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生物脫硫的研究發(fā)展

  生物脫硫,又稱生物催化脫硫(簡稱BDS),是一種在常溫常壓下利用需氧、厭氧菌除去石油含硫雜環(huán)化合物中結合硫的一種新技術。早在1948年美國就有了生物脫硫的專利,但一直沒有成功脫除烴類硫化物的實例,其主要原因是不能有效的控制細菌的作用。此后有幾個成功的“微生物脫硫”報道,但卻沒有多少應用價值,原因在于微生物盡管脫去了油中的硫,但同時也消耗了油中的許多炭而減少了油中的許多放熱量??茖W工作者一直對其進行了深入的研究,直到1998年美國的Institute of Gas Technology(IGT)的研究人員成功的分離了兩種特殊的菌株,這兩種菌株可以有選擇性的脫除二苯并噻吩中的硫,去除油品中雜環(huán)硫分子的工業(yè)化模型相繼產(chǎn)生,1992年在美國分別申請了兩項專利(5002888和5104801)。美國Energy BioSystems Corp (EBC)公司獲得了這兩種菌株的使用權,在此基礎上,該公司不僅成功地生產(chǎn)和再生了生物脫硫催化劑,并在降低催化劑生產(chǎn)成本的同時也延長了催化劑的使用壽命。此外該公司又分離得到了玫鴻球菌的細菌,該細菌能夠使C-S鍵斷裂,實現(xiàn)了脫硫過程中不損失油品烴類的目的。EBC公司已成為世界上對生物脫硫技術研究廣泛的公司。此外,日本工業(yè)技術研究院生命工程工業(yè)技術研究所與石油產(chǎn)業(yè)活化聯(lián)合開發(fā)出了柴油脫硫的新菌種,此菌種可以同時脫除柴油中的二苯并噻吩和苯并噻吩中的硫,而這兩種硫化物中的硫是用其它方法難以脫除的。

  Biological desulfurization, also known as biocatalytic desulfurization (BDS), is a new technology that uses aerobic and anaerobic bacteria to remove bound sulfur from petroleum sulfur-containing heterocyclic compounds at room temperature and pressure. As early as 1948, the United States had a patent for biological desulfurization, but there has been no successful example of removing hydrocarbon sulfides, mainly due to the inability to effectively control the action of bacteria. There have been several successful reports of "microbial desulfurization" since then, but they have little practical value because although microorganisms remove sulfur from oil, they also consume a lot of carbon in the oil and reduce a lot of heat release in the oil. Scientists have been conducting in-depth research on it until 1998, when researchers from the Institute of Gas Technology (IGT) in the United States successfully isolated two special strains of bacteria that can selectively remove sulfur from dibenzothiophene and develop industrial models for removing heterocyclic sulfur molecules from oil products. In 1992, two patents (5002888 and 5104801) were applied for in the United States. Energy BioSystems Corp (EBC) in the United States has obtained the right to use these two strains. Based on this, the company has not only successfully produced and regenerated biological desulfurization catalysts, but also extended the service life of the catalysts while reducing their production costs. In addition, the company also isolated bacteria of Streptococcus pyogenes, which can break C-S bonds and achieve the goal of not losing oil hydrocarbons during desulfurization process. EBC has become a company with extensive research on biological desulfurization technology in the world. In addition, the Life Engineering Industrial Technology Research Institute of the Japan Industrial Technology Research Institute has jointly developed a new strain for diesel desulfurization with the activation of the petroleum industry. This strain can simultaneously remove sulfur from dibenzothiophene and benzothiophene in diesel, which are difficult to remove using other methods.20211108044951783

  BDS過程是以自然界產(chǎn)生的有氧細菌與有機硫化物發(fā)生氧化反應,選擇性氧化使C-S鍵斷裂,將硫原子氧化成硫酸鹽或亞硫酸鹽轉入水相,而DBT的骨架結構氧化成羥基聯(lián)苯留在油相,從而達到脫除硫化物的目的。BDS技術從出現(xiàn)至今已發(fā)展了幾十年,仍處于開發(fā)研究階段。由于BDS技術有許多優(yōu)點,它可以與已有的HDS裝置有機組合,不僅可以大幅度地降低生產(chǎn)成本,而且由于有機硫產(chǎn)品的附加值較高,BDS比HDS在經(jīng)濟上有更強的競爭力。同時BDS還可以與催化吸附脫硫組合,是實現(xiàn)對燃料油深度脫硫的有效方法。因此BDS技術具有廣闊的應用前景,預計在2010年左右將有工業(yè)化裝置出現(xiàn)。

  The BDS process involves the oxidation reaction between naturally occurring aerobic bacteria and organic sulfides. Selective oxidation breaks the C-S bond, oxidizing sulfur atoms into sulfates or sulfites and transferring them into the aqueous phase. Meanwhile, the skeleton structure of DBT is oxidized into hydroxybiphenyl and left in the oil phase, thereby achieving the goal of removing sulfides. BDS technology has been developed for decades and is still in the stage of development and research. Due to the many advantages of BDS technology, it can be organically combined with existing HDS devices, which not only significantly reduces production costs, but also has stronger economic competitiveness than HDS due to the high added value of organic sulfur products. Meanwhile, BDS can also be combined with catalytic adsorption desulfurization, which is an effective method for achieving deep desulfurization of fuel oil. Therefore, BDS technology has broad application prospects, and it is expected that industrial devices will appear around 2010.

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