Dioxide removal

Process selectivity indicates the preference with which the process removes one acid gas component relative to or in preference to another. For example, some processes remove both hydrogen sulfide and carbon dioxide, whereas other processes are designed to remove hydrogen sulfide only. Thus it is important to consider the process selectivity for hydrogen sulfide removal compared to carbon dioxide removal, ie, the carbon dioxide-to-hydrogen sulfide ratio in the natural gas, in order to ensure minimal concentrations of these components in the product. 

The saturated, cleaned raw synthesis gas from a Texaco partial oxidation system is first shifted by use of a sulfur resistant catalyst. Steam required for shifting is already present ia the gas by way of the quench operation ia the generator. The shifted gas is then processed for hydrogen sulfide and carbon dioxide removal followed by Hquid nitrogen scmbbiag. 

Capital costs which foUow the same trend as energy consumption, can be about 1.5 to 2.0 times for partial oxidation and coal gasification, respectively, that for natural gas reforming (41). A naphtha reforming plant would cost about 15—20% more than one based on natural gas because of the requirement for hydrotreatiag faciUties and a larger front-end needed for carbon dioxide removal. 

Steam-Reforming Natural Gas. Natural gas is the single most common raw material for the manufacture of ammonia. A typical flow sheet for a high capacity single-train ammonia plant is iadicated ia Figure 12. The important process steps are feedstock purification, primary and secondary reforming, shift conversion, carbon dioxide removal, synthesis gas purification, ammonia synthesis, and recovery. 

Carbon Dioxide Removal. The effluent gases from the shift converters contain about 17—19 vol % (dry) carbon dioxide (qv) which is ultimately reduced to a few ppm by bulk CO2 removal, followed by a final purification step. Commercial CO2 removal systems can be broadly classified as... 

It is generally unacceptable to emit sulfur dioxide, thus the scmbber effluent must be treated for sulfur dioxide removal. If the plant aheady possesses faciUties for the production of sulfuric acid, this rather concentrated sulfur dioxide stream can be easily fed into the wet gas cleaning circuit and disposed of in the sulfuric acid plant. The quantity is so small that it does not put any additional burden on the sulfuric acid plant. Because no tellurium is carried over with the selenium dioxide during roasting, it is possible to produce a selenium product which can be purified to commercial grade (99.5-99.7%). 

As worldwide attention has been focused on the dangers of acid rain, the demand to reduce sulfur dioxide [7446-09-5] emissions has risen. Several processes have been developed to remove and recover sulfur dioxide. Sulfur can be recovered from sulfur dioxide as Hquid sulfur dioxide, sulfuric acid, or elemental sulfur. As for the case of hydrogen sulfide, sulfur dioxide removal processes are categorized as adsorption, absorption, or conversion processes. 

An additional benefit of adsorption-based sulfur dioxide removal processes is that nitrogen oxides, NO, are also removed by the sorbent. Nitrogen oxides desorb when the sorbent is heated using hot air. 

Regenerable absorption processes have also been developed. In these processes, the solvent releases the sulfur dioxide in a regenerator and then is reused in the absorber. The WelLman-Lord process is typical of a regenerable process. Figure 11 illustrates the process flow scheme. Sulfur dioxide removal efficiency is from 95—98%. The gas is prescmbbed with water, then contacts a sodium sulfite solution in an absorber. The sulfur dioxide is absorbed into solution by the following reaction ... 

Liade AG offers the Clintox process for sulfur dioxide removal. This process uses a physical solvent to absorb the sulfur dioxide. A concentrated sulfur dioxide stream is produced by regeneration. The Clintox process can be iategrated with the Claus process by recovering sulfur dioxide from the iaciaerated tail gases and recycling the sulfur dioxide to the front of the Claus unit. 

Figure 3 shows a simple schematic diagram of an oxygen-based process. Ethylene, oxygen, and the recycle gas stream are combined before entering the tubular reactors. The basic equipment for the reaction system is identical to that described for the air-based process, with one exception the purge reactor system is absent and a carbon dioxide removal unit is incorporated. The CO2 removal scheme illustrated is based on a patent by Shell Oil Co. (127), and minimises the loss of valuable ethylene in the process. 

Ethylene Oxide Recovery. An economic recovery scheme for a gas stream that contains less than 3 mol % ethylene oxide (EO) must be designed. It is necessary to achieve nearly complete removal siace any ethylene oxide recycled to the reactor would be combusted or poison the carbon dioxide removal solution. Commercial designs use a water absorber foUowed by vacuum or low pressure stripping of EO to minimize oxide hydrolysis. Several patents have proposed improvements to the basic recovery scheme (176—189). Other references describe how to improve the scmbbiag efficiency of water or propose alternative solvents (180,181). 

Experience in air separation plant operations and other ciyogenic processing plants has shown that local freeze-out of impurities such as carbon dioxide can occur at concentrations well below the solubihty limit. For this reason, the carbon dioxide content of the feed gas sub-jec t to the minimum operating temperature is usually kept below 50 ppm. The amine process and the molecular sieve adsorption process are the most widely used methods for carbon dioxide removal. The amine process involves adsorption of the impurity by a lean aqueous organic amine solution. With sufficient amine recirculation rate, the carbon dioxide in the treated gas can be reduced to less than 25 ppm. Oxygen is removed by a catalytic reaction with hydrogen to form water. 

Mounting electrodes in a bioreactor is costly, and there is an additional contamination risk for sensitive cell cultures. Some other sensors of prac ticai importance are those for dissolved oxygen and for dissolved carbon dioxide. The analysis of gas exiting from a bioreactor with an infrared unit that detects carbon dioxide or a paramagnetic unit that detects oxygen (after carbon dioxide removal) has been replaced by mass spec trophotometry. Gas chromatographic procedures coupled with a mass spectrophotometer will detect 1 the volatile components. 

Direct hydrogen cyanide (HCN) gas in a fuel oil gasification plant to a combustion unit to prevent its release. 4. Consider using purge gases from the synthesis process to fire the reformer strip condensates to reduce ammonia and methanol. 5. Use carbon dioxide removal processes that do not release toxics to the environment. When monoethanolamine (MEA) or other processes, such as hot potassium carbonate, are used in carbon dioxide removal, proper operation and maintenance procedures should be followed to minimize releases to the environment. 

Figure 19. Variable venturi scrubber for flyash and sulfur dioxide removal.

The carbon dioxide removed in synthesis gas preparation can be reacted with ammonia, to lonn urea CO(NH2)2- This is an excellent fertilizer, highly concentrated in nitrogen (46.6%) and also useful as an additive in animal feed to provide the nitrogen for formation of meat protein. Urea is also an important source of resins and plastics by reacting it with formaldehyde from methanol. 

Fig. 8.7 shows a second example (Cycle A2) of carbon dioxide removal by chemical absorption from a CCGT plant, but one in which the semi-closed concept is introduced— exhaust gas leaving the HRSG is partially recirculated. This reduces the flow rate of the gas to be treated in the removal plant, so that less steam is required in the stripper and the extra equipment to be installed is smaller and cheaper. This is also due to the better removal efficiency achievable—for equal reactants flow rate—when the volumetric fraction of CO2 in the exhaust gas is raised from the 4-6% value typical of open cycle gas turbines to about 12% achievable with semi-clo.sed operation. 

The second step after secondary reforming is removing carbon monoxide, which poisons the catalyst used for ammonia synthesis. This is done in three further steps, shift conversion, carbon dioxide removal, and methanation of the remaining CO and CO2. 

Carbon Dioxide Removal. Aside from contained carbon dioxide which is removed from syngas when absorbing hydrogen sulfide, the total carbon dioxide produced in the methanation system is removed by conventional absorption in a single-stage operation in which the volume of gas to be treated is minimum and the partial pressure of the carbon dioxide is maximum. 

Where silica and carbon dioxide removal is necessary, the anion unit should contain SBA (OH) resin, and the degasser should precede the anion. 

In some cases, the solids themselves are subjected to extraction by a solvent. For example, in one process used to decaffeinate coffee, the coffee beans are mixed with activated charcoal and a high-pressure stream of supercritical carbon dioxide (carbon dioxide at high pressure and above its critical temperature) is passed over them at approximately 90°C. A supercritical solvent is a highly mobile fluid with a very low viscosity. The carbon dioxide removes the soluble caffeine preferentially without extracting the flavoring agents and evaporates without leaving a harmful residue. 

It is estimated that photosynthesis is a sink for around 60 billion tons of carbon every year, by far the strongest mechanism for carbon dioxide removal from the atmosphere. (This removal is almost exactly balanced by the respiration of animals, which combines oxygen with hydrocarbons to produce carbon dioxide and water vapor.)... 

While the use of low-sulfur fuels is one mechanism to reduce sulfur dioxide emission, alternatively most approaches focus on scrubbing or ridding the emissions in smoke stacks of sulfur dioxide gas. A number of different types of scrubbers, i.e., sulfur dioxide removal systems, are available for industry. One system sprays the flue gas into a liquid solution of sodium hydroxide. The hydroxide combines with SO2 and O2 to form the corresponding sulfate which can be removed from the aqueous solution ... 

Li, W., S.K. Gangwal, R.P Gupta, and B.S. Turk, Development of Fluidizable Lithium Silicate-Based Sorbents for High Temperature Carbon Dioxide Removal, 2006 Pittsburgh Coal Conference, Pittsburgh, PA, September 2006. 

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