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Hydrogen Applications

Industry

Hydrogen in the industry

 

Vast quantities of hydrogen are used for commercial day-to-day operations, from nitrogen fixation using the Haber ammonia process, to the hydrogenation of fats and oils. It is also used in large quantities in the production of methanol, hydrodealkylation, hydrocracking, and hydrodesulfurization. Other uses include rocket fuel, reducing metallic ores, producing hydrochloric acid, welding or filling balloons. Liquid hydrogen is used in the research of superconductors and, when combined with liquid oxygen, makes a superb rocket fuel. In conclusion, H2 is used in a varied array of activities, either on its own or in combination with other substances.

Around the world, industrial enterprises use hydrogen as raw material for their processes. Each of these industries drives the world economy and our lives. Almost all of the hydrogen is being extracted from fossil fuels, about 70 million tonnes are utilized for industrial purposes of which, 76% is extracted from natural gas, almost 23% from coal, and about 2% from water (through electrolysis). Around 6% of the annual consumption of natural gas and 2% of the annual consumption of coal is destined for hydrogen production. 

Hydrogen combines with other elements to form numerous compounds: water (H2O), ammonia (NH3), methane (CH4), table sugar (C12H22O11), hydrogen peroxide (H2O2) or hydrochloric acid (HCl).

In order to reduce the greenhouse emissions (GHG) from the use of hydrogen in heavy industry, it is necessary to replace the current sources of gray hydrogen with green hydrogen production. It is important to pay attention to the fact that in this transition from gray to green hydrogen, the benefits for businesses are not limited to a reduction in emissions from production processes. The main advantage of green hydrogen produced on-site is the transformation of the enterprise into a less dependent on the prices of fossil fuels and increasing its competitiveness. One of the main problems, especially for ammonia producers, is the constantly price change of natural gas, which leads to significant difficulties in a number of processes. Large industrial actors that heavily rely on the use of hydrogen and are currently buying it from third parties, can reduce price uncertainties and supply shortages by installing their own production facilities for green hydrogen. Not to mention the probable positive financial impact from not requiring to purchase of CO2 certificates and gaining access to low-interest rates funding from the EU.

Bulgaria has a well-developed industry and has enterprises for the production of glass, methanol, ammonia, as well as refineries and steel mills. Some of the country's enterprises in which hydrogen plays a leading role, have small electrolysis plants, but the main raw materials used to extract hydrogen remain natural gas, oil or coal. This has a highly negative impact on the environment for the emission of GHG and particulate matter.

Petroleum Refining Source: Unsplash.com

Petroleum Refining

Oil refining – turning crude oil into various end-user products such as transport fuels and petrochemical feedstock – is one of the largest users of hydrogen today. Some 38 MtH2/yr, or 33% of the total global demand for hydrogen (in both pure and mixed forms), is consumed by refineries as feedstock, reagent and energy source. Around two-thirds of this hydrogen is produced in dedicated facilities at refineries or acquired from merchant suppliers (together called “on-purpose” supply)

 

The sulfur content of the world’s diminishing crude oil resources is higher than ever before as oil companies are forced to tap into a cheaper but lower quality of crude that requires more refining to meet tightening environmental standards and while maximising margins. To be competitive in this challenging landscape, modern refineries must operate efficiently, ensure adequate capacity, and control emission levels. Operators are therefore keen to maximise profitability factors, often by optimising the efficiency of their assets.

Refineries use hydrogen to lower the sulfur content of diesel fuel. Refinery demand for hydrogen has increased as demand for diesel fuel has risen both domestically and internationally, and as sulfur-content regulations have become more stringent.

 

Only a few decades ago, the thick, heavy crudes being utilised today would not have even been a consideration for the production of mainstream products and were used mainly as bunker fuels. Thirty years ago crude quality was a good match with what was being demanded by the market, but today’s refiners are being compelled to dig deeply into the dregs of the remaining resources and must upgrade these crudes to reduce sulfur content and to keep up with market demand and environmental regulations.

Hydrotreating is one such process, introduced to remove sulfur, a downstream pollutant, and other undesirable compounds, such as unsaturated hydrocarbons and nitrogen from the process stream. Hydrogen is added to the hydrocarbon stream over a bed of catalyst that contains molybdenum with nickel or cobalt at intermediate temperature, pressure and other operating conditions. This process causes sulfur compounds to react with hydrogen to form hydrogen sulfide, while nitrogen compounds form ammonia. Aromatics and olefins are saturated by the hydrogen and lighter products are created. The final product of the hydrotreating process is typically the original feedstock free of sulfur and other contaminants. 

Hydrogen is also used for upgrading oil sands and hydrotreating biofuels. For oil sands, the amount of hydrogen needed to remove Sulphur from the raw bitumen varies considerably depending on the upgrading technology and the quality of the synthetic crude oil produced. Overall around 10 kg of hydrogen is used per tonne of bitumen processed. The resulting synthetic crude oil still needs to be refined at a refinery, using hydrogen. For biofuels, hydrotreatment removes oxygen and improves the fuel quality of vegetable oils and animal fats processed into diesel substitutes. This process requires around 38 kg of hydrogen per tonne of biodiesel produced, but no further hydrogen is needed in subsequent refining steps.

Ammonia Production Source: Shutterstock.com

Ammonia Production

Ammonia is mostly used in the manufacture of fertilisers such as urea and ammonium nitrate (around 80%). The remainder is used for industrial applications such as explosives, synthetic fibres and other specialty materials, which are an increasingly important source of demand. It accounts for roughly 31 MtH2/yr, making it the second biggest source of demand for H2.

Demand for ammonia (and methanol) could rise further if these chemicals were to become established as energy carriers for the transmission, distribution and storage of hydrogen, facilitating its use in new applications, or if they were to be used as fuels in their own. If these new applications become widespread, the chemical sector could evolve to share the role that refineries play today in providing energy to downstream users.

Methanol Production Source: Rupec.ru

Methanol Production

Methanol is used for a diverse range of industrial applications, including the manufacture of formaldehyde, methyl methacrylate and various solvents. It accounts for 12 MtH2/yr, making it the third biggest user of H2. Methanol is also used in the production of several other industrial chemicals, and for the methanol-to-gasoline process that produces gasoline from both natural gas and coal, which has proven attractive in regions with abundant coal or gas reserves but with little or no domestic oil production. This is one of the fuel applications of methanol, whether blended in pure form or used after further conversion (e.g. to methyl-tert butlyl ether), that account for around a third of the chemical’s use globally. The development of methanol-to-olefins and methanol-to-aromatics technology has opened up a route from methanol to high-value chemicals (HVCs), and thus to plastics.

Methanol-to-olefins technology is currently deployed at commercial scale in China, accounting for 9 million tonnes per year (Mt/yr). Methanol-to-aromatics, which is used to produce more complex HVC molecules, is currently still in the demonstration phase. Unlike ammonia and methanol, HVCs – the precursors of most plastics – are produced mostly from oil products such as ethane, liquefied petroleum gas and naphtha. HVCs produced directly from oil products do not require Hfeedstock, but their production generates by-product Hthat can be used in oil refining and other chemical sector operations, such as the upgrading of other cracker by-products. Steam cracking and propane dehydrogenation processes for HVC manufacture produce around 18 MtH2/yr as a by-product globally. HVC demand is growing at a faster rate than refined oil product demand, which means that an increasing quantity of this by-product Hcould be available for use in other industries. Chlor-alkali processes are another source of by-product Hin the chemical sector, supplying around 2 MtH2/yr. While by-product hydrogen generated in the steam cracking process stems from oil products (mainly ethane and naphtha), the chlor-alkali process is a form of electrolysis (of brine) and is powered by electricity.

Iron & Steel Source: zkg.de

Iron & Steel

Direct reduced iron (DRI) is a method for producing steel from iron ore. This process constitutes the fourth-largest single source of hydrogen demand today (4 MtH2/yr, or around 3% of total hydrogen used in both pure and mixed forms), it entails oxygen from iron bearing materials without melting them. 

 

High-temperature heat Source: IEA (2019)

High-temperature heat

Industry uses heat for a variety of different purposes, including melting, mobilising a wide array of chemical reactions, gasifying, and drying, virtually no dedicated hydrogen is produced for this application today. Heat can be used both directly, for example in a furnace, or indirectly, for example by first raising steam and then transferring it for heating needs. There are three main temperature ranges for industrial heat: low temperature (< 100°C), medium temperature (100–400°C) and high temperature (> 400°C). 

Although small amounts of biomass and waste are used in certain sectors, fossil fuels are the primary source of high-temperature heat (around 65% from coal, 20% natural gas and 10% from oil). Electricity is also used extensively to generate high-temperature heat in specific applications, either directly (e.g. electric arc and induction furnaces in the steel industry) or indirectly (e.g. to drive electro-chemical reactions in aluminium smelting). Resistance heaters are used in the production of carbon fibre, reaching temperatures of 1 800°C, and there are ways to utilise electromagnetic heating technologies (e.g. microwave and infrared) to achieve similar temperatures for other specific heating applications. However, several large-scale processes, such as steam crackers and cement kilns, remain challenging to electrify although demonstration and feasibility studies are being conducted in both of these areas.

Aerospace Applications Source: NASA

Aerospace Applications

In combination with an oxidizer such as liquid oxygen, liquid hydrogen yields the highest specific impulse, or efficiency in relation to the amount of propellant consumed, of any known rocket propellant.

Despite criticism and early technical failures, the taming of liquid hydrogen proved to be one of NASA's most significant technical accomplishments.

Nowadays, Blue Origin's rockets (Jeff Bezos's aerospace enterprise) also use liquid hydrogen as rocket fuel.

 

Food Processing Source: Abcmach.com

Food Processing

Hydrogen is used to turn unsaturated fats to saturated oils and fats. Food industries, for instance, use hydrogen to make hydrogenated vegetable oils such as margarine and butter. 

Hydrogenation of saturated oils and fats is a process which takes place in a heated tank. The oil feed (sunflower seed or olive oil) is pumped into a heated pressure vessel and then vacuum is applied to inhibit oxidation. The temperature is raised to 140-250°C and the mixture is stirred to ensure an even temperature. Nickel catalyst solids, mixed with a small amount of oil, are then pumped in, followed by hydrogen gas, which brings the pressure to 2.7–4 barg. The hydrogenation reaction is exothermic, so the external heating is removed and cooling applied, vigorous stirring ensuring the temperature remains in the 70-80°C range. After 40–60 minutes the hydrogenated oil mixture is pumped out as a slurry and the catalyst solids removed in filters. Cooling to room temperature allows the hydrogenated oil to solidify.

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