CN101374598B - 用于石脑油加氢脱硫的具有高温氧化铝载体的选择性催化剂 - Google Patents
用于石脑油加氢脱硫的具有高温氧化铝载体的选择性催化剂 Download PDFInfo
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- CN101374598B CN101374598B CN200780003295.6A CN200780003295A CN101374598B CN 101374598 B CN101374598 B CN 101374598B CN 200780003295 A CN200780003295 A CN 200780003295A CN 101374598 B CN101374598 B CN 101374598B
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- catalyst
- alumina
- high temperature
- naphtha
- temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
本发明涉及用于石脑油加氢脱硫的催化剂和方法。更特别,CoMo金属加氢组份在分散剂参与情况下负载在高温氧化铝载体上以生产催化剂,随后其用作石脑油加氢脱硫。该高温氧化铝载体具有确定的表面积,使烯烃饱和度减到最少。
Description
发明领域
本发明涉及用于石脑油加氢脱硫的催化剂和方法。更特别地,CoMo金属加氢脱硫组份在有机添加剂参与情况下负载在高温氧化铝载体上以生产催化剂,在硫化作用之后,然后其用于石脑油加氢脱硫。该高温氧化铝载体具有确定的特性,使烯烃饱和度减到最少。
发明背景
环境保护法规要求降低车用汽油(mogas)中的硫含量。例如,人们预期到2006年条例将要求车用汽油硫含量为30ppm或更小。在许多情况下,通过加氢处理从流化催化裂化(FCC催化石脑油)生成的石脑油实现这样的硫含量,所述的流化催化裂化是车用汽油库中最大的硫来源。因为车用汽油中的硫还可以导致催化转化器性能的降低,因此甚至在其中条例许可较高水平的情况下,也希望硫目标(含量)为30ppm。因此,需要减少催化石脑油中的硫同时使有益性能例如辛烷值的减小降至最小的技术。
常规的固定床加氢处理能使裂化石脑油的硫含量降低到非常低的含量。然而,由于烯烃含量的大量减少,以及氢的过度消耗,这样的加氢处理同样导致严重的辛烷值损失。最近开发了选择性的加氢处理方法以避免显著的烯烃饱和度和辛烷值损失。令人遗憾地,在这样的过程中,释放的H2S与残留的烯烃反应通过返硫形成硫醇式硫。这样的方法可在苛刻(条件)下进行生产在硫条例规定之内的产物。然而,同样发生明显的辛烷值损失。
提出了一种用于在脱硫期间保持辛烷值的方法是利用烯烃改性的催化剂改善原料中的烯烃含量,随后与加氢脱硫(HDS)催化剂接触(美国专利6,602,405)。该烯烃改性的催化剂使烯烃齐聚。
最近开发的一种加氢脱硫方法是SCANfining,是由Exxonmobil公司开发的方法。SCANfining描述于National Petroleum RefinersAssociation paper(国家炼油厂联合会论文)#AM-99-31中,题目为“具有最小辛烷损失的选择性的催化石脑油的加氢精制”,和美国专利5,985,136和6,013,598中。典型的SCANfining条件包括用于使石脑油原料加氢脱硫的一步法和两步法。原料与加氢脱硫催化剂接触,所述的催化剂由约1wt%-约10wt%的MoO3和约0.1wt%-约5wt%的CoO组成;Co/Mo原子比约0.1-约1.0;和孔径中值为约-约
即使SCANfining可控制烯烃饱和度,同时实现高度的加氢脱硫,但仍需要改进该催化剂体系的选择性以进一步降低烯烃饱和度,因此进一步使辛烷值损失降至最小。
发明内容
本发明涉及一种适用于石脑油加氢脱硫(HDS)的催化剂,所述的催化剂通过如下方法制备,包括:(i)将氧化铝前体加热到大于至少约800℃的温度以形成高温氧化铝,用(a)钴盐、(b)钼盐和(c)至少一种有机添加剂的水溶液浸渍高温氧化铝以形成浸渍的高温氧化铝,条件是该高温氧化铝基于氧化铝总重量的γ、η和χ氧化铝含量小于约50wt%;中值孔径为约-约表面积为约40m2/g-约200m2/g;(ii)在小于约200℃的温度下干燥该浸渍的高温氧化铝以形成干燥的浸渍高温氧化铝催化剂前体;和(iii)硫化该干燥的浸渍高温氧化铝催化剂前体以形成加氢脱硫催化剂,条件是该加氢脱硫催化剂或者催化剂前体在硫化或者用于加氢脱硫之前未煅烧。
在优选实施方案中,该加氢脱硫催化剂前体基于催化剂载体包含约1wt%-约8wt%的钴,和基于催化剂载体约6wt%-约20wt%的钼。该加氢脱硫催化剂除其他的高温氧化铝例如δ、θ和κ之外,可以进一步包含α氧化铝。
另一个实施方式涉及制造加氢脱硫催化剂的方法,该催化剂通过如下制备:(i)将氧化铝前体加热到大于至少约800℃的温度以形成高温氧化铝;(ii)用(a)钴盐、(b)钼盐和(c)至少一种有机添加剂的水溶液浸渍高温氧化铝以形成浸渍的高温氧化铝,条件是该高温氧化铝基于氧化铝总重量的γ、θ、χ氧化铝含量小于约50wt%;中值孔径为约-约和表面积为约40m2/g-约200m2/g;(iii)在小于约200℃的温度下干燥该浸渍的高温氧化铝以形成干燥的浸渍高温氧化铝催化剂前体;和(iv)硫化该干燥的浸渍高温氧化铝催化剂前体以形成加氢脱硫催化剂,条件是该加氢脱硫催化剂或者催化剂前体在硫化或者用于加氢脱硫之前未煅烧。
另一个实施方式涉及加氢脱硫基于石脑油重量的烯烃含量至少约5wt%的石脑油的方法,包括:(i)使石脑油与加氢脱硫催化剂在加氢脱硫条件下接触,其中该催化剂通过以下制备,即将氧化铝前体加热到大于至少约800℃的温度以形成高温氧化铝;用(a)钴盐、(b)钼盐和(c)至少一种有机添加剂的水溶液浸渍高温氧化铝以形成浸渍的高温氧化铝,条件是该高温氧化铝基于氧化铝总重量的γ、θ和χ氧化铝含量小于约50wt%;中值孔径为约-约表面积为约40m2/g-约200m2/g;(ii)在小于约200℃的温度下干燥该浸渍的高温氧化铝以形成干燥的浸渍高温氧化铝催化剂前体;和(iii)硫化该干燥的浸渍高温氧化铝催化剂前体以形成加氢脱硫催化剂,条件是该加氢脱硫催化剂或者催化剂前体在硫化或者用于加氢脱硫之前未煅烧。
该加氢脱硫催化剂,当用于石脑油加氢脱硫时,显示出对于烯烃饱和度改进的选择性,同时保持石脑油原料的高水平加氢脱硫。
附图简述
附图1是实施例1-5的煅烧载体的x-射线衍射图样。
附图2是说明实施例2通过Hg孔隙率测定法的孔径分布曲线。
附图3是说明实施例3通过Hg孔隙率测定法的孔径分布曲线。
附图4是说明实施例4通过Hg孔隙率测定法的孔径分布曲线。
附图5是说明实施例5通过Hg孔隙率测定法的孔径分布曲线。
附图6是实施例6的载体的x-射线衍射图样。
附图8是说明在90%加氢脱硫转化率下C5烯烃饱和度的百分比相对用于制备实施例12催化剂的氧化铝载体的中值孔径(基于Hg侵入孔面积)的曲线变化图。
附图9是说明在90%加氢脱硫转化率下C5烯烃饱和度的百分比相对用于制备实施例12催化剂的氧化铝载体的(1/中值孔径)的曲线变化图。
本发明的详细说明
术语“石脑油”用来指中间沸程的碳氢化合物馏分或者主要组分为汽油的馏分,而术语“FCC石脑油”指优选的通过众所周知的流化催化裂化过程生成的石脑油。具有中间沸程的石脑油是在大气压力下沸点从约10℃(即从约C5)到约232℃(50°F-450°F),优选从约21℃到约221℃(70-430°F)的那些。在没有加入氢的情况下,在FCC工艺中生产石脑油会导致相对高烯烃和芳烃的石脑油。其他的石脑油例如蒸汽裂化石脑油和焦化石脑油也可以包含相对高浓度的烯烃。典型的烯烃石脑油基于石脑油重量,烯烃含量至少为约5wt%,最高达约60wt%,优选为约5wt%-约40wt%wt%;基于石脑油重量硫含量为约300ppmw-约7000ppmw;和基于石脑油重量氮含量为约5ppmw-约500ppmw。烯烃包括开链烯烃、环状的烯烃、二烯和具有烯烃侧链的环烃。因为烯烃和芳烃是高辛烷值的组份,烯烃石脑油通常比加氢裂化石脑油呈现更高的研究法和马达法辛烷值。同时烯烃石脑油通常烯烃含量高,它们也可以包含其他的化合物,尤其是含硫和含氮化合物。
选择性的催化剂
使用高温氧化铝作为载体材料制备从烯烃石脑油中选择性脱硫,同时使烯烃饱和度最小的催化剂。高温氧化铝是中等到高表面积(从约40m2/g-约200m2/g)的大孔氧化铝。α氧化铝是最稳定的高温氧化铝相,因为当其他的氧化铝相被加热到足够高的温度例如约1000℃-约1200℃或以上的温度时,形成α氧化铝。因此,氧化铝前体例如勃姆石或者假勃姆石(AlO(OH)和拜耳石或者三水铝矿(A1(OH)3),当被加热到渐增的高温时,从不同的氧化铝相转化为α相。一般认为相变与温度升高有联系,从勃姆石起变化如下:勃姆石→γ氧化铝/χ氧化铝→δ氧化铝/θ氧化铝→α氧化铝。相变与温度升高有联系,从三水铝矿起变化如下:三水铝矿→χ氧化铝→κ氧化铝→α氧化铝。相变与温度升高有联系,从拜耳石起变化如下:拜耳石→η氧化铝→θ氧化铝→α氧化铝。正如以上所指出的,α氧化铝是加热其他的氧化铝相例如γ、χ、η、δ、κ和θ的终止相。如本发明使用的,高温氧化铝意思是包含θ、δ、κ和α氧化铝的氧化铝,和它们仅含有少量γ、χ或者η相氧化铝的混合物。基于氧化铝重量,γ、χ和η氧化铝的总和小于约50wt%,优选小于约30wt%,更优选小于约20wt%。在实施方式中,基于氧化铝总重量,高温氧化铝包含大于约50wt%的θ、κ、δ和α氧化铝的至少一种,优选大于约70wt%,更优选大于约80wt%。
本发明的高温氧化铝可通过加热前体例如γ氧化铝、拜耳石、三水铝矿和/或勃姆石到大于约800℃的温度制备。使用的温度同样是初相性质以及加热时间的函数,控制时间以达到希望的相。因此,制备的高温氧化铝优选主要是θ、κ和α氧化铝的混合物,更优选主要是θ和α氧化铝的混合物。主要的意思是指,指定组份或者指定的多种组份的重量占大于约50%混合物的重量。还注意到用蒸汽加热可用于生产高温氧化铝。例如,在大约95%的湿度下,在大约1000℃下,汽蒸氧化铝前体一小时产生纯θ相材料。能使用的其他的用于制备高温氧化铝的方法,包括常规方法,能提供具有描述特性的高温氧化铝。
氧化铝相通过x-射线衍射技术确定。每一不同的相具有通过基本峰强度与d-间距确定的特性x-射线衍射图样。因此,x-射线衍射可用于证实已经制造的高温氧化铝。
然后,用(a)钴盐、(b)钼盐和(c)一种或多种有机添加剂例如有机配位体的混合物浸渍该高温氧化铝载体。用于浸渍氧化铝载体的钴和钼盐可以是任何的水溶性盐。优选的盐包括碳酸盐、硝酸盐、七钼酸盐等。盐的量是如此以致氧化铝载体基于载体的重量包含约2wt%-约8wt%,优选约3wt%-约6wt%的氧化钴(CoO),和约8wt%-约30wt%,优选约10wt%-约25wt%的氧化钼(MoO3)。
有机配位体是认为有助于在二氧化硅载体上分布Co和Mo组份的有机添加剂。该有机添加剂包含氧和/或氮原子,并包括单齿、双齿和多齿配位体。该有机添加剂(配位体)也可以是螯合剂。有机配位体包括羧酸、多羟基化合物、氨基酸、胺、氨基醇、酮、酯等的至少一种。有机配位体的例子包括菲咯啉、羟基喹啉、水杨酸、乙酸、乙二胺四乙酸(EDTA)、环己二胺四乙酸(CYDTA)、丙氨酸、精氨酸、三乙醇胺(TEA)、甘油、组氨酸、乙酰丙酮化物、胍、和次氮基三乙酸(NTA)、柠檬酸和脲。
该高温氧化铝载体具有大的孔体积,所述的体积通过使用ASTm方法D4284,使用约140度的接触角,通过水银孔率法测量。孔体积为约0.3立方厘米/g-约1.5立方厘米/g,优选约0.5立方厘米/g-约1.5立方厘米/g。通过汞侵入体积测量的中值孔径为约-约优选约-约通过使用氮的BET法测量的表面积为约40m2/g-约200m2/g,优选约40m2/g-约150m2/g。
尽管不希望束缚于任何特定的理论,但认为本发明的具有大孔径的高温氧化铝载体,当与有机配位体例如精氨酸、柠檬酸和脲结合时,并经不太苛刻的干燥,得到具有对于烯烃饱和度希望选择性的加氢脱硫催化剂,同时保持加氢脱硫催化剂用于石脑油原料脱硫的活性。认为有机配位体有助于使金属有效地分散在整个氧化铝载体中,这反过来是本发明催化剂所呈现的选择性增加的一个因素。
该高温氧化铝载体也可以掺杂有基于IUPAC版式具有1-18族周期表的第2-4族的金属,优选第2和4族的金属。这样的金属例子包括Zr、Mg、Ti,例如见The Merck Index,Twelfth Edition,Merck & Co.,Inc.,1996。
催化剂制备和应用
使用常规方法即加氢处理催化剂设计、合成、生产和/或应用领域的本领域的普通技术人员熟知的技术,用Co和Mo盐水溶液浸渍高温氧化铝载体。该有机配位体可以加入到盐的水溶液中,之后与该氧化铝载体接触。用金属盐浸渍氧化铝载体的一种实施方式是通过初始湿润方法进行。在该方法中,使用常规方法,包含金属盐和有机添加剂的水溶液与载体混合达到初始湿润点。
通过金属盐浸渍该氧化铝载体的方式包括用钴盐和有机配位体的混合物使用初始湿润法浸渍该氧化铝载体,干燥该浸渍的载体,然后用钼盐溶液或者包含有机配位体的钼盐溶液浸渍该干燥的载体,达到初始湿润点。在另一个实施方式中,通过钴盐随后通过钼盐的浸渍次序可以相反。在又一个实施方式中,该载体可以用钴盐和钼盐加上有机配位体的混合物共浸渍到初始湿润。该共浸渍的载体可以干燥,并重复共浸渍过程。在又一个实施方式中,用钴盐、钼盐和有机配位体的混合物浸渍挤出的氧化铝载体,并干燥浸渍的载体。如果希望,可以重复该处理。在上述所有的实施方式中,该有机配位体可以是单配位体或者可以是配位体的混合物。加热从反应混合物中分离的浸渍的氧化铝载体,在约50℃-约200℃的温度下干燥以形成催化剂前体。干燥可以在真空下、或者在空气中或者惰性气体例如氮中进行。
在足以使金属氧化物、金属盐或者金属络合物转变为相应硫化物的温度下,用基于存在的气体总体积,浓度为约0.1体积%-约10体积%硫化氢处理干燥催化剂前体一段时间,以形成加氢脱硫催化剂。硫化氢可以通过在催化剂前体中或者在催化剂前体上引入硫化剂产生。在一个实施方式中,硫化剂与稀释剂结合。例如,二甲基二硫化物能与石脑油稀释剂混合在一起。可以使用更少量的硫化氢,但是这会延长活化需要的时间。可以存在惰性载体,活化可以液相或者气相方式进行。惰性载体的例子包括氮和轻质烃例如甲烷。如果存在,则惰性气体作为气体总体积的一部分包括在内。温度为约150℃-约700℃,优选约160℃-约343℃。在活化期间,该温度可以保持恒定,或者可以通过从较低的温度开始并增加温度的方式升高。总压为最高达约5000psig(34576kPa),优选约0psig-约5000psig(101-34576kPa),更优选约50psig-约2500psig(446-17338kPa)。如果存在液态的载体,则液时空速(LHSV)为约0.1hr-1-约12hr-1,优选约0.1h-1-约5hr-1。该液时空速针对连续方式。然而,活化也可以以分批地方式进行。总的气体速率为约89m3/m3-约890m3/m3(500-5000scf/B)。
催化剂可以原位或者非原位进行硫化。硫化可以通过使催化剂与硫化剂接触进行硫化,并可以用液相或者气相的硫化剂进行硫化。或者,可以预硫化该催化剂因此在硫化期间可以产生H2S。在液相硫化剂中,要硫化的催化剂与包含硫化剂的载液接触。可以将硫化剂加入到载液中,或者该载液本身可以为硫化剂。该载液优选是未用过的碳氢化合物物流,可以是要与加氢处理催化剂接触的原料,但是可以是任意的碳氢化合物物流,例如来源于矿物(石油)或者合成源的馏出物。如果硫化剂加入到载液中,则硫化剂本身可以是在活化条件下能够生成硫化氢的气体或者液体。例子包括硫化氢,氧硫化碳,二硫化碳,硫化物例如二甲基硫化物,二硫化物例如二甲基二硫化物,和多硫化物例如二-叔-壬基多硫化物。存在于某些原料例如石油原料中的硫化物,可以作为硫化剂,并包括各式各样的能够生成硫化氢的含硫物质,包括脂族、芳香族和杂环化合物。
该干燥催化剂在硫化或者用于加氢脱硫之前不被煅烧。不煅烧意思是该干燥催化剂不被加热到大于约300℃,优选约200℃的温度。通过不煅烧催化剂,在硫化或者用于加氢脱硫之前约60%-约100%的分散助剂留存在催化剂上。
硫化之后,催化剂在加氢脱硫的条件下可以与石脑油接触。加氢脱硫的条件包括温度约150℃-约400℃,压力为约445kpa-约13890kpa(50-2000psig),液时空速约0.1-约12,氢处理气体速率为约89m3/m3-约890m3/m3(500-5000scf/B)。在加氢脱硫之后,脱硫石脑油可被导出用于储藏或者进一步处理加工,例如汽提除去硫化氢。脱硫石脑油可用于与其他的石脑油沸程的烃共混以制造车用汽油。
在以下实施例中描述实施方案,包括优选实施方案。
实施例1-5
通过混合Versal-300(UOP)和作为有机填料的30%的Avicel(FMC)和2%的HNO3,随后通过1/20″四叶草形模头挤出,制备用作载体的氧化铝挤出物。得到的挤出物使用不同的温度、时间和部分蒸汽条件煅烧,生产实施例1-实施例5的氧化铝载体。具体的煅烧条件、氧化铝相的鉴定、通过N2测量的BET表面积和通过Hg测量的孔体积/直径列在表1中。这些煅烧氧化铝载体的x射线衍射图样显示于附图1中。使用铜阳极。强度结果相对散射角(2θ)绘图。附图2-5说明通过压汞测量的实施例2、3、4和5的孔径分布。
表1
实施例# | VersaI-300氧化铝载体 | 氧化铝相 | SA,m2/g | Hg PV,cc/g | 中值孔径(Hg面积) | 中值孔径(Hg体积) | SC# |
1 | Versal/400℃/1 hr煅烧 | γ(宽) | 340 | 0.81 | 67 | 94 | 1369 |
2 | VersaI/800℃/8 hr煅烧 | γ(纯) | 199 | 0.82 | 102 | 126 | 1371 |
3 | Versal/1000℃/1 hr煅烧 | θ+δ | 143 | 0.75 | 143 | 175 | 1373(1247) |
4 | Versal/1000℃/1 hr蒸汽(95%)煅烧 | θ(纯) | 86 | 0.78 | 256 | 307 | 1375 |
5 | Versal/1100℃/10 hr煅烧 | α(主要)+θ | 43 | 0.59 | 285 | 805 | 1378 |
实施例6
如实施例1-5中描述的,通过x-射线衍射技术试验包含混合θ和α氧化铝相的市售氧化铝载体(Norpro SA31132)。附图6是载体的x-射线衍射图样。附图7是孔径分布的对数-对数曲线变化图。附图7显示基于Hg侵入体积的孔径分布。基于压汞体积确定的中值孔径是而基于孔面积确定的中值孔径是载体通过N2BET法测量的表面积为62m2/g,通过汞(ASTM-D 4284方法)测量的孔体积为0.77cc/g。通过将8.34g脲和4.20g柠檬酸一水化物溶解在10ml的水中,随后溶解2.13g的碳酸钴水合物(46.2%Co)和6.13g的七钼酸铵制备浸渍溶液。使用初始湿润浸渍技术将浸渍溶液加入到氧化铝载体中。在110℃下干燥浸渍催化剂,并在没有煅烧的情况下用于硫化作用和加氢脱硫评价。浸渍的固体基于干基包含3.9wt%的CoO和15.5wt%的MoO3。
实施例7-11
使用柠檬酸和脲作为有机添加剂用Co和Mo盐浸渍实施例1-5的氧化铝载体。如实施例6描述的进行浸渍和干燥。表2列出干催化剂前体的金属含量。
表2
实施例# | 实施例载体# | 载体SC# | MoO3 | CoO |
7 | 1 | 1369 | 18.1 | 4.5 |
8 | 2 | 1371 | 19.6 | 4.9 |
9 | 3 | 1373 | 16.8 | 4.2 |
10 | 4 | 1375 | 17.5 | 4.4 |
11 | 5 | 1378 | 15.5 | 3.9 |
实施例12
硫化实施例6-11的催化剂前体并与市场上可买到的参比CoMo/Al2O3催化剂(RT-225)平行地进行催化石脑油加氢脱硫选择性试验。使用在H2和直馏石脑油中3%的H2S硫化催化剂前体。用于催化剂评价的原料是C5-177℃(350°F)的包含1408ppm的S和46.3%烯烃的FCC石脑油原料。在MCFB-48装置(多通道固定床-48反应器)中,在274℃(525°F)、220psig下,使用H2评价催化剂。调整原料流速实现65%-95%的2-甲基噻吩脱硫。使用在线GCs和SCDs分析产品流。产物中C5烯烃含量与原料中C5烯烃含量相比以计算烯烃饱和度的百分比(%OSAT)。在物流上约30小时的催化剂运转之后,加氢脱硫%和OSAT%的结果稳定,并用于评价在不同的加氢脱硫转化率(%HDS)下烯烃的饱和度(%OSAT)。
附图8绘制在90%加氢脱硫转化率下C5烯烃饱和度的百分比相对用于制备实施例12催化剂的氧化铝载体的中值孔径(基于Hg侵入孔面积)的曲线变化图。在相同条件下试验中值孔径为的商品催化剂,在90%加氢脱硫转化率下显示出14wt%的C5烯烃饱和度。将商品催化剂和基于在较低温度下形成的氧化铝(实施例7和8的前体)的催化剂对比,本发明有创造性的负载在高温氧化铝上的催化剂具有更低的烯烃饱和度。
附图9绘制在90%加氢脱硫转化率下的C5烯烃饱和度百分比相对用于制备实施例12催化剂的氧化铝载体的(1/中值孔径)的曲线变化图。
Claims (32)
1.一种用于石脑油的选择性加氢脱硫(HDS)的催化剂,所述的催化剂通过如下方法制备,包括:
(i)将氧化铝前体加热到大于至少800℃的温度以形成高温氧化铝,用(a)钴盐、(b)钼盐和(c)至少一种有机添加剂的水溶液浸渍高温氧化铝以形成浸渍的高温氧化铝,条件是该高温氧化铝基于氧化铝总重量的γ、η和χ氧化铝含量小于30wt%;中值孔径为;使用氮的BET法测量的表面积为40m2/g-200m2/g;
(ii)在小于200℃的温度下干燥该浸渍的高温氧化铝以形成干燥的浸渍高温氧化铝催化剂前体;和
(iii)硫化该干燥的浸渍高温氧化铝催化剂前体以形成加氢脱硫催化剂,条件是该加氢脱硫催化剂或者催化剂前体在硫化或者用于加氢脱硫之前未煅烧,
其中所述干燥的催化剂前体或者硫化的催化剂在硫化或者用于加氢脱硫之前不被加热到大于300℃的温度,其中所述有机添加剂是有机配位体。
2.制造权利要求1的选择性加氢脱硫催化剂的方法,该方法包括如下步骤:
(i)将氧化铝前体加热到大于至少800℃的温度以形成高温氧化铝;
(ii)用(a)钴盐、(b)钼盐和(c)至少一种有机添加剂的水溶液浸渍高温氧化铝以形成浸渍的高温氧化铝,条件是该高温氧化铝基于氧化铝总重量的γ、η和χ氧化铝含量小于30wt%;中值孔径为;和使用氮的BET法测量的表面积为40m2/g-200m2/g;
(iii)在小于200℃的温度下干燥该浸渍的高温氧化铝以形成干燥的浸渍高温氧化铝催化剂前体;和
(iv)硫化该干燥的浸渍高温氧化铝催化剂前体以形成加氢脱硫催化剂,条件是该加氢脱硫催化剂或者催化剂前体在硫化或者用于加氢脱硫之前未煅烧,
其中所述干燥的催化剂前体或者硫化的催化剂在硫化或者用于加氢脱硫之前不被加热到大于300℃的温度,其中所述有机添加剂是有机配位体。
3.一种用于选择性加氢脱硫基于石脑油重量的烯烃含量至少为5wt%的石脑油的方法,包括:
(i)使石脑油与加氢脱硫催化剂在加氢脱硫条件下接触,其中该催化剂通过以下制备,将氧化铝前体加热到大于至少800℃的温度以形成高温氧化铝,用(a)钴盐、(b)钼盐和(c)至少一种有机添加剂的水溶液浸渍高温氧化铝以形成浸渍的高温氧化铝,条件是该高温氧化铝基于氧化铝总重量的γ、η和χ氧化铝含量小于30wt%;中值孔径为;使用氮的BET法测量的表面积为40m2/g-200m2/g;
(ii)在小于200℃的温度下干燥该浸渍的高温氧化铝以形成干燥的浸渍高温氧化铝催化剂前体;和
(iii)硫化该干燥的浸渍高温氧化铝催化剂前体以形成加氢脱硫催化剂,条件是该加氢脱硫催化剂或者催化剂前体在硫化或者用于加氢脱硫之前未煅烧,
其中所述干燥的催化剂前体或者硫化的催化剂在硫化或者用于加氢脱硫之前不被加热到大于300℃的温度,其中所述有机添加剂是有机配位体。
4.权利要求1的催化剂,其中高温氧化铝包括θ、δ、κ和α氧化铝的至少一种。
5.权利要求4的催化剂,其中高温氧化铝的量基于氧化铝总量大于70wt%。
6.权利要求5的催化剂,其中高温氧化铝的量基于氧化铝总量大于80wt%。
8.权利要求1的催化剂,其中通过使用ASTM方法D4284,使用140度的接触角,通过水银孔率法测量的孔体积为0.3cc/g-1.5cc/g。
9.权利要求1的催化剂,其中使用氮的BET法测量的表面积为40m2/g-150m2/g。
10.权利要求3的方法,其中该石脑油是FCC石脑油、蒸汽裂化石脑油或者焦化石脑油的至少一种。
11.权利要求3的方法,其中基于石脑油,该石脑油的烯烃含量为5wt%-60wt%,含氮量为5ppmw-500ppmw,硫含量为300ppmw-7000ppmw。
12.权利要求1的催化剂,其中钴盐和钼盐的量要足以使催化剂载体包含基于氧化铝载体1wt%-8wt%的钴和6wt%-20wt%的钼。
13.权利要求1的催化剂,其中该有机配位体是单齿、双齿或者多齿配位体。
14.权利要求13的催化剂,其中该有机配位体是羧酸、多元醇、氨基酸、胺、酰胺、氨基醇、酮或者酯的至少一种。
15.权利要求14的催化剂,其中该有机配位体是菲咯啉、羟基喹啉、水杨酸、乙酸、乙二胺四乙酸(EDTA)、环己二胺四乙酸(CYDTA)、丙氨酸、精氨酸、三乙醇胺(TEA)、甘油、组氨酸、乙酰丙酮化物、胍、次氮基三乙酸(NTA)、柠檬酸或者脲的至少一种。
16.权利要求1的催化剂,其中该催化剂前体在50℃-200℃的温度下干燥。
17.权利要求1的催化剂,其中所述催化剂前体在有至少一种硫化剂参与情况下被原位或者非原位硫化。
18.权利要求17的催化剂,其中硫化剂是基于存在的气体总体积浓度为0.1体积%-10体积%的硫化氢。
19.权利要求3的方法,其中加氢脱硫的条件包括温度150℃-400℃,压力为445kPa-13890kPa(50-2000psig),液时空速0.1-12,氢处理气体速率为89m3/m3-890m3/m3(500-5000scf/B)。
20.权利要求2或3的方法,其中所述高温氧化铝包括θ、δ、κ和α氧化铝的至少一种。
21.权利要求20的方法,其中所述高温氧化铝的量基于氧化铝总量大于70wt%。
22.权利要求21的方法,其中所述高温氧化铝的量基于氧化铝总量大于80wt%。
23.权利要求2或3的方法,其中所述中值孔径为。
24.权利要求2或3的方法,其中所述通过使用ASTM方法D4284,使用140度的接触角,通过水银孔率法测量的孔体积为0.3cc/g-1.5cc/g。
25.权利要求2或3的方法,其中所述使用氮的BET法测量的表面积为40m2/g-150m2/g。
26.权利要求2或3的方法,其中所述钴盐和钼盐的量要足以使催化剂载体包含基于氧化铝载体1wt%-8wt%的钴和6wt%-20wt%的钼。
27.权利要求2或3的方法,其中所述有机配位体是单齿、双齿或者多齿配位体。
28.权利要求27的方法,其中所述有机配位体是羧酸、多元醇、氨基酸、胺、酰胺、氨基醇、酮或者酯的至少一种。
29.权利要求28的方法,其中所述有机配位体是菲咯啉、羟基喹啉、水杨酸、乙酸、乙二胺四乙酸(EDTA)、环己二胺四乙酸(CYDTA)、丙氨酸、精氨酸、三乙醇胺(TEA)、甘油、组氨酸、乙酰丙酮化物、胍、次氮基三乙酸(NTA)、柠檬酸或者脲的至少一种。
30.权利要求2或3的方法,其中所述催化剂前体在50℃-200℃的温度下干燥。
31.权利要求2或3的方法,其中所述催化剂前体在有至少一种硫化剂参与情况下被原位或者非原位硫化。
32.权利要求32的方法,其中所述硫化剂是基于存在的气体总体积浓度为0.1体积%-10体积%的硫化氢。
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PCT/US2007/001000 WO2007084437A2 (en) | 2006-01-17 | 2007-01-12 | Selective catalysts having high temperature alumina supports for naphtha hydrodesulfurization |
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