控制萃取平衡时间选择性分离回收FCC废催化剂酸浸液中的钒

以2-乙基己基膦酸单2-乙基己基酯（P507）为萃取剂,采用控制萃取平衡时间的方法从催化裂化（FCC）废催化剂的含铁酸浸出液中选择性萃取分离回收钒。试验结果表明：采用P507、磷酸三丁酯（TBP）、磺化煤油体积分数分别为10%,5%,85%的协萃体系,在萃取剂皂化率为50%、萃取相比（有机相与水相的体积比）为1∶1、萃取平衡时间为10 min的条件下,经五级逆流萃取,钒的萃取率达99.5%,而铁的萃取率仅为5.2%;在反萃取剂硫酸的质量浓度为150 g/L、反萃取相比为6∶1、反萃取平衡时间为15 min的条件下,经四级逆流反萃取,反萃取液中钒的质量浓度为18 630 mg/L,钒的多级反萃取率达99.5%,反萃取液中铁的质量浓度仅为70 mg/L,实现了钒的有效富集回收。通过控制萃取平衡时间可实现FCC废催化剂硫酸浸出液中钒与铁的有效分离及钒的富集回收。     

Microwave Leaching of Vanadium From Petroleum Coke

The effects of microwave power, temperature, concentration of alkali and surfactant, sodium atoms ratio, liquid-solid ratio, and the leaching time on the leaching rate of vanadium were studied. Compared with microwave leaching and water bath heating leaching, the results showed that microwave heating can shorten the reaction time and improve the leaching efficiency. The reasons that microwave heating strengthened vanadium leaching from petroleum coke are discussed as well. The optimal conditions are determined: microwave power 500 W, leaching temperature 95°C, alkali concentration 125 g/L, sodium atom ratio of 3:1, surfactant concentration 400 mg/L, solid-liquid ratio 5:1, and leaching time 120 min. Under the best condition, the leaching rate of vanadium can be 89.54%.     

Physical Chemical Properties of Leachate in the Process of Improving Vanadium Leaching From Petroleum Coke: Part I

Petroleum coke is the main raw material to produce carbon anode. The content of vanadium in petroleum coke seriously affects the quality of carbon anode. Physical chemical properties of leachate in the process of improving vanadium leaching from petroleum coke were investigated. The effects of different parameters on vanadium removal were chiefly introduced. Systematic studies indicate that the high removal can be achieved under the following conditions: 10 g of petroleum coke, 20 mL of oxidation, 3 h of leaching time, 500 W of microwave power, and 400 mg/L of surfactant amount. Physical chemical properties of leachate changed along with the parameters. This is one reason for the leaching amount of change.     

从废FCC催化剂中回收稀土的研究

废FCC催化剂(催化裂化催化剂)中含有2%以上的富La或富ce稀土,用盐酸浸取后可得到含有稀土元素和非稀土杂质的氯化稀土溶液,然后通过溶剂萃取的方法可回收稀土元素。本课题研究了浸取过程中酸的浓度、浸取温度和浸取时间等因素对稀土浸出的影响;考察了用P507(2-乙基己基膦酸单-2-乙基己基酯,HEH/EHP)萃取剂从盐酸介质中萃取回收稀土的方法及影响稀土萃取的主要因素。结果表明,增加浸取酸浓度、升高浸取温度和延长浸取时间均有利于稀土的浸取;采用P507-煤油-盐酸体系可有效地萃取回收浸出液中的稀土元素,较好地实现稀土元素和非稀土杂质的分离。     

Changes in Vanadium Acid Radical Ions During Leaching From Petroleum Coke

The infrared spectrogram of vanadium leachate from petroleum coke was studied under different conditions. The change in vanadium acid radical ions in leachate was analyzed, and the three kinds of vanadate ions can be transformed while leaching condition was changed. When the leaching time was prolonged, the ion of vanadium dimer acid radical ions was formed to V-O chemical bond by depolymerization; when the leaching temperature increased, the ion of vanadium dimer V-O-V was exploded to V-O and V-OH chemical bond; when the leaching environment was under medium and low NaOH concentration, the V-OH was partly turned to vanadium dimer acid radical ions and V-O; and when the leaching environment was under high NaOH concentration, the leaching rate did not change essentially, and the ions remained unchanged. At last, the ions changing rules were further verified through the Raman spectrum of leachate under different NaOH concentrations.     

含锌废脱硫催化剂的合理利用

用含锌废脱硫催化剂生产附加值较高的活性氧化锌比生产硫酸锌在经济上更为合理，用氨浸法和氯化铵法生产活性氧化锌的浸取液可回收循环使用，单耗低、工艺简单、无三废，是硫酸法的替代工艺。     

Microwave-ultrasonication method for leaching vanadium from petroleum coke

The effects of ultrasonic power, liquid-solid ratio and time on the vanadium leaching rate, surface tension, and contact angle were studied in this experiment. The optimum process conditions were determined: 10g for the sample; 1000w for ultrasonic power; 4:1 (mL/g) for liquid-solid ratio; 90?min for leaching time. The leaching rate of vanadium can reach 92.22%. The leaching rate of vanadium can be much improved with same time, when ultrasonic was used.     

Recovery of precious metals from spent Mo–Co–Ni/Al2O3 catalyst in organic acid medium: Process optimization and kinetic studies

In present study, the leaching kinetics of the spent Mo–Co–Ni/Al₂O₃ catalyst was investigated in the presence of formic acid as an organic leaching agent. Firstly, the spent catalyst was roasted in different roasting temperature (200–700?°C) and time (15–240?min), the maximum metal extraction was achieved that at 500?°C with 90?min. Then, the leaching experiments were carried out to determine the influences of process parameters following; particle size, liquid/solid ratio, formic acid concentration, leaching temperature, leaching time and stirring speed. According to the experimental results, the highest dissolution rates of molybdenum (Mo, 75.82%), cobalt (Co, 96.81%), nickel (Ni, 93.44%) and aluminum (Al, 19.46%) were reached under optimum experimental conditions; particle size +75???30?µm; liquid/solid ratio 10?ml/g; formic acid concentration 0.6?M; leaching temperature 80?°C; leaching time 90?min and stirring speed 300 r/min. Moreover, the leaching kinetics clearly reveal that the leaching reaction is controlled by liquid film diffusion and that the activation energy values (E_a) of Co, Ni, Mo and Al were to be 24.49, 25.98, 32.36 and 33.47?kJ/mol, respectively. In conclusion, the leaching process can be conducted in the presence of formic acid for the various industrial wastes in similar structure and composition to Mo–Co–Ni/Al₂O₃ spent catalyst.     

硅胶表面积碳催化作用的研究

研究了硅胶表面积碳经化学改性后在环氧乙烷水合制备乙二醇反应系统中的催化作用 ,探讨了硫酸处理时间、硫酸处理温度、反应温度、空速对环氧乙烷转化率和乙二醇选择性的影响。实验表明 ,硅胶表面积碳经化学改性后作为环氧乙烷水合制备乙二醇反应的催化剂 ,具有很好的催化活性     

DEMINERALIZATION OF PETROLEUM COKES AND FLY ASH SAMPLES OBTAINED FROM THE UPGRADING OF ATHABASCA OIL SANDS BITUMEN

Ash reduction of the cokes and fly ash samples derived from the Athabasca oil sands bitumen was attempted by dissolving the mineral matter in acids. The samples used for this investigation included Syncrude fluid coking coke, Suncor delayed coking coke and the two fly ash samples obtained from the combustion of these cokes. All samples were analyzed for C,H,N,0 and S before and after acid demineralization and the analyses results compared. Further, the ash from the samples before and after acid demineralization was analyzed for silica, alumina, iron, titanium, nickel and vanadium to assess the acid leaching of these elements. CP/ MAS, ¹³C NMR spectroscopic study of the demineralized coke and fly ash samples was also attempted     

The Effect of Sodium Sulfate on Vanadium Leaching From Petroleum Coke and Surface Physical–chemical Properties of Leaching Solution

The relationship of viscosity, conductivity, contact angle, and surface tension with the leaching rate of vanadium in the process of petroleum coke leaching by adding sodium sulfate was studied. Results show that the increase in sodium sulfate amount first increases and then declines the leaching rate. The variation of viscosity is opposite this trend. Conductivity first increases, then decreases, and finally increases in the same condition. Surface tension first decreases, then remains unchanged, and finally presents an increasing trend. The change in contact angle has approximately the same trend as the leaching rate. Surface tension and contact angle increase, inhibiting the reaction of pentavalent vanadium ion and sodium hydroxide, and consequently reducing the leaching rate.     

DEMINERALIZATION OF PETROLEUM COKES AND FLY ASH SAMPLES OBTAINED FROM THE UPGRADING OF ATHABASCA OIL SANDS BITUMEN

ABSTRACT

Ash reduction of the cokes and fly ash samples derived from the Athabasca oil sands bitumen was attempted by dissolving the mineral matter in acids. The samples used for this investigation included Syncrude fluid coking coke, Suncor delayed coking coke and the two fly ash samples obtained from the combustion of these cokes. All samples were analyzed for C,H,N,0 and S before and after acid demineralization and the analyses results compared. Further, the ash from the samples before and after acid demineralization was analyzed for silica, alumina, iron, titanium, nickel and vanadium to assess the acid leaching of these elements. CP/ MAS, ¹³C NMR spectroscopic study of the demineralized coke and fly ash samples was also attempted     

油砂沥青油的加工利用

利用溶剂抽提分离油砂沥青,比较了油砂沥青油的沸腾床加氢实验和焦化实验,以及油砂的干馏实验。结果表明,以甲苯为溶剂抽提分离油砂沥青,可使沥青油回收超过90%。油砂沥青油具有密度大、灰分高、盐含量高的特点,胶质沥青质质量分数超过90%。采用沸腾床加氢处理脱盐沥青油,可使其硫、残炭、镍、钒的脱除率分别达到7283%、6685%、9616%和9824%,胶质和沥青质的转化率分别为7353%和9863%,加氢产物是优质的深加工原料。采用焦化处理非脱盐沥青油,总液收6164%,焦炭产率2895%,资源相对有效利用率低。油砂直接干馏,沥青油总回收率只有7856%。从油砂沥青油的有效回收和利用上看,沸腾床加氢是最有效的手段。     

大豆蛋白分离工艺研究

阐述了大豆蛋白质的分离原理,分析了运用“碱提酸沉”分离法提取大豆蛋白质过程中,豆粕的粉碎方式、浸提温度、浸提时间、浸提液的pH值以及离心工艺对提取效果的影响,为大豆蛋白／聚丙烯腈纤维的工业化生产提供了依据。     

从混合铜矿制取硫酸铜工艺研究

将安徽省齐云山铜矿以混合酸浸出,石灰乳中和水解及二段浓缩除铁和钙,以结晶、重结晶制得五水硫酸铜,铜回收率可达 95％。产品质量符合GB437-80-级标准。     

THE SOLVENT EXTRACTION APPROACH TO PETROLEUM DEMETALLATION

Metals are present in petroleum depending on age and conditions of diagenesis, and concentrate during refining in heavy fractions and residua. Nickel and vanadium show particularly deleterious effects on catalysts, such as poisoning, excessive gas and coke formation. Besides, removing vanadium from fuel oils reduces the environmental impact of “acid rain” due to the oxidation of sulphur dioxide in the atmosphere.

In this paper, research and industrial practice literature concerning the removal. of nickel and vanadium from petroleum and its fractions by solvent extraction and related techniques is reviewed and arranged into four groups as follows:

i) Processes employing hydrocarbon solvents, used to modify the oily matrix solubility parameter in such a way that asphalt/enes be separated. Because a fraction of total metals present are associated to asphalt/enes, deasphaltation implies partial demetallation.

ii) Processes using polar solvents, scarcely miscible with petroleum and able to selectively extract from it metallic complexes of heteroatomic ligands (e.g. metalloporphyri ns).

iii) Processes not based on molecular phase equilibria like i) and ii) but on the formation, by contact with aqueous solutions, of a separate, colloidally stabilized phase. Either surface active agents are added or the surface activity of substances naturally occurring in petroleum is promoted.

iv) Processes based on extraction with chemical reaction (oxidation, chelation) orion exchange between organometallic species in petroleum and ligandsin solution of non-miscibile media.     

THE SOLVENT EXTRACTION APPROACH TO PETROLEUM DEMETALLATION

ABSTRACT

Metals are present in petroleum depending on age and conditions of diagenesis, and concentrate during refining in heavy fractions and residua. Nickel and vanadium show particularly deleterious effects on catalysts, such as poisoning, excessive gas and coke formation. Besides, removing vanadium from fuel oils reduces the environmental impact of “acid rain” due to the oxidation of sulphur dioxide in the atmosphere.

In this paper, research and industrial practice literature concerning the removal. of nickel and vanadium from petroleum and its fractions by solvent extraction and related techniques is reviewed and arranged into four groups as follows:

i) Processes employing hydrocarbon solvents, used to modify the oily matrix solubility parameter in such a way that asphalt/enes be separated. Because a fraction of total metals present are associated to asphalt/enes, deasphaltation implies partial demetallation.

ii) Processes using polar solvents, scarcely miscible with petroleum and able to selectively extract from it metallic complexes of heteroatomic ligands (e.g. metalloporphyri ns).

iii) Processes not based on molecular phase equilibria like i) and ii) but on the formation, by contact with aqueous solutions, of a separate, colloidally stabilized phase. Either surface active agents are added or the surface activity of substances naturally occurring in petroleum is promoted.

iv) Processes based on extraction with chemical reaction (oxidation, chelation) orion exchange between organometallic species in petroleum and ligandsin solution of non-miscibile media.     

Desulfurization of high sulfur petroleum coke by molten caustic leaching

Desulfurization by molten caustic leaching (MCL) at 400–500 °C has been investigated in order to reduce the sulfur content of petroleum coke. Effective parameters on desulfurization of petroleum coke, other than temperature, include alkali to feed (petroleum coke) mass ratio, time and mesh size in the ranges of 0.5–1.5, 1–3 h and 200–600 µm, respectively. In this work, petroleum coke desulfurization conditions using solid KOH have been studied. Maximum petroleum coke desulfurization by MCL method has been obtained by Taguchi L9 design using alkali to feed mass ratio of 1, temperature of 600 °C, time of 2 h and mesh size of 200 µm. The changes in the main groups on the coke surface have been determined using FTIR spectroscopy. In addition, SEM-EDX, TGA and XRD analyses have been used to investigate the changes in coke physical and chemical properties.     

原子吸收光谱法测定石油焦中镍和钙含量

用火焰原子吸收光谱法测定生石油焦和煅烧石油焦中镍和钙。样品在高温炉内于 5 2 5℃下灰化 ,灰份用四硼酸锂在铂坩埚内熔融 ,将熔融物溶解于稀盐酸中 ,用火焰原子吸收光谱法测定该溶液中镍和钙的含量。方法简便、快速、准确。加标回收率为 98 2 %～ 10 3 6 % ,相对标准偏差为 1 0 0 %～ 4 0 3%。     

Physical Chemical Properties of Leachate in the Process of Improving Vanadium Leaching From Petroleum Coke: Part II

The effects of NaOH concentration, leaching time, temperature, Na molar ratio of NaOH and Na₂CO₃ and liquid to solid mass ratio on vanadium removal, and physical chemical properties of leachate were investigated. The optimum conditions were 10 g of petroleum coke, 20 mL of oxidation, 6:1 liquid to solid ratio, 150 g/L of NaOH concentration, 62 g/L of Na₂CO₃ concentration, and 95°C temperature. Physical chemical properties of leachate changed along with the parameters. The microstructures of petroleum coke before and after leaching were also analyzed by scanning electron microscope.