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Hydrophobic polyurethanes naturally repel water (similar to the way oil would repel water and stay separate if you were trying to mix them in a glass). These products push water out of the area in question as they expand. Hydrophobics are used with catalysts which allow you to adjust the set time. They also have zero shrinkage after curing.
Hydrophilic polyurethanes naturally mix with water before curing (similar to the way gin and tonic mix thoroughly in a glass). This characteristic allows for a very strong chemical and mechanical bond, as water helps pull the material into the pores of the concrete. These products do not require a catalyst. You can pump them straight out of the pail.
AP Seal 500 is used for sealing cracks in concrete structures through pressure injection. Applications include sealing hairline cracks, expansion joints, wide cracks, pipe joints, and pipe penetrations. It's also ideal for saturating dry oakum to create a flexible gasket for sealing pipe penetrations, joints and larger defects in concrete structures.
This polyurethane injection does not require a catalyst. Other advantages include its tenacious bond to wet concrete and high elongation charactaristics. It's also thin enough to penetrate tight cracks, moderately hydrophilic, and phthalate free (more environmentally friendly). Last but not least, it's certified To NSF 61-5 (approved for contact with drinking water).
Haber, with his assistant Robert Le Rossignol, developed the high-pressure devices and catalysts needed to demonstrate the Haber process at laboratory scale.[9][10] They demonstrated their process in the summer of 1909 by producing ammonia from air, drop by drop, at the rate of about 125 mL (4 US fl oz) per hour. The process was purchased by the German chemical company BASF, which assigned Carl Bosch the task of scaling up Haber's tabletop machine to industrial-level production.[5][11] He succeeded in 1910. Haber and Bosch were later awarded Nobel prizes, in 1918 and 1931 respectively, for their work in overcoming the chemical and engineering problems of large-scale, continuous-flow, high-pressure technology.[5]
This conversion is typically conducted at pressures above 10 MPa (100 bar; 1,450 psi) and between 400 and 500 °C (752 and 932 °F), as the gases (nitrogen and hydrogen) are passed over four beds of catalyst, with cooling between each pass for maintaining a reasonable equilibrium constant. On each pass only about 15% conversion occurs, but any unreacted gases are recycled, and eventually an overall conversion of 97% is achieved.[3]
The major source of hydrogen is methane from natural gas. The conversion, steam reforming, is conducted with steam in a high-temperature and pressure tube inside a reformer with a nickel catalyst, separating the carbon and hydrogen atoms in the natural gas, yielding hydrogen gas and carbon monoxide waste (converted to carbon dioxide later in the process). Other fossil fuel sources include coal, heavy fuel oil and naphtha. Green hydrogen is produced without fossil fuels or carbon dioxide waste from biomass, electrolysis of water and the thermochemical (solar or other heat source) splitting of water, however, these sources of hydrogen are not competitive with the steam reforming process.[19][20][21] Green ammonia can become competitive with current trends in technology improvements and e.g. carbon taxes. [22]
Above this temperature, the equilibrium quickly becomes quite unfavorable for the reaction product at atmospheric pressure, according to the Van 't Hoff equation. Lowering the temperature is also unhelpful because the catalyst requires a temperature of at least 400 °C to be efficient.[3]
The catalyst typically consists of finely divided iron bound to an iron oxide carrier containing promoters possibly including aluminium oxide, potassium oxide, calcium oxide, potassium hydroxide,[26] molybdenum,[27] and magnesium oxide.
In industrial practice, the iron catalyst is obtained from finely ground iron powder, which is usually obtained by reduction of high-purity magnetite (Fe3O4). The pulverized iron is burnt (oxidized) to give magnetite or wüstite (FeO, ferrous oxide) particles of a specific size. The magnetite (or wüstite) particles are then partially reduced, removing some of the oxygen in the process. The resulting catalyst particles consist of a core of magnetite, encased in a shell of wüstite, which in turn is surrounded by an outer shell of metallic iron. The catalyst maintains most of its bulk volume during the reduction, resulting in a highly porous high-surface-area material, which enhances its effectiveness as a catalyst. Other minor components of the catalyst include calcium and aluminium oxides, which support the iron catalyst and help it maintain its surface area. These oxides of Ca, Al, K, and Si are unreactive to reduction by the hydrogen.[3]
The production of the required magnetite catalyst requires a particular melting process in which the used raw materials must be free of catalyst poisons and the promoter aggregates must be evenly distributed in the magnetite melt. Rapid cooling of the magnetite melt, which has an initial temperature of about 3500 °C, produces the precursor desired highly active catalyst. Unfortunately, the rapid cooling ultimately forms a catalyst of reduced abrasion resistance. Despite this disadvantage, the method of rapid cooling is often preferred in practice.[3]
The reduction of the catalyst precursor magnetite to α-iron is carried out directly in the production plant with synthesis gas. The reduction of the magnetite proceeds via the formation of wüstite (FeO), so that particles with a core of magnetite surrounded by a shell of wüstite are formed. The further reduction of magnetite and wüstite leads to the formation of α-iron, which forms together with the promoters the outer shell.[28] The involved processes are complex and depend on the reduction temperature: At lower temperatures, wüstite disproportionates into an iron phase and a magnetite phase; at higher temperatures, the reduction of the wüstite and magnetite to iron dominates.[29]
The reduction of fresh, fully oxidized catalyst or precursor to full production capacity takes four to ten days.[3] The wüstite phase is reduced faster and at lower temperatures than the magnetite phase (Fe3O4). After detailed kinetic, microscopic and X-ray spectroscopic investigations it was shown that wüstite reacts first to metallic iron. This leads to a gradient of iron(II) ions, whereby these diffuse from the magnetite through the wüstite to the particle surface and precipitate there as iron nuclei.
In industrial practice, pre-reduced, stabilised catalysts have gained a significant market share. They are delivered showing the fully developed pore structure, but have been oxidized again on the surface after manufacture and are therefore no longer pyrophoric. The reactivation of such pre-reduced catalysts requires only 30 to 40 hours instead of the usual time periods of several days. In addition to the short start-up time, they also have other advantages such as higher water resistance and lower weight.[3]
Due to the comparatively low price, high availability, easy processing, lifespan and activity, iron was ultimately chosen as catalyst. The production of 1800 tons ammonia per day requires a gas pressure of at least 130 bar, temperatures of 400 to 500 °C and a reactor volume of at least 100 m³. According to theoretical and practical studies, further improvements of the pure iron catalyst are limited. It was noticed that the activity of iron catalysts were increased by inclusion of cobalt.[32]
Ruthenium forms highly active catalysts. Allowing milder operating pressures and temperatures, Ru-based materials are referred to as second-generation catalysts. Such catalysts are prepared by decomposition of triruthenium dodecacarbonyl on graphite.[3] A drawback of activated-carbon-supported ruthenium-based catalysts is the methanation of the support in the presence of hydrogen. Their activity is strongly dependent on the catalyst carrier and the promoters. A wide range of substances can be used as carriers, including carbon, magnesium oxide, aluminium oxide, zeolites, spinels, and boron nitride.[33]
Ruthenium-activated carbon-based catalysts have been used industrially in the KBR Advanced Ammonia Process (KAAP) since 1992.[34] The carbon carrier is partially degraded to methane; however, this can be mitigated by a special treatment of the carbon at 1500 °C, thus prolonging the lifetime of the catalyst. In addition, the finely dispersed carbon poses a risk of explosion. For these reasons and due to its low acidity, magnesium oxide has proven to be a good alternative. Carriers with acidic properties extract electrons from ruthenium, make it less reactive, and have the undesirable effect of binding ammonia to the surface.[33]
Catalyst poisons lower the activity of the catalyst. They are usually impurities in the synthesis gas (a raw material). Concerning gaseous catalyst poisons, a distinction should be made between permanent poisons causing an irreversible loss of catalytic activity and temporary poisons which lower the activity while present in the synthesis gas. Sulfur compounds, phosphorus compounds, arsenic compounds, and chlorine compounds are permanent catalyst poisons. Oxygenic compounds like water, carbon monoxide, carbon dioxide and oxygen are temporary catalyst poisons.[3][35]
Although chemically inert components of the synthesis gas mixture such as noble gases or methane are not catalyst poisons in the strict sense, they accumulate through the recycling of the process gases and thus lower the partial pressure of the reactants, which in turn has a negative effect on the conversion.[36]
Since the reaction is exothermic, the equilibrium of the reaction shifts at lower temperatures to the side of the ammonia. Furthermore, four volumetric parts of the raw materials produce two volumetric parts of ammonia. According to Le Chatelier's principle, a high pressure therefore also favours the formation of ammonia. In addition, a high pressure is necessary to ensure sufficient surface coverage of the catalyst with nitrogen.[39] For this reason, a ratio of nitrogen to hydrogen of 1 to 3, a pressure of 250 to 350 bar, a temperature of 450 to 550 °C and α iron are used as catalysts. 2b1af7f3a8