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1.发明授权Microemulsion process for direct biocatalytic desulfurization of organosulfur molecules 失效用于直接生物催化脱硫有机硫分子的微乳液法
公开(公告)号：US5358870A
公开(公告)日：1994-10-25
申请号：US897314
申请日：1992-06-11
IPC分类号： C10L1/14 , C07K1/113 , C10G32/00 , C10L9/00 , C12N1/20 , C12N9/00 , C12P1/04 , C12P3/00 , C12P21/06 , C12R1/07 , C12R1/365 , C12S1/02 , C12N1/00 , C12N1/12 , C12N9/14
CPC分类号： C07K1/1133 , C10G32/00 , C12N1/20 , C12P21/06 , C12P3/00 , C12R1/00 , C12R1/01 , C12R1/07 , Y10S435/822 , Y10S435/832
摘要： A method of desulfurizing a petroleum liquid containing organosulfur molecules is disclosed. The method relies upon the use of an aqueous biocatalytic agent comprising, in preferred embodiments, a substantially cell free extract of a microorganism which functionally expresses an enzyme capable of selectively cleaving organic carbon-sulfur bonds even in sulfur-bearing heterocycles, wherein the extract contains a substantial proportion of the total activity of said enzyme expressed by the microorganism. An emulsion, preferably a microemulsion, is formed between this biocatalytic agent and the petroleum liquid. Reversible microemulsions are particularly preferred, due to facilitated recovery of a desulfurized petroleum liquid at the conclusion of treatment. The invention described is particularly well suited to the desulfurization of petroleum liquids having a high relative abundance of refractory organosulfur molecules, such as dibenzothiophene.
摘要翻译： 公开了一种含有有机硫分子的石油液体脱硫方法。 该方法依赖于使用水性生物催化剂，其在优选的实施方案中包括微生物的基本上无细胞的提取物，其功能性表达即使在含硫杂环中也能选择性地裂解有机碳 - 硫键的酶，其中所述提取物包含 由微生物表达的所述酶的总活性的相当大的比例。 在该生物催化剂和石油液体之间形成乳液，优选微乳液。 由于在处理结束时促进脱硫石油液体的回收，所以可逆微乳液是特别优选的。 所描述的发明特别适用于具有高相对含量的难熔有机硫分子如二苯并噻吩的石油液体的脱硫。
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2.发明授权
公开(公告)号：US5811285A
公开(公告)日：1998-09-22
申请号：US715554
申请日：1996-09-19
IPC分类号： C12N15/09 , C10G31/00 , C10G32/00 , C12N1/20 , C12N1/21 , C12N9/02 , C12N9/04 , C12N15/52 , C12N15/53 , C12P1/00 , C12R1/01 , C12S1/02 , C12N15/00 , C07H21/04
CPC分类号： C12N1/20 , C10G31/00 , C10G32/00 , C12N15/52 , C12N9/0004 , C12N9/0006 , C12P1/00 , C12R1/01
摘要： The invention relates to the discovery that the rate of reaction of the desulfurization of fossil fuels is enhanced by the addition of an oxidoreductase to the biocatalyst. The invention is drawn to a method for enhancing the rate of desulfurizing a fossil fuel containing organic sulfur compounds, comprising the steps of: a) contacting the fossil fuel with an aqueous phase containing a biocatalyst capable of cleaving carbon-sulfur bonds and a rate-enhancing amount of an oxidoreductase, thereby forming a fossil fuel and aqueous phase mixture; b) maintaining the mixture of step (a) under conditions sufficient for cleavage of the carbon-sulfur bonds of the organic sulfur molecules by the biocatalyst, thereby resulting in a fossil fuel having a reduced organic sulfur content; and c) separating the fossil fuel having a reduced organic sulfur content from the resulting aqueous phase. The invention also relates to a recombinant microorganism containing one or more recombinant DNA molecules which encode a biocatalyst capable of desulfurizing a fossil fuel containing organic sulfur molecules and which encode an oxidoreductase. The invention also relates to a composition comprising (a) a biocatalyst capable of desulfurizing a fossil fuel containing organic sulfur molecules and (b) an oxidoreductase.
摘要翻译： 本发明涉及通过向生物催化剂中加入氧化还原酶来提高化石燃料脱硫反应速率的发现。 本发明涉及提高含有机硫化合物的化石燃料脱硫速率的方法，包括以下步骤：a）使化石燃料与含有能够裂解碳 - 硫键的生物催化剂的水相接触， 增加氧化还原酶的量，从而形成化石燃料和水相混合物; b）将步骤（a）的混合物保持在足以通过生物催化剂裂解有机硫分子的碳 - 硫键的条件下，从而导致具有降低的有机硫含量的化石燃料; 和c）从所得水相中分离具有降低的有机硫含量的化石燃料。 本发明还涉及含有一种或多种重组DNA分子的重组微生物，所述重组DNA分子编码能够脱硫含有有机硫分子的化石燃料并编码氧化还原酶的生物催化剂。 本发明还涉及一种组合物，其包含（a）能够使含有机硫分子的化石燃料脱硫的生物催化剂和（b）氧化还原酶。
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公开(公告)号：US5496729A
公开(公告)日：1996-03-05
申请号：US298921
申请日：1994-08-31
申请人： Daniel J. Monticello
发明人： Daniel J. Monticello
摘要： This invention relates to an integrated method for the desulfurization and desalting of a fossil fuel, comprising the steps of: (a) contacting a fossil fuel with; (i) a sufficient amount of an aqueous solution capable of depleting the fossil fuel of forms of water soluble salt contaminants; and (ii) an effective amount of a biocatalyst capable of depleting the fossil fuel of forms of sulfur-bearing organic molecules; (b) incubating the above mixture whereby; (i) the fossil fuel is significantly depleted of forms of water soluble salt contaminants; and (ii) the biocatalytic agent selectively catalyzes carbon-sulfur bonds in sulfur-bearing organic molecules generating a significant amount of water-soluble inorganic sulfur molecules; both reactions occurring without depleting the fossil fuel of combustible organic molecules; and (c) separating the aqueous component from the fossil fuel component, the fossil fuel now being significantly reduced in sulfur and salt contamination and the aqueous component now being significantly enriched with inorganic salts and inorganic sulfur molecules.
摘要翻译： 本发明涉及一种用于化石燃料脱硫和脱盐的综合方法，包括以下步骤：（a）使化石燃料与 （i）足够量的能够消耗化石燃料形式的水溶性盐污染物的水溶液; 和（ii）有效量的能够耗尽含硫有机分子形式的化石燃料的生物催化剂; （b）培养上述混合物; （i）化石燃料显着耗尽了水溶性盐类污染物的形式; 和（ii）生物催化剂选择性地催化产生大量水溶性无机硫分子的含硫有机分子中的碳 - 硫键; 这两种反应都不会消耗可燃有机分子的化石燃料; 和（c）从矿物燃料成分中分离含水组分，化石燃料现在在硫和盐污染中显着降低，并且水性组分现在显着富含无机盐和无机硫分子。
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公开(公告)号：US5468626A
公开(公告)日：1995-11-21
申请号：US169433
申请日：1993-12-17
CPC分类号： C10G32/00 , Y10S435/822
摘要： The present invention relates to a method for separating a sulfur compound from a fossil fuel containing sulfur compounds comprising contacting said fossil fuel with a biosorption agent which binds said sulfur compound, thereby forming a sulfur-biosorption complex and separating said sulfur-biosorption complex. The method can further include introducing said separated sulfur biosorption complex to an aqueous phase having an effective amount of oxygen and water to form a reaction medium, optionally adding a biocatalyst which degrades the sulfur compound; incubating the medium for a sufficient period of time to produce an organic product, an inorganic sulfur and spent biocatalyst; and isolating said biosorption agent and/or biocatalyst from said organic product and said inorganic sulfur. The invention also relates to the preparation of the products of the oxidation reaction of organic sulfur compounds by a biocatalyst, such as 2-hydroxybiphenyl compounds.
摘要翻译： 本发明涉及一种从含硫化合物的化石燃料中分离硫化合物的方法，包括使所述化石燃料与结合所述硫化合物的生物吸附剂接触，由此形成硫 - 生物吸附络合物并分离所述硫 - 生物吸附络合物。 该方法可以进一步包括将所述分离的硫生物吸附复合物引入具有有效量的氧和水的水相以形成反应介质，任选地加入降解硫化合物的生物催化剂; 将培养基培养足够的时间以产生有机产物，无机硫和废生物催化剂; 以及从所述有机产物和所述无机硫分离所述生物吸附剂和/或生物催化剂。 本发明还涉及通过生物催化剂如2-羟基联苯化合物制备有机硫化合物的产物。
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公开(公告)号：US5529930A
公开(公告)日：1996-06-25
申请号：US69295
申请日：1993-05-28
摘要： A method for reducing the viscosity of viscous petroleum liquids, such as heavy crude oil and bitumen, is disclosed. The method is appropriate for use with viscous petroleum liquids that contain sulfur-bearing heterocycles, the physicochemical properties of the heterocycles contributing significantly to the viscosity of the liquid. The method comprises contacting the viscous petroleum liquid with a biocatalyst that converts sulfur-bearing heterocycles into molecules that lack physicochemical properties condusive to viscosity. The biocatalyst works in a sulfur-specific manner, such that the sulfur-bearing heterocycle is altered at the sulfur heteroatom thereof. Through biocatalysis, carbon-sulfur bonds are cleaved and/or polar substituents such as hydroxyl groups are joined to the sulfur heteroatom, the hydrocarbon framework of the sulfur-bearing heterocycle, or both. Preferred biocatalysts for viscosity reduction include preparations of Rhodococcus rhodochrous ATCC No. 53968 microorganisms and enzymes obtained therefrom.
摘要翻译： 公开了一种用于降低粘稠石油液体如重质原油和沥青的粘度的方法。 该方法适用于含有含硫杂环的粘性石油液体，杂环的物理化学性质显着影响液体的粘度。 该方法包括使粘性石油液体与生物催化剂接触，所述生物催化剂将含硫杂环转化为不具有粘性的物理化学性质的分子。 生物催化剂以硫特异性方式工作，使得含硫杂环在其硫杂原子处被改变。 通过生物催化裂解碳 - 硫键和/或极性取代基如羟基与硫杂原子，含硫杂环的烃骨架或两者相连。 用于粘度降低的优选生物催化剂包括玫瑰色红球菌ATCC No.53968微生物和由其获得的酶的制剂。
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6.发明授权
公开(公告)号：US5472875A
公开(公告)日：1995-12-05
申请号：US134742
申请日：1993-10-12
申请人： Daniel J. Monticello
发明人： Daniel J. Monticello
CPC分类号： C10G32/00
摘要： A continuous cyclic process for desulfurizing a petroleum liquid which contains organic sulfur molecules, a significant portion of which are comprised of sulfur-bearing heterocycles. This process involves oxygenating the petroleum liquid and treating it with a biocatalyst capable of catalyzing the sulfur-specific oxidative cleavage of organic carbon-sulfur bonds in sulfur-bearing aromatic heterocyclic molecules such as dibenzothiophene. a particularly preferred biocatalyst is a culture of mutant Rhodococcous rhodocrous bacteria, ATCC No. 53968. In the present process, the activity of this biocatalyst is regenerated; it can be used for many cycles of treatment. A system for conducting the continuous cyclic process of biocatalytic desulfurization of petroleum liquids is also disclosed.
摘要翻译： 用于脱硫含有有机硫分子的石油液体的连续循环方法，其中很大一部分由含硫杂环组成。 该方法包括使石油液体氧化并用能够催化含硫芳族杂环分子如二苯并噻吩中的有机碳 - 硫键的硫特异性氧化裂解的生物催化剂处理。 特别优选的生物催化剂是突变型红球菌Rhodocrous细菌ATCC No.53968的培养物。在本方法中，该生物催化剂的活性被再生; 它可以用于许多治疗周期。 还公开了用于进行石油液体的生物催化脱硫的连续循环过程的系统。
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公开(公告)号：US5356813A
公开(公告)日：1994-10-18
申请号：US876187
申请日：1992-04-30
申请人： Daniel J. Monticello
发明人： Daniel J. Monticello
摘要： This invention relates to an integrated method for the desulfurization and desalting of a fossil fuel, comprising the steps of: (a) contacting a fossil fuel with; (i) a sufficient amount of an aqueous solution capable of depleting the fossil fuel of forms of water soluble salt contaminants; and (ii) an effective amount of a biocatalyst capable of depleting the fossil fuel of forms of sulfur-bearing organic molecules; (b) incubating the above mixture whereby; (i) the fossil fuel is significantly depleted of forms of water soluble salt contaminants; and (ii) the biocatalytic agent selectively catalyzes carbon-sulfur bonds in sulfur-bearing organic molecules generating a significant amount of water-soluble inorganic sulfur molecules; both reactions occurring without depleting the fossil fuel of combustible organic molecules; and (c) separating the aqueous component from the fossil fuel component, the fossil fuel now being significantly reduced in sulfur and salt contamination and the aqueous component now being significantly enriched with inorganic salts and inorganic sulfur molecules.
摘要翻译： 本发明涉及一种用于化石燃料脱硫和脱盐的综合方法，包括以下步骤：（a）使化石燃料与 （i）足够量的能够消耗化石燃料形式的水溶性盐污染物的水溶液; 和（ii）有效量的能够耗尽含硫有机分子形式的化石燃料的生物催化剂; （b）培养上述混合物; （i）化石燃料显着耗尽了水溶性盐类污染物的形式; 和（ii）生物催化剂选择性地催化产生大量水溶性无机硫分子的含硫有机分子中的碳 - 硫键; 这两种反应都不会消耗可燃有机分子的化石燃料; 和（c）从矿物燃料成分中分离含水组分，化石燃料现在在硫和盐污染中显着降低，并且水性组分现在显着富含无机盐和无机硫分子。
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公开(公告)号：US5232854A
公开(公告)日：1993-08-03
申请号：US669914
申请日：1991-03-15
申请人： Daniel J. Monticello
发明人： Daniel J. Monticello
摘要： A method of deeply desulfurizing a fossil fuel which contains a variety of organic sulfur compounds, some of which are labile to hydrodesulfurization (HDS) and some of which are refractory to HDS, comprising the steps of (a) subjecting the fossil fuel to HDS or a similar method of desulfurizing labile organic sulfur compounds, and (b) subjecting the fossil fuel to biocatalytic desulfurization (BDS) using a biocatalyst which is capable of selectively liberating sulfur from HDS-refractory organic sulfur compounds. In this manner, a fossil fuel is produced which does not generate sufficient levels of hazardous, sulfur-containing combustion products that it requires post-combustion desulfurization when it is burned. Moreover, the deeply desulfurized fossil fuel can be produced using only a mild HDS treatment, rather than requiring conditions which may be severe enough to be detrimental to the fuel value of the desired product. The biocatalyst employed in the BDS stage of the instant invention is capable of catalyzing the sulfur-specific, oxidative cleavage of organic carbon-sulfur bonds in sulfur-bearing aromatic heterocyclic molecules such as dibenzothiophene. A particularly preferred biocatalyst is a culture of Rhodococcus rhodocrous bacteria, ATCC No. 53968.
摘要翻译： 一种深层脱硫化石燃料的方法，其中含有各种有机硫化合物，其中一些对加氢脱硫（HDS）是不稳定的，其中一些对HDS是难治的，包括以下步骤：（a）使化石燃料经受HDS或 脱硫不稳定有机硫化合物的类似方法，和（b）使用能够从HDS难熔有机硫化合物中选择性释放硫的生物催化剂对化石燃料进行生物催化脱硫（BDS）。 以这种方式，产生化石燃料，其不产生足够水平的危险的含硫燃烧产物，其在燃烧时需要燃烧后脱硫。 而且，深度脱硫的化石燃料可以仅使用温和的HDS处理来生产，而不是要求可能严重到不利于所需产品的燃料值的条件。 在本发明的BDS阶段中使用的生物催化剂能够催化含硫芳族杂环分子如二苯并噻吩中的硫特异性氧化裂解有机碳 - 硫键。 特别优选的生物催化剂是Rhodococcus rhodocrous细菌，ATCC No.53968的培养物。
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公开(公告)号：US20090311783A1
公开(公告)日：2009-12-17
申请号：US12398269
申请日：2009-03-05
IPC分类号： C07K14/475 , C12N5/06
摘要： The present invention relates to IGF-I variants that bind to the Insulin-like Growth Factor Receptor I (IGF-IR) but do not initiate signal transduction and the subsequent metabolic, growth and anti-apoptotic activities associated with this molecule and the progression of cancer. These novel variants act to block the binding of the cognate ligands but do not bind to the insulin receptor.
摘要翻译： 本发明涉及结合胰岛素样生长因子受体I（IGF-1R）但不启动信号转导的IGF-1变体，以及与该分子相关的随后的代谢，生长和抗凋亡活性 癌症。 这些新型变体用于阻断同源配体的结合，但不结合胰岛素受体。
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公开(公告)号：US5510265A
公开(公告)日：1996-04-23
申请号：US298147
申请日：1994-08-30
申请人： Daniel J. Monticello
发明人： Daniel J. Monticello
摘要： A method for the deep desulfurization of a liquid fossil fuel containing organic sulfur comprising aromatic sulfur-bearing heterocycles is described, wherein the fossil fuel is (a) subjected to hydrodesulfurization or microbial desulfurization, (b) contacted with a biocatalyst in an aqueous medium in an amount and under conditions sufficient for the conversion of aromatic sulfur-bearing heterocycles to inorganic sulfur, wherein the biocatalyst comprises bacteria or a substantially cell-free preparation thereof having the capability of the parent microorganism for catalyzing the removal of sulfur from aromatic sulfur-bearing heterocycles, thereby preparing a deeply desulfurized fossil fuel; and (c) separated from the aqueous medium.
摘要翻译： 描述了含有芳族含硫杂环的含有机硫的液体化石燃料的深度脱硫方法，其中化石燃料是（a）进行加氢脱硫或微生物脱硫，（b）在水介质中与生物催化剂接触 一定量和足以将芳香族含硫杂环转化为无机硫的条件，其中生物催化剂包括具有母体微生物催化从含硫芳香中除去硫的能力的细菌或基本上无细胞的制剂 杂环，从而制备深度脱硫的化石燃料; 和（c）与水介质分离。
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