Fluorides are important chemicals with wide applications

The team of chemists from the University of Oxford in the UK has produced fluoride for the first time without using hazardous gases. This new approach, published in the latest issue of Science, may have a huge impact on global industrial security and reducing carbon footprint.   Fluorides are important chemicals with wide applications, including polymers, agricultural chemicals, pharmaceuticals, as well as lithium-ion batteries in smartphones and electric vehicles. Currently, all fluorides are generated through highly energy intensive processes from the toxic and corrosive gas hydrogen fluoride. Despite strict safety regulations, hydrogen fluoride leaks have occurred multiple times in the past few decades, sometimes leading to fatal accidents.   In order to develop a safer method, the research team drew inspiration from the natural biomineralization process that forms teeth and bones. Usually, hydrogen fluoride itself is produced by a crystalline mineral called fluorite reacting with sulfuric acid under harsh conditions, which is then used to manufacture fluorinated compounds. In the new method, fluoride is directly made from fluorite, completely bypassing hydrogen fluoride.   Solid fluorite is activated by the process of biomineralization, which mimics the way calcium phosphate minerals are biologically formed in teeth and bones. The team used a mechanochemical process to grind fluorite and powdered potassium phosphate in a ball mill for several hours. The resulting powdered product can directly synthesize over 50 different fluorides from fluorite.

The first air conditioning and heating strategy

On February 16, 2016, the European Commission introduced the first EU heating and air conditioning strategy, aiming to promote smarter, more efficient, and sustainable heating and cooling systems in buildings and industries. The strategy highlights that phasing out fluorinated gases under the EU F-Gas Regulation framework will accelerate the transformation of building air conditioning and heating systems. The European Parliament has explicitly stated that natural refrigerants possess high energy-saving potential.   Miguel Arias Canete, the EU Commissioner for Climate Action and Energy, stated, “90% of buildings in Europe are energy inefficient, with most using inefficient old boilers. Of course, it’s not surprising that over half of the buildings were constructed before energy efficiency standards were in place and ended up being inefficient. However, the renovation rate for these buildings is less than 1%, so we need to do more work. Heating and cooling sector is one of the main driving forces to achieve the European climate and energy goals.”   Decarbonizing Buildings: Opportunities with Natural Refrigerants   According to the strategy, the F-Gas Regulation will continue to drive innovation in heating and air conditioning technologies in buildings. It states that eco-friendly refrigerants can offer further energy-saving potential but require revised existing standards to ensure their safe use. Additionally, the Commission highlights that the choice of refrigerant also impacts the energy efficiency of heat pump technologies. Reducing fluorinated greenhouse gases under the F-Gas Regulation can trigger the use of natural refrigerants, thereby enhancing energy efficiency. This means that there will be significant changes in the types of refrigerants used in the next decade, inevitably driving investments in equipment replacement and upgrades for higher efficiency.   The document also presents the application of natural refrigerants in different sectors. It notes that ammonia is widely used in large and medium-sized industrial refrigeration units. For small-scale equipment such as bottle coolers or vending machines, hydrocarbon refrigerants are gradually gaining popularity due to their high energy efficiency.   Regarding the development of commercial refrigeration, CO2 is gradually being adopted by large supermarket systems, either in complex systems with other refrigerants or as a standalone refrigerant in transcritical systems. Currently, there are nearly 5,000 CO2 systems in Europe, and their numbers are rapidly growing.   Financial Support for Building Renovations   Europe needs to accelerate the pace of building renovations. The 2016 European Energy Efficiency Directive will address the replacement of inefficient boilers and encourage innovation in multi-dwelling buildings. The European Commission has established a financial support mechanism through the European Structural Investment Fund. Energy efficiency renovations for private residential buildings have been included in the first batch of projects. Additionally, the Commission will launch “Smart Financing for Smart Buildings,” establishing new and innovative financing mechanisms for energy efficiency renovations, such as bundling and integrating numerous small-scale renovation projects.   Next Steps   To transition to low-carbon heating and cooling systems, the European Commission will conduct a comprehensive review of the Energy Efficiency Directive, the Energy Performance of Buildings Directive, and the Smart Financing for Smart Buildings initiative in 2016.   The Commission will also present proposals on new electricity market design and renewable energy framework in 2016. Other actions to be promoted by the EU Commission include the development of a toolkit to stimulate multi-dwelling building renovations, enhancing energy efficiency in public education and healthcare facilities, and expanding training for building professionals through the BUILD UP skill competition.

R134a and R410a will gradually replace R22

Refrigerant R22, while experiencing a sales boom before the holiday season, faced pessimism and concerns in the post-holiday market. The significant price surge will inevitably lead to a subsequent decline in the future. According to the Refrigeration Express reporter, most refrigerant manufacturers have a bleak outlook for the upcoming 2012 cooling year, due to the anticipated production and sales difficulties in the household appliance and automotive industries.   From the current technological conditions, R134a and R410a will gradually replace R22 as air conditioning refrigerants. The use of the co-boiling working fluids HFC134a/HFC152a to replace R12 as refrigerator refrigerants has become the main HFCs new refrigerant for the present and the next several decades. Statistics show that in 2009/2010, with the explosive growth of the Chinese automotive market and the increase in the number of automobiles in China, the consumption of R134a in China exceeded 20,000 tons in 2010, all of which were used for refrigerant consumption. Based on the current global phase-out timetable for HCFCs, including China, and the existing materials and technological level of refrigerants, R134a, R152a, R125, R32, etc., will be the main directions for future refrigerant applications.   In recent years, as low-end fluorine chemical industry gradually shifted to China with more abundant fluorite resources, China’s capacity for low-end fluorine chemicals, especially anhydrous hydrofluoric acid, has expanded rapidly. According to a survey conducted by the major market of air conditioning and refrigeration, by the end of 2009, China’s capacity for hydrofluoric acid had increased from 560,000 tons in 2005 to over 1.1 million tons, accounting for more than half of the global total capacity. The rapid expansion of hydrofluoric acid capacity directly increased the demand for fluorite resources and subsequently drove up the price of fluorite powder (97%) from around 400 yuan/ton at the end of 2009 to a peak of 3000 yuan/ton in June 2011. Although it has since declined due to the decrease in prices of refrigerants and polyfluorinated compounds, it currently remains at around 2500 yuan/ton.   In terms of the current manufacturing cost of hydrofluoric acid in China, producing one ton of hydrofluoric acid requires about 2.2 tons of fluorite, 2.8 tons of sulfuric acid, 2.1 tons of bituminous coal, and 1400 kWh of electricity. Calculated based on the current prices of 2500 yuan/ton for fluorite, 570 yuan/ton for sulfuric acid, 800 yuan/ton for 5500 kcal power coal, and 0.5 yuan/kWh for electricity, the production cost of hydrofluoric acid may have exceeded 10,000 yuan/ton. Additionally, the production of R134a requires about four tons of hydrofluoric acid per ton, which means the actual production cost of R134a may exceed 40,000 yuan/ton. Considering the current market price of approximately 38,500-39,200 yuan/ton, if all hydrofluoric acid is purchased externally to produce new refrigerants, there may be a loss of about 1000 yuan per ton of refrigerant. This poses significant cost pressure for manufacturers of these new refrigerants.   For producers with abundant fluorite resources and engaged in the entire fluorine chemical industry chain, although they face considerable production cost pressure for high-end fluorine chemical products such as refrigerants and polyfluorinated compounds, their low-cost fluorite resources, which only cost a few hundred yuan to mine, and the recycling and reuse of their complete industry chain can still ensure profitability. However, their profit margins have been somewhat compressed. Moreover, these producers engaged in the entire industry chain can also obtain CDM subsidies in global carbon emissions trading.