' CRYOGENICS IN CHEMICAL TECHNOLOGY 11 3. Methods of Production 3.1. Classification All major production methods ae based oa Hquefcton and subenuea! fractionation of air, Process modifications include: © Variations in compression, purification, and refrigeration cycles * Variations in equipment design for all major unit operations such as heat exchange, rectification, gas compression and expansion 3.1.1. Specific process eyele nomenclature ‘The two basic cycles are: * Linde—uses refrigeration by Joule-Thomson cooling * Claude—obiains refrigeration by adisbatic expansion of compressed air in turbo-reciprocating or rotating expansion machine ‘The process to be described in detail is the conventional Linde-Prankl cycle. 3.2. Conventional Linde-Frankl Cycle 3.2.1. Reference flow sheet: Figure IK-4 3.2.2. Chemical reaction For CO, scrubbing tower 2NaOH + CO, Na,CO, + H;0 3.2.3. Raw materials Air of usual composition by volume N, 78.03 H, 10* 0, 20.97 CO, —0.02-+0.07 ar 0.94 H,O 0,010.03 ‘Minor quantities of NaOH, NH, and silica gel 3.2.4. Quantitative requirements (a) Basis: 1 ton of 95% oxygen in 300 tons/day plant Air 3,600 Nm? Steam 1.75 tons Cooling water S tons Electricity 450-480 KWH ‘(b) Plant capacities: 50-500 tons/day 3.2.5. Process description Air is compressed to 4-5 atms., cooled with H,O and passed into regenerative exchangers. These are cylindrical pressure vessels packed with alumi it is an _operating_in_pait . .Air is cooled in one, while cold product gas (Q, or N,) is “qemaiing sensible heat from the packing inthe other. After 2-2 minutes, tecycté is reversed by automatic valves. Air entering the cold exchanger contains both H,O and CO, which must be removed before entering the fractionation section operated at —183 10 —195°C to prevent plugging. These impurities dre removed on the cold packing throughout the exchanger and then reevaporated by the product gas which starts with zero concentration of H,O and CO, and thus provides an equilibrium driving force for the vaporization process. Both the O, and N, product gas necessarily contain H,O and CO, impurities in this type of cycle design and only low purity oxygen can be obtained.ES INORGANIC CHEMICAL INDUSTRI 200atms Hign pressure after-cooler purity ventional Linde-Frankl cycle producing law tonnage oxygen pro Oxygen-nitrngen Fig. 11C-4.CRYOGENICS IN CHEMICAL TECHNOLOGY 103 The ir leaving the regenerative heat exchangers is cooled to —170°C and fed to the rehoiler section of the double column where further cooling takes place. The double column is, in fact, two distillation columas with a low pressure (1.4 atms.) column standing an the top of the high pressure (5.7 alms.) column, the reboiler of the upper column working as the condenser of the vapors from the lower column. In the high pressure section, the more volatile nitrogen works its way to the top of the column and is condensed inside the tubes of the reboiler section of the low pressure column by the liquid oxygen surrounding the tubes, This is accomplished because the: temperature of liquid oxygen al 1.4 atms. is lower than the condensation temperature: of the saturated nitrogen vapor al 5.7 alms. This condensed nitrogen is then sprayed into the top of the low pressure column for reflux. The less volatile oxygen still containing 50% N, is pumped to the middle of the low pressure column where final rectification takes place. The removal of argon, which boils 2.9°C lower than oxygen, requires a much larger number of plates in the columns. Such designs are used only for high purity ©, product (see Section 3.3). To provide heat balance and flow control, a 3-6% side stream is drawn from the compressed air before entering the regenerators. This air is dried and freed of CO; by the NaOH scrubbing tower. The purified air is next compressed to 200 alms., cooled by H,O, NH, refrigeration, and N, product heat exchange before entering a turbo-expander operating on the Claude principle. This balancing stream of cold air is fed near the bottom of the low pressure column, 3.3, Cycles for Producing High Purity Oxygen Reference flow sheet: Figure IIC-5 (Kellogg process) Process description ‘The major difference between the Kellogg and Linde-Frankl cycle is the use of a recuperative-reversing heat exchanger. These arc built in a concentric triple-tube design with high purity oxygen moving through the inner tube, never contacting the incoming air. This is known as recuperative heat exchange. The reversing principle js used to remove CO, and H,O from the incoming air stream by switching the flow of the N, product stream and the air stream in the outer two annuli. Other purification details includ © Accatalytic oxidation chamber inserted after the initial compression to 70 psig. to convert hydrocarbons to CO, and H,0. = Silica gel filter ahead of the double column. 3.4. Other Cycles Various modifications have been incorporated since Linde first invented the basic cycle with Joule-Thomson cooling about 1900. These include various chemical methods for removing (1) water and carbon dioxide and (2) operating at pressures as high as 200 atms. "A novel process (Elliott) does not use air expansion for refrigeration, but sets up heat exchange with nitrogen coolant in strictly recuperative heat exchangers. This design sliminates the heat balance control stream, bat requires cleaning the heat exchangers by melt- down every 3-5 hours. A strictly Claude-opérated process uses adiabatic expansion of 70-80% of the incoming ‘air from 25-50 aims, to the 5.7 atms. column pressure,"uadhxa Ayind gary Suvanposd ajado ainssaad-moy Boyjay tssavcud wopanpoud uadonw-uadkxQ “s-D “HdCRYQGENICS IN CHEMICAL TECHNOLOGY los _ Cycles differ aleo in detail of seperation of products. Liquid products can be drawn directly from the column, Rare gases can also be separated, i.e. , * Argon side-streamed for fractionation from residual N, and O, in separate column * — Neon-helium from N, product by venting from top of main condenser Krypton-xenon from O, product by adsorption from top of main condenser 3.5. Major Engineering Problems (a) Complete removal of HO, CO, and hydrocarbons to prevent plugging in the low temperature sections of the plant (b) Developing effective low temperature insulation and lubricants (©) Complex heat balancing designs (@) Prevention of explosive mixtures in oxygen-rich regionsOxygen and Nitrogen 1, Pertinent Properties Oxygen Mol. wt. 32.00 MP. —218.8°C Ee —133°C Grades: High purity 9.5% 0; 0.5% Ar Low purity 90-95% 0, 45% Ar Balance N,, CO;, HO Nitrogen Mol. wt. 28.02 M.P. —210.00°C BP. —195.8°C Grades: Technical 99% Nz Balance Ar and O; 2. Consumption Pattern 2.1. End Uses 2.11, Oxygen © High purity oxygen used for welding and cutting of metals, 0 purification, medicinal purposes © Low purity oxygen used for blast furnace operations, many industrial chemical oxidation processes. The reasons for increasing use of low purity hearth steel tonnage") oxygen are: (1) N; diluent from air not as desirable from a rate and equilibrium standpoint R+0, 2 RO, ry = APy 7 Pa Pp, is at least 5 times larger than when using air Saves sensible heat losses from N; inert Q) (3) Increases capacity of equipment designed for use of air (4) Product less dilute: in effluent 2.1.2. Nitrogen * Protective atmosphere to prevent oxidation in metal working and food preservation © Captive usage in NH, and nitrogen chemicals Liquid N, used for refrigerative cooling in transportation industry