Research and Development of Novel Heavy Oil Catalytic Cracking Catalyst RCC-1

A novel heavy oil catalytic cracking catalyst RCC-1 was developed by using the ultra-stable zeolite, which was hydrothermally treated and modified through cleaning its pores to serve as the active component. The chemical composition and physicochemical properties of RCC-1 catalyst were studied by XRF, BET, pore volume analysis, attrition index analysis, and particle size distribution determination methods, and its catalytic cracking performance was also evaluated by a microreactor for light oil cracking and the ACE device. The test results showed that the new type of heavy oil catalytic cracking catalyst RCC-1 had good physicochemical properties and heavy oil cracking ability, strong anti-metallic contamination capability, good product distribution, good coke selectivity and gasoline selectivity, and excellent reduction of gasoline olefin content characteristics.

Effects of Temperature and Catalyst to Oil Weight Ratio on the Catalytic Conversion of Heavy Oil to Propylene Using ZSM-5 and USY Catalysts

It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.

Application of New Heavy Metals Resistant Porous Binder Material Used in Fluid Catalytic Cracking Reaction

A novel porous binder was obtained from acid-treated kaolin. This new binder possessed abundant meso/macropores, good hydrothermal stability and heavy metal resistance. The prepared catalyst using new binder featured low attrition index and large pore volume. The catalysts were contaminated with Ni, V, and tested in a fixed-fluidized bed reactor unit. In comparison with the reference sample, the oil conversion achieved by the above-mentioned catalyst increased by 3.50 percentage points, and heavy oil yield decreased by 2.86 percentage points, while the total liquid yield and light oil yield increased by 2.82 percentage points and 0.79 percentage points, respectively. The perfect pore structure, good hydrothermal stability and heavy metal resistant performance of new binder were the possible causes leading to its outstanding performance.

U-model Enhanced Dynamic Control of a Heavy Oil Pyrolysis/Cracking Furnace

This paper proposes a case study in the control of a heavy oil pyrolysis/cracking furnace with a newly extended U-model based pole placement controller(U-PPC). The major work of the paper includes: 1) establishing a control oriented nonlinear dynamic model with Naphtha cracking and thermal dynamics; 2) analysing a U-model(i.e., control oriented prototype) representation of various popular process model sets; 3)designing the new U-PPC to enhance the control performance in pole placement and stabilisation; 4) taking computational bench tests to demonstrate the control system design and performance with a user-friendly step by step procedure.

Targeted Catalytic Cracking to Olefins(TCO):Reaction Mechanism,Production Scheme,and Process Perspectives

Light olefins are important organic building blocks in the chemicals industry.The main low-carbon olefin production methods,such as catalytic cracking and steam cracking,have considerable room for improvement in their utilization of hydrocarbons.This review provides a thorough overview of recent studies on catalytic cracking,steam cracking,and the conversion of crude oil processes.To maximize the production of light olefins and reduce carbon emissions,the perceived benefits of various technologies are examined.Taking olefin generation and conversion as a link to expand upstream and downstream processes,a targeted catalytic cracking to olefins(TCO)process is proposed to meet current demands for the transformation of oil refining into chemical production.The main innovations of this process include a multiple feedstock supply,the development of medium-sized catalysts,and a diameter-transformed fluidizedbed reactor with different feeding schemes.In combination with other chemical processes,TCO is expected to play a critical role in enabling petroleum refining and chemical processes to achieve low carbon dioxide emissions.

In situ preparation of well-dispersed CuO nanocatalysts in heavy oil for catalytic aquathermolysis

We developed an in situ synthesis strategy for preparing well-dispersed CuO nanoparticles as aquathermolysis catalyst for viscosity reduction in Shengli heavy oil(China). A Cu(OH)_2-contained microemulsion was employed as a carrier to disperse the precursor Cu(OH)_2 to the heavy oil phase. Under aquathermolysis condition(240 ℃, 2.5 MPa of N_2), the Cu(OH)_2 precursors would first be converted in situ to well-crystallized and size-homogeneous CuO nanoparticles naturally, catalyzed by which the viscosity of Shengli heavy oil could be reduced as much as 94.6%; simultaneously, 22.4% of asphaltenes were converted to light components. The agglomeration of the in situ prepared monoclinic CuO nanoparticles could be negligible throughout the catalytic reaction. Based on the characterization results of ~1 H NMR, elemental analysis and GC-MS of oil samples before and after catalytic aquathermolysis, the mechanism for viscosity reduction of heavy oil in the catalytic system was investigated.

Study on the in situ desulfurization and viscosity reduction of heavy oil over MoO_(3)–ZrO_(2)/HZSM-5 catalyst

Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ desulfurization and viscosity reduction of heavy oil.The physical and chemical properties of catalysts were characterized by XPS,XRD,TEM,NH3-TPD,etc.The effects of temperature,catalyst type and addition amount on viscosity and composition of heavy oil were evaluated.The results showed that the presence of MoO_(3)–ZrO_(2)/HZSM-5 nanoparticles during aquathermolysis could improve the oil quality by reducing the heavy fractions.It reduced viscosity by 82.56%after the reaction at 280℃ and catalyst addition of 1 wt%.The contents of resins and asphaltic in the oil samples were 5.69%lower than that in the crude oil.Sulfur content decreased from 1.45%to 1.03%.The concentration of H2S produced by the reaction was 2225 ppm.The contents of sulfur-containing functional groups sulfoxide and sulfone sulfur in the oil samples decreased by 19.92%after the catalytic reaction.The content of stable thiophene sulfur increased by 5.71%.This study provided a basis for understanding the mechanism of heavy oil desulfurization and viscosity reduction.

Distribution of nitrogen and oxygen compounds in shale oil distillates and their catalytic cracking performance

The positive-and negative-ion electrospray ionization(ESI)coupled with Fourier transform-ion cyclotron resonance mass spectrometry(FT-ICR MS)was employed to identify the chemical composition of heteroatomic compounds in four distillates of Fushun shale oil,and their catalytic cracking performance was investigated.There are nine classes of basic nitrogen compounds(BNCs)and eleven classes of non-basic heteroatomic compounds(NBHCs)in the different distillates.The dominant BNCs are mainly basic N1 class species.The dominant NBHCs are mainly acidic O2 and O1 class species in the300-350℃,350-400℃,and 400-450℃distillates,while the neutral N1,N1 O1 and N2 compounds become relatively abundant in the>450℃fraction.The basic N1 compounds and acidic O1 and O2 compounds are separated into different distillates by the degree of alkylation(different carbon number)but not by aromaticity(different double-bond equivalent values).The basic N1 O1 and N2 class species and neutral N1 and N2 class species are separated into different distillates by the degrees of both alkylation and aromaticity.After the catalytic cracking of Fushun shale oil,the classes of BNCs in the liquid products remain unchanged,while the classes and relative abundances of NBHCs vary significantly.

Fluid Catalytic Cracking Technology for Maximum Gasoline Production

Increasing gasoline production in FCC unit can improve the utilization efficiency of petroleum resources and gain economic benefit.This paper discusses the technical principles for increasing FCC gasoline yield from the aspects of feedstock properties,operating conditions,LCO(light cycle oil)recycling,catalyst selection and reactor type,and illustrates the industrial application examples for maximizing gasoline production.The technical measures,such as optimizing the feedstock,properly increasing the catalyst activity and reaction temperature,recycling LCO or hydrotreated LCO,applying high gasoline yield catalyst,and adopting the two-zone riser reactor,are proposed to enhance the gasoline yield.

Study on Application of Bi-directional Combination Technology Integrating Residue Hydrotreating with Catalytic Cracking RICP

After analysing the disadvantages of the traditional residue hydrotreating-catalytic cracking combination process, RIPP has proposed a bi-directional combination technology integrating residue hydrotreating with catalytic cracking called RICP which does not further recycles the FCC heavy cycle oil (HCO) inside the FCC unit and delivers HCO to the residue hydrotreating unit as a diluting oil for the residue that is concurrently subjected to hydrotreating prior to being used as the FCC feed oil. The RICP technology can stimulate residue hydrotreating reactions through utilization of HCO along with an in- creased yield of FCC light distillate, resulting in enhanced petroleum utilization and economic benefits of the refinery.

Synthesis of La-Modified Ultra Stable Zeolite L and Its Application to Catalytic Cracking Catalyst

A new type of zeolite La-USL （ultra stable zeolite L （zeolite USL） modified by La）, which has superior activity, stability and selectivity in catalytic cracking of hydrocarbons and thus can be used as an active catalyst component, is reported in this paper. The zeolite L with relative crystallinity of above 90% was synthesized by the hydrothermal crystallization method under optimum conditions and characterized by means of XRD, NH3-TPD and isotherm adsorption techniques. The in-situ synthesized zeolite L with a SiO2/Al2O3 mole ratio of 5-6 was modified by cation ion exchange, hydrothermal dealumination and chemical modifications with La in order to prepare La-containing USL with a higher framework SiO2/Al2O3 mole ratio of 15-30. The modified zeolite La-USL was used as an active additive component of fluid catalytic cracking （FCC） catalyst and the resulting catalysts were evaluated by microactivity test （MAT） and fixed-fluidized bed （FFB） experiments using heavy oil as feedstock. The influence of La content in La- USL on cracking product distribution, gasoline group composition and research octane number （RON） was investigated. The results showed that when La content in La-USL was 0.8 wt%, the addition of the corresponding La-USL could result in a FCC catalyst that produced significant improvement in product distribution and gasoline quality.

Commercial Application of CPP for Producing Ethylene and Propylene from Heavy Oil Feed

A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene andpropylene from heavy oil feedstock has been developed. The catalyst CEP was specially designedfor this process, which has bi-functional catalytic activities for both carbonium ion reaction andfree radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trialshowed that the yield of ethylene and propylene was 20.37% and 18.23% respectively inmaximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylenewas 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene andpropylene.

Study on the Catalytic Reforming Law of Solid-Phase Carbon and Nitrogen Sources Loaded with MnO_(2)at Low Temperatures in Tahe Heavy Oil

MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.

In situ catalytic upgrading of heavy crude oil through low-temperature oxidation

The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screening,oil-soluble catalysts,copper naphthenate and manganese naphthenate,are more attractive,and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil.The heavy oil compositions and molecular structures were characterized by column chromatography,elemental analysis,and Fourier transform infrared spectrometry before and after reaction.An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity-temperature characteristics.Results show that the two oil-soluble catalysts can crack part of heavy components into light components,decrease the heteroatom content,and achieve the transition of reaction mode from oxygen addition to bond scission.The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil（oil viscosity and contents of heavy fractions）.It is found that the temperature,oil composition,and internal molecular structures are the main factors affecting its flow ability.Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.

Synthesis of silica/metatitanic acid nanocomposite and evaluation of its catalytic performance for aquathermolysis reaction of extra-heavy crude oil

A lipophilic silica/metatitantic acid（denoted as Si O2/H2 TiO 3） nanocomposite was synthesized by hydrothermal reaction with surface-modified Si O2 as the lipophilic carrier. As-synthesized Si O2/H2 TiO 3nanocomposite was used as a catalyst to promote the aquathermolysis reaction of extra-heavy crude oil thereby facilitating the recovering from the deep reservoirs at lowered temperature. The catalytic performance of the as-synthesized Si O2/H2 TiO 3catalyst for the aquathermolysis reaction of the heavy oil at a moderate temperature of 150 °C was evaluated in relation to the structural characterizations by TEM,FTIR,XRD and FESEM as well as the determination of the specific surface area by N2adsorption–desorption method. Findings indicate that as-synthesized Si O2/H2 TiO 3nanocomposite exhibits an average size of about 20 nm as well as good lipophilicity and dispersibility in various organic solvents; and it shows good catalytic performance for the aquathermolysis reaction of the extra-heavy oil extracted from Shengli Oilfield of China. Namely,the assynthesized Si O2/H2 TiO 3catalyst is capable of significantly reducing the viscosity of the tested heavy oil from58,000 c P to 16,000 c P（referring to a viscosity reduction rate of 72.41%） at a mass fraction of 0.5%,a reaction temperature of 150 °C and a reaction time of 36 h,showing potential application in downhole upgrading heavy crude oils.

Catalytic Cracking and PSO-RBF Neural Network Model of FCC Cycle Oil

Catalytic cracking experiments of FCC cycle oil were carried out in a fixed fluidized bed reactor. Effects of reac- tion conditions, such as temperature, catalyst to oil ratio and weight hourly space velocity, were investigated. Hydrocarbon composition of gasoline was analyzed by gas chromatograph. Experimental results showed that conversion of cycle oil was low on account of its poor crackability performance, and the effect of reaction conditions on gasoline yield was obvi- ous. The paraffin content was very high in gasoline. Based on the experimental yields under different reaction conditions, a model for prediction of gasoline and diesel yields was established by radial basis function neural network （RBFNN）. In the model, the product yield was viewed as function of reaction conditions. Particle swarm optimization （PSO） algorithm with global search capability was used to obtain optimal conditions for a highest yield of light oil. The results showed that the yield of gasoline and diesel predicted by RBF neural network agreed well with the experimental values. The optimized reac- tion conditions were obtained at a reaction temperature of around 520 ~C, a catalyst to oil ratio of 7.4 and a space velocity of 8 h~. The predicted total yield of gasoline and diesel reached 42.2% under optimized conditions.

Catalytic aquathermolysis of Shengli heavy crude oil with an amphiphilic cobalt catalyst

An interfacially active cobalt complex,cobalt dodecylbenzenesulfonate,was synthesized.Elemental analysis,atomic absorption spectroscopy,Fourier transform infrared spectroscopy（FT-IR）,thermogravimetric analysis,and surface/interfacial tension determination were performed to investigate the properties of the catalyst.Results showed that the synthesized catalyst showed active interfacial behavior,decreasing the surface tension and interfacial tension between heavy oil and liquid phase to below 30 and 1.5 mN/m,respectively.The catalyst was not thermally degraded at a temperature of 400 ℃,indicating its high thermal stability.Catalytic performance of the catalyst was evaluated by carrying out aquathermolysis.The viscosity determination showed that the viscosity of the heavy oil decreased by 38%.The average molecular weight,group compositions,and average molecular structure of various samples were analyzed using elemental analysis,FT-IR,electrospray ionization Fourier transform ion cyclotron resonance（ESI FT-ICR MS）,and ～1H nuclear magnetic resonance.Results indicated that the catalyst could attack the sulfur- and O_2-type heteroatomic compounds in asphaltene and resin,especially the compounds with aromatic structure,leading to a decrease in the molecular weight and then the reduction in the viscosity of heavy oil.Therefore,the synthesized catalyst might find an application in catalytic aquathermolysis of heavy oil,especially for the high-aromaticity heavy oil with high oxygen content.

Catalytic Cracking Characteristics of Plant Oil for Producing Light Olefins and Light Aromatics

Catalyst containing shape selective zeolite is used to investigate the catalytic cracking characteristics of palm oil and three types of hydrocarbon VGOs on a fixed fluidized bed(FFB) unit. The advantage of producing light olefins and light aromatics by catalytic cracking of plant oil is discussed. Results indicate that the hydrocarbyl group of the plant oil molecule is quite readily crackable; the C_6—C_8 aromatics yield is well above and the light olefins yield is about the same with the hydrocarbon feeds, while the yields of low value products are lower; the hydrocarbyl group of the plant oil molecule has strong tendency of aromatization, and can enter the zeolite pores to selectively form C_6—C_8 aromatics; during catalytic cracking of plant oil and fatty acids, a portion of the oxygen is removed in the form of water through hydrogen transfer reaction, while olefins are prevented from being saturated, which can ensure proper yields of both low-carbon olefins and light aromatics.

FCC Study of Canadian Heavy Gas Oils—Comparisons of Product Yields and Qualities between Reactors

Several series of cracking tests in a comprehensive study were conducted on separate occasions involving all or parts of ten Canadian vacuum gas oils (VGOs) and two catalysts with bottoms-cracking or octane-barrel capability. VGOs were cracked in fixed- and/or fluid-bed microactivity test (MAT) units, in an Advanced Cracking Evaluation (ACE) unit, and in a modified ARCO riser reactor. Individual yields of gas, liquid, and coke from the MATs at 55, 65, 70, and 81 wt% conversion levels were compared with their respective pilot plant data. Good linear correlations could be established between MAT and riser yields except for liquefied petroleum gas (LPG) and light cycle oil (LCO). At a given conversion, correlations existed among the fixed- and fluid-bed MAT units and the ACE for each product yield. Liquid products from the fixed or fluid-bed MAT were analyzed for hydrocarbon types, sulfur, nitrogen and density, most of which showed good agreement with those obtained from the riser study. When cracking Canadian oil-sands-derived VGOs, the bottoms-cracking catalyst containing a large-pore active matrix was found to be more suitable than the octane-barrel catalyst with smaller pores to produce higher yields of valuable distillates, but with less superior qualities (in terms of sulfur and nitrogen contents). The advantages of hydrotreating some poor feeds to improve product yields and qualities were demonstrated and discussed.

Some Fundamental Aspects of Residuum Catalytic Cracking

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