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Bone char

Bone char, also known as bone black or bone charcoal, is a porous, carbon-rich material derived from the thermochemical conversion of animal bones, primarily consisting of calcium hydroxyapatite (70–76%), calcium carbonate (6–9%), and amorphous carbon (8–11%). It is produced by collecting, washing, and drying waste animal bones, followed by pyrolysis or carbonization in an oxygen-limited environment at temperatures ranging from 400°C to 1000°C for 2–4 hours, yielding 45–75% bone char with a surface area of 80–120 m²/g or higher when activated. This process removes organic matter, creating a mesoporous structure with functional groups that enhance its adsorptive properties. Bone char has been traditionally employed as a decolorizing in sugar refining, where it removes impurities and colorants from cane liquors in fixed or moving bed systems. Beyond , it serves as an adsorbent for , efficiently removing fluoride from drinking water (as approved by the ), heavy metals like lead, , , iron, , and from (with removal rates of 75–98%), and organic pollutants such as dyes. In , bone char acts as a soil conditioner and fertilizer, providing 19.5–33.1 wt% P₂O₅ to immobilize contaminants like and lead while improving nutrient retention. Additionally, its catalytic properties support applications in (yields up to 97%), , and selective oxidation reactions. Emerging uses include in supercapacitors and batteries, leveraging its hierarchical for high (up to 804 ).

History

Ancient and Pre-Industrial Uses

Bone char, also known as bone black, has one of its earliest documented applications in around 2400 BC during the Old Kingdom's 5th Dynasty. Archaeological analysis of s from the tomb of Perneb at reveals the use of black derived from charred animal s to paint interior walls and decorative elements, providing a deep, stable black tone for artistic representations. This material was ground into powder and mixed with binders to create paints that adhered well to surfaces, highlighting bone char's role as an early synthetic in . During the New Kingdom's 18th Dynasty (circa 1550–1292 BC), bone char saw expanded use in for artistic and decorative purposes. Artists in this period charred animal bones to produce pigments for temple murals, statues, and elite tomb decorations, often combining the black with to form durable paints that symbolized , the Nile's , and the . Evidence from pigment residues in Theban tombs confirms bone black's prevalence alongside other carbon-based blacks, underscoring its importance in the vibrant palette of royal and religious . In pre-industrial and , bone char found practical applications beyond art, serving as a key base for black inks, mixed with binders to create deep-hue formulations for manuscripts and early , persisting through the medieval and periods. Archaeological findings of bone char residues in ancient cooking and craft sites across these regions indicate byproduct utilization from animal processing, repurposed for needs. These early uses laid the groundwork for bone char's later industrial-scale adoption in the 19th century.

Industrial Development

The industrial development of bone char began in the early 19th century with its commercialization for sugar refining. In 1815, Peter and John Martineau received a patent in the United Kingdom for utilizing bone char to decolorize sugar solutions, recommending 2 to 5 pounds of char per 100 pounds of sugar to achieve effective clarification. This innovation marked a pivotal advancement over earlier methods, enabling more efficient processing of raw sugar. Throughout the , bone char production expanded rapidly to support the decolorization of cane sugar imported through colonial trade networks, particularly from plantations in the and . Refineries in and adopted it as a standard filtering agent, transforming the global sugar industry by improving the yield and purity of from these distant sources. This period aligned with the Industrial Revolution's demand for scalable refining techniques, positioning bone char as a key enabler of mass-produced sweeteners. In the , bone char underwent adaptations for broader industrial applications, including its use in filters derived from animal bone black as described in a . By the mid-20th century, global production hubs emerged in regions like , and , where slaughterhouse bones were systematically collected and processed to supply refineries worldwide. These developments solidified bone char's role in international supply chains, building on its ancient precursors in production for more refined, commercial-scale outputs.

Production

Raw Materials

Bone char is primarily produced from animal bones sourced as byproducts of the processing industry. These bones are typically obtained from , pigs, sheep, and other mammals, providing a sustainable utilization of waste materials that would otherwise require disposal. Major suppliers include slaughterhouses in countries such as , , and , where bones form a significant portion of the due to the scale of farming and in these regions. The bones are collected from these operations and transported to processing facilities, often in developing countries where availability supports cost-effective . Preferred bone types for bone char production are large, dense hard bones, such as bovine femurs, which yield higher quantities of the final product owing to their elevated content and structural integrity during processing. While large bones are preferred for traditional applications like sugar refining due to higher content, softer bones from sources like or fish can also be used in certain contexts, such as . To maintain quality and comply with standards, only bones free from diseases, contaminants, or chemical residues—verified through inspections and testing—are selected, preventing risks in applications like sugar refining or . Pre-processing of the bones begins with thorough cleaning to remove adhering , , and debris, followed by using volatile solvents or treatment to extract fats and gelatinous materials. Following , the bones are washed and dried. Sorting then eliminates non-bone organics, such as or remnants, ensuring a uniform raw material suitable for subsequent . The global depends on consistent access to slaughterhouse waste, highlighting bone char's role in amid growing consumption worldwide.

Manufacturing Process

The manufacturing process of bone char primarily involves the of animal bones through in a low-oxygen to convert components into a carbon-rich . Degreased bones, typically sourced from slaughterhouse by-products, are loaded into retorts or and heated to temperatures between 450°C and 1000°C for 1 to 5 hours under an inert atmosphere such as , producing char alongside byproduct gases and oils. This step yields approximately 45% to 75% char by weight, depending on the bone type and process conditions. Traditional bone char, particularly for , is produced without to preserve its natural adsorption properties derived from the structure. However, optional may be applied post-pyrolysis through physical methods like steaming at temperatures above 700°C or chemical treatments with agents such as to increase and surface area, though this is more common in modern applications for . After pyrolysis or activation, the resulting char is cooled, milled using equipment like ball mills, and sieved to achieve particle sizes of 0.5 to 2 mm, which are optimal for filtration uses in industrial settings. Quality control measures during this stage assess carbon content, typically 8-11%, and phosphate levels to ensure consistency for specific applications. The process is inherently energy-intensive due to the high temperatures required, with traditional batch kilns being gradually replaced by modern continuous furnaces for better efficiency and reduced variability. Emissions generated include carbon dioxide, sulfur dioxide, and particulates, which are quantified and mitigated through life cycle assessments in contemporary production facilities.

Properties

Chemical Composition

Bone char is primarily composed of 70–76% hydroxyapatite (\mathrm{Ca_{10}(PO_4)_6(OH)_2}), 9–11% amorphous carbon, and 7–9% calcium carbonate, along with trace elements such as magnesium. The exact proportions can vary based on production parameters, with higher pyrolysis temperatures generally reducing the carbon content while increasing the relative proportion of calcium phosphate minerals. This material typically exhibits a pH in the range of 8–11, owing to the buffering capacity provided by its phosphate components. In contrast to or , which are largely carbonaceous and rely on physical adsorption, bone char's inorganic matrix facilitates ion-exchange processes that enhance its selectivity for certain contaminants. The structure in bone char is confirmed through diffraction (XRD) analysis, which identifies characteristic crystalline phases, while Brunauer–Emmett–Teller (BET) analysis measures the , typically ranging from 50 to 100 m²/g for standard preparations.

Physical and Adsorption Characteristics

Bone char exhibits a porous granular structure, characterized by a predominantly mesoporous architecture with pore diameters ranging from 2 to 50 nm, which contributes significantly to its high surface area and adsorption efficiency. The material appears black due to its carbon content and has a bulk density typically between 0.4 and 0.8 g/cm³, making it lightweight yet durable for filtration applications. This porosity arises from the thermal decomposition of organic components in animal bones during production, resulting in a network of interconnected pores that facilitate the diffusion and trapping of contaminants. The adsorption properties of bone char stem from its content, enabling high affinity for anions such as through ligand exchange mechanisms involving groups, with reported capacities of 5-11 mg/g under optimal conditions like 3-7. It also effectively binds , including lead and , via surface complexation and electrostatic attraction, achieving capacities up to 50-78 mg/g for ions like Pb²⁺ and Zn²⁺ depending on and modification. Additional mechanisms include , where metal ions form insoluble compounds with calcium and on . Adsorption behavior is often modeled using the Langmuir isotherm, which assumes coverage on homogeneous sites: q_e = \frac{q_{\max} K_L C_e}{1 + K_L C_e} where q_e is the equilibrium adsorption capacity (mg/g), q_{\max} is the maximum adsorption capacity (mg/g), K_L is the Langmuir constant (L/mg), and C_e is the equilibrium concentration (mg/L). This model fits experimental data well for fluoride removal, highlighting the finite binding sites on bone char. Bone char demonstrates good durability and regenerability, particularly when treated with NaOH solutions to desorb contaminants, retaining 70-80% of its initial adsorption capacity after multiple cycles. This process involves ion exchange to release bound fluoride or metals, allowing reuse in batch or column systems without significant structural degradation. The phosphate-based composition briefly supports this binding, enhancing long-term performance in repeated applications.

Uses

Sugar Refining

Bone char is extensively used in the refining of cane to decolorize and purify the liquor during the affination process. Raw is first melted into a , which is then percolated downward through large fixed-bed columns or cisterns filled with bone char granules, typically around 36 metric tons per column. The porous structure of the bone char adsorbs colorants such as melanoidins, , , and other impurities, along with inorganic ions like and divalent cations, yielding a clear, colorless fine for subsequent into . This adsorption process achieves high efficiency, removing 90-99% of color from the liquor, with the highest removal rates occurring early in each operational cycle. A single filter column requires approximately 70,000 pounds (31,751 kg) of bone char, derived from the bones of about 7,800 cows, highlighting the scale of material needed in industrial operations. In the United States, bone char remains the preferred decolorizing agent for most cane refineries, including major producers like and , accounting for the majority of refined cane on store shelves as of the early ; it is not used for beet refining. Globally, bone char continues to be a standard in cane processing, particularly for non-organic and non-vegan-certified products, though exact usage percentages vary by region and have shifted toward alternatives in some markets. After use, spent bone char is regenerated through backwashing with hot water to displace and remove residual syrup, followed by thermal treatment in at approximately 550°C (1,022°F) to oxidize and eliminate adsorbed , restoring its adsorptive capacity. This regeneration allows the char to be reused multiple times per operational cycle, with columns typically running for about 60 hours before regeneration; the material can last 5-10 years in service before requiring full rejuvenation or replacement due to gradual degradation. In 1974, bone char was employed in 42% of U.S. refineries but handled 69% of the nation's sugar refining capacity, underscoring its prevalence in larger facilities.

Water Treatment

Bone char is widely applied in water treatment for the removal of from in regions affected by endemic fluorosis, such as (e.g., and ) and , where elevated levels exceed the (WHO) guideline of 1.5 mg/L. The adsorption capacity of bone char for typically ranges from 1 to 20 mg/g, with optimal performance observed at pH levels between 5 and 7, where the component facilitates and surface complexation. In addition to , bone char effectively removes such as (As), lead (Pb), and (Cd) through mechanisms involving precipitation and cation exchange with calcium sites on the structure. Bone char adsorbs from , leveraging its high calcium content. Bone char is integrated into point-of-use systems, including household ceramic pot filters infused with the material for decentralized treatment, and larger community-scale fixed-bed columns capable of processing 10 to 2,000,000 L per day. These systems align with the WHO guideline of 1.5 mg/L for in , supporting provision in resource-limited settings. Performance evaluations demonstrate that bone char can reduce concentrations from 10 mg/L to below 1.5 mg/L, often requiring approximately 496 kg per 100 m³ of treated, depending on rates and initial contaminant levels. Breakthrough curves for column-based systems are commonly modeled using the Thomas equation to predict adsorption bed exhaustion and optimize design parameters for sustained operation.

Pigment Production

Bone char, when used as a pigment, is processed by finely milling the charred material to a of approximately 1 μm, resulting in bone black or ivory black with a carbon content of 10-20% that imparts opacity and depth to the color. This fine grinding enhances the 's dispersibility in media, distinguishing it from coarser forms used in other applications. In artistic and industrial contexts, bone black serves as a versatile colorant in oil paints, where it provides a warm, opaque black suitable for and glazing; in inks for and , offering reliable flow and adhesion; and in ceramics, where it contributes stable black tones to glazes and underglazes. Its and non-toxicity make it a preferred natural alternative to synthetic carbon blacks, particularly in fine arts where permanence is essential. Historically, bone black was the dominant black pigment from prehistoric times through the 19th century, valued for its warm undertone in oil paintings and murals, until synthetic iron oxide blacks like Mars black emerged in the mid-20th century as cheaper, more consistent alternatives. Despite this shift, it remains favored in fine arts for its subtle brownish-black hue and traditional appeal. Ancient applications, such as in Egyptian tomb paintings around 2650 BC, served as early precursors to these refined uses. Key properties for pigment applications include high tinting strength, allowing effective color dilution up to a 1:100 masstone-to-tint ratio, and in alkaline environments owing to its matrix of calcium . These attributes ensure durability in without fading or reactivity issues.

Agricultural and Remediation Applications

Bone char serves as an effective amendment by providing a source of , typically containing 20–30% P₂O₅, which acts as a to address nutrient deficiencies in agricultural soils. This content enhances , particularly in phosphorus-limited environments, while the calcium structure contributes to long-term nutrient supply. In sandy soils, bone char improves nutrient retention by 30-45%, reducing losses and promoting sustained availability of essential elements like and . In , bone char adsorbs from contaminated sites, facilitating immobilization of pollutants such as (Cd) through mechanisms including and surface complexation, with adsorption capacities reaching up to 228 mg/g for Cd²⁺. It is often incorporated into blends to support , combining the high content of bone char with the organic carbon stabilization properties of plant-derived biochars to improve and reduce metal . Recent studies from the demonstrate that bone char application increases crop yields by 20-36% in -deficient soils, as observed in trials with and soybeans where it enhanced plant-available sevenfold compared to unamended controls. Additionally, bone char has shown promise in and applications for pollutant degradation, such as mediating the dechlorination of or enhancing persulfate-based oxidation of pharmaceuticals like acetaminophen. Typical dosages for soil application range from 1-5% by weight, equivalent to 4-10 t/ depending on depth, allowing for gradual release without overwhelming the system. The slow-release involves the acid-driven of in bone char, following the reaction: \text{Ca}_5(\text{PO}_4)_3\text{OH} + 8\text{H}^+ \rightarrow 5\text{Ca}^{2+} + 3\text{H}_2\text{PO}_4^- + \text{H}_2\text{O} This process ensures controlled phosphate availability, minimizing runoff and supporting prolonged crop nutrition.

Societal and Environmental Aspects

Ethical and Sustainability Concerns

Bone char, produced from charred animal bones—predominantly cattle—raises significant ethical concerns due to its animal-derived nature, rendering products like refined white sugar non-vegan despite the absence of direct animal residues in the final product. Organizations such as People for the Ethical Treatment of Animals (PETA) have campaigned against its use in sugar refining since the early 2000s, highlighting the inhumane slaughter involved in sourcing the bones and urging consumers to boycott cane sugars processed with it in favor of vegan alternatives like beet sugar. These efforts have led to widespread awareness and selective avoidance among vegans, with PETA recommending unrefined options such as Sucanat or turbinado sugar to eliminate any involvement of animal byproducts. The sourcing of bones from waste indirectly supports factory farming practices, where endure cramped, unsanitary conditions prioritizing profit over welfare, exacerbating ethical dilemmas for consumers opposed to animal exploitation. In regions with cultural reverence for , such as under , the use of cow bones in bone char evokes sensitivities, as foreign refined sugars are often deemed non-vegetarian, prompting calls for purely plant-based clarification methods in local production. This has fueled broader societal discussions on hidden animal ingredients, with media references in vegan advocacy videos and online resources debunking myths, such as unfounded claims of human bones from being incorporated into bone char, which lack historical evidence and stem from wartime misconceptions about resource use. Regulatory frameworks in the and address these issues through voluntary vegan labeling standards, which prohibit animal-derived processing aids like bone char to ensure product integrity for ethical consumers. Certifications such as the Vegan Trademark explicitly verify avoidance of bone char, while growing consumer tools, including apps like "Is It Vegan?", enable barcode scanning to identify sugar sources and flag non-vegan items, enhancing awareness and choice.

Alternatives and Future Prospects

Activated carbon serves as a primary to bone char for general adsorption applications, such as and refining, though it typically incurs higher costs due to energy-intensive activation processes from sources like shells or wood. derived from plant waste, including agricultural residues like or shells, offers an eco-friendly substitute particularly for amendment and remediation uses, avoiding animal-derived materials while providing similar benefits. Synthetic , produced through chemical precipitation methods, is another viable option for targeted removal from , leveraging its structure for without relying on biological feedstocks. In terms of comparative efficacy, plant-based biochars exhibit 20-50% lower fluoride adsorption capacity than bone char—for instance, coconut shell-derived activated carbon achieves up to 4.55 mg/g and 90% removal under optimal conditions, compared to bone char's 9.09 mg/g and 96% efficiency—yet they eliminate animal input concerns and maintain broad applicability in low-concentration scenarios. For sugar decolorization, wood-based activated carbons from agricultural by-products like demonstrate superior performance to bone char in color removal, though less effective in ash reduction while operating in granular systems with comparable retention times. Future prospects for bone char include the development of hybrid composites, such as ZnO/bone-char materials, which enhance catalytic and adsorptive properties for removal by combining bone char's structure with metal oxides for improved and selectivity. Ongoing research emphasizes waste bones through to create adsorbents in a framework; for example, 2024 studies on slow of cow bones have produced bone char with high surface area (up to 77 m²/g) and effective removal capacities exceeding 20 mg/g from acidic solutions. Life cycle assessments reveal that bone char production generates 2-5 kg CO₂-equivalent emissions per kg, primarily from high-temperature processes, whereas from plant sources emits 1-2 kg CO₂-eq/kg but offers potential for net carbon-negative applications in through stabilization. These comparisons underscore opportunities for hybrid systems to reduce environmental footprints while preserving efficacy.

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