Michoud Air Products
A shortage of Hydrogen (a key component in chemical production) caused some chemical companies to consider shutting down in the next few days, and the impact on the National economy and security was being assessed. The Department of Commerce requested a priority effort is given to getting the New Orleans Air Products liquid hydrogen facility back into operation as quickly as possible. The facility represents 31% of North American industrial hydrogen production.
A total of 44% of America's liquid hydrogen supply has been lost due to a previously scheduled shut down of APC's hydrogen plant in Sarnia, Ontario, Canada. The Sarnia facility was offline for a scheduled two-month shutdown because of a temporary interruption of its feedgas supply. That left Air Products with one operating liquid hydrogen plant in Sacramento, CA, with a capacity of only 2.3 million standard cubic feet a day. The New Orleans plant can produce 26.8 million cubic feet, while the Sarnia facility can make 11.5 million cubic feet. In 1980, there were only six liquid hydrogen plants in the United States. The largest was in New Orleans with a hydrogen production capacity of 60 tpd (2,300 kg/h [5,000 lb/h]).
The International Trade Administration and Bureau of Industry and Security (BIS) of the Department of Commerce began working with the Interagency team to prioritize restoration of the Air Products and Chemical (APC) liquid hydrogen production facility in New Orleans. NSC, DOC and DHS are working with industry to offset losses from Air Products, but it appears best case only part of the loss can be made up. The Corps of Engineers began unwatering the facility on September 5th and Air Products was in the final stages of determining how long it will take to get the facility operational again.
Liquid hydrogen is an essential commodity for the steel and petrochemical industries and public utilities, as well as NASA and the Air Force. Parts of the steel industry have begun to curtail operations with potentially negative impacts on the economy. On September 8, 2005 it was reported that Winner Steel Co. in Sharon PA had laid off 70 workers because a materials supplier's plant was damaged by Hurricane Katrina. Winner Steel gets liquid hydrogen, which is used to produce galvanized steel, from Air Products. Another steel company, Steel Dynamics of Fort Wayne, Ind., said it is not taking orders for galvanized or cold-rolled steel until it can make other supply arrangements.
The Towanda, Pennsylvania plant is OSRAM SYLVANIA's largest factory, producing the widest variety of tungsten and molybdenum materials and inorganic phosphors in the world. A laboratory devoted to high-temperature metallurgy and inorganic chemistry is also housed here, along with the headquarters for the company's Chemical & Metallurgical Products business unit. The plant is dealing with the raw-materials shortage resulting from Hurricane Katrina. On 09 September 2005 the plant announced that "The plant's supply of hydrogen, a vital raw material, has become extremely limited in recent days ... the number of temporary contract manufacturing workers may vary over the coming months as a result."
Hurricane Katrina significantly impacted Air Products operations and employees in the New Orleans area. To prepare for the storm, the company shut down operations in New Orleans and the other Gulf Coast plants but we did not escape damage. An Air Products crisis management team worked hard to assess the damage to operations. Pensacola and the other Gulf Coast plants had minimal impact and by 01 September were preparing to start-up. The New Orleans site was heaviest hit by the storm.
On 31 August 2005 Air Products announced that extensive damage caused by Hurricane Katrina had impacted the company's industrial gas complex in New Orleans, LA. Based on initial assessments, damage from the hurricane will affect Air Products' ability to supply customers with hydrogen from the New Orleans plant for an extended period of time. In addition, the company's liquid hydrogen production facility at Sarnia, Ontario, Canada, will be experiencing a scheduled shutdown due to a temporary suspension of its supplier's feedgas plant. As a result, the company declared force majeure for liquid hydrogen at these two industrial gas locations.
In these extraordinary circumstances, Air Products was actively working to assist customers with their supply needs, including obtaining product from other sources and geographies. Communications with all customers were underway.
Other suppliers of electronic-grade hydrogen are increasing their output to compensate for the shortfall. Furthermore, alternative purification techniques are being implemented by silicon manufacturers that will allow lower grades of hydrogen gas to be used for making silicon and epitaxial films. The full impact on the semiconductor supply chain remains unknown.
Praxair's four liquid hydrogen plants were operating at 75 percent capacity before Hurricane Katrina. They are now running at full capacity. Praxair's plants, in Alabama, California, Indiana and New York, have a combined capacity of 46.5 million standard cubic feet a day. The increase of approximately 12 million standard cubic feet a day will only partially offset the loss of 26.8 million cubic feet per day from the New Orleans plant, which supplies 50% to 60% of the total hydrogen consumed by the steel industry.
On 12 September 2005 Air Products announced an update on its liquid hydrogen supply and the status of its New Orleans, LA production facility impacted by Hurricane Katrina. The company reported that it has been able to secure additional hydrogen supplies from other sources and find different ways to improve the liquid hydrogen shortage situation with product management. Air Products is in the process to begin repairing its New Orleans facility, but water must be drained from the site area to regain road access and power supply.
"To date, we have been able to maintain supply to the majority of our customers. While we will not be able to meet full demand of all customers, the situation has improved, and we informed our customers of this a few days ago," said Mark Bye, group vice president, Gases and Equipment Group for Air Products. "We have been working closely with our customers to understand their precise requirements and identify options to best manage their current and future hydrogen supply."
Air Products was encouraged that it has been able to continue supplying customers with hydrogen by converting some customer operations from liquid to gaseous hydrogen supply. The company wes also securing product from other sources, such as customers without immediate needs releasing their stored hydrogen back to Air Products. Additionally, the company has determined that some inventory at its New Orleans facility was undamaged and can be distributed when safe road access becomes available. Air Products also worked on arrangements for alternative feedgas supply to its liquid hydrogen facility in Sarnia, Ontario, Canada.
"We're ready to make plant repairs. We have our people and contractors positioned, and we're lining up materials. We need the continued help of the government to get the water out of the surrounding plant area to get safe road access and restore infrastructure. Then we can deliver the stored inventory to our customers and begin repairs. At that point, we can begin looking to a start-up date," said Bye.
Despite the improved situation in continuing to supply customers, the force majeure on liquid hydrogen remains in effect. "We understand our customers' concerns and appreciate their support and flexibility in these difficult times. They recognize the challenges we face from the storm and have been supportive," said Bye. "We are committed to resolve these issues as rapidly as possible."
Air Products (NYSE:APD) serves customers in technology, energy, healthcare and industrial markets worldwide with a unique portfolio of products, services and solutions, providing atmospheric gases, process and specialty gases, performance materials and chemical intermediates. Founded in 1940, Air Products has built leading positions in key growth markets such as semiconductor materials, refinery hydrogen, home healthcare services, natural gas liquefaction, and advanced coatings and adhesives. The company is recognized for its innovative culture, operational excellence and commitment to safety and the environment and is listed in the Dow Jones Sustainability and FTSE4Good Indices. The company has annual revenues of $7.4 billion, operations in over 30 countries, and nearly 20,000 employees around the globe.
Hydrogen makes up 98% of the known universe, and it is the third most abundant element on the earth's surface. It is the lightest of all the gases, with a gaseous specific gravity of 0.0695. It is a component of water, minerals and acids, and it makes up a fundamental part of all hydrocarbons and organic substances. At atmospheric temperatures and pressures, hydrogen exists as a gas; however, it liquefies at -252.9°C (-423°F). Next to helium, it is the coldest known fluid.
Under ordinary conditions hydrogen gas is a mixture of two kinds of molecules, known as ortho- and para-hydrogen, which differ from one another by the spins of their electrons and nuclei. Normal hydrogen at room temperature contains 25% of the para form and 75% of the ortho form. The ortho form cannot be prepared in the pure state. Since the two forms differ in energy, the physical properties also differ. The melting and boiling points of parahydrogen are about 0.1oC lower than those of normal hydrogen. Sources differ as to the boiling point of liquid hydrogen at 1 atm with some quoting 20.3 K and others 20.4 K. Some of the confusion comes from the fact that liquid hydrogen can be "normal" hydrogen (75% ortho, 25% Para), "equilibrium" hydrogen (21%, ortho, 79%) or parahydrogen (99.8% para).
The uncatalyzed conversion from ortho to para-hydrogen proceeds very slowly, so without a catalyzed conversion step, the hydrogen may be liquefied, but may still contain significant quantities of ortho-hydrogen. This orthohydrogen will eventually be converted into the para form in an exothermic reaction. This poses a problem because the transition from ortho to para-hydrogen releases a significant amount of heat (527 kJ/kg [227 Btu/lb]). If ortho-hydrogen remains after liquefaction, this heat of transformation will slowly be released as the conversion proceeds, resulting in the evaporation of as much as 50% of the liquid hydrogen over about 10 days. This means long-term storage of hydrogen requires that the hydrogen be converted from its ortho form to its para form to minimize boil-off losses.
A major concern in liquid hydrogen storage is minimizing hydrogen losses from liquid boil-off. Because liquid hydrogen is stored as a cryogenic liquid that is at its boiling point, any heat transfer to the liquid causes some hydrogen to evaporate. The source of this heat can be ortho-to-para conversion, mixing or pumping energy, radiant heating, convection heating or conduction heating. Any evaporation will result in a net loss in system efficiency, because work went into liquefying the hydrogen, but there will be an even greater loss if the hydrogen is released to the atmosphere instead of being recovered.
The majority of merchant hydrogen is produced by a process called steam methane reforming. Hydrogen is generated from a hydrocarbon (such as natural gas) and water at high temperatures in catalytic reactors. The hydrogen is typically purified using pressure swing adsorption.
In steam reforming hydrocarbon fuel reacts with steam at high temperatures over a catalyst. Hydrogen atoms are stripped from water and hydrocarbon molecules to produce hydrogen gas. The reforming process converts the hydrocarbon fuel to useful hydrogen (H2), plus harmful species such as H2S, SO2, NH3.
In refineries, hydrogen is produced as a by-product of naphtha reforming, and any supplemental hydrogen is produced from steam reforming of natural gas. Hydrogen for the chemical industry is produced from steam reforming of natural gas, although some chemical plants use coal gasification (i.e., partial oxidation) to produce hydrogen. In total, about 95 percent of U.S. hydrogen production for supplemental refinery needs and the chemical industry is produced from natural gas using steam reforming technology.
Some of the merchant hydrogen sold is recovered from industrial processes. While this is still fossil fuel based, it is allowing recovery of the hydrogen for direct application instead of being combusted by its industrial producer for its heating value. About 95% of the total global hydrogen production is captive, meaning it is used at the site where it is produced. Merchant hydrogen represents the balance.
Hydrogen is used daily as a gas and liquid by many industries, including the petroleum industry and in manufacturing processes for producing chemicals, foods and electronics. Great quantities of hydrogen are required commercially for nitrogen fixation using the Haber ammonia process, and for the hydrogenation of fats and oils. It is also used in large quantities in methanol production, in hydrodealkylation, hydrocracking, and hydrodesulfurization. Other uses include rocket fuel, welding, producing hydrochloric acid, reducing metallic ores, and filling balloons.
In the mid-1990s demand for industrial hydrogen was expected to grow 5%/yr. Growth of 7.7%/yr is projected for processing and production of chemicals, 4.2%/yr for food processing in hydrogenation of fats and oils, and 3.3%/yr in metal manufacture. There was also higher demand for hydrogen in alcohols, acetic acid, and urethane production and at refineries for producing cleaner-burning fuels.
The US demand for hydrogen currently is about 9 million tons per year. Of this amount, about 1.5 million tons is merchant hydrogen production that is sold to refineries and chemical plants. The chemical industry also uses hydrogen, mostly to manufacture ammonia and other nitrogen-based fertilizers.
Typical hydrogen applications in the electronics industry include circuit manufacture, semiconductor production, quartz melting, polysilicon production, epitax wafer production, and fiber optic production. Hydrogen is used in the deposition of epitaxial films on silicon wafers, which are used for manufacturing of semiconductors worldwide. It is used in the manufacturing of epitaxial films deposited on silicon substrates. These films are critical in the manufacturing of higher-voltage semiconductors used in power management applications.
Hydrogen annealed wafers offer an exceptionally pure silicon wafer surface on which devices can be built. The main difference between hydrogen annealed wafers and prime polished wafers is that the hydrogen annealing process serves to remove most of the oxygen from the near surface of the wafer. This results in reduced bulk micro defects (BMD) as well as improved gate oxide integrity. Polished wafers are annealed in hydrogen atmosphere at about 1200 degrees Celsius in order to improve the surface crystalline perfection. Due to the inherent requirement for high purity, electronics companies generally require liquid hydrogen, gas vaporized from liquid, or lower purity H2 that is purified at the customer's site.
Trans fat is made when food manufacturers add hydrogen to vegetable oil -- a process called hydrogenation. Hydrogenated refers to oils that have become hardened (such as hard butter and margarine). The terms "hydrogenated" and "saturated" are related; an oil becomes saturated when hydrogen is added (i.e., becomes hydrogenated). Partially hydrogenated refers to oils that have become partially hardened. Trans fatty acids can raise LDL levels. They can also lower HDL levels ("good cholesterol"). Trans-fatty acids are found in fried foods, commercial baked goods (donuts, cookies, crackers), processed foods, and margarines. Foods made with hydrogenated oils should be avoided because they contain high levels of trans fatty acids, which are linked to heart disease.
Hydrogenation increases the shelf life and flavor stability of foods containing these fats. Unlike other fats, the majority of trans fat is formed when food manufacturers turn liquid oils into solid fats like shortening and hard margarine. A small amount of trans fat is found naturally, primarily in dairy products, some meat, and other animal-based foods.
Trans fat can be found in vegetable shortenings, some margarines, crackers, cookies, snack foods, and other foods made with or fried in partially hydrogenated oils. Cooking oils, fried foods, baked goods and prepared foods served in restaurants are common sources of dietary trans fat because they are made with partially hydrogenated vegetable oil. Prepared restaurant foods commonly containing trans fat include pre-fried vegetables (e.g., French fries, fried zucchini, mozzarella sticks, etc.), pre-fried chicken and fish (e.g.,. chicken nuggets, fish fillets, etc.), baked goods (e.g., hamburger buns, cakes, cookies, pies, crackers, etc.) and pre-mixed foods (e.g., croissant dough, pancake mix, salad dressing, hot chocolate). Products that often contain trans fat include packaged foods made with partially hydrogenated vegetable oil, such as snack foods (e.g., potato, corn and tortilla chips; candy; packaged and microwave popcorn; and doughnuts).
Hydrogenation is a process to modify the melting points of vegetable oils intended for margarines, shortening and frying fats. As well as edible applications, fats and oils are processed for oleochenical, cosmetic and pharmaceutical uses. Hydrogenation is a process to convert liquid oils into semi-solid, plastic fats suitable for manufacturing margarine and baking fats. Hydrogenation of fats and oils is the largest single reaction in the edible oil and oleochemical industries. It also achieves various other desirable properties, such as enhancement of oxidative stability (to prevent rancidity) and improvement in the appearance of the fat.
For hydrogenation to take place, gaseous hydrogen, liquid oil, and a powdered catalyst (usually nickel) are brought together at a specific temperature and pressure and then they are agitated within a reactor vessel. The higher the hydrogen purity, the faster the reaction rate and the lower the catalyst consumption.
In some cases, companies could switch to standard, non-hydrogenated, liquid oils that are both low in saturated fat and virtually free of trans fat. Many of these replacements can include or be derived from soy, corn, sunflower, or canola oil. For example, specially-developed varieties of soybeans and other crops, as well as oils processed in novel ways, have healthier fatty acid profiles that reduce or eliminate the need for partial hydrogenation. If partial hydrogenation is necessary, these new varieties and their blends will contain less trans fats than conventional options.
Liquid hydrogen is used to make high-quality metal products, such as galvanized and cold-rolled steel. Metal Reduction Oxidation uses Tuyeres and/or porous plugs to inject the powerful reducing agent hydrogen into molten metals such as copper to convert oxides back to metal. Often combined with inert gases to increase mixing, it can be preceded with oxygen injection to oxidize unwanted components from the melt.
Annealing steel strip, rod and wire using advanced bell type furnaces using 100% hydrogen atmosphere produces more consistent mechanical properties and better surface finish than those obtained by annealing in conventional bell type furnaces using HNX (purified exothermic and nitrogen plus 5-7% hydrogen) atmospheres. Hydrogen annealing results in excellent cyclic oxidation resistance for a number of advanced superalloys. Effective desulfurization to less than 1 ppmw can be accomplished by hydrogen annealing and is governed by sulfur diffusion kinetics in nickel.
To produce sheets of flawless glazing for windows, doors, etc., a continuous ribbon of glass is "floated" on a bed of tin. In order to allow the irregularities in the glass to even out, the glass is held in a controlled atmosphere with a ratio of approximately 90% N2:10% H2. Once it is cooled, the flat glass becomes hard enough to be removed. The hydrogen in the controlled atmosphere acts as a scavenging agent to ensure an oxygen-free environment, because the molten tin is highly sensitive to oxidation, even in trace quantities. Even the glass itself can be negatively affected by oxygen presence, which can cause residue formation on the surface of the glass, creating a hazy appearance.
Hydrogen can be delivered by truck as a liquid or compressed gas, or it can be generated on-site. It is also delivered by pipeline. The primary reason hydrogen is liquefied is for its higher storage density, which allows easier deliver.
NASA's nearby Stennis Space Center utilizes 70 percent of all the liquid hydrogen used by NASA. As NASA's Center of Excellence for large propulsion systems testing, Stennis has expertise in the handling and application of cryogenic materials. NASA uses supercold liquid hydrogen as the fuel to help power the Shuttle three main engines during the ascent phase of flight, ground testing and propulsion development. Liquid hydrogen also acts as the propellant for the Shuttle's onboard fuel cells.
Space Shuttle Main Engine test at NASA's Stennis Space Center depend on the NASA tug Clermont II. helper push barges of super-cool liquid hydrogen and liquid oxygen through the canal system at Stennis. Connected to the Pearl River, the canals are kept at a constant level by a lock system, spillway and replenishment pumps.
The barges are moored to docks at the test stands, then the fuel -- a lot of fuel -- is pumped from the barges into tanks on the stands. Each time a Shuttle Main Engine is test-fired for the 8 minutes it takes to launch a Shuttle into orbit, it burns 132,000 gallons of liquid hydrogen and 49,000 gallons of liquid oxygen.
Between February 1979 and February 2005, the Clermont II crew made more than 7,000 fuel barge moves, most through the 7-mile, 16-foot-deep Stennis canal system. About 900 of the fuel barge moves took the Clermont II and crew beyond the Stennis canals - usually to New Orleans, almost five hours one way. They also made more than 1,000 work-barge moves and nearly 200 weather-buoy moves. That's a total of almost 8,500 barge moves without a major accident or loss of a barge.
The barges -- attached to the bow of the 65-foot-long tug with steel cables -- are no lightweights. Each weighs 700 to 800 tons fully loaded. They are almost constantly being refilled, depending on the Shuttle Main Engine testing schedule. That schedule can require more than 100 total truckloads of fuel a week and as many as seven barge moves in a day.
One liquid oxygen barge holds about 100,000 gallons, or 18 to 20 truckloads. A liquid hydrogen barge holds about 270,000 gallons, or about 15 truckloads. The nine technicians and supervisor of the Cryogenic Propellant Storage Facility at Stennis make sure the fuels are safely transferred to the barges and from the barges to the test stands. Liquid oxygen is transferred directly from the trucks to the barges. The liquid hydrogen goes from the trucks to a 600,000-gallon storage sphere, then to the barges.
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