NNI-1型C_5/C_6烷烃异构化催化剂长周期运行分析及建议

中国石化海南炼油化工有限公司0.2 Mt/a C5/C6烷烃异构化装置以连续重整装置的拔头油为原料,使用NNI-1催化剂,采用一次通过流程,不设脱异戊烷塔和稳定塔,经设在连续重整装置内的脱丁烷塔稳定处理后作为汽油调合组分。该装置于2006年9月开工投产,截至2015年3月已连续运行3个周期。长周期运行分析结果表明:前两个周期中NNI-1催化剂具有较高的异构化活性及选择性,C5异构化率为60%左右,C6异构化率为80%左右,C6选择性为15%左右,产品辛烷值基本达到技术指标要求(RON≥78);而在第三周期运行中,催化剂积炭增加等原因导致其异构化活性及选择性降低,异构化产品辛烷值提升能力呈现逐步衰减的趋势,提高反应苛刻度已不能弥补催化剂活性下降造成的产品辛烷值降低。为保证装置长周期运行,建议择机停工对催化剂进行再生,或是直接换用与装置原料性质匹配的异构化催化剂。     

Skeletal Isomerization and Inter—molecular Hydrogen Transfer Reactions in Catalytic Cracking

Bimolecular hydrogen transfer and skeletal isomerization the important secondary reac-tions among catalytic cracking reactions,which affect product yield distribution and product quality,Catalyst properties and operating parameters have great impact on bimolecular hydrogen transfer and skeletal isomerization reactions .Bimolecular hydrogen transfer activity and skeletal isomrization activity of USY-containing catalysts are higher thn that of ZSM-5-containing catalyst.Coke deposition on the active sites of catalyst may suppress bimolecular hydrogen transfer activity and skeletal isomer-ization activity of catlys in different degrees.Short raction time causes a decrease of hydrogen trans-fer reaction,but and increase of skeletal isomerization reaction compared to cracking reaction in catalytic cracking process.     

沸石孔结构对1-己烯异构化性能的影响

采用1-己烯为原料,对硅铝比相近、不同孔结构的沸石在脉冲微反装置上进行了评价试验,考察了FCC条件下沸石孔结构对烯烃异构化性能的影响。结果表明,大孔径的Y型沸石具有良好的异构化性能,异构化能力由强到弱的排列顺序为Y>β>ZRP>丝光沸石>镁碱沸石。     

C5/C6异构化催化剂的首次工业应用

采用中石化金陵分公司研究院研制的CI-50(Pd/丝光沸石)作C5/C6烷烃异构化催化剂.详细介绍了该催化剂的工业放大试验装置的工艺流程、首次开工过程中技术问题及处理方法.     

Cis–trans isomerization of olefinic alcohols promoted by Rh(I) complexes

Homogeneous hydrogenation and isomerization reaction of cis-2-butene-1,4-diol has been investigated in ethanol by using tris(triphenylphosphine)chlororhodium(I), RhCl(PPh₃)₃, and triethylamine at 303 K and 0.01–0.1 MPa partial hydrogen pressure. Under reduced H₂ pressure, the geometric isomerization reaction occurs, to a high extent, leading to trans-2-butene-1,4-diol up to 93% selectivity at 90% conversion of the cis analogous. Effects of H₂ partial pressure as well as triethylamine, added phosphine and olefin concentrations on the rate of reaction and on the products distribution were also investigated. The results obtained can be interpreted on the basis of a proposed mechanism in which RhH(PPh₃)₃ is the active species. The high selectivity towards cis-trans isomerization of cis-2-butene-1,4-diol is attributed to steric factors of the Rh(I) coordinated triphenylphosphine groups.     

Platinum promoted zirconia-sulfate catalysts: one-pot preparation,physical properties and catalytic activity

A new innovative methodology for the single-stage preparation of ZrO₂-SO₄ and Pt/ZrO₂-SO₄ catalysts is reported, based on the sol-gel technique. Catalysts are characterized by analysis, XRPD, BET and IR methods and are tested in the isomerization of butane.     

清洁汽油的研究与生产技术Ⅱ. 生产清洁汽油的非加氢精制技术进展

对国内外生产清洁汽油的非加氢精制技术，如异构化、烷基化、吸附脱硫、生物催化脱硫、碱性抽提脱硫等进行了综述．介绍了汽油清净剂及乙醇汽油的开发使用情况。针对国内清洁汽油生产技术现状，提出了增强自主创新能力，加快间接烷基化技术、催化裂化汽油吸附脱硫工艺及高选择性降硫助剂研发力度的建议。     

直馏汽油异构化装置的运行

长庆油田公司第二助剂厂新建的 70kt a直馏汽油异构化装置 ,采用二个反应器 ,以常压直馏汽油为原料 ,采用非临氢重整催化剂 ,生产的异构化汽油的研究法辛烷值约 90 ,但改质汽油收率较低 ,仅 65 %左右     

Tetragonal structure, anionic vacancies and catalytic activity of SO4-ZrO2 catalysts for n-butane isomerization

An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO₄²⁻-ZrO₂ with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO₄²⁻-ZrO₂ catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H₂ was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work.

A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO₄²⁻-ZrO₂ is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.     

Effect of Pt Incorporation into Ni/ZrO2–SO 4 = /Al2O3 Catalyst for n-Butane Isomerization

Three Ni/ZrO₂–SO₄⁼/Al₂O₃ catalysts with different concentrations of platinum (0.2, 0.3 and 0.4 wt%) were prepare and tested for n-butane isomerization reaction at 338 K, in absence and in presence of hydrogen. The results shown that, at low temperature, platinum contributes to the olefin or butyl ion formation and the reaction follows a bimolecular pathway. However, when the reaction occurs in the presence of hydrogen, the formation of butyl ions is inhibited. The main feature of platinum addition is the stabilization of the catalytic activity, which is indicated by the slow deactivation constants compared to that of the unpromoted catalyst.