脱硫脱硝助剂对催化裂化反应的影响

考察了催化裂化催化剂中添加烟气脱硫脱硝助剂后对催化裂化反应性能的影响,探讨了该混合催化剂(简称混合剂)返回催化裂化装置的可行性。固定流化床反应装置(FFB)试验结果表明:以安庆蜡油为原料,催化剂CGP-C中添加质量分数为4.2%不同类别的脱硫脱硝助剂后,对催化裂化反应产物中裂化气和柴油的收率、液体产品的硫含量等均造成一定程度的影响。催化裂化小型评价装置(ACE)试验结果表明:添加助剂RESN-3的质量分数不大于2%时对催化裂化反应的影响较小或没有影响,混合剂返回催化裂化装置再生具有可行性。     

TUD-DNS3脱硝助剂在催化裂化装置的工业应用

TUD-DNS3脱硝助剂在中韩（武汉）石油化工有限公司1号催化裂化装置上进行了工业应用。结果表明：针对两段再生工艺,当系统中助剂占总催化剂藏量的质量分数为2.6%时,烟气脱硫装置外排污水中的氨氮质量浓度由加剂前的100 mg/L下降至40 mg/L以内;助剂的加入降低了CO焚烧炉的炉膛温度,有利于烟气的合格排放,并对装置操作、产品分布及汽油、柴油产品质量无不良影响。     

TUD-DNS3脱硝助剂在催化裂化装置的工业应用

TUD-DNS3脱硝助剂在中韩（武汉）石油化工有限公司1号催化裂化装置上进行了工业应用。结果表明：针对两段再生工艺，当系统中助剂占总催化剂藏量的质量分数为2.6%时，烟气脱硫装置外排污水中的氨氮质量浓度由加剂前的100 mg/L下降至40 mg/L以内；助剂的加入降低了CO焚烧炉的炉膛温度，有利于烟气的合格排放，并对装置操作、产品分布及汽油、柴油产品质量无不良影响。     

脱硝助剂QKJ-DN/1在不完全再生催化裂化装置的工业应用

介绍了脱硝助剂QKJ-DN/1在中国石油宁夏石化公司催化裂化装置的应用情况。结果表明:与空白标定期相比,当系统中脱硝助剂占总催化剂藏量的质量分数为2.76%时,烟气中氮氧化物质量浓度由185 mg/m^(3)降至142 mg/m^(3),脱硝效率为23.2%;烟气脱硫装置外排废水中氨氮质量浓度由25.62 mg/L降至1.39 mg/L;产品中液化气、汽油和焦炭收率依次降低了0.87,0.75,0.11个百分点;柴油和干气收率分别增加了1.72,0.06个百分点;脱硝助剂的加入,对催化裂化装置汽油、柴油产品质量无影响。     

助剂热洗-离心技术脱除催化裂化外甩油浆中的固体

利用助剂热洗-离心技术对催化裂化外甩油浆进行脱固处理,考察了反应温度、增重剂、沉降助剂、破乳剂种类及加入量、离心转速等工艺条件对脱固效果的影响。结果表明：在反应温度为70℃,催化裂化油浆/增重助剂（质量比）为10∶3,CS-11型沉降助剂投加质量分数为0.4%,PE-12型破乳剂投加质量分数为0.2%的条件下充分反应后,在离心转速为8 000 r/min时,对催化裂化外甩油浆进行脱固处理后,油浆灰分质量分数由0.390%降至0.041%。     

钒镍污染对催化裂化增产丙烯助剂性能的影响

采用浸渍法对流化催化裂化（FCC）中的增产丙烯助剂（LHP-A）进行了重金属钒、镍污染复配。考察了不同含量钒、镍单独或共同污染作用下对LHP-A的比表面积、相对结晶度和微反活性的影响,并分别在固定床微型反应评价装置（MAT）和先进的催化裂化评价装置（ACE）上评价了增产丙烯助剂相应污染复配后催化剂的反应性能。结果表明:无论LHP-A是否被重金属钒、镍单独或共同污染,只要FCC主催化剂复配了含质量分数10%的丙烯助剂后,丙烯收率均可提升4个百分点以上;在钒污染质量分数低于1%时,LHP-A具有良好的水热稳定性;当重金属镍污染LHP-A时,干气产率显著增加,但在钒污染量相同的前提下,镍的存在可以减缓钒对丙烯助剂性能的影响。     

JF-SN2型脱硝剂在催化裂化装置的工业应用

介绍JF-SN2型脱硝剂在大连西太平洋石油化工有限公司催化裂化装置上的工业应用情况,结果表明:该装置再生系统加注JF-SN2型脱硝剂占系统藏量(质量分数)的2.5%后,贫氧段烟气中NH_(3)含量降至80 mg/m^(3)以下,烟气脱硫塔外排烟气中的NO_(x)含量降至100 mg/m^(3)以下,CO含量降至0,每吨焦炭产汽量增加至7.55 t;JF-SN2型脱硝剂应用期间,催化裂化装置产品分布、汽/柴油性质及主催化剂磨损状况基本稳定。     

烟气脱硝助剂在催化裂化装置上的应用

为了降低催化裂化再生烟气中NOx的排放浓度,中海石油炼化有限责任公司惠州炼化分公司催化裂化装置按照CO助燃剂的添加方式,往再生系统加入烟气脱硝助剂D。试用结果表明,通过加注烟气脱硝助剂D,可以在不停工、不动改的前提下实现催化裂化装置烟气中NOx达标排放的目标,并且烟气脱硝助剂D的加入对催化裂化催化剂的活性、产品分布及汽油、柴油性质无明显影响。     

催化裂化脱硫钝钒双功能液体助剂的研究

以催化裂化原料油脱硫钝钒为目的,制备了以镁铝为基本元素,添加铈和铁的一系列液态助剂。利用固定床反应器、微反应活性评价(MAT)装置和红外光谱,并结合X光衍射等研究了助剂组成与脱硫活性的关系。结果表明,在镁铝二元助剂中Mg、Al原子比为1：1的助剂脱硫活性最高,在用量为8.0 mg/g时脱硫活性达38.31%;在此基础上Ce、Fe的加入明显提高了助剂的脱硫活性,组成为10%Ce/Mg-Al-Fe(2：1.8：0.2)的助剂在使用量为8.0 mg/g时,脱硫活性达57.44%。模拟含钒催化剂的MAT实验表明,助剂的加入有利于催化剂活性的恢复,即助剂具有钝钒脱硫双功能作用,同时对催化裂化没有影响。探讨了助剂脱硫作用机理和钝钒的机理。     

低过剩氧含量催化裂化硫转移助剂的研究

采用溶胶-凝胶法制备了适应于低过剩氧含量操作条件的流化催化裂化(FCC)硫转移助剂,考察了反应温度、助剂添加量、过剩氧含量对助剂脱硫活性的影响。结果表明:反应温度对脱硫活性的影响不显著;增加助剂添加量,脱硫活性逐渐提高;当过剩氧的体积分数低于1.0%时,过剩氧含量对SO_2脱除率影响较小,当过剩氧的体积分数为1.0%时,SO_2脱除率比过剩氧分数为0.5%时仅高5百分点左右;硫转移助剂在不同的过剩氧含量条件下,脱硫活性均高于其他3种市售硫转移助剂,且过剩氧含量越低,优势越明显。上述结果表明制备的低氧含量FCC硫转移助剂适用于低过剩氧含量操作的FCC装置。     

The Addition of ZSM-5 to a Fluid Catalytic Cracking Catalyst for Increasing Olefins in Fluid Catalytic Cracking Light Gas

Abstract

The second largest source of propylene supplied for petrochemical application is from fluid catalytic cracking (FCC) units. The primary function of the FCC unit has typically been to produce gasoline. However, refiners have been taking advantage of opportunity to produce and recover more propylene from their FCC unit by increasing reaction severity via riser temperature, adding shape selective catalyst, and installing a propylene recovery unit (PRU). At a conventional FCC process propylene exists in the off gas of FCC and it is about 6 wt% of off gas by changing the FCC process parameter quantity of propylene in off gas can be more than 20 wt% by using ZSM-5 additives and increasing temperature The effects of operating parameters, such as reaction temperature, and ZSM-5 as FCC catalyst additive, on the distribution of the product and the yield of propylene were investigated on a bench-scale fluidized bed reactor. It is the aim of this work to perform an overall analysis of the yields and selectivity of hydrocarbons obtained in the vacuum gas-oil conversion over FCC and ZSM-5 catalysts. The effectiveness of ZSM-5 additive in the FCC process was investigated by doing experimental work in a bench-scale setup. The experiment data of off gas analysis showed that vacuum gas oil cracking at high reaction temperatures of 450–550°C increases the yield of propylene. Similar behavior is observed with the addition of 10–25 wt% ZSM-5 additive. The combination of the two effects (high temperature and ZSM-5 addition) makes the FCC unit an excellent source of light olefins for downstream petrochemical units. Higher FCC reactor temperatures (600–650°C) would not have positive effects for increasing propylene yield.     

Physico-chemical Characterization and Evaluation of Fluid Catalytic Cracker LPG Boosting Catalyst Additives

Fluid catalytic cracking (FCC) unit is a major secondary catalytic process in the refinery, converting low value vacuum gas oil (VGO) feeds to high value streams such as gasoline and light olefins. Continuous attempts are being made to improve this margin through process optimization, selection, and use of improved catalysts and additives as well as hardware modifications. LPG, mainly propylene maximization, is targeted in refineries to tap the market demands and making profit. Use of FCC additives is relatively easy and flexible option for enhancing the propylene production in FCC unit. Five different LPG maximization catalyst additive formulations were evaluated in the lab and selected better LPG catalyst additive. All five formulations were thoroughly characterized for textural properties as well as for mechanical properties. Attempts were made to correlate the physico-chemical characterization data with activity studies. Based on physico-chemical, mechanical and activity studies ranking of the formulations was made and optimum LPG catalyst additive was identified.     

多功能裂解助剂SF-100的工业应用

介绍了多功能裂解助剂SF-100（简称SF-100助剂）在中国石化青岛石油化工有限责任公司140 万t/a催化裂化装置中的工业化应用情况,并对其使用效果进行了评价。结果表明:SF-100助剂在原料油性质变化不大、操作条件基本相同的条件下,当SF-100助剂占催化剂系统藏量的10%时,使该装置平稳运行时的催化裂化产物中的丙烯、液化气、汽油、柴油收率相应分别增加了1.10,0.78,0.33,1.08个百分点,总液体收率增加了2.19个百分点,而且油浆收率降低了1.92个百分点,还使其稳定汽油、混合汽油研究法辛烷值相应分别增加了0.9,1.2个单位,显著优化了该催化裂化装置进口混合原料油的催化裂化产物整体分布。     

催化裂化与芳构化反应耦合多产优质汽油催化剂的研究

以NiO／HZSM-5为增强芳构化助剂，通过催化裂化与芳构化反应耦合，使催化裂化汽油和裂化气中的部分烯烃转化为芳烃，以降低汽油馏分中的烯烃含量，改善催化裂化汽油的组成。考察了助剂添加量对催化裂化催化剂降烯烃性能的影响，并与以CoAPO-11分子筛和HZSM-5与APO-11复合分子筛为助剂的催化裂化催化剂进行了对比。结果表明，NiO／HZSM-5的芳构化降烯烃效果最好，当添加量为5％时，汽油馏分中烯烃含量降低了5．8个百分点，而芳烃含量提高了9．7个百分点。并对催化裂化与芳构化反应耦合的机理进行了初步探讨。     

催化裂化汽油脱硫降烯烃助剂的研制

本研究旨在开发一种能同时降低FCC汽油中硫和烯烃含量的助剂,该助剂配方含强度和含量适中的L酸、B酸组分,有较高的噻吩饱和能力和氢转移能力,对FCC催化剂活性和选择性以及汽油性质不会产生明显不利影响。研究中将助剂按一定比例与FCC平衡剂混合装入固体流化床反应器（FFB）进行催化裂化反应,评价了几种金属组分和载体的脱硫和降烯烃性能及对FCC产品分布的影响。不但筛选了合适的金属和载体组分,而且作了必要的改性研究,多个样品小试结果表明,该助剂脱硫和降烯烃均超过30％,产品分布基本没有恶化,汽油辛烷值不下降。     

The Selection of Fluid Catalytic Cracking Catalysts and Additives: The Significance of Attrition Studies

Fluid catalytic cracking (FCC) is an important secondary conversion process in refinery that converts heavier gas oils and residues to valuable petroleum products. In the present and future crude oil availability scenario demand for FCC process that increases the refinery margins is growing. Continuous attempts are being made to improve FCC margin through process optimization, selection and use of improved catalysts and additives as well as hardware modifications. Refiners often face challenging task of judiciously selecting and switching to improved catalysts and additives for maximizing profits without violating hardware constraints. It is very difficult to select catalyst or additives based on vendor's claims and testing the catalyst directly in the plant is also risky business. It is important to match the plant performance closely to understand unit constraints and exploit the new catalyst capabilities to full extent. Detailed study with respect to catalyst deactivation, microactivity studies, complete characterization, and prediction of performance on the commercial scale, as well as economic evaluation, are key steps in catalyst or additive selection. Catalyst attrition is key issue now days due to heavy losses observed in the plant and frequent shut downs of the CO boiler units. In riser and regenerator reactor of FCC process, catalyst undergoes attrition due to various reasons such as inherent characteristics of catalyst/additive or due to process environment. Poor attrition of either catalyst/additive result into catalyst loss, fouling, and plugging of down stream units. In this communication the attrition behavior of different catalysts and additives and combined effect of base fluid catalytic cracking catalyst along with different additives in various proportions have been evaluated using an ASTM method in laboratory. Attrition behavior of different FCC additives such as CO combustion promoter, Octane and LPG booster and gasoline sulfur reduction additives were measured in isolation as well as by mixing with base catalyst in different proportion. Certain when studied alone exhibited higher attrition when compared with others. It is observed that even though absolute attrition strength of certain additives such as gasoline sulfur is poor, when used along with base catalyst in desired proportion the loss due to attrition was minimized. This study in combination with VGO cracking activity results helps to select suitable catalyst/additive for enhancing FCC process profits.     

催化裂化烟气硫转移剂的工业试验

以镁铝尖晶石为活性组分,制备不含钒氧化物的催化裂化烟气硫转移剂,并在中国石油大港催化裂化装置中进行了工业化试验。结果表明,在硫转移剂用量为催化裂化催化剂总藏量2%的情况下,SO2的脱除率高于90%;在原料油性质基本不变的条件下,硫转移剂的使用没有对催化裂化产品分布和质量产生不良的影响。     

Study on Catalytic Cracking of VGO Derived from Kazakhstan-Russian Mixed Crude

1 Introduction Currently the Dushanzi Petrochemical Company operates on the pipeline transported Karamai crude and a part of Kazakhstan crude. With the official commissioning of the Sino- Kazakhstan pipeline, the refinery of Dushanzi Petrochemical Company with a capacity of 10.0 Mt/a will officially process the Kazakhstan-Russian mixed crude starting 2007. The refin- ery of Dushanzi Petrochemical Company boasts two FCC units composed of a parallel riser reactor-regenerator configura- t…     

EFFECT OF ZSM-5 ADDITION ON PRODUCT DISTRIBUTION IN A HIGH SEVERITY FCC MODE

The high-severity fluid catalytic cracking (HS-FCC) process is a novel FCC process that enhances light olefins yield under high severity reaction conditions. The process has been investigated by using a small-scale FCC pilot plant (0.1 BPD) with a down-flow reactor. High severity reaction conditions are preferable for enhancing the production of light olefins by catalytic cracking of heavy oils. As another option for the light olefin production, adoption of ZSM-5 additive in conventional FCC units is well known. This presentation describes the effect of ZSM-5 additive on the catalytic cracking of vacuum gas oil under high severity reaction conditions, particularly focusing on the synergistic effect with the base catalyst. Three kinds of FCC catalysts with different activity were used as base catalysts. Although the employment of a ZSM-5 additive resulted in significant increase in the light olefins yield at the expense of gasoline in each catalyst system tested, the effectiveness was varied depending on the nature of the base catalysts. By choosing a suitable base cracking catalyst, more than 20 wt% of propylene yield was obtained at a one-pass conversion of fresh feed.