催化裂化汽油的选择性催化加氢脱硫技术

论述了催化裂化汽油选择性加氢脱硫技术的现状和发展趋势 ,着重介绍了催化裂化汽油选择性加氢催化剂的制备、影响选择性的若干因素 ,以及选择性加氢脱硫工艺技术的进展。对选择性加氢技术与临氢改质技术的差异、选择性加氢工艺与其它工艺的组合应用等问题也进行了讨论。     

OCT-M催化裂化汽油选择性加氢脱硫技术

介绍了抚顺石油化工研究院开发的OCT-M催化裂化汽油选择性加氢脱硫技术及其在中国石油化工股份有限公司广州分公司0．20ML／a重油催化裂化汽油加氢装置进行首次工业应用试验的情况。该技术将催化裂化汽油切割为轻、重馏分，采用专门的催化剂对重馏分进行选择性加氢脱硫，脱硫后再与轻馏分词合，脱硫率高，汽油烯烃含量降低不大、抗爆指数损失小。工业应用初期标定结果表明：硫质量分数为400-600μg/g、烯烃体积分数为29．6％、研究法辛烷值92．4、马达法辛烷值81．0的重油催化裂化汽油经过该技术处理后，产物汽油硫质量分数为73～89μg／g、烯烃体积分数约21．8％，研究法辛烷值约90．5，马达法辛烷值约80．3，混合汽油质量收率为99．4％，达到了攻关指标。     

催化裂化汽油选择性加氢脱硫催化剂RSDS-1的开发

介绍了用于催化裂化汽油选择性加氢脱硫催化剂RSDS-1的研究开发，考察了载体、活性组元、金属原子比以及助剂对催化剂选择性的影响。研究结果表明，催化裂化汽油中烯烃的加氢饱和受扩散限制；Co—Mo组合对烯烃饱和的能力相对较弱；较高的Co／Mo原子比有利于提高催化剂选择性；助剂的加入对催化剂选择性有明显的影响；RSDS—1催化剂用于催化裂化汽油选择性脱硫，对不同原料油适应性好，脱硫率可达80％，RON损失小于2个单位，且可长周期稳定运转。     

催化裂化汽油选择性加氢脱硫催化剂及工艺技术开发

2010年以来,我国车用汽油向国际先进标准迈进,逐步实现与国际水平接轨。为了适应清洁汽油生产的需要,中国石油天然气股份有限公司石油化工研究院开发了催化裂化汽油选择性加氢脱硫DSO工艺技术及配套的催化裂化汽油选择性加氢脱硫催化剂。该催化剂制备流程简单,无贵金属、无分子筛,通过精细调控氧化铝载体孔结构、采用化学助剂改性、配制稳定多组元活性组分共浸液等技术手段,实现了催化剂孔结构、酸性质、活性相三者优化匹配,使其具有高活性、高选择性、高稳定性,达到深度脱硫的同时有效抑制烯烃饱和的目的。该产品已成功在玉门炼化32×104t/a、大连石化20×104t/a、乌鲁木齐石化60×104t/a催化汽油加氢装置进行工业应用,结果表明,该产品原料适应性强,反应条件缓和,脱硫率高,辛烷值损失小,液收高,运转周期长,技术成熟可靠。     

催化汽油加氢脱硫催化剂选择性调控技术的工业应用

介绍了催化汽油加氢脱硫催化剂选择性调控(RSAT)技术在中国石化青岛石油化工有限责任公司60万t/a催化汽油加氢脱硫装置上的工业应用情况。装置经过18个月的长周期稳定运转,工业标定结果表明,以催化裂化MIP(多产异构烷烃)汽油为原料(硫含量690~849μg/g),生产硫含量小于10μg/g的国Ⅴ汽油时,产品汽油研究法辛烷值(RON)损失约1.5个单位,收率大于99.5%,在深度脱硫条件下产品汽油RON损失较调控前减少约0.4个单位。     

OCT-M催化汽油选择性加氢脱硫技术的工业应用

中国石化抚顺石油化工研究院开发的OCT-M催化汽油选择性加氢脱硫技术,能将催化汽油切割为轻、重2种馏分并进行脱硫处理,克服了传统催化汽油加氢脱硫工艺中脱硫与辛烷值损失的矛盾。在中国石化广州分公司30万t/a加氢精制装置的首次工业应用结果表明,催化汽油的含硫质量分数从处理前的(419～461)×10-6降低至处理后的(104～108)×10-6,含烯烃质量分数从29.8%降至21.1%,而混合汽油的研究法辛烷值下降了约2个单位,马达法辛烷值降幅不到1个单位,达到了脱硫率高而汽油辛烷值尽量不损失的预定目标。     

汽油选择性加氢脱硫催化剂研制

NHO—1是一种具有加氢精制功能和提高汽油辛烷值功能的双功能催化剂、用NHO—1催化剂加氢处理高含硫催化、重催和焦化汽油时,能脱除硫,保持辛烷值基本不变,催化剂表观上显示了选择性加氢脱硫的特点。     

催化裂化汽油选择性加氢脱硫催化剂的研制及性能评价

报道了催化裂化汽油选择性加氢脱硫催化剂HL－07的研制及小试性能评价结果，该剂对催化裂化汽油有较脱硫活性和较低的烯烃饱和活性，硫含量为1100μg/g的原料加氢脱硫后硫含量降为295μg/g,RON及MON的损失分别为0．6及0．7个单位。     

催化裂化汽油选择性加氢脱硫装置的工艺选择

为生产超低硫清洁汽油,对比分析了ＣＤＨＤＳ及Ｐｒｉｍｅ－Ｇ＋这２种典型催化裂化汽油选择性加氢脱硫工艺的流程选择、催化剂选用、主要操作参数、产品质量和主要公用工程消耗情况。结果表明,在工艺流程方面,２种工艺在轻汽油处理单元均采用全馏分汽油加氢技术,ＣＤＨＤＳ工艺在重汽油加氢脱硫单元采用的是催化蒸馏加氢脱硫技术,略优于Ｐｒｉｍｅ－Ｇ＋工艺采用的固定床加氢脱硫技术;２种工艺使用的催化剂略有不同;在工业设计方面,采用这２种工艺虽然均可生产出超低硫清洁汽油,但与 Ｐｒｉｍｅ－Ｇ＋工艺相比,ＣＤＨＤＳ工艺的主要操作参数略优,公用工程消耗较低。     

制备因素对催化裂化汽油加氢脱硫催化剂性能的影响

针对催化裂化汽油脱硫技术要求,介绍了一种以共沉淀法制备的载体负载Co、Mo活性金属组分的催化汽油加氢脱硫催化剂,考察了载体Mg／Al原子比、焙烧温度、活性金属含量对催化剂活性及选择性的影响,并对本研究的催化剂进行了1000h的稳定性试验。实验结果表明,采用Mg／Al=X 0、5、焙烧温度(y 200)℃所制备的载体,在其活性金属MoO3含量8％、CoO含量2.0％时,催化剂具有适宜的酸性中心数和最佳的脱硫选择性;本研究催化剂在1000h的试验运转过程中,具有较高的脱硫率和较低的烯烃饱和率,其活性稳定性良好。     

FCC汽油重馏分催化蒸馏加氢脱硫研究

利用LH-02型常规加氢脱硫催化剂,在催化蒸馏小试装置上对FCC汽油重馏分进行了加氢脱硫研究。在压力(表压)1.7MPa、床层平均温度286℃、氢油体积比200、体积空速2h-1、回流比3的条件下,FCC汽油重馏分脱硫率达到92.4%,总硫质量分数由1480μg/g降到112μg/g;脱硫后的重馏分油与FCC轻馏分油调合得到的脱硫后FCC汽油,总硫质量分数由1107μg/g降到295μg/g,抗爆指数损失2.0个单位;脱硫后的重馏分油与醚化后的FCC轻馏分油调合得到的脱硫后FCC醚化汽油,总硫质量分数为289μg/g,抗爆指数损失1.0个单位;脱硫后的FCC汽油性质良好,部分性质指标有较大幅度改善;液体收率高达99.6%以上。     

Aromatization of FCC Gasoline Over Modified HZSM-5 Catalyst

Zinc and phosphorus incorporated HZSM-5 catalyst was prepared by adopting incipient wet co-impregnation (Zn-P/HZSM-5). Zn-P/HZSM-5 catalyst exhibited the lowest acidity but the highest aromatization activity with stable performance in the studied period of 16 hr. The process conditions on aromatization reaction and the coke deactivation mechanism of Zn-P/HZSM-5 catalyst were studied on a small-scale, fixed bed reactor using FCC naphtha (75-120°C). The weight contents of ZnO and P₂O₅ were 2% and 4%, respectively. Results showed that Zn-P/HZSM-5 catalyst under a temperature of 450°C, liquid hourly space velocity of 1.0 h^-1, and pressure of 0.1 MPa, the conversions of olefins and alkanes are 96.77% and 88.94%, respectively, the contents of olefins, aromatics in liquid product are 6.79% and 74.57%, respectively. Carbon deposition was the major reason for catalyst deactivation due to the catalyst's good performance as a fresh catalyst after regeneration. All of the blending products fitted the standards of Chinese gasoline.     

利用废渣制备催化裂化催化剂及其催化性能研究

采用X射线荧光光谱、N₂吸附-脱附、吡啶吸附红外光谱等分析手段对催化裂化催化剂生产过程所产生的废渣进行分析,并研究了废渣脱除杂质的处理工艺;利用优化处理的废渣或/和高岭土为载体、分子筛为活性组分经喷雾干燥制备催化裂化催化剂,分析催化剂的物化性质,并利用固定流化床装置评价催化剂性能。结果表明：pH为3.0、搅拌时间为20 min、NH₄Cl投料比为20%、温度为60℃、洗涤介质为NH₄Cl、先洗涤后焙烧再洗涤是处理催化剂废渣的最佳工艺条件;在反应温度为480℃、剂油质量比为7.5、质量空速为4 h^-1、原料油为大庆减压蜡油的条件下,与以高岭土为载体的催化剂相比,综合考虑优选载体中废渣质量分数在10%～20%的催化剂具有更强的重油转化能力,产物液体收率和汽油选择性更高,汽油组成中异构烷烃含量高、烯烃含量低。     

Desulfurization of FCC Gasoline Over Mordenite Modified with Al2O3

Mordenite modified with Al₂O₃ (Al₂O₃/mordenite) was synthesized and used for the desulfurization of FCC gasoline. The influences of operating parameters on the results were studied for the model solution composed of dibenzothiophene (DBT) and isooctane. Al₂O₃/mordenite exhibits higher sulfur capacity than other kinds of chemisorbents. The suitable composition of the chemisorbent is 30 wt% Al₂O₃ to 70 wt% mordenite. The optimal operating parameters are: temperature 160°C; velocity 3 h^-1 (WHSV). Under the stated conditions, desulfurization was carried out for the FCC gasoline with sulfur content of 220.4 μg/g. The chemisorbent can maintain the sulfur content under 50 μg/g for 40 h and has good regeneration ability after desorption using benzene.     

An Orthogonal Method for Aromatization Reactions of Shenghua FCC Gasoline

Using a confined fluidized bed reactor and aromatization catalysts (LBO-A and LBO-16), the aromatization performance of Shenghua fluid catalytic cracking (FCC) gasoline has been studied in an orthogonal method. The experimental results reveal that the optimum reaction condition for the light oil yield was reaction temperature 420°C, WHSV 40 h^-1, mass ratio catalyst to oil 4 and 75% LBO-A and 25% LBO-16; the optimum reaction condition for aromatics amount in the light oil was reaction temperature 420°C, WHSV 30 h^-1, mass ratio catalyst to oil 5 and 65% LBO-A and 35% LBO-16, the olefin content is remarkably reduced from about 54.7% to 12.8% and 8.7% (by mass), respectively, at the same time the reaction mechanism of aromatization reaction is put forward based on the experimental result.     

Desulfurization of FCC Gasoline by Solvent Extraction and Photooxidation

A deep desulfurization process for FCC light gasoline has been investigated. The process is comprised of liquid-liquid extraction with acetonitrile, and photooxidation with ultraviolet light from a high-pressure mercury lamp. After the extraction the sulfur-containing compounds transfer from the oil to the solvent and then the solvent containing these sulfur compounds was photo-irradiated with ultraviolet light from a high pressure mercury lamp 300 W and with λ 200-300 nm, using strengthen electronic stirrer during the irradiation .The oil from the solvent was recovered with water. An azeotropic mixture (containing 86% acetonitrile and 14% water) was recovered successfully with one distillation column, and can reuse. The total sulfur content in this gasoline decreased from 309 to 68 ppm following 8 h of photo-irradiation .The total yield of the oil vary between 90-96%. The main sulfur compounds of this gasoline are alkyl substituted thiophenes.     

Synthesis of Chloroaluminate Ionic Liquids and Use for Olefin Reduction in FCC Gasoline

Room temperature ionic liquids (RTILs) are mainly referred to melting salt systems composed by organic cations and organic or inorganic anions that exhibit liquid-like behavior at or around room temperature. Chloroaluminate room temperature ionic liquid (chloroaluminate RTILs) is one kind of RTIL synthesized by chloride quaternary ammonium salts and anhydrous AlCl₃. Three kinds of chloroaluminate RTILs were synthesized using trimethylamine hydrochloride (TA), 1-butylpyrinium chloride (BPyC), or 1-methyl-3-alkylimidazolium (BMIC), respectively, with anhydrous AlCl₃ and their application in reducing the content of olefin in FCC gasoline from the Jinzhou Petrochemical Corporation was studied. The effects of chloroaluminate RTIL component and operation conditions on olefin reduction were investigated as well as the repeatability of chloroaluminate RTILs. The results show that at room temperature, when the ratio of anhydrous AlCl₃ to quaternary ammonium (mole/mole), the solvent-oil ratio (g/g), and the reaction time were 2/1, 20/100, and 1/2 h, respectively, the content of olefin in FCC gasoline was deduced more than 30%. The chloroaluminate RTILs could be used at least four times on the basis of keeping their activity.     

催化裂化柴油加氢生产高密度喷气燃料过程研究

利用催化裂化柴油（LCO）密度较高且富含芳烃的性质特点,开展了以LCO为原料生产高密度喷气燃料的工艺研究。结果表明,以LCO为原料,采用高芳烃饱和活性的NiMoW/Al₂O₃加氢精制催化剂,在适当的工艺条件下进行超深度加氢饱和,可使LCO中芳烃质量分数降低至5%以下。进一步通过气相色谱-质谱（GC-MS）方法进行详细的烃类分析,可明确各烃类的分布规律并考察富集单环、二环及三环环烷烃的馏分,确定全馏分LCO加氢生产高密度喷气燃料时理想的终馏点为270～280 ℃,在此分馏温度下可得到冰点低于－47 ℃、密度（20 ℃）大于0.835 g/cm³ 的高密度喷气燃料组分。     

Reducing Olefins Content of FCC Gasoline Using a NANO-HZSM-5 Catalyst

The study of reducing olefins properties on nano-HZSM-5 catalyst was investigated with a continuous fixed reactor using fraction of fluid catalytic cracking gasoline (75N120°C). The experimental results showed that nano-HZSM-5 catalyst has the best reducing olefins properties under the optimal conditions: temperature 430°C, pressure 0.3 MPa, and liquid hourly space velocity 1 h^-1, and the content of olefins in the feed stock decreased to 12.11% and dropped 31 percentage points. The yield of liquid product, the content of aromatics, and the content of isoalkane in liquid product are up to 84.98%, 39.58%, and 35.23% respectively.     

FCC汽油烷基化脱硫的中试研究

针对加氢脱硫技术(HDS)存在的操作条件苛刻、装置投资及操作费用高等缺点,无锡蓝星石化公司与西南石油大学合作,采用后者研制的催化剂SW-Ⅰ对无锡蓝星石化公司FCC汽油进行烷基化脱硫中试试验研究。在SW-Ⅰ催化剂用量0.61%、反应温度60 ℃、压力0.5~0.8 MPa、空速3.77 h-1的条件下,100 mL催化剂SW-Ⅰ可处理原料油27.5 L,烷基化脱硫汽油的硫含量为191 μg/g、收率为87.90%,。将烷基化脱硫汽油与直馏汽油、C9芳烃以及MTBE按质量比67：15：10：8调合生产车用汽油,调合汽油RON为93.4,密度为0.721 5 g/cm3,硫含量为142 μg/g,硫含量符合国Ⅲ标准。与HDS相比,FCC汽油烷基化脱硫技术工艺流程简单、操作条件缓和、不损耗辛烷值、装置投资及操作费用低、能耗低,具有一定的工业应用前景。