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1. 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。

2. 发明授权

US4017382A Hydrodesulfurization process with upstaged reactor zones 失效
标题翻译：加氢脱硫工艺与上阶段反应器区
公开(公告)号：US4017382A
公开(公告)日：1977-04-12
申请号：US632374
申请日：1975-11-17
申请人： William S. Bonnell , Robert D. Christman , Jordan S. Lasher , John A. Paraskos , Stephen J. Yanik
发明人： William S. Bonnell , Robert D. Christman , Jordan S. Lasher , John A. Paraskos , Stephen J. Yanik
IPC分类号： C10G45/02 , C10G49/00 , C10G65/04 , C10G23/02
CPC分类号： C10G49/002 , B01J2208/0053 , B01J2208/00548 , C10G2300/107
摘要： A process for the hydrodesulfurization of residual oil in a plurality of catalyst zones in series with the upstream reactor being removed periodically for a catalyst change. When an upstream zone is taken off-stream for a catalyst change, the fresh feed oil is passed to a succeeding downstream zone so that the downstream catalyst zone is upstaged to the status of an upstream catalyst zone. When a zone is returned to service after a catalyst change, it enters the process as a downstream reactor in the series.
摘要翻译：在与上游反应器串联的多个催化剂区中的残余油的加氢脱硫的方法被周期性地除去以进行催化剂改变。当上游区域脱离催化剂改变时，新鲜进料油被传送到后续的下游区域，使得下游催化剂区域上升到上游催化剂区域的状态。当催化剂更换后，当一个区域恢复使用时，它将作为该系列中的下游反应器进入该过程。

3. 发明授权

US4016070A Multiple stage hydrodesulfurization process with extended downstream catalyst life 失效
标题翻译：多级加氢脱硫工艺具有延长的下游催化剂寿命
公开(公告)号：US4016070A
公开(公告)日：1977-04-05
申请号：US632376
申请日：1975-11-17
申请人： Robert D. Christman , Jordan S. Lasher , John A. Paraskos , Stephen J. Yanik
发明人： Robert D. Christman , Jordan S. Lasher , John A. Paraskos , Stephen J. Yanik
IPC分类号： C10G65/04 , C10G23/02
CPC分类号： C10G65/04 , C10G2300/107
摘要： A multiple stage process for hydrodesulfurizing a residual oil while passing the oil downwardly through a plurality of stages in series with an interstage flashing step. After the catalyst in the downstream stage is deactivated by coke deposition, fresh feed oil is passed directly to the deactivated catalyst to obtain an extended life in the downstream catalyst.
摘要翻译：一种多级方法，用于在将油向下通过与级间闪蒸步骤串联的多个级的同时将残余油加氢脱硫。在下游阶段的催化剂通过焦炭沉积失活后，新鲜进料油直接通入失活的催化剂，以在下游催化剂中延长使用寿命。

4. 发明授权

US3997430A Hydrodesulfurization process involving blending high boiling streams 失效
标题翻译：加氢脱硫工艺涉及混合高沸点流
公开(公告)号：US3997430A
公开(公告)日：1976-12-14
申请号：US568555
申请日：1975-04-16
申请人： Robert D. Christman , Joel D. McKinney , Thomas C. Readal , Stephen J. Yanik
发明人： Robert D. Christman , Joel D. McKinney , Thomas C. Readal , Stephen J. Yanik
IPC分类号： C10G45/02 , C10G23/02
CPC分类号： C10G45/02
摘要： A process is described for fixed bed hydrodesulfurizing a non-asphaltic oil feed blend for a zeolitic FCC riser cracking system in which cracking occurs at a space velocity sufficiently high to prevent formation of a catalyst bed. It is shown that sulfur dioxide emissions from the zeolite catalyst regenerator associated with the riser are reduced to a lower extent than total sulfur removal from the feed oil. This indicates uneven sulfur removal in the hydrodesulfurization step whereby a smaller portion of sulfur is removed from the heavy portion of the feed from which the coke is derived than from the lighter portion of the feed. The present invention demonstrates a synergistic effect upon sulfur removal from the heavy portion of the feed by widening the boiling range of the feed and this synergistic effect is converted to practical advantage by reducing the amount of hydrodesulfurization catalyst in proportion to said synergistic effect, thereby keeping hydrocracking to a specified low level. The boiling range of the feed is widened by adding to the higher boiling portion of the feed a portion of a second stream to lower the average boiling point of the hydrodesulfurization feed whereby the sulfur content of the remaining portion of the second stream is sufficiently low that the second stream does not require desulfurization. The further discovery is demonstrated herein that the ratio of gasoline to total conversion during the subsequent riser cracking step of the hydrodesulfurizer effluent is enhanced by reducing the amount of the hydrodesulfurization catalyst as permitted by said synergistic effect.
摘要翻译：描述了用于沸石FCC提升管裂解系统的非沥青油进料混合物的固定床加氢脱硫的方法，其中裂纹以足够高的空间速度发生以防止形成催化剂床。显示与提升管相关联的沸石催化剂再生器的二氧化硫排放量比从进料油中除去总硫的程度减少到更低的程度。这表示在加氢脱硫步骤中不均匀的硫去除，其中较少部分的硫从可得到焦炭的进料的重部分除去，而不是从进料的较轻部分除去。本发明通过扩大进料的沸程来显示从进料重部分除去硫的协同效应，并且通过与所述协同效应成比例地减少加氢脱硫催化剂的量将该协同效应转化为实际优点，从而保持加氢裂化至特定的低水平。进料的沸点范围通过向进料的较高沸点部分加入第二料流的一部分来降低加氢脱硫进料的平均沸点，从而第二料流的剩余部分的硫含量足够低，使得第二流不需要脱硫。在本文中证明了进一步的发现，通过减少所述协同效应允许的加氢脱硫催化剂的量，加氢脱硫剂流出物的后续提升管裂化步骤期间汽油与总转化率之比得以提高。

5. 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。

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

US4016069A Multiple stage hydrodesulfurization process including partial feed oil by-pass of first stage 失效
标题翻译：多级加氢脱硫工艺，包括第一阶段的部分原油旁路
公开(公告)号：US4016069A
公开(公告)日：1977-04-05
申请号：US632375
申请日：1975-11-17
申请人： Robert D. Christman , Jordan S. Lasher , John A. Paraskos , Stephen J. Yanik
发明人： Robert D. Christman , Jordan S. Lasher , John A. Paraskos , Stephen J. Yanik
IPC分类号： C10G49/00 , C10G65/04 , C10G23/02
CPC分类号： C10G65/04 , C10G2300/107
摘要： A multiple stage process for hydrodesulfurizing a residual oil comprising passing the oil downwardly through a plurality of stages in series with an interstage flashing step. A portion of the fresh feed oil continuously or intermittently by-passes the first stage and flows directly to the second stage.
摘要翻译：用于对残余油进行加氢脱硫的多级方法，包括将油向下通过与级间闪蒸步骤串联的多个级。新鲜进料油的一部分连续地或间歇地绕过第一阶段并直接流到第二阶段。

9. 发明授权

US4111796A Method for presulfiding hydrodesulfurization catalysts 失效
标题翻译：用于确定加氢脱硫催化剂的方法
公开(公告)号：US4111796A
公开(公告)日：1978-09-05
申请号：US673075
申请日：1976-04-02
申请人： Stephen J. Yanik , Angelo A. Montagna , James A. Frayer
发明人： Stephen J. Yanik , Angelo A. Montagna , James A. Frayer
IPC分类号： B01J37/20 , C10G45/08 , C10G23/02 , B01J27/02
CPC分类号： C10G45/08 , B01J37/20
摘要： An improved method for presulfiding a hydrodesulfurization catalyst which comprises continuously contacting the catalyst with a sulfiding treating agent at a relatively low temperature and pressure and only until the total amount of sulfur in the treating agent contacting the catalyst is no more than 55 percent of the amount of sulfur required to sulfide the supported metals on the catalyst to their completely sulfided forms.

10. 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。

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