CN103270143B - 用于精炼原油的方法 - Google Patents
用于精炼原油的方法 Download PDFInfo
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- CN103270143B CN103270143B CN201180051713.5A CN201180051713A CN103270143B CN 103270143 B CN103270143 B CN 103270143B CN 201180051713 A CN201180051713 A CN 201180051713A CN 103270143 B CN103270143 B CN 103270143B
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000010779 crude oil Substances 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title abstract description 19
- 238000007670 refining Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
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- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 27
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 13
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- 239000007787 solid Substances 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
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- 239000000463 material Substances 0.000 description 13
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- 238000006317 isomerization reaction Methods 0.000 description 10
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 10
- 238000002309 gasification Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 239000002737 fuel gas Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
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- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- -1 propylene, butylene Chemical group 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
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- 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
- C10G45/14—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 with moving solid particles
- C10G45/16—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 with moving solid particles suspended in the oil, e.g. slurries
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- 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
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
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- C10G67/16—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural parallel stages only
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- C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
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- C10G7/00—Distillation of hydrocarbon oils
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
一种用于精炼原油的方法,包括原油的分离单元,分离单元由至少一个用于分离各种馏分的常压蒸馏单元、用于转化获得的重馏分的单元、用于通过对其成分的化学组分的作用而改进获得的一些馏分的质量的单元、和用于去除不希望的成分的单元,其特征在于将最重的馏分常压蒸馏渣油送至包括浆态床加氢转化反应器或流化床型加氢转化反应器的转化单元,在合适的纳米分散的加氢催化剂的存在下向该转化单元中引入氢气或氢气与3/4S的混合物。
Description
技术领域
本发明描述了一种用于精炼原油的方法,其中原油的分离单元仅由常压蒸馏塔组成,负压蒸馏塔被加氢转化步骤取代。
背景技术
当前的炼油厂被认为是始于上世纪第二次世界大战后,且从1950-1960年(当对机动性的需求大量增加引起对汽油的需要的快速增加时)开始快速的发展。因此发展了两种精炼方案,简单循环方案或初馏-加氢(Hydroskimming)和复杂方案(“Laraffinazione del petrolio”(Oil refining),Carlo Giavarini和Alberto Girelli,Editorial ESA1991)。在两种方案中,主要操作是相同的:预处理(过滤、脱盐)原油,然后送至初级蒸馏部件。在这个部件中,在常压下将原油第一次进料至蒸馏塔(初馏),分离较轻馏出物,而将常压渣油转移至负压蒸馏塔(真空),从真空渣油中分离重馏出物。在简单循环方案中,真空渣油主要用于生产沥青和燃料油。复杂循环方案被认为用于进一步将桶的残渣转化为馏出物且用于将汽油产量和其辛烷含量最大化。因此,与用于促进具有最大辛烷含量的汽油的产量的单元(液流催化裂化、重整、异构化、烷基化)一起,加入用于促进较重馏分的转化的单元(各种催化裂化、热裂化、减粘裂化、炼焦技术)。
图1示出了复杂循环炼油的简化框图,在对比示例1中提供了该图的描述。
对于考虑这些方案的时代,周围的背景已经发生了巨大的变化。原油价格与环境需要的增加促使更加有效地使用化石资源。例如,在电能的生产中燃料油几乎全部被天然气取代。因此,必要的是降低或消除较重馏分(燃料油、沥青、焦炭)的生产且增加中等馏出物的转化,而生产用于柴油机发动机的柴油,特别是在欧洲,柴油的需要已经超过了对汽油的需求。在对降低环境冲击的调整性发展下,其他重要的变化因素在于:可用原油的质量的日益退化和用于汽车的燃料的质量的增加。这些需求的压力引起炼油厂的复杂程度的进一步增加,加入新型的强制转化技术:高压下的加氢裂化、重质渣油的气化技术联合组合循环的使用用于生产电能、焦炭的气化或燃烧技术用于生产电能。
复杂程度的增加导致转化效率的增加,但是导致增加的能量消耗且使操作管理和环境管理更困难。因此,必须发现新的精炼方案,尽管满足新的需求,也要允许重获效率和操作简单性。
在近二十年内,已经做出了重要的努力用于发展加氢裂化工艺,该加氢裂化工艺能够将重原油与常压蒸馏渣油完全转化为馏出物,避免燃料油和焦炭的副产物。随着描述于以下专利申请的EST技术(Eni Slurry Technology)的发展,在这个方面获得了重要的结果:
IT-MI95A001095,IT-MI2001A001438,IT-MI2002A002713,
IT-MI2003A000692,IT-MI2003A000693,IT-MI2003A002207,
IT-MI2004A002445,IT-MI2004A002446,IT-MI2006A001512,
IT-MI2006A001511,IT-MI2007A001302,IT-MI2007A001303,
IT-MI2007A001044,IT-MI2007A1045,IT-MI2007A001198,
IT-MI2008A001061。
发明内容
实际上,应用该技术,达到将重馏分转化为馏出物所需的总转化率结果是可能的。现在已经发现,通过用根据该EST技术的加氢转化部件替换负压蒸馏部件,可以获得新的炼油方案,该新的炼油方案(尽管允许原油的总转化率)从操作、环境和经济的观点来看是更简单且更有利的。该请求保护的方法的应用,除了相对于现代炼油厂(用作参考)增加了精炼利润之外,还允许降低整体操作的数目、原料和中间产物的存储罐的数目以及消耗的数目。
请求保护的方法允许获得进料的原油至气体、石脑油和具有作为单一副产物的适量焦油的柴油的总转化率。
本发明的目的的用于精炼原油的方法,包括用于分离原油的单元,该用于分离原油的单元由至少一个用于分离各种馏分的常压蒸馏单元、用于转化获得的重馏分的单元、用于通过对其成分的化学组分的作用而改进获得的一些馏分的质量的单元、和用于去除不希望的成分的单元组成,特征在于将最重的馏分、常压蒸馏渣油送至包括至少一个浆态床加氢转化反应器或流化床型加氢转化反应器的转化单元,在合适的纳米分散的加氢催化剂的存在下向该转化单元中引入氢气或氢气与H2S的混合物。
该转化单元替代负压蒸馏部件。
在当前的炼油厂中,负压蒸馏部件由常压蒸馏单元和分离单元组成。
术语纳米分散是指尺寸为几百纳米单位的分散的催化剂。
纳米分散的加氢催化剂可基于Mo的硫化物和/或Fe的硫化物和/或W的硫化物和/或Cr的硫化物和/或Ni的硫化物和/或Co的硫化物及其混合物,且可从前驱体原位形成。加氢转化中还可能存在助催化剂,该助催化剂具有纳米级或微米级尺寸,选自裂化催化剂和/或脱氮催化剂,诸如具有小尺寸晶体的、初级颗粒之间具有低聚结度的沸石类、与Mo和/或W混合的Ni和/或Co的氧化物、硫化物或前驱体。关于该助催化剂的使用的另外细节在以上提到的专利申请IT-MI2008A001061中可找到。
本发明所使用的反应器优选地在氢气压力或氢气和硫化氢的混合物的100至200大气压下,在350℃至480℃的温度下、优选地在380℃至450℃的温度下运行。尽管可使用用浆态床加氢转化反应器(其中催化剂为纳米分散的)实现的任何加氢转化方法,且特别地是以上引用的专利申请中描述的EST技术的所用方法,优选的是使用以下指出的EST技术的方法。
优选的加氢转化方法为EST技术的加氢转化方法,其中采用固体累积反应器作为加氢转化反应器。这些优选方法中的一个包括将蒸馏渣油送至包括一个或多个具有合适热汽提气体的汽提相的固体累积加氢转化反应器(RIAS)、优选地为鼓泡塔,以获得汽相的转化产物。关于这种特定的加氢转化方法的另外细节在以上指出的专利申请IT-MI-2007A-001044中可找到。
这些优选的方法的另一个包括:在基于钼的催化剂的存在下,将蒸馏渣油送至鼓泡塔型的固体累积加氢转化反应器,以在反应器中直接获得汽相的加氢转化产物。关于这种特定的加氢转化方法的另外细节在以上已经指出的专利申请IT-MI-2007A-001044中可找到。
另一优选的、其中发生脱氮反应的加氢转化方法包括:将蒸馏渣油送至加氢转化反应器,其中在未转化的沥青质液体的分离之前或之后通过部分冷凝从该反应器离开的气相获得的、且在沥青质液体被再循环至该反应器之前通过真空提取沥青质液体本身可能获得的、沸点高于380℃的产物被送回至该加氢转化反应器,以使提取的转化产物在380℃下可被蒸馏至少60重量%。这种脱氮和加氢转化方法描述于本申请人的专利申请IT-MI2010A00198中,该申请中提供了最重要的细节。
本专利申请要求保护的、用于将重质油脱氮和加氢裂化为完全转化产物的方法,包括将重质油送至加氢裂化步骤,在引入氢气或氢气与H2S的混合物的情况下用合适的加氢催化剂在适当的反应器中实现,其特征在于:在未转化的沥青质液体的分离之前或之后通过部分冷凝从该反应器离开的气相获得的、且在沥青质液体被再循环至反应器之前通过真空提取沥青质液体本身可能获得的、沸点高于380℃的产物被送回至该加氢裂化反应器,以使提取的转化产物在380℃下可被蒸馏至少60重量%、优选地至少80重量%、更选地至少95重量%、甚至更选地至少99重量%。通过调节该部分冷凝的条件且可能调节真空塔(该真空塔从未转化的沥青质液体中提取产物)中的回流条件,确定被送回加氢裂化步骤的高沸点产物的量,且补充地确定反之亦被提取的加氢转化产物的馏分的量。
甚至当在高温条件下操作时,能够使高浓度的加氮最后馏分保持反应的方法允许提取具有低氮含量的、具有完全转化度(在380℃下,可蒸馏产物的95%)、能被直接进料至脱硫单元的产物。
加氢催化剂优选地基于钼,更优选地为浆态,且可为可分解的前驱体或预形成的化合物且可可能地另外包含一种或多种过渡金属。所用的反应器优选地在氢气压力或氢气和硫化氢的混合物100至200大气压下,在400℃至480℃的温度下运行。本发明可应用于任何类型的加氢裂化反应器,诸如搅拌罐式反应器或优选地浆料鼓泡塔。浆料鼓泡塔、优选地固体累积型的浆料鼓泡塔(描述于以上专利申请IT-MI2007A001045中)装有回流回路,由此以汽相获得的加氢转化产物被部分地冷凝且冷凝物被送回加氢裂化步骤。再次,在使用浆料鼓泡塔的情况下,优选的是通过合适设计的装置(在一个或多个水平线(level)上的布料器)将氢气进料至反应器的底部,以获得气泡的最好的分布和最方便的平均尺寸,且因此搅拌体制是这样的:甚至当在高浓度固体(在固体累积中操作时,通过被处理的炉料产生和制备的)的存在下操作时,保证均匀性和稳定的温度控制的条件。如果将在汽相的分离之后获得的沥青质液流经过蒸馏来提取产物,提取条件必须为回流重馏分以获得所需的转化度。
关于使用流化床反应器的加氢转化方法,除了纳米分散的加氢催化剂外,合适的负载型多相加氢转化催化剂的存在也是必要的。在这种情况下,加氢转化方法包括:将蒸馏渣油送至一个或多个流化床加氢转化反应器,向该流化床加氢转化反应器中引入氢气或H2S且将来自该反应器的流出液流送至分离步骤,在分离步骤被分离的且包含纳米分散的催化剂的液体馏分被再循环至该流化床反应器。关于使用流化床反应器和负载型多相加氢转化催化剂的方法的另外的细节在已经提到的专利申请IT-MI 2007A001198中可找到。
在一些实施例中,当所述加氢转化反应器为浆态床加氢转化反应器时,还存在合适的负载型多相加氢转化助催化剂。
在一些实施例中,将所述蒸馏渣油送至一个或多个流化床加氢转化反应器,将来自所述反应器的流出液流送至分离步骤,其中被分离且包含纳米分散的催化剂的液体馏分被再循环至所述反应器。
具体实施方式
示例
以下提供一些示例,在不限制其范围的情况下,这些示例有助于更好地限定本发明。以这些年来用于使进料原料的总转化率达到最佳的、实际的复杂-循环现代炼油厂作为参考。
示例1、2、3所用的参考原料如下(以千吨/月为单位):
与示例2、3和4提供的简化框图对应的、EST部件的物料的平衡与消耗涉及使用加氢转化反应器的结构,该结构使用基于钼的纳米分散的催化剂且根据以上提到的专利申请提供的信息再循环和提取汽相的产物(160巴,440℃)。
消耗:77KgEP/吨(包括H2)其中:
MP气流7.7,HP燃料气79.4,LP燃料气-107.3,
EE-56.8
使用2010年7月这个月可用的Platt的数据用于升级产品,其中使用表1中所示的Eni参考值用于半成品。
表1:产物的升级
示例1(对比的)
在这个示例中,提供现存的复杂-循环炼油厂的简化框图,该炼油厂位于意大利北部,在2010年6月这个月具有平均的容量和物料平衡(图1)。这个炼油厂具有强制转化单元,诸如FCC、减粘裂化和渣油气化且以原油的总转化率为导向。
以下简单地描述精炼循环。
初馏装置
将被脱盐和预加热的ATZ和BTZ原油的混合物送至用于常压分馏的初馏装置,除了燃料气和LPG外,还获得以下产物:
-轻质直馏石脑油(LVN):LVN在异戊烷馏除装置中馏除异戊烷且随后在异构化装置(TIP)中加工。被异构化的产物流入汽油池。
-直馏石脑油炉料重整油(VNCR):VNCR是比前述在重整装置RC2中加工的石脑油更重的石脑油。获得的轻馏分为在TIP装置中被加工且随后流入汽油池的LVN,而重馏分为流向汽油池的重整油。
-煤油:将液流送至脱硫单元HDS1和HDS3,获得被脱硫的煤油,该煤油流入最终产物。
-初馏柴油:将液流送至脱硫单元HDS3和HDS1,获得脱硫的柴油,该柴油流入最终产物。
-常压渣油(RA):在真空装置中加工RA。
真空装置
该装置容纳常压渣油(AR)且将AR经过真空蒸馏过程。除了气态产物外,还获得真空柴油(LGAS),真空柴油在单元HDS1中被脱硫,然后与被送至加氢裂化的转化装置和FCC的转化装置的催化原料或深真空产物(deep-vaccum)(DPV)一起,流入最终产物。然后在减粘裂化单元中加工真空渣油(RV)。
减粘裂化单元
该单元将真空渣油(VR)转化为气态产物(燃料气、丙烷、丁烷等)和随后在重整单元RC3中被加工的直馏石脑油:获得的重整油流入汽油池。通过氢化裂化装置和FCC装置加工减粘裂化的柴油和催化原料,而渣油(TAR VB)部分地用于制备F.O.(燃料油)和沥青且部分地经过脱沥青工艺。
加氢裂化装置
炼油厂具有两个加氢裂化装置。第一个HDC具有真空催化原料(DPV)和减粘裂化催化原料,减粘裂化柴油和其他半加工的产物作为输入液流。获得气态产物(燃料气、丙烷、丁烷等)、轻质和重质直馏石脑油、煤油和脱硫柴油,轻质和重质直馏石脑油、煤油和脱硫柴油流入最终产物。
直馏石脑油经历与以上描述的相同的加工,流入汽油池。
渣油(BOT HDC)与真空催化原料(DPV)一起形成用于第二HCD的输入液流。产物与第一HDC的产物相同。
为了简单的目的,两个HDC单元以单个HDC表示,将渣油(BOT HDC)送至该HDC中用于转化为FCC。
脱硫装置
该示例中的炼油厂装有三个不同的脱硫装置(HDS),用于满足硫的技术要求。进料至这些单元的主要液流为煤油、柴油、LCO。
脱沥青装置
将减粘裂化渣油(TAR VB)进料至脱沥青装置。输出液流由随后在FCC中加工的被脱沥青的油(DAO),和向气化装置(部分氧化POX)中进料以制备合成气的沥青质组成。获得的合成气用于电力供应网以生产能量且还用于制备氢气。
FCC装置
向FCC装置中进料来自脱沥青装置中的DAO、减粘裂化的催化原料、HDC渣油(BOTHDC)和常压渣油(RA)。
除了气体外,获得的产物还为丙烯、丁烯和被送至汽油池的裂化石脑油(LCN、MCN、HCN)。
还获得了LCO,LCO在HDS2装置中被脱硫且与HCO使用的用于沥青和FO的熔剂一起,被送至柴油池。
ETBE装置
向该装置加入购买的生物乙醇和异丁烯,以获得生物ETBE,将该生物ETBE送至烷基化装置(ALK),ALK的输出物烷基化产物流入汽油池。
异戊烷馏除装置
该装置的目的是从LVN液流中分离异戊烷且将其送至汽油池。将被馏除了异戊烷的LVN送至异构化装置。
重整装置
这两个重整装置(RC)的目的是增加重质直馏石脑油的辛烷值,制备送至汽油池的重整油且同时制备用于炼油的氢气。除了输入的原油外,描述的精炼循环还考虑使用可用于优化同一个循环的、购买的或炼油厂存储的、包括常压渣油、MTBE的半加工产物,以使汽油池和催化原料满足具体的需求。
下表分别示出可用的容量/使用的百分数(表2)和产物的物料平衡(表3):
表2:容量/使用
千吨/月;%使用 | 基本例示例1 |
CDU | 731.0(100%) |
VDU | 327.0(78%) |
柴油HDS 1 | 46.0(100%) |
煤油HDS 1 | 16.8(100%) |
HDS 2 | 144.0(100%) |
HDS 3 | 72.0(100%) |
EST | |
重整2 | 57.0(100%) |
重整3 | 75.0(100%) |
异构化 | 41.1(100%) |
氢气 | 6.0 |
烷基化 | 17.7(57%) |
ETBE | 3.6(57%) |
FCC | 159.0(60%) |
加氢裂化装置1 | 115.2(100%) |
加氢裂化装置2 | 115.2(100%) |
减粘裂化装置 | 153.0(73) |
BDA | 48.0(100%) |
气化 | 36.0(100%) |
表3:物料平衡
产物 千吨/月 | 742.1 |
合成气 | 35.7 |
燃料气 | |
LPG | 17.9 |
汽油 | 213.6 |
直馏石脑油FR | 13.6 |
煤油 | 79.0 |
柴油 | 344.2 |
O.C.ATZ/沥青 | 24.9 |
O.C.BTZ | 7.3 |
硫 | 5.9 |
原料 千吨/月 | 792 |
混合原油 | 731.0 |
常压渣油 | 7.5 |
MTBE | 8.1 |
催化原料 | 45.4 |
总C&P | 49.9 |
消耗 | 44.3 |
损失 | 5.7 |
相关的经济利润在表4中示出。
表4:经济结果
示例2(高效炼油厂,HER,以汽油、煤油和柴油为导向)。
该示例的参考方案在图2中示出。相对于复杂-循环炼油厂,负压蒸馏部件被用描述于以上已经提到的专利申请IT-MI2010A001989中的EST技术的、制成合适的尺寸以容纳所有常压渣油原料(AR)的反应器替代。
对于离开初馏装置的液流,可采用前述复杂-循环炼油厂的描述。来自EST部件(包括一个或多个加氢转化单元和产物的分离单元和吹扫单元)的输出液流由用于制备燃料气和LPG的C4-馏分、轻质直馏石脑油(LVN)、重质直馏石脑油(HVN)、柴油和适量扫气组成。
而将柴油送至脱硫单元且随后至柴油池,在异构化装置中处理轻质石脑油由此获得异构油(isomerate),且在重整装置中处理重质石脑油由此获得重整油。异构油与重整油流入汽油池。合适地增加脱硫装置HDS2和HDS3、异构化装置和重整装置RC3的容量以容纳来自EST装置的液流。
下表分别示出可用容量/使用的百分数(表5)和产物的物料平衡(表6):
表5:容量/使用
千吨/月;%使用 | 基本例 示例1 | HER 示例2 |
CDU | 731.0(100%) | 731.0(100%) |
VDU | 327.0(78%) | |
柴油HDS 1 | 46.0(100%) | 46.0(100%) |
煤油HDS 1 | 16.8(100%) | 16.8(100%) |
HDS 2 | 144.0(100%) | 347.0(100%) |
HDS 3 | 72.0(100%) | 76.0(100%) |
EST | 324.1(100%) | |
重整2 | 57.0(100%) | 57.0(100%) |
重整3 | 75.0(100%) | 84.3(100%) |
异构化 | 41.1(100%) | 67.1(100%) |
氢气 | 6.0 | 12.5 |
烷基化 | 17.7(57%) | |
ETBE | 3.6(57%) | |
FCC | 159.0(60%) | |
加氢裂化装置1 | 115.2(100%) | |
加氢裂化装置2 | 115.2(100%) | |
减粘裂化装置 | 153.0(73) | |
BDA | 48.0(100%) | |
气化 | 36.0(100%) |
表6:物料平衡
表7中示出的经济数据来自这些物料平衡。
表7:经济结果
示例3(高效炼油厂,RAE,以直馏石脑油、煤油和柴油为导向)。
在这种情况下,炼油方案更简单且提供于图3中。该炼油厂包括与以上示例2相同的EST部件,相同的液流从该EST部件排出,且在相同的操作条件下运行。因为轻质和重质VN全部用于石油化学,不再需要异构化单元和重整单元。这导致装置的显著简化和相关投资的由此降低。
下表分别示出可用容量/使用的百分数(表8)和产物的物料平衡(表9):
表8:容量/使用
千吨/月;%使用 | 基本例 示例1 | HER 示例2 |
CDU | 731.0(100%) | 731.0(100%) |
VDU | 327.0(78%) | |
柴油HDS 1 | 46.0(100%) | 46.0(100%) |
煤油HDS 1 | 16.8(100%) | 16.8(100%) |
HDS 2 | 144.0(100%) | 347.0(100%) |
HDS 3 | 72.0(100%) | 76.0(100%) |
EST | 324.1(100%) | |
重整2 | 57.0(100%) | |
重整3 | 75.0(100%) | |
异构化 | 41.1(100%) | |
氢气 | 6.0 | 12.5 |
烷基化 | 17.7(57%) | |
ETBE | 3.6(57%) | |
FCC | 159.0(60%) | |
加氢裂化装置1 | 115.2(100%) | |
加氢裂化装置2 | 115.2(100%) | |
减粘裂化装置 | 153.0(73) | |
BDA | 48.0(100%) | |
气化 | 36.0(100%) |
表9:物料平衡
表10中示出的经济数据来自这些物料平衡。
表10:经济结果
该示例说明了,同样在用于生产用于化学的直馏石脑油和柴油的情况下,相对于基本例,还相对于示例2,尽管单元操作的复杂性、数目和因此所需的投资已经被进一步降低,利润还是获得了高的增加。
示例4
EST的存在允许炼油厂接受比通过现代复杂-循环炼油厂通常处理的原料更重的原料,且这个机会进一步增加经济回报。所说明的炼油厂包括与以上示例2相同的EST部件,相同的液流从该EST部件排出,且在相同的操作条件下运行。这个示例提供了从高效炼油厂获得的结果,该高效炼油厂用于生产汽油和柴油,与示例1示出的基本例的结果相比,原料中仅具有ATZ原油。
该示例所用的原料表示如下(以千吨/月为单位):
高效炼油方案与示例2提供的相同。
下表分别示出可用容量/使用的百分数(表11)和产物的物料平衡(表12):
表11:容量/使用
千吨/月;%使用 | 基本例 示例1 | HER 示例4 |
CDU | 731.0(100%) | 731.0(100%) |
VDU | 327.0(78%) | |
柴油HDS 1 | 46.0(100%) | 60.0(100%) |
煤油HDS 1 | 16.8(100%) | |
HDS 2 | 144.0(100%) | 348.1(100%) |
HDS 3 | 72.0(100%) | 75.6(100%) |
EST | 356.5(100%) | |
重整2 | 57.0(100%) | 57.0(100%) |
重整3 | 75.0(100%) | 80.5(100%) |
异构化 | 41.1(100%) | 63.0(100%) |
氢气 | 6.0 | 13.7 |
烷基化 | 17.7(57%) | |
ETBE | 3.6(57%) | |
FCC | 159.0(60%) | |
加氢裂化装置1 | 115.2(100%) | |
加氢裂化装置2 | 115.2(100%) | |
减粘裂化装置 | 153.0(73) | |
BDA | 48.0(100%) | |
气化 | 36.0(100%) |
表12:物料平衡
表13中示出的经济数据来自这些物料平衡。
表13:经济结果
从这些结果中可以看出,相对于基本例,对于获得的产物,使用更低量的原油允许提高精炼利润,实现原料中的原油的更低成本。本发明的目的的方案的优点在于使ATZ原油和BTZ原油之间的价格差增加。随着市场上非常规原油(诸如,例如,Orinoco盆地的非常重质的原油或来自油砂和油页岩的原油)的出现,这个因素变得非常重要。
使用EST技术替代负压部件的本发明的另一个重要优点涉及消耗和损失(C&P)的显著降低,这导致排放至大气中的CO2的量更低。表14示出了总消耗和损失以及单位消耗和损失。相对于基本例,这些值是假定每吨未耗尽的等效石油的3.5t CO2值而估计的。
表14:CO
2
排放的降低-消耗和损失
示例 | 示例1 | 示例2 | 示例3 | 示例4 |
产物(千吨/月) | 742.1 | 702.5 | 707.8 | 701.6 |
总C&P(千吨/月) | 49.9 | 28.5 | 23.2 | 29.7 |
单位C&P(吨/千吨产物) | 67.2 | 40.6 | 32.8 | 42.3 |
与基本例的差Δ | - | -40% | -51% | -57% |
排放的较少CO2(吨/千吨产物) | - | 93.1 | 120.4 | 87.1 |
在示例2的情况下,CO2的排放低于68千吨/月。
Claims (9)
1.一种用于精炼原油的方法,包括所述原油的分离单元,所述分离单元由至少一个用于分离各种馏分的常压蒸馏单元、用于转化获得的重馏分的单元、用于通过对其成分的化学组分的作用而改进获得的一些馏分的质量的单元、和用于去除不希望的成分的单元组成,其特征在于将最重的馏分常压蒸馏渣油送至包括至少一个浆态床加氢转化反应器或流化床型加氢转化反应器的转化单元,其中在合适的纳米分散的加氢催化剂的存在下引入氢气或氢气与H2S的混合物,所述转化单元替代负压蒸馏部件。
2.根据权利要求1所述的方法,其中所述纳米分散的加氢催化剂基于Mo的硫化物和/或Fe的硫化物和/或W的硫化物和/或Cr的硫化物和/或Ni的硫化物和/或Co的硫化物及其混合物。
3.根据权利要求1所述的方法,其中,当所述加氢转化反应器为流化床型加氢转化反应器时,还存在合适的负载型多相加氢转化助催化剂。
4.根据权利要求1所述的方法,其中,当所述加氢转化反应器为浆态床加氢转化反应器时,还存在合适的负载型多相加氢转化助催化剂。
5.根据权利要求3或4所述的方法,其中所述助催化剂具有纳米级尺寸或微米级尺寸的颗粒,且选自裂化催化剂和/或脱氮催化剂。
6.根据权利要求1或4所述的方法,其中将所述蒸馏渣油送至一个或多个流化床加氢转化反应器,将来自所述反应器的流出液流送至分离步骤,其中被分离且包含纳米分散的催化剂的液体馏分被再循环至所述反应器。
7.根据权利要求1所述的方法,其中将所述蒸馏渣油送至至少一个固体累积浆态床加氢转化反应器,其中包括一种或多种具有合适的热汽提气体的汽提相,以获得汽相的转化产物。
8.根据权利要求1所述的方法,其中在基于钼的催化剂的存在下,将所述蒸馏渣油送至鼓泡塔型的固体累积浆态床加氢转化反应器,以在所述反应器中直接获得汽相的转化产物。
9.根据权利要求1所述的方法,其中将所述蒸馏渣油送至加氢转化反应器,其中在未转化的沥青质液体的分离之前或之后通过部分冷凝所述反应器的出口处的气相而获得的、和在所述未转化的沥青质液体再循环至所述反应器之前通过真空提取所述未转化的沥青质液体而可能获得的、沸点高于380℃的所述产物,被送回到所述加氢转化反应器,以使提取的所述转化产物在380℃下可被蒸馏至少60重量%。
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