Oxidation reactor

The crankcase of a gasoline or diesel engine is in reality a hydrocarbon oxidation reactor oil is submitted to strong agitation in the presence of air at high temperature (120°C) furthermore, metals such as copper and iron, excellent catalysts for oxidation, are present in the surroundings. 

High purity acetaldehyde is desirable for oxidation. The aldehyde is diluted with solvent to moderate oxidation and to permit safer operation. In the hquid take-off process, acetaldehyde is maintained at 30—40 wt % and when a vapor product is taken, no more than 6 wt % aldehyde is in the reactor solvent. A considerable recycle stream is returned to the oxidation reactor to increase selectivity. Recycle air, chiefly nitrogen, is added to the air introducted to the reactor at 4000—4500 times the reactor volume per hour. The customary catalyst is a mixture of three parts copper acetate to one part cobalt acetate by weight. Either salt alone is less effective than the mixture. Copper acetate may be as high as 2 wt % in the reaction solvent, but cobalt acetate ought not rise above 0.5 wt %. The reaction is carried out at 45—60°C under 100—300 kPa (15—44 psi). The reaction solvent is far above the boiling point of acetaldehyde, but the reaction is so fast that Httle escapes unoxidized. This temperature helps oxygen absorption, reduces acetaldehyde losses, and inhibits anhydride hydrolysis. 

In the first step cumene is oxidized to cumene hydroperoxide with atmospheric air or air enriched with oxygen ia one or a series of oxidizers. The temperature is generally between 80 and 130°C and pressure and promoters, such as sodium hydroxide, may be used (17). A typical process iavolves the use of three or four oxidation reactors ia series. Feed to the first reactor is fresh cumene and cumene recycled from the concentrator and other reactors. Each reactor is partitioned. At the bottom there may be a layer of fresh 2—3% sodium hydroxide if a promoter (stabilizer) is used. Cumene enters the side of the reactor, overflows the partition to the other side, and then goes on to the next reactor. The air (oxygen) is bubbled ia at the bottom and leaves at the top of each reactor. 

Wet Oxidation Reactor Design. Several types of reactor designs have been employed for wet oxidation processes. Zimpro, the largest manufacturer of wet oxidation systems, typically uses a tower reactor system. The reactor is a bubble tower where air is introduced at the bottom to achieve plug flow with controlled back-mixing. Residence time is typically under one hour. A horizontal, stirred tank reactor system, known as the Wetox process, was initially developed by Barber-Cohnan, and is also offered by Zimpro. 

Wetox uses a single-reactor vessel that is baffled to simulate multiple stages. The design allows for higher destmction efficiency at lower power input and reduced temperature. Its commercial use has been limited to one faciHty in Canada for treatment of a complex industrial waste stream. Kenox Corp. (North York, Ontario, Canada) has developed a wet oxidation reactor design (28). The system operates at 4.1—4.7 MPa (600 to 680 psi) with air, using a static mixer to achieve good dispersion of Hquid and air bubbles. 

Herm/es/Djnamit JS obe/Process. On a worldwide basis, the Hercules Inc./Dynamit Nobel AG process is the dorninant technology for the production of dimethyl terephthalate the chemistry was patented in the 1950s (67—69). Modifications in commercial practice have occurred over the years, with several variations being practiced commercially (70—72). The reaction to dimethyl terephthalate involves four steps, which alternate between liquid-phase oxidation and liquid-phase esterification. Two reactors are used. Eirst, -xylene is oxidized with air to -toluic acid in the oxidation reactor, and the contents are then sent to the second reactor for esterification with methanol to methyl -toluate. The toluate is isolated by distillation and returned to the first reactor where it is further oxidized to monomethyl terephthalate, which is then esterified in the second reactor to dimethyl terephthalate. 

Eigure 3 is a flow diagram which gives an example of the commercial practice of the Dynamit Nobel process (73). -Xylene, air, and catalyst are fed continuously to the oxidation reactor where they are joined with recycle methyl -toluate. Typically, the catalyst is a cobalt salt, but cobalt and manganese are also used in combination. Titanium or other expensive metallurgy is not required because bromine and acetic acid are not used. The oxidation reactor is maintained at 140—180°C and 500—800 kPa (5—8 atm). The heat of reaction is removed by vaporization of water and excess -xylene these are condensed, water is separated, and -xylene is returned continuously (72,74). Cooling coils can also be used (70). 

The oxidation reactor effluent and methanol ate sent to the esterification reactor, which operates at up to 250°C and a pressure sufficient to maintain the Hquid phase. This latter is about 2500 kPa (25 atm). The oxidation products are converted to methyl -toluate and dimethyl terephthalate without a catalyst. Excess methanol is suppHed, and steam and vaporized methanol ate removed and enter a methanol recovery column. The esterification products flow to a cmde ester column, which separates the toluate from the terephthalate. The overhead stream of methyl -toluate is returned to the oxidation reactor, and the bottoms stream of dimethyl terephthalate goes to a primary distillation. The distillate is dissolved in methanol, crystallized, and sohd dimethyl terephthalate is recovered. The dimethyl terephthalate can then be either recrystallized or distilled to yield the highly pure material needed for the polyesterification reaction. 

Ethylbenzene Hydroperoxide Process. Figure 4 shows the process flow sheet for production of propylene oxide and styrene via the use of ethylbenzene hydroperoxide (EBHP). Liquid-phase oxidation of ethylbenzene with air or oxygen occurs at 206—275 kPa (30—40 psia) and 140—150°C, and 2—2.5 h are required for a 10—15% conversion to the hydroperoxide. Recycle of an inert gas, such as nitrogen, is used to control reactor temperature. Impurities ia the ethylbenzene, such as water, are controlled to minimize decomposition of the hydroperoxide product and are sometimes added to enhance product formation. Selectivity to by-products include 8—10% acetophenone, 5—7% 1-phenylethanol, and <1% organic acids. EBHP is concentrated to 30—35% by distillation. The overhead ethylbenzene is recycled back to the oxidation reactor (170—172). 

The model that best describes the mechanism is usually very complicated. For dynamic studies that require much more computation (and on a more limited domain) a simplified model may give enough information as long as the formalities of the Arrhenius expression and power law kinetics are incorporated. To study the dynamic behavior of the ethylene oxide reactor. 

The first observation of sensitivity-stability was reported by Liljenroth (1918) in connection with the autothermal operation of ammonia oxidation reactors. Papers of Damkdhler (1937) and Wagner (1945) went unnoticed. At Union Carbide Corp. Perkins (1938) used zero order kinetics to define a safe range for ethylene oxidation in an unpublished report. His result,... 

Figure 1-3. The Merox process (1) extractor, (2) oxidation reactor.

Figure 10-14. The SNIA BPD process for producing caprolactam (1) toluene oxidation reactor, (2) fractionator, (3) hydrogenation reactor (stirred autoclave), (4) multistage reactor (conversion to caprolactam), (5) water dilution, (6) crystallizer, (7) solvent extraction, (8) fractionator.

The scheme of the methanation demonstration units is presented in Figure 2. Synthesis gas is heated in heater El and is then mixed with recycle gas. Zinc oxide reactor D1 serves as an emergency catchpot for sulfur breakthrough from the purification plant. The total feed is heated... 

Other variations of the dual-bed scheme exist as a combination of thermal oxidizing reactors and catalytic reducing reactors. The Questor company has developed a reactor with three zones the first zone is a thermal reactor with limited air to raise the temperature of the exhaust gas, the second zone is a catalytic bed of metallic screens to reduce NO, and the third zone is another thermal reactor where secondary air is injected to complete the oxidation of CO and hydrocarbons (45). 

If the catalytic HBr oxidation reactor is required to serve as a central facility for recycling a variety of waste HBr streams and conditions that combust all of the organic contaminants cannot be discovered, then further bromine purification operations are probably required. The simplest operation is distillation of the bromine. Due to the high bromine vapor pressure, bromine distillation can be accomplished using relatively small equipment. This is expected to be a highly effective method of purification, particularly where the boiling points of any contaminants are greater than 10°C different from that of bromine. In other applications, absorption or extraction may be needed. 

Evaluation of acetaldehyde oxidation reactor especially by determining reaction conversion and selectivity. 

Mechanism of Scaling on the Oxidation Reactor Wall in TiOi Synthesis by Chloride Process... 

Figure 5.18. Schematic of the batch enzymatic oxidation reactor.

Fig. 8. Observed temperature profiles in a single, flow-reversal S02 oxidation reactor processing (I) 40,000 m3/h, (II) 20,000 m3/h of a smelter effluent containing 2.3 vol% S02. (Figure adapted from Matros, 1989, with permission, 1989 Elsevier Science Publishers.)...

Silveston, P. L., Hudgins, R. R., Bogdashev, S., Vernijakovskaja, N and Matros, Yu. Sh., Modelling of a periodically operated packed bed S02 oxidation reactor at high conversion in Unsteady-state Processes in Catalysis (Matros, Yu. Sh., Ed.). VNU Science Press, Utrecht, 1990. 

Modelling of a periodically operated packed bed S02 oxidation reactor at high conversion. Chem. Eng. Sci. 49(3), 335-341 (1994). 

Titanium dioxide chloride process oxidation reactor... 

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