CN101506332B - 生物质的处理方法、燃料电池用燃料、汽油、柴油机燃料、液化石油气和合成树脂 - Google Patents
生物质的处理方法、燃料电池用燃料、汽油、柴油机燃料、液化石油气和合成树脂 Download PDFInfo
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- CN101506332B CN101506332B CN2007800307041A CN200780030704A CN101506332B CN 101506332 B CN101506332 B CN 101506332B CN 2007800307041 A CN2007800307041 A CN 2007800307041A CN 200780030704 A CN200780030704 A CN 200780030704A CN 101506332 B CN101506332 B CN 101506332B
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Classifications
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
- C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
- C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
-
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/62—Catalyst regeneration
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M8/0625—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 in a modular combined reactor/fuel cell structure
- H01M8/0631—Reactor construction specially adapted for combination reactor/fuel cell
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M8/0643—Gasification of solid fuel
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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
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- C10G2300/10—Feedstock materials
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- C10G2300/1014—Biomass of vegetal origin
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- C—CHEMISTRY; METALLURGY
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/1018—Biomass of animal origin
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Abstract
在使用具有反应带、分离带、汽提带和再生带的流化催化裂化装置,通过催化裂化处理生物质时,在反应带中,用含有10~50质量%超稳定Y型沸石的催化剂,在反应带出口温度为580~680℃、催化剂/油比率为10~40wt/wt、反应压力为1~3kg/cm2G和反应带中的原料油与催化剂的接触时间为0.1~1.0秒的条件下处理含有生物质的原料油,然后,在再生带中,在再生带温度为640~720℃、再生带压力为1~3kg/cm2G和再生带出口处的废气中的氧气浓度为0~3mol%的条件下处理催化剂。
Description
技术领域
本发明涉及生物质的处理方法以及由此获得的燃料电池用燃料、汽油、柴油机燃料、液化石油气和合成树脂。
背景技术
以往,从能源安全和减少二氧化碳的观点考虑,生物质有望被当作汽车燃料和石油化学燃料。关于利用生物质作为汽车等的燃料油的方法,目前进行了许多尝试。例如,在以下专利文献1~5中公开了将属于生物质的植物油、动物油与矿物油混合并作为柴油发动机用燃料的方法。
然而,如以上专利文献1~5中所述,仅仅将生物质与矿物油混合的话,由于生物质含有不饱和键和氧等原因,所得燃料的稳定性变得不充分,管理很困难。另外,这些成分对汽车中使用的材料可能有不良影响。
另一方面,在下述专利文献6中公开了一种将高级脂肪酸甘油酯与含沸石的催化剂接触来制造汽油的方法。
专利文献1:日本特开昭61-57686号公报
专利文献2:日本特表平6-510804号公报
专利文献3:日本特开平7-82576号公报
专利文献4:日本特开平8-41468号公报
专利文献5:日本特开平10-152687号公报
专利文献6:日本特开昭59-62694号公报
发明内容
发明要解决的问题
然而,即使是上述专利文献6中所述的方法,从实际应用的角度来看,在以下方面仍然有改善的余地。
也就是说,根据上述专利文献6所述的方法,可以进行实验室规模的汽油制造,但在使用工业规模的流化催化裂化装置(以下有时称为“FCC”)处理生物质时,与通常作为矿物油类的FCC原料所使用的减压瓦斯油(以下称为“VGO”)相比,焦炭生成量增大。在FCC中,伴随催化剂再生的焦炭燃烧所产生的热量用作原料油气化、裂化反应所需的热量,通过使它们平衡来运行。在焦炭增加而热量剩余时,需要通过催化剂冷却或者从催化剂两段再生中的一段再生塔中除去一氧化碳来除去多余的热量。通过各FCC除去余热的能力虽有不同,但通常在各自能力的上限运行。此外,近年来由于环境规定的加强,限制二氧化碳的排出量,事实上在几乎所有FCC中焦炭量都成为了运行上的制约条件。由于存在这种情况,在通过引入生物质而增加焦炭时,要么是降低运行的苛刻度以降低焦炭收率,牺牲汽油收率,要么降低处理量(throughput)自身,在经济上是不利的。
本发明基于以上现有技术中的问题而提出,其目的是提供可在流化催化裂化装置中以良好的效率稳定地处理生物质的生物质处理方法。另外,本发明的另一个目的是提供通过所述生物质处理方法获得的燃料电池用燃料、汽油、柴油机燃料、液化石油气和合成树脂原料。
用于解决问题的方案
为了解决上述问题,本发明提供一种生物质处理方法,其特征在于,该方法是使用具有反应带、分离带、汽提带和再生带的流化催化裂化装置通过催化裂化处理生物质的方法,其包括以下工序:在反应带中,使用含有10~50质量%超稳定Y型 沸石的催化剂在反应带出口温度为580~680℃、催化剂/油比率为10~40wt/wt、反应压力为1~3kg/cm2G和反应带中的原料油与催化剂的接触时间为0.1~1.0秒的条件下处理含有生物质的原料油的第一工序;在再生带中,在再生带温度为640~720℃、再生带压力为1~3kg/cm2G和再生带出口处的废气中的氧气浓度为0~3mol%的条件下处理供于第一工序的催化剂的第二工序。
根据上述本发明的生物质的处理方法,在使用流化催化裂化装置处理生物质时,使用上述特定催化剂在上述特定条件下在反应带中处理含有生物质的原料油,而且通过在再生带中在上述特定条件下处理供于处理的催化剂,可以充分抑制随着生物质处理的焦炭生成量的增大。因此,可以在流化催化裂化装置中以良好的效率稳定地处理生物质。
在本发明的生物质的处理方法中,作为反应带,优选使用下行式反应器(down flow reacton)。
另外,在本发明中使用的生物质优选含有来源于动植物油的氧含量为0.1~13质量%并且沸点为230℃以上的油脂成分。
另外,在本发明中,催化剂上的Δ焦炭优选是0.2~1.5质量%。
另外,在流化催化裂化装置中,再生带的催化剂浓相的温度与反应带的出口温度之差优选在150℃以内。
另外,在本发明的第一工序中,优选的是,使用相当于原料油的2~8质量%的蒸汽,将原料油喷雾到反应带内。
另外,在本发明的催化剂中,超稳定Y型沸石的Si/Al原子比优选是3~20,更优选是5~20,还更优选是7~15。
另外,在该催化剂中,优选在超稳定Y型沸石的离子交换部位引入有碱性稀土金属。
另外,该催化剂优选进一步含有氧化硅-氧化铝作为活性基质。
另外,本发明提供了燃料电池用燃料,其特征在于,含有通过上述本发明的生物质处理方法获得的氢气。
另外,本发明提供了汽油,其特征在于,含有通过上述本发明的生物质处理方法获得的沸点25~220℃的部分馏分或全部馏分或其氢化物。
另外,本发明提供了汽油,其特征在于,含有通过上述本发明的生物质处理方法获得的异丁烯与甲醇或乙醇反应所得到的醚。
另外,本发明提供了汽油,其特征在于,含有使用烷基化装置使通过上述本发明的生物质处理方法获得的丁烯与异丁烷反应而形成的反应物。
另外,本发明提供了汽油,其特征在于,含有由上述本发明的生物质处理方法获得的丁烯的二聚体。
另外,本发明提供了柴油机燃料,其特征在于,含有由上述本发明的生物质处理方法获得的沸点170~370℃的部分馏分或全部馏分。
另外,本发明提供了液化石油气,其特征在于,含有由上述本发明的生物质处理方法获得的碳原子数3或者4的烃。
另外,本发明提供了合成树脂,其特征在于,含有由上述本发明的生物质处理方法获得的丙烯作为构成单体。所述合成树脂特征在于优选在燃烧废弃时环境法规上的二氧化碳排出量可以为零。
发明的效果
根据本发明,提供了生物质处理方法,该方法可以在流化催化裂化装置中以良好的效率稳定地处理生物质。另外,通过使用上述本发明的生物质处理方法,从能源安全和减少二氧化碳(碳酸气)的观点来看,可以提供有用的燃料和石油化学原料。
具体实施方式
以下详细地说明本发明的优选实施方案。
在本发明中,作为原料油,使用含有生物质的原料油。作为生物质,可以使用植物或动物来源的油脂。所述油脂为含有高级脂肪酸和甘油的酯,更具体地说,可以例举棕榈油、菜籽油、玉米油、大豆油、葡萄籽油等植物油,猪油等动物油等。这些油脂可以是使用过的废油。该生物质优选含有沸点230℃以上的油脂馏分。这些生物质可以以混合物形式使用。
在本发明中,可以单独将上述生物质用作原料油,也可以使用生物质与矿物油的混合油作为原料油。作为矿物油,可以列举蒸馏原油所获得的常压渣油(atmospheric residue)、进一步减压蒸馏常压渣油所获得的减压瓦斯油、减压渣油(vacuumresidue)、它们的氢化处理油或者热裂化油以及它们的混合物。在这些矿物油中,常压渣油、减压渣油以及它们的氢化物或者热裂化物在本发明中称为“渣油”。以质量比表示原料油中的渣油的比率的数值称之为“渣油比率”(质量%)。
对本发明的渣油比率没有特定限制,本发明的生物质处理方法优选应用于使用渣油比率为10质量%以上的原料油运行的流化催化裂化装置。渣油比率更优选为30质量%以上。
本发明中使用的催化剂(流化催化裂化催化剂)含有10~50质量%、优选15~40质量%的超稳定Y型沸石。优选使用Si/Al的原子比为3~20的该超稳定Y型沸石。Si/Al的原子比更优选是5~20,更优选为7~15。在Si/Al的原子比小于3时,催化剂活性变得明显过剩,气体和LPG的产生量增大。另外,Si/Al的原子比超过20时,沸石的成本增大,在经济上是不优选的。
根据本发明中使用的催化剂的优选实施方案,可以列举用粘结剂将超稳定Y型沸石与作为副活性成分的、能够分解重质油的大分子的基质和高岭土等增量剂一起成型为颗粒状的物质。作为用于本发明催化剂中的基质成分,优选使用氧化硅-氧化铝。该催化剂的平均粒径优选是50~90μm,堆密度优选为0.6~0.9g/cm3,表面积优选为50~350m2/g,细孔容积优选为0.05~0.5ml/g。
另外,该催化剂除了超稳定Y型沸石以外,还可进一步含有细孔径比Y型沸石小的铝硅酸盐沸石、硅磷酸铝(silicoaluminophosphate,SAPO)等。作为这种沸石,可以列举ZSM-5,此外,作为SAPO,可以列举SAPO-5、SAPO-11和SAPO-34。这些沸石或SAPO可以与含有超稳定Y型沸石的催化剂颗粒包含在同一催化剂颗粒中,或者作为其它催化剂颗粒含有。
另外,本发明中使用的流化催化裂化装置(FCC)没有特定限制,只要是具有反应带、分离带、汽提带和再生带的装置即可。另外,该FCC可以是以往用于处理矿物油的现有装置,或者是用于处理生物质的新制造的装置。
另外,在本发明的FCC的反应带中,在反应带的出口温度为580~680℃、催化剂/油比率为10~40wt/wt、反应压力为1~ 3kg/cm2G、原料油与催化剂的接触时间为0.1~1.0秒的条件下进行流化催化裂化。本发明中所述的“流化催化裂化”是指让上述生物质、矿物油等重质原料油与保持流动状态的催化剂接触,将重质原料油裂化为汽油和以轻质烯烃为主体的轻质的烃。为了该流化催化裂化,大多使用催化剂颗粒与原料油一起在管内上升的所谓的提升管裂化(riser cracking)。另外,在本发明中,也可以优选使用催化剂颗粒与原料油共同在管内下降的下行式反应器。在裂化提升管内,发生了称之为逆向混合(backmixing)的现象,催化剂与原料的滞留时间分布变宽,具有容易产生焦化干气的倾向,而在使用下行式反应器时,可以抑制逆向混合。
另外,本发明中所述的“反应带的出口温度”是高速流化床反应器即上述裂化提升管或下行式反应器的出口温度,是裂化产物骤冷或者与催化剂分离之前的温度。本发明的反应带的出口温度如上所述是580~680℃,优选是590~650℃,更优选是600~630℃。在反应带的出口温度低于580℃时,无法以高收率获得目标产物汽油和轻质烯烃,另外在超过680℃时,热裂化显著,干气产生量增大。
另外,本发明中所述的“催化剂/油比率”是指催化剂循环量(ton/h)与原料油的供给速度(ton/h)的比率。本发明中的催化剂与油比率如上所述是10~40wt/wt,优选是15~35wt/wt,更优选是20~30wt/wt。在催化剂/油比率低于10wt/wt时,不能获得充分的裂化率,在催化剂/油比率超过40wt/wt时,催化剂循环量增大,不能确保再生带中催化剂再生所需的催化剂滞留时间,另外由于再生温度降低,催化剂再生不充分。在本发明中,通过将催化剂/油比率增高到10~40wt/wt,可以应对合成油处理时的焦炭不足。
另外,本发明所述的“反应压力”是指流化床反应器的总压 力。本发明中所述的反应压力如上所述是1~3kg/cm2G,优选是1.2~2kg/cm2G。在反应压力低于1kg/cm2G时,与大气压的差变得过小,通过控制阀调节压力变得困难。另外,在反应压力低于1kg/cm2G时,再生带的压力也相应地变小,为了确保再生所需的气体滞留时间,必须加大容器,在经济上是不利的。另一方面,当反应压力超过3kg/cm2G时,氢转移反应(等二分子反应相对于作为单分子反应的裂化反应的比例增大。另外,这里所述的“氢转移反应”是烯烃从环烷烃等接受氢、转化为链烷烃的反应,是成为目标物轻质烯烃减少、汽油的辛烷值降低等原因的反应。
另外,本发明中所述的“原料油与催化剂的接触时间”是指原料油与催化剂在反应器入口处接触起至反应产物与催化剂在反应器出口处分离的时间。本发明的原料油与催化剂的接触时间如上所述是0.1~1.0秒,优选是0.3~0.7秒。在接触时间小于0.1秒时,裂化无法充分进行。另一方面,在超过1.0秒时,发生了过度反应、氢转移等不利的二次反应,目标产物减少。
另外,在本发明中,在反应带中引入原料油时,优选使用蒸汽进行喷雾。此时的蒸汽量相对于原料油优选是2~8质量%。在蒸汽量相对于原料油低于2质量%时,由于喷雾时液滴的粒径没有变得充分小,液滴与催化剂的接触不能充分进行,具有反应效率降低的倾向。另一方面,在超过8质量%时,下述产物回收带中的水的回收量增大,在经济上是不利的。
另外,在本发明中,在反应带中进行催化裂化而获得的产物、未反应物和催化剂的混合物被送入到分离带,在该分离带中从混合物中分离催化剂。作为分离带,优选使用旋风分离器等利用离心力的固液分离装置。
在本发明中,分离带中分离出的催化剂被送入到汽提带, 在汽提带中从催化剂颗粒中除去大部分的产物、未反应物等烃类。一方面,反应中,原料的一部分变成更重质的炭质(焦炭),附着在催化剂上,附着有焦炭和一部分重质烃类的催化剂从该汽提带被输送到再生带(再生塔)。
另外,在本发明的FCC装置的再生带中,来自汽提带的催化剂在再生带温度为640~720℃、再生带压力为1~3kg/cm2G、再生带出口废气中的氧气浓度为0~3mol%的条件下进行处理。
在本发明中,为了将所需的热量供给到FCC装置的再生带,优选的是,在再生带中投入用常压蒸馏装置处理原油所获得的常压渣油且该供给量是投入反应带中的上述原料油重量的1~10重量%。
另外,本发明的再生带温度如上所述是640~720℃,优选是650~710℃,更优选是660~700℃。在再生带液温低于640℃时,焦炭的燃烧变得不充分。在超过720℃时,促进了催化剂的劣化。另外,作为再生带的材料,需要使用耐受再生带温度的更高价格的部件,因此在经济上是不利的。
另外,在本发明中,再生带的催化剂浓相的温度与反应带出口温度之差优选是150℃以内。在该温度差超过150℃时,来自再生塔的废气带到系统外的热量增大,不能保持反应温度。
另外,“再生带的催化剂浓相的温度”是指在再生带中在浓状态下流动的催化剂颗粒从再生带出来之前的部分的温度。
另外,本发明的再生带压力如上所述是1~3kg/cm2G。在再生带温度低于1kg/cm2G时,为了确保再生所需的气体滞留时间,再生带的容器变大,在经济上是不利的。另外,在再生带的温度超过3kg/cm2G时,随之而来的是反应带的压力增大,促进了反应带中诸如氢转移反应之类的二分子反应,这是不优选的。
另外,本发明的再生带出口处的废气中的氧气浓度是0~3mol%。在氧气浓度超过3mol%时,要使用额外的动力将多余的空气输送到再生带,因此在经济上是不利的。
经受上述氧化处理的催化剂是再生催化剂,在催化剂上沉积的焦炭和重质烃类通过燃烧而减少。该再生催化剂在上述反应带中连续循环。根据情况,为了抑制不必要的热裂化或者过度裂化,将裂化产物在分离带正前或正后骤冷。催化剂被伴随再生带的碳质燃烧所产生的热量所加热,该热与催化剂一起被带入到反应带。原料油通过该热量被加热和气化。另外,由于裂化反应是吸热反应,该热量也用作裂化反应热。这种再生带的放热与反应带的吸热成为FCC运行的必需条件。
作为热剩余时的对策,有一种冷却催化剂的方法。该方法是排出再生带的一部分催化剂,通过将热用于蒸汽产生等而夺取催化剂热量的方法。作为热剩余的其它对策,有一种将再生带分为两段、再生带的第一段在氧气不足的气氛下运行的方法。在该情况下,再生带的第一段的焦炭燃烧变成不完全燃烧,一氧化碳作为废气被排出。碳氧化为一氧化碳时的反应热与碳氧化为二氧化碳时的反应热的差可以作为多余的热排出到系统外。排出系统外的一氧化碳进一步氧化为二氧化碳,该能量可以作为电力或蒸汽回收。
伴随催化裂化产生的焦炭量的上限值通常取决于各FCC。例如,根据可通过上述热剩余时的对策排出到系统外的热量的大小,决定焦炭量的容许值。另外,也有所产生的二氧化碳的上限值根据FCC的布局来确定的情况,焦炭量的容许值受该数值所限制。通常,FCC在尽可能大的处理量和尽可能高的裂化率下运行,结果变成在焦炭量的上限值下运行。
然而,在FCC中处理以往的生物质来源的含氧原料时,跟 通常作为矿物油类的FCC原料所使用的减压瓦斯油(以下有时称为“VGO”)相比,焦炭生成量增大。与之相反,在本发明中,含有生物质和矿物油的原料在反应带中,使用上述特定的催化剂,在上述特定条件下处理,而且供于处理的催化剂在再生带中在上述特定条件下处理,可以充分抑制焦炭生成量的增大,从而可以维持在焦炭的上限值下运行。
在本发明中,每单位原料油的焦炭生成量(质量%)称为“焦炭收率”,本发明的焦炭收率优选是4~15质量%,更优选6~11质量%,还更优选7~10质量%。在焦炭收率低于上述下限值时,具有反应所需的热不足的倾向。另外,在焦炭收率超过上述上限值时,再生带中产生的热量明显过剩,受到裂化率降低、处理量降低等的运行制约,因此是不优选的。
另外,本发明的Δ焦炭优选是0.2~1.5质量%,更优选是0.3~1.0质量%。在Δ焦炭低于0.2质量%时,具有反应所需的热不足的倾向。另一方面,在Δ焦炭超过1.5质量%时,再生带中产生的热量过剩,受到裂化率降低、处理量降低等运行制约,因此是不优选的。这里的“Δ焦炭”是指用下式表示的值。
另外,下式中的“焦炭附着量”和“焦炭残存量”分别是焦炭相对于催化剂重量的比例(质量%)。
(Δ焦炭)=(焦炭在再生处理前的催化剂上的附着量(质量%))-(再生处理后的催化剂上的焦炭残存量(质量%))
另外,本发明的FCC优选进一步设有裂化产物回收带。作为所述产物回收带,可以列举根据沸点等分离和回收裂化产物的裂化产物回收装置。该裂化产物回收装置包括多个蒸馏塔、吸收塔、压缩机、汽提塔、热交换器等。反应带获得的产物经过上述分离带后,输送到第一蒸馏塔(设置在最上游侧的蒸馏塔)。在这里通过热交换器夺取产物的热,从塔底排出轻油和比 轻油更重的重质馏分,从塔顶分别排出汽油和比汽油更轻的轻质馏分。另外,也可以从蒸馏塔的中间段排出轻油,从塔底仅排出重油。从第一蒸馏塔获得的轻质组分输送到压缩机进行压缩,此后,经过设置在第一蒸馏塔下游侧的多个吸收塔、蒸馏塔,分离成回收汽油、C4馏分、C3馏分和干气。
这里“C4馏分”是指碳原子数为4的烃即丁烷和丁烯。另外,“C3馏分”是指碳原子数为3的烃即丙烷和丙烯。另外,“干气”是指碳原子数为2以下的烃即甲烷、乙烯和分子量更小的氢气等气体。另外,根据蒸馏塔的能力,有时C4馏分的一部分混入到汽油中,有时C4馏分的一部分混入到C3馏分中。
上述第一蒸馏塔的塔顶部及其附近,由于温度低于水的露点,在以往的生物质处理方法中,来源于生物质中含有的酯(油脂)的水聚集,存在由于水中含有的酸腐蚀装置的问题。相对于此,根据本发明的生物质处理方法,通过裂化来源于生物质的酸,可以充分抑制腐蚀。
如上所述,根据本发明的生物质处理方法,在流化催化裂化装置中,可以良好的效率稳定地处理生物质。
另外,本发明的生物质处理方法由于以生物质为原料,从能源安全和减少二氧化碳的观点来看是优异的,在各种燃料的基料和石化制品的原料的制备中是非常有用的。
例如,通过上述本发明的生物质处理方法获得的氢气可以用作燃料电池用燃料。
另外,通过本发明的生物质处理方法获得的沸点25~220℃的馏分可以用作汽油基料。这里,沸点25~220℃的馏分可以作为含有其一部分或全部或者其氢化物的汽油基料来使用。
另外,通过本发明的生物质处理方法获得的沸点170~370℃的馏分可以用作柴油机燃料基料。这里可以使用它的一部 分或全部作为柴油机燃料基料。
另外,通过本发明的生物质处理方法获得的碳原子数3或4的烃可以用作液化石油气基料。
另外,通过本发明的生物质处理方法获得的丙烯可以用作合成树脂的构成单体。所述合成树脂由于以生物质为原料,具有的优点是,在燃烧或废弃时,环境法规上的二氧化碳排出量可以为零。
另外,通过本发明的生物质处理方法获得的异丁烯与甲醇或乙醇反应得到的醚可以用作汽油基料。
另外,使用烷基化装置使通过本发明的生物质处理方法获得的丁烯与异丁烷反应而形成的反应物可以用作汽油基料。
另外,通过本发明的生物质处理方法获得的丁烯的二聚体可以用作汽油基料。
实施例
以下根据实施例和比较例来更具体地说明本发明,然而,本发明决不限于以下实施例。
[实施例1]
将21550g的JIS3号水玻璃的稀释溶液(SiO2浓度=11.6%)滴入到3370g的40%硫酸中,获得pH3.0的硅溶胶。在全部硅溶胶中添加3000g的超稳定Y型沸石(Tosoh Corporation制造:HSZ-370HUA)和4000g高岭土并混炼,在250℃的热风下喷雾干燥。在50℃下用0.2%硫酸铵清洗这样获得的喷雾干燥物,然后在110℃的烘箱内干燥,进一步在600℃下烧成,获得催化剂。该催化剂中的超稳定Y型沸石的含量为30质量%,Si/Al原子比为10,晶格常数为29.33,结晶度为97%。另外,催化剂颗粒的堆密度为0.7g/ml,平均粒径为71μm,BET比表面积为180m2/g,细孔容积为0.12ml/g。另外,使用氧化硅-氧化铝作为活性基质。
使用这样获得的催化剂,在流化催化裂化反应装置中进行生物质的裂化反应。作为流化催化裂化反应装置,使用设有下流式反应塔、具有绝热型反应带和再生带的FCC中试装置(Xytel公司制造)。另外,作为原料油,使用属于大豆油与菜籽油的混合油的生物质(以下称为“原料油A”)。表1中示出了原料油A的性质。另外,在催化剂供给到上述装置之前通过在800℃下6小时的100%蒸汽处理来进行模拟平衡化。此时的装置规模是物料量(inventory,催化剂总量)2kg、给料量1kg/h。运行条件是催化剂/原料油比率20、反应带出口温度600℃、接触时间0.5秒。另外,在反应带中,通过使用相当于原料油的5质量%的蒸汽来喷出原料油,将原料油供给反应带。
表2示出了上述催化裂化反应中由原料油至裂化产物的转化率、裂化产物的收率、Δ焦炭以及所获得的汽油的研究法辛烷值(research method octane number)。另外,在表2中,裂化产物的收率表示为按百分率计的裂化产物相对于全部原料油的质量比,C1表示甲烷气、C2表示乙烷气(下同)。
[实施例2]
与实施例1同样地制备催化剂,除了该催化剂与市售的辛烷值提高用添加剂(GRACE Davison公司制造:Olefinsmax)组合使用并且该添加剂的量为物料量(催化剂与添加剂的总量)的20%以外,与实施例1同样地进行原料油A的催化裂化反应。表2示出了由原料油至裂化产物的转化率、裂化产物的收率、Δ焦炭以及所获得的汽油的研究法辛烷值。
[比较例1]
除了用中东脱硫VGO(以下称为“原料油B”)代替原料油A以外,与实施例1同样地进行催化裂化反应。表1示出了原料油B的性质,表2示出了由原料油至裂化产物的转化率、裂化产物 的收率、Δ焦炭以及所获得的汽油的研究法辛烷值。
[比较例2]
除了用原料油B代替原料油A以外,与实施例2同样地进行催化裂化反应。表2示出了由原料油至裂化产物的转化率、裂化产物的收率、Δ焦炭以及所获得的汽油的研究法辛烷值。
[比较例3]
除了将催化剂/原料油比率改变为5.5、将反应带出口温度改变为500℃和接触时间改变为2秒以外,与实施例1同样地进行原料油A的催化裂化反应。表2示出了由原料油至裂化产物的转化率、裂化产物的收率、Δ焦炭以及所获得的汽油的研究法辛烷值。
表1
表2
从表2中所示的结果可以看出,使用含有超稳定Y型沸石的催化剂,在上述反应条件下裂化生物质,可以高收率获得高辛烷值的裂化汽油和轻烯烃。另外,从实施例2的结果可以看出,通过将含有超稳定Y型沸石的催化剂与辛烷值提高用添加剂组合使用,在提高裂化汽油的辛烷值的同时,可以进一步提高更高附加值的轻烯烃的产量。
另外,可以看出,与处理中东脱硫VGO的比较例1和2相比,在实施例1和2中,汽油的收率高5质量%以上。此外,实施例1和2获得的裂化汽油的研究法辛烷值为90~94,具有非常高的实用价值。
另一方面,比较例3相当于在催化剂/原料油比率为5.5、反应带出口温度500℃、接触时间2秒的以往FCC的同样条件下裂化时的情况。在该情况下,裂化汽油的收率是同等的,裂化汽油的研究法辛烷值具有78的低值,这样没有充分的实用性能。
Claims (8)
1.一种生物质处理方法,其特征在于,该方法是使用具有反应带、分离带、汽提带和再生带的流化催化裂化装置通过催化裂化处理生物质的方法,其包括以下工序:
在所述反应带中,使用含有10~50质量%超稳定Y型沸石的催化剂,在所述反应带出口温度为580~680℃、催化剂/油比率为10~40wt/wt、反应压力为1~3kg/cm2G和反应带中的所述原料油与所述催化剂的接触时间为0.1~1.0秒的条件下处理含有生物质的原料油的第一工序;
在所述再生带中,在再生带温度为640~720℃、再生带压力为1~3kg/cm2G和再生带出口处的废气中的氧气浓度为0~3mol%的条件下处理供于所述第一工序的所述催化剂的第二工序,
所述生物质含有来源于动植物油的、氧含量为0.1~13质量%并且沸点为230℃以上的油脂成分。
2.根据权利要求1所述的生物质处理方法,其特征在于,使用下行式反应器作为所述反应带。
3.根据权利要求1所述的生物质处理方法,其特征在于,所述催化剂上的用下式表示的Δ焦炭是0.2~1.5质量%,
Δ焦炭=焦炭在再生处理前的催化剂上的附着量-再生处理后的催化剂上的焦炭残存量,所述附着量和焦炭残存量的单位均为质量%。
4.根据权利要求1所述的生物质处理方法,其特征在于,在所述流化催化裂化装置中,在再生带中在浓状态下流动的催化剂颗粒从再生带出来之前的部分的温度与所述反应带的出口温度之差在150℃以内。
5.根据权利要求1所述的生物质处理方法,其特征在于,在所述第一工序中,使用相当于原料油的2~8质量%的蒸汽,将所述原料油喷雾到所述反应带内。
6.根据权利要求1所述的生物质处理方法,其特征在于,在所述催化剂中,所述超稳定Y型沸石的Si/Al比率以原子比计为3~20。
8.根据权利要求1所述的生物质处理方法,其特征在于,所述催化剂进一步含有氧化硅-氧化铝作为活性基质。
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