Catalyst preheating

On-board electrical systems Electromagnetic valve control, catalysts preheating, brake actuators, and steering... 

Efficient catalyst preheating facilities, vented to the chimney. At least two catalyst stages must be above "strike" temperature before sulfur dioxide is admitted to contact the catalyst. 

Yoshihara K, Honda S, Lee J-G, Mori H, Oura K, Katayama M. High-density growth of vertically aligned carbon nanotubes with high linearity by catalyst preheating in acetylene. Jpn J Appl Phys 2008 47 1941-3. 

From Ethyl Alcohol. Some acetaldehyde is produced commercially by the catalytic oxidation of ethyl alcohol. The oxidation is carried out by passing alcohol vapors and preheated air over a silver catalyst at 480°C (98). 

Ma.nufa.cture. Butyrolactone is manufactured by dehydrogenation of butanediol. The butyrolactone plant and process in Germany, as described after World War II (179), approximates the processes presendy used. The dehydrogenation was carried out with preheated butanediol vapor in a hydrogen carrier over a supported copper catalyst at 230—250°C. The yield of butyrolactone after purification by distillation was about 90%. 

Oxidation Step. A review of mechanistic studies of partial oxidation of propylene has appeared (58). The oxidation process flow sheet (Fig. 2) shows equipment and typical operating conditions. The reactors are of the fixed-bed shell-and-tube type (about 3—5 mlong and 2.5 cm in diameter) with a molten salt coolant on the shell side. The tubes are packed with catalyst, a small amount of inert material at the top serving as a preheater section for the feed gases. Vaporized propylene is mixed with steam and ak and fed to the first-stage reactor. The feed composition is typically 5—7% propylene, 10—30%... 

The preheated gases react exothermically over the first-stage catalyst with the peak temperature ia the range of 330—430°C, depending on conditions and catalyst selectivity. The conversion of propylene to waste gas (carbon dioxide and carbon monoxide) is more exothermic than its conversion to acroleia. At the end of the catalyst bed the temperature of the mixture drops toward that of the molten salt coolant. 

Naphtha desulfurization is conducted in the vapor phase as described for natural gas. Raw naphtha is preheated and vaporized in a separate furnace. If the sulfur content of the naphtha is very high, after Co—Mo hydrotreating, the naphtha is condensed, H2S is stripped out, and the residual H2S is adsorbed on ZnO. The primary reformer operates at conditions similar to those used with natural gas feed. The nickel catalyst, however, requires a promoter such as potassium in order to avoid carbon deposition at the practical levels of steam-to-carbon ratios of 3.5—5.0. Deposition of carbon from hydrocarbons cracking on the particles of the catalyst reduces the activity of the catalyst for the reforming and results in local uneven heating of the reformer tubes because the firing heat is not removed by the reforming reaction. 

Fresh reducing gas is generated by reforming natural gas with steam. The natural gas is heated in a recuperator, desulfurized to less than 1 ppm sulfur, mixed with superheated steam, further preheated to 620°C in another recuperator, then reformed in alloy tubes filled with nickel-based catalyst at a temperature of 830°C. The reformed gas is quenched to remove water vapor, mixed with clean recycled top gas from the shaft furnace, reheated to 925°C in an indirect fired heater, and injected into the shaft furnace. For high (above 92%) metallization a CO2 removal unit is added in the top gas recycle line in order to upgrade the quaUty of the recycled top gas and reducing gas. 

Reducing gas is generated from natural gas in a conventional steam reformer. The natural gas is preheated, desulfurized, mixed with steam, further heated, and reformed in catalyst-filled reformer tubes at 760°C. The reformed gas is cooled to 350°C in a waste heat boiler, passed through a shift converter to increase the content, mixed with clean recycled top gas, heated to 830°C in an indirect-fired heater, then injected into reactor 4. 

Alcohol Amination. There are many similarities in the process technologies for Methods 1 and 2. In both, an alcohol reacts with ammonia over a fixed catalyst bed at elevated temperature. The reaction section consists of feed systems, vapori2ers, and/or preheaters which pass a Hquid or gaseous feed mixture over the catalyst bed in the desired ratio, temperature, and pressure. Possible amination catalysts for each method are as foUows. 

A Hquid-phase variation of the direct hydration was developed by Tokuyama Soda (78). The disadvantages of the gas-phase processes are largely avoided by employing a weakly acidic aqueous catalyst solution of a siHcotungstate (82). Preheated propylene, water, and recycled aqueous catalyst solution are pressurized and fed into a reaction chamber where they react in the Hquid state at 270°C and 20.3 MPa (200 atm) and form aqueous isopropyl alcohol. Propylene conversions of 60—70% per pass are obtained, and selectivity to isopropyl alcohol is 98—99 mol % of converted propylene. The catalyst is recycled and requites Htde replenishment compared to other processes. Corrosion and environmental problems are also minimized because the catalyst is a weak acid and because the system is completely closed. On account of the low gas recycle ratio, regular commercial propylene of 95% purity can be used as feedstock. 

The OLEFLEX process uses multiple side-by-side, radial flow, moving-bed reactors connected in series. The heat of reaction is suppHed by preheated feed and interstage heaters. The gas-phase reaction is carried out over a catalyst, platinum supported over alumina, under very near isothermal conditions. The first commercial installation of this technology, having an annual capacity of 100,000 t, was made in 1990 by the National Petrochemical Corporation in Thailand. A second unit, at 245,000 t capacity, has been built in South Korea by the ISU Chemical Company (70). 

In a typical oxychlorination reaction, preheated gas streams at temperatures of 180—200°C are fed onto a fixed- or fiuidized-catalyst bed containing 2—10% copper impregnated on an activated alumina. The reaction occurs during a 15—22 s residence time on the catalyst bed at a temperature of 230—315°C. Typical yields to 1,2-dichloroethane range from 92—97%. 

Gas Phase. The gas-phase methanol hydrochlorination process is used more in Europe and Japan than in the United States, though there is a considerable body of Hterature available. The process is typicaHy carried out as foHows vaporized methanol and hydrogen chloride, mixed in equimolar proportions, are preheated to 180—200°C. Reaction occurs on passage through a converter packed with 1.68—2.38 mm (8—12 mesh) alumina gel at ca 350°C. The product gas is cooled, water-scmbbed, and Hquefied. Conversions of over 95% of the methanol are commonly obtained. Garnma-alurnina has been used as a catalyst at 295—340°C to obtain 97.8% yields of methyl chloride (25). Other catalysts may be used, eg, cuprous or zinc chloride on active alumina, carbon, sHica, or pumice (26—30) sHica—aluminas (31,32) zeoHtes (33) attapulgus clay (34) or carbon (35,36). Space velocities of up to 300 h , with volumes of gas at STP per hour per volume catalyst space, are employed. 

Fig. 5. Catalytic system designs (11) of (a) basic VOC catalytic converter containing a preheater section, a reactor housing the catalyst, and essential controls, ducting, instmmentation, and other elements (b) a heat exchanger using the cleaned air exiting the reactor to raise the temperature of the incoming process exhaust and (c) extracting additional heat from the exit gases by a secondary heat exchanger.

These various reactions should be minimized to avoid plugging the catalyst and to prevent fouling of the downstream air preheaters, when these components condense from the gas at the lower temperatures. 

NO -laden fumes are preheated by effluent from the catalyst vessel in the feed/effluent heat exchanger and then heated by a gas- or oil-fired heater to over 600° F. A controlled quantity of ammonia is injected into the gas stream before it is passed through a metal oxide, zeolite, or promoted zeolite catalyst bed. The NO is reduced to nitrogen and water in the presence or ammonia in accordance with the following exothermic reactions ... 

NO analyzers at the preheater inlet and catalyst vessel outlet monitor NO concentrations and control the ammonia feed rate. The effluent gives up much of its heat to the incoming gas in the feed/effluent exchanger. The vent gas is discharged at about 350° F. 

The tube is much longer than needed for the catalyst volume to provide a surface for preheating and to minimize temperature losses at the discharge end. The tube can be bent into a U shape and immersed in a fluidized sand bath, or it can be straight and placed inside a tubular furnace in a temperature-equalizing bronze block. Thermocouples are usually inserted... 

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