiler with the flue gas consist of unreacted and spent sorbent, unburned carbon, and ash. Multiclones after the convection pass remove much of the particulate matter and recvcle it to the combustor, increasing the in-furnace residence time an improving combustion efficiency and sulfur retention performance. Bubbling PFBC units do not have convection-pass tube banks and do not recycle solids to the boiler. 

Thermal oxidizers must be built to provide the residence time and temperatures to achieve the desired destruction efficiency (DE). As such, thermal oxidizers are comparatively larger than catalytic oxidizers since their residence time is two to four times greater. Historical designs of thermal oxidizers were comprised of carbon steel for the outer shell and castable refractory or brick as the thermal liner (a refractory is like a cement, which is put on the inside of the rector shell to act as a thermal insulation barrier). Modern units are designed and built using ceramic fiber insulation on the inside, which is a lightweight material, and has a relatively long life. Old refractory would tend to fail over a period of years by attrition of expansion and contraction. 

Enclosed flares are composed of multiple gas burner heads placed at ground level in a staeklike enclosure that is usually refractory or ceramic lined. Many flares are equipped with automatic damper controls that regulate the supply of combustion air depending on temperature which is monitored upstream of the mixing, but inside the staek. This class of flare is becoming the standard in the industry due to its ability to more effectively eontrol emissions. Requirements on emissions includes carbon monoxide limits and minimal residence time and temperature. Exhaust gas temperatures may vary from 1,000 to 2,000 F. 

Air pollution problems in which adsorption is considered a unit operation involve gaseous contaminants. The number of molecules present at the carbon surface is dependent on the number that reach the surface and on the residence time of these molecules on the carbon surface. If n molecules strike a unit area of a surface per unit time, and remain there for an average time, t, then a number of molecules are present per unit area of surface ... 

Glaser and Lichtenstein (G3) measured the liquid residence-time distribution for cocurrent downward flow of gas and liquid in columns of -in., 2-in., and 1-ft diameter packed with porous or nonporous -pg-in. or -in. cylindrical packings. The fluid media were an aqueous calcium chloride solution and air in one series of experiments and kerosene and hydrogen in another. Pulses of radioactive tracer (carbon-12, phosphorous-32, or rubi-dium-86) were injected outside the column, and the effluent concentration measured by Geiger counter. Axial dispersion was characterized by variability (defined as the standard deviation of residence time divided by the average residence time), and corrections for end effects were included in the analysis. The experiments indicate no effect of bed diameter upon variability. For a packed bed of porous particles, variability was found to consist of three components (1) Variability due to bulk flow through the bed... 

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