Steam residence time

PyrolysB takes place in a furnace at about 650 to 7Q0 C, in the presence of radical initiators (HBr or preferably peroxides) and steam. Residence time is about 1/10. The effluent is quenched to recover the catalyst, and then demethanized. The other tight hydrocarbons are stripped and the isoprene is separated by simple distillation. A process flow sheet is given in Fig. 6.4. 

When injecting steam, residence time is reduced and so does the conversion. An increase in temperature is needed to compensate this reduction in conversion. One weight percentage of steam is a common injection proportion with the feed. 

The conversion takes place at high temperature (820-850°C) and very short residence time (hundredth of seconds) in the presence of steam. The by-products are hydrogen, methane and a highly aromatic residual fuel-oil. 

In this condenser, part of the stripper off-gases are condensed (the heat of condensation is used to generate low pressure steam). The carbamate formed and noncondensed NH and CO2 are put into the reactor bottom and conversion of the carbamate into urea takes place. The reactor is sized to allow enough residence time for the reaction to approach equiUbrium. The heat required for the urea reaction and for heating the solution is suppHed by additional condensation of NH and CO2. The reactor which is lined with 316 L stainless steel, contains sieve trays to provide good contact between the gas and Hquid phases and to prevent back-mixing. The stripper tubes are 25-22-2 stainless steel. Some strippers are still in service after almost 30 years of operation. 

Olefins are produced primarily by thermal cracking of a hydrocarbon feedstock which takes place at low residence time in the presence of steam in the tubes of a furnace. In the United States, natural gas Hquids derived from natural gas processing, primarily ethane [74-84-0] and propane [74-98-6] have been the dominant feedstock for olefins plants, accounting for about 50 to 70% of ethylene production. Most of the remainder has been based on cracking naphtha or gas oil hydrocarbon streams which are derived from cmde oil. Naphtha is a hydrocarbon fraction boiling between 40 and 170°C, whereas the gas oil fraction bods between about 310 and 490°C. These feedstocks, which have been used primarily by producers with refinery affiliations, account for most of the remainder of olefins production. In addition a substantial amount of propylene and a small amount of ethylene ate recovered from waste gases produced in petroleum refineries. 

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%. 

The unit Kureha operated at Nakoso to process 120,000 metric tons per year of naphtha produces a mix of acetylene and ethylene at a 1 1 ratio. Kureha s development work was directed toward producing ethylene from cmde oil. Their work showed that at extreme operating conditions, 2000°C and short residence time, appreciable acetylene production was possible. In the process, cmde oil or naphtha is sprayed with superheated steam into the specially designed reactor. The steam is superheated to 2000°C in refractory lined, pebble bed regenerative-type heaters. A pair of the heaters are used with countercurrent flows of combustion gas and steam to alternately heat the refractory and produce the superheated steam. In addition to the acetylene and ethylene products, the process produces a variety of by-products including pitch, tars, and oils rich in naphthalene. One of the important attributes of this type of reactor is its abiUty to produce variable quantities of ethylene as a coproduct by dropping the reaction temperature (20—22). 

Fresh butane mixed with recycled gas encounters freshly oxidized catalyst at the bottom of the transport-bed reactor and is oxidized to maleic anhydride and CO during its passage up the reactor. Catalyst densities (80 160 kg/m ) in the transport-bed reactor are substantially lower than the catalyst density in a typical fluidized-bed reactor (480 640 kg/m ) (109). The gas flow pattern in the riser is nearly plug flow which avoids the negative effect of backmixing on reaction selectivity. Reduced catalyst is separated from the reaction products by cyclones and is further stripped of products and reactants in a separate stripping vessel. The reduced catalyst is reoxidized in a separate fluidized-bed oxidizer where the exothermic heat of reaction is removed by steam cods. The rate of reoxidation of the VPO catalyst is slower than the rate of oxidation of butane, and consequently residence times are longer in the oxidizer than in the transport-bed reactor. 

Some slurry processes use continuous stirred tank reactors and relatively heavy solvents (57) these ate employed by such companies as Hoechst, Montedison, Mitsubishi, Dow, and Nissan. In the Hoechst process (Eig. 4), hexane is used as the diluent. Reactors usually operate at 80—90°C and a total pressure of 1—3 MPa (10—30 psi). The solvent, ethylene, catalyst components, and hydrogen are all continuously fed into the reactor. The residence time of catalyst particles in the reactor is two to three hours. The polymer slurry may be transferred into a smaller reactor for post-polymerization. In most cases, molecular weight of polymer is controlled by the addition of hydrogen to both reactors. After the slurry exits the second reactor, the total charge is separated by a centrifuge into a Hquid stream and soHd polymer. The solvent is then steam-stripped from wet polymer, purified, and returned to the main reactor the wet polymer is dried and pelletized. Variations of this process are widely used throughout the world. 

Dilute (1—3%), chloride-containing solutions of either HOCl, hypochlorite, or aqueous base, can be stripped in a column against a current of CI2, steam, and air at 95—100°C and the vapors condensed giving virtually chloride-free HOCl solutions of higher concentration in yields as high as 90% (122—124). Distillation of more concentrated solutions requires reduced pressure, lower temperature, and shorter residence times to offset the increased decomposition rates. 

Still another process, called BI-GAS, was developed by Bituminous Coal Research in a 73 t/d pilot plant in Homer City, Peimsylvania. In this entrained-bed process, pulverized coal slurry was dried and blown into the second stage of the gasifier to contact 1205°C gases at ca 6.9 MPa (1000 psi) for a few seconds residence time. Unreacted char is separated and recycled to the first stage to react with oxygen and steam at ca 1650°C to produce hot gas and molten slag that is tapped. 

Product Distribution. In addition to ethylene, many by-products are also formed. Typical product distributions for various feeds from a typical short residence time furnace are shown in Table 5. The product distribution is strongly influenced by residence time, hydrocarbon partial pressure, steam-to-od ratio, and coil outlet pressure. 

Advanced Cracking Reactor. The selectivity to olefins is increased by reducing the residence time. This requires high temperature or reduction of the hydrocarbon partial pressure. An advanced cracking reactor (ACR) was developed jointly by Union Carbide with Kureha Chemical Industry and Chiyoda Chemical Constmction Co. (72). A schematic of this reactor is shown in Figure 6. The key to this process is high temperature, short residence time, and low hydrocarbon partial pressure. Superheated steam is used as the heat carrier to provide the heat of reaction. The burning of fuel... 

Dynamically, the response of hquid temperature to a step in steam flow is that of a distributed lag, shown in Fig. 8-48. The time required to reach 63 percent complete response, X "t, is essentially the residence time of the fluid in the exchanger, which is its volume divided... 

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