Carbon monoxide recovery

Of the four commercial processes for the purification of carbon monoxide two processes are based on the absorption of carbon monoxide by salt solutions, the third uses either low temperature condensation or fractionation, and the fourth method utilizes the adsorption of carbon monoxide on a soHd adsorbent material. AH four processes use similar techniques to remove minor impurities. Particulates are removed in cyclones or by scmbbing. Scmbbing also removes any tars or heavy hydrocarbon fractions. Acid gases are removed by absorption in monoethanolamine, hot potassium carbonate, or by other patented removal processes. The purified gas stream is then sent to a carbon monoxide recovery section for final purification and by-product recovery. 

The carbon monoxide-rich, Hquid condensate from the primary separator is expanded and exchanged against the incoming feed and is then sent to a distillation column where the carbon monoxide is purified. The bottoms Hquor from the methane wash column is expanded, heat-exchanged, and sent to the bottom section of the distillation column for methane rectification and carbon monoxide recovery. The methane bottom stream is recompressed and recycled to the top of the wash column after subcooling. A sidestream of methane is withdrawn to avoid a buildup of impurities in the system. 

A. Carbon Monoxide Recovery from Offgas Streams... 

Feed gas for carbon monoxide recovery is pretreated to remove carbon dioxide and water. The gas must be dried to remove all traces of moisture. Both carbon dioxide and water will freeze and heat transfer will be impaired at cryogenic temperatures. The feed gas is also compressed to the pressure required for the partial condensation of carbon monoxide at the temperatures that can be reached with the refrigeration system available. Typically, this is between 350 and 500 psig. The operating temperatures are approximately — 160 F to — 200°F. 

George E. Haddeland, Carbon Monoxide Recovery, Process Economics Program, SRI International, Menlo Park, CA (1979), pp. 18-19. 

Vacuum swing adsorption (VSA) air separation in, 2, 32, 34 carbon monoxide recovery in, 107, 108 vacuum pressure swing adsorption (VPSA), 2, 32-34 Valeric acid, 263... 

Carbon monoxide High-pressure Off-gas Light ends Catalyst recovery Dehydration... 

The acetic anhydride process employs a homogeneous rhodium catalyst system for reaction of carbon monoxide with methyl acetate (36). The plant has capacity to coproduce approximately 545,000 t/yr of acetic anhydride, and 150,000 t/yr of acetic acid. One of the many challenges faced in operation of this plant is recovery of the expensive rhodium metal catalyst. Without a high recovery of the catalyst metal, the process would be uneconomical to operate. 

Prior to methanation, the gas product from the gasifier must be thoroughly purified, especially from sulfur compounds the precursors of which are widespread throughout coal (23) (see Sulfurremoval and recovery). Moreover, the composition of the gas must be adjusted, if required, to contain three parts hydrogen to one part carbon monoxide to fit the stoichiometry of methane production. This is accompHshed by appHcation of a catalytic water gas shift reaction. 

The sodium formate process is comprised of six steps (/) the manufacture of sodium formate from carbon monoxide and sodium hydroxide, (2) manufacture of sodium oxalate by thermal dehydrogenation of sodium formate at 360°C, (J) manufacture of calcium oxalate (slurry), (4) recovery of sodium hydroxide, (5) decomposition of calcium oxalate where gypsum is produced as a by-product, and (6) purification of cmde oxahc acid. This process is no longer economical in the leading industrial countries. UBE Industries (Japan), for instance, once employed this process, but has been operating the newest diaLkyl oxalate process since 1978. The sodium formate process is, however, still used in China. 

Landfill G as Recovery. This process has emerged from the need to better manage landfill operations. Landfill gas is produced naturally anaerobic bacteria convert the disposed organic matter into methane, carbon monoxide, and other gases. The quantity of methane gas is substantial and could be utilized as fuel, but generally is not. Most of the methane simply leaks into the surrounding atmosphere. 

Lateritic Ores. The process used at the Nicaro plant in Cuba requires that the dried ore be roasted in a reducing atmosphere of carbon monoxide at 760°C for 90 minutes. The reduced ore is cooled and discharged into an ammoniacal leaching solution. Nickel and cobalt are held in solution until the soflds are precipitated. The solution is then thickened, filtered, and steam heated to eliminate the ammonia. Nickel and cobalt are precipitated from solution as carbonates and sulfates. This method (8) has several disadvantages (/) a relatively high reduction temperature and a long reaction time (2) formation of nickel oxides (J) a low recovery of nickel and the contamination of nickel with cobalt and (4) low cobalt recovery. Modifications to this process have been proposed but all include the undesirable high 760°C reduction temperature (9). 

The waste gas remaining after removal of ammonia and recovery of hydrogen cyanide contains enough hydrogen and carbon monoxide that it is flammable and has enough heat value to make it a valuable fuel. It is usually used to displace other fuel ia boilers. 

The iron smelting process in the blast furnace is a classic example worth mentioning in order to illustrate some general features of waste heat recovery. With respect to the combustion of its fuel and the resultant formation of gases, the iron blast furnace is like a huge gas producer. There is always an excess of carbon in the combustion zone, and the product formed in it is carbon monoxide. There is, of course, no steam blown in as such, but whatever moisture is present in the blast is decomposed by carbon, as in creating producer gas ... 

The reactor is followed by a gas-liquid separator operating at 30 bar from which the liquid phase is heated with steam to decompose the catalyst for recovery of cobalt by filtration. A second gas-liquid separator operating at atmospheric pressure subsequently yields a liquid phase of aldehydes, alcohols, heavy ends and water, which is free from propane, propylene, carbon monoxide and hydrogen. 

Sodium hydrosulfite is produced through the Formate process where sodium formate solution, sodium hydroxide, and liquid sulfur dioxide reacted in the presence of a recycled stream of methanol solvent. Other products are sodium sulfite, sodium bicarbonate, and carbon monoxide. In the reactor, sodium hydrosulfite is precipitated to form a slurry of sodium hydrosulfite in the solution of methanol, methyl formate, and other coproducts. The mixture is sent to a pressurized filter system to recover sodium hydrosulfite crystals that are dried in a steam-heated rotary drier before being packaged. Heat supply in this process is highly monitored in order not to decompose sodium hydrosulfite to sulfite. Purging is periodically carried out on the recycle stream, particularly those involving methanol, to avoid excessive buildup of impurities. Also, vaporized methanol from the drying process and liquors from the filtration process are recycled to the solvent recovery system to improve the efficiency of the plant. 

Calcor A process for making carbon monoxide from natural gas or liquid petroleum gas. It combines steam reforming with carbon dioxide recovery or recycle. Designed and licensed by Caoric GmbH. Five commercial plants have been installed as of 1992. 

Air emissions may arise from fugitive propane emissions and process vents. These include heater stack gas (carbon monoxide, sulfur oxides, nitrogen oxides, and particulate matter) as well as hydrocarbon emission, such as fugitive propane and fugitive solvents. Steam stripping wastewater (oil and solvents) and solvent recovery wastewater (oil and propane) are also produced. 

---