CN1671825A - 液体烃类脱硫的方法和生产用于燃料电池的氢的方法 - Google Patents
液体烃类脱硫的方法和生产用于燃料电池的氢的方法 Download PDFInfo
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- CN1671825A CN1671825A CNA038173964A CN03817396A CN1671825A CN 1671825 A CN1671825 A CN 1671825A CN A038173964 A CNA038173964 A CN A038173964A CN 03817396 A CN03817396 A CN 03817396A CN 1671825 A CN1671825 A CN 1671825A
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- Prior art keywords
- ope
- desulfurization
- sweetening agent
- kerosene
- hydrogen
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Links
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
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- 150000002815 nickel Chemical class 0.000 description 1
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Classifications
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/04—Metals, or metals deposited on a carrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
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Abstract
本发明提供一种将脱硫剂用于液体烃类例如煤油的最佳方法,所述的方法可在不外加氢的条件下从煤油中有效除去硫含量达到低的硫浓度,以及所述的方法有较长的寿命。本发明提供一种包括使用金属脱硫剂在不外加氢的条件下从液体烃类中除去硫含量的脱硫方法,其特征在于,所述的方法使用能满足以下式(1)的脱硫条件:1.06×Pope 0.44<Tope/T50<1.78×Pope 0.22……(1)(式中Tope为操作温度(℃);Pope为操作压力(兆帕)和T50为JISK2254“石油产品—蒸馏特性的测定”中规定的“常压蒸馏的试验方法”中测定的每回收50%的温度)。
Description
技术领域
本发明涉及一种使用金属脱硫剂从液体烃类中有效地除去硫和含硫化合物(下文统称为硫含量)达到低浓度的方法,以及涉及一种生产用于燃料电池的氢的方法。
背景技术
近年来,从环境问题的观点出发,新型的能源生产技术已引起注意;在这些技术中,燃料电池引起特别的兴趣。燃料电池通过氢和氧的电化学反应将化学能转化成电能,得到高的能源利用效率。所以,在燃料电池用于民用、工业用、汽车用等方面已进行了广泛研究。
燃料电池按使用电解质的类型分类,其中已知磷酸盐类、熔融碳酸盐类、固体氧化物类和固体聚合物类。就氢源来说,研究集中在甲醇;主要含甲烷的液化天然气;主要含天然气的城市气体;天然气用作原料生产的合成液体燃料;和石油生产的烃类,例如石油生产的液化石油气、石脑油和煤油。
根据燃料电池的应用(例如民用或汽车用),上述石油生产的烃类,尤其是煤油、瓦斯油和汽油优选用作氢源,因为这些烃类在环境温度和压力下为液体,易于贮存和处理,并很好地建立了各种供应***(例如汽油站和服务站)。
当由石油生产的烃类生产氢时,烃类通常在转化催化剂存在下进行自热转化、水蒸汽转化或部分氧化转化。在这样的转化过程中,上述转化催化剂被烃类中的硫含量中毒。因此,从催化剂使用寿命的观点出发的一个关键问题是,烃类应脱硫到低的硫浓度。
当商业煤油产品转化以便生产用于燃料电池的氢时,为了防止转化催化剂被煤油中毒,在长时期内煤油中的硫含量必需下降到0.2ppm或更低、优选0.1ppm或更低。
在生产脱硫煤油的工业方法中,通常使用加氢脱硫。在这种方法的一个实施方案中,使用加氢脱硫催化剂例如Co-Mo/氧化铝或Ni-Mo/氧化铝以及H2S吸附剂例如ZnO在常压至5兆帕和200-400℃下进行加氢脱硫。但是,这一方法存在一些缺点。具体地说,氢必需循环,因此需要复杂的设备来生产燃料电池用燃料油。此外,公用工程(utilities)的消耗增加。在小型燃料电池体系中,用于生产燃料电池用燃料油的加氢脱硫使这一体系变得很复杂。所以,需要一种不需外加氢的脱硫体系。
同时,已知镍基或镍-铜基的吸附剂(脱硫剂)为在缓和条件下通过吸附而不进行加氢转化就能从石油生产的烃类中除去硫含量的脱硫剂,以致使硫浓度下降到0.2ppm或更低(日本专利公报(kokoku)6-65602、7-115842和7-115843;日本专利申请公开(kokai)1-188405、2-275701、2-204301、5-70780、6-80972、6-91173和6-228570(镍基的吸附剂);和日本专利申请公开(kokai)6-315628(镍-铜基的吸附剂)
已提出了使用上述镍基的或镍-铜基的脱硫剂将煤油脱硫的各种脱硫条件。但是,虽然用作原料的煤油的质量随生产方法变化,但是迄今还不清楚作为原料的煤油的质量和最佳脱硫条件之间的关系。因此,迄今还未达到这些脱硫剂的最大性能。此外,对于汽油馏分或瓦斯油馏分用作原料的情况来说,详细的脱硫条件还未公开。
其中,上述日本专利公报(kokoku)6-65602和7-115842公开了使用镍基的脱硫剂在没有外加氢的条件下使煤油脱硫的方法,还公开了脱硫反应条件。但是,这些专利都未详细公开由煤油质量适当确定的最佳脱硫条件。
上述日本专利申请公开(kokai)1-188405也公开了一种使用镍基的脱硫剂在没有外加氢的条件下使煤油脱硫的方法,以及脱硫反应条件。但是,在这里公开的反应条件通过简单地加宽上述的日本专利公报(kokoku)6-65602中公开的反应条件的范围来得到。因此,与上述情况类似,所述专利并未详细公开由煤油质量适当确定的最佳脱硫条件。
在日本专利公报(kokoku)6-65602的实施例中以及在日本专利申请公开(kokai)1-188405中使用的煤油原料其质量几乎相同,但脱硫的最佳温度范围不同。据认为这一不一致是由于煤油质量和最佳脱硫条件之间的关系不清楚造成的。
上述日本专利公报(kokoku)7-115843还公开了一种使用镍基的脱硫剂在没有外加氢的条件下使煤油脱硫的方法,以及脱硫条件的最佳范围。但是,该专利公报包括日本专利公报(kokoku)6-65602和7-115842和日本专利申请公开(kokai)1-188405中公开的条件范围,而没有包括新的信息。此外,该专利公报未公开煤油质量和最佳脱硫条件之间的关系。
除了上述专利公开物外,日本专利申请公开(kokai)2001-342466、2001-342465、2001-279274、2001-279281、2001-279260、2001-279259、2001-279257、2001-279255、2001-278602、2001-276605和2001-252556(已由本申请人提交)也公开了使用镍基的脱硫剂在没有外加氢的条件下使煤油脱硫的方法,以及脱硫反应条件。但是,未说明煤油质量和适合于该质量的最佳脱硫条件之间的关系。
发明内容
考虑到上述内容,本发明的一个目的是要提供一种将脱硫剂用于液体烃类例如煤油的最佳方法,所述的方法可从液体烃油例如煤油中有效除去硫含量达到低的硫浓度,优选不外加氢,以及所述的方法有较长的寿命。
本发明人已就液体烃油例如煤油的质量和脱硫性能之间的关系进行了广泛的研究,并已发现液体烃类的蒸馏特性和烃类的最佳脱硫条件之间存在特定的关系。本发明已在这一发现的基础上完成。
因此,本发明提供以下内容。
1.一种脱硫方法,包括使用金属脱硫剂从液体烃类中除去硫含量,其特征在于,所述的方法使用能满足下式(1)的脱硫条件:
1.06×Pope 0.44<Tope/T50<1.78×Pope 0.22……(1)
(式中Tope为操作温度(℃);Pope为操作压力(兆帕)和T50为JISK2254“石油产品—蒸馏特性的测定”中规定的“常压蒸馏的试验方法”中测定的每回收50%的温度。)
2.在上述项目1中描述的脱硫方法,其中脱硫条件满足下式(2)的脱硫条件:
1.19×Pope 0.35<Tope/T50<1.68×Pope 0.24……(2)
(式中Tope、Pope和T50与上述项目1中规定的相同。)
3.在上述项目1或2中描述的脱硫方法,其中所述的方法不用外加氢。
4.在上述项目1-3中任一项描述的脱硫方法,其中金属脱硫剂包含多孔的无机氧化物和负载其上的至少包括镍(Ni)的金属元素。
5.在上述项目4中描述的脱硫方法,其中金属脱硫剂为一种基于镍-铜的脱硫剂。
6.在上述项目1-5中任一项描述的脱硫方法,其中液体烃类为选自汽油馏分、煤油馏分和瓦斯油馏分中的一种。
7.一种生产用于燃料电池的氢的方法,其特征在于,所述的方法包括转化通过上述项目1-6中任一项描述的脱硫方法已进行脱硫的液体烃类。
8.在上述项目7中描述的生产用于燃料电池的氢的方法,其中所述的转化为部分氧化转化、自热转化或水蒸汽转化。
9.在上述项目8中描述的生产用于燃料电池的氢的方法,其中部分氧化转化、自热转化或水蒸汽转化在含有钌或镍的转化催化剂存在下进行。
10.在上述项目9中描述的生产用于燃料电池的氢的方法,其中转化催化剂含有氧化锰、氧化铈或氧化锆。
实施本发明的最好方式
下文将详细描述本发明。
本发明的脱硫方法包括使用金属脱硫剂在不外加氢的条件下从液体烃类中除去硫含量,其特征在于,所述的方法使用能满足下式(1)的脱硫条件:
1.06×Pope 0.44<Tope/T50<1.78×Pope 0.22……(1)
(式中Tope为操作温度(℃);Pope为操作压力(兆帕)和T50为JISK2254“石油产品—蒸馏特性的测定”中规定的“常压蒸馏的试验方法”中测定的每回收50%的温度)。
对用于本发明的脱硫方法的金属脱硫剂没有特别的限制。但是,优选(至少包括镍的金属元素)/载体型催化剂。如果需要,除镍以外的少量金属元素也可与镍共存。这些金属元素的例子包括铜、钴、铁、锰和铬。基于镍-铜的脱硫剂特别优选作为金属脱硫剂。
按脱硫剂的总量计,至少含有镍的金属脱硫剂优选含有30%(质量)或更多的负载型镍含量(还原成金属镍)。当负载的金属镍的数量为30%(质量)或更多时,可完全达到脱硫性能。相反,当负载镍的数量过大时,载体的相对数量下降,因此使脱硫剂的机械强度和脱硫性能下降。考虑到脱硫性能、机械强度等,负载金属镍的数量优选在50-80%(质量)范围内。
载体中,多孔载体是优选的,多孔无机氧化物是特别优选的。多孔无机氧化物的例子包括氧化硅、氧化铝、氧化硅-氧化铝、氧化钛、氧化锆、氧化镁、氧化锌、石膏粉(terra alba)、粘土(clay)和硅藻土。这些氧化物可单独使用或两种或多种组合使用。其中,氧化硅-氧化铝是特别优选的。
对金属负载在载体上的方法没有特别的限制,任何传统上已知的方法例如浸渍、共沉积和捏合都可使用。
优选的脱硫剂之一是负载在氧化铝-氧化硅载体上的镍。脱硫剂例如可通过以下共沉积方法来制备。
在共沉积方法中,预先制备含有镍源和铝源的酸性水溶液或酸性水分散液以及含有硅源和无机基质的碱性水溶液。用于酸性水溶液或酸性水分散液中的镍源的例子包括氯化镍、硝酸镍、硫酸镍及其水合物。铝源的例子包括硝酸铝;水合氧化铝例如假勃姆石、勃姆石、三羟铝石和三水铝石;以及γ-氧化铝。
对用于碱性水溶液的硅源没有特别的限制,只要硅源可溶于碱性水溶液并通过焙烧生成氧化硅就可以。例子包括原硅酸、偏硅酸、其钠盐、钾盐和水玻璃。无机基质的例子包括碱金属碳酸盐和碱金属氢氧化物。
随后,将如此制备的酸性水溶液或酸性水分散液和碱性水溶液分别加热到约50至90℃,然后将两种水溶液合并。再将混合物保持在约50至90℃下,从而完全反应。
反应完全以后,充分洗涤生成的固体,随后从液体中取出洗涤的固体。另一方法,从液体中取出生成的固体,随后充分洗涤。将如此处理的固体用传统上已知的方法在约80至150℃下干燥。优选将干燥的产物在200-400℃下焙烧,从而得到镍负载在氧化硅-氧化铝载体上的脱硫剂。
下文将描述使用上述制备的金属脱硫剂对液体烃类的脱硫条件。
本发明人已发现,液体烃类的脱硫条件(操作压力和操作温度)必需在由所用液体烃类的蒸馏特性适当确定的某一范围内。也就是说,当操作压力(Pope)和操作温度(Tope)满足下式(1)时,液体烃类的硫含量可充分除去,以及金属脱硫剂的脱硫性能可长期保持:
1.06×Pope 0.44<Tope/T50<1.78×Pope 0.22……(1)。
更优选的是,操作压力(Pope)和操作温度(Tope)满足以下式(2):
1.19×Pope 0.35<Tope/T50<1.68×Pope 0.24……(2)。
在上述式中,Tope为操作温度(℃);Pope为操作压力(兆帕)和T50为JISK2254“石油产品—蒸馏特性的测定”中规定的“常压蒸馏的试验方法”中测定的每回收50%的温度。当操作压力的单位从兆帕变成公斤/厘米2绝对时,上述式(1)和(2)变成以下方程式(1’)和(2’):
0.38×Pope 0.44<Tope/T50<1.07×Pope 0.22……(1’)和
0.53×Pope 0.35<Tope/T50<0.96×Pope 0.24……(2’)。
T50为一个显示所用液体烃类的蒸馏特性的参数。当脱硫条件在T50和上述方程式中任一个的基础上决定时,所决定的脱硫条件最适合所述液体烃类的蒸馏特性。
当Tope/T50低于下限(式(1)中的1.06×Pope 0.44)时,脱硫反应的速率下降,使脱硫性能变差,而当Tope/T50超过上限(式(1)中的1.78×Pope 0.22)时,焦炭前体或焦炭的数量增加,而金属脱硫剂的脱硫性能不可能长期保持。
随后,将描述使用金属脱硫剂使液体烃类脱硫的步骤。
首先,将脱硫剂装入脱硫设备。装在脱硫设备中的脱硫剂在约150至400℃下、在送入设备的氢气中进行还原处理。或者,也可使用在单独的还原设备中通过还原预先稳定的脱硫剂。在后一情况下,在约150至300℃下将脱硫剂在脱硫设备中还原。氢气停止送入脱硫设备以后,使液体烃类例如煤油在脱硫设备中向上或向下流动。在这种情况下,优选使液体烃类例如煤油以液时空速(LHSV)例如为0.1-2小时-1流过。使用满足上述式(1)、优选式(2)的操作压力和操作温度。
用本发明的脱硫方法生产的脱硫液体烃类(例如煤油)的硫浓度为0.2ppm或更低、优选0.1ppm或更低、更优选0.05ppm或更低。所以,脱硫的液体烃类非常适合用作生产用于燃料电池的氢的燃料油。在本发明的脱硫方法中,可将或可不将氢加到液体烃类例如煤油。但是,优选使用不包含加入氢的方法,因为这样的方法不需要复杂的体系,并适合于生产用于小型燃料电池的燃料油。
随后,将描述本发明用于生产用于燃料电池的氢的方法(下文称为本发明的生产方法)。
本发明用于生产用于燃料电池的氢的方法,其特征在于包含转化使用上述本发明的脱硫方法脱硫的液体烃类例如煤油。
在本发明的生产方法中,用上述本发明的脱硫方法脱硫的液体烃类例如煤油通过与部分氧化转化催化剂、自热转化催化剂或水蒸汽转化催化剂(下文简单统称为转化催化剂)接触来转化,从而生产用于燃料电池的氢。
对用于本发明生产方法的转化催化剂没有特别的限制,传统上已知用作烃类转化催化剂的任何催化剂都适合选择和应用。这样的转化催化剂的例子包括镍、锆和贵金属例如钌、铑或铂,它们都负载在适合的载体上。要负载的上述金属可单独使用或两种或两种以上组合使用。在这些催化剂中,负载镍的催化剂(下文称镍基催化剂)和负载钌的催化剂(下文称钌基催化剂)是优选的。这两类催化剂在部分氧化转化、自热转化或水蒸汽转化过程中对炭的沉积有明显的阻止作用。
上述转化催化剂的载体优选包括氧化锰、氧化铈、氧化锆等。
在镍基催化剂的情况下,按载体的质量计,负载在载体上的镍数量优选为3-60%(质量)。当所述的数量小于3%(质量)时,部分氧化转化催化剂、自热转化催化剂或水蒸汽转化催化剂不能达到充分的活性,而所述的数量大于60%(质量)时,与所述数量相当的催化活性增加的效果不明显,就经济性来说,这可能是不利的。所以,从催化活性和价格的观点出发,负载在载体上的镍数量优选为5-50%(质量)、特别优选10-30%(质量)。
在钌基催化剂的情况下,按载体的质量计,负载在载体上的镍数量优选为0.05-20%(质量)。当所述的数量小于0.05%(质量)时,部分氧化转化催化剂、自热转化催化剂或水蒸汽转化催化剂不能达到充分的活性,而当所述的数量大于20%(质量)时,与所述数量相当的催化活性增加的效果不明显,就经济性来说,这可能是不利的。所以,从催化活性和价格的观点出发,负载在载体上的钌数量优选为0.05-15%(质量)、特别优选0.1-2%(质量)。
通常在部分氧化转化中使用的反应条件如下:压力为常压至5兆帕表压,温度为400-1100℃,氧(O2)/碳(C)摩尔比为0.2-0.8以及液时空速(LHSV)为0.1-100小时-1。
通常在自热转化中使用的反应条件如下:压力为常压至5兆帕表压,温度为400-1100℃,水蒸汽/碳(C)摩尔比为0.1-10,氧(O2)/碳(C)摩尔比为0.1-1以及液时空速(LHSV)为0.1-2小时-1以及气时空速(GHSV)为1000-100000小时-1。
通常在水蒸汽转化中使用的反应条件如下:水蒸汽/碳(C)摩尔比(即水蒸汽与源自燃料油中的碳之比)通常为1.5-10、优选1.5-5、更优选2-4。当水蒸汽/碳摩尔比小于1.5时,生成氢的数量可能减少,而当水蒸汽/碳摩尔比大于10时,需要过量的水蒸汽,造成热损失,而在某些情况下,氢生产的效率可能下降,这是不希望的。
优选的是,水蒸汽转化在水蒸汽转化催化剂层的入口温度为630℃或更低、更优选600℃或更低下进行。当入口温度高于630℃时,促使燃料油的热分解,如此生成的原子团使碳沉积在催化剂或反应器管壁上,从而在某些情况下引起操作困难。对催化剂层的出口温度没有特别的限制,但出口温度优选在650-800℃范围内。当出口温度低于650℃时,生成氢的数量不够多,而当出口温度高于800℃时,反应器必需用耐热材料制造,从经济性的观点出发,这不是优选的。
反应压力通常为常压至3兆帕表压、优选常压至1兆帕表压。LHSV通常为0.1-100小时-1、优选0.2-50小时-1。
在本发明的生产方法中,在上述部分氧化转化、自热转化或水蒸汽转化过程中,副产的CO对氢的生成有不良影响。所以,优选通过反应转化成CO2来除去生成的CO。
正如上述,根据本发明的生产方法,用于燃料电池的氢可高效率地生产,因此转化催化剂的使用寿命可通过防止催化剂被液体烃油中的硫含量中毒来延长。
实施例
下面将通过实施例更详细地描述本发明,但不应将这些实施例作为对本发明的限制。
<脱硫剂的生产>
将六水合硫酸镍(特级,Wako Pure Chemical Industries,Ltd.)(730.2克)和五水合硫酸铜(专用级,Wako Pure ChemicalIndustries,Ltd.)(151.3克)溶于加热到80℃的离子交换水(8升)中。将假勃姆石(C-AP,Al2O3含量:67%(质量),Catalysts and ChemicalsIndustries Co.,Ltd.的产品)(16.0克)加到溶液中。再将1N硫酸(300毫升)加到混合物中,以便将pH值调节到2,从而生成液体制剂A。将碳酸钠(600.0克)溶于单独提供的加热到80℃的离子交换水中,然后将水玻璃(J-1,Si浓度为29%(质量),Nippon Chemical IndustrialCo.,Ltd.的产品)(180.2克)加到溶液中,从而生成液体制剂B。在液体温度保持在80℃时,将液体制剂A和B彼此瞬间混合。将混合物搅拌1小时。随后,使用过滤器,用离子交换水(60升)洗涤沉积的滤饼,然后使用鼓风型干燥器将产物在120℃下干燥12小时,随后在350℃下焙烧3小时。此后,将如此制成的脱硫剂模化成小球。再将小球粉碎,从而得到基于镍-铜的脱硫剂,其平均粒度为0.8毫米。
<脱硫剂的性能评价>
将上述生产的脱硫剂(23毫升)装入SUS反应器管(内径:17毫米)中。在常压和氢气流下,将反应器管的温度升至120℃,在120℃下保持30分钟,然后逐渐升至350℃,并在350℃下保持20小时,从而使脱硫剂活化。随后,将反应器管的温度下降到140℃,并保持在140℃下。
将具有表1所列的蒸馏特性或其他性质的每一液体烃类样品以液时空速(LHVS)3小时-1送入反应器管,并用反应器出口处安装的压力控制阀将压力控制到下表2所列的水平。在表2所列的温度下进行脱硫。结果列入表2。
表1所列的液体烃类的蒸馏特性用JIS K2254“石油产品—蒸馏特性的测定”中规定的“常压下蒸馏的试验方法”来测定。
表1:煤油的蒸馏特性和其他特性
每回收百分数的温度 | |||||
回收百分数(%(体积)) | 煤油A | 煤油B | 煤油C | 瓦斯油A | 汽油A |
0 | 150.0 | 152.0 | 152.5 | 148.0 | 31.0 |
5 | 162.5 | 166.0 | 171.0 | 161.0 | 40.0 |
10 | 164.0 | 167.0 | 176.0 | 170.0 | 44.5 |
20 | 170.0 | 175.5 | 185.5 | 182.0 | 55.0 |
30 | 176.0 | 184.0 | 193.5 | 196.0 | 64.0 |
40 | 183.0 | 193.5 | 200.5 | 213.0 | 77.0 |
(T50)50 | 191.5 | 203.5 | 208.5 | 231.0 | 95.0 |
60 | 201.0 | 214.0 | 216.0 | 252.0 | 109.0 |
70 | 211.5 | 224.0 | 224.0 | 271.0 | 123.0 |
80 | 221.5 | 237.5 | 235.0 | 293.0 | 133.0 |
90 | 236.5 | 254.0 | 249.0 | 322.0 | 142.0 |
95 | 247.0 | 265.5 | 258.5 | - | 153.0 |
97 | 254.0 | 271.0 | 264.0 | - | - |
100 | 259.5 | 274.5 | 267.0 | 352.0 | 172.0 |
回收总百分数(%(体积)) | 98.5 | 98.5 | 99.0 | 99.0 | 99.5 |
渣油(%(体积)) | 1.5 | 1.5 | 1.0 | 1.0 | 1.0 |
蒸馏损失(%(体积)) | 0.0 | 0.0 | 0.0 | 0.0 | 0.5 |
密度(克/毫升),15℃ | 0.7893 | 0.7968 | 0.7971 | 0.8082 | 0.7500 |
硫浓度(ppm) | 31 | 64 | 48 | 11 | 6 |
在表2中,“0.2ppm突破寿命(液体烃类/脱硫剂)”为脱硫剂性能的一个指标,规定为从脱硫开始一直到经脱硫的液体烃类例如煤油的硫浓度大于0.2ppm所测量的,每单位体积(毫升)脱硫剂处理的液体烃类的体积(毫升)。
在表2中,“式(1)”和“式(2)”表示从所用的煤油样品的蒸馏特性适当确定脱硫条件的上述表达式。
表2(1/3):液体烃类样品的脱硫试验结果
液体烃类 | 操作压力[兆帕]*1(公斤/厘米2绝对) | 操作温度(℃) | Tope/T50 | 式(1) | 式(2) | 0.2ppm突破寿命(液体烃类/脱硫剂) | |||
1.06×Pope 0.44 | 1.78×Pope 0.22 | 1.19×Pope 0.35 | 1.68×Pope 0.24 | ||||||
实施例1 | 煤油AT50:191.5℃ | 0.29(3) | 220 | 1.15 | 0.62 | 1.36 | 0.78 | 1.25 | 650 |
实施例2 | 250 | 1.31 | 400 | ||||||
对比例1 | 0.49(5) | 140 | 0.73 | 0.77 | 1.52 | 0.93 | 1.42 | 220 | |
实施例3 | 250 | 1.31 | 1,400 | ||||||
对比例2 | 300 | 1.57 | 120 | ||||||
对比例3 | 煤油BT50:203.5℃ | 0.10(1) | 250 | 1.23 | 0.38 | 1.07 | 0.53 | 0.96 | 80 |
实施例4 | 0.29(3) | 250 | 1.23 | 0.62 | 1.36 | 0.78 | 1.25 | 580 | |
实施例5 | 0.49(5) | 270 | 1.33 | 0.77 | 1.52 | 0.93 | 1.42 | 920 | |
实施例6 | 300 | 1.47 | 740 |
*1操作压力基于兆帕(转换成公斤/厘米2绝对的数值)
表2(2/3):液体烃类样品的脱硫试验结果
液体烃类 | 操作压力[兆帕]*1(公斤/厘米2绝对) | 操作温度(℃) | Tope/T50 | 方程式(1) | 方程式(2) | 0.2ppm突破寿命(液体烃类/脱硫剂) | |||
1.06×Pope 0.44 | 1.78×Pope 0.22 | 1.19×Pope 0.35 | 1.68×Pope 0.24 | ||||||
对比例4 | 煤油CT50:208.5℃ | 0.10(1) | 250 | 1.20 | 0.38 | 1.07 | 0.53 | 0.96 | 90 |
实施例7 | 0.29(3) | 230 | 1.10 | 0.62 | 1.36 | 0.78 | 1.25 | 450 | |
实施例8 | 260 | 1.25 | 600 | ||||||
对比例5 | 0.49(5) | 150 | 0.72 | 0.77 | 1.52 | 0.93 | 1.42 | 160 | |
实施例9 | 220 | 1.06 | 510 | ||||||
实施例10 | 270 | 1.29 | 1,100 | ||||||
对比例6 | 330 | 1.58 | 40 | ||||||
实施例11 | 0.69(7) | 200 | 0.96 | 0.90 | 1.64 | 1.04 | 1.53 | 430 | |
实施例12 | 250 | 1.20 | 820 |
*1操作压力基于兆帕(转换成公斤/厘米2绝对的数值)
表2(3/3):液体烃类样品的脱硫试验结果
液体烃类 | 操作压力[兆帕]*1(公斤/厘米2绝对) | 操作温度(℃) | Tope/T50 | 式(1) | 式(2) | 0.2ppm突破寿命(液体烃类/脱硫剂) | |||
1.06×Pope 0.44 | 1.78×Pope 0.22 | 1.19×Pope 0.35 | 1.68×Pope 0.24 | ||||||
实施例13 | 瓦斯油AT50:231.0℃ | 0.29(3) | 280 | 1.21 | 0.62 | 1.36 | 0.78 | 1.25 | 2,500 |
实施例14 | 220 | 0.95 | 2,000 | ||||||
对比例7 | 340 | 1.47 | 790 | ||||||
实施例15 | 汽油AT50:95.0℃ | 0.29(3) | 110 | 1.16 | 0.62 | 1.36 | 0.78 | 1.25 | 2,900 |
实施例16 | 80 | 0.84 | 2,000 | ||||||
对比例8 | 50 | 0.53 | 890 |
*1操作压力基于兆帕(转换成公斤/厘米2绝对的数值)
正如从表2清楚的,在对比例中进行的所有脱硫试验中,其中Tope/T50数值大于式(1)的上限或小于式(1)的下限,0.2ppm突破寿命为40-220的较低范围。相反,在实施例中,其中Tope/T50数值为式(1)或(2)的下限至式(1)或(2)的上限,0.2ppm突破寿命为400-1400的较高范围。
结果表明,当脱硫条件(操作温度和操作压力)受控以致式(1)或(2)的Tope/T50在相应的下限至相应的上限范围内时,煤油的硫含量可长期有效除去,使硫浓度为0.2ppm或更低以及脱硫剂的工作寿命可延长。
<脱硫煤油的转化试验>
将表2所列的在实施例5中脱硫的煤油样品(硫浓度为0.2ppm或更低)用作燃料油。使用装有钌基的转化催化剂(负载钌的数量:3%(质量))(20毫升)的转化装置,将燃料油进行水蒸汽转化。使用的转化条件如下:压力为常压,水蒸汽/碳(摩尔比)为3,LHSV为0.5小时-1,入口温度为550℃以及出口温度为750℃。
发现转化开始500小时以后,在转化装置的入口处生成氢的转化率为100%。
工业应用
根据本发明的脱硫方法,由使用的液体烃类例如煤油的蒸馏特性来适当控制脱硫条件。通过使用这样的适当脱硫条件,液体烃类例如煤油的硫含量可长期有效地除去,使硫浓度达到0.2ppm或更低,并可延长脱硫剂的使用寿命。
根据本发明生产用于燃料电池的氢的方法,用于燃料电池的氢可有效地通过已通过本发明的脱硫方法脱硫的液体烃类例如煤油的转化来生产,并可延长转化催化剂的使用寿命。
Claims (10)
1.一种脱硫方法,包括使用金属脱硫剂从液体烃类中除去硫含量,其特征在于,所述的方法使用能满足下式(1)的脱硫条件:
1.06×Pope 0.44<Tope/T50<1.78×Pope 0.22……(1)
式中Tope为操作温度(℃);Pope为操作压力(兆帕)和T50为JIS K2254“石油产品—蒸馏特性的测定”中规定的“常压蒸馏的试验方法”中测定的每回收50%的温度。
2.根据权利要求1的脱硫方法,其中脱硫条件满足下式(2)的脱硫条件:
1.19×Pope 0.35<Tope/T50<1.68×Pope 0.24……(2)
式中Tope、Pope和T50与权利要求1中规定的相同。
3.根据权利要求1或2的脱硫方法,其中所述的方法不外加氢。
4.根据权利要求1-3中任一项的脱硫方法,其中金属脱硫剂含有多孔无机氧化物和负载其上的至少包含镍(Ni)的金属元素。
5.根据权利要求4的脱硫方法,其中金属脱硫剂为基于镍-铜的脱硫剂。
6.根据权利要求1-5中任一项的脱硫方法,其中液体烃类为选自汽油馏分、煤油馏分和瓦斯油馏分中的一种。
7.一种生产用于燃料电池的氢的方法,其特征在于,所述的方法包括转化已通过上述权利要求1-6中任一项的脱硫方法脱硫的液体烃类。
8.根据权利要求7生产用于燃料电池的氢的方法,其中转化为部分氧化转化、自热转化或水蒸汽转化。
9.根据权利要求8生产用于燃料电池的氢的方法,其中部分氧化转化、自热转化或水蒸汽转化在含有钌或镍的转化催化剂存在下进行。
10.根据权利要求9生产用于燃料电池的氢的方法,其中转化催化剂含有氧化锰、氧化铈或氧化锆。
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CN101591554A (zh) * | 2008-05-30 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | 一种常温复合脱硫脱砷剂及其制备方法 |
CN102239004A (zh) * | 2008-12-04 | 2011-11-09 | 环球油品公司 | 同时进行的暖气体脱硫作用和co轮换反应来改进合成气净化 |
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JP2006117921A (ja) * | 2004-09-22 | 2006-05-11 | Idemitsu Kosan Co Ltd | 液体燃料の硫黄除去方法及び水素の製造方法と燃料電池システム |
US7216549B2 (en) | 2004-11-04 | 2007-05-15 | Endress + Hauser Flowtec Ag | Vibration-type measurement transducer |
CN101253256B (zh) * | 2005-08-01 | 2011-11-16 | 日本能源株式会社 | 烃油脱硫的方法 |
JP5224651B2 (ja) * | 2006-03-31 | 2013-07-03 | Jx日鉱日石エネルギー株式会社 | 固体酸化物形燃料電池 |
JP5028070B2 (ja) * | 2006-11-01 | 2012-09-19 | 出光興産株式会社 | 脱硫方法、脱硫装置、燃料電池用燃料ガスの製造装置、および、燃料電池システム |
CN110832056B (zh) | 2017-07-04 | 2022-02-15 | 三菱化学株式会社 | 芳香族烃的制造方法 |
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US5130115A (en) * | 1988-01-22 | 1992-07-14 | Nippon Oil Co., Ltd. | Process for hydrogen production from kerosene |
EP0495534A3 (en) * | 1988-03-12 | 1992-10-07 | Akira C/O Kohgakuin University Igarashi | Catalyst for steam reforming of hydrocarbon |
US5026536A (en) * | 1988-12-20 | 1991-06-25 | Nippon Oil Co., Ltd. | Hydrogen production from hydrocarbon |
JP2812486B2 (ja) * | 1989-05-15 | 1998-10-22 | 大阪瓦斯株式会社 | 炭化水素の水蒸気改質方法 |
FR2773085B1 (fr) * | 1997-12-29 | 2000-02-18 | Elf Exploration Prod | Procede catalytique pour oxyder directement en soufre, a basse temperature, l'h2s contenu en faible concentration dans un gaz et catalyseur pour sa mise en oeuvre |
JP4197073B2 (ja) | 1999-08-27 | 2008-12-17 | 株式会社コスモ総合研究所 | 深度脱硫触媒、その製造方法及びそれを用いた脱硫方法 |
US6274533B1 (en) * | 1999-12-14 | 2001-08-14 | Phillips Petroleum Company | Desulfurization process and novel bimetallic sorbent systems for same |
JP4531939B2 (ja) | 2000-03-31 | 2010-08-25 | 出光興産株式会社 | ニッケル−銅系脱硫剤の製造方法 |
JP2001279274A (ja) | 2000-03-31 | 2001-10-10 | Idemitsu Kosan Co Ltd | 燃料電池用燃料油、脱硫方法及び水素の製造方法 |
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CN101591554A (zh) * | 2008-05-30 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | 一种常温复合脱硫脱砷剂及其制备方法 |
CN101591554B (zh) * | 2008-05-30 | 2013-05-08 | 北京三聚环保新材料股份有限公司 | 一种常温复合脱硫脱砷剂及其制备方法 |
CN102239004A (zh) * | 2008-12-04 | 2011-11-09 | 环球油品公司 | 同时进行的暖气体脱硫作用和co轮换反应来改进合成气净化 |
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US7510648B2 (en) | 2009-03-31 |
KR20050028045A (ko) | 2005-03-21 |
JPWO2004009735A1 (ja) | 2005-11-17 |
WO2004009735A1 (ja) | 2004-01-29 |
CN100358978C (zh) | 2008-01-02 |
KR100976296B1 (ko) | 2010-08-16 |
US20060131215A1 (en) | 2006-06-22 |
CA2493034A1 (en) | 2004-01-29 |
AU2003252231A1 (en) | 2004-02-09 |
JP4322804B2 (ja) | 2009-09-02 |
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CA2493034C (en) | 2012-07-17 |
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