溶剂精制对焦化蜡油和催化回炼油催化裂化反应性能的影响

采用糠醛对辽河超稠原油直接延迟焦化得到的劣质焦化蜡油及其与催化回炼油的混合油进行溶剂精制,并在连续反应-再生催化裂化中型实验装置中进行了溶剂精制前后劣质焦化蜡油及其与催化回炼油混合油的催化裂化反应。结果表明,在精制油收率67%～70%的条件下,溶剂精制法可脱除劣质焦化蜡油中78%～85%的氮和36%～39%的芳烃、胶质及沥青质。劣质焦化蜡油及其与催化回炼油的混合油溶剂精制后,其催化裂化反应转化率大幅度提高。精制油的催化裂化反应性能优于辽河渣油催化裂化（RFCC）原料,与RFCC原料掺炼后,轻质油产率提高,生焦率下降,产品质量明显改善。     

重油催化裂化装置技术改造及其效果

为使重油催化裂化装置适应原料油重质化、劣质化的要求,提高产品柴汽比,降低装置能耗和新鲜催化剂单耗,提高装置效益,广州石油化工总厂重油催化裂化装置1999年大修中进行了一系列技术改造,主要是增设外取热器和应用石油化工科学研究院开发的MGD工艺技术,实践证明改造是成功的,效果显著,达到了预期目的.     

MILD HYDROCRACKING OF VACUUM GAS OILS TO IMPROVE FCC PERFORMANCE AND MAXIMIZE DISTILLATE YIELDS

A pilot plant study was conducted on mild hydrocracking of heavy vacuum gas oils derived from two different crude sources over a commercially available catalyst to determine the possibility of utilizing mild hydrocracker bottoms as fluidized catalytic cracking feedstock along with improved middle distillate yields. The mild hydrocracking experiments were conducted at 390°C, 60 kg/cm², 1.0/h liquid hourly space velocity and H₂/oil ratio of 390 l/l in a pilot plant trickle bed reactor using two catalyst beds for pretreatment and mild hydrocracking reactions. The experimental results showed that mild hydrocracking would result in valuable middle distillates with low sulphur and nitrogen content. With research octane number of 78, the naphtha obtained from mild hydrocracking was found to be a good blending stock for gasoline pool. The middle distillate fraction (140-370°C) obtained from mild hydrocracking product was found to have cetane number in the range of 48-54. The bottom product from mild hydrocracking of heavy vacuum gas oils was found to be a good feedstock for fluidized catalytic cracking unit because of its low sulphur, nitrogen and aromatic contents. The data obtained from pilot plant studies showed that the processing of mild cracker bottom in FCC unit would result in better quality fuels.     

CGP-1QD催化剂在青岛石化催化裂化装置中的应用

介绍了CGP-1QD型催化剂在中国石化青岛石油化工有限责任公司催化裂化装置上的工业应用情况。结果表明:该催化剂能够适应催化裂化原料的重质化和劣质化,具有较强的裂化能力、抗氮及金属污染能力和较好的焦炭选择性。在原料发生变化后,总液收高达88.69%,说明具有良好的原料适应性。     

镍污染方式对催化剂裂化性能的影响

研究了催化裂化催化剂中镍含量及镍污染方式对催化剂活性和选择性的影响机理。结果表明，镍对催化剂性能的影响与污染方式有关，镍的存在使催化剂的活性下降，在镍含量相当的情况下，对催化剂活性的影响程度接近。镍的毒性表现为强烈的催化脱氢作用，它使裂化反应选择性变差，但工业平衡剂中镍对催化剂选择性的影响小于实验室污染剂。工业平衡剂中的镍通过减少催化剂活性中心数量，从而影响催化剂的活性；实验室污染剂上的镍通过在催化剂表面附着、阻塞分子筛孔道，减少反应物分子对活性中心的可接近性，从而影响催化剂的活性和选择性。     

大庆类原油常压渣油催化裂化生产90号汽油

提高大庆类原油催化裂化汽油辛烷值工业试验于1996年10月至1997年1月在前郭炼油厂800Kt／a重油催化裂化装置上进行。结果表明，采用DOCR－1催化剂和相应的工艺技术能有效地提高催化裂化汽油的辛烷值。与不用DOCR－1催化剂的结果相比，汽油RON达到90．1，提高1．4个单位；MON达到79.8，提高2．4个单位。轻质油收率降低1．75个百分点，干气和焦炭选择性明显改善，是一种理想的生产高辛烷值汽油和提高重油转化的技术，对汽油的升级换代和无铅化具有重要意义。     

MILD HYDROCRACKING OF VACUUM GAS OILS TO IMPROVE FCC PERFORMANCE AND MAXIMIZE DISTILLATE YIELDS

ABSTRACT

A pilot plant study was conducted on mild hydrocracking of heavy vacuum gas oils derived from two different crude sources over a commercially available catalyst to determine the possibility of utilizing mild hydrocracker bottoms as fluidized catalytic cracking feedstock along with improved middle distillate yields. The mild hydrocracking experiments were conducted at 390°C, 60 kg/cm², 1.0/h liquid hourly space velocity and H₂/oil ratio of 390 l/l in a pilot plant trickle bed reactor using two catalyst beds for pretreatment and mild hydrocracking reactions. The experimental results showed that mild hydrocracking would result in valuable middle distillates with low sulphur and nitrogen content. With research octane number of 78, the naphtha obtained from mild hydrocracking was found to be a good blending stock for gasoline pool. The middle distillate fraction (140–370°C) obtained from mild hydrocracking product was found to have cetane number in the range of 48–54. The bottom product from mild hydrocracking of heavy vacuum gas oils was found to be a good feedstock for fluidized catalytic cracking unit because of its low sulphur, nitrogen and aromatic contents. The data obtained from pilot plant studies showed that the processing of mild cracker bottom in FCC unit would result in better quality fuels.     

地下水热催化裂化降粘开采稠油新技术研究

针对辽河油田的3种稠油,筛选陋一种合适的水热裂解催化剂（过渡金属盐）,确定了水热裂解的最佳条件,在0．2％该催化剂顾在下,3种稠油样在240℃经水热裂解反应24h后,50℃粘度分别下降89．9％－77．7％,饱和烃和芳香烃含量大幅上升,胶质,沥青质含量下降,烃碳数分布移向低碳数方向,产生大量气体和少量固体,在辽河油田曙光采油3口蒸汽吞吐井进行的地下稠油催化剂水热裂解降粘开采现场试验获得成功,采出的稠油粘度大同度降低。     

Catalytic cracking of vegetable oils for production of high-octane gasoline and petrochemical feedstock

The routes of transformation of vegetable oils under catalytic cracking conditions have been investigated. The influence of the component composition of the catalyst on distribution of the desired cracking products and their chemical group composition has been revealed. It has been shown that introduction of H-ZSM-5 zeolite into the composition of the oil cracking catalyst promotes the formation of C₂-C₄ light olefins??the yield of propylene and butylene mainly increases. During cracking on bizeolites catalysts, high yields of both gasoline fractions and light olefins are observed. The relationship between the unsaturation index of the vegetable oils and the product distribution during their catalytic cracking has been established. Oils with a high index of unsaturation are cracked on the bizeolite catalyst yielding primarily mono- and polyaromatic hydrocarbons.     

RS—1催化剂对3号喷气燃料临氢脱色的研究

为解决直馏喷气燃料颜色差的问题,在200mL加氢装置上进行了3号喷气燃料直馏组分临氢脱色工艺研究。试验结果表明：RS－1催化剂具有较好的脱色、脱硫醇性能,对性质较差的阿曼与江汉油生产的喷气燃料脱色后产品色号达到＋30号,且脱色活性十分稳定,经2000h寿命试验,产品色号仍保护＋30号。该工艺反应温度、压力和氢油体积比低,空速 高,可降低能耗,具有工业应用价值。     

南疆原油重组分适宜加工方向分析

对南疆原油350～520℃减压馏分进行综合分析,发现该原油减压馏分黏度指数较低(64～85),不适合生产高黏度指数润滑油,可考虑生产低凝点润滑油。该馏分平均分子中烷基侧链上的碳原子占总碳原子的百分数为59.30%,重金属镍+钒质量分数仅0.15μg/g,可直接作为重油催化裂化的原料。南疆原油520℃以上的渣油组分性质分析表明,该渣油属于第3类渣油,其密度在980.0 kg/m3以上,残炭值达24.80%,100℃运动黏度高达13 000 mm2/s,硫质量分数达1.98%,钒质量分数高达170.5μg/g。该渣油作为焦化原料硫含量较高,将对焦化产品的质量产生影响,可采用溶剂脱沥青工艺生产一定量的沥青。如果作为重油催化裂化原料的掺料,必须考虑调配比例,控制硫和金属钒含量,以防催化剂中毒。     

钒镍污染对催化裂化增产丙烯助剂性能的影响

采用浸渍法对流化催化裂化（FCC）中的增产丙烯助剂（LHP-A）进行了重金属钒、镍污染复配。考察了不同含量钒、镍单独或共同污染作用下对LHP-A的比表面积、相对结晶度和微反活性的影响,并分别在固定床微型反应评价装置（MAT）和先进的催化裂化评价装置（ACE）上评价了增产丙烯助剂相应污染复配后催化剂的反应性能。结果表明:无论LHP-A是否被重金属钒、镍单独或共同污染,只要FCC主催化剂复配了含质量分数10%的丙烯助剂后,丙烯收率均可提升4个百分点以上;在钒污染质量分数低于1%时,LHP-A具有良好的水热稳定性;当重金属镍污染LHP-A时,干气产率显著增加,但在钒污染量相同的前提下,镍的存在可以减缓钒对丙烯助剂性能的影响。     

A REVIEW OF THE CHEMISTRY FOR CATALYTIC CRACKING OF HEAVY OILS

The chemistry of catalytic cracking of heavy oils is basic and essential to the research, use and development of advanced catalytic cracking techniques for heavy oils. The effect of physic-chemical characteristics of heavy oils on the catalytic cracking process were discussed. The researches on chemical composition and structure of heavy oils were summarized in terms of separation methods and the determination of chemical composition and structural parameters. Studies and developments of the chemistry of catalytic cracking of heavy oils were reviewed in this paper. At last, some problems to be resolved about the feed, catalyst, processing and regeneration were put forward based on information in hand.     

适于生产大宗石油化工原料的原油优化选择

原油特性与工艺路线相匹配是炼油厂最大化生产大宗石油化工原料的重要途径。针对典型原油加工路线,就适宜于生产大宗石油化工原料的世界主要油区原油进行了优化选择,结果表明：采用<350 ℃馏分收率和链烷烃含量2种性能比较原油直接裂解性能时,中东地区原油是生产乙烯的较理想原料。构建由链烷烃、一环环烷烃和一环芳烃组成的裂化指数,对减压馏分油的催化裂解性能进行比较,发现来自北非、亚太等地区的原油是生产丙烯同时兼顾芳烃的较好原料。针对以加氢裂化为核心工艺的多产芳烃加工路线,以残炭和金属含量对渣油加氢工艺进行优选,表明南美地区渣油需采用浆态床加氢工艺加工,中东地区渣油采用沸腾床加氢工艺加工较好,亚太、非洲地区渣油可采用固定床加氢工艺加工。     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.     

沸石基油砂沥青改质催化剂的性能研究

研究和开发高效减黏、抗硫氮和重金属的水热催化裂化改质催化剂是油砂沥青资源利用技术的关键,以天然斜发沸石为基质制备氢型沸石载体和微孔镍基沸石催化剂,考察其应用于模型化合物水热裂化的性能和对加拿大麦肯河SAGD油砂沥青减黏改质的效果。结果表明：在正十六烷为模型化合物的水热裂化过程中,微孔镍基沸石催化剂表现出良好的催化裂化性能和优良的水热稳定性;在油砂沥青改质试验中,微孔镍基沸石催化剂能够显著降低油砂的黏度,增产中间馏分油,并在一定程度上降低硫、氮含量,可用于中低温和非临氢条件下的油砂沥青减黏改质。     

Gasoline- and diesel-like products from heavy oils via catalytic pyrolysis

Heavy oil is less expensive than light crude oil, but heavy oil is more expensive to obtain light oil products. Conventional light crude oil resources are decreasing, therefore heavy oil resources will be needed more in the future. There are huge differences from field to field for heavy oil deposits. In terms of final productive use, heavy oil is considered as an unconventional resource. Heavy oil upgrading depends on four important factors: catalyst selection, heavy oil classification, process design, and production economics. Heavy and extra-heavy oils are unconventional reservoirs of oil. Globally, 21.3% of total oil reserves are heavy oil. Heavy oil is composed of long chain organic molecules called heavy hydrocarbons. The thermal degradation of the heavy hydrocarbons in heavy oil generates liquid and gaseous products. All kinds of heavy oils contain asphaltenes, and therefore are considered to be very dense material. The most similar technologies for upgrading of heavy oils are pyrolysis and catalytic pyrolysis, thermal and catalytic cracking, and hydrocracking. The amount of liquid products obtained from pyrolysis of heavy oil was dependent on the temperature and the catalyst. Pyrolytic oil contains highly valuable light hydrocarbons as gasoline and diesel components range. The constant increase in the use of crude oils has raised prices of the most common commercial conventional products and consequently seeking for new alternative petroleum resources, like some unconventional oil resources, becomes an interesting issue. The mass contents of gasoline, diesel, and heavy oil in the crude oil are 44.6%, 38.3%, and 17.1%, respectively. The gasoline yield from the heavy oil catalytic (Na₂CO₃) pyrolysis is higher than the diesel efficiency for all conditions. The yield of gasoline products increases with increasing pyrolysis temperature (from 230°C to 350°C) and percentage of catalyst (from 5% to 10%). The yields of gasoline-like product are from 21.5% to 39.1% in 5% catalytic run and from 32.5% to 42.5% in 10% catalytic run. The yields of diesel-like product are from 9.3% to 29.8% in 5% catalytic run and from 15.5% to 33.7% in 10% catalytic run.     

劣质重油高选择性催化裂化(RTC-G)技术开发

为了达到劣质重油催化裂化多产汽油和低碳烯烃的目的,基于拟全浓相、拟均温、拟匀速反应概念,提出使用快速流化床反应器对劣质重油原料进行催化裂化的思路。以中国石化济南分公司2号催化裂化装置原料油为原料,进行了快速流化床反应器催化裂化反应研究,开发了劣质重油原料高选择性催化裂化（RTC-G）技术。研究结果表明：相比于提升管反应器,使用快速流化床反应器催化裂化时的液化气产率和汽油产率分别高2.33百分点和0.35百分点,干气产率低0.34百分点,产品转化率和高价值产品选择性均有一定优势。在快速流化床反应器内选用适当的催化剂,可使劣质重油催化裂化的液化气产率达25.52%,丙烯产率达11.84%。     

LC－8裂化催化剂产品性能的表征

介绍了ＬＣ－８裂化催化剂制备工艺，采用ＸＲＤ、ＩＲ、ＴＰＤ等手段对ＬＣ－８中试产品及工业试生产产品的性能进行表征，并经固定流化床及小型提升管反应，评价了ＬＣ－８催化剂裂化反应性能。结果表明，ＬＣ－８催化剂具有高强度、高活性、中等堆积密度、良好的活性稳定性、优良的抗重金属污染性能及较强的重油转化能力，有较高的汽油收率、较好的焦炭选择性，是优良的重油加工用催化剂。