This review aims to analyze the technological and scientific applications regarding cocoa fermentation through a prospective study of patent documents and research articles. The Espacenet database was used as a patent research tool by searching both the IPC code “A23G1” and the terms “cocoa” and “ferment*”. A total of 130 documents were found—49 were related to the subject. The Scopus database was also searched for scientific articles using the terms “cocoa” and “fermentation”. A total of 812 articles were found—517 were related to the subject. Cocoa fermentation has not yet reached technological maturity, despite the growth in patent documents and scientific research observed in the last two decades. The creation of the Cacao of Excellence Program (2009), among others, has incentivized sustainability and quality in cocoa-producing countries. Brazil, Colombia, and Indonesia are leading with scientific publications in the last 5 years, despite the lack of patents filed. The United Kingdom, France, China, Canada, and Germany, despite not being cocoa-producing countries, are the main holders of the technology. Patent documents analyzed relate to food science, biotechnology, engineering, and chemistry. Microbial biotechnology has gained attention as a key factor to produce a higher-quality cocoa bean. Saccharomyces is the most frequent genus of yeast used as a starter culture in patent documents. Some patent documents propose the addition of fruits during cocoa fermentation, but a few scientific studies have been found on the matter. Overall, technological applications and scientific studies have focused on improving cocoa quality. The cocoa market is expected to increase significantly in the next few years, representing an opportunity to develop high-quality cocoa using novel fermentation techniques.

This work describes the development of a method for the extraction of methylxanthines from cocoa bean shell (CBS) by employing the novel Energized Dispersive Guided Extraction (EDGE) system. The mixtures were composed of ethanol–methanol–water and the ratio was optimized using a simplex-centroid design. Doehlert design (DD) was used to optimize the variables of temperature and time while using methylxanthine content obtained by HPLC-DAD as an analytical response. The optimized mixture consisted of water–ethanol in a 3:2 ratio. The optimum operating conditions for extraction were achieved at a temperature of 148.5 °C and 382 s. Under optimal conditions, 20.14 mg g⁻¹ DM of theobromine and 3.53 mg g⁻¹ DM of caffeine were found in the CBS extract. Methylxanthines were quantified with good linearity, LOQs, LODs, precision, and accuracy. The EDGE system, a newly automated extraction instrument, has proven to be very efficient for the recovery of theobromine and caffeine, and is considered a green extraction procedure, as demonstrated by the analytical greenness metric for sample preparation.

This study reports the development of a sustainable biocatalyst system for free fatty acid (FFA) production from cocoa bean shell (CBS) oil using Burkholderia cepacia lipase (BCL). CBS was explored as both a support material and a reaction substrate. Six immobilized systems were prepared using organic (CBS), inorganic (silica), and hybrid (CBS–silica) supports via physical adsorption or covalent binding. Among them, the covalently immobilized enzyme on CBS (ORG-CB) showed the most balanced performance, achieving a catalytic efficiency (Ke) of 0.063 mM⁻¹·min⁻¹ (18.6% of the free enzyme), broad pH–temperature tolerance, and over 50% activity retention after eight reuse cycles. Thermodynamic analysis confirmed enhanced thermal resistance for ORG-CB (Ed = 32.3 kJ mol⁻¹; ΔH‡ = 29.7 kJ mol⁻¹), while kinetic evaluation revealed that its thermal deactivation occurred faster than for the free enzyme under prolonged heating. In application trials, ORG-CB reached 60.1% FFA conversion from CBS oil, outperforming the free enzyme (49.9%). These findings validate CBS as a dual-function material for enzyme immobilization and valorization of agro-industrial waste. The results also reinforce the impact of immobilization chemistry and support composition on the operational and thermal performance of biocatalysts, contributing to the advancement of green chemistry strategies in enzyme-based processing.