CN104762104A - 生产低硫柴油的集成方法 - Google Patents
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- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及生产低硫柴油和所含硫浓度降低的残余烃流的集成方法。本发明方法利用残余烃原料和重质馏出烃原料。残余烃原料与富含氢气的气流在加氢脱硫反应区中反应,生成柴油沸程的烃和硫浓度降低的残余产物流。将加氢脱硫反应区的排出物在热的高压气液分离器中分离,得到含氢气和柴油沸程烃的气体烃流以及硫浓度降低的残余液体烃流。将含氢气和柴油沸程烃的气流与重质馏出烃流一起引入加氢裂化反应区。将从加氢裂化区得到的排出物在冷的气液分离器中分离,得到富含氢气的气流,并优选将该气流循环到脱硫反应区。从冷的气液分离器中移出含超低硫柴油的液体烃流,并优选在分馏区将其分离,得到超低硫柴油产品流。
Description
本申请是申请号为200610167068.4、申请日为2006年12月14日、发明名称为“生产低硫柴油的集成方法”的专利申请的分案申请。
技术领域
本发明所涉及的技术领域是通过加氢裂化和加氢脱硫,将两种低价值的烃原料催化转化成包括低硫柴油的有用烃产品。
背景技术
炼油厂通过加氢裂化源自原油或其重馏分的烃原料生产期望产品,例如喷气燃料、柴油燃料和其它已知是中间馏分的产品,以及低沸烃液体,例如石脑油和汽油。最常用的经历加氢裂化的原料是通过分馏从原油回收的粗柴油和粗重柴油。典型的粗重柴油包含大部分在371℃以上沸腾的烃组分,通常至少50wt%在371℃以上沸腾。典型的减压柴油的沸点范围通常为315℃-565℃。
加氢裂化一般通过在升高的温度和压力的条件下,在氢气的存在下使粗柴油或其它待处理原料与合适的加氢裂化催化剂在加氢裂化反应器或区中接触,生成含有炼油厂所期望的烃产物分布的产品来实现。
炼油厂还对残余烃流进行加氢脱硫,以生成硫浓度降低的重质烃化合物。残余烃包含原油中最重的组分,并且大部分是不可蒸馏的。残余烃流是从原油中移出或分馏出馏出烃之后的剩余物。大部分残余原料在高于565℃的温度下沸腾。在残余烃原料的脱硫过程中,会生成一定量的包含柴油沸程烃的馏出烃。然而,由此生成的柴油沸程烃往往因其较高的硫浓度而不适合用作超低硫柴油。虽然在商业实践中使用了各种工艺流程方案、操作条件和催化剂,但仍需要新的能提供更低成本、更有价值产品的产率和操作性改善的加氢处理方法。
信息公开内容
US 5,403,469B1公开了并联的加氢处理和加氢裂化工艺。将这两段工艺的排出物合并在同一分离容器中,并分离成含氢气的气体和含烃的液体。氢气如所示的作为部分原料流供给加氢裂化器和加氢处理器。
US 4,810,361公开了将石油残渣改良的方法。该方法包括使减压或常压残渣原料与催化剂接触,由此将残余原料同时脱金属和脱硫。
发明内容
本发明是生产低硫柴油和所含硫浓度降低的残余烃流的集成方法。本发明方法利用残余烃原料和重质馏出烃原料。残余烃原料与富含氢气的气流在加氢脱硫反应区中反应,生成柴油沸程的烃和硫浓度降低的残余产物流。将加氢脱硫反应区的排出物在热的高压气液分离器中分离,得到含氢气和柴油沸程烃的气体烃流以及硫浓度降低的残余液体烃流。将含氢气和柴油沸程烃的气流与重质馏出烃流一起引入加氢裂化反应区。将从加氢裂化区得到的排出物在冷的气液分离器中分离,得到富含氢气的气流,并优选将该气流循环到脱硫反应区。从冷的气液分离器中移出含超低硫柴油的液体烃流,并优选在分馏区将其分离,得到超低硫柴油产品流。
利用单个的氢气管路将两个加氢处理单元集成使得对压缩设备的要求最小,由此降低了处理两种独立且分开的原料以得到更有价值的产物流的投资和操作成本。
本发明的其它实施方案包括其它细节,例如有关原料、加氢脱硫催化剂、加氢裂化催化剂和优选操作条件的详细描述,所有这些都将在以下关于本发明这些方面的讨论中公开。
附图说明
附图是本发明优选实施方案的简化工艺流程图。附图意在示意性地说明本发明,而并非对其进行限定。
发明详述
本发明是残余烃原料加氢脱硫和重质馏出烃原料加氢裂化的集成方法。加氢脱硫反应区的优选的残余烃原料包括在原油分馏过程中生成的减压或常压残渣。优选的残余烃原料具有至少25vol%在高于565℃的温度下沸腾。更优选的残余烃原料具有至少50vol%在高于565℃的温度下沸腾。
将残余烃原料与富含氢气的气流在加氢脱硫反应区中反应,生成柴油沸程的烃和含沥青质且硫浓度降低的残余烃。该加氢脱硫反应区将原料不可蒸馏地转化并脱硫。将从加氢脱硫反应区得到的排出物引入优选在7.0MPa-20.7MPa的压力和204℃-454℃的温度下运行的热的气液分离器中,得到含氢气和柴油沸程烃的气流以及含沥青质且硫浓度降低的液体烃流。
加氢脱硫反应区优选在包括260℃-454℃的温度和7.0MPa-20.7MPa的压力的条件下运行。
用在本发明中的合适脱硫催化剂是任何已知的常规脱硫催化剂,包括在高表面积的载体材料,优选氧化铝上含有至少一种第VIII族金属,优选铁、钴和镍,更优选钴和/或镍,以及至少一种第VI族金属,优选钼和钨的那些。其它合适的脱硫催化剂包括沸石催化剂以及其中贵金属选自钯和铂的贵金属催化剂。在同一反应容器中使用一种以上的脱硫催化剂也在本发明范围内。在反应容器中可以使用两个以上的催化剂床和一个以上的骤冷点。第VIII族金属一般以2-20wt%,优选4-12wt%的量存在。第VI族金属一般以1-25wt%,优选2-25wt%的量存在。
优选将从热的气液分离器中回收的含沥青质且硫浓度降低的液体烃流引入分馏区,以提供流体催化裂化器的原料或低硫燃料油产品流。将热的气液分离器的含氢气和柴油沸程烃的气流与重质馏出烃原料混合,并引入包含加氢裂化催化剂且优选在包括260℃-454℃的温度和7.0MPa-14.0MPa的压力的条件下运行的加氢裂化区中。
本发明的集成方法特别适用于加氢裂化包含烃和/或其它有机物质的烃油,以得到具有低的平均沸点和低的平均分子量、包含烃和/或其它有机物质的产物。可以通过本发明方法进行加氢裂化的烃原料包括所有矿物油和合成油(例如页岩油、焦油及其产品等)及其馏分。示例性的烃原料包括含有在288℃以上沸腾的组分的那些,例如常压粗柴油和减压柴油。优选的加氢裂化原料是粗柴油或具有至少50wt%,最通常至少75wt%在288℃以上的温度下沸腾的组分的其它烃馏分。最优选的粗柴油原料之一包含在288℃以上沸腾的烃组分,并且含有至少25vol%在315℃-565℃沸腾的组分的原料可获得最好结果。
加氢裂化区可以包括一个以上相同或不同的催化剂床。在一种实施方案中,优选的加氢裂化催化剂使用无定形基材或低级沸石基材与一种以上第VIII族或第VIB族金属加氢组分的组合。在另一实施方案中,加氢裂化区包含一般在任何晶态沸石裂化基材上沉积有少量第VIII族金属加氢组分的催化剂。其它加氢组分可以选自第VIB族,用于与沸石基材结合。沸石裂化基材在本领域中有时称为分子筛,并且通常由氧化硅、氧化铝和一种以上的可交换阳离子,例如钠、镁、钙、稀土元素等组成。它们的特征还在于直径相对均一地为4-14埃的晶孔。优选地,使用氧化硅/氧化铝的摩尔比为3-12的沸石。合适的天然沸石包括例如丝光沸石、stillbite、片沸石、镁碱沸石、环晶石、菱沸石、毛沸石和八面沸石。合适的合成沸石包括例如B、X、Y和L晶型,例如合成八面沸石和丝光沸石。优选的沸石是晶孔直径为8-12埃的那些,其中氧化硅/氧化铝的摩尔比为4-6。落在优选范围中的最佳沸石例子是合成Y分子筛。
天然沸石一般是钠型、碱土金属型或它们的混合型。合成沸石几乎总是首先制成钠型。在任何情况下,对于用作裂化基材,优选地将大部分或全部原沸石单价金属与多价金属和/或铵盐离子交换,随后加热到与沸石结合的铵离子热分解,在其位置上留下氢离子和/或交换位点,而实际又通过脱水将其除阳离子。这种氢或“除阳离子化”的Y沸石更特别描述在US3,130,006。
多价金属-氢混合沸石可以通过首先与铵盐离子交换,再部分回头与多价金属盐交换,接着煅烧而制得。在某些情况下,如在合成丝光沸石的情况下,可以通过对碱金属沸石直接进行酸处理,制得氢型。优选的裂化基材是基于最初离子交换容量至少10%,优选至少20%金属阳离子空缺的那些。特定期望且稳定的一类沸石是其中至少20%离子交换容量被氢离子占据的那些。
在本发明优选加氢裂化催化剂中用作加氢组分的活性金属是第VIII族的那些,即铁、钴、镍、钌、铑、钯、锇、铱和铂。除了这些金属以外,其它助剂也可以与它们一起使用,包括第VIB族金属,例如钼和钨。加氢金属在催化剂中的量可以在宽范围中变化。广义上讲,0.05wt%-30wt%之间的任何量都可以使用。在贵金属的情况下,一般优选使用0.05-2wt%。混入加氢金属的优选方法是将沸石基材与所期望金属的合适化合物的水溶液(其中金属以阳离子形式存在)接触。加入所选定加氢金属之后,接着对所得催化剂粉末进行过滤,干燥,如果期望与加入的润滑剂、粘结剂等造粒,并在例如371-648℃的温度下在空气中煅烧,以使催化剂活化,铵离子热分解。或者,可以首先将沸石组分造粒,随后加入加氢组分,并通过煅烧进行活化。前述的催化剂可以以未被稀释的形式使用,或者可以将粉末化沸石催化剂与5-90wt%的其它活性较低的催化剂、稀释剂或粘结剂,例如氧化硅、硅胶、硅铝共凝胶、活化粘土等混合并一起造粒。这些稀释剂可以直接使用,或者它们可以包含少量加入的加氢金属,例如第VIB和/或第VIII族金属。
含有其它金属助剂的加氢裂化催化剂也可以用在本发明方法中,包括例如铝磷酸盐分子筛、晶态铬硅酸盐(chromosilicate)和其它晶态硅酸盐。晶态铬硅酸盐更全面描述在US 4,363,718中。
将从加氢裂化区得到的排出物优选与含水流接触以溶解任何铵盐,部分冷凝,并接着将其引入在基本等于加氢裂化区的压力和38-71℃的温度下运行的高压气液分离器中。从气液分离器回收含水流。将富含氢气的气流从该气液分离器移出,以提供引入集成的加氢脱硫反应区的氢气的至少大部分,优选全部。从该高压气液分离器中回收含低沸烃和硫浓度降低的柴油沸程烃的液体烃流,并将其分离,以回收含硫浓度降低的柴油沸程烃的料流。该分离优选在分馏区中进行,以不仅得到含柴油沸程烃的料流,而且得到其它有价值的馏出烃流,例如汽油和煤油。该分馏区可以与上述分馏区相同或不同。
现在参照附图,将含沥青质的残余烃原料经管线1引入工艺中,并与经管线23提供的富含氢气的循环气流混合。所得混合物经管线2引入加氢脱硫区3。从加氢脱硫区3得到的排出物经管线4携出,并引入热的气液分离器5。含柴油沸程烃的气体烃流从该热的气液分离器5经管线6移出,并与经管线32提供的重质馏出烃原料合并,所得混合物经管线33引入加氢裂化区7。从加氢裂化区7得到的排出物经管线8移出,并与经管线9提供的含水流合并。将所得混合物经管线10引入热交换器11。将所得部分冷凝的料流从热交换器11经管线12移出,并引入冷的气液分离器13。将含无机化合物的含水流从冷的气液分离器13经管线14移出并回收。从冷的气液分离器13经管线15移出含硫化氢的富含氢气的气流,并将其引入吸收区16。将贫含胺的吸收溶液经管线17引入吸收区16,并从吸收区16经管线18移出含硫化氢的富含胺的溶液,并回收。从吸收区16经管线19移出硫化氢浓度降低的富含氢气的气体,并与经管线20提供的氢气补充流混合;所得混合物经管线21携着引入压缩机22。从压缩机22经管线23移出所得压缩的富含氢气的气流,并如上所述的经管线23和2引入加氢脱硫区3。从冷的气液分离器13经管线25移出含柴油沸程烃的液体烃流,并引入分馏区26。从热的气液分离器5经管线24移出含沥青质且硫浓度降低的热的液体烃流,并引入分馏区26。从分馏区26经管线27移出一般是气体的烃流,经管线28移出含石脑油的料流,并回收。从分馏区26经管线29移出含煤油的料流,经管线30移出含柴油的料流,并回收。从分馏区26经管线31移出含沥青质且硫浓度降低的重质烃流,并回收。
通过下面的示例性实施方案,进一步说明本发明方法。但是,该示例性实施方案并非用来过度地限制本发明方法,而是进一步举例说明上述实施方案的优点。
示例性实施方案
将性质如表1中所示的减压残渣原料以56.5质量单位的量引入在19.4MPa的压力和399℃的温度下运行的加氢脱硫反应区中,以得到包含柴油沸程烃且硫浓度降低的排出流。将加氢脱硫反应区的排出流引入在18.7MPa的压力和404℃的温度下运行的热的气液分离器,以提供包含氢气、硫化氢、一般为气态的烃和9质量单位的石脑油和柴油的烃气流。从该热的气液分离器回收包含硫浓度降低的可蒸馏减压柴油和不可蒸馏的烃化合物的液体烃流。将性质如表1所示的减压柴油和重质炼焦器粗柴油(VGO/HCGO)的混合物与上述烃气流一起引入加氢裂化反应区。加氢裂化区的排出物具有5.2质量单位的硫化氢、17.6质量单位的C1-C6烃和83质量单位的硫含量低于10wppm的石脑油和柴油。
表1-原料分析
前述描述、附图和示例性实施方案都清楚地举例说明了本发明方法所包括的优点以及利用该方法可获得的有益效果。
Claims (9)
1.一种由低品质原料生产超低硫柴油的集成方法,所述方法包括:
(a)使具有至少部分在高于565℃下沸腾的、含沥青质的原料(1)与压缩的富含氢气的气流(23)在包含加氢脱硫催化剂的加氢脱硫反应区中反应,生成硫浓度降低、包含柴油沸程烃和氢气的加氢脱硫反应区排出流(4);
(b)将所述加氢脱硫反应区排出流分离,以得到包含柴油沸程烃和氢气的气流(6),以及包含沥青质且硫浓度降低的液体烃流(24);
(c)使来自步骤(b)的包含柴油沸程烃和氢气的气流(6)与馏出烃原料(32)在包含加氢裂化催化剂的加氢裂化区(7)中反应,生成包含低沸烃、硫浓度降低的柴油沸程烃和氢气的加氢裂化区排出流(8);
(d)将包含低沸烃、硫浓度降低的柴油沸程烃和氢气的加氢裂化区排出流(8)分离,以得到富含氢气的气流(15)和硫浓度降低的柴油沸程烃(30);
(e)将所述富含氢气的气流(15)引入吸收区(16)中,其中将贫含胺的吸收溶液(17)引入吸收区(16),并将含硫化氢的富含胺的溶液(18)从吸收区(16)移出,并回收;
(f)将硫化氢浓度降低的富含氢气的气体(19)从吸收区(16)移出;
(g)将富含氢气的气体(19)与氢气补充流(20)混合;
(h)将所得富含氢气和氢气补充流的混合物(21)携着引入压缩机22;
(i)将所得压缩的富含氢气的气流(23)从压缩机22经管线23移出;和
(j)将压缩的富含氢气的气流(23)引入加氢脱硫区3。
2.权利要求1的方法,其中步骤(a)的含沥青质的原料(1)的至少25vol%在高于565℃的温度下沸腾。
3.权利要求1的方法,其中步骤(c)的馏出烃原料(32)在315℃-565℃下沸腾。
4.权利要求2的方法,其中步骤(c)的馏出烃原料(32)在315℃-565℃下沸腾。
5.权利要求1-4中任一项的方法,其中加氢脱硫反应区(3)在包括7.0MPa-20.7MPa的压力和204℃-454℃的温度的条件下运行。
6.权利要求5的方法,其中加氢脱硫反应区(3)在包括7.0MPa-20.7MPa的压力和260℃-454℃的温度的条件下运行。
7.权利要求6的方法,其中加氢裂化区(7)在包括7.0MPa-14.0MPa的压力和260℃-454℃的温度的条件下运行。
8.权利要求6的方法,其中加氢裂化区(7)在包括7.0MPa-20.7MPa的压力和260℃-426℃的温度的条件下运行。
9.权利要求5的方法,其中硫浓度降低的柴油沸程烃(30)包含低于100ppm的硫。
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