Haber process

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https://en.wikipedia.org/wiki/Haber_process 

 

Fritz Haber, 1918

The Haber process, also called the Haber–Bosch process, is the main industrial procedure for the production of ammonia. It is named after its inventors, the German chemists: Fritz Haber and Carl Bosch, who developed it in the first decade of the 20th century. The process converts atmospheric nitrogen (N₂) to ammonia (NH₃) by a reaction with hydrogen (H₂) using a metal catalyst under high temperatures and pressures. This reaction is slightly exothermic (i.e. it releases energy), meaning that the reaction is favoured at lower temperatures and higher pressures. It decreases entropy, complicating the process. Hydrogen is produced via steam reforming, followed by an iterative closed cycle to react hydrogen with nitrogen to produce ammonia.

The primary reaction is:

${\displaystyle {\text{N}}_2^{}+3{\text{H}}_2^{}⟶2{\text{NH}}_3^{}\mathrm{\Delta }{H}^{\circ }=-91.8\text{kJ/mol}}$

Before the development of the Haber process, it had been difficult to produce ammonia on an industrial scale, because earlier methods, such as the Birkeland–Eyde process and the Frank–Caro process, were too inefficient.

History

Main article: History of the Haber process

 

Carl Bosch, 1927

During the 19th century, the demand for nitrates and ammonia for use as fertilizers and industrial feedstocks rapidly increased. The main source was mining niter deposits and guano from tropical islands. At the beginning of the 20th century these reserves were thought insufficient to satisfy future demands, and research into new potential sources of ammonia increased. Although atmospheric nitrogen (N₂) is abundant, comprising ~78% of the air, it is exceptionally stable and does not readily react with other chemicals.

Haber, with his assistant Robert Le Rossignol, developed the high-pressure devices and catalysts needed to demonstrate the Haber process at a laboratory scale. They demonstrated their process in the summer of 1909 by producing ammonia from the 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 scale. 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.

Ammonia was first manufactured using the Haber process on an industrial scale in 1913 in BASF's Oppau plant in Germany, reaching 20 tonnes/day in 1914. During World War I, the production of munitions required large amounts of nitrate. The Allies had access to large deposits of sodium nitrate in Chile (Chile saltpetre) controlled by British companies. India had large supplies too, but it was also controlled by the British. Germany had no such resources, so the Haber process proved essential to the German war effort. Synthetic ammonia from the Haber process was used for the production of nitric acid, a precursor to the nitrates used in explosives.

The original Haber–Bosch reaction chambers used osmium as the catalyst, but it was available in extremely small quantities. Haber noted uranium was almost as effective and easier to obtain than osmium. In 1909, BASF researcher Alwin Mittasch discovered a much less expensive iron-based catalyst that is still used. A major contributor to the elucidation of this catalysis was Gerhard Ertl. The most popular catalysts are based on iron promoted with K₂O, CaO, SiO₂, and Al₂O₃.

During the interwar years, alternative processes were developed, most notably the Casale process, Claude process, and the Mont-Cenis process developed by Friedrich Uhde Ingenieurbüro. Luigi Casale and Georges Claude proposed to increase the pressure of the synthesis loop to 80–100 MPa (800–1,000 bar; 12,000–15,000 psi), thereby increasing the single-pass ammonia conversion and making nearly complete liquefaction at ambient temperature feasible. Claude proposed to have three or four converters with liquefaction steps in series, thereby avoiding recycling. Most plants continue to use the original Haber process (20 MPa (200 bar; 2,900 psi) and 500 °C (932 °F)), albeit with improved single-pass conversion and lower energy consumption due to process and catalyst optimization.

Process

A historical (1921) high-pressure steel reactor for the production of ammonia via the Haber process is displayed at the Karlsruhe Institute of Technology, Germany

Combined with the energy needed to produce hydrogen and purified atmospheric nitrogen, ammonia production is energy-intensive, accounting for 1% to 2% of global energy consumption, 3% of global carbon emissions, and 3% to 5% of natural gas consumption.

The choice of catalyst is important for synthesizing ammonia. In 2012, Hideo Hosono's group found that Ru-loaded calcium-aluminum oxide C12A7:e⁻ electride works well as a catalyst and pursued more efficient formation. This method is implemented in a small plant for ammonia synthesis in Japan. In 2019, Hosono's group found another catalyst, a novel perovskite oxynitride-hydride BaCeO_3−xN_yH_z, that works at lower temperature and without costly ruthenium.

Hydrogen production

The major source of hydrogen is methane. Steam reforming extracts hydrogen from methane in a high-temperature and pressure tube inside a reformer with a nickel catalyst. Other fossil fuel sources include coal, heavy fuel oil and naphtha.

Green hydrogen is produced without fossil fuels or carbon dioxide emissions from biomass, water electrolysis and thermochemical (solar or another heat source) water splitting. However, these hydrogen sources are not economically competitive with steam reforming.

Starting with a natural gas (CH
₄) feedstock, the steps are:

• Remove sulfur compounds from the feedstock, because sulfur deactivates the catalysts used in subsequent steps. Sulfur removal requires catalytic hydrogenation to convert sulfur compounds in the feedstocks to gaseous hydrogen sulfide (hydrodesulfurization, hydrotreating):

H₂ + RSH → RH + H₂S_(gas)

• Hydrogen sulfide is adsorbed and removed by passing it through beds of zinc oxide where it is converted to solid zinc sulfide:

Illustrating inputs and outputs of steam reforming of natural gas, a process to produce hydrogen

H₂S + ZnO → ZnS + H₂O

• Catalytic steam reforming of the sulfur-free feedstock forms hydrogen plus carbon monoxide:

CH₄ + H₂O → CO + 3 H₂

• Catalytic shift conversion converts the carbon monoxide to carbon dioxide and more hydrogen:

CO + H₂O → CO₂ + H₂

• Carbon dioxide is removed either by absorption in aqueous ethanolamine solutions or by adsorption in pressure swing adsorbers (PSA) using proprietary solid adsorption media.
• The final step in producing hydrogen is to use catalytic methanation to remove residual carbon monoxide or carbon dioxide:

CO  + 3 H₂ → CH₄ + H₂O

CO₂ + 4 H₂ → CH₄ + 2 H₂O

Ammonia production

The hydrogen is catalytically reacted with nitrogen (derived from process air) to form anhydrous liquid ammonia. It is difficult and expensive, as lower temperatures result in slower reaction kinetics (hence a slower reaction rate) and high pressure requires high-strength pressure vessels that resist hydrogen embrittlement. Diatomic nitrogen is bound together by a triple bond, which makes it relatively inert. Yield and efficiency are low, meaning that the ammonia must be extracted and the gases reprocessed for the reaction to proceed at an acceptable pace.

This step is known as the ammonia synthesis loop:

3 H₂ + N₂ → 2 NH₃

The gases (nitrogen and hydrogen) are passed over four beds of catalyst, with cooling between each pass to maintain a reasonable equilibrium constant. On each pass, only about 15% conversion occurs, but unreacted gases are recycled, and eventually conversion of 97% is achieved.

Due to the nature of the (typically multi-promoted magnetite) catalyst used in the ammonia synthesis reaction, only low levels of oxygen-containing (especially CO, CO₂ and H₂O) compounds can be tolerated in the hydrogen/nitrogen mixture. Relatively pure nitrogen can be obtained by air separation, but additional oxygen removal may be required.

Because of relatively low single pass conversion rates (typically less than 20%), a large recycle stream is required. This can lead to the accumulation of inerts in the gas.

Nitrogen gas (N₂) is unreactive because the atoms are held together by triple bonds. The Haber process relies on catalysts that accelerate the scission of these bonds.

Two opposing considerations are relevant: the equilibrium position and the reaction rate. At room temperature, the equilibrium is in favor of ammonia, but the reaction doesn't proceed at a detectable rate due to its high activation energy. Because the reaction is exothermic, the equilibrium constant decreases with increasing temperature following Le Châtelier's principle. It becomes unity at around 150–200 °C (302–392 °F).

K(T) for N
₂ + 3 H
₂ ⇌ 2 NH
₃

Temperature (°C)	Kp
300	4.34 × 10−3
400	1.64 × 10−4
450	4.51 × 10−5
500	1.45 × 10−5
550	5.38 × 10−6
600	2.25 × 10−6

Above this temperature, the equilibrium quickly becomes unfavorable at atmospheric pressure, according to the Van 't Hoff equation. Lowering the temperature is unhelpful because the catalyst requires a temperature of at least 400 °C to be efficient.

Increased pressure favors the forward reaction because 4 moles of reactant produce 2 moles of product, and the pressure used (15–25 MPa (150–250 bar; 2,200–3,600 psi)) alters the equilibrium concentrations to give a substantial ammonia yield. The reason for this is evident in the equilibrium relationship:

$${\displaystyle K=\frac{y_{{\text{NH}}_3^{}}^2}{y_{{\text{H}}_2^{}}^3{y}_{{\text{N}}_2^{}}}\frac{{\hat{\varphi }}_{{\text{NH}}_3^{}}^2}{{\hat{\varphi }}_{{\text{H}}_2^{}}^3{\hat{\varphi }}_{{\text{N}}_2^{}}}{\left(\frac{P^{\circ }}{P}\right)}^2,}$$

where ${\displaystyle {\hat{\varphi }}_i}$ is the fugacity coefficient of species ${\displaystyle i}$, ${\displaystyle y_i}$ is the mole fraction of the same species, ${\displaystyle P}$ is the reactor pressure, and ${\displaystyle P^{\circ }}$ is standard pressure, typically 1 bar (0.10 MPa).

Economically, reactor pressurization is expensive: pipes, valves, and reaction vessels need to be strong enough, and safety considerations affect operating at 20 MPa. Compressors take considerable energy, as work must be done on the (compressible) gas. Thus, the compromise used gives a single-pass yield of around 15%.

While removing the ammonia from the system increases the reaction yield, this step is not used in practice, since the temperature is too high; instead it is removed from the gases leaving the reaction vessel. The hot gases are cooled under high pressure, allowing the ammonia to condense and be removed as a liquid. Unreacted hydrogen and nitrogen gases are returned to the reaction vessel for another round. While most ammonia is removed (typically down to 2–5 mol.%), some ammonia remains in the recycle stream. In academic literature, a more complete separation of ammonia has been proposed by absorption in metal halides or zeolites. Such a process is called an absorbent-enhanced Haber process or adsorbent-enhanced Haber–Bosch process.

Pressure/temperature

The steam reforming, shift conversion, carbon dioxide removal, and methanation steps each operate at absolute pressures of about 25 to 35 bar, while the ammonia synthesis loop operates at temperatures of 300–500 °C (572–932 °F) and pressures ranging from 60 to 180 bar depending upon the method used. The resulting ammonia must then be separated from the residual hydrogen and nitrogen at temperatures of −20 °C (−4 °F).

Catalysts

First reactor at the Oppau plant in 1913

 

Profiles of the active components of heterogeneous catalysts; the top right figure shows the profile of a shell catalyst.

The Haber–Bosch process relies on catalysts to accelerate N₂ hydrogenation. The catalysts are heterogeneous, solids that interact with gaseous reagents.

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, molybdenum, and magnesium oxide.

Iron-based catalysts

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 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. 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 catalytic effectiveness. Minor components 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 hydrogen.

The production of the catalyst requires a particular melting process in which 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, which has an initial temperature of about 3500 °C, produces the desired precursor. Unfortunately, the rapid cooling ultimately forms a catalyst of reduced abrasion resistance. Despite this disadvantage, the method of rapid cooling is often employed.

The reduction of the 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 become surrounded by a shell of wüstite. The further reduction of magnetite and wüstite leads to the formation of α-iron, which forms together with the promoters of the outer shell. 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.

The α-iron forms primary crystallites with a diameter of about 30 nanometers. These crystallites form a bimodal pore system with pore diameters of about 10 nanometers (produced by the reduction of the magnetite phase) and of 25 to 50 nanometers (produced by the reduction of the wüstite phase). With the exception of cobalt oxide, the promoters are not reduced.

During the reduction of the iron oxide with synthesis gas, water vapor is formed. This water vapor must be considered for high catalyst quality as contact with the finely divided iron would lead to premature aging of the catalyst through recrystallization, especially in conjunction with high temperatures. The vapor pressure of the water in the gas mixture produced during catalyst formation is thus kept as low as possible, target values are below 3 gm⁻³. For this reason, the reduction is carried out at high gas exchange, low pressure, and low temperatures. The exothermic nature of the ammonia formation ensures a gradual increase in temperature.

The reduction of fresh, fully oxidized catalyst or precursor to full production capacity takes four to ten days. 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.

Pre-reduced, stabilized catalysts occupy 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 several days. In addition to the short start-up time, they have other advantages such as higher water resistance and lower weight.

Typical catalyst composition	Iron (%)	Potassium (%)	Aluminium (%)	Calcium (%)	Oxygen (%)
Volume composition	40.5	0.35	2.0	1.7	53.2
Surface composition before reduction	8.6	36.1	10.7	4.7	40.0
Surface composition after reduction	11.0	27.0	17.0	4.0	41.0

Catalysts other than iron

Many efforts have been made to improve the Haber–Bosch process. Many metals were tested as catalysts. The requirement for suitability is the dissociative adsorption of nitrogen (i. e. the nitrogen molecule must be split into nitrogen atoms upon adsorption). If the binding of the nitrogen is too strong, the catalyst is blocked and the catalytic ability is reduced (self-poisoning). The elements in the periodic table to the left of the iron group show such strong bonds. Further, the formation of surface nitrides makes, for example, chromium catalysts ineffective. Metals to the right of the iron group, in contrast, adsorb nitrogen too weakly for ammonia synthesis. Haber initially used catalysts based on osmium and uranium. Uranium reacts to its nitride during catalysis, while osmium oxide is rare.

According to theoretical and practical studies, improvements over pure iron are limited. The activity of iron catalysts is increased by the inclusion of cobalt.

Ruthenium

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 the decomposition of triruthenium dodecacarbonyl on graphite. 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.

Ruthenium-activated carbon-based catalysts have been used industrially in the KBR Advanced Ammonia Process (KAAP) since 1992. 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 catalyst lifetime. 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 choice of carrier. Carriers with acidic properties extract electrons from ruthenium, make it less reactive, and have the undesirable effect of binding ammonia to the surface.

Catalyst poisons

Catalyst poisons lower catalyst activity. They are usually impurities in the synthesis gas. Permanent poisons cause irreversible loss of catalytic activity and, while temporary poisons lower the activity while present. Sulfur compounds, phosphorus compounds, arsenic compounds, and chlorine compounds are permanent poisons. Oxygenic compounds like water, carbon monoxide, carbon dioxide, and oxygen are temporary poisons.

Although chemically inert components of the synthesis gas mixture such as noble gases or methane are not strictly poisons, they accumulate through the recycling of the process gases and thus lower the partial pressure of the reactants, which in turn slows conversion.

Industrial production

Synthesis parameters

Change of the equilibrium constant K_eq as a function of temperature

Temperature (°C)	Keq
300	4.34 × 10−3
400	1.64 × 10−4
450	4.51 × 10−5
500	1.45 × 10−5
550	5.38 × 10−6
600	2.25 × 10−6

The reaction is:

${\displaystyle {\text{N}}_2^{}+3{\text{H}}_2^{}\stackrel{-\rightharpoonup }{\leftharpoondown -}2{\text{NH}}_3^{}\mathrm{\Delta }{H}^{\circ }=-92.28\text{kJ}(\mathrm{\Delta }{H}_{298\mathrm{K}}^{\circ }=-46.14\mathrm{k}\mathrm{J}/\mathrm{m}\mathrm{o}\mathrm{l})}$

The reaction is an exothermic equilibrium reaction in which the gas volume is reduced. The equilibrium constant K_eq of the reaction (see table) is obtained from:

${\displaystyle K_{eq}=\frac{p^2({\text{NH}}_3^{})}{p({\text{N}}_2^{})\cdot p^3({\text{H}}_2^{})}}$

Since the reaction is exothermic, the equilibrium of the reaction shifts at lower temperatures to the ammonia side. Furthermore, four volumetric units of the raw materials produce two volumetric units of ammonia. According to Le Chatelier's principle, higher pressure favours ammonia. High pressure is necessary to ensure sufficient surface coverage of the catalyst with nitrogen. 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 optimal.

The catalyst ferrite (α-Fe) is produced in the reactor by the reduction of magnetite with hydrogen. The catalyst has its highest efficiency at temperatures of about 400 to 500 °C. Even though the catalyst greatly lowers the activation energy for the cleavage of the triple bond of the nitrogen molecule, high temperatures are still required for an appropriate reaction rate. At the industrially used reaction temperature of 450 to 550 °C an optimum between the decomposition of ammonia into the starting materials and the effectiveness of the catalyst is achieved. The formed ammonia is continuously removed from the system. The volume fraction of ammonia in the gas mixture is about 20%.

The inert components, especially the noble gases such as argon, should not exceed a certain content in order not to reduce the partial pressure of the reactants too much. To remove the inert gas components, part of the gas is removed and the argon is separated in a gas separation plant. The extraction of pure argon from the circulating gas is carried out using the Linde process.

Large-scale implementation

Modern ammonia plants produce more than 3000 tons per day in one production line. The following diagram shows the set-up of a Haber–Bosch plant:

 primary reformer  air feed  secondary reformer  CO conversion  washing tower  ammonia reactor  heat exchanger  ammonia condenser

Depending on its origin, the synthesis gas must first be freed from impurities such as hydrogen sulfide or organic sulphur compounds, which act as a catalyst poison. High concentrations of hydrogen sulfide, which occur in synthesis gas from carbonization coke, are removed in a wet cleaning stage such as the sulfosolvan process, while low concentrations are removed by adsorption on activated carbon. Organosulfur compounds are separated by pressure swing adsorption together with carbon dioxide after CO conversion.

To produce hydrogen by steam reforming, methane reacts with water vapor using a nickel oxide-alumina catalyst in the primary reformer to form carbon monoxide and hydrogen. The energy required for this, the enthalpy ΔH, is 206 kJ/mol.

${\displaystyle {\text{CH}}_{4(\text{g})}^{}+{\text{H}}_2^{}{\text{O}}_{(\text{g})}^{}⟶{\text{CO}}_{(\text{g})}^{}+3{\text{H}}_{2(\text{g})}^{}\mathrm{\Delta }H=+206\text{kJ}/\text{mol}}$

The methane gas reacts in the primary reformer only partially. To increase the hydrogen yield and keep the content of inert components (i. e. methane) as low as possible, the remaining methane gas is converted in a second step with oxygen to hydrogen and carbon monoxide in the secondary reformer. The secondary reformer is supplied with air as the oxygen source. Also, the required nitrogen for the subsequent ammonia synthesis is added to the gas mixture.

${\displaystyle 2{\text{CH}}_{4(\text{g})}^{}+{\text{O}}_{2(\text{g})}^{}⟶2{\text{CO}}_{(\text{g})}^{}+4{\text{H}}_{2(\text{g})}^{}\mathrm{\Delta }H=-71\text{kJ}/\text{mol}}$

In the third step, the carbon monoxide is oxidized to carbon dioxide, which is called CO conversion or water-gas shift reaction.

${\displaystyle {\text{CO}}_{(\text{g})}^{}+{\text{H}}_2^{}\text{O}(\text{g})⟶{\text{CO}}_{2(\text{g})}^{}+{\text{H}}_{2(\text{g})}^{}\mathrm{\Delta }H=-41\text{kJ}/\text{mol}}$

Carbon monoxide and carbon dioxide would form carbamates with ammonia, which would clog (as solids) pipelines and apparatus within a short time. In the following process step, the carbon dioxide must therefore be removed from the gas mixture. In contrast to carbon monoxide, carbon dioxide can easily be removed from the gas mixture by gas scrubbing with triethanolamine. The gas mixture then still contains methane and noble gases such as argon, which, however, behave inertly.

The gas mixture is then compressed to operating pressure by turbo compressors. The resulting compression heat is dissipated by heat exchangers; it is used to preheat raw gases.

The actual production of ammonia takes place in the ammonia reactor. The first reactors were bursting under high pressure because the atomic hydrogen in the carbonaceous steel partially recombined into methane and produced cracks in the steel. Bosch, therefore, developed tube reactors consisting of a pressure-bearing steel tube in which a low-carbon iron lining tube was inserted and filled with the catalyst. Hydrogen that diffused through the inner steel pipe escaped to the outside via thin holes in the outer steel jacket, the so-called Bosch holes. A disadvantage of the tubular reactors was the relatively high-pressure loss, which had to be applied again by compression. The development of hydrogen-resistant chromium-molybdenum steels made it possible to construct single-walled pipes.

Modern ammonia reactor with heat exchanger modules: The cold gas mixture is preheated to reaction temperature in heat exchangers by the reaction heat and cools in turn the produced ammonia.

Modern ammonia reactors are designed as multi-storey reactors with a low-pressure drop, in which the catalysts are distributed as fills over about ten storeys one above the other. The gas mixture flows through them one after the other from top to bottom. Cold gas is injected from the side for cooling. A disadvantage of this reactor type is the incomplete conversion of the cold gas mixture in the last catalyst bed.

Alternatively, the reaction mixture between the catalyst layers is cooled using heat exchangers, whereby the hydrogen-nitrogen mixture is preheated to the reaction temperature. Reactors of this type have three catalyst beds. In addition to good temperature control, this reactor type has the advantage of better conversion of the raw material gases compared to reactors with cold gas injection.

Uhde has developed and is using an ammonia converter with three radial flow catalyst beds and two internal heat exchangers instead of axial flow catalyst beds. This further reduces the pressure drop in the converter.

The reaction product is continuously removed for maximum yield. The gas mixture is cooled to 450 °C in a heat exchanger using water, freshly supplied gases, and other process streams. The ammonia also condenses and is separated in a pressure separator. Unreacted nitrogen and hydrogen are then compressed back to the process by a circulating gas compressor, supplemented with fresh gas, and fed to the reactor. In a subsequent distillation, the product ammonia is purified.

Mechanism

Elementary steps

The mechanism of ammonia synthesis contains the following seven elementary steps:

1. transport of the reactants from the gas phase through the boundary layer to the surface of the catalyst.
2. pore diffusion to the reaction center
3. adsorption of reactants
4. reaction
5. desorption of product
6. transport of the product through the pore system back to the surface
7. transport of the product into the gas phase

Transport and diffusion (the first and last two steps) are fast compared to adsorption, reaction, and desorption because of the shell structure of the catalyst. It is known from various investigations that the rate-determining step of the ammonia synthesis is the dissociation of nitrogen. In contrast, exchange reactions between hydrogen and deuterium on the Haber–Bosch catalysts still take place at temperatures of −196 °C (−320.8 °F) at a measurable rate; the exchange between deuterium and hydrogen on the ammonia molecule also takes place at room temperature. Since the adsorption of both molecules is rapid, it cannot determine the speed of ammonia synthesis.

In addition to the reaction conditions, the adsorption of nitrogen on the catalyst surface depends on the microscopic structure of the catalyst surface. Iron has different crystal surfaces, whose reactivity is very different. The Fe(111) and Fe(211) surfaces have by far the highest activity. The explanation for this is that only these surfaces have so-called C7 sites – these are iron atoms with seven closest neighbours.

The dissociative adsorption of nitrogen on the surface follows the following scheme, where S* symbolizes an iron atom on the surface of the catalyst:

N₂ → S^*–N₂ (γ-species) → S*–N₂–S^* (α-species) → 2 S*–N (β-species, surface nitride)

The adsorption of nitrogen is similar to the chemisorption of carbon monoxide. On a Fe(111) surface, the adsorption of nitrogen first leads to an adsorbed γ-species with an adsorption energy of 24 kJmol⁻¹ and an N-N stretch vibration of 2100 cm⁻¹. Since the nitrogen is isoelectronic to carbon monoxide, it adsorbs in an on-end configuration in which the molecule is bound perpendicular to the metal surface at one nitrogen atom. This has been confirmed by photoelectron spectroscopy.

Ab-initio-MO calculations have shown that, in addition to the σ binding of the free electron pair of nitrogen to the metal, there is a π binding from the d orbitals of the metal to the π* orbitals of nitrogen, which strengthens the iron-nitrogen bond. The nitrogen in the α state is more strongly bound with 31 kJmol⁻¹. The resulting N–N bond weakening could be experimentally confirmed by a reduction of the wave numbers of the N–N stretching oscillation to 1490 cm⁻¹.

Further heating of the Fe(111) area covered by α-N₂ leads to both desorption and the emergence of a new band at 450 cm⁻¹. This represents a metal-nitrogen oscillation, the β state. A comparison with vibration spectra of complex compounds allows the conclusion that the N₂ molecule is bound "side-on", with an N atom in contact with a C7 site. This structure is called "surface nitride". The surface nitride is very strongly bound to the surface. Hydrogen atoms (H_ads), which are very mobile on the catalyst surface, quickly combine with it.

Infrared spectroscopically detected surface imides (NH_ad), surface amides (NH_2,ad) and surface ammoniacates (NH_3,ad) are formed, the latter decay under NH₃ release (desorption). The individual molecules were identified or assigned by X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and Ir Spectroscopy.

Drawn reaction scheme

On the basis of these experimental findings, the reaction mechanism is believed to involve the following steps (see also figure):

1. N₂ (g) → N₂ (adsorbed)
2. N₂ (adsorbed) → 2 N (adsorbed)
3. H₂ (g) → H₂ (adsorbed)
4. H₂ (adsorbed) → 2 H (adsorbed)
5. N (adsorbed) + 3 H (adsorbed) → NH₃ (adsorbed)
6. NH₃ (adsorbed) → NH₃ (g)

Reaction 5 occurs in three steps, forming NH, NH₂, and then NH₃. Experimental evidence points to reaction 2 as being slow, rate-determining step. This is not unexpected, since the bond is broken, the nitrogen triple bond is the strongest of the bonds that must be broken.

As with all Haber–Bosch catalysts, nitrogen dissociation is the rate-determining step for ruthenium-activated carbon catalysts. The active center for ruthenium is a so-called B5 site, a 5-fold coordinated position on the Ru(0001) surface where two ruthenium atoms form a step edge with three ruthenium atoms on the Ru(0001) surface. The number of B5 sites depends on the size and shape of the ruthenium particles, the ruthenium precursor and the amount of ruthenium used. The reinforcing effect of the basic carrier used in the ruthenium catalyst is similar to the promoter effect of alkali metals used in the iron catalyst.

Energy diagram

Energy diagram

An energy diagram can be created based on the Enthalpy of Reaction of the individual steps. The energy diagram can be used to compare homogeneous and heterogeneous reactions: Due to the high activation energy of the dissociation of nitrogen, the homogeneous gas phase reaction is not realizable. The catalyst avoids this problem as the energy gain resulting from the binding of nitrogen atoms to the catalyst surface overcompensates for the necessary dissociation energy so that the reaction is finally exothermic. Nevertheless, the dissociative adsorption of nitrogen remains the rate-determining step: not because of the activation energy, but mainly because of the unfavorable pre-exponential factor of the rate constant. Although hydrogenation is endothermic, this energy can easily be applied by the reaction temperature (about 700 K).

Economic and environmental aspects

Further information: Ammonia production § Sustainable ammonia production

 

Severnside fertilizer plant northwest of Bristol, UK

When first invented, the Haber process competed against another industrial process, the cyanamide process. However, the cyanamide process consumed large amounts of electrical power and was more labor-intensive than the Haber process.

As of 2018, the Haber process produces 230 million tonnes of anhydrous ammonia per year. The ammonia is used mainly as a nitrogen fertilizer as ammonia itself, in the form of ammonium nitrate, and as urea. The Haber process consumes 3–5% of the world's natural gas production (around 1–2% of the world's energy supply). In combination with advances in breeding, herbicides, and pesticides, these fertilizers have helped to increase the productivity of agricultural land:

With average crop yields remaining at the 1900 level the crop harvest in the year 2000 would have required nearly four times more land and the cultivated area would have claimed nearly half of all ice-free continents, rather than under 15% of the total land area that is required today.

— Vaclav Smil, Nitrogen cycle and world food production, Volume 2, pages 9–13

The energy-intensity of the process contributes to climate change and other environmental problems such as the leaching of nitrates into groundwater, rivers, ponds, and lakes; expanding dead zones in coastal ocean waters, resulting from recurrent eutrophication; atmospheric deposition of nitrates and ammonia affecting natural ecosystems; higher emissions of nitrous oxide (N₂O), now the third most important greenhouse gas following CO₂ and CH₄. The Haber–Bosch process is one of the largest contributors to a buildup of reactive nitrogen in the biosphere, causing an anthropogenic disruption to the nitrogen cycle.

Since nitrogen use efficiency is typically less than 50%, farm runoff from heavy use of fixed industrial nitrogen disrupts biological habitats.

Nearly 50% of the nitrogen found in human tissues originated from the Haber–Bosch process. Thus, the Haber process serves as the "detonator of the population explosion", enabling the global population to increase from 1.6 billion in 1900 to 7.7 billion by November 2018.

Reverse fuel cell technology converts renewable energy, water and air into ammonia without a separate hydrogen electrolysis process.

Sustainable biofuel

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Sustainable_biofuel

Sustainable biofuel is biofuel produced in a sustainable manner. It is not based on petroleum or other fossil fuels. It includes not using plants that are used for food stuff to produce the fuel thus disrupting the world's food supply.

Sustainability standards

See also: Low-carbon fuel standard

In 2008, the Roundtable for Sustainable Biofuels released its proposed standards for sustainable biofuels. This includes 12 principles:

1. "Biofuel production shall follow international treaties and national laws regarding such things as air quality, water resources, agricultural practices, labor conditions, and more.
2. Biofuels projects shall be designed and operated in participatory processes that involve all relevant stakeholders in planning and monitoring.
3. Biofuels shall significantly reduce greenhouse gas emissions as compared to fossil fuels. The principle seeks to establish a standard methodology for comparing greenhouse gases (GHG) benefits.
4. Biofuel production shall not violate human rights or labor rights, and shall ensure decent work and the well-being of workers.
5. Biofuel production shall contribute to the social and economic development of local, rural and indigenous peoples and communities.
6. Biofuel production shall not impair food security.
7. Biofuel production shall avoid negative impacts on biodiversity, ecosystems and areas of high conservation value.
8. Biofuel production shall promote practices that improve soil health and minimize degradation.
9. Surface and groundwater use will be optimized and contamination or depletion of water resources minimized.
10. Air pollution shall be minimized along the supply chain.
11. Biofuels shall be produced in the most cost-effective way, with a commitment to improve production efficiency and social and environmental performance in all stages of the biofuel value chain.
12. Biofuel production shall not violate land rights".

Several countries and regions have introduced policies or adopted standards to promote sustainable biofuels production and use, most prominently the European Union and the United States. The 2009 EU Renewable Energy Directive, which requires 10 percent of transportation energy from renewable energy by 2020, is the most comprehensive mandatory sustainability standard in place as of 2010.

The EU Renewable Energy Directive requires that the lifecycle greenhouse gas emissions of biofuels consumed be at least 50 percent less than the equivalent emissions from gasoline or diesel by 2017 (and 35 percent less starting in 2011). Also, the feedstocks for biofuels "should not be harvested from lands with high biodiversity value, from carbon-rich or forested land, or from wetlands".

As with the EU, the U.S. Renewable Fuel Standard (RFS) and the California Low Carbon Fuel Standard (LCFS) both require specific levels of lifecycle greenhouse gas reductions compared to equivalent fossil fuel consumption. The RFS requires that at least half of the biofuels production mandated by 2022 should reduce lifecycle emissions by 50 percent. The LCFS is a performance standard that calls for a minimum of 10 percent emissions reduction per unit of transport energy by 2020. Both the U.S. and California standards currently address only greenhouse gas emissions, but California plans to "expand its policy to address other sustainability issues associated with liquid biofuels in the future".

In 2009, Brazil also adopted new sustainability policies for sugarcane ethanol, including "zoning regulation of sugarcane expansion and social protocols".

Motivation

Biofuels, in the form of liquid fuels derived from plant materials, are entering the market, driven by factors such as oil price spikes and the need for increased energy security. However, many of these first-generation biofuels that are currently being supplied have been criticised for their adverse impacts on the natural environment, food security, and land use.

The challenge is to support second, third and fourth-generation biofuel development. Second-generation biofuels include new cellulosic technologies, with responsible policies and economic instruments to help ensure that biofuel commercialization is sustainable. Responsible commercialization of biofuels represents an opportunity to enhance sustainable economic prospects in Africa, Latin America and Asia.

Biofuels have a limited ability to replace fossil fuels and should not be regarded as a ‘silver bullet’ to deal with transport emissions. However, they offer the prospect of increased market competition and oil price moderation. A healthy supply of alternative energy sources will help to combat gasoline price spikes and reduce dependency on fossil fuels, especially in the transport sector. Using transportation fuels more efficiently is also an integral part of a sustainable transport strategy.

Biofuel options

Biofuel development and use is a complex issue because there are many biofuel options which are available. Biofuels, such as ethanol and biodiesel, are currently produced from the products of conventional food crops such as the starch, sugar and oil feedstocks from crops that include wheat, maize, sugar cane, palm oil and oilseed rape. Some researchers fear that a major switch to biofuels from such crops would create a direct competition with their use for food and animal feed, and claim that in some parts of the world the economic consequences are already visible, other researchers look at the land available and the enormous areas of idle and abandoned land and claim that there is room for a large proportion of biofuel also from conventional crops.

Second generation biofuels are now being produced from a much broader range of feedstocks including the cellulose in dedicated energy crops (perennial grasses such as switchgrass and Miscanthus giganteus), forestry materials, the co-products from food production, and domestic vegetable waste. Advances in the conversion processes will improve the sustainability of biofuels, through better efficiencies and reduced environmental impact of producing biofuels, from both existing food crops and from cellulosic sources. One promising development in biobutanol production technology was discovered in the late summer of 2011—Tulane University's alternative fuel research scientists discovered a strain of Clostridium bacteria, called "TU-103", a key feature of the discovery is that the "TU-103" organism can convert nearly any form of cellulose into butanol, and is the only known strain of Clostridium-genus bacteria that can do so in the presence of oxygen. The university's researchers have stated that the source of the "TU-103" Clostridium bacteria strain was most likely from the solid waste from one of the plains zebra at New Orleans' Audubon Zoo.

In 2007, Ronald Oxburgh suggested in The Courier-Mail that production of biofuels could be either responsible or irresponsible and had several trade-offs: "Produced responsibly they are a sustainable energy source that need not divert any land from growing food nor damage the environment; they can also help solve the problems of the waste generated by Western society; and they can create jobs for the poor where previously were none. Produced irresponsibly, they at best offer no climate benefit and, at worst, have detrimental social and environmental consequences. In other words, biofuels are pretty much like any other product. In 2008 the Nobel prize-winning chemist Paul J. Crutzen published findings that the release of nitrous oxide (N₂O) emissions in the production of biofuels means that they contribute more to global warming than the fossil fuels they replace.

According to the Rocky Mountain Institute, sound biofuel production practices would not hamper food and fibre production, nor cause water or environmental problems, and would enhance soil fertility. The selection of land on which to grow the feedstocks is a critical component of the ability of biofuels to deliver sustainable solutions. A key consideration is the minimisation of biofuel competition for prime cropland.

Biofuels are different from fossil fuels in regard to carbon emissions being short term, but are similar to fossil fuels in that biofuels contribute to air pollution. Raw biofuels burned to generate steam for heat and power, produces airborne carbon particulates, carbon monoxide and nitrous oxides. The WHO estimates 3.7 million premature deaths worldwide in 2012 due to air pollution.

Plants used as sustainable biofuel

Sugarcane in Brazil

Sugarcane (Saccharum officinarum) plantation ready for harvest, Ituverava, São Paulo State, Brazil.

 

Mechanized harvesting of sugarcane, Piracicaba, São Paulo, Brazil.

 

Cosan's Costa Pinto sugar cane mill and ethanol distillery plant at Piracicaba, São Paulo, Brazil.

 

See also: Environmental and social impacts of Brazilian ethanol fuel

Brazil’s production of ethanol fuel from sugarcane dates back to the 1970s, as a governmental response to the 1973 oil crisis. Brazil is considered the biofuel industry leader and the world's first sustainable biofuels economy.Inslee, Jay; Bracken Hendricks (2007). "6. Homegrown Energy". Apollo's Fire. Island Press, Washington, D.C. pp. 153–155, 160–161. ISBN 978-1-59726-175-3. In 2010 the U.S. Environmental Protection Agency designated Brazilian sugarcane ethanol as an advanced biofuel due to EPA's estimated 61% reduction of total life cycle greenhouse gas emissions, including direct indirect land use change emissions. Brazil sugarcane ethanol fuel program success and sustainability is based on the most efficient agricultural technology for sugarcane cultivation in the world, uses modern equipment and cheap sugar cane as feedstock, the residual cane-waste (bagasse) is used to process heat and power, which results in a very competitive price and also in a high energy balance (output energy/input energy), which varies from 8.3 for average conditions to 10.2 for best practice production.

A report commissioned by the United Nations, based on a detailed review of published research up to mid-2009 as well as the input of independent experts world-wide, found that ethanol from sugar cane as produced in Brazil "in some circumstances does better than just "zero emission". If grown and processed correctly, it has negative emission, pulling CO₂ out of the atmosphere, rather than adding it. In contrast, the report found that U.S. use of maize for biofuel is less efficient, as sugarcane can lead to emissions reductions of between 70% and well over 100% when substituted for gasoline. Several other studies have shown that sugarcane-based ethanol reduces greenhouse gases by 86 to 90% if there is no significant land use change.

In another study commissioned by the Dutch government in 2006 to evaluate the sustainability of Brazilian bioethanol concluded that there is sufficient water to supply all foreseeable long-term water requirements for sugarcane and ethanol production. This evaluation also found that consumption of agrochemicals for sugar cane production is lower than in citric, corn, coffee and soybean cropping. The study found that development of resistant sugar cane varieties is a crucial aspect of disease and pest control and is one of the primary objectives of Brazil's cane genetic improvement programs. Disease control is one of the main reasons for the replacement of a commercial variety of sugar cane.

Another concern is the fact that sugarcane fields are traditionally burned just before harvest to avoid harm to the workers, by removing the sharp leaves and killing snakes and other harmful animals, and also to fertilize the fields with ash. Mechanization will reduce pollution from burning fields and has higher productivity than people, and due to mechanization the number of temporary workers in the sugarcane plantations has already declined. By the 2008 harvest season, around 47% of the cane was collected with harvesting machines.

Regarding the negative impacts of the potential direct and indirect effect of land use changes on carbon emissions, the study commissioned by the Dutch government concluded that "it is very difficult to determine the indirect effects of further land use for sugar cane production (i.e. sugar cane replacing another crop like soy or citrus crops, which in turn causes additional soy plantations replacing pastures, which in turn may cause deforestation), and also not logical to attribute all these soil carbon losses to sugar cane". The Brazilian agency Embrapa estimates that there is enough agricultural land available to increase at least 30 times the existing sugarcane plantation without endangering sensible ecosystems or taking land destined for food crops. Most future growth is expected to take place on abandoned pasture lands, as it has been the historical trend in São Paulo state. Also, productivity is expected to improve even further based on current biotechnology research, genetic improvement, and better agronomic practices, thus contributing to reduce land demand for future sugarcane cultures.

Location of environmentally valuable areas with respect to sugarcane plantations. São Paulo, located in the Southeast Region of Brazil, concentrates two-thirds of sugarcane cultures.

Another concern is the risk of clearing rain forests and other environmentally valuable land for sugarcane production, such as the Amazon rainforest, the Pantanal or the Cerrado. Embrapa has rebutted this concern explaining that 99.7% of sugarcane plantations are located at least 2,000 km from the Amazon, and expansion during the last 25 years took place in the Center-South region, also far away from the Amazon rainforest, the Pantanal or the Atlantic forest. In São Paulo state growth took place in abandoned pasture lands. The impact assessment commissioned by the Dutch government supported this argument.

In order to guarantee a sustainable development of ethanol production, in September 2009 the government issued by decree a countrywide agroecological land use zoning to restrict sugarcane growth in or near environmentally sensitive areas. According to the new criteria, 92.5% of the Brazilian territory is not suitable for sugarcane plantation. The government considers that the suitable areas are more than enough to meet the future demand for ethanol and sugar in the domestic and international markets foreseen for the next decades.

Regarding the food vs fuel issue, a World Bank research report published in July 2008 found that "Brazil's sugar-based ethanol did not push food prices appreciably higher". This research paper also concluded that Brazil's sugar cane–based ethanol has not raised sugar prices significantly. An economic assessment report also published in July 2008 by the OECD agrees with the World Bank report regarding the negative effects of subsidies and trade restrictions, but found that the impact of biofuels on food prices are much smaller. A study by the Brazilian research unit of the Fundação Getúlio Vargas regarding the effects of biofuels on grain prices concluded that the major driver behind the 2007–2008 rise in food prices was speculative activity on futures markets under conditions of increased demand in a market with low grain stocks. The study also concluded that there is no correlation between Brazilian sugarcane cultivated area and average grain prices, as on the contrary, the spread of sugarcane was accompanied by rapid growth of grain crops in the country.

Jatropha

India and Africa

Jatropha gossipifolia in Hyderabad, India.

Crops like Jatropha, used for biodiesel, can thrive on marginal agricultural land where many trees and crops won't grow, or would produce only slow growth yields. Jatropha cultivation provides benefits for local communities:

Cultivation and fruit picking by hand is labour-intensive and needs around one person per hectare. In parts of rural India and Africa this provides much-needed jobs – about 200,000 people worldwide now find employment through jatropha. Moreover, villagers often find that they can grow other crops in the shade of the trees. Their communities will avoid importing expensive diesel and there will be some for export too.

Cambodia

Cambodia has no proven fossil fuel reserves, and is almost completely dependent on imported diesel fuel for electricity production. Consequently, Cambodians face an insecure supply and pay some of the highest energy prices in the world. The impacts of this are widespread and may hinder economic development.

Biofuels may provide a substitute for diesel fuel that can be manufactured locally for a lower price, independent of the international oil price. The local production and use of biofuel also offers other benefits such as improved energy security, rural development opportunities and environmental benefits. The Jatropha curcas species appears to be a particularly suitable source of biofuel as it already grows commonly in Cambodia. Local sustainable production of biofuel in Cambodia, based on the Jatropha or other sources, offers good potential benefits for the investors, the economy, rural communities and the environment.

Mexico

Jatropha is native to Mexico and Central America and was likely transported to India and Africa in the 1500s by Portuguese sailors convinced it had medicinal uses. In 2008, recognizing the need to diversify its sources of energy and reduce emissions, Mexico passed a law to push developing biofuels that don't threaten food security and the agriculture ministry has since identified some 2.6 million hectares (6.4 million acres) of land with a high potential to produce jatropha. The Yucatán Peninsula, for instance, in addition to being a corn-producing region, also contains abandoned sisal plantations, where the growing of Jatropha for biodiesel production would not displace food.

On April 1, 2011, Interjet completed the first Mexican aviation biofuels test flight on an Airbus A320. The fuel was a 70:30 traditional jet fuel biojet blend produced from Jatropha oil provided by three Mexican producers, Global Energías Renovables (a wholly owned subsidiary of U.S.-based Global Clean Energy Holdings), Bencafser S.A. and Energy JH S.A. Honeywell's UOP processed the oil into Bio-SPK (Synthetic Paraffinic Kerosene). Global Energías Renovables operates the largest Jatropha farm in the Americas.

On August 1, 2011, Aeromexico, Boeing, and the Mexican Government participated in the first biojet powered transcontinental flight in aviation history. The flight from Mexico City to Madrid used a blend of 70 percent traditional fuel and 30 percent biofuel (aviation biofuel). The biojet was produced entirely from Jatropha oil.

Pongamia Pinnata in Australia and India

Pongamia pinnata seeds in Brisbane, Australia.

Pongamia pinnata is a legume native to Australia, India, Florida (USA) and most tropical regions, and is now being invested in as an alternative to Jatropha for areas such as Northern Australia, where Jatropha is classed as a noxious weed. Commonly known as simply 'Pongamia', this tree is currently being commercialised in Australia by Pacific Renewable Energy, for use as a Diesel replacement for running in modified Diesel engines or for conversion to Biodiesel using 1st or 2nd Generation Biodiesel techniques, for running in unmodified Diesel engines.

Sweet sorghum in India

Sweet sorghum overcomes many of the shortcomings of other biofuel crops. With sweet sorghum, only the stalks are used for biofuel production, while the grain is saved for food or livestock feed. It is not in high demand in the global food market, and thus has little impact on food prices and food security. Sweet sorghum is grown on already-farmed drylands that are low in carbon storage capacity, so concerns about the clearing of rainforest do not apply. Sweet sorghum is easier and cheaper to grow than other biofuel crops in India and does not require irrigation, an important consideration in dry areas. Some of the Indian sweet sorghum varieties are now grown in Uganda for ethanol production.

A study by researchers at the International Crops Research Institute for the Semi-Arid Tropics (ICRISAT) found that growing sweet sorghum instead of grain sorghum could increase farmers incomes by US$40 per hectare per crop because it can provide food, feed and fuel. With grain sorghum currently grown on over 11 million hectares (ha) in Asia and on 23.4 million ha in Africa, a switch to sweet sorghum could have a considerable economic impact.

International collaboration on sustainable biofuels

Roundtable on Sustainable Biomaterials

Public attitudes and the actions of key stakeholders can play a crucial role in realising the potential of sustainable biofuels. Informed discussion and dialogue, based both on scientific research and an understanding of public and stakeholder views, is important.

The Roundtable on Sustainable Materials, previously Roundtable on Sustainable Biofuels, is an international initiative which brings together farmers, companies, governments, non-governmental organizations, and scientists who are interested in the sustainability of biofuels production and distribution. During 2008, the Roundtable used meetings, teleconferences, and online discussions to develop a series of principles and criteria for sustainable biofuels production.

In April 2011, the Roundtable on Sustainable Biofuels launched a set of comprehensive sustainability criteria – the "RSB Certification System." Biofuels producers that meet to these criteria are able to show buyers and regulators that their product has been obtained without harming the environment or violating human rights.

Sustainable Biofuels Consensus

The Sustainable Biofuels Consensus is an international initiative which calls upon governments, the private sector, and other stakeholders to take decisive action to ensure the sustainable trade, production, and use of biofuels. In this way biofuels may play a key role in energy sector transformation, climate stabilization, and resulting worldwide revitalisation of rural areas.

The Sustainable Biofuels Consensus envisions a "landscape that provides food, fodder, fiber, and energy, which offers opportunities for rural development; that diversifies energy supply, restores ecosystems, protects biodiversity, and sequesters carbon".

Better Sugarcane Initiative / Bonsucro

See also: Bonsucro

In 2008, a multi-stakeholder process was initiated by the World Wildlife Fund and the International Finance Corporation, the private development arm of the World Bank, bringing together industry, supply chain intermediaries, end-users, farmers and civil society organisations to develop standards for certifying the derivative products of sugar cane, one of which is ethanol fuel.

The Bonsucro standard is based around a definition of sustainability which is founded on five principles:

1. Obey the law
2. Respect human rights and labour standards
3. Manage input, production and processing efficiencies to enhance sustainability
4. Actively manage biodiversity and ecosystem services
5. Continuously improve key areas of the business

Biofuel producers that wish to sell products marked with the Bonsucro standard must both ensure that they product to the Production Standard, and that their downstream buyers meet the Chain of Custody Standard. In addition, if they wish to sell to the European market and count against the EU Renewable Energy Directive, then they must adhere to the Bonsucro EU standard, which includes specific greenhouse gas calculations following European Commission calculation guidelines.

Oil price moderation

Biofuels offer the prospect of real market competition and oil price moderation. According to the Wall Street Journal, crude oil would be trading 15 per cent higher and gasoline would be as much as 25 per cent more expensive, if it were not for biofuels. A healthy supply of alternative energy sources will help to combat gasoline price spikes.

Sustainable transport

See also: BioEthanol for Sustainable Transport

Biofuels have a limited ability to replace fossil fuels and should not be regarded as a 'silver bullet' to deal with transport emissions. Biofuels on their own cannot deliver a sustainable transport system and so must be developed as part of an integrated approach, which promotes other renewable energy options and energy efficiency, as well as reducing the overall energy demand and need for transport. Consideration needs to be given to the development of hybrid and fuel cell vehicles, public transport, and better town and rural planning.

In December 2008, an Air New Zealand jet completed the world's first commercial aviation test flight partially using jatropha-based fuel. More than a dozen performance tests were undertaken in the two-hour test flight which departed from Auckland International Airport. A biofuel blend of 50:50 jatropha and Jet A1 fuel was used to power one of the Boeing 747-400's Rolls-Royce RB211 engines. Air New Zealand set several criteria for its jatropha, requiring that "the land it came from was neither forest nor virgin grassland in the previous 20 years, that the soil and climate it came from is not suitable for the majority of food crops and that the farms are rain fed and not mechanically irrigated". The company has also set general sustainability criteria, saying that such biofuels must not compete with food resources, that they must be as good as traditional jet fuels, and that they should be cost competitive.

In January 2009, Continental Airlines used a sustainable biofuel to power a commercial aircraft for the first time in North America. This demonstration flight marks the first sustainable biofuel demonstration flight by a commercial carrier using a twin-engined aircraft, a Boeing 737-800, powered by CFM International CFM56-7B engines. The biofuel blend included components derived from algae and jatropha plants. The algae oil was provided by Sapphire Energy, and the jatropha oil by Terasol Energy.

In March 2011, Yale University research showed significant potential for sustainable aviation fuel based on jatropha-curcas. According to the research, if cultivated properly, "jatropha can deliver many benefits in Latin America and greenhouse gas reductions of up to 60 percent when compared to petroleum-based jet fuel". Actual farming conditions in Latin America were assessed using sustainability criteria developed by the Roundtable on Sustainable Biofuels. Unlike previous research, which used theoretical inputs, the Yale team conducted many interviews with jatropha farmers and used "field measurements to develop the first comprehensive sustainability analysis of actual projects".

As of June 2011, revised international aviation fuel standards officially allow commercial airlines to blend conventional jet fuel with up to 50 percent biofuels. The renewable fuels "can be blended with conventional commercial and military jet fuel through requirements in the newly issued edition of ASTM D7566, Specification for Aviation Turbine Fuel Containing Synthesized Hydrocarbons".

In December 2011, the FAA awarded $7.7 million to eight companies to advance the development of commercial aviation biofuels, with a special focus on alcohol to jet fuel. The FAA is assisting in the development of a sustainable fuel (from alcohols, sugars, biomass, and organic matter such as pyrolysis oils) that can be "dropped in" to aircraft without changing current practices and infrastructure. The research will test how the new fuels affect engine durability and quality control standards.

GreenSky London, a biofuels plant under construction in 2014, aimed to take in some 500,000 tonnes of municipal rubbish and change the organic component into 60,000 tonnes of jet fuel, and 40 megawatts of power. By the end of 2015, it was hoped all British Airways flights from London City Airport would be fuelled by waste and rubbish discarded by London residents, leading to carbon savings equivalent to taking 150,000 cars off the road. The £340m scheme was mothballed in January 2016 following low crude oil prices, jittery investors and a lack of support from the UK government.

North magnetic pole

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/North_magnetic_pole

 

Location of the north magnetic pole and the north geomagnetic pole in 2017. The magnetic-north of the earth as a magnet is actually on the southern hemisphere: The north side of magnets are by definition attracted to the geographic north, and opposite poles attract.

The north magnetic pole, also known as the magnetic north pole, is a point on the surface of Earth's Northern Hemisphere at which the planet's magnetic field points vertically downward (in other words, if a magnetic compass needle is allowed to rotate in three dimensions, it will point straight down). There is only one location where this occurs, near (but distinct from) the geographic north pole. The geomagnetic north pole is the northern antipodal pole of an ideal dipole model of the Earth's magnetic field, which is the most closely fitting model of Earth's actual magnetic field.

The north magnetic pole moves over time according to magnetic changes and flux lobe elongation in the Earth's outer core. In 2001, it was determined by the Geological Survey of Canada to lie west of Ellesmere Island in northern Canada at 81°18′N 110°48′W. It was situated at 83°06′N 117°48′W in 2005. In 2009, while still situated within the Canadian Arctic at 84°54′N 131°00′W, it was moving toward Russia at between 55 and 60 km (34 and 37 mi) per year. In 2013, the distance between the north magnetic pole and the geographic north pole was approximately 800 kilometres (500 mi). As of 2021, the pole is projected to have moved beyond the Canadian Arctic to 86.400°N 156.786°E.

Its southern hemisphere counterpart is the south magnetic pole. Since Earth's magnetic field is not exactly symmetric, the north and south magnetic poles are not antipodal, meaning that a straight line drawn from one to the other does not pass through the geometric center of Earth.

Earth's north and south magnetic poles are also known as magnetic dip poles, with reference to the vertical "dip" of the magnetic field lines at those points.

Recent locations of Earth's magnetic (dip) poles, IGRF-13 estimate

Year	1990 (definitive)	2000 (definitive)	2010 (definitive)	2020
North magnetic pole	78.095°N 103.689°W	80.972°N 109.640°W	85.020°N 132.834°W	86.494°N 162.867°E
South magnetic pole	64.910°S 138.902°E	64.661°S 138.303°E	64.432°S 137.325°E	64.081°S 135.866°E

Polarity

See also: Magnet § Pole naming conventions

All magnets have two poles, where the lines of magnetic flux enter and emerge. By analogy with Earth's magnetic field, these are called the magnet's "north" and "south" poles. The north-seeking pole of a magnet was defined to have the north designation, according to their use in early compasses. Because opposite poles attract, this means that as a physical magnet, the magnetic north pole of the earth is actually on the southern hemisphere.

The direction of magnetic field lines is defined such that the lines emerge from the magnet's north pole and enter into the magnet's south pole.

History

Part of the carta marina of 1539 by Olaus Magnus, depicting the location of magnetic north vaguely conceived as "Insula Magnetū[m]" (Latin for "Island of Magnets"), off modern-day Murmansk. The man holding the rune staffs is the Norse hero Starkad ("Starcaterus").

Early European navigators, cartographers and scientists believed that compass needles were attracted to a hypothetical "magnetic island" somewhere in the far north (see Rupes Nigra), or to Polaris, the pole star. The idea that Earth itself acts as essentially a giant magnet was first proposed in 1600, by the English physician and natural philosopher William Gilbert. He was also the first to define the north magnetic pole as the point where Earth's magnetic field points vertically downwards. This is the current definition, though it would be a few hundred years before the nature of Earth's magnetic field was understood with modern accuracy and precision.

Expeditions and measurements

See also: Arctic exploration, Farthest North, and List of Arctic expeditions

First observations

The first group to reach the north magnetic pole was led by James Clark Ross, who found it at Cape Adelaide on the Boothia Peninsula on June 1, 1831, while serving on the second arctic expedition of his uncle, Sir John Ross. Roald Amundsen found the north magnetic pole in a slightly different location in 1903. The third observation was by Canadian government scientists Paul Serson and Jack Clark, of the Dominion Astrophysical Observatory, who found the pole at Allen Lake on Prince of Wales Island in 1947.

Project Polaris

At the start of the Cold War, the United States Department of War recognized a need for a comprehensive survey of the North American Arctic and asked the United States Army to undertake the task. An assignment was made in 1946 for the Army Air Forces' recently formed Strategic Air Command to explore the entire Arctic Ocean area. The exploration was conducted by the 46th (later re-designated the 72nd) Photo Reconnaissance Squadron and reported on as a classified Top Secret mission named Project Nanook. This project in turn was divided into many separate, but identically classified, projects, one of which was Project Polaris, which was a radar, photographic (trimetrogon, or three-angle, cameras) and visual study of the entire Canadian Archipelago. A Canadian officer observer was assigned to accompany each flight.

Frank O. Klein, the director of the project, noticed that the fluxgate compass did not behave as erratically as expected—it oscillated no more than 1 to 2 degrees over much of the region—and began to study northern terrestrial magnetism. With the cooperation of many of his squadron teammates in obtaining many hundreds of statistical readings, startling results were revealed: The center of the north magnetic dip pole was on Prince of Wales Island some 400 km (250 mi) NNW of the positions determined by Amundsen and Ross, and the dip pole was not a point but occupied an elliptical region with foci about 400 km (250 mi) apart on Boothia Peninsula and Bathurst Island. Klein called the two foci local poles, for their importance to navigation in emergencies when using a "homing" procedure. About three months after Klein's findings were officially reported, a Canadian ground expedition was sent into the Archipelago to locate the position of the magnetic pole. R. Glenn Madill, Chief of Terrestrial Magnetism, Department of Mines and Resources, Canada, wrote to Lt. Klein on 21 July 1948:

… we agree on one point and that is the presence of what we can call the main magnetic pole on northwestern Prince of Wales Island. I have accepted as a purely preliminary value the position latitude 73°N and longitude 100°W. Your value of 73°15'N and 99°45’W is in excellent agreement, and I suggest that you use your value by all means.

— R. Glenn Madill

(The positions were less than 30 km (20 mi) apart.)

Modern (post-1996)

The movement of Earth's north magnetic pole across the Canadian Arctic in recent centuries, continuing in recent years across the Arctic Ocean towards Siberia

 

Speed of the north magnetic pole drift according to the IGRF-12 model

The Canadian government has made several measurements since, which show that the north magnetic pole is moving continually northwestward. In 2001, an expedition located the pole at 81°18′N 110°48′W.

In 2007, the latest survey found the pole at 83°57′00″N 120°43′12″W. During the 20th century it moved 1,100 km (680 mi), and since 1970 its rate of motion has accelerated from 9 to 52 km (5.6 to 32.3 mi) per year (2001–2007 average; see also polar drift). Members of the 2007 expedition to locate the magnetic north pole wrote that such expeditions have become logistically difficult, as the pole moves farther away from inhabited locations. They expect that in the future, the magnetic pole position will be obtained from satellite data instead of ground surveys.

This general movement is in addition to a daily or diurnal variation in which the north magnetic pole describes a rough ellipse, with a maximum deviation of 80 km (50 mi) from its mean position. This effect is due to disturbances of the geomagnetic field by charged particles from the Sun.

As of early 2019, the magnetic north pole is moving from Canada towards Siberia at a rate of approximately 55 km (34 mi) per year.

Exploration

The first team of novices to reach the magnetic north pole did so in 1996, led by David Hempleman-Adams. It included the first British woman Sue Stockdale and first Swedish woman to reach the Pole. The team also successfully tracked the location of the Magnetic North Pole on behalf of the University of Ottawa, and certified its location by magnetometer and theodolite at 78°35′42″N 104°11′54″W.

The Polar Race was a biannual competition that ran from 2003 until 2011. It took place between the community of Resolute, on the shores of Resolute Bay, Nunavut, in northern Canada and the 1996 location of the north magnetic pole at 78°35′42″N 104°11′54″W, also in northern Canada.

On 25 July 2007, the Top Gear: Polar Special was broadcast on BBC Two in the United Kingdom, in which Jeremy Clarkson, James May, and their support and camera team claimed to be the first people in history to reach the 1996 location of the north magnetic pole in northern Canada by car. Note that they did not reach the actual north magnetic pole, which at the time (2007) had moved several hundred kilometers further north from the 1996 position.

Magnetic north and magnetic declination

Main article: Magnetic declination

 

Magnetic declination from true north in 2000.

Historically, the magnetic compass was an important tool for navigation. While it has been widely replaced by Global Positioning Systems, many airplanes and ships still carry them, as do casual boaters and hikers.

The direction in which a compass needle points is known as magnetic north. In general, this is not exactly the direction of the north magnetic pole (or of any other consistent location). Instead, the compass aligns itself to the local geomagnetic field, which varies in a complex manner over Earth's surface, as well as over time. The local angular difference between magnetic north and true north is called the magnetic declination. Most map coordinate systems are based on true north, and magnetic declination is often shown on map legends so that the direction of true north can be determined from north as indicated by a compass.

In North America the line of zero declination (the agonic line) runs from the north magnetic pole down through Lake Superior and southward into the Gulf of Mexico (see figure). Along this line, true north is the same as magnetic north. West of the agonic line a compass will give a reading that is east of true north and by convention the magnetic declination is positive. Conversely, east of the agonic line a compass will point west of true north and the declination is negative.

North geomagnetic pole

Main article: Geomagnetic pole

As a first-order approximation, Earth's magnetic field can be modeled as a simple dipole (like a bar magnet), tilted about 10° with respect to Earth's rotation axis (which defines the geographic north and geographic south poles) and centered at Earth's center. The north and south geomagnetic poles are the antipodal points where the axis of this theoretical dipole intersects Earth's surface. If Earth's magnetic field were a perfect dipole then the field lines would be vertical at the geomagnetic poles, and they would coincide with the magnetic poles. However, the approximation is imperfect, and so the magnetic and geomagnetic poles lie some distance apart.

Like the north magnetic pole, the north geomagnetic pole attracts the north pole of a bar magnet and so is in a physical sense actually a magnetic south pole. It is the center of the region of the magnetosphere in which the Aurora Borealis can be seen. As of 2015 it was located at approximately 80°22′12″N 72°37′12″W, over Ellesmere Island, Canada but it is now drifting away from North America and toward Siberia.

Geomagnetic reversal

Main article: Geomagnetic reversal

Over the life of Earth, the orientation of Earth's magnetic field has reversed many times, with magnetic north becoming magnetic south and vice versa – an event known as a geomagnetic reversal. Evidence of geomagnetic reversals can be seen at mid-ocean ridges where tectonic plates move apart and the seabed is filled in with magma. As the magma seeps out of the mantle, cools, and solidifies into igneous rock, it is imprinted with a record of the direction of the magnetic field at the time that the magma cooled.