FCC汽油中硫化物在改性纳米HZSM-5催化剂上的脱除
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摘要
催化裂化(FCC)汽油约占我国成品油总量的80%。FCC汽油中的烯烃和硫含量很高,常用的加氢脱硫催化剂如Ni-Mo/Al_2O_3等虽然可以降低汽油中的硫含量,但在加氢脱硫过程中会造成烯烃大幅减少,使辛烷值损失。
纳米ZSM-5分子筛催化剂由于晶粒小、微孔短、孔口多和外表面酸量大等特点,在催化脱除噻吩硫及烃类芳构化方面表现出比微米ZSM-5分子筛更好的活性和稳定性。负载稀土金属氧化物和过渡金属氧化物如Ni、Mo都可以进一步提高催化剂的活性及稳定性。本论文首先采用乙酸镍、硝酸镍和硫酸镍作为镍源,比较了用不同镍盐改性的纳米HZSM-5催化剂在FCC汽油脱硫降烯烃过程中的催化活性:在此基础上研究了稀土氧化物对HZSM-5及NiSO_4改性HZSM-5催化剂催化活性的影响:研究了HZSM-5负载NiSO_4制备的芳构化降烯烃脱硫工业催化剂(FDO)再生后SO_4~(2-)的流失对催化剂脱硫活性的影响;最后还研究了MoO_3改性对HZSM-5负载La_2O_3和NiSO_4制备的Ni-La/HZSM-5催化脱硫活性的影响。
得到如下主要结果:
1.Ni(Ac)_2和Ni(NO_3)_2改性的纳米HZSM-5催化剂的脱硫稳定性有明显改善,当用NiSO_4改性后,脱硫率达80%,并且稳定性有了很大提高。
以γ-Al_2O_3和SiO_2小球为载体,分别负载NiSO_4、Ni(Ac)_2和Ni(NO_3)_2所做的对比研究表明,NiSO_4中的S=O与HZSM-5催化剂和γ-Al_2O_3载体中的铝氧化物之间存在着强的相互作用。这种强相互作用可以产生以下影响:(1)产生大量的L酸中心,提高L/B比值,增强L酸与B酸的协同作用;(2)使Ni盐在催化剂表面形成单层分布;(3)减少NiO与Al_2O_3作用生成尖晶石结构NiAl_2O_4的机会:(4)增强催化剂对噻吩的选择性吸附能力,促进脱硫反应的进行。而SO_4~(2-)与SiO_2之间则不存在类似的相互作用。
单纯γ-Al_2O_3负载SO_4~(2-)制备的SO_4~(2-)/Al_2O_3催化剂上虽然会有大量L酸产生,且酸性较强,催化剂却依然没有脱硫活性。这表明在酸性催化剂上,B酸中心是脱硫反应所必不可少的活性中心。
2.用硫含量为1000μg/g的模拟油品(噻吩+环己烷)研究发现,原料中加入烯烃有利于HZSM-5以及Ni/HZSM-5催化剂的脱硫活性和稳定性。这是由于以环己烷和1-辛烯为反应原料时,烯烃和环烷烃的芳构化反应会产生大量的活性氢,这些活性氢可以极大地提高催化剂的脱硫活性和稳定性。
3.适量的La_2O_3和CeO_2改性可以降低HZSM-5上强B酸中心的数量,减少噻吩在催化剂上生成噻吩衍生物的副反应,提高脱硫选择性。La_2O_3或CeO_2改性后再负载NiSO_4制备的双金属化合物改性HZSM-5催化剂上,NiSO_4与催化剂间的强相互作用被削弱,NiSO_4的分解温度从928℃降低到了827℃,NiSO_4的分布状态被改变。La_2O_3与NiSO_4双金属化合物改性HZSM-5催化剂较好的保持了NiSO_4改性催化剂的脱硫稳定性,而CeO_2与NiSO_4之间可能还存在着其它的相互作用,导致CeO_2与NiSO_4双金属化合物改性HZSM-5催化剂的脱硫稳定性急剧下降。
4.以NiSO_4改性HZSM-5制备的芳构化降烯烃脱硫工业催化剂FDO的再生研究表明,经过烧炭再生后,催化剂的芳构化降烯烃活性基本恢复,但催化剂的脱硫活性降低了约20个百分点。脱硫活性的降低主要归因于长运转反应(5400 h)后,再生FDO催化剂上的SO_4~(2-)部分流失,部分NiSO_4转化成为NiO。SO_4~(2-)的流失造成S=O与Al_2O_3之间的相互作用减弱,催化剂的总酸量降低,L/B值变小。在再生FDO催化剂上补载适量NiSO_4可以恢复催化剂的脱硫活性。
5.在负载La_2O_3和NiSO_4制备的Ni-La/HZSM-5催化剂上引入MoO_3,预硫化后,NiSO_4中的Ni同样可以与Mo形成Ni-Mo-S相,增强催化剂的加氢脱硫活性,尤其是提高通过裂解方式难以脱除的噻吩、苯并噻吩等硫化物的脱除能力。但是,3%Mo-Ni-La/HZSM-5的反应结果也表明,MoO_3的引入在使催化剂的总硫脱除率达到了90%以上的同时,烯烃降低幅度多达20个百分点,而芳烃只增加了约7个百分点,造成产物的辛烷值损失了约1.8个单位。
Fluid catalytic cracking(FCC) gasoline contributes about 80%of the total gasoline pool in China.For high content of olefins and sulfur,the FCC gasoline provides over 95%sulfur and almost all of the olefins for the gasoline pool.The gasoline sulfur could be reduced effectively by using traditional hydrotreating catalysts,such as Ni-Mo/Al_2O_3.But there would be a great loss of RON for the decrease of olefins in the hydrotreating process.
ZSM-5 zeolites are widely used in transforming olefins and light alkanes to aromatics and iso-paraffins for excellent aromatization,isomerization and alkylation activities.Nanosize ZSM-5 zeolites show more stable and higher catalytic activity because of smaller crystals, shorter micropore,more micropores and more acid sites at external surface.The catalytic activity of HZSM-5 could be promoted by supporting rare earth metal oxides and transition metal oxides,such as Ni and Mo.In this article,catalysts were prepared by supporting NiSO_4, Ni(Ac)_2 and Ni(NO_3)_2 over nano-HZSM-5.Investigations were performed to evaluate the catalytic performance for the upgrading of FCC gasoline.Effect of rare earth metal oxides modification on desulfurization activity of HZSM-5 and NiSO_4/HZSM-5 catalyst was studied. And the effect of SO_4~(2-) loss upon desulfruization activity of regenerated industrial catalyst FDO,which was prepared by supporting NiSO_4 on HZSM-5,was also studied.Meanwhile, effect of MoO_3 modification on desulfurization activity of Ni-La/HZSM-5,which was prepared by supporting La_2O_3 and NiSO_4 over HZSM-5,was also studied.
Based on all above investigations,the following conclusions were reached:
1.The incorporation of Ni(Ac)_2 and Ni(NO_3)_2 into the HZSM-5 catalysts improved the stability of desulfurization.And the incorporation of NiSO_4 increased not only the desulfurization activity,but also the desulfurization stability largely.
γ-Al_2O_3 and SiO_2 were chosed as the supports to prepare catalysts by impregnating with NiSO_4,Ni(Ac)_2 and Ni(NO_3)_2.And the results showed that there was a strong interaction between S=O in SO_4~(2-) and alumina oxides in both HZSM-5 zeolites andγ-Al_2O_3 supports. The strong interaction could bring following effects:(1) creates a large amount of Lewis acid sites and enhances the ratio of Lewis acid sites to Brφnsted acid sites(L/B);(2) help Ni species disperse in monolayer on catalyst;(3) prevents the forming of NiAl_2O_4 between NiO and Al_2O_3;(4) increases the adsorbing capability for thiophene impurities.
Although a large of amount of lewis(L) acid sites,which was strong enough,was created on SO_4~(2-)/Al_2O_3,there was little desulfurization activity on the catalyst.This was because Brφnsted(B) acid sites were indispensable for the cracking of thiophenic species over acidic catalyst.
2.Thiophene+cyclohexane,in which the sulfur content was 1000μg/g,was used as a model of gasoline.The study showed that the blending of 20 v%1- octene into thiophene +cyclohexane model was beneficial to desulfurization activity and stability.This was becaused that a large amount of active hydrogen was generated in the aromatization process of 1-octene and cyclohexane on HZSM-5 catalyst.And the active hydrogen could accelerate the desulfurization activity and stability.
3.The modifications of La_2O_3 and CeO_2 to HZSM-5 catalysts decreased the amount of strong B acid sites of HZSM-5.The decrease of strong B acid sites inhibited thiophene from transforming into thiophene derives and increased the selectivity of H_2S.HZSM-5 modified by bimetals of La_2O_3 and NiSO_4 or CeO_2 and NiSO_4 showed that the strong interaction between NiSO_4 and HZSM-5 catalysts was weakened.The decomposition tempreture of NiSO_4 on HZSM-5 catalyst decreased from 928℃to 827℃.
4.Industrial catalyst FDO was prepared by impregnating NiSO_4 into HZSM-5 and was used to transform olefin into aromatics.The deactivated FDO was sampled from the industrial unit(200 kt/a) after 5400 h.The regeneration of deactivated FDO showed that the aromatization and de-olefin activities recovered basically after carefully coke calcinations. But the desulfuriaztion activity decreased about 20%.This was because that there was a loss of SO_4~(2-) in RFDO catalyst after 5400 h run.And part of NiSO_4 was transformed into NiO after calcinations.The loss of SO_4~(2-) weakened the interaction between S=O and HZSM-5 catalyst.This led to a dcrease of total amount of acid and smaller L/B.The reloading of proper amount of NiSO_4 could recover the desulfurization activity.
5.La_2O_3 and NiSO_4 were supported on nano-HZSM-5 to prepare Ni-La/HZSM-5 catalyst.The incorporation of MoO_3 into Ni-La/HZSM-5 catalyst increased the desulfurization activity largely,especially the desulfurization activity for thiophene and benzothiophene,which were difficult to be removed by cracking method on HZSM-5.The formation of Ni-Mo-S,which exhibited higher hydrogenating activity,was supposed to be the main cause.The results of 3%Mo-Ni-La/HZSM-5 also indicated that although the desufurization ratio was over 90%,the olefin content in product decreased from 34.0 v%to 14.2 v%.Meanwhile,the aromatic content increased from 31.4 v%to 38.0 v%.This led to a loss of RON,which was about 1.8.
纳米ZSM-5分子筛催化剂由于晶粒小、微孔短、孔口多和外表面酸量大等特点,在催化脱除噻吩硫及烃类芳构化方面表现出比微米ZSM-5分子筛更好的活性和稳定性。负载稀土金属氧化物和过渡金属氧化物如Ni、Mo都可以进一步提高催化剂的活性及稳定性。本论文首先采用乙酸镍、硝酸镍和硫酸镍作为镍源,比较了用不同镍盐改性的纳米HZSM-5催化剂在FCC汽油脱硫降烯烃过程中的催化活性:在此基础上研究了稀土氧化物对HZSM-5及NiSO_4改性HZSM-5催化剂催化活性的影响:研究了HZSM-5负载NiSO_4制备的芳构化降烯烃脱硫工业催化剂(FDO)再生后SO_4~(2-)的流失对催化剂脱硫活性的影响;最后还研究了MoO_3改性对HZSM-5负载La_2O_3和NiSO_4制备的Ni-La/HZSM-5催化脱硫活性的影响。
得到如下主要结果:
1.Ni(Ac)_2和Ni(NO_3)_2改性的纳米HZSM-5催化剂的脱硫稳定性有明显改善,当用NiSO_4改性后,脱硫率达80%,并且稳定性有了很大提高。
以γ-Al_2O_3和SiO_2小球为载体,分别负载NiSO_4、Ni(Ac)_2和Ni(NO_3)_2所做的对比研究表明,NiSO_4中的S=O与HZSM-5催化剂和γ-Al_2O_3载体中的铝氧化物之间存在着强的相互作用。这种强相互作用可以产生以下影响:(1)产生大量的L酸中心,提高L/B比值,增强L酸与B酸的协同作用;(2)使Ni盐在催化剂表面形成单层分布;(3)减少NiO与Al_2O_3作用生成尖晶石结构NiAl_2O_4的机会:(4)增强催化剂对噻吩的选择性吸附能力,促进脱硫反应的进行。而SO_4~(2-)与SiO_2之间则不存在类似的相互作用。
单纯γ-Al_2O_3负载SO_4~(2-)制备的SO_4~(2-)/Al_2O_3催化剂上虽然会有大量L酸产生,且酸性较强,催化剂却依然没有脱硫活性。这表明在酸性催化剂上,B酸中心是脱硫反应所必不可少的活性中心。
2.用硫含量为1000μg/g的模拟油品(噻吩+环己烷)研究发现,原料中加入烯烃有利于HZSM-5以及Ni/HZSM-5催化剂的脱硫活性和稳定性。这是由于以环己烷和1-辛烯为反应原料时,烯烃和环烷烃的芳构化反应会产生大量的活性氢,这些活性氢可以极大地提高催化剂的脱硫活性和稳定性。
3.适量的La_2O_3和CeO_2改性可以降低HZSM-5上强B酸中心的数量,减少噻吩在催化剂上生成噻吩衍生物的副反应,提高脱硫选择性。La_2O_3或CeO_2改性后再负载NiSO_4制备的双金属化合物改性HZSM-5催化剂上,NiSO_4与催化剂间的强相互作用被削弱,NiSO_4的分解温度从928℃降低到了827℃,NiSO_4的分布状态被改变。La_2O_3与NiSO_4双金属化合物改性HZSM-5催化剂较好的保持了NiSO_4改性催化剂的脱硫稳定性,而CeO_2与NiSO_4之间可能还存在着其它的相互作用,导致CeO_2与NiSO_4双金属化合物改性HZSM-5催化剂的脱硫稳定性急剧下降。
4.以NiSO_4改性HZSM-5制备的芳构化降烯烃脱硫工业催化剂FDO的再生研究表明,经过烧炭再生后,催化剂的芳构化降烯烃活性基本恢复,但催化剂的脱硫活性降低了约20个百分点。脱硫活性的降低主要归因于长运转反应(5400 h)后,再生FDO催化剂上的SO_4~(2-)部分流失,部分NiSO_4转化成为NiO。SO_4~(2-)的流失造成S=O与Al_2O_3之间的相互作用减弱,催化剂的总酸量降低,L/B值变小。在再生FDO催化剂上补载适量NiSO_4可以恢复催化剂的脱硫活性。
5.在负载La_2O_3和NiSO_4制备的Ni-La/HZSM-5催化剂上引入MoO_3,预硫化后,NiSO_4中的Ni同样可以与Mo形成Ni-Mo-S相,增强催化剂的加氢脱硫活性,尤其是提高通过裂解方式难以脱除的噻吩、苯并噻吩等硫化物的脱除能力。但是,3%Mo-Ni-La/HZSM-5的反应结果也表明,MoO_3的引入在使催化剂的总硫脱除率达到了90%以上的同时,烯烃降低幅度多达20个百分点,而芳烃只增加了约7个百分点,造成产物的辛烷值损失了约1.8个单位。
Fluid catalytic cracking(FCC) gasoline contributes about 80%of the total gasoline pool in China.For high content of olefins and sulfur,the FCC gasoline provides over 95%sulfur and almost all of the olefins for the gasoline pool.The gasoline sulfur could be reduced effectively by using traditional hydrotreating catalysts,such as Ni-Mo/Al_2O_3.But there would be a great loss of RON for the decrease of olefins in the hydrotreating process.
ZSM-5 zeolites are widely used in transforming olefins and light alkanes to aromatics and iso-paraffins for excellent aromatization,isomerization and alkylation activities.Nanosize ZSM-5 zeolites show more stable and higher catalytic activity because of smaller crystals, shorter micropore,more micropores and more acid sites at external surface.The catalytic activity of HZSM-5 could be promoted by supporting rare earth metal oxides and transition metal oxides,such as Ni and Mo.In this article,catalysts were prepared by supporting NiSO_4, Ni(Ac)_2 and Ni(NO_3)_2 over nano-HZSM-5.Investigations were performed to evaluate the catalytic performance for the upgrading of FCC gasoline.Effect of rare earth metal oxides modification on desulfurization activity of HZSM-5 and NiSO_4/HZSM-5 catalyst was studied. And the effect of SO_4~(2-) loss upon desulfruization activity of regenerated industrial catalyst FDO,which was prepared by supporting NiSO_4 on HZSM-5,was also studied.Meanwhile, effect of MoO_3 modification on desulfurization activity of Ni-La/HZSM-5,which was prepared by supporting La_2O_3 and NiSO_4 over HZSM-5,was also studied.
Based on all above investigations,the following conclusions were reached:
1.The incorporation of Ni(Ac)_2 and Ni(NO_3)_2 into the HZSM-5 catalysts improved the stability of desulfurization.And the incorporation of NiSO_4 increased not only the desulfurization activity,but also the desulfurization stability largely.
γ-Al_2O_3 and SiO_2 were chosed as the supports to prepare catalysts by impregnating with NiSO_4,Ni(Ac)_2 and Ni(NO_3)_2.And the results showed that there was a strong interaction between S=O in SO_4~(2-) and alumina oxides in both HZSM-5 zeolites andγ-Al_2O_3 supports. The strong interaction could bring following effects:(1) creates a large amount of Lewis acid sites and enhances the ratio of Lewis acid sites to Brφnsted acid sites(L/B);(2) help Ni species disperse in monolayer on catalyst;(3) prevents the forming of NiAl_2O_4 between NiO and Al_2O_3;(4) increases the adsorbing capability for thiophene impurities.
Although a large of amount of lewis(L) acid sites,which was strong enough,was created on SO_4~(2-)/Al_2O_3,there was little desulfurization activity on the catalyst.This was because Brφnsted(B) acid sites were indispensable for the cracking of thiophenic species over acidic catalyst.
2.Thiophene+cyclohexane,in which the sulfur content was 1000μg/g,was used as a model of gasoline.The study showed that the blending of 20 v%1- octene into thiophene +cyclohexane model was beneficial to desulfurization activity and stability.This was becaused that a large amount of active hydrogen was generated in the aromatization process of 1-octene and cyclohexane on HZSM-5 catalyst.And the active hydrogen could accelerate the desulfurization activity and stability.
3.The modifications of La_2O_3 and CeO_2 to HZSM-5 catalysts decreased the amount of strong B acid sites of HZSM-5.The decrease of strong B acid sites inhibited thiophene from transforming into thiophene derives and increased the selectivity of H_2S.HZSM-5 modified by bimetals of La_2O_3 and NiSO_4 or CeO_2 and NiSO_4 showed that the strong interaction between NiSO_4 and HZSM-5 catalysts was weakened.The decomposition tempreture of NiSO_4 on HZSM-5 catalyst decreased from 928℃to 827℃.
4.Industrial catalyst FDO was prepared by impregnating NiSO_4 into HZSM-5 and was used to transform olefin into aromatics.The deactivated FDO was sampled from the industrial unit(200 kt/a) after 5400 h.The regeneration of deactivated FDO showed that the aromatization and de-olefin activities recovered basically after carefully coke calcinations. But the desulfuriaztion activity decreased about 20%.This was because that there was a loss of SO_4~(2-) in RFDO catalyst after 5400 h run.And part of NiSO_4 was transformed into NiO after calcinations.The loss of SO_4~(2-) weakened the interaction between S=O and HZSM-5 catalyst.This led to a dcrease of total amount of acid and smaller L/B.The reloading of proper amount of NiSO_4 could recover the desulfurization activity.
5.La_2O_3 and NiSO_4 were supported on nano-HZSM-5 to prepare Ni-La/HZSM-5 catalyst.The incorporation of MoO_3 into Ni-La/HZSM-5 catalyst increased the desulfurization activity largely,especially the desulfurization activity for thiophene and benzothiophene,which were difficult to be removed by cracking method on HZSM-5.The formation of Ni-Mo-S,which exhibited higher hydrogenating activity,was supposed to be the main cause.The results of 3%Mo-Ni-La/HZSM-5 also indicated that although the desufurization ratio was over 90%,the olefin content in product decreased from 34.0 v%to 14.2 v%.Meanwhile,the aromatic content increased from 31.4 v%to 38.0 v%.This led to a loss of RON,which was about 1.8.
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