炼化一体化企业中乙烯原料的优化利用

为降低乙烯生产成本,中国石化天津分公司通过优化整合内部资源,拓宽裂解原料来源,将重整液化气、加氢液化气、抽余油、加氢裂化尾油、加氢裂化柴油作为裂解乙烯原料,实现了裂解乙烯原料的自给自足。详细分析了各种原料的性质和裂解收率情况,对于同类装置增加裂解原料来源具有很重要的借鉴意义。     

焦化液化气混合焦化汽油加氢技术及工业应用

焦化液化气作为延迟焦化装置产品,长期以来作为民用烃出厂,经济效益未得到充分开发.镇海炼化公司采用中石化大连石油化工研究院的焦化液化气和汽油混合加氢制备乙烯裂解料技术,建设了一套60万t·a-1的焦化液化气与焦化汽油混合加氢装置.生产出烯烃质量分数不大于1.0％的精制液化气和溴价不大于2.5 g Br·(100 g)-1的精制石脑油,可作为优质的乙烯裂解原料.对该工艺路线的技术特点、工业运行状况、经济效益等进行探讨分析,数据表明,焦化液化气和焦化汽油经新工艺路线加工后作为乙烯裂解原料,工艺路线简洁,经济效益显著.     

原料变重后的瓶颈现象分析及改进措施

抚顺乙烯装置以丙烷、丁烷馏分、重整液化气、重整拔头油为主要原料,以直馏石脑油、焦化加氢石脑油为补充。投产后,由于原料供应波动,石脑油成为主要裂解原料。原料构成变重,给装置操作带来一系列变化。     

扬子石化提出用加氢裂化液化气作裂解原料

中国石化扬子石化研究院完成了“液化气用作乙烯原料”项目研究，提出了合理化建议。经预测，加氢裂化装置液化气用作裂解原料经济效益十分可观，和目前扬子石化石脑油原料相比，生产1t乙烯，液化气产生的经济效益要比石脑油高出约800元人民币，按年耗液化气220kt计，用液化气生产乙烯每年将比石脑油多创效益5000多万元人民币。     

乙烯装置液化气裂解模式优化

阐述了通过对液化气裂解模式的优化,将裂解液相液化气模式改为裂解气相液化气模式,并且在优化裂解炉运行参数,选取最佳裂解深度的基础上,改善裂解炉的结焦情况,延长裂解炉的运行周期,真正实现了以液化气为原料,裂解炉的长周期运行以及乙烯装置主要技术经济指标相应地提高。     

混合C4作乙烯原料的研究及经济性分析

以混合C₄作乙烯裂解原料,通过GK-Ⅵ型蒸汽裂解炉分别进行了4个不同稀释比(水和物料的质量比)及裂解温度评价试验,并进行未加氢混合C₄与加氢混合C₄裂解性能对比评价实验。结果表明,在裂解温度为838℃、反应压力为0.085 MPa、稀释比为0.55的条件下,加氢混合C₄三烯收率大于50%,并且经济效益达到最大,为最佳裂解条件。加氢混合C₄可以作为原料蒸汽裂解制烯烃的有效补充。     

加氢碳四做裂解原料的应用研究

介绍了四川石化公司加氢碳四用做乙烯裂解原料的工艺生产概况。通过对加氢碳四物料组成的分析,选择了加氢工艺路线并优化操作控制参数,从而获得优质裂解原料。通过对裂解控制参数的摸索,最终确定了最佳生产工艺参数,实现了加氢碳四做裂解原料的可观经济价值。     

芳烃液化气蒸汽裂解工艺优化与评价

对以芳烃液化气为原料裂解生产乙烯工艺进行了评价，提出了在SRT-Ⅲ型炉上裂解的最佳工艺操作条件。总结了芳烃液化气在SRT-Ⅲ型炉上运行情况，并对乙烯装置整体经济效益的影响进行了分析。     

液化气(LPG)作为裂解原料的生产工艺分析

通过茂名1#裂解装置裂解炉投用液化气(LPG)为裂解原料,针对裂解炉及回收系统在实际生产中遇到的问题进行研究和讨论,得出液化气作为裂解原料,在工艺上是可行的.     

CBL—Ⅰ型裂解炉加工加氢裂化尾油的工业试验

为了扩大乙烯裂解原料的来源,对CBL-Ⅰ型裂解炉进行了技术改造。在小试工作基础上,利用改造的CBL-Ⅰ型炉以加氢尾油作裂解原料进行了工业化试验。运行结果证明,应用CBL加工尾油是成功的。     

Study on co-cracking performance of different hydrocarbon mixture in a steam pyrolysis furnace

Co-cracking is a process where the mixtures of different hydrocarbon feed stocks are cracked in a steam pyrolysis furnace, and widely adopted in chemical industries. In this work, the simulations of the co-cracking of ethane and propane, and LPG and naphtha mixtures have been conducted, and the software packages of COILSIM1D and SimCO are used to account for the cracking process in a tube reactor. The effects of the mixing ratio, coil outlet temperature, and pressure on cracking performance have been discussed in detail. The co-cracking of ethane and propane mixture leads to a lower profitability than the cracking of single ethane or single propane. For naphtha, cracking with LPG leads to a higher profitability than single cracking of naphtha, and more LPG can produce a higher profitability.     

催化裂解和蒸汽裂解制烯烃工艺技术经济分析

根据近年来乙烯裂解发展趋势,以炼厂液化气和LNG凝析液等轻烃资源为主要原料,通过实例对比分析催化裂解和蒸汽裂解制烯烃的技术以及经济性,并提出石油石化公司应根据区域丙烯和丁二烯市场需求以及企业自身的发展定位,因地制宜地选取合理的烯烃裂解工艺。     

加氢裂化尾油在倒梯台裂解炉上的工业应用

随着中国石化上海石油化工股份有限公司炼化部2号乙烯装置的改扩建项目投产,乙烯裂解原料的缺口也将相应增大。为满足企业生产物料平衡的需求,拓宽并优化1号乙烯装置裂解原料,在1号乙烯装置F-101倒梯台裂解炉上进行加工加氢裂化尾油的试验。由于加氢裂化尾油组分重、干点高,加工试验的主要目的是验证加氢裂化尾油在1号乙烯装置倒梯台炉上裂解的可行性,包括加氢裂化尾油裂解性能,裂解炉运行周期。     

Systematics and modelling representations of LPG thermal cracking for olefin production

Pyrolysis of hydrocarbons is an important commercial process for the production of ethylene, propylene and 1,3 butadiene. These low molecular weight olefins are among the most important base chemicals for the petrochemical industries for polymer production. A simulation program of the reaction kinetics and coke formation inside the coils of a thermal cracking unit can provide information on the effects of operating conditions on the product distribution. The aim of this study was to develop a mechanistic reaction model for the pyrolysis of LPG that can be used to predict the yields of the major products from a given LPG sample with commercial indices. A complete reaction network, using a rigorous kinetic model, for the decomposition of the LPG feed has been developed, which is used for the simulation of industrial LPG crackers. This model has been adapted using industrial data for the pyrolysis yields of LPG. The present paper attends on the asymptotic coking mechanism and describes the development of a kinetic coking model in the pyrolysis of LPG. Detailed and accurate information about the product distribution, growth of coke layer, the evolution of the tube skin temperatures can be obtained from this simulation. Simulations of this kind can be used to optimize the furnace operation. They can be used as a guide for the adaptation of the operating variables aiming at prolonging the run length of the furnace. The reactor model, as well as kinetic scheme, is tested in an industrial cracking furnace.     

β分子筛的催化裂化性能考察

以重油（70%新疆蜡油掺和30%新疆渣油）为原料,在FFB和ACE装置上对3种不同硅铝质量比β分子筛和工业应用的ZSM-5分子筛制备的催化裂化助剂的反应性能进行对比评价。结果表明,β分子筛对重油组分的裂化能力强于ZSM-5,对汽油组分的选择裂化能力弱于ZSM-5,液化气增加量小于ZSM-5,提高汽油辛烷值能力与ZSM-5相当。同时,随着β分子筛硅铝质量比升高,其催化裂化产物中汽油和总液收增加,重油减少。因此,β分子筛助剂适用于以追求燃料汽油生产为主的炼油企业,满足液化气增加不多和提高汽油辛烷值的需要。     

Preparation of bio-fuels by catalytic cracking reaction of vegetable oil sludge

Biofuel production from vegetable oil is potentially a good alternative to conventional fossil derived fuels. Moreover, liquid biofuel offers many environmental benefits since it is free from nitrogen and sulfur compounds. Biofuel can be obtained from biomass (e.g. pyrolysis, gasification) and agricultural sources such as vegetable oil, vegetable oil sludge, rubber seed oil, and soybean oil. One of the most promising sources of biofuel is vegetable oil sludge. This waste is a major byproduct of vegetable oil factories. It consists of triglycerides (61%), free fatty acid (37%) and impurities (2%). The hydrocarbon chains of triglycerides and free fatty acid are mainly made up of C₁₆ (30%) and C₁₈ (36%) hydrocarbons. The others consist of C₁₂-C₁₇ hydrocarbon chains. Transesterification can help in converting vegetable oil sludge into biofuel. The disadvantage of this method is that a large amount of methanol is required. The alternative method for this conversion is catalytic cracking. The objective of this research is to evaluate and compare the pyrolysis process with cracking catalytic reaction of vegetable oil sludge by Micro-activity test MAT 5000 of Zeton-Canada.A ZSM-5/MCM-41 multiporous composite (MC-ZSM-5/MCM-41), was successfully synthesized using silica source extracted from rice husk. The material has the MCM-41 mesoporous structure, and its wall is constructed by ZSM-5 nanozeolite crystals. The porous system of the material includes pores of the following sizes: 5 Å (ZSM-5 zeolite), 40 Å (MCM-41 mesoporous material), and another porous system whose diameter is in the range of 100-500 Å (mesoporous system) formed by the burning of organic compounds that remain in the material during the calcination process. This pore system contributes to an increase in the catalytic performance of synthesized material.The results of vegetable oil sludge cracking reaction show that the product consists of fractions such as dry gas, liquefied petroleum gas (LPG), gasoline, light cycle oil (LCO), and (heavy cycle oil) HCO, which are similar to those of petroleum cracking process.MC-ZSM-5/MCM-41 catalyst is efficient in the catalytic cracking reaction of vegetable oil sludge as it has higher conversion and selectivity for LPG and gasoline products in comparison to the pyrolysis process. Product distribution (% of oil feed) of cracking reaction over MC-ZSM-5/MCM-41 is coke (3.4), total dry gas (7.0), LPG (31.1), gasoline (42.4), LCO (8.9), HCO (7.2); and that of pyrolysis are coke (19.0), total dry gas (9.3), LPG (16.9), gasoline (28.8), LCO (13.7), and HCO (12.3).These results have indicated a new way to use agricultural waste such as rice husk for the production of promising catalysts and the processing of vegetable oil sludge to obtain biofuel.     

动植物油生产清洁燃料和低碳烯烃的替代加工工艺

Since the production cost of biodiesel is now the main hurdle limiting their applicability in some areas, catalytic cracking reactions represent an alternative route to utilization of vegetable oils and animal fats. Hence, catalytic transformation of oils and fats was carried out in a laboratory-scale two-stage riser fluid catalytic cracking （TSRFCC） unit in this work. The results show that oils and fats can be used as FCC feed singly or co-feeding with vacuum gas oil （VGO）, which can give high yield （by mass）of liquefied petroleum gas （LPG）, C2-C4 oletms, tor example 45% LPG, 47% C2-C4 olefins, and 77.6% total liquid yield produced with palm oil cracking. Co-feeding with VGO gives a high yield of LPG （39.1%） and propylene （18.1%）. And oxygen element content is very low （about 0.5%） in liquid products, hence, oxygen is removed in the form of H2O, CO and CO2. At the same time, high concentration of aromatics （C7-C9 aromatics predominantly） in the gasoline fraction is obtained after TSRFCC reaction of palm oil, as a result of large amount of hydrogen-transfer, cyclization and aromatization reactions, Additionally, most of properties of produced gasoline and diesel oil fuel meet the requirements of national standards, containing little sulfur. So TSRFCC technology is thought to be an alternative processing technology leading to production of clean fuels and light olefins.     

Dilution effect of the feed on yield of olefins during catalytic cracking of vacuum gas oil

A vacuum gas oil has been co-fed with nitrogen at different partial pressures in a microacitivity (MAT) unit. The cracking rate versus hydrocarbon partial pressure can be fitted to a first-order kinetic rate equation. On the other hand, hydrogen transfer reactions, which follow second-order kinetics, are more affected than conversion by the decrease in hydrocarbon partial pressure, resulting in an increase in the yield of propylene and in general of LPG olefins. The decrease in conversion, due to the lowering of hydrocarbon partial pressure, could be compensated by a mechanical mixing effect introduced by the dilution gas that improves feed vaporization and mixing.

It will be shown that a MAT unit can be used to show both effects separately, i.e. feed dilution and feed dispersion.     

在用液化石油气贮罐裂纹成因的探讨

本文对在用液化石油气贮罐产生裂纹的原因进行分析,并提出了一些减少此类裂纹产生的办法。