CN1122702C - 一种烃类催化裂化硫转移助剂及其使用方法 - Google Patents
一种烃类催化裂化硫转移助剂及其使用方法 Download PDFInfo
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- CN1122702C CN1122702C CN98122187.4A CN98122187A CN1122702C CN 1122702 C CN1122702 C CN 1122702C CN 98122187 A CN98122187 A CN 98122187A CN 1122702 C CN1122702 C CN 1122702C
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Abstract
一种烃类催化裂化硫转移助剂及其使用方法，该助剂是由金属化合物、溶剂和辅助组分组成的油溶性或水溶性的分子或胶体的溶液、乳液或悬浮液，其中金属化合物是金属的氧化物、氢氧化物、有机酸盐、无机酸盐或其络合物，所述金属是碱土金属、过渡金属和稀土金属三组金属中的两种或两种以上，且其选自至少两组金属，溶剂是水、醇类或烃类，辅助组分是醇类、醚类、酯类、胺类、酰胺类、醇胺类或离子型、非离子型表面活性剂，助剂为水溶性时，金属化合物的含量为30～80%(重量)，溶剂的含量为10～40%(重量)，辅助组分的含量为10～30%(重量)；助剂为油溶性时，金属化合物的含量为50～85%(重量)，溶剂的含量为10～30%(重量)，辅助组分的含量为5～20%(重量)。该硫转移助剂可以随催化裂化进料或水蒸汽一起注入到反应器中，也可以单独注入到反应器或再生器中，其在催化剂上的沉积量为0～3%(重量)。
Description
本发明涉及烃类催化裂化硫转移助剂及其使用方法，尤其是石油炼制领域中，用于烃类催化裂化的硫转移助剂及其使用方法。
通常，催化裂化原料中含有0.3～3.0％的硫，经过裂化后进料中的硫大约20～60％以H2S形式进入裂化气，20～70％进入液体产品，其余5～30％进入焦炭，沉积在催化剂上。其中裂化气中的H2S可转化为硫磺进行回收；而进入轻质油品中的有机硫化物须通过加氢精制手段脱除。但当裂化原料硫含量较高时，轻质油品往往因含硫量偏高不符合质量标准。通过降低油品干点或采取更苛刻精制手段，可以解决上述问题，但势必使得加工成本增加、利润减少；沉积在催化剂焦炭中的硫，在催化剂再生烧焦过程中会氧化为SO2和SO3(统称SOX)，随烟气排入大气，造成环境污染。此外再生烟气中SOX含量较高时，还会造成再生器设备腐蚀。
目前，降低催化裂化再生烟气中SOX含量和轻质油品中硫含量的一种广泛使用的技术是采用固态的硫转移助剂。固态的硫转移助剂可以分为两类：一类是为降低再生烟气中SOX浓度的助剂；另一类是为降低轻质油品中含硫量特别是汽油中含硫量的助剂。其中美国专利US4,589,978和US5,021,228公开的一种硫转移助剂属于第一类，中国专利CN1,093,735A公开的一种硫转移助剂属于第二类。在美国专利US4,589,978中，公开了一种固体硫转移催化剂，该催化剂由含量为1％～20％的镧(La)、铈(Ce)和载体组成，其中La∶Ce为1∶10～10∶1，载体可以是氧化铝、氧化硅、硅藻土、沸石等，该催化剂作为单独颗粒和催化裂化催化剂混合使用，使用过程中要求催化裂化再生器要达到完全再生，氧气过量0～2％(体积)，在加入量约占系统藏量的0.5～8.0％时，SOX脱除率可达30～80％。在US5,021,228中，公开了一种固体硫转移组合物，其组成是：(1)多孔氧化铝载体；(2)第一组分锕系金属，主要为钍、铀，含量为0.5～10％(重量)；(3)第二组分碱土金属，主要为钾、钠，含量为1～5％(重量)，该组合物可作为催化裂化催化剂组分使用，可使60％的SOX转化为H2S。在CN1,093,735A中，公开了一种催化裂化催化剂组合物，包括作为单独的组分分散在无机氧化物基质中的分子筛和以氧化铝为载体的路易斯酸，其单独的组分包括约1～50％(重量)以氧化铝为载体的选自Ni、Cu、Zn、Cd、Ti、Bi、B、Al等的元素和化合物，该组合物的其它组分为5～50％(重量)合成八面沸石，约10～60％(重量)粘土以及10～30％(重量)选自二氧化硅、氧化铝和二氧化硅—氧化铝无机粘合剂，该组合物在提升管再生器中型设备试验中观察到汽油中的硫含量明显降低，同时并没降低汽油产率。在上述专利公开的技术中，硫转移助剂的性能单一，即只能降低再生烟气中的SOX浓度或者是只能降低轻质油品中的硫含量，且硫转移助剂本身没有催化裂化活性，这些助剂加入到系统中，实际上对催化裂化催化剂起到稀释作用，使系统中的催化剂混合物活性降低，选择性变差。例如，对于微反活性(MA)为60的平衡催化剂，当加入5％的硫转移助剂时，微反活性大约要降低3个单位，其选择性要明显变差。另一方面，现有的硫转移助剂都是固体，要求有与催化裂化催化剂协调一致的颗粒度分布、机械强度及球形度，因此这种固体颗粒加入系统后，其在系统藏量中所占的比例不能进行灵活调节，对原料含硫量经常变化的装置适应性较差，且制备这种固体颗粒时需要严格复杂的工艺设备。
本发明的目的在于提供一种可同时降低再生烟气中的SOX浓度和轻质油品中的硫含量，且对系统中催化剂的活性和选择性无不良影响的液体硫转移助剂及其使用方法，以改善现有技术中固体硫转移助剂的单一性能，即只能降低再生烟气中的SOX浓度或者是只能降低轻质油品中的硫含量，并克服硫转移助剂对系统中催化剂的活性和选择性所造成的不良影响。
本发明提供的一种液体硫转移助剂，是由金属化合物、溶剂和辅助组分组成的油溶性或水溶性的分子或胶体的溶液、乳液或悬浮液。其中金属化合物是金属的氧化物、氢氧化物、有机酸盐、无机酸盐或其络合物，而所述金属是碱土金属、过渡金属和稀土金属三组金属中的两种或两种以上，且其选自这三组金属中的至少两组，具体地讲，可以按所述方法从Mg、Ca、Zn、Ag、Cd、La、Sn、Ce、Ti、Bi、Pb、Al、B、Pr、Ba、Ga中选取金属；所述有机酸盐所用的有机酸选自饱和羧酸、不饱和羧酸、取代羧酸和苯磺酸中的一种或一种以上，如丙酸、丙二酸、丁酸、异丁酸、2-甲基丁酸、辛酸、异辛酸、异壬酸、苯甲酸、环烷酸、柠檬酸、酒石酸、脂肪酸、油酸、十二烷基苯磺酸、对甲基苯磺酸等；所述无机酸盐所用的无机酸选自硝酸、磷酸、磺酸。溶剂是水、醇类或烃类，如甲醇、乙醇、苯、甲苯、二甲苯、乙基苯、异辛烷、十二烷、200号溶剂油等。辅助组分是醇类、醚类、酯类、胺类、酰胺类、醇胺类或离子型、非离子型表面活性剂，如乙二醇、丙三醇、二甘醇、异丁醇、甲基叔丁基醚、乙二醇二甲醚、丙胺、丁胺、乙二胺、1，4-丁二胺、二甲基甲酰胺、苯甲酰胺、单乙醇胺、二甘醇胺、聚乙稀醇、壬基酚聚氧乙稀醚、脂肪醇聚氧乙稀醚、油酸二乙醇酰胺等，辅助组分主要起分散、稳定或助溶作用。该助剂为水溶性时，金属化合物的含量为30～80％(重量)，溶剂的含量为10～40％(重量)，辅助组分的含量为10～30％(重量)，此时助剂的成本低，使用方便，易于清洗，有利于劳动保护；而当助剂为油溶性时，金属化合物的含量为50～85％(重量)，溶剂的含量为10～30％(重量)，辅助组分的含量为5～20％(重量)，此时助剂的成本高，毒性大，但与催化裂化原料互溶，分散性能好。
本发明提供的液体硫转移助剂的使用方法，其特征是它可以随催化裂化进料或水蒸汽一起注入到反应器中，也可以单独注入到反应器或再生器中，加注系统无需复杂设备，只需一个贮罐、一台泵和相应管线即可。硫转移助剂可以单独使用，也可以与其它液体催化裂化助剂或物流一起使用，如与金属钝化剂或油浆阻垢剂或提升管反应器急冷油混合后注入反应器。这里所说的催化裂化进料是指新鲜原料和/或循环进料，即回炼油和回炼油浆。
本发明提供的液体硫转移助剂的加注量并非越多越好，催化剂上如果过多地沉积硫转移助剂，助剂中的金属元素会影响催化剂的活性和选择性，一般地说，催化剂上硫转移助剂的沉积量为0～3％(重量)，最好在2000～10000μg/g范围内，其加注速度取决于催化裂化装置的处理量、原料硫含量、烟气SOX排放要求及助剂本身有效成份的含量等多种因素，可以根据实际情况灵活调节，也可以随时停止使用。
本发明提供的液体硫转移助剂的实验室典型制备方法如下：将一定量的金属化合物加入到带有冷凝管的圆底烧瓶中，同时加入等当量的有机酸或无机酸，并加入适量的溶剂，在不断搅拌下，加热回流3～15小时，最好是5～10小时，使温度升高到100℃～130℃，然后冷却到50℃～80℃，再加入适量的辅助组分，搅拌1～2小时，即可得到均匀液体产品。
本发明提供的液体硫转移助剂及其使用方法适用于流化催化裂化的各种装置模式，包括馏份油催化裂化(FCC)、渣油催化裂化(RFCC)、深度催化裂化(DCC，又称催化裂解)，以及其它利用流化催化裂化连续反应—再生原理进行烃类催化转化的工艺过程，如MGG、ARGG、MIO等催化裂化家族技术工艺过程。
本发明提供的液体硫转移助剂可以使再生烟气中的SOX浓度降低40～80％，同时使轻质油品中的硫含量降低5～30％，且对系统中催化裂化催化剂的活性和选择性无不良影响。由于该硫转移助剂是液体，所以制备过程中不需要喷雾干燥等复杂的工艺设备，价格较低。本发明提供的液体硫转移助剂的使用方法，使液体硫转移助剂的加注量易于灵活调节，操作易于实现自动化控制。
本发明提供的液体硫转移助剂的硫转移性能是在固定床装置上进行评价的。首先向反应器上装入用硫转移助剂浸渍和老化处理的催化剂5克，然后在730℃温度下，用反应气SO2、N2、O2吸附1小时，再用N2汽提10分钟，最后用还原气H2、H2O在520℃下脱附，脱SOX率可以按下式计算：
以下通过实施例来进一步说明本发明提供的液体硫转移助剂及其使用方法和效果。
实施例1
称22.9克市售的碳酸镧(纯度＞99％)，8.4克碳酸镁(纯度＞99％)，6.7克氧化亚锡，86.3克异辛酸，10克200号溶剂油和0.5克壬基酚聚氧乙稀醚一起加入到带有冷凝管的圆底烧瓶中。在不断搅拌下，升温到103～110℃，反应3小时，然后冷却到80℃，加入9.7克市售的三异丁基铝，混合均匀。产品为深棕色均匀液体，其性质见表1。
实施例2
称23克市售的碳酸铈(纯度＞99％)，8.4克碳酸镁(纯度＞99％)，11.6克三氧化二铋，4.1克氧化锌，55.5克丙酸和10克水，同时加入带有冷凝管回流的三口烧瓶中。在不断搅拌下依此加入8克二甲基甲酰胺，3克二甘醇，然后升温到100～105℃，反应8小时，然后冷却到50℃，加入3克甲酸乙酯，混合均匀。产品为棕黄色均匀液体，其性质见表1。
表1 液体硫转移助剂的主要理化性质
| 项目 | 实施例1 | 实施例2 |
| 物理状态 | 深棕色均匀液体 | 棕黄色均匀液体 |
| 密度，20℃，kg/m3 | 1260 | 1530 |
| 粘度，40℃，mm2/s | 98 | 38 |
| 溶解性 | 油可溶 | 水可溶 |
| 金属含量m％镧铈镁铋锡锌铝 | 10.81.904.61.0 | 10.91.98.32.6 |
实施例3
选取A、B、C、D四种催化剂，其中A、B为新鲜催化剂，C、D为工业平衡催化剂，其性质见表2。首先使催化剂A、B、C、D在450℃下焙烧2小时，接着用实施例1制备的液体硫转移助剂浸渍催化剂A，用实施例2制备的液体硫转移助剂浸渍催化剂B、C、D，然后分别在760℃、100％水蒸汽的条件下老化6小时，用大港柴油(237～337℃)在微反装置上测其微反活性，数据列在表3中。可以看出，所制备的液体硫转移助剂对催化剂活性无不良影响，具有一定程度的提高。对新鲜催化剂和平衡催化剂的活性进行比较后，可以看出，液体硫转移助剂对新鲜催化剂活性的提高更大一些。
表2 催化剂主要物化性质数据
| 催化剂 | A | B | C | D | |
| 化学组成％ | Al2O3 | 41.96 | 50.4 | 41.5 | 42.45 |
| Fe2O3 | 0.64 | 0.45 | 1.2 | 0.59 | |
| Na2O | 0.38 | 0.17 | 0.3 | 0.49 | |
| Re2O3 | 1.96 | / | 2.98 | 1.42 | |
| 筛分组成m％ | ＜20μm | 3.6 | 2.8 | 3.1 | 0.50 |
| 20～40μm | 14.3 | 18.9 | 18.4 | 3.30 | |
| 40～80μm | 55.9 | 60.8 | 54.8 | 70.70 | |
| ＞80μm | 26.2 | 17.5 | 23.7 | 25.50 | |
| 物理性质 | 表面积，m2/g | 189 | 190 | 107 | 106 |
| 孔体积，ml/g | 0.152 | 0.34 | 0.26 | 0.125 | |
| 堆积密度，g/cm3 | 0.72 | 0.76 | / | / | |
| 晶胞常数，A | 24.39 | / | 24.42 | / | |
| 微反活性(760℃，6h) | 70.5 | 67.0 | 60 | 61.7 | |
| 金属含量μg/g | Ni | / | / | 4400 | 5800 |
| V | / | / | 520 | 1050 | |
| Fe | / | / | 3600 | 4050 | |
| Na | / | / | 4600 | 6100 | |
表3 催化剂活性评价试验结果
| 催化剂有效硫转移助剂载量，μg/g | 催化剂微反活性，m％ | |||
| M* | 催化剂A | 催化剂B | 催化剂C | 催化剂D |
| 02000400080001200015000 | 70.170.870.571.472.673.0 | 67.067.267.868.468.970.1 | 60.259.860.061.461.962.2 | 61.761.561.862.563.162.8 |
*M∶Ce∶Mg∶Bi∶Zn∶Al＝2∶2∶1∶1∶1(摩尔比)
实施例4
选用实施例3制备的催化剂样品A、C、D，考察其硫转移及再生性能。为此，在固定床反应器上分别用反应气(SO20.12％(体积)、O23.5％(体积)、N296.38％(体积))和还原气(H298％(体积)、H2O2％(体积))进行吸附、脱附循环试验，气体流量为30毫升/分。首先在730℃用反应气吸附1小时，然后用N2汽提10分钟，再用还原气在520℃下脱附，反复进行这一过程，测定硫转移效果。试验结果列表4。
表4 液体硫转移助剂硫转移试验效果
| 催化剂有效硫转移助剂载量 | 脱SOX率(v％) | ||
| 催化剂A | 催化剂C | 催化剂D | |
| M＝0 μg/g | 0 | 0 | 0 |
| M＝2000 μg/g | 38.1 | 45.5 | 43.7 |
| M＝4000 μg/g | 45.0 | 49.7 | 51.6 |
| M＝6000 μg/g | 48.8 | 54.6 | 57.3 |
| M＝8000 μg/g | 53.3 | 60.5 | 62.4 |
| M＝10000 μg/g | 63.8 | 70.9 | 74.1 |
实施例5
使用实施例1制备的液体硫转移助剂和催化剂C，在催化剂藏量为4kg的FCC提升管中试试验装置上采用本发明提供的使用方法，用柱塞泵将液体硫转移助剂注入到试验所用的中原混合常压渣油(其性质见表5)中，并一起进入反应器。在表6所列试验条件下，考察该液体硫转移助剂的使用效果，以烟气中SOX与空白对比所减少的百分数表示其硫转移效率。
表7列出在原料油中采用不同液体硫转移助剂加注量时FCC裂化产品中的硫分布情况，表8列出在原料油中采用不同液体硫转移助剂加注量时FCC裂化汽油中硫醇硫和噻吩硫的分布情况，可以看出，沉积在催化剂上的硫转移助剂金属总量为5000～12000ppm时，再生烟气中SOX排放量降低了40～80％，轻质油中硫含量降低了5～30％。
表5 原料油性质
| 项目 | 数据 | |
| 密度，20℃，kg/m3 | 910.2 | |
| 分子量 | 454 | |
| 残炭，m％ | 5.68 | |
| 粘度，mm2/s | 80℃ | 89.5 |
| 100℃ | 15.6 | |
| 元素分析，m％碳氢硫氮 | 86.4912.600.73840.1628 | |
| 族组成，m％饱和烃芳烃胶质+沥青质 | 52.633.414.0 | |
| 馏程，℃10％30％60％90％ | 319413508678 | |
表6 提升管FCC中型试验条件
| 提升管出口温度，℃ | 520 |
| 进料预热温度，℃ | 340 |
| 再生器温度，℃ | 720 |
| 反应器压力，MPa | 0.15 |
| 反应时间，s | 2.9 |
| 剂油比 | 7.0 |
| 雾化水量，m％ | 6.5 |
表7 原料硫在FCC产物中的分布(m％)
| 催化剂C* μg/g | 汽油 | 轻柴油 | 油浆 | 裂化气 | 焦炭 | 烟气 |
| M＝0 | 5.43 | 13.28 | 10.27 | 56.08 | 14.62 | 14.62 |
| M＝5000 | 5.18 | 13.16 | 10.62 | 56.32 | 14.72 | 8.79 |
| M＝8000 | 4.69 | 12.84 | 10.96 | 56.66 | 14.85 | 7.43 |
| M＝12000 | 3.80 | 12.49 | 11.20 | 57.35 | 15.16 | 2.92 |
注：*M Ce∶Mg∶Bi∶Zn∶Al＝2∶2∶1∶1∶1(摩尔比)
原料硫在FCC产物中的分布(％)符合下式：
汽油％+轻柴油％+油浆％+裂化气％+烟气％
＝汽油％+轻柴油％+油浆％+焦炭％+裂化气％-(焦炭％-烟气％)＝100％
表8 FCC裂化汽油中硫醇硫和噻吩硫的变化
| 催化剂C* μg/g | M＝0 | M＝5000 | M＝8000 | M＝12000 |
| 硫醇硫(m％) | 0.23 | 0.16 | 0.08 | 0.17 |
| 噻吩硫(m％) | 5.20 | 5.02 | 4.57 | 3.99 |
*M Ce∶Mg∶Bi∶Zn∶Al＝2∶2∶1∶1∶1(摩尔比)
Claims (8)
1.一种烃类催化裂化硫转移助剂，其特征在于：该助剂是由金属化合物、溶剂和辅助组分组成的油溶性或水溶性的分子或胶体的溶液、乳液或悬浮液，其中金属化合物是金属的氧化物、氢氧化物、有机酸盐、无机酸盐或其络合物，所述金属是碱土金属、过渡金属和稀土金属三组金属中的两种或两种以上，且其选自至少两组金属，溶剂是水、醇类或烃类，辅助组分是醇类、醚类、酯类、胺类、酰胺类、醇胺类或离子型、非离子型表面活性剂，当助剂为水溶性时，金属化合物的含量为30～80重量％，溶剂的含量为10～40重量％，辅助组分的含量为10～30重量％；当助剂为油溶性时，金属化合物的含量为50～85重量％，溶剂的含量为10～30重量％，辅助组分的含量为5～20重量％。
2.根据权利要求1所述的烃类催化裂化硫转移助剂，其中金属化合物是金属的有机酸盐，有机酸盐所用的有机酸选自饱和羧酸、不饱和羧酸、取代羧酸和苯磺酸中的一种或一种以上。
3.根据权利要求1所述的烃类催化裂化硫转移助剂，其中金属化合物是金属的无机酸盐，无机酸盐所用的无机酸选自硝酸、磷酸和磺酸。
4.根据权利要求1所述的烃类催化裂化硫转移助剂，其中所说的催化裂化是指馏份油催化裂化、渣油催化裂化、深度催化裂化和其它利用流化催化裂化反应—再生原理进行烃类催化转化的工艺过程。
5.权利要求1所述的烃类催化裂化硫转移助剂的使用方法，硫转移助剂使用时，可以随催化裂化进料或水蒸汽一起注入到反应器中，也可以单独注入到反应器或再生器中，其在催化剂上的沉积量为0～3重量％。
6.根据权利要求5所述的烃类催化裂化硫转移助剂的使用方法，其中硫转移助剂在催化剂上的沉积量为2000～10000μg/g。
7.根据权利要求5所述的烃类催化裂化硫转移助剂的使用方法，其中催化裂化进料是指新鲜原料和/或循环油进料。
8.根据权利要求5或6或7所述的烃类催化裂化硫转移助剂的使用方法，其中硫转移助剂可以与其它液态催化裂化助剂或物流一起使用，也可以单独使用。
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| CN98122187.4A CN1122702C (zh) | 1998-12-29 | 1998-12-29 | 一种烃类催化裂化硫转移助剂及其使用方法 |
| JP5020A JP2000204378A (ja) | 1998-12-29 | 2000-01-04 | 炭化水素の接触分解のための硫黄除去剤およびそれを用いた炭化水素の接触分解方法 |
| US10/292,681 US6790343B2 (en) | 1998-12-29 | 2002-11-12 | Sulfur transfer additive for catalytic cracking of hydrocarbons and a catalytic cracking process of hydrocarbons using the same |
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| US7591939B2 (en) * | 2004-06-22 | 2009-09-22 | Stone & Webster Process Technology, Inc. | Integrated desulfurization and FCC process |
| US20070259052A1 (en) | 2006-05-05 | 2007-11-08 | Shire International Licensing B.V. | Assay for lanthanum hydroxycarbonate |
| US8623199B2 (en) * | 2006-06-28 | 2014-01-07 | Saudi Arabian Oil Company | Clay additive for reduction of sulfur in catalytically cracked gasoline |
| CN101190416B (zh) * | 2006-12-01 | 2011-06-15 | 石大卓越科技股份有限公司 | 一种催化裂化催化剂及其制备方法 |
| EP2280777A1 (en) * | 2008-01-11 | 2011-02-09 | W. R. Grace & Co.-Conn | Rare earth carbonate compositions for metals tolerance in cracking catalysts |
| EP3222345A1 (en) * | 2008-07-30 | 2017-09-27 | King Fahd University Of Petroleum&Minerals | Metallic clay based fcc gasoline sulfur reduction additive compositions |
| CN102068888A (zh) * | 2010-12-28 | 2011-05-25 | 北京博奇电力科技有限公司 | 一种湿法烟气同时脱硫脱硝方法 |
| CN103525451A (zh) * | 2012-07-05 | 2014-01-22 | 中国石油化工集团公司 | 一种催化裂化添加剂及其使用方法 |
| CN103525450A (zh) * | 2012-07-05 | 2014-01-22 | 中国石油化工集团公司 | 一种烃油催化裂化添加剂加注方法 |
| CN102755817B (zh) * | 2012-07-17 | 2015-01-21 | 中国石油天然气股份有限公司 | 一种大比表面积催化裂化烟气硫转移剂的制备方法 |
| CN103657729B (zh) * | 2012-09-20 | 2015-10-21 | 中国石油化工股份有限公司 | 烃油催化裂化硫转移助催化剂及其制备方法 |
| US9480946B2 (en) * | 2013-04-15 | 2016-11-01 | Baker Hughes Incorporated | Metal carboxylate salts as H2S scavengers in mixed production or dry gas or wet gas systems |
| CN105778979B (zh) * | 2014-12-22 | 2017-11-07 | 中国石油天然气股份有限公司 | 一种降低催化裂化汽油硫含量的催化剂及其制备方法 |
| CN105664680A (zh) * | 2016-03-29 | 2016-06-15 | 黄河三角洲京博化工研究院有限公司 | 一种液体fcc再生烟气硫转移剂 |
| CN108267540B (zh) * | 2016-12-30 | 2020-11-06 | 中国石油天然气股份有限公司 | 一种催化裂化再生烟气硫转移助剂的脱硫性能测试方法 |
| CN113041989B (zh) * | 2021-03-19 | 2023-05-16 | 润和催化材料(浙江)有限公司 | 一种表面富含碱性位点的硫转移剂及其制备方法 |
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| US4243557A (en) * | 1978-12-26 | 1981-01-06 | Exxon Research & Engineering Co. | Sulfur transfer cracking catalyst |
| US4238317A (en) * | 1979-08-20 | 1980-12-09 | Standard Oil Company (Indiana) | Catalytic cracking with reduced emission of noxious gases |
| US4240899A (en) * | 1979-11-05 | 1980-12-23 | Exxon Research & Engineering Co. | Sulfur transfer process in catalytic cracking |
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| FR2627105B3 (fr) | 1988-02-16 | 1990-06-08 | Inst Francais Du Petrole | Procede de presulfuration de catalyseur de traitement d'hydrocarbures |
| US5371055A (en) | 1988-07-07 | 1994-12-06 | W. R. Grace & Co.-Conn. | Increasing metal-tolerance of FCC catalyst by sulfur oxide removal |
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-
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| JP2000204378A (ja) | 2000-07-25 |
| US20030121824A1 (en) | 2003-07-03 |
| US6790343B2 (en) | 2004-09-14 |
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