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生物脱硫的研究发展

  生物脱硫,又称生物催化脱硫(简称BDS),是一种在常温常压下利用需氧、厌氧菌除去石油含硫杂环化合物中结合硫的一种新技术。早在1948年美国就有了生物脱硫的专利,但一直没有成功脱除烃类硫化物的实例,其主要原因是不能有效的控制细菌的作用。此后有几个成功的“微生物脱硫”报道,但却没有多少应用价值,原因在于微生物尽管脱去了油中的硫,但同时也消耗了油中的许多炭而减少了油中的许多放热量。科学工作者一直对其进行了深入的研究,直到1998年美国的Institute of Gas Technology(IGT)的研究人员成功的分离了两种特殊的菌株,这两种菌株可以有选择性的脱除二苯并噻吩中的硫,去除油品中杂环硫分子的工业化模型相继产生,1992年在美国分别申请了两项专利(5002888和5104801)。美国Energy BioSystems Corp (EBC)公司获得了这两种菌株的使用权,在此基础上,该公司不仅成功地生产和再生了生物脱硫催化剂,并在降低催化剂生产成本的同时也延长了催化剂的使用寿命。此外该公司又分离得到了玫鸿球菌的细菌,该细菌能够使C-S键断裂,实现了脱硫过程中不损失油品烃类的目的。EBC公司已成为世界上对生物脱硫技术研究广泛的公司。此外,日本工业技术研究院生命工程工业技术研究所与石油产业活化联合开发出了柴油脱硫的新菌种,此菌种可以同时脱除柴油中的二苯并噻吩和苯并噻吩中的硫,而这两种硫化物中的硫是用其它方法难以脱除的。

  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过程是以自然界产生的有氧细菌与有机硫化物发生氧化反应,选择性氧化使C-S键断裂,将硫原子氧化成硫酸盐或亚硫酸盐转入水相,而DBT的骨架结构氧化成羟基联苯留在油相,从而达到脱除硫化物的目的。BDS技术从出现至今已发展了几十年,仍处于开发研究阶段。由于BDS技术有许多优点,它可以与已有的HDS装置有机组合,不仅可以大幅度地降低生产成本,而且由于有机硫产品的附加值较高,BDS比HDS在经济上有更强的竞争力。同时BDS还可以与催化吸附脱硫组合,是实现对燃料油深度脱硫的有效方法。因此BDS技术具有广阔的应用前景,预计在2010年左右将有工业化装置出现。

  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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