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1. 发明授权

US4170546A Multistage residual oil hydrodesulfurization process 失效
标题翻译：多级残油加氢脱硫工艺
公开(公告)号：US4170546A
公开(公告)日：1979-10-09
申请号：US843876
申请日：1977-10-20
申请人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
发明人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
IPC分类号： C10G65/00 , C10G23/02
CPC分类号： C10G65/00 , C10G2300/107
摘要： In the hydrodesulfurization of residual oil the amount of hydrogen consumed per atom of sulfur removed is relatively low until the desulfurization becomes deep, whereupon the amount of hydrogen consumed per atom of sulfur removed becomes relatively high. The present invention provides a multistage hydrodesulfurization process capable of producing products of low sulfur level while avoiding deep desulfurization of the heavy portion of the residual oil so that hydrogen consumption is diminished. The feed oil is fractionated to provide distillate and residual fractions. The residual fraction and hydrogen are charged to an upstream catalytic hydrodesulfurization stage. A portion of the upstream stage effluent stream is diverted from the process for use as refinery fuel and the remaining portion of the upstream stage effluent stream is charged to a downstream catalytic stage together with the feed distillate oil and hydrogen. The interstage diminution of the residual oil fraction provides a non-aliquot distillate-residual oil second stage feed stream which is relatively enriched in distillate oil. Since the sulfur in distillate oil is considerably less refractory than the sulfur in residual oil, the resulting dilution of the residual content of the downstream stage feed stream reduces hydrogen consumption by diminishing the depth of residual oil hydrodesulfurization required in the downstream stage to produce a low sulfur product.
摘要翻译：在残油的加氢脱硫中，除去的硫原子所消耗的氢的量相对较低，直到脱硫变深为止，因此除去的硫原子消耗的氢量相对较高。本发明提供一种能够产生低硫含量的产品的多级加氢脱硫方法，同时避免残油重垢的深度脱硫，从而消耗氢气。进料油分馏以提供馏出物和残余馏分。将剩余馏分和氢气加入到上游催化加氢脱硫阶段。上游级流出物流的一部分从用作炼油厂燃料的方法转移，并且将剩余部分的上游流出物流与进料馏出物油和氢一起加入到下游催化级。残余油馏分的级间减少提供了相对富含馏出油的非等分馏出物 - 残油第二级进料流。由于馏出油中的硫比残留油中的硫低很多，因此下游进料流的剩余含量的稀释通过减少下游阶段所需的残余油加氢脱硫深度来降低氢消耗，从而产生低的硫产品。

2. 发明授权

US3968026A Hydrodesulfurization process with parallel first stages in series with a unified second stage 失效
标题翻译：加氢脱硫工艺与并联第一阶段串联统一第二阶段
公开(公告)号：US3968026A
公开(公告)日：1976-07-06
申请号：US572419
申请日：1975-04-28
申请人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
发明人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
IPC分类号： C10G65/04 , B01J23/00 , B01J23/85 , C10G45/08 , C10G65/00 , C10G23/02
CPC分类号： C10G45/08 , B01J23/85 , C10G2300/107
摘要： An asphaltene-containing oil hydrodesulfurization process employing parallel first stages in series with a unified second stage. The second stage catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The catalyst in the first stage comprises supported Group VI and Group VIII metals without promotion with Group IV-B metal. In the process, deactivated non-promoted catalyst is replaced at least once from at least one of the parallel first stages while continuing to operate the other of the parallel first stages to supply a reduced oil flow to the second stage during the catalyst replacement step.
摘要翻译：含沥青质的油加氢脱硫工艺采用并联的第一阶段与统一的第二阶段串联。第二阶段催化剂包含负载的VI族和VIII族金属以及促进量的IV-B族金属。第一阶段的催化剂包括不受IV-B族金属促进作用的载体为VI族和VIII族金属。在该过程中，去活化的非促进催化剂至少从平行的第一级中的至少一个代替至少一次，同时继续操作另一个平行的第一级，以在催化剂置换步骤期间向第二级提供减少的油流。

3. 发明授权

US4170545A Multistage residual oil hydrodesulfurization process with an interstage flashing step 失效
标题翻译：多级残油加氢脱硫工艺与级间闪烁步骤
公开(公告)号：US4170545A
公开(公告)日：1979-10-09
申请号：US843877
申请日：1977-10-20
申请人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
发明人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
IPC分类号： C10G65/04 , C10G23/02
CPC分类号： C10G65/04 , C10G2300/107
摘要： In the hydrodesulfurization of residual oil the amount of hydrogen consumed per atom of sulfur removed is relatively low until the desulfurization becomes deep, whereupon the amount of hydrogen consumed per atom of sulfur removed becomes relatively high. The present invention provides a multistage catalytic hydrodesulfurization process capable of producing products of low sulfur level while avoiding deep desulfurization of the heavy portion of the residual oil so that hydrogen consumption is diminished. The feed oil and hydrogen are passed through an upstream hydrodesulfurization stage and the upstream stage effluent is flashed to separate a distillate oil fraction from a concentrated residual oil fraction. A portion of the concentrated residual oil fraction is diverted from the process for use as refinery fuel and the remaining portion of the flash residue and hydrogen are charged to an upstream stage together with the flash distillate. Since the sulfur in distillate oil is less refractory than the sulfur in residual oil, removal of a portion of the concentrated residual oil fraction provides a nonaliquot distillate-residual oil downstream stage feed stream which is easier to desulfurize to a low sulfur level than an aliquot distillate-residual oil stream. The dilution of the high sulfur residue in the downstream stage diminishes the depth of hydrodesulfurization required for residual components in the downstream stage, thereby reducing the level of hydrogen consumption required to produce a product having a low sulfur level.
摘要翻译：在残油的加氢脱硫中，除去的硫原子所消耗的氢的量相对较低，直到脱硫变深为止，因此除去的硫原子消耗的氢量相对较高。本发明提供一种多级催化加氢脱硫方法，其能够生产低硫含量的产物，同时避免残油重垢的深度脱硫，从而消耗氢气。进料油和氢气通过上游加氢脱硫阶段，并且上游级流出物被闪蒸以将馏出油馏分与浓缩的残油分离分离。浓缩的残余油馏分的一部分从用作炼油厂燃料的方法转移，并且闪蒸残余物和氢的剩余部分与闪蒸馏分一起加入到上游阶段。由于馏出油中的硫比残留油中的硫难易，所以除去一部分浓缩的残油部分提供了非等分馏出物 - 残余油下游进料流，其比等分试样更容易脱硫至低硫水平馏出物 - 残油流。下游阶段的高硫残渣的稀释会降低下游阶段残留组分所需的加氢脱硫深度，从而降低了生产具有低硫含量的产品所需的氢消耗水平。

4. 发明授权

US3968031A Multi-stage hydrodesulfurization process utilizing multi-cycle second stage promoted catalyst 失效
标题翻译：多阶段加氢脱硫工艺采用多循环第二阶段促进催化剂
公开(公告)号：US3968031A
公开(公告)日：1976-07-06
申请号：US572418
申请日：1975-04-28
申请人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
发明人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
IPC分类号： B01J23/00 , B01J23/85 , C10G45/08 , C10G65/04 , C10G23/02
CPC分类号： C10G45/08 , B01J23/85 , C10G2300/107
摘要： An asphaltene-containing oil hydrodesulfurization process employing stages in series with an interstage flashing step. The second stage catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The first stage catalyst comprises supported Group VI and Group VIII metals without promotion with Group IV-B metal. In the process, deactivated first stage catalyst is replaced at least once without replacing the promoted second stage catalyst so that the promoted second stage catalyst is onstream for at least two first stage catalyst cycles.
摘要翻译：含沥青质的油加氢脱硫工艺采用与级间闪蒸步骤串联的阶段。第二阶段催化剂包含负载的VI族和VIII族金属以及促进量的IV-B族金属。第一阶段催化剂包括不伴随IV-B族金属催化的负载的VI族和VIII族金属。在此过程中，将不活化的第一阶段催化剂替换至少一次，而不替代促进的第二阶段催化剂，使得促进的第二阶段催化剂在流动上至少两个第一阶段催化剂循环。

5. 发明授权

US3968029A Desulfurization process employing multi-catalyst reactor 失效
标题翻译：采用多催化反应器的脱硫工艺
公开(公告)号：US3968029A
公开(公告)日：1976-07-06
申请号：US572417
申请日：1975-04-28
申请人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
发明人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
IPC分类号： B01J23/00 , B01J23/85 , C10G45/08 , C10G65/04 , C10G23/02
CPC分类号： C10G45/08 , B01J23/85 , C10G2300/107
摘要： An asphaltene-containing oil hydrodesulfurization process employing a downstream catalyst and an upstream catalyst in a reactor. The downstream catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The upstream catalyst comprises Group VI and Group VIII metals without promotion with Group IV-B metal.
摘要翻译：在反应器中使用下游催化剂和上游催化剂的含沥青烯的油加氢脱硫方法。下游催化剂包含负载的VI族和VIII族金属以及促进量的IV-B族金属。上游催化剂包括VI族和VIII族金属，不用IV-B族金属促进。

6. 发明授权

US4179355A Combination residual oil hydrodesulfurization and thermal cracking process 失效
标题翻译：组合残油加氢脱硫和热裂解工艺
公开(公告)号：US4179355A
公开(公告)日：1979-12-18
申请号：US843880
申请日：1977-10-20
申请人： James A. Frayer , Harry C. Stauffer , Francis E. Wynne, Jr. , Stephen J. Yanik
发明人： James A. Frayer , Harry C. Stauffer , Francis E. Wynne, Jr. , Stephen J. Yanik
IPC分类号： C10G65/00 , C10G69/06 , C10G23/02
CPC分类号： C10G65/00 , C10G2300/107
摘要： Residual oils which are thermally cracked with entrained hot solids in a low residence time riser must be hydrodesulfurized so that sulfur oxide emissions in the flue gas of the solids regenerator are maintained within environmentally acceptable limits. Of a full range residual oil thermal cracking feedstock, the lower boiling distillate feed components are capable of providing a higher ethylene yield with a lower dispersant steam requirement as compared to the high boiling residual feed components. In accordance with the present invention, the high boiling residual components of a thermal cracker feed residual oil are selectively removed during hydrodesulfurization to provide a non-aliquot distillate-residual oil hydrodesulfurization product in which the ratio of lower boiling distillate oil to high boiling residual oil is enhanced. Modifying the aliquot distribution of distillate and residual components in this manner provides an interdependent effect in the combination process since the distillate-enriched cracking feedstock not only provides both an improved ethylene yield and a greater steam economy in the thermal cracking operation but it also reduces hydrogen consumption in the hydrodesulfurization operation. Further interdependence between the hydrodesulfurization and thermal cracking operations is obtained by utilizing the residual oil which is selectively removed during the hydrodesulfurization step as fuel in the solids regenerator of the cracking unit, thereby making the more valuable, highly aromatic black oil produced in the thermal cracking process available for conversion to needle coke and carbon black.
摘要翻译：在低停留时间提升管中被夹带的热固体热裂解的残余油必须进行加氢脱硫，使得固体再生器的烟道气中的硫氧化物排放物保持在环境可接受的限度内。在全范围残油热裂解原料中，与高沸点残余进料组分相比，低沸点馏出物进料组分能够提供较高的乙烯产率，较低的分散剂蒸汽需求。根据本发明，在加氢脱硫期间选择性地除去热裂化器进料残余油的高沸点残余成分，以提供非等分馏出物 - 残油加氢脱硫产物，其中低沸点馏出油与高沸点残余油的比例增强了。以这种方式改变馏出物和残留组分的等分试样分布在组合方法中提供相互依赖的效果，因为富含馏出物的裂化原料不仅在热裂解操作中同时提供改进的乙烯产率和更高的蒸汽经济性，而且还降低了氢消耗在加氢脱硫作业中。加氢脱硫和热裂解操作之间的进一步相互依赖是通过利用在加氢脱硫步骤中选择性除去的残余油作为裂化装置的固体再生器中的燃料，由此在热裂解中产生更有价值的高度芳族的黑油可用于转向针状焦炭和炭黑的方法。

7. 发明授权

US4173528A Multistage residual oil hydrodesulfurization process employing segmented feed addition and product removal 失效
公开(公告)号：US4173528A
公开(公告)日：1979-11-06
申请号：US843879
申请日：1977-10-20
申请人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
发明人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
IPC分类号： C10G65/00 , C10G23/02
CPC分类号： C10G65/00 , C10G2300/107
摘要： In the catalytic hydrodesulfurization of residual oil the amount of hydrogen consumed per atom of sulfur removed is relatively low until the desulfurization becomes deep, whereupon the amount of hydrogen consumed per atom of sulfur removed becomes relatively high. The present invention provides a multistage process capable of producing products of low sulfur content while avoiding deep desulfurization of the heavy portion of the residual oil so that hydrogen consumption is diminished. The feed oil is fractionated to provide a residual fraction, a heavy distillate fraction and a light distillate fraction. The residual fraction and hydrogen are charged to an upstream hydrodesulfurization stage. A portion of the upstream stage residual oil effluent stream is split out of the process for use as refinery fuel and the remaining portion of the upstream stage effluent stream is charged to an intermediate hydrodesulfurization stage together with the heavy distillate feed fraction and hydrogen. A portion of the intermediate stage effluent stream is split out of the process as product fuel oil and the remaining portion of the intermediate stage effluent stream is passed to a downstream hydrodesulfurization stage together with the light distillate feed fraction and hydrogen. The downstream stage effluent stream constitutes the final and highest grade product of the process. Because of the combination of segmented feed addition and segmented product removal, not only are residue-containing streams removed from the process at the earliest possible time to avoid overtreating relative to their intended use, but also the removed streams are diluted with a reduced amount of low boiling distillate oil, conserving as much of the low boiling distillate oil as possible for inclusion in the product of the final stage. This method conserves distillate feed oil for the final and highest grade product and allows each hydrodesulfurization stage to be provided with a non-aliquot distillate-residual oil stream which is richer in low boiling distillate oil than its predecessor hydrodesulfurization stage.

8. 发明授权

US3968028A Process for onstream regeneration of a hydrodesulfurization catalyst 失效
标题翻译：加氢脱硫催化剂的流动再生方法
公开(公告)号：US3968028A
公开(公告)日：1976-07-06
申请号：US572504
申请日：1975-04-28
申请人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
发明人： James A. Frayer , Richard E. Hildebrand , John A. Paraskos
IPC分类号： B01J23/85 , C10G45/08 , C10G65/04 , C10G23/02
CPC分类号： C10G45/08 , B01J23/85 , C10G2300/107
摘要： An asphaltene-containing oil hydrodesulfurization process employing stages in series with an interstage flashing step. The second stage catalyst comprises Group VI and Group VIII metals together with a promoting amount of Group IV-B metal. The coke level on the second stage catalyst is reduced by intermittent increase and decrease of the hydrogen pressure in the second stage.
摘要翻译：含沥青质的油加氢脱硫工艺采用与级间闪蒸步骤串联的阶段。第二级催化剂包含VI族和VIII族金属以及促进量的IV-B族金属。第二阶段催化剂中的焦炭含量由于第二阶段的氢气压力的间歇性增加而降低。

9. 发明授权

US4179354A Combination residual oil hydrodesulfurization and catalytic cracking process 失效
标题翻译：组合残油加氢脱硫和催化裂化过程
公开(公告)号：US4179354A
公开(公告)日：1979-12-18
申请号：US843878
申请日：1977-10-20
申请人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
发明人： James A. Frayer , Harry C. Stauffer , Stephen J. Yanik
IPC分类号： C10G65/00 , C10G69/04 , C10G23/02
CPC分类号： C10G65/00 , C10G2300/107
摘要： When residual oil is cracked to gasoline in the presence of a fluidized zeolite catalyst the oil is first catalytically hydrodesulfurized so that sulfur oxide emissions from the catalyst regenerator are held to environmentally acceptable levels. The hydrodesulfurized residual oil is flash vaporized at the elevated temperature at the inlet of the cracking riser and most of the residual oil feedstock passes into the vapor state and is cracked to valuable products. However, a portion of the 1050.degree. F.+ (566.degree. C.+) residual material cannot be flash vaporized at the riser temperature and instead deposits upon the catalyst and is coked. Data are presented which show that as the proportion of the 1050.degree. F.+ (566.degree. C.+) components in a cracking feedstock decreases, the amount of these high boiling components in each barrel of cracker feedstock which are flash vaporized can actually increase. A multistage hydrodesulfurization operation is provided in which the proportion of 1050.degree. F.+ (566.degree. C.+) residual components in the cracking feedstock is diminished whereby the amount of 1050.degree. F.+ (566.degree. C.+) residuals vaporized per barrel of feedstock during the subsequent cracking step is increased. The present method provides an interdependent advantage in the hydrodesulfurization operation since it reduces hydrogen consumption during hydrodesulfurization.
摘要翻译：当在流化沸石催化剂存在下将残余油裂解成汽油时，首先对该油进行催化加氢脱硫，使得来自催化剂再生器的硫氧化物排放物保持在环境可接受的水平。加氢脱硫残余油在裂化提升管入口处的高温下闪蒸，大部分残油进料进入蒸汽状态，并破裂成有价值的产物。然而，一部分1050°F +（566℃+）残留物质不能在提升管温度下闪蒸，而是沉积在催化剂上并被焦化。数据显示，随着裂解原料中1050°F +（566℃+）组分的比例降低，闪蒸汽化的每桶裂解原料中的这些高沸点组分的量实际可以增加。提供了多级加氢脱硫操作，其中裂化原料中的1050°F +（566℃+）残留组分的比例降低，从而使1050°F +（566℃+）残余物的量蒸发为在随后的裂化步骤期间原料桶增加。本方法在加氢脱硫操作中提供了相互依赖的优点，因为它降低了加氢脱硫期间的氢消耗。

10. 发明授权

US4133777A Hydrodesulfurization catalyst 失效
标题翻译：加氢脱硫催化剂
公开(公告)号：US4133777A
公开(公告)日：1979-01-09
申请号：US810810
申请日：1977-06-28
申请人： James A. Frayer , Henri K. Lese , Joel D. McKinney , Kirk J. Metzger , John A. Paraskos
发明人： James A. Frayer , Henri K. Lese , Joel D. McKinney , Kirk J. Metzger , John A. Paraskos
IPC分类号： C10G45/04 , B01J23/64 , B01J23/85 , B01J35/02 , B01J21/04 , B01J21/06 , B01J23/84
CPC分类号： B01J35/026 , B01J23/85
摘要： A catalyst having utility as a downstream catalyst in processes for hydrodesulfurization of asphaltene-containing petroleum oils, coal liquids, shale oils or oils from tar sands which employ both upstream and downstream catalysts in series. The downstream catalyst comprises supported Group VI and Group VIII metals together with a promoting amount of a Group IV-B metal. The particles of said promoted catalyst are elongated extrudates whose surface is provided with a plurality of alternating longitudinal grooves and protrusions. In processes using this catalyst, the upstream catalyst comprises Group VI and Group VIII metals without promotion with Group IV-B metal and the particles of the upstream catalyst may or may not have similar surface grooves. The adaptation of the grooved particle configuration to the promoted catalyst composition provided the early development of a plateau-like aging curve which was not achieved by the adaptation of the grooved shape to a non-promoted catalyst.
摘要翻译：一种催化剂，其用作下游催化剂，用于沥青质的石油，含煤油，页岩油或来自焦油砂的油的加氢脱硫，其中采用上游和下游两种催化剂。下游催化剂包括负载的VI族和VIII族金属以及促进量的IV-B族金属。所述促进的催化剂的颗粒是细长的挤出物，其表面设置有多个交替的纵向槽和突起。在使用该催化剂的方法中，上游催化剂包括VI族和VIII族金属，而不用IV-B族金属促进，并且上游催化剂的颗粒可以具有或不具有相似的表面凹槽。槽形颗粒构型对促进的催化剂组合物的适应性提供了通过将沟槽形状适应于非促进催化剂而不能实现的平台状老化曲线的早期开发。

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