南京扬子石化公司芳烃装置催化剂国产化取得重大进展

南京扬子石油化工公司芳烃厂坚持走科技合作开发之路 ,目前 ,芳烃装置用催化剂国产化率达到 90 % ,其中主要生产装置的催化剂国产化率达到了 1 0 0 % ,取得了显著的经济效益。芳烃联合装置催化剂占扬子石化公司催化剂用量的 65% ,如何实现芳烃装置催化剂国产化在扬子石化公司的降本增效中具有举足轻重的地位。1 993年 ,该厂根据周密的市场调查 ,把目光由国外转向国内 ,主动与上海石油化工研究院联系 ,首次与上海石化研究院共同制定了歧化装置催化剂的国产化方案 ,共同开发了 ZA- 94型催化剂 ,并获国家科技成果二等奖。 1 997年 ,又与上海石…     

我国开发成功芳烃歧化催化剂

扬子石化公司芳烃歧化装置年处理量为 12 3万吨 ,是目前国内最大的苯生产装置 ,投产以来一直使用美国ＵＯＰ公司的ＴＡ 3型催化剂 ,但存在投料温度高 ,不能处理高纯度芳烃原料等问题。为此 ,该公司与上海石化研究院合作开发了ＺＡ 94型催化剂 ,并于 1995年首次进行试验性生产使用获得成功。1997年扬子芳烃联合装置扩容改造后 ,双方又联合推出并使用了ＨＡＴ 0 95型催化剂 ,降低了投料温度 ,提高了转化率和选择性 ,并有效地提高了原料处理量 ,增加了苯和二甲苯的产量。 2 0 0 1年 ,该公司芳烃厂根据装置运行特点 ,又使用了上海石化研究院开发…     

PAI-01型C_8芳烃异构化催化剂的工业应用及再生

介绍了PAI-01型C8芳烃异构化催化剂在辽阳石化公司25万吨/年对二甲苯芳烃联合装置异构化单元上替代I-300催化剂的工业应用和再生情况。在乙苯脱烷基型异构化装置上换装了乙苯转化型催化剂,对装置进行改造,增加一轻烃分离塔。结果表明,PAI-01型催化剂的技术指标达到国际先进水平。催化剂应用满三年后,进行了器内再生,再生后催化剂活性可达到新鲜催化剂水平。     

辽阳石化开发脱烷基PX催化剂

<正>脱烷基型碳八芳烃异构化催化剂是PX(对二甲苯)装置生产过程中必需使用的催化剂。由于没有自主知识产权的催化剂技术,中国石油集团现有的两套大型脱烷基型PX生产装置所使用的该催化剂一直依赖进口。辽阳石化研制开发碳八芳烃异构化催化剂放大制备及异构化反应侧线试验项目,今年8月上旬通过了1000小时现场侧线考评和催化剂再生试验。考评结果表明,该脱烷基型碳八芳烃异构化催化剂性能良好,各项技术指标达到了国外同类产品     

SKI-100型C8芳烃异构化催化剂的工业应用

介绍了北京石科院研制开发的SKI-100型二甲苯异构化催化剂在中国石油吉林石化公司炼油厂联合芳烃装置的使用情况。标定结果表明,该催化剂满足了邻二甲苯和苯产品的产量要求,且实现了车间的扩能降耗。同时该催化剂在工业装置运行4年,可满足生产要求,操作简单,活性和稳定性高。     

炼化副产稠环芳烃资源化工型利用的技术策略

近年来,我国的炼油、芳烃和烯烃产业正发生深刻的变化,炼油工业也从大量生产清洁燃料逐步转型为兼产基础化工原料。本工作分析了传统炼油型方案加工催化柴油(LCO)等劣质资源的技术现状,指出稠环芳烃资源化工型利用是助力传统炼厂向化工转型和提质增效的有效途径,可低成本生产芳烃和烯烃等化工原料。在提出化工型转化方案必须满足的五项标准的基础上,重点讨论了可实现联合副产稠环芳烃资源化工型利用的催化剂和工艺技术策略。不同于炼油型加氢裂化催化剂,建议采用低空间指数沸石开发化工型加氢裂化催化剂,提高芳烃产品收率和纯度。为消除加氢精制过程生成的氨对沸石酸性中心的抑制作用,建议采用加氢精制-选择转化两段转化工艺方案。结合化工型加氢裂化催化剂和两段转化工艺方案,能够实现稠环芳烃资源的高效化工利用,轻质芳烃的质量收率大于45%,二甲苯纯度大于98.7%,碳九、碳十重芳烃满足芳烃装置进料要求,联产的饱和轻烃产品和乙烷满足蒸汽裂解装置进料要求。     

RIC-200型二甲苯异构化催化剂再生性能

RIC-200型二甲苯异构化催化剂2010年9月在中国石油化工股份有限公司天津分公司芳烃联合装置上首次工业应用,催化剂的异构化活性为23.6%,乙苯转化率为21.5%,C8芳烃损失质量分数2.67%。连续运转45个月,需对催化剂进行再生。RIC-200型催化剂的首次工业再生采用低氧氮气分步烧焦法。结果表明,催化剂上积炭去除干净,再生催化剂的初始异构化活性为23.7%,乙苯转化率为30.4%,活性恢复良好。调整稳定后,C8芳烃损失质量分数2.2%,选择性良好,表明RIC-200型催化剂具有良好的再生性能。     

HDO-18选择性加氢催化剂的工业应用

抚顺石油化工研究院（FRJPP）开发的HDO-18选择性加氢催化剂是以γ-Al2O3为载体的的贵金属催化剂,主要应用于催化重整生成油选择性加氢。中国石化长岭分公司50万t/a重整装置主要是为25万t／a C6-C8馏分芳烃分离装置提供原料,2006年3月选用HDO-18催化剂,在较缓和的反应条件下,得到了产品溴指数不大于30mg Br／100g,芳烃损失小于0．5个百分点的抽提原料,同时由于反应温度的降低,消除了芳烃分离装置扩能的热源瓶颈,提高了抽提原料加氢处理能力。     

提高半再生重整装置甲苯产率的优化应用

炼厂受限于装置改造、与催化剂成本,半再生重整由于催化剂不能连续再生、反应运行条件苛刻度低等因素,催化剂芳烃转化率低,导致重整产物中芳烃含量低。通过对进重整反应原料进行优化,在不改变炼厂原有催化剂设计的基础上,可提高甲苯产量及装置效益,从而适应化工品市场需求,并且还能够提高装置操作的灵活性,保持装置高效益运行。以某炼厂月加工石脑油4万吨为例,甲苯产率提高后月产值可增加近百万元。     

PS-VI重整催化剂的工业应用试验

PS-VI型催化剂在天津石化80万吨/年连续重整装置上工业应用成功,使用PS-VI型催化剂,重整产品液收率、重整生成油辛烷值,纯氢产率及芳烃产率均达到协议的要求,达到了重整装置扩产改造的目的;PS-VI催化剂具有高活性、选择性和稳定性,与使用PS-IV催化剂进行比较,发现使用PS-VI催化剂时,空速由1.00提高到1.44,氢烃比由2.8下降到1.9,同时PS-VI催化剂持氯能力更强,产生粉尘量更低。     

官能化高岭土负载双金属催化芳香氯化物水相脱氯的研究

利用双金属可协同催化作用,筛选出催化活性较高的两种金属Pd-Mn,用聚乙烯吡咯烷酮(PVP)将Pd-Mn按摩尔比4∶1配位后,再负载于起相转移催化作用的聚乙二醇(PEG)官能化的高岭土(GLM)上,制成一种双负载双金属催化剂PVP-PdCl2-MnCl2/GLM - PEG400,并用于催化难溶于水的芳香氯化物的水相脱...     

The Fischer-Tropsch Synthesis in the Liquid Phase

The hydrogenation of carbon monoxide by the Fischer-Tropsch (F-T) process [1] forms saturated and unsaturated compounds of the homologous hydrocarbon series. It permits the synthesis of hydrocarbons ranging from methane to high-melting paraffins with molecular weights above 20,000, depending on the catalyst, temperature, and type of process employed. By-products such as alcohols, aldehydes, ketones, acids, and esters are formed on a smaller scale. Small amounts of aromatic compounds are formed at high temperatures by secondary dehydrocyclization reactions from the primary hydrocarbons formed.     

PVP-PdCl_2-CrCl_3/GLM-PEG400催化芳香卤化物的脱卤研究

用聚乙烯吡咯烷酮(PVP)配合双金属Pd2+、Cr3+后,再负载于平均相对分子质量为400的聚乙二醇(PEG-400)与高岭土(GLM)组成的载体上,制成双金属双负载催化剂PVP-PdCl2-CrCl3/GLM-PEG400,以甲酸钠为氢转移试剂,催化难溶于水的芳香卤化物水相脱卤,转化率可达97.36%,且催化剂易于分离,在重复使用5次后转化率仍在60%以上。     

The Fischer-Tropsch Synthesis in the Liquid Phase

Abstract

The hydrogenation of carbon monoxide by the Fischer-Tropsch (F-T) process [1] forms saturated and unsaturated compounds of the homologous hydrocarbon series. It permits the synthesis of hydrocarbons ranging from methane to high-melting paraffins with molecular weights above 20,000, depending on the catalyst, temperature, and type of process employed. By-products such as alcohols, aldehydes, ketones, acids, and esters are formed on a smaller scale. Small amounts of aromatic compounds are formed at high temperatures by secondary dehydrocyclization reactions from the primary hydrocarbons formed.     

FCC粗汽回炼生产低烯烃汽油

车用汽油烯烃含量高将带来严重环保问题.FCC装置在正常使用重油提升管时,可设计汽油提升管,用来回炼粗汽油,在降烯烃催化剂作用下,汽油中的C5～C8烯烃可进一步裂化为小分子烯烃,成为液化气组分;另外烯烃参与氢转移反应,得氢饱和为烷烃;同时烯烃环化可生成芳烃,最终使改质汽油的烯烃体积含量降至35%以下.由于芳烃辛烷值较高,从而使汽油保持稳定的高辛烷值.在有效解决芳烃缩合生焦的问题后,该工艺对汽油降烯烃效果理想.     

降低植物油抽提溶剂中芳烃含量的研究

采用新型的脱芳催化剂,对植物油抽提溶剂进行了加氢脱芳试验。结果表明,在温度130~140℃、压力0.15~0.25 MPa(表压)的温和工艺条件下,可将粗植物油抽提溶剂中的苯质量分数由(600~800)×10-6降到10×10-6以下,产品质量符合目前国内外市场上高标植物油抽提溶剂的要求。     

A comparative study of liquid product on non-catalytic and catalytic degradation of waste plastics using spent FCC catalyst

Non-catalytic and catalytic degradation of waste plastics (high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS)) using spent fluid catalytic cracking (FCC) catalyst into liquid product were comparatively studied with a stirred semi-batch reactor at 400 ‡C, under nitrogen stream. Liquid product characteristics were described by cumulative distribution as a function of lapse time of reaction, paraffin, olefin, naphthene and aromatic (PONA) composition, and also carbon number distribution on plastic type of reactant. For degradation of waste PE with relatively high degradation temperature, the effect of adding spent FCC catalyst greatly appeared on cumulative distribution of liquid product with a reaction lapse time, whereas those for waste PP and PS with low degradation temperature showed a similar trend in both non-catalytic and catalytic degradation at 400 ‡C. In PONA and carbon number distribution of liquid product, the characteristics of waste PS that was mainly degraded by end chain scission mechanism were not much altered in presence of spent FCC catalyst. However, waste polyolefinic polymer that was degraded by a random chain scission mechanism significantly differed on PONA and carbon number distribution of liquid product with or without spent FCC catalyst. The addition of spent FCC catalyst in degradation of polyolefinic polymer, which economically has a benefit in utilization of waste catalyst, significantly improved the light olefin product by its high cracking ability and also the aromatic product by cyclization of olefin as shape selectivity in micropore of catalyst.     

Nickel–molybdenum and cobalt–molybdenum sulfide hydrogenation and hydrodesulphurization catalysts synthesized in situ from bimetallic precursors

Unsupported nickel–molybdenum and cobalt–molybdenum sulfide catalysts are synthesized via the in situ decomposition of water-soluble bimetallic precursors in a hydrocarbon feedstock using nickel–molybdenum and cobalt–molybdenum complexes with citric, oxalic, succinic, glutaric, and tartaric acids as precursors. The sulfide catalysts are characterized by means of transmission electron microscopy and X-ray photoelectron spectroscopy. The catalyst activity in the hydrogenation of bicyclic aromatic hydrocarbons and the hydrodesulfurization of dibenzothiophene is studied. The effect the composition of the precursor solution in the hydrocarbon feedstock emulsion has on the activity of the resulting catalyst is determined. It is shown that the activity reaches high values even after 1 h of reaction. The hydrogenation of mono-, di-, and trimethylnaphthalenes and ethylnaphthalene is studied. The optimum promoter-to-molybdenum ratio (0.25: 1) is found. It is shown that the catalyst activity does not fall during recycling, due to the elimination of the negative effect of water contained in the emulsion, which results in oxidation of the catalyst surface. After the second reaction cycle, the catalyst particles are longer and have a greater number of MoS₂ layers than the respective parameters of the catalyst particles after the first cycle. XPS shows that the content of oxygen on the catalyst’s surface falls during recycling, while the fraction of metals in the sulfide environment and the sulfur in the sulfide state grows.     

HZSM-5催化剂在MTG反应中的积炭失活

在固定床不锈钢反应器中进行了HZSM-5分子筛催化甲醇制汽油(MTG)反应的催化性能和失活实验。采用热重、X射线衍射、FT-IR、低温氮吸附-脱附、色谱-质谱联用仪等方法对催化剂进行了表征。结果表明,在反应进行到336 h时,甲醇转化率为40%,汽油收率低至12.6%,催化剂严重失活,但在700℃有氧再生后活性恢复,且保持了完整的MFI结构。积炭是催化剂失活的主要原因,大部分积炭沉积在分子筛微孔中,积炭物种主要是带有双键的聚合态化合物和稠环芳烃。     

Effect of hydrocarbon compositions in the M85 fuel on catalytic conversion

To identify hydrocarbon components suitably blended in the M85 (Methanol: 85 vol%, Gasoline: 15 vol%) fuel while maintaining high emission control performance of the catalyst, the effects of various hydrocarbons on the methanol conversion efficiency were investigated. Saturated hydrocarbons having about 5–7 carbon atoms did not inhibit the methanol conversion efficiency. In contrast, unsaturated hydrocarbons and aromatic hydrocarbons inhibited the methanol conversion efficiency. It was concluded that low saturated hydrocarbons such as light-naphtha were suitable for hydrocarbons mixed with methanol fuel.