炼化企业“油转化”进程中的原料选择优化

炼油产能过剩、化工原料短缺为当前中国石化企业面临的结构性难题,炼化企业实施减产成品油、增产化工原料与化工产品的“油转化”转型发展成为必然选择,具体实施路径包括调整生产装置、优化生产经营、引进新型技术等多种手段。通过引入PIMS优化工具,模拟炼化企业在波动的市场环境中做出的最优选择结果,分析原油及化工原料采购决策变化,测算催化裂化工艺替代前后企业利润和原料选择变化,为企业实施“油转化”战略进程中的生产经营优化提供决策依据。建议炼化企业在“油转化”过程中加强轻质原油与凝析油经济性测算,优化原料采购策略;加强工艺路线负荷调节,安排好芳烃与裂解两条化工路线的生产负荷;加强新装置经济性分析,掌握流程局部变动对全厂整体生产经营的影响,从而实现降本增效。

2023年化工轻油市场回顾及2024年展望

2023年,全球石化行业均处于需求疲弱、利润低迷的景气周期底部,石脑油裂解价差创近5年来次低。由于我国处于化工装置投产高峰期,直接拉动化工轻油进口规模突破千万吨,国内石化行业处在原料供应严重不足及终端需求低迷的双重压力下。预计2024年,随着下游消费逐步恢复,全球石脑油需求将回归正常增长,裂解价差有所修复,但仍处于较弱水平;化工原料不足的困境略有缓解,短期内国内化工轻油缺口维持在千万吨左右。中长期化工轻油缺口将持续扩大,进口规模进一步增加,建议企业扩大全球资源采购力度,加大石脑油储罐建设,提高炼厂化工轻油自供比重。

PEG-mediated Transformation of Lentinus edodes

Expression vector p301-bG1 contains a Sw gene and a bialaphos resistance gene both driven by glyceraldehydes-3-phosphate dehydrogenase (GPD) gene promoter isolated from Lentinus edodes ( Berk.) Sing. Using p301-bG1, PEG-mediated transformation of protoplast of L. edodes was studied. Mixed with PEG-purified plasmid DNA, the protoplasts of L. edodes were treated with PEG solution and cultured on CYM regeneration plate containing 40 mug/mL bialaphos. Bialaphos-resistant and GUS-positive transformants were obtained using this transformation system. Although the transformation efficiency was relatively low, the protocols release large expenses on expensive instrument and restriction enzymes, providing a simple and economical method for mushroom breeding at the molecular level.

Analysis of Measures and Effect on Reducing Olefin Content in Gasoline

This article refers to major measures for reducing olefin content of automotive gasoline and the effect after adoption of these measures. The key for reducing olefin content in China's automotive gasoline pool is to reduce the olefin content of FCC naphtha. The domestic refiners apply the olefinreducing catalyst to decrease the olefin content of FCC gasoline as a convenient and cheap means to meet the national standard for automotive gasoline at the present phase. Furthermore, the novel domestic FCC reaction processes, such as the MIP, MGD, FDFCC and other processes can also apparently reduce olefin content in FCC gasoline. In order to further reduce the olefin content in gasoline to meet more stringent standard for automotive gasoline, Chinese refiners should optimize the processing scheme while aggressively disseminating hydrogenation process along with development of catalytic reforming,alkylation, etherification and other processes to completely change the simplistic composition of domestic gasoline pool.

Study on Agrobacterium tumefaciens-mediated Transformation of Brassica campestris L. with Fusion Gene Ycoil-bFGF

[ Objective] The study is to generate pharmaceutical protein via plant transgenic technique. [Methed] Using the cotyledons with petiole as transformation receptor, the fusion gene of rapeseed oil-body gene and bFGF was introduced into the rapeseed （ Brassica campestris L. ） by Agrobacterium tumefaciens-mediated transformation; meanwhile regeneration conditions of rapeseed were also optimized, and the regenerated resistant plantlets were detected by PCR and Southern blot. [ Result] This fusion gene had been integrated into rapeseed genome successfully, and the optimized conditions of transformation and regeneration were as follows： explants pre-culture for 2 d, co-culture for 3 d, bacteria solution OD600 for 0.3 and infection time for 5 min. [ Conclusion] The results laid a solid foundation for extraction, isolation and purification of protein in transgenic plant seeds.

Analysis of Current Status of Steam Cracking Feed Production and Measures for Maximization of Steam Cracking Feed

In recent years China has seen speedy development of its ethylene industry. Compared to other advanced countries the per capita ethylene consumption in China is still low. With successive startup of grassroots ethylene projects in China after 2006 and debottlenecking and expansion of existing ethylene units China will be confronted with the major issues related with increase of feedstocks for steam cracking. Naphtha is the main feedstock for producing ethylene, and the hydrocracked tail oil is increasing its share in the steam cracker feedstock pool over recent years. This article has analyzed the possibility for maximization of steam cracking feedstock and estimated steam cracker feedstock output based on processing 5 Mt/a of different crudes including the mixed crude transferred through Lu-Ning pipeline and Arabian light crude using corresponding process technologies at the refinery.

The FCC Flue Gas SOx Transfer Additive RFS Developed by RIPP

The present paper introduces the development of FCC flue gas SOx transfer additives by RIPP with a brief discussion of SOx transfer mechanism. The second-generation SO transfer additives of the RFS series are RIPP＇s proprietary additives with significantly improved performances. The results of commercial tests indicate that the RFS additive can effectively control SO emission of the FCC regenerator while maintaining product yields and product quality when the additive is used in a proper concentra- tion range.

Residue Upgrading in Slurry Phase over Ultra-fine NiMo/γ-Al_2O_3 Catalyst

In this article, residual oil hydroconversion was studied in slurry phase in the presence of fine solid Ni Mo/γ-Al2O3 catalyst and the effects of operating conditions were carefully studied. The results showed that residue conversion was only affected by the reaction temperature and reaction time. The coke yield increased with a higher reaction temperature, a bigger catalyst particle size, a longer reaction time, a lower initial hydrogen pressure and a lower catalyst concentration. Heteroatoms removal rate increased with a higher reaction temperature, a longer reaction time, a higher initial hydrogen pressure, a higher catalyst concentration, and a smaller catalyst particle size. The role of catalyst in the slurry bed technology was discussed and its function could be stated as follows: the metal was applied to activate the hydrogen atoms for removing heteroatoms and saturating aromatics, while the support of the catalyst was used to prevent the mesophase coalescence for reducing coke formation.

Modified graphene‐based materials as effective catalysts for transesterification of rapeseed oil to biodiesel fuel

Production of biodiesel by the transesterification process using different modified graphene‐based materials as catalysts was studied.Solid acid graphene‐based samples were prepared by grafting sulfonic or phosphate groups on the surface of thermally reduced graphene oxide.The obtained materials were thoroughly characterized using scanning electron microscopy,X‐ray diffraction,thermogravimetric analysis,X‐ray photoelectron spectroscopy,N2 adsorption‐desorption measurements,potentiometric titration,elemental analysis,and Fourier transform infrared spectroscopy.The prepared catalysts were tested in the transesterification of rapeseed oil with methanol at 130°C under pressure,and their activities were compared to the performance of a commercially available heterogeneous acidic catalyst,Amberlyst‐15.All modified samples were active in the transesterification process;however,significant differences were observed in the yield of biodiesel,depending on the method of catalyst preparation and strength of the acidic sites.The highest yield of fatty acid methyl esters of 70%was obtained for thermally reduced graphene oxide functionalized with 4‐benzenediazonium sulfonate after 6 h of processing,and this result was much higher than that obtained for the commercial catalyst Amberlyst‐15.The results of the reusability test were also promising.

Study on the Effect of Catalyst Properties on Residue Hydroconversion

The effect of catalyst properties on residue oil hydroconversion was studied at moderate operating conditions(at a temperature of 400 ℃, an initial hydrogen pressure of 10 MPa, and a reaction time of 4 h) in a batch mode slurry phase with different catalyst samples. The results showed that the catalyst acidity had a good effect on residue conversion and MCR(micro carbon residue) conversion but brought about higher coke yield. Residue conversion was thermally induced but the catalyst acidity changed its conversion route. A catalyst with higher metal loading, higher hydrogenation activity and appropriate pore size had higher sulfur and metal removal rate, higher MCR conversion and also a lower coke formation. The activity of spent commercial catalyst AS1 and DS1 was slightly lower than the corresponding fresh ones but was still high enough for residue oil hydroconversion. It assumes that the role of the catalyst is to activate hydrogen species toward reaction with an aromatic carbon radical to yield a cyclohexadienyl type intermediate which will turn into liquid and also to absorb the mesophase which can easily aggregate to form coke.

Development and Application of the CGP-2 Catalyst in the MIP-CGP Process

The research and development of the CGP-2 catalyst, which was used in the MIP-CGP process for reducing the olefin and sulfur contents of FCC naphtha and enhancing the propylene yield, were introduced. A specific type of metal compound was added into the matrix to provide active centers for reactions including catalytic conversion and selective adsorption of sulfur containing compounds. The CGP-2 catalyst possessed excellent hydrothermal stability to meet the requirements of the 2rid reaction zone of the MIP-CGP process. The commercial test of the said catalyst at the SINOPEC Cangzhou refinery showed that in comparison with the base case （using the CGP-1Z catalyst） the CGP-2 catalyst could reduce the sulfur content of FCC naphtha by 30.32% and increase the propylene yield along with good coke selectivity. Thus, the naphtha produced by the MIP-CGP process at the Cangzhou refinery can meet the new gasoline standard enforced in July 2005.

Hierarchically Structured Monolithic ZSM-5 through Macroporous Silica Gel Zeolitization

The hierarchically structured ZSM-5 monolith was prepared through transforming the skeletons of the macroporous silica gel into ZSM-5 by the steam-assisted conversion method. The morphology and monolithic shapes of macroporous silica gel were well preserved. The hierarchically structured ZSM-5 monolith exhibited the hierarchical porosity, with mesopores and macropores existing inside the macroporous silica gel, and micropores formed by the ZSM-5. The products have been characterized properly by using the XRD, SEM and N2 adsorption–desorption methods.

Study on Influence of Gasoline Sulfur Content on Performance of Vehicle Exhaust Catalytic Converter

This paper has investigated the influence of gasoline sulfur content on durability of catalytic converter for vehicle exhaust gas. Two gasoline samples with different sulfur contents (equating to 150 μg/g and 50 μg/g of sulfur, respectively) were used to examine the durability and performance of catalytic converter on the bench test. The test results have revealed that in comparison to the influence of sulfur on ageing of catalytic converter the thermal ageing had a more remarkable impact on the performance of catalytic converter, and the performance of catalytic converter could be restored by high-temperature desulfurization process after ageing by the high-sulfur gasoline sample (containing 150 μg/g of sulfur) .

Influence of Conditions on Reuterin Accumulation by the Resting Cell Biotransformation Process

3-Hydroxypropionaldehyde （3-HPA） is a potential valuable chemical and new broad-spectrum antim-icrobial substance. In order to improve the conversion of 3-HPA/glycerol, our work studied the two-step process from glycerol to 3-HPA, and investigated the influence of cell harvest time, glycerol concentration, biomass con-centration, pH and temperature on the production of 3-HPA by Lactobacillus reuteri CG001, respectively. The re-sults showed that molar conversion yield of 3-HPA/glycerol reached 97.9% under the condition that 200 mmol·L-1 glycerol was converted by 25.3 g·L-1 resting cell for 1 h at 30 ℃. The cells could not be reused directly because the L. reuteri almost lost its bioconversion activity completely, but the ability of glycerol conversion could gradually recover if the fresh medium was added to the deactivated cell for 4 h.

Spectroscopic Analysis of Structural Transformation in Biodiesel Oxidation

The oxidation behavior of three biodiesels of different origins,viz.rapeseed oil derived biodiesel,soybean oil derived biodiesel and waste oil based biodiesel,were tested on an oxidation tester.The chemical compositions of the biodiesels were characterized by gas chromatography.Thereafter,the structural transformation of fatty acid methyl ester(FAME)of the biodiesels was analyzed by an infrared spectrometer and an ultraviolet absorption spectrometer.The results demonstrated that the oxidation behavior of biodiesels of different origins was closely related to the composition and distribution of FAMEs.Higher concentration of unsaturated FAME with multi-double bonds exhibited poorer oxidation resistance.Furthermore,cis-trans isomerization transformation occurred in the unsaturated FAME molecules and conjugated double-bond produced during the oxidation process of biodiesel.Greater cis-trans variations corresponded to deeper oxidation degree.The higher the content of unsaturated FAME with multi-double bonds in a biodiesel,the more the conjugated double bonds was formed.

Co-processing petroleum catalytic slurry with coal

It is studied that reactivity of petroleum catalytic slurry （PCS） and coal with Fe catalyst in 1 L autoclave, the fol- lowing is mainly discussed, coal conversion and asphalt properties, especially related with petroleum cracking slurry （PCS） properties. The results show that co-processing conversion and asphalt yield increase with the increase of PCS ratio. PCS prop- erties have important effect on coal conversion and asphalt properties. One kind of PCS shows negative effect on coal conver- sion. High aromatic PCS can lead to high ductility asphalt with good colloid properties. Coal and the PCS can lead to a strong matching effect.

Distributed Bio-Hydrogen Refueling Stations

Hydrogen fuel cell cars are now available for lease and for sale. Renewable hydrogen fuel can be produced from water via electrolysis, or from biomass via gasification. Electrolysis is power-hungry with high demand from solar or wind power. Gasification, however, can be energy self-sufficient using a recently-patented thermochemical conversion technology known as I-HPG （indirectly-heated pyrolytic gasification）. I-HPG produces a tar-free syngas from non-food woody biomass. This means the balance of plant can be small, so the overall system is economical at modest sizes. This makes it possible to produce renewable hydrogen from local agricultural residues; sufficient to create distributed refueling stations wherever there is feedstock. This work describes the specifics of a novel bio-hydrogen refueling station whereby the syngas produced has much of the hydrogen extracted with the remainder powering a generator to provide the electric power to the I-HPG system. Thus the system runs continuously. When paired with another new technology, moderate-pressure storage of hydrogen in porous silicon, there is the potential to also power the refueling operation. Such systems can be operated independently. It is even possible to design an energy self-sufficient farm where all electric power, heat, and hydrogen fuel is produced from the non-food residues of agricultural operations. No water is required, and the carbon footprint is negative, or at least neutral.

Expression of green fluoscrescent protein gene in Sclerotinia sclerotiorum

Protoplasts of the pathogenic plant fungus,Sclerotinia sclerotiorum,were transformed using the pPGF plasmid,which contains green fluorescent protein gene,under the control of Aspergillus nidulans regulatory sequences. The pPGF plasmid was introduced by PEG/CaCl2 treatment. Positive transformants were harvested with hygromycin B (HYG) resistance as selective marker,and then were observed with green fluorescence phenomena in response to blue light,which suggested that GFP gene was cloned into genome DNA of S. sclerotiorum. The transformants were verified mitotically stable by Southern blotting analysis and passage culturing. This study is developed as an initial step for further research into infection mechanisms of S. sclerotiorum to plants and interactions with bio-control fungus.

Catalytic Degradation of Mixed Polypropylene, Low and High Density Polyethylene into Environmental Friendly and Useful Products

Using novel catalyst the pyrolysis of mixed plastics has been considered as an effective way to convert waste plastics into environmental friendly and industrially useful hydrocarbon gas and liquid products. Catalytic cracking is a promising alternative for plastic wastes recycling. More than 99% of a polymer mixed converted into combustible hydrocarbon in a catalytic converting reaction. The products are mainly middle distillates. In this work equally weighted mixed HDPE （high density polyethylene）, LDPE （low density polyethylene） and Polypropylene were degraded. The reaction occurred in a semi batch reactor at several temperatures and catalyst/polymer ratios in search for an optimum operating condition. The products are liquid and gaseous hydrocarbons with minor of residue. The liquid and gas products were in the range of middle distillate cuts of gasoline, kerosene and gas oil. Finally, with a metallic base, yielded 99.5% of given mixed to valuable middle distillate products that include 86% liquid hydrocarbon and 13.5% gas, ranging between C1 and C5 with less percent of residue. The optimum condition for this yield reports at a temperature of 450 ℃ and 10% of catalyst w/w at atmosphere pressure.

Thermal transformation of acid compounds in high TAN crude oil

The Liaohe crude oil with high total acid number （TAN） was subjected to thermal reaction at 300 ℃ to 500℃. Reaction products were collected and analyzed by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry （ESI FT-ICR MS） to determine acid compounds in the crude oil. The double-bond equivalence （DBE） versus carbon number was used to characterize the oxygenated components in the feed and reaction products. The 02 class which mainly corresponds to naphthenic acids decarboxylated at 350-400℃, resulting in a sharply decrease in TAN. Phenols （O1 class） are more thermally stable than carboxylic acids. Carboxylic acids were also thermally cracked into smaller molecular size acids, evidenced by the presence of acetic acid, propanoic acid, and butyric acid in the liquid product. These small acid species are strong acids likely responsible for corrosion problems in refineries.