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Stainless Steels in Ammonia Production Stainless Steels in Ammonia Production Committee of Stainless Steel Producers American Iron and Steel Institute Washington, D.C. CONTENTS INTRODUCTION ...................... 4 PROCESS DESCRIPTION ....... 5 CORROSIVES IN AMMONIA PROCESSES .......... 5 CONSIDERATIONS FOR SELECTING STAINLESS STEELS .................................... 6 Desulfurization of Natural Gas ................. 6 Catalytic Steam Reforming of Natural Gas ................. 6 Carbon Monoxide Shift ......... 8 Removal of Carbon Dioxide . 10 Methanation .......................... 11 Synthesis of Ammonia ......... 11 Turbine-Driven Centrifugal Compression Trains ........ 14 STAINLESS STEELS ................ 15 Metallurgical Structure ......... 16 High-Temperature Mechanical Properties ..... 16 Thermal Conductivity ........... 20 Oxidation Resistance ........... 21 Sulfidation Resistance .......... 22 REFERENCES .......................... 22 The material presented in this booklet has been prepared for the general information of the reader. It should not be used without first securing competent advice with respect to its suitability for any given application. While the material is believed to be technically correct, neither the Committee of Stainless Steel Pro- ducers nor the companies represented on the The Committee of Stainless Steel Producers acknowledges the help Committee warrant its suitability for any gen- by Gregory Kobrin, Senior Consultant, Materials Engineering, E.I. eral or particular use. DuPont de Nemours & Company in assembling data for this booklet. single-train plants came increasing demands on materials of construc- INTRODUCTION tion. The process for making am- monia is considered to be only Approximately 12 elements are es- moderately corrosive, so considera- sential to plant growth. Of these, nit- ble use is made of carbon and low- rogen is the main nutrient and is re- alloy steels for vessels and piping. quired in much larger amounts than However, numerous applications any other element. Ammonia is the have been found for the AISI 300 and principal source of fertilizer nitrogen, 400 Series stainless steels because and most of the ammonia production of their superior performance under a in the world is applied directly to the wide variety of process conditions, soil or used in the manufacture of not only for original fabrication but for urea and other important nitrogen- replacement equipment and piping as base fertilizers. (1)* Because of am- well. monia's importance to human needs, For example, stainless steels are it is considered to be one of the most used in valuable and most widely produced Catalytic steam reforming because chemicals in the world. of resistance to oxidation, carburi- The ammonia production industry zation and nitriding at elevated has grown by leaps and bounds since temperatures; 1964, with U.S. production in 1977 an estimated 17 million to 18 million short Carbon dioxide removal systems tons per year, about four tirnes that of where piping and vessels are sub- 1960 (4.8 million short tons). (2) jected to hot, aqueous solutions Up until 1963, plant capacities containing carbon dioxide at ranged between 50 and 400 short moderate to high velocities; tons per day, many using a multiplicity Ammonia synthesis for superior of parallel process systems, called performance in hot nitriding gases, multiple trains. In 1963, the first 600- resistance to hydrogen embrittle- short-tons-per-day single-train am- ment and hydrogen attack, and ex- monia plant came on stream. This cellent toughness at low tempera- represented the beginning of large- tures; capacity, single-train plants and was the first to use centrifugal compres- Centrifugal turbomachinery where sors driven by steam turbines to com- rotating and stationary components press synthesis gas to elevated pres- are subjected to erosion by high- sures. (2) velocity steam and corrosion by Between 1965 and 1970, many ammonium carbamate, CO and single-train ammonia plants with CO2; capacities of 600 to 1000 short tons Coolers and condensers for resis- per day were built throughout the tance to corrosion and fouling by world. In recent years, larger plants natural waters. have been commissioned, several with 1500 short tons per day capacity The purpose of this booklet is to and one of 1700 short tons per day, identify the many applications of ranked the largest in the world at pre- stainless steels in a typical process sent. (2) for manufacturing anhydrous am- With the advent of high-capacity monia. *Numbers in ( ) indicate reference. 4 Partial oxidation of heavy hydro- 1. Desulfurization of natural gas carbons (oils, distillates); 2. Catalytic steam reforming of PROCESS Cryogenic recovery from petroleum natural gas refinery gases or other cracking 3. Carbon monoxide shift DESCRIPTION operations; 4. Removal of carbon dioxide 5. Methanation Anhydrous ammonia is manufac- Gasification of coal or coke. 6. Synthesis of ammonia. tured by combining hydrogen and The first, third, fourth and fifth Currently, a high percentage of nitrogen in a molar ratio of 3:1, com- steps are designed to remove im- world ammonia production (an esti- pressing the gas and then cooling it purities such as sulfur, carbon mated 70 to 80%) uses hydrogen to about –27ºF (–33ºC). monoxide, carbon dioxide and water produced by catalytic steam reform- Nitrogen is obtained from air. Hy- from the feed, hydrogen and syn- ing operations, with natural gas drogen is produced from a feedstock thesis gas streams. In the second (methane) as the primary feedstock. step, hydrogen is manufactured and by one of the following processes; As a result, the following process de- nitrogen is introduced into the pro- scription is limited to ammonia pro- Catalytic steam reforming of natu- cess. The sixth step produces duction by catalytic steam reforming ral gas or naphtha; anhydrous ammonia from synthesis of natural gas, using six basic gas. All ammonia plants use this basic process, although process condltions such as temperatures, pressures and flow rates vary from plant to plant. Approximately 65 to 75% of the natural gas is used as feedstock for the primary reformer; and 25 to 35% is used as fuel for the reformer radiant section and for steam pro- duction. As natural gas reserves continue to dwindle, feedstocks based on heavier hydrocarbons and coal gasification processes (3) will undoubtedly be used increasingly in ammonia plants in years to come. A process flow schematic of a typi- cal ammonia plant which uses catalytic steam reforming of natural gas is shown in Figure 1. The six process steps are described in detail in the following sections. CORROSIVES FOUND IN MANY AMMONIA PROCESSES Sulfur–present in natural gas feedstock, it causes high- temperature sulfidation of metals, 5 and it combines with other ele- poisoning the nickel catalyst in the Applications for Stainless Steels ments to form aggressive com- primary reformer and depositing The system for removing sulfur from pounds, such as hydrogen sulfide, carbon on the catalyst. Sulfur can be the feedstock natural gas consists of sulfur dioxide, and carbonyl sulfide. present as hydrogen sulfide, mer- two pressure vessels, each containing captans, carbonyl sulfide and organic Chlorides–may be present, either by activated carbon for removal of sulfur compounds. Carbon beds are entrainment in natural gas, as mercaptan sulfur and hydrogen usually used when the sulfur content carryover from boiler feedwater, or sulfide. Each vessel is designed to is less than 10 grains/per standard in cooling waters. They may cause handle all the sulfur expected in the cubic foot (SCF), whereas hot iron localized attack of some stainless feed gas. As soon as the activated oxide or zinc oxide (4) beds are used steels. carbon in the first vessel becomes for gas with higher sulfur content. saturated with sulfur, the feed gas Carbon Dioxide–occurs in steam Most modern ammonia plants use stream is diverted to the second reforming of natural gas. It com- activated carbon for feedstock vessel to allow steam regeneration of bines with moisture to form car- desuIfurization. the carbon bed in the first vessel. bonic acid. Natural gas at several hundred For the most part, operation takes psig and ambient temperature is Ammonia–at high temperature has place above the dew point and carbon passed through the activated carbon steel is a satisfactory material of con- high potential for nitriding metals. bed. Sulfur compounds are absorbed At high pressure, corrosive am- struction for the vessels and related on the carbon or reacted with the piping. However, AISI Types 304, 321, monium carbamate may be metallic oxide in the carbon to form a formed. Condensed ammonia is a or 316 stainless steels are specified metallic sulfide by this equation: for the wire mesh screens and grating corrodent, and in anhydrous state CuO + H S → CuS + H O it can cause stress-corrosion 2 2 which support the activated carbon When the carbon bed becomes cracking of stressed carbon steels beds in the desulfurizers. For this loaded with sulfur, it is regenerated or high-strength, low-alloy steels. application, corrosion rates must be with steam or a mixture of steam and virtually nil, otherwise a corroded Hydrogen–in itself not corrosive but air at 300 to 555ºF (149 to 290ºC) for screen could result in carbon can lead to blistering and embrit- several hours. The free oxygen reacts breakthrough and carryover into the tlement of steel. Also, it readily with the metal sulfide to form the cor- primary remormer with potentially combines with
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