Fluorine Flows in China.

[NNadir]

The paper I'll discuss in this post is this one: Advancing Sustainable Fluorine Management in China Based on Evolution of the Anthropogenic Cycle during 2000–2020 Kun Hu, Hui Gong, Guoning Zhou, Chao Zhang, Shuyan Zhou, Guangming Li, Ling Chen, and Xiaohu Dai Environmental Science & Technology 2025 59 (11), 5521-5533.

The chemistry of fluorine represents one of the most important environmental issues in the world, impacting health and technology in the form of PFOS (perfluoro organic substances), extreme global heating (in the form of gaseous fluorocarbons, chlorofluorocarbons, and sulfur fluorides), and in a case near to my heart, nuclear energy technology.

The world industrial powerhouse after (and actually preceding) the fall of the United States, is China, and thus fluorine flows in China are important to all humanity.

From the text of the paper under discussion:

Fluorine (F), the most electronegative element, exhibits exceptional oxidative reactivity, enabling interactions with organic and inorganic materials even at ambient temperatures. (1) Despite its relative abundance in the Earth’s crust (0.059%, ∼1.5 × 1016 metric tons), (2) accessible F reserves remain constrained, as most occurs in nonrenewable forms. The primary extractable source, fluorspar (49% F content), is classified as a strategic mineral by major economies, including the European Union, (3) the United States, (4) China, (5) and Japan, (6) due to its irreplaceable role in critical industries. Modern applications span various sectors of aerospace, (7) nuclear power, (8) semiconductors, (9) fluorinated pharmaceuticals, and pesticides, (10,11) with expanding demand driven by green technologies like photovoltaics, (12,13) low-carbon refrigeration systems, (14,15) and lithium batteries. (16,17) Its versatility makes it indispensable for socioeconomic progress and enhancing human well-being. Paradoxically, F’s industrial utility correlates with severe environmental externalities: ozone-depleting chlorofluorocarbon emissions, (18) groundwater contamination (more than 1.5 mg/L F– affecting 180 million people globally), (19) and health risks including skeletal fluorosis and neurological disorders, (20) which underscore the urgency of sustainable F management.

Sustainable F resource management necessitates balancing extraction, utilization, recycling, and environmental safeguards to meet the present needs without compromising future availability. As the global leader in F production and consumption (≥55% of fluorochemicals output), (21) China faces acute supply risks. While industry consolidation policies, (22−24) the inclusion of strategic minerals list, (5) export tariffs, (25−27) and capacity controls for traditional sectors and fluorinated commodities (e.g., hydrofluoric acid (HF)) (28) stabilized short-term supply in the past two decades, the impending scarcity is still signaled by low static reserves-to-production ratio (R/P ratio, representing the number of years the country or region has left to mine at the current level of ore production, expressed in years, which changes dynamically each year). (29,30) China’s static fluorspar R/P ratio was less than 8 years in 2020 according to statistics from the United States Geological Survey (USGS). (31) Given the nation’s pivotal role in global fluorochemicals production, such depletion would destabilize international supply chains for F^-dependent technologies, including electronics, energy storage, and agrochemicals. This disruption could also propagate cascading effects across industries reliant on fluorinated materials, threatening manufacturing stability worldwide. Concurrently, rapid growth in emerging sectors (e.g., photovoltaics and lithium batteries) exacerbates demand–supply mismatches, (32) compounded by fragmented regulations: (33−35) strict discharge limits for legacy industries (36−39) contrast with inadequate controls for newer applications (e.g., semiconductor etching), resulting in inefficient recycling and persistent pollution. (40)

A systematic understanding of China’s F resource lifecycle─tracking extraction, transformation, utilization, and waste management across sectors─is critical for advancing sustainable governance. Material flow analysis (MFA) provides a robust framework to map these dynamics, quantifying the spatial, temporal, and sectoral distribution of F resources. Such analysis enables policymakers to identify inefficiencies, optimize recycling, and mitigate environmental risks. (41) However, previous MFA studies remain fragmented, focusing narrowly on specific compounds (e.g., fluorocarbons (42−44) and perfluorinated compounds (45−48)) or sectors (e.g., metallurgy (49) and electrolytic aluminum (50,51)), while neglecting the diversity of F applications. For instance, F^-containing materials serve distinct roles across industries: as functional additives (e.g., pharmaceutical intermediates), embedded components (e.g., fluorocarbon refrigerants), or single-use consumables (e.g., semiconductor etching agents). Each application follows unique flow pathways with varying environmental consequences. Existing frameworks also fail to address evolving sectoral dynamics, particularly post-2010 innovations in F^-based green technologies...

Bold, italics and underlining are all mine. Anyone familiar with my writings, by the way, will understand that I question what the much abused word "green" might actually mean, and I insist it's more familiar in abuse than meaningful use.

It's useful to look at the pictures in this paper. First Sankey diagrams of Chinese fluorine flows in recent times:



The caption:

Figure 3. China’s anthropogenic F flows in 2000 (a), 2005 (b), 2010 (c), 2015 (d), and 2020 (e). Supporting Information S1.6 shows China’s anthropogenic F flows in each year from 2000 to 2020.

Some additional text:

At the manufacturing stage, F consumption for manufacturing F^-containing products rose from 270.1 kt in 2000 to 2462.9 kt in 2020. This amount was significantly lower than the F resources supplied in the production stage, largely due to the inefficiency in the phosphorus chemical industry, where only 14.0% of F was recovered for the production of fluorine chemical products. As a result, fluorspar became the primary mineral for F^-containing product manufacturing, contributing about 85% of the required F resources. In the early 2000s, fluorspar supply exceeded demand, but rapid demand growth led to a supply demand imbalance, peaking with a 712.1 kt gap in 2017. This imbalance was not resolved until 2020 when fluorspar production increased significantly. Domestically manufactured F^-containing products accounted for 98.2% (31,134.2 kt) of the total supply, with fluorspar fluxes and mineralizers (9367.7 kt, 30.1%), inorganic fluorides (8385.6 kt, 26.9%), and fluorocarbons (6068.9 kt, 19.5%) being the major products. Imports contributed 1.8% (581.6 kt), primarily inorganic fluorides (172.1 kt, 29.6%), fluoropolymers (208.0 kt, 35.8%), and fluorinated fine chemicals (98.8 kt, 17.0%). Domestic use sectors consumed 69.9% of these products, while 5.4% ended up as F^-containing wastes and 24.7% was exported, with the main exports being HF (2930.0 kt, 37.4%), inorganic fluorides (1415.4 kt, 18.0%), and fluorocarbons (2581.2 kt, 32.9%).

Another figure from the text:



The caption:

Figure 4. (a) The F usage for manufacturing of products (fluorspar fluxes/mineralizers and fluorine chemical final products, the same below) from 2000 to 2020 (CFCs, chlorofluorocarbons; HCFCs, hydrochlorofluorocarbons; HFCs, hydrofluorocarbons; HFOs, hydrofluoroolefins). (b) The proportion of F usage for manufacturing of products from 2000 to 2020 (solid lines) and the proportion of products for different applications, categorized into products used as consumables for the production of industrial products and products used as fillers or additives for the production of fluorinated industrial products (dashed lines). (c) The F usage for manufacturing of products in these two decades in percentage (the legends are the same as in (b)). (d) The F usage for manufacturing of products used as fillers/additives or consumables in these two decades in percentage (the legends are the same as in (b)). (e) The F consumption in various sectors and the annual growth rate of F consumption in each sector (dashed lines indicate traditional F-using sectors, and solid lines indicate emerging F-using sectors).

Figure 5. (a) China’s F imports and exports of all F-containing commodities (LBS, lithium batteries; PHS, photovoltaics; PCS, paints and coatings; FFCS, fluoroplastic and fluororubber components; ACS, air conditioners; FOP, foamed plastic; GL, glass; CE, cement; FFC, fluorinated fine chemicals; FP, fluoropolymers; FC, fluorocarbons; IF, inorganic fluorides; FSA, fluorosilicic acid; HF, hydrofluoric acid; AC, anthracite coal; BC, bituminous coal; PR, phosphate rock; MS, metspar; AS, acidspar; RC, raw coal). (b) China’s F imports and exports of F-containing commodities by commodity type. (c) The variation of F export proportion by commodity type. (d) The variation of F import proportion by commodity type.

Two of these applications, lithium batteries and photovoltaics, are often represented as "green," a description with which I emphatically disagree, considering such use as abuse, since materials requirements make them unsustainable, fluorine requirements being only a part of the problem, the mere tip of the tailings pile, since the word "iceberg" is now threatened by extreme global heating, which neither photovoltaics nor batteries have done anything to address, faith in them having actually made things worse.

The carbon fluorine bond is one of the strongest in chemistry. Breaking it photochemically - really the best option in my view - requires high energy radiation, short wave length UV, x-rays or gamma radiation. These are accessible from components of used nuclear fuel, an application I am working to push to my son and anyone else who will listen, primarily from radioisotopes of cesium, in particular ¹³⁴Cs and ¹³⁷Cs, the latter an isotope that generates some huge, but silly, fear.

I've advanced some continuous flow ideas to my son on this topic. It cannot be said, however, under the best of circumstances, that the recovery of fluorine from atmospheric and water pollutants will necessarily lead to a closed system. I very much doubt it will.

For nuclear fuel reprocessing I favor fluoride volatility methods, but the high energy density of nuclear fuel makes such use relatively trivial. I oppose nuclear fuel enrichment, regarding it is as unnecessary and perhaps unwise, particularly since many nations, fearful of the criminal Putin-Trump axis are considering developing nuclear armaments. This, of course, is not a good thing. We need to isotopically denature weapons grade uranium and plutonium, not produce more of it.