2.0 Mt／a 焦化汽柴油加氢精制装置催化剂活性分析

中海石油炼化有限责任公司惠州炼化分公司2.0 Mt/a加氢精制装置以焦化汽柴油为原料,目的生产乙烯料石脑油和符合欧IV车用柴油标准（硫＜50μg/g）的清洁柴油。该装置选用了抚顺石油化工研究院开发的HPS-02A/B脱硅剂和FH-40C精制剂。自2009年4月24日一次开车成功,到目前已经运行五年多。分析催化剂活性情况,有助于在生产末期及时调整操作,保证产品质量,促进安全生产。     

FH-98加氢精制催化剂和FC-20临氢降凝催化剂在工业上的联合应用

抚顺石油化工研究院开发的FH-98加氢精制催化剂和FC-20临氢降凝催化剂应用于杭州炼油厂的油品精制装置，对混合汽柴油(焦化汽油、焦化柴油、催化柴油、直馏柴油)进行中压加氢降凝精制。工业应用结果表明，加氢催化剂和降凝催化剂的联合使用，降低了其硫氮含量，降低了其凝点，提高了其安定性，生产的加氢精制稳定汽油可作合格化工轻油，加氢精制柴油可作0^#柴油调和组分。较好地解决了焦化汽柴油、催化柴油、直馏柴油的出路问题。     

PH-98型催化剂用于大庆焦化柴油和重油催化轻柴油混合油加氢精制的研究

为解决大庆焦化柴油和重油催化轻柴油产品的安定性和对加氢装置扩能的需要,进行了FH-98型催化剂用于大庆焦化柴油和重油催化轻柴油混合油加氢精制工艺的研究。研究结果表明,FH-98型催化剂对大庆焦化和重油催化混合柴油进行加氢精制,可以生产出0^#一等品柴油,能满足加氢装置扩能的需要。     

FHUDS-2催化剂在天津石化的工业应用

中国石油化工股份有限公司天津分公司为生产硫含量符合欧Ⅲ排放标准S≯350（μg／g）柴油及满足未来更为严格的欧Ⅳ排放标准S≯50（μg/g）柴油,在320万t/a柴油加氢装置上选用了中国石油化工股份有限公司抚顺石油化工研究院（FRIPP）开发的柴油超深度加氢脱硫催化剂FHUDS-2。工业应用结果表明,FHUDS-2催化剂对各种油品的适应性强,反应温度低,具有优异的加氢脱硫性能,是生产清洁柴油的理想催化剂。     

1.7Mt/a煤柴油加氢精制装置的设计与标定

国内某炼厂1.7 Mt/a煤柴油加氢精制装置包括1.4 Mt/a柴油加氢精制部分和0.3 Mt/a煤油加氢精制部分,两部分热量联合,共用一套公用工程系统。对该装置的工程设计与工业标定进行总结,简要介绍了工艺及工程技术特点,并对装置的工业运转标定结果作了简要分析。结果表明,柴油加氢精制催化剂DN-3630和煤油加氢精制催化剂FH-40B效果良好,柴油产品硫含量达到15μg/g,满足国IV车用柴油排放标准,煤油产品全面满足GB6537-2006标准3#喷气燃料要求,装置能耗达到国内先进水平。     

FH-98加氢催化剂在石油三厂120万 t/a 中压加氢装置的应用

抚顺石化公司石油三厂120万 t/a 柴油中压加氢装置于2002年7月建成投产,并开车一次成功.2010年装置换用 FH-98加氢精制催化剂,工业应用表明,FH-98催化剂具有优异的加氢性能和高的加氢脱硫活性,加氢处理焦化汽油、柴油混合油,生产清洁柴油和合格的乙烯裂解原料.     

FHUDS-5柴油深度脱硫催化剂国外工业应用分析

受清洁油品需求的增长,柴油深度加氢脱硫催化剂需求日益增加。抚顺石油化工研究院针对满足欧Ⅳ和欧Ⅴ清洁柴油的生产,开发出Mo-Co型FHUDS-5柴油深度加氢脱硫催化剂。FHUDS-5催化剂被BP公司测试中心评为一流催化剂,为该催化剂推向国际市场提供了有力支撑。该催化剂成功应用在 Paramo 公司一套38万吨/年的低压柴油装置上,生产柴油产品硫含量小于10μg/g,完全满足客户要求。同时,FHUDS-5催化剂顺利通过印度IOCL公司Panipat炼厂催化剂评价,并成功应用在该炼厂一套70万t/a的柴油装置,生产柴油产品硫含量小于50μg/g,远远超过该公司生产柴油产品硫含量小于170μg/g的要求。     

PHF-101型催化剂在2.0Mt·a~(-1)柴油加氢装置的工业应用

介绍了PHF-101型柴油加氢精制催化剂在中国石油乌鲁木齐石化分公司2.0 Mt·a~(-1)柴油加氢装置的工业应用情况,结果表明,在反应器入口压力7.83 MPa、空速1.84 h~(-1)、平均温度358℃和氢油体积比476∶1条件下,加工硫含量1 835μg·g~(-1)的混合汽油和柴油原料,精制柴油硫含量4.8μg·g~(-1),十六烷值提高4.0个单位。PHF-101型催化剂加氢性能优良,运转稳定性良好,满足国Ⅳ和国Ⅴ柴油生产需求。     

离子液体脱氮-加氢精制处理高氮焦化汽柴油的研究

采用离子液体对高含氮焦化汽柴油进行脱氮预处理,确定了处理过程适宜脱氮预处理条件,并对预脱氮后焦化汽柴油进行加氢精制工艺评价。结果表明,离子液体预脱氮处理适宜条件为：剂油质量比1∶100,反应温度50 ℃,搅拌时间30 min,沉降时间1.0 h,此条件下,焦化汽柴油的碱氮脱除率为94.9％,且离子液体具有较好的重复使用性。在相同条件下,经预脱氮处理后的柴油与未处理柴油相比,加氢生成油中硫、氮和芳烃含量明显降低,尤其是氮含量低,氮化物的含量高低对催化剂的加氢精制性能有影响。采用离子液体脱氮-加氢精制可深度脱除焦化汽柴油中硫化物与氮化物,降低芳烃含量,改善产品质量,达到生产低硫和低芳烃清洁燃料的目的。
     

预硫化型FF-66/FC-20催化剂组合应用生产国Ⅵ低凝柴油

为实现柴油产品质量升级,选择抚顺石油化工研究院研制的新一代加氢精制催化剂FF-66替换原加氢精制催化剂FF-36,与加氢裂化催化剂FC-20组合使用生产国Ⅵ低凝柴油。结果表明,采用FF-66/FC-20组合催化剂处理催化柴油、焦化汽油和直馏柴油组成的混合原料(平均硫含量为2 742μg/g),标定工况下的柴油产品硫含量降低至4.5μg/g,氮含量降低至0.35μg/g,多环芳烃质量分数降低至3.3%,十六烷值提高了3.5个单位,凝点降至-24℃。说明FF-66/FC-20催化剂活性匹配良好,具有优异的脱硫、脱氮性能和十六烷值增值能力,能够满足柴油加氢改质异构降凝装置生产国Ⅵ低凝柴油的需求。     

Preparation and properties of poly(Nε,Nε-dicarboxymethyl-l-lysine)

A new ampholytic homopolypeptide, $\text{poly}\text{(N}{}^{\mathrm{\epsilon }}\text{,N}{}^{\mathrm{\epsilon }}\text{-}\text{dicarboxy-methyl-}\text{l}\text{-lysine}\text{)}$, which has one tertiary amino and two carboxyl groups in the side chain has been derived from a hydrochloride salt of poly(L-lysine). The polymer in aqueous solution seems to be in the coil form with locally extended structure (LES) at neutral pH. In both the acidic and alkaline regions, the molar ellipticity of the polymer changes as a result of change in net charge on the side chain. The conformational changes may be from the coil with LES to other coiled forms. 5–7 M NaClO₄ and 80% aqueous methanol induce the α-helix in the polymer at neutral pH. Divalent cations, Cu²⁺ and Ca²⁺, do not induce any remarkably ordered structures such as α-helix or β-structure in the polymer in aqueous solution at any pH. Ultraviolet absorption studies show an absorption peak of the polymer-Cu²⁺ complex near 240 nm. Dependence of the peak intensity on pH at various q values ($\text{q =}\text{[}\text{Cu}{}^{\mathrm{2+}}\text{]}\text{[}\text{residue}\text{]}$) indicates the two steps of the complex formation. At q less than 0.64, the formation is described only with the first step. An average coordination number for Cu²⁺ at the first step was calculated to be about 2 by the method of Mandel and Leyte. The association constant of Cu²⁺ with the residue at the step was determined from the absorption data to be far smaller than that for the Cu²⁺-EDTA complex. The second step of the formation occurs in the case of large q but the absorption data for the second step cannot be obtained exactly due to precipitation.     

Wet Milling of Fe/Al/Al2O3 and Fe2O3/Al/Al2O3 Powder Mixtures

Wet milling of Al₂O₃-aluminide alloy (3A) precursor powders in acetone has been investigated by milling Fe/Al/Al₂O₃ and Fe₂O₃/Al/Al₂O₃ powder mixtures. The influence of the milling process on the physical and chemical properties of the milled powders has been studied. Particle refinement and homogenization were found not to play a dominant role, whereas plastic deformation of the metal particles leads to the formation of dislocations and a highly disarranged polycrystalline structure. Although no chemical reactions among the powder components in Fe₂O₃/Al/Al₂O₃ powder mixtures were observed, the formation of a nanocrystalline, ordered intermetallic FeAl phase in Fe/Al/Al₂O₃ powder mixtures caused by mechanical alloying was detected. Chemical reactions of Fe and Al particle surfaces with the atmosphere and the milling media lead to the formation of highly porous hydroxides on the particle surfaces. Hence the specific surface area of the powders increases, while the powder density decreases during milling. The fraction of Fe oxidized during milling was determined to be 0.13. The fraction of Al oxidized during milling strongly depends on the metal content of the powder mixture. It ranges between 0.4 and 0.8.     

Participation of lewis base on vinyl chloride polymerization with Al(C2H5)3CCl4 catalyst system

The polymerization of vinyl chloride has been investigated using an $\text{Al}\text{(}\text{C}{}_2\text{H}{}_5\text{)}{}_3\text{CCl}{}_4$ catalyst system in the presence of various Lewis bases. Effective Lewis bases are γ-butyrolactone, diglyme and diethylenetriamine which are multidentate. The rate of polymerization is dependent not only on the basicity of the Lewis base used but also on a coordination number of one. The latter is the predominant factor. For the effect of polymeric amines, a tentative hypothesis is discussed.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.     

Synthesis and Characterization of Ti0.33Ta0.33Nb0.33C and Ti0.33Ta0.33Nb0.33CxN1-x Whiskers

Ta_0.33Ti_0.33Nb_0.33C and Ta_0.33Ti_0.33Nb_0.33C _x N_{1− x} whiskers were synthesized via a carbothermal vapor-liquid-solid growth mechanism in the temperature range 900°-1450°C in Ar or N₂. The optimum temperature was 1250°C. Whiskers were obtained in a yield of 70-90 vol%. The whiskers were 0.5–1 µm in diameter and 10–30 µm in length. The starting materials that produced the highest whisker yield were: TiO₂, Ta₂O₅, Nb₂O₅, C, Ni, and NaCl. C was added to reduce the oxides, and Ni to catalyze whisker growth. NaCl was used as a source of Cl for vapor-phase transportation of Ta and Nb oxochlorides and Ti chlorides to the catalyst. The catalyst metal was recycled several times during the synthesis and was transported as NiCl₂( g ) according to thermodynamic calculations. The rate of formation and the chemical composition of the whiskers depended on the synthesis temperature, the choice of catalyst, and the atmosphere. At low temperatures, the whiskers were enriched in Nb and Ta, whereas the Ti content increased with increased synthesis temperature.