For ammonia

Similar, very detailed studies were made by Ebert [112] on water adsorbed on alumina with similar conclusions. Water adsorbed on zeolites showed a dielectric constant of only 14-21, indicating greatly reduced mobility of the water dipoles [113]. Similar results were found for ammonia adsorbed in Vycor glass [114]. Klier and Zettlemoyer [114a] have reviewed a number of aspects of the molecular structure and dynamics of water at the surface of an inorganic material. 

The addition of potassium to Fe single crystals also enliances the activity for ammonia synthesis. Figure A3.10.19 shows the effect of surface potassium concentration on the N2 sticking coefficient. There is nearly a 300-fold increase in the sticking coefficient as the potassium concentration reaches -1.5 x 10 K atoms cm ... 

For this second reaction Kjgs = 181 x 10" and hence pK, for ammonia solution is 4.75. The entity NHj. H2O is often referred to as ammonium hydroxide, NH4OH, a formula which would imply that either nitrogen has a covalency of five, an impossible arrangement, or that NH4OH existed as the ions NH4 and OH". It is possible to crystallise two hydrates from concentrated ammonia solution but neither of these hydrates is ionic. Hence use of the term ammonium hydroxide is to be discouraged in favour of ammonia solution . 

Oxygen enrichment of steel blast furnaces accounts for the greatest use of the gas. Large quantities are also used in making synthesis gas for ammonia and methanol, ethylene oxide, and for oxy-acetylene welding. 

All other things being equal, the strength of a weak acid increases if it is placed in a solvent that is more basic than water, whereas the strength of a weak base increases if it is placed in a solvent that is more acidic than water. In some cases, however, the opposite effect is observed. For example, the pKb for ammonia is 4.76 in water and 6.40 in the more acidic glacial acetic acid. In contradiction to our expectations, ammonia is a weaker base in the more acidic solvent. A full description of the solvent s effect on a weak acid s piQ or on the pKb of a weak base is beyond the scope of this text. You should be aware, however, that titrations that are not feasible in water may be feasible in a different solvent. 

Resources for Nitrogen Fertilizers. The production of more than 95% of all nitrogen fertilizer begins with the synthesis of ammonia, thus it is the raw materials for ammonia synthesis that are of prime interest. Required feed to the synthesis process (synthesis gas) consists of an approximately 3 1 mixture (by volume) of hydrogen and nitrogen. 

Cmde gas leaves from the top of the gasifier at 288—593°C depending on the type of coal used. The composition of gas also depends on the type of coal and is notable for the relatively high methane content when contrasted to gases produced at lower pressures or higher temperatures. These gas products can be used as produced for electric power production or can be treated to remove carbon dioxide and hydrocarbons to provide synthesis gas for ammonia, methanol, and synthetic oil production. The gas is made suitable for methanation, to produce synthetic natural gas, by a partial shift and carbon dioxide and sulfur removal. 

The presence of ammonia and hydrogen peroxide in permanent hair color products is a disadvantage. Both are considered by consumers to be harsh chemicals. The odor of ammonia is unpleasant for a personal care product. Monoethanol amine has been used as a substitute for ammonia in some commercial permanent hair color products. It is not as effective as ammonia in allowing the hair to be lightened but it does not have as strong an odor. 

MPa (300—400 psig), using a Ni-based catalyst. Temperatures up to 1000°C and pressures up to 3.79 MPa (550 psia) are used in an autothermal-type reformer, or secondary reformer, when the hydrogen is used for ammonia, or in some cases methanol, production. 

High temperature steam reforming of natural gas accounts for 97% of the hydrogen used for ammonia synthesis in the United States. Hydrogen requirement for ammonia synthesis is about 336 m /t of ammonia produced for a typical 1000 t/d ammonia plant. The near-term demand for ammonia remains stagnant. Methanol production requires 560 m of hydrogen for each ton produced, based on a 2500-t/d methanol plant. Methanol demand is expected to increase in response to an increased use of the fuel—oxygenate methyl /-butyl ether (MTBE). 

This excess hydrogen is normally carried forward to be compressed into the synthesis loop, from which it is ultimately purged as fuel. Addition of by-product CO2 where available may be advantageous in that it serves to adjust the reformed gas to a more stoichiometric composition gas for methanol production, which results in a decrease in natural gas consumption (8). Carbon-rich off-gases from other sources, such as acetylene units, can also be used to provide supplemental synthesis gas. Alternatively, the hydrogen-rich purge gas can be an attractive feedstock for ammonia production (9). 

Dual-Pressure Process. Dual-pressure processes have a medium pressure (ca 0.3—0.6 MPa) front end for ammonia oxidation and a high pressure (1.1—1.5 MPa) tail end for absorption. Some older plants still use atmospheric pressure for ammonia conversion. Compared to high monopressure plants, the lower oxidation pressure improves ammonia yield and catalyst performance. Platinum losses are significantiy lower and production mns are extended by a longer catalyst life. Reduced pressure also results in weaker nitric acid condensate from the cooler condenser, which helps to improve absorber performance. Due to the spHt in operating conditions, the dual-pressure process requires a specialized stainless steel NO compressor. 

Reforming is completed in a secondary reformer, where air is added both to elevate the temperature by partial combustion of the gas stream and to produce the 3 1 H2 N2 ratio downstream of the shift converter as is required for ammonia synthesis. The water gas shift converter then produces more H2 from carbon monoxide and water. A low temperature shift process using a zinc—chromium—copper oxide catalyst has replaced the earlier iron oxide-catalyzed high temperature system. The majority of the CO2 is then removed. 

The mature Haber-Bosch technology is unlikely to change substantiaHy in the foreseeable future. The centers for commercial ammonia production may, however, relocate to sites where large quantities of natural gas are flared from cmde oil production, eg, Saudi Arabia or Venezuela. Relocation would not offset the problems for agriculture of high transportation and storage costs for ammonia production and distribution. Whereas the development of improved lower temperature and pressure catalysts is feasible, none is on the horizon as of this writing. 

The pH is plant specific, depending on additive used and secondary system materials. Feedwater generally should be equivalent to pH = 9.3 at 25°C for ammonia and carbon steel equipment. 

The dibydrochloride salt is used as a photographic developer. It also is employed as an intermediate in the manufacture of fur dyes, in hair dyeing, as a reagent in testing for ammonia and formaldehyde, and as an oxygen scavenger in water to prevent boiler corrosion (173). 

Fig. 1. MoUier diagram for ammonia. Numbers on dashed lines represent specific volume values ia m /kg. To convert from kPa to psi, multiply by 0.145.

Synthesis Gas Preparation Processes. Synthesis gas for ammonia production consists of hydrogen and nitrogen in about a three to one mole ratio, residual methane, argon introduced with the process air, and traces of carbon oxides. There are several processes available for synthesis gas generation and each is characterized by the specific feedstock used. A typical synthesis gas composition by volume is hydrogen, 73.65% nitrogen, 24.55% methane, <1 ppm-0.8% argon, 100 ppm—0.34% carbon oxides, 2—10 ppm and water vapor, 0.1 ppm. 

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