Liquid Hydrogen

Safetygram 9

Hydrogen is colorless as a liquid. Its vapors are colorless, odorless, tasteless, and highly flammable.

Liquid hydrogen is noncorrosive. Special materials of construction are not required. However, because of its extremely cold temperature, equipment must be designed and manufactured of material that is suitable for extremely low temperature operation. Vessels and piping must be selected and designed to withstand the pressure and temperatures involved and comply with applicable codes and regulations.

Flammability The wide flammability range, 4% to 74% in air, and the small amount of energy required for ignition necessitate special handling to prevent the inadvertent mixing of hydrogen with air. Care should be taken to eliminate sources of ignition, such as sparks from electrical equipment, static electricity sparks, open flames, or any extremely hot objects. Hydrogen and air mixtures within the flammable range can explode and may burn with a pale blue, almost invisible flame.

Manufacture Hydrogen is produced by the steam reforming of natural gas, the electrolysis of water and the dissociation of ammonia. Hydrogen is also a by-product of petro- leum distillation and chlorine manufacture. The primary method of hydrogen generation is steam reforming of natural gas. Other feedstocks, which are less common, can include ethane, propane, butane, and light and heavy naphtha. The steam reforming process produces syngas, which is a mixture of hydrogen and carbon monoxide. Regardless of the method of production, the product stream is separated into its components. The hydrogen is dried and purified. This gaseous hydrogen is then compressed and cooled to sufficiently low cryogenic temperatures by the use of heat exchangers, along with reciprocating and tube expanders, to form liquid hydrogen. Table 1: Liquid Hydrogen Physical and Chemical Properties

Chemical Formula H2 Molecular Weight 2.016 Boiling Point @ 1 atm –423.2°F (–252.9°C) Freezing Point @ 1 atm –434.8°F (–259.3°C) Critical Temperature –400.4°F (–240.2°C) Uses Critical Pressure 186 psia (12.7 atm) Liquid hydrogen is used in large Density, Liquid @ B.P., 1 atm 4.42 lb./cu.ft. volumes in the space program as a (70.8 kg/cubic meter) primary rocket fuel for combustion Density, Gas @ 68°F (20°C), 1 atm 0.005229 lb./cu.ft. with oxygen or fluorine, and as a pro- (0.0838 kg/cubic meter) pellent for nuclear powered rockets Specific Gravity, Gas (air=1) @ 68°F (20°C), 1 atm 0.0696 and space vehicles. Although used Specific Gravity, Liquid @ B.P., [water=1 @ 68˚F (20˚C)] 0.0710 more commonly in the gaseous state, Specific Volume @ 68°F (20°C), 1 atm 191 cu. ft./lb. hydrogen is stored and transported as Latent Heat of Vaporization 389 Btu/lb. mole a liquid. Hydrogen is a raw material Flammable Limits @ 1 atm in air 4.00%–74.2% (by Volume) for innumerable chemical processes Flammable Limits @ 1 atm in oxygen 3.90%–95.8% (by Volume) ranging from the manufacturing Detonable Limits @ 1 atm in air 18.2%–58.9% (by Volume) of high-density polyethylene and Detonable Limits @ 1 atm in oxygen 15%–90% (by Volume) polypropylene to the hydrogenation Autoignition Temperature @ 1 atm 1,060°F (571°C) of food-grade oils. In the metallurgical Expansion Ratio, Liquid to Gas, B.P. to 68°F (20°C) 1 to 845 industry, hydrogen is used to reduce metal oxides and prevent oxidation in heat treating certain metals and alloys. Hydrogen is also used by semi- Figure 1: Typical Liquid Hydrogen Tanker conductor manufacturers.

Health effects Hydrogen gas is odorless and nontoxic but may produce suffocation by dilut- ing the concentration of oxygen in air below levels necessary to support life.

Caution: The amount of hydrogen gas necessary to produce oxygen-deficient atmospheres is well within the flammable range, making fire and explosion the primary hazards associated with hydrogen and air atmospheres.

Containers Tanks Liquid hydrogen is normally stored Tanks are usually cylindrical in shape in on-site storage systems typically and placed in a horizontal position. consisting of a tank, vaporizer and However, some vertical cylindrical controls. Systems are selected in ac- tanks and spherical tanks are in use. cordance to usage rate, pressure and Standard tank sizes range from 1,500 regulations. gallons to 25,000 gallons. Tanks are vacuum-insulated. Pressure relief valves protect the tanks and are designed to ASME specifications. 2 Transferring liquid Shipment Hydrogen burns with a very pale blue Two persons should be present when Liquid hydrogen is transported by to almost invisible flame, therefore liquid hydrogen is being used or trans- liquid semitrailers with a capacity of injury may result from unknowingly ferred or when a container is moved. 12,000 to 17,000 gallons. The station- walking into a hydrogen fire. The This does not apply where specially ary tanks are filled from these tank- fire and explosion hazards can be trained employees of the liquid hydro- ers. Tankers are basically of the same controlled by appropriate design and gen supplier, who routinely handle design as the stationary tanks but in operating procedures. Preventing the liquid hydrogen, are involved. addition must meet the requirements formation of combustible fuel-oxidant of the Department of Transportation. mixtures and removing or otherwise Hydrogen is normally vaporized Figure 1 is a typical liquid hydrogen inerting potential sources of igni- and used as a gas. Withdrawal of tanker. tion (electric spark, static electricity, liquid from a tanker, tank, or liquid open flames, etc.) in areas where the cylinder requires the use of a closed Safety considerations hydrogen will be used is essential. system, with proper safety relief de- The hazards associated with handling Careful evacuation and purge opera- vices, which can be evacuated and/or liquid hydrogen are fire, explosion, tions should be used to prevent the purged to eliminate the possibility of asphyxiation, and exposure to ex- formation of flammable or explosive creating a flammable atmosphere or tremely low temperatures. Consult mixtures. Adequate ventilation will explosive mixture of liquid air and liq- the Air Products Safety Data Sheet help reduce the possible formation of uid hydrogen. Purging should be done (SDS) for safety information on the flammable mixtures in the event of with helium since liquid hydrogen gases and equipment you will be a hydrogen leak or spill and will also can solidify other gases, such as nitro- using. The potential for forming and helps eliminate the potential hazard gen, and cause plugging and possible igniting flammable mixtures contain- of asphyxiation. Protective clothing rupture of the transfer line or stor- ing hydrogen may be higher than for should be worn to prevent exposure age vessel. Liquid transfer lines must other flammable gases because: to extremely cold liquid and cold hy- be vacuum-insulated to minimize drogen vapors, and also the potential product loss through vaporization or 1. Hydrogen migrates quickly exposure to a flash fire. the formation of liquid air on the lines through small openings. with subsequent oxygen enrichment. 3. Cold burns may occur from short All equipment must be electrically 2. The minimum ignition energy for contact with frosted lines, liquid grounded and bonded before transfer- flammable mixtures containing air that may be dripping from cold ring liquid. hydrogen is extremely low. lines or vent stacks, vaporizer fins, and vapor leaks.

Air will condense at liquid hydrogen temperatures and can become an oxygen-enriched liquid due to the vaporization of nitrogen. Oxygen- enriched air increases the combustion rate of flammable and combustible materials, including clothing.

3 Purging Buildings Gaseous and liquid hydrogen systems Liquid hydrogen is normally vapor- must be purged of air, oxygen, or other ized into its gaseous state and piped oxidizers prior to admitting hydrogen into buildings for usage. For storage to the systems, and purged of hydro- of liquid hydrogen in a building, refer gen before opening the system to the to regional codes or standards (e.g., atmosphere. Purging should be done National Fire Protection Association to prevent the formation of flamma- (NFPA) “Storage, Use and Handling ble mixtures and can be accomplished of Compressed Gases and Cryogenic in several ways. Fluids” - NFPA 55). The following items pertain to a building in which gaseous Piping systems and vessels intended hydrogen is being used. for gaseous hydrogen service should be inerted by suitable purging or 1. Provide adequate ventilation, evacuation procedures. If the piping particularly in roof areas where systems are extensive or complicated, hydrogen might collect. Forced ven- successive evacuations broken first by tilation may be necessary in some an inert gas and finally with hydrogen applications. are most reliable. 2. The atmosphere in areas in which Evacuating and purging of equipment hydrogen gas may be vented and in gaseous hydrogen service should might collect should be tested with include the following considerations: a portable or continuous flammable gas analyzer. 1. Evacuate the equipment and break vacuum with an inert gas, such as 3. Provide an explosion venting nitrogen. If equipment design does surface or vents, taking care to vent not permit evacuation, then pres- a pressure wave to areas where surize and purge the system with people or other equipment will an inert gas. not become involved. Explosion vents may not be required where 2. Repeat step 1 at least three times. If small quantities of hydrogen are analytical equipment is available, involved. purge system until oxygen content of residual gas is either less than 4. Buildings should be electrically or meets the process specification grounded. impurity level. 5. Electrical equipment must conform 3. Hydrogen may now be introduced to the existing National Electrical to the equipment. Codes. Electrical equipment not conforming must be located out- 4. Flush system with hydrogen until side the electrical area classified as required purity is reached. Vent all hazardous. All electrical equipment waste hydrogen through a flue or must be grounded. flare stack. 6. Building materials should be Any purge method should be repeated noncombustible. as often as required to be certain a flammable mixture cannot be formed 7. Post “No Smoking” and “No Open upon introducing hydrogen or air to Flames” signs. the system.

4 Outdoor storage tank Location—specific requirements 6. The liquefied hydrogen container and associated piping shall be elec- requirements 1. The minimum distance in feet from liquefied hydrogen systems trically bonded and grounded. of indicated storage capacity Location—general requirements 7. Adequate lighting shall be provided located outdoors to any specified 1. The storage containers should for nighttime transfer operations. exposure should be in accordance be located so that they are read- with the current version of NFPA 55: ily accessible to mobile supply “Compressed Gases and Cryogenic equipment at ground level and to Fluid Code.”* Personal protection authorized personnel, and where 1. Personnel must be thoroughly they are not exposed to electric 2. Roadways and yard surfaces located familiar with the properties and power lines, flammable liquid lines, below liquefied hydrogen piping, safety precautions before being flammable gas lines, or lines carry- from which liquid air may drip, shall allowed to handle hydrogen and/or ing oxidizing materials. be constructed of noncombustible associated equipment. materials. 2. It is advisable to locate the lique- 2. Full face shield, safety glasses, insu- fied hydrogen container on ground 3. If protective walls are provided, they lated or leather gloves, long-sleeved higher than flammable liquid shall be constructed of noncombus- shirts, and pants without cuffs storage or liquid oxygen storage. tible materials. should be worn when working on Where it is necessary to locate the liquid hydrogen systems. Pant legs liquefied hydrogen container on 4. Electrical wiring and equipment should be worn outside of boots. ground that is lower than adjacent located within three feet of a point Flame retardant clothing is strong- flammable liquid storage or liquid where connections are regularly ly recommended when working on oxygen storage, suitable protective made and disconnected shall be in or around liquid hydrogen systems. means (such as diking, diversion accordance with national standards. curbs, or grading) should be taken. In the United States the applicable 3. In the event of emergency situ- codes are; Article 501 of the National ations, a fire-resistant suit and 3. Storage sites should be fenced Electrical Code, NFPA No. 70, for gloves should be worn. SCBA is also and posted to prevent entrance Class 1, Group B, Division 1 locations. recommended, but remember that by unauthorized personnel. Sites oxygen-deficient atmospheres are should also be placarded as follows: 5. Electrical wiring and equipment within the flammable range and “Liquefied Hydrogen Flammable located beyond three feet but should not be entered. Increase Gas – No Smoking – No Open within 25 feet of a point where ventilation to areas potentially Flames.” connections are regularly made and containing a flammable atmo- disconnected, or within 25 feet of a sphere before entering. 4. Weeds or similar combustibles liquid hydrogen storage container should not be permitted within shall be in accordance with national 25 feet of any liquefied hydrogen standards. In the United States the equipment. applicable codes are; Article 501 of the National Electrical Code, NFPA No. 70, for Class 1, Group B, Division 2 locations. This requirement does not apply to electrical equipment that is installed on mobile supply trucks * Publication is available from NFPA, or tank cars from which the storage 1 Batterymarch Park, Quincy, MA container is filled. 02169-7471

5 First aid Note to physician Persons suffering from lack of oxy- Frozen tissues should be treated gen should be moved to areas with promptly by immersion in a wa- normal atmosphere. Self-contained ter bath at a temperature between breathing apparatus may be required 105°F–115°F (41°C–46°C). Avoid the use to prevent asphyxiation of rescue of dry heat. workers. Rescue workers should not enter a flammable atmosphere. Frozen tissues are painless and ap- Assisted respiration and supplemen- pear waxy with a pallid yellow color. tal oxygen should be given if the Tissues become painful and edema- victim is not breathing. tous upon thawing, and the pale color turns to pink or red as circulation of Extensive tissue damage or burns can blood is restored. Potent analgesics result from exposure to liquid hydro- are often indicated. Tissues that have gen or cold hydrogen vapors. Flush been frozen show severe, widespread affected areas with large volumes of cellular injury and are highly sus- tepid water 105°F–115°F (41°C–46°C) to ceptible to infections and additional reduce freezing. Loosen any clothing trauma. Therefore, rapid rewarming which may restrict circulation. Do not of tissues in the field is not recom- apply heat. Do not rub frozen skin, mended if transportation to a medical as tissue damage may result. Cover facility will be delayed. affected area with a sterile protective dressing or with clean sheets if If the body temperature is depressed, area is large, and protect area from the patient must be warmed gradu- further injury. Seek medical attention ally. Shock may occur during the promptly. correction of hypothermia. Cardiac dysrhythmias may be associated with severe hypothermia.

6 Fire fighting The usual fire fighting practice is to Hydrogen is easily ignited by heat, prevent the fire from spreading and open flames, electrical sparks, and let it burn until the hydrogen is con- static electricity. It will burn with sumed. Dry powder fire extinguish- a pale blue, almost invisible flame. ers should be available in the area. A Most hydrogen fires will have the fire blanket should be conveniently flame characteristic of a torch or jet located. An adequate water supply and will originate at the point where should be available to keep surround- the hydrogen is discharging. If a leak ing equipment cool in the event of a is suspected in any part of a system, hydrogen fire. The local fire depart- a hydrogen flame can be detected ment should be advised of the nature by cautiously approaching with an of the products handled and made outstretched broom, lifting it up and aware of the best known methods for down. combating hydrogen fires.

The most effective way to fight a Pipeline fires, where shutoff is pos- hydrogen fire is to shut off the flow sible and with flame characteristics of gas. If it is necessary to extinguish of a jet or torch, can be effectively the flame in order to get to a place controlled as follows: where the flow of hydrogen can be 1. Slowly reduce the flow of hydrogen shut off, a dry powder extinguisher is feeding the fire. Do not completely recommended. However, if the fire is stop the flow. extinguished without stopping the flow of gas, an explosive mixture may 2. When the jet is small enough to be form, creating a more serious hazard approached, put out the flame with than the fire itself, should reignition a carbon dioxide or dry powder occur from the hot surfaces or other extinguisher. sources. 3. Close off the supply of hydrogen completely.

4. Ventilate the area thoroughly.

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