裂解装置增产丁二烯的方法研究

通过自生成热裂解反应网络模型对单组分碳四烯烃的裂解反应进行模拟。模拟结果表明,1-丁烯和2-丁烯的裂解产物中丁二烯收率高于常规裂解原料。利用模拟裂解实验装置,进行富烯烃碳四物料的裂解实验,验证了模拟计算结果;并将富烯烃碳四物料与石脑油原料进行混合裂解,产物中丁二烯收率有所提高。进一步在工业裂解炉上进行了富烯烃碳四物料与石脑油混合裂解试验。工业试验结果表明,裂解产品中丁二烯收率明显提高,同时三烯(乙烯、丙烯和丁二烯)收率有所提高,达到了增产丁二烯的目的。     

轻烃-碳四共裂解性能优化研究

针对乙烯原料日益短缺和碳四过剩的问题,利用小型蒸汽裂解模拟实验装置对轻烃—碳四混合原料进行裂解性能研究,考察了在SC-1型裂解炉中碳四掺入量及工艺参数对目的产物（乙烯+丙烯+丁二烯）三烯收率的影响。实验结果表明,混合原料中碳四最佳掺入量为10～20%,适宜的裂解温度为840～850℃,稀释比（水/油质量比）为0.5时,乙烯质量分数为31.87%,丙烯质量分数为16.57%,三烯质量分数为53.60%,可见碳四与轻烃共裂解,既扩大了乙烯原料来源,又提高了碳四产品附加值。     

不同烃类催化裂解生产低碳烯烃的性能

为了拓宽乙烯裂解原料并合理利用焦化石脑油资源,对比研究了烷烃、烯烃、环烷烃同系物及相同碳数不同结构烃在Cu改性ZSM-5分子筛及其与金属氧化物复合催化材料上的裂解性能。结果表明,同系物烃类裂解性能随着碳数增加,裂解生成低碳烯烃的性能增强,高碳数的烯烃和烷烃的转化率和低碳烯烃收率较高,是较好的催化裂解生成低碳烯烃原料。在相同条件下,烷烃和环烷烃的转化率明显低于相同碳数烯烃的转化率。复合催化材料A中的金属氧化物与Cu改性ZSM-5分子筛之间具有很好的协同作用,能够提高烷烃和环烷烃的裂解活性。     

不同烃类催化裂解生产低碳烯烃的性能

 为了拓宽乙烯裂解原料并合理利用焦化石脑油资源,对比研究了烷烃、烯烃、环烷烃同系物及相同碳数不同结构烃在Cu改性ZSM-5分子筛及其与金属氧化物复合催化材料上的裂解性能。结果表明,同系物烃类裂解性能随着碳数增加,裂解生成低碳烯烃的性能增强,高碳数的烯烃和烷烃的转化率和低碳烯烃收率较高,是较好的催化裂解生成低碳烯烃原料。在相同条件下,烷烃和环烷烃的转化率明显低于相同碳数烯烃的转化率。复合催化材料A中的金属氧化物与Cu改性ZSM-5分子筛之间具有很好的协同作用,能够提高烷烃和环烷烃的裂解活性。     

微型裂解方法研究金属表面的结焦和结焦抑制

提出一种用微型裂解炉与气相色谱仪并联的高灵敏试验系统，采用脉冲进料，裂解后的微量焦炭用Ｏ２脉冲燃烧转化成ＣＯ２，并由热导检测器检测，碳的最小检测量为３．５×１０－８ｇ。其结果可有效反映裂解原料在金属表面上最初的结焦行为。考察在脉冲条件下不同金属表面（铁、镍、铜、镍－铬合金和不锈钢）对裂解原料催化生焦的相对活性；金属表面氧化后的催化生焦活性；沿炉管轴向金属表面催化生焦的分布；硫化物对裂解原料在金属表面结焦的抑制作用等     

裂解碳五抽余液用作乙烯原料的研究

对掺混轻质石脑油的裂解碳五抽余液加氢产物用作乙烯原料可行性进行研究,对比裂解产物收率及裂解产物价值,并考察其结焦性能。结果表明:与轻质石脑油相比,掺混石脑油的乙烯和苯收率分别增加了0.75个百分点和0.24个百分点,产物价值增加83.3元/t,结焦速率增加22.36%;借助于结焦抑制剂,消除了两者结焦速率的差异;裂解碳五抽余液与轻质石脑油掺混后用作乙烯原料是可行的。     

碳四烃综合应用技术的进展

为提高碳四烃资源的利用率,从生产燃料油的添加剂或调和油、作为增产乙烯和丙烯的原料、通过深加工生产高附加值的化工产品3个方面综述了碳四烃综合利用的技术进展。介绍了生产燃料油添加剂的醚化、烷基化、芳构化等技术;介绍了将碳四烃作为蒸汽裂解的原料之一,将碳四烃催化裂解和催化歧化以增产乙烯和丙烯的技术;介绍了以丁二烯、正丁烯、正丁烷、异丁烷为原料生产高附加值产品的技术。提出碳四烃芳构化装置向生产苯、甲苯和二甲苯产品转型,将碳四烃催化裂解装置与甲醇制烯烃装置耦合以及炼化一体化企业进一步整合碳四烃资源以提高碳四烃利用率的建议。     

乙烯原料的裂解性能和结焦规律的研究 Ⅰ.微反色谱装置中乙烯原料的裂解试验

自制的微反色谱装置具有设备简单、反应时间短、操作方便、参数变更容易、用样量少等特点，可用于研究乙烯原料的裂解及结焦性能。通过对国内５个乙烯厂用的原料的裂解试验，所得到的气相产物和结焦量与中型模拟裂解装置的试验结果基本相符，表明此装置可为快速筛选乙烯原料提供参数，也可用于研究各类烃族的裂解特性和结焦机理。     

齐鲁公司炼厂干气优化利用

介绍齐鲁公司炼厂焦化干气、加氢干气回收利用情况。通过工艺改造及流程优化,实现炼厂干气中碳一至碳五组分精确分离及利用。同时,将炼厂含氢气体中的氢气较大效率回收利用,极大地降低了用氢成本,也为制氢装置及乙烯裂解装置提供了优质廉价原料,效益显著。     

毛细管色谱测定裂解原料及其产物

建立了质谱及HPIC测定轻柴油族组成的方法,并用毛细管邑谱对裂解原料及产物气态烃、裂解汽油及裂解焦油诸组份进行分离,用保留指数、色-质联用、加氢反应等手段定性,用峰面积归一法定量。在30万吨乙烯装置考核中应用,数据符合工艺实际情况。     

MODIFICATIONS INDUCED BY VISBREAKING ON COMPOSITION AND STRUCTURE OF ATMOSPHERIC RESIDUES

The atmospheric residues, the corresponding visbroken residues and the related asphaltenes have been characterized by elemental analysis, liquid and gel permeation chromatography (LC, GPC), nuclear magnetic resonance (NMR) and pyrolysis/gas chromatography/mass spectrometry ( Py/GC/MS) before and after the thermal process. The results show that visbreaking (VB) increases the aromaticity (Car) of the residues and decreases their resins/ asphaltenes ratio. A relationship between δC_ar and resins/as-phaltenes ratio has been found.

The cracking of aliphatic chains which takes place during the thermal process produces asphalthenes with lower molecular weight and more condensed aromatic structures. The rise up to 60% of the ratio of aromatic to paraffinic carbon (C_ar/C_p ( greatly affects the solubility of VB asphaltenes in a oily medium.     

Reactivity of Fluid Catalytic Cracking Feedstocks as a Function of Reactive Hydrogen Content

Detailed feedstock composition analysis is a reasonable support for predicting product yields and quality parameters from the chemistry involved in FCC processing. Nonetheless, given the huge number of individual hydrocarbons present in common FCC feedstocks, it is necessary to lump them in Hydrocarbon Types (HT). In order to understand the interactions during FCC processing between these different hydrocarbon types and its relationship to yield and quality of end products, it is necessary to consider relative content and reactivity of these carbon families in the raw material. Hydrogen content of each hydrocarbon is a good measure of the cracking performance of this hydrocarbon. As hydrogen content increases in a molecule, the yields to LPG and gasoline increase. In this article, based on HT identification and refinery-measured feedstock properties, an estimation of reactivity for any feedstock is obtained. Two types of hydrogen, which are commonly part of the same molecule were defined as refractory (nonreactive) and reactive. Based on these types of hydrogen, a Reactivity Factor (RF) was introduced and defined as a relative index that measures cracking potential of FCC feedstocks. The described approach to classify FCC feedstocks, will be useful in future developing of correlations predicting yields and quality of end products.     

Characterization of Different Molecular Weight Fractions Separated from Utah Maltenes by Gel Permeation Chromatography

Maltenes derived from Utah bitumens were separated by gel permeation chromatography ( OPC) into fractions having number average molecular weights ( MW) in the range from 300 to 11985. The fractions were examined by vapor pressure osmometry, absorption spectrometry in the visible region as well as proton and carbon -13 NMR. The results are reported in comparison with those for the corresponding fractions separated from Athabasca maltenes. Utah fractions appeared to be more aliphatic with longer average aliphatic chains lengths. Branched and alicyciic types were more abundant in Utah samples, especially those with low MW, There was an apparent difference in the hydrocarbon structure of both Utah and Athabasca maltenes GPC     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.     

STRUCTURAL CHARACTERIZATION OF PETROLEUM BASED FEEDSTOCKS FOR CARBON BLACK PRODUCTION

Some selected petroleum based feedstocks have been characterized by ¹H and ¹³C NMR spectroscopy for their possible use as carbon black feedstock (CBFS). Feedstocks studied are pyrolysis tars, clarified oils, aromatic extracts and vacuum residue. Analysis of average structural NMR parameters show that pyrolysis tars because of their being highly aromatic in character (high BMCI) are the most suitable feedstock for carbon black. Aromatic extracts rank the next. Clarified oils of Indian refinery origin needs further processing due to middle distillate mode refining severity.     

催化裂解技术及其应用前景

介绍催化裂解技术的特点并与相关的工艺进行了比较。相对于催化裂化工艺可以大幅度提高低碳烯烃产率，具有较大操作弹性，产品结构可以灵活调整；相对于蒸汽裂解工艺，可以加工比蒸汽裂解更重的原料，反应温度大幅度地下降。催化裂解工艺有很大的社会效益和经济效益，具有广泛的应用前景。     

Characterization of Different Molecular Weight Fractions Separated from Utah Maltenes by Gel Permeation Chromatography

ABSTRACT

Maltenes derived from Utah bitumens were separated by gel permeation chromatography ( OPC) into fractions having number average molecular weights ( MW) in the range from 300 to 11985. The fractions were examined by vapor pressure osmometry, absorption spectrometry in the visible region as well as proton and carbon -13 NMR. The results are reported in comparison with those for the corresponding fractions separated from Athabasca maltenes. Utah fractions appeared to be more aliphatic with longer average aliphatic chains lengths. Branched and alicyciic types were more abundant in Utah samples, especially those with low MW, There was an apparent difference in the hydrocarbon structure of both Utah and Athabasca maltenes GPC     

SPECTROSCOPIC CHARACTERIZATION OF SOLVENT SOLUBLE FRACTIONS OF PETROLEUM VACUUM RESIDUES

NMR and FTIR spectroscopic techniques were used to investigate the effect of different solvent extraction schemes on the composition and chemical nature of species of vacuum residues of two Indian crude oils (namely Jodhpur and Heera) extractable into polar (ethyl acetate) and non-polar (n-pentane and n-heptane) solvents. The obtained soluble fractions were found to consist of mainly simple aliphatic and naphthenic ring structures, while insoluble fractions consisted primarily aromatic compounds. The results were used to draw inferences on the relative utility of different extraction schemes to upgrade vacuum residues as feedstocks for secondary conversion processes in petroleum industry.     

5种催化裂化原料的裂化性能研究

利用XTL-5型提升管中试装置,对中国石油化工股份有限公司洛阳分公司催化裂化原料各组分的裂化性能进行了评价。结果表明:在完全相同的催化剂和操作条件下,减压蜡油、脱沥青油、常压重油、混合原料和拔头轻油浆的转化率分别为74.00%,69.91%,70.43%,67.16%和36.84%;其裂化性能从优到劣的顺序为:减压蜡油,脱沥青油(与常压重油相似),混合原料,拔头轻油浆;其中掺炼拔头轻油浆对催化进料的裂化性能影响很大,使催化裂化产品的分布明显变差。     

The transformation of basic nitrogen compounds in coker gas oil during catalytic cracking

Two narrow fractions distilled from Liaohe coker gas oil were used for the research. The distribution of basic nitrogen compounds in feedstocks and their liquid products were characterized by ESI FT-ICR MS. The results showed that N1 class species were the most predominant in both feedstocks and products. The catalytic cracking progress reduced the relative abundance of all class species, except for the N1 and N1S1 class species. Although the N1 class species had longer side chains and higher condensation in the heavier feedstock, the distribution of N1 class species became similar in the two liquid products.