CN101336282A - 使用具有新型反应器分离系统的反应器对重油进行改质的方法 - Google Patents

使用具有新型反应器分离系统的反应器对重油进行改质的方法 Download PDF

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CN101336282A
CN101336282A CNA2006800518885A CN200680051888A CN101336282A CN 101336282 A CN101336282 A CN 101336282A CN A2006800518885 A CNA2006800518885 A CN A2006800518885A CN 200680051888 A CN200680051888 A CN 200680051888A CN 101336282 A CN101336282 A CN 101336282A
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slurry
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D·法希德
J·墨菲
B·雷诺兹
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Chevron USA Inc
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Abstract

申请人已经开发了新型渣油完全加氢转化浆料反应器系统，该系统允许所述催化剂、未转化的油、氢气和转化了的油以连续混合物在整个反应器循环，而对所述混合物没有限制。所述混合物在一个或多个所述反应器的内部被分离，以便仅分离出所述转化了的油和氢气进入蒸气产物，而允许未转化的油和浆料催化剂作为液体产物继续进入下一个后续反应器。然后在下一个反应器中将一部分未转化的油转化成较低沸点的烃，再一次产生未转化的油、氢气、转化了的油和浆料催化剂的混合物。可以在额外的反应器中进行进一步加氢处理，完全转化所述油。所述油可以被交替地部分转化，在未转化的油中留下浓缩的催化剂，可将其直接再循环至所述第一反应器。

Description

使用具有新型反应器分离系统的反应器对重油进行改质的方法
发明领域
本发明涉及使用浆料催化剂组合物对重油进行改质的方法。
发明背景
由于全世界对于石油产品的更大的需求，目前对于重油加工的兴趣提高了。加拿大和委内瑞拉是重油的来源地。导致重油原料完全转化为有用产品的方法是特别令人感兴趣的。
美国专利号6278034陈述了加氢工艺，其采用具有将气体产物与油和催化剂的浆料分开的内部装置的反应器。
下面的专利申请，在此引用作为参考，涉及高活性浆料催化剂组合物的制备和它们在重油改质方法中的用途：
美国专利序列号10/938202涉及适合于重油加氢转化的催化剂组合物的制备。所述催化剂组合物通过一系列步骤制备，包括混合VIB族金属和氨水以形成含水混合物，并硫化所述混合物以形成浆料。然后用VIII族金属促进所述浆料。随后的步骤包括将所述浆料与烃油混合，并使得到的混合物与氢气和第二种烃油混合，其中所述第二种烃油比所述第一种油的粘度低。从而制得活性催化剂组合物。
美国专利序列号10/938003涉及浆料催化剂组合物的制备。所述浆料催化剂组合物在一系列步骤中制备，包括混合VIB族金属氧化物和氨水以形成含水混合物并硫化所述混合物以形成浆料。然后用VIII族金属促进所述浆料。随后的步骤包括使所述浆料与烃油混合，并使得到的混合物与氢气(在维持水为液相的条件下)混合以生成活性浆料催化剂。
美国专利序列号10/938438涉及将浆料催化剂组合物用于重油改质的方法。不允许所述浆料催化剂组合物沉降，沉降可能导致失活。将所述浆料再循环至改质反应器来重复使用，且产物不需要进一步分离程序来除去催化剂。
美国专利序列号10/938200涉及使用浆料组合物进行重油改质的方法。所述浆料组合物在一系列步骤中制备，包括混合VIB族金属氧化物和氨水以形成含水混合物并硫化所述混合物以形成浆料。然后用VIII族金属化合物促进所述浆料。随后的步骤包括使所述浆料与烃油混合，并使得到的混合物与氢气(在维持水为液相的条件下)混合以生成活性浆料催化剂。
美国专利序列号10/938269涉及使用浆料组合物进行重油改质的方法。所述浆料组合物通过一系列步骤中制备，包括混合VIB族金属氧化物和氨水以形成含水混合物，和硫化所述混合物以形成浆料。然后用VIII族金属促进所述浆料。随后的步骤包括使所述浆料与烃油混合，并使得到的混合物与氢气和第二种烃油混合，其中所述第二种烃油比所述第一种油的粘度低。由此生成活性催化剂组合物。
发明概述
重油的加氢转化方法，所述方法采用内部具有分离器的上流式反应器，所述分离器用来进行相分离。可采用至少一个具有内部分离器的反应器，尽管更通常使用多个串联反应器。使用多个串联反应器的加氢转化方法可采用以下步骤：
(a)使加热后的重油原料、活性浆料催化剂组合物和含氢气体混合以形成混合物；
(b)使步骤(a)的混合物进入反应器的底部，所述反应器维持在包括升高的温度和压力在内的加氢处理条件下；
(c)在所述反应器内部将包含反应产物、氢气、未转化的油和浆料催化剂的物流分成两股物流：包含反应产物和氢气的蒸气物流，和包含未转化的物料和浆料催化剂的液体物流；
(d)将所述蒸气物流从顶部送去进一步加工，并将所述液体物流的至少一部分送到下一个串联的反应器中。
本发明打算在所描述的工艺方案中在一个或多个反应器内进行相分离，以使得单一的蒸气相产物是离开所述反应器顶部的唯一产物。液相产物是离开所述反应器的较低部分(经过底部或侧线)的用于进一步加工的唯一物流。如果进行内部分离，不需要热的高压分离器或闪蒸罐来分离所述相，然后它们离开所述反应器。
本发明还采用了反应器差压控制系统，该系统调节离开所述反应器顶部的蒸气产物，因此不再需要通往下一个反应器的原料物流的控制阀。
附图简述
附图显示了应用至多个串联的反应器系统的本发明的工艺方案。
发明详述
本发明涉及催化剂活化的浆料加氢裂化方法。气体反应产物与包含未转化的油和催化剂的液体物流的级间分离对于维持工艺中的热平衡是有效的。在附图中，物流1包含重原料，例如减压渣油。其它原料可以包括常压渣油、减压渣油、来自溶剂脱沥青单元的焦油、常压瓦斯油、减压瓦斯油、脱沥青油、烯烃、衍生自焦油砂或沥青的油、衍生自煤的油、重原油、来自费-托工艺的合成油以及衍生自回收废油和聚合物的油。
所述原料进入炉80中加热，并以物流4离开。物流4与含氢气体(物流2)、再循环浆料(物流17)和包含活性浆料组合物的物流(物流3)混合，得到混合物(物流24)。物流24进入所述第一反应器10的底部。由于所述反应器内部的分离装置(未示出)，主要包含反应产物和氢气的蒸气物流31离开所述反应器的顶部。液体物流26，其含有与未转化的油混合的浆料，离开反应器10的底部或侧线。
物流26与包含氢气的气体物流(物流15)混合产生物流27。物流27进入第二反应器20的底部。
主要包含反应产物和氢气的蒸气物流8，离开所述反应器20的顶部并汇入来自反应器20的蒸气产物。液体物流27，其含有与未转化的油混合的浆料，离开反应器20的底部或侧线。
物流32与包含氢气的气体物流(物流16)混合产生物流28。物流28进入反应器30的底部。蒸气物流12，其主要包含反应产物和氢气，离开所述反应器的顶部并汇入来自前两个反应器的作为物流14的蒸气产物。液体物流17，其含有与未转化的油混合的浆料，离开反应器30的底部或侧线。该物流的一部分可以作为物流18排放，或作为物流17再循环回所述第一反应器10。
来自反应器10、20和30的顶部物流(分别为物流31、8和12)产生物流14，该物流进入下游设备进一步加工。
本发明中优选的反应器类型是液体循环反应器，但也可以使用其它类型的上流式反应器。液体循环反应器在同时待审的申请S.N.-(T-6493)中有进一步讨论，将该申请引入供参考。
液体循环反应器是上流式反应器，其在升高了的压力和温度下进料重烃油和富氢气体用于加氢转化。用于该液体循环反应器的工艺条件包括：压力为1500-3500psia，优选2000-3000psia。温度为700-900F，优选775-850F。
加氢转化包括例如加氢裂化和除去杂原子污染物(例如硫和氮)的工艺。在浆料催化剂的使用中，催化剂颗粒非常小(1-10微米)。可以使用泵来循环浆料，但通常不需要用泵。
在本发明中使用的催化剂浆料组合物的制备方法陈述于美国专利序列号10/938003和美国专利序列号10/938202中，将它们引入供参考。所述催化剂组合物用于但不限于加氢改质工艺，例如加氢裂化、加氢处理、加氢脱硫、加氢脱氮和加氢脱金属。

Claims (11)

1.重油的加氢转化方法，所述方法采用带有分离器的多个上流式反应器，所述分离器位于至少一个反应器的内部，所述方法包括以下步骤：
(a)使加热后的重油原料、活性浆料催化剂组合物和含氢气体混合以形成混合物；
(b)使步骤(a)的混合物进入所述第一反应器的底部，所述第一反应器维持在包括升高的温度和压力在内的加氢处理条件下；
(c)在所述第一反应器内部将包含反应产物、氢气、未转化的物料和浆料催化剂的物流分成两股物流：包含反应器产物和氢气的蒸气物流，和包含未转化的物料和浆料催化剂的液体物流；
(d)将所述蒸气物流从顶部送去进一步加工，并使包含未转化的物料和浆料催化剂的所述液体物流作为底部物流从所述第一反应器流出；
(e)将步骤(d)的所述液体物流的至少一部分送至所述第二反应器的底部，所述第二反应器维持在包括升高的温度和压力在内的加氢处理条件下；
(f)在所述第二反应器内部将包含反应产物、氢气、未转化的物料和浆料催化剂的物流分成两股物流：包含反应器产物和氢气的蒸气物流，和包含未转化的物料和浆料催化剂的液体物流；
(g)将所述蒸气物流从顶部送去进一步加工，并使包含未转化的物料和浆料催化剂的所述液体物流作为底部物流从所述第二反应器送去进一步加工。
2.权利要求1的方法，其中将步骤(g)的液体物流再循环至步骤(a)，步骤(a)的混合物还包含再循环的未转化的物料和浆料催化剂。
3.权利要求1的方法，其中第三反应器的底部维持在包括升高的温度和压力在内的浆料加氢处理条件下。
4.权利要求1的方法，其中所述循环反应器使用泵。
5.权利要求1的方法，其中在每个反应器中所采用的加氢处理条件包括1500-3500psia的总压和700-900F的反应温度。
6.权利要求5的方法，其中优选的总压为200-3000psia，和优选的温度为775-850F。
7.权利要求1的加氢转化方法，其中所述重油选自常压渣油、减压渣油、来自溶剂脱沥青单元的焦油、常压瓦斯油、减压瓦斯油、脱沥青油、烯烃、衍生自焦油砂或沥青的油、衍生自煤的油、重原油、来自费-托工艺的合成油以及衍生自回收废油和聚合物的油。
8.权利要求1的加氢转化方法，其中所述方法选自加氢裂化、加氢处理、加氢脱硫、加氢脱氮和加氢脱金属。
9.权利要求1的方法，其中权利要求1的活性浆料催化剂组合物通过以下步骤来制备：
(a)混合VIB族金属氧化物和氨水以形成VIB族金属化合物的含水混合物；
(b)在初始反应区域中，用包含硫化氢的气体将步骤(a)的含水混合物硫化至大于8SCF硫化氢每磅VIB族金属的剂量，以形成浆料；
(c)用VIII族金属化合物促进所述浆料；
(d)将步骤(c)的浆料与在212°F下粘度至少为2cSt的烃油混合以形成中间混合物；
(e)在第二反应区中在维持所述中间混合物中的水为液相的条件下将所述中间混合物与氢气混合，从而形成与液体烃混合的活性催化剂组合物；和
(f)回收所述活性催化剂组合物。
10.权利要求1的方法，其中至少90wt％的原料转化为更低沸点的产物。
11.权利要求1的加氢转化方法，其中所述重油选自常压渣油、减压渣油、来自溶剂脱沥青单元的焦油、常压瓦斯油、减压瓦斯油、脱沥青油、烯烃、衍生自焦油砂或沥青的油、衍生自煤的油、重原油、来自费-托工艺的合成油以及衍生自回收废油和聚合物的油。
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