微泡沫的制备及其在重油悬浮床加氢催化剂分散上的应用
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摘要
悬浮床加氢水溶性催化剂在分散方面存在诸多问题,需要开发新型的分散工艺。微泡沫——包括胶质气体泡沫(CGA)和胶质液体泡沫(CLA)——因其特殊的结构和性质在水溶性催化剂在分散方面有较好的应用前景。
实验中,根据悬浮床加氢催化剂的分散要求对微泡沫发泡体系进行了筛选,并对微泡沫的制备条件进行了优化分析,通过光学显微镜及动态光散射仪等对其结构和性质进行了探讨。以辽河常渣和委内瑞拉常渣为原料对微泡沫分散催化剂的效果进行了光学显微镜观察和高压釜悬浮床加氢反应评价。
针对悬浮床加氢水溶性催化剂分散过程中存在的问题,实验进行了纯水、单一及复配水溶性催化剂前体水溶液中CGA发泡体系的筛选及制备条件的优化分析,主要考察了发泡剂种类及浓度、金属离子种类及浓度、温度、搅拌速率、搅拌时间等对CGA泡沫量及稳定性的影响,研究发现:10℃、搅拌速率9000rpm、搅拌时间3min条件下在复配催化剂水溶液中CTAB(3.4 g/L)与SDS(1.1g/L)复配效果较好,制备的CGA泡沫量3850 mL/L,半衰期2140s;经光学显微镜观察其形状呈多层透明球状;经动态光散射仪测试,其粒径集中分布在10～100μm之间;体系中液晶相的产生有助于提高CGA稳定性。
根据悬浮床加氢油溶性催化剂与水溶性催化剂的经验配比确定了CLA的制备方案,研究发现油水体积比(PVR)等于2时,所得产物呈咖啡色乳液状,可存储长达三个月之久,未见有明显的相分离发生,十分稳定。经光学显微镜观察其形状呈正多面体或球状;经动态光散射仪测试,其粒径集中分布在1～3μm之间;体系中液晶相的形成有助于CLA的稳定性的改善。
通过光学显微观察发现以微泡沫形态加入到原料油中的催化剂分散效果明显好于剪切分散形式。经釜反应评定,与剪切分散分散方式相比,采用微泡沫分散催化剂的辽河常渣和委内瑞拉常渣油样,悬浮床加氢反应生焦率都有明显的降低;馏分油收率都有所增加。
There are some problems in the dispersion of catalysts for slurry-bed hydroprocessing, so it is necessary to develop a new dispersion technology. Because of the special structure and nature of microfoam which includes colloidal liquid aphron(referred to as CLA) and colloidal gas aphron(referred to as CGA), it is of a great potential in this aspect.
At the first of this experiment, the prescription to prepare microfoam was determined according to the need to disperse the catalysts for slurry-bed hydroprocessing, optimization analysis of conditions to prepare microfoam was then carried on, structure and stability of it was also discussed by optical microscopy, dynamic light scattering and so on. Liao-he and Venezuela residual oil were taken as base oil to study on the dispersion condition of catalysts in the form of microfoam, microscope observation and autoclave reaction were used to evaluate the dispersion state.
In this experiment, aimming at problems of the dispersion of water-soluble catalysts for slurry phase hydroprocessing, foam system is filtered and optimization analysis of conditions to prepare CGA was then carried on under pure water, single and mixed metal ion catalyst solution, mainly seeing about the impact of frother concentration, the type and concentration of metal ions, temperature, stirring rate and stirring time. Solution of catalysts is used as solvent with foaming agent as solute to prepare CGA. The results showed that under the conditions: 3min stirring time and 9000rpm stirring rate、pH=2~3, the output and half-life of CGA made of combination of SDS(1.1g/L) and CTAB (3.4g/L) is 1150ml and 2140s; CGA shows a shape with a transparent multi-layer spherical under the optical microscope; and its diameter concentrated in 10~100μm tested by dynamic light scattering instrument. The formation of liquid crystal in the system can help to improve the stability of CGA.
The prescription to prepare CLA was determined according to the experiential ratio of oil-soluble and water-soluble catalysts.When PVR is 2, the products presented as brown emulsion and can be stored for up to three months, and no obvious phase separation occurs, which is very stable. It shows a shape of regular polyhedron or spherical under the optical microscope; the diameter of CLA concentrated between 1~3μm tested by dynamic light scattering instrument. The formation of liquid crystal in the system can help to improve the stability of CLA.
It is observed by optical microscopy that the effect of catalyst material dispersed to base oil in form of micro-foam is better than traditional forms. The result of autoclave reaction showed that compared to traditional dispersion technology, slurry-bed hydro-processing coke yield of Liao-he residual oil dispersed by CGA reduced from 1.25% to 0.98%, coke yield of Venezuela residual oil reduced from 1.31% to 1.06%, coke yield of Liao-he residual oil dispersed by CGA reduced from 2.39% to 1.67%, coke yield of Venezuela residual oil reduced from 2.78% to 2.05%; with yield of light oil increased to some extent.
实验中,根据悬浮床加氢催化剂的分散要求对微泡沫发泡体系进行了筛选,并对微泡沫的制备条件进行了优化分析,通过光学显微镜及动态光散射仪等对其结构和性质进行了探讨。以辽河常渣和委内瑞拉常渣为原料对微泡沫分散催化剂的效果进行了光学显微镜观察和高压釜悬浮床加氢反应评价。
针对悬浮床加氢水溶性催化剂分散过程中存在的问题,实验进行了纯水、单一及复配水溶性催化剂前体水溶液中CGA发泡体系的筛选及制备条件的优化分析,主要考察了发泡剂种类及浓度、金属离子种类及浓度、温度、搅拌速率、搅拌时间等对CGA泡沫量及稳定性的影响,研究发现:10℃、搅拌速率9000rpm、搅拌时间3min条件下在复配催化剂水溶液中CTAB(3.4 g/L)与SDS(1.1g/L)复配效果较好,制备的CGA泡沫量3850 mL/L,半衰期2140s;经光学显微镜观察其形状呈多层透明球状;经动态光散射仪测试,其粒径集中分布在10～100μm之间;体系中液晶相的产生有助于提高CGA稳定性。
根据悬浮床加氢油溶性催化剂与水溶性催化剂的经验配比确定了CLA的制备方案,研究发现油水体积比(PVR)等于2时,所得产物呈咖啡色乳液状,可存储长达三个月之久,未见有明显的相分离发生,十分稳定。经光学显微镜观察其形状呈正多面体或球状;经动态光散射仪测试,其粒径集中分布在1～3μm之间;体系中液晶相的形成有助于CLA的稳定性的改善。
通过光学显微观察发现以微泡沫形态加入到原料油中的催化剂分散效果明显好于剪切分散形式。经釜反应评定,与剪切分散分散方式相比,采用微泡沫分散催化剂的辽河常渣和委内瑞拉常渣油样,悬浮床加氢反应生焦率都有明显的降低;馏分油收率都有所增加。
There are some problems in the dispersion of catalysts for slurry-bed hydroprocessing, so it is necessary to develop a new dispersion technology. Because of the special structure and nature of microfoam which includes colloidal liquid aphron(referred to as CLA) and colloidal gas aphron(referred to as CGA), it is of a great potential in this aspect.
At the first of this experiment, the prescription to prepare microfoam was determined according to the need to disperse the catalysts for slurry-bed hydroprocessing, optimization analysis of conditions to prepare microfoam was then carried on, structure and stability of it was also discussed by optical microscopy, dynamic light scattering and so on. Liao-he and Venezuela residual oil were taken as base oil to study on the dispersion condition of catalysts in the form of microfoam, microscope observation and autoclave reaction were used to evaluate the dispersion state.
In this experiment, aimming at problems of the dispersion of water-soluble catalysts for slurry phase hydroprocessing, foam system is filtered and optimization analysis of conditions to prepare CGA was then carried on under pure water, single and mixed metal ion catalyst solution, mainly seeing about the impact of frother concentration, the type and concentration of metal ions, temperature, stirring rate and stirring time. Solution of catalysts is used as solvent with foaming agent as solute to prepare CGA. The results showed that under the conditions: 3min stirring time and 9000rpm stirring rate、pH=2~3, the output and half-life of CGA made of combination of SDS(1.1g/L) and CTAB (3.4g/L) is 1150ml and 2140s; CGA shows a shape with a transparent multi-layer spherical under the optical microscope; and its diameter concentrated in 10~100μm tested by dynamic light scattering instrument. The formation of liquid crystal in the system can help to improve the stability of CGA.
The prescription to prepare CLA was determined according to the experiential ratio of oil-soluble and water-soluble catalysts.When PVR is 2, the products presented as brown emulsion and can be stored for up to three months, and no obvious phase separation occurs, which is very stable. It shows a shape of regular polyhedron or spherical under the optical microscope; the diameter of CLA concentrated between 1~3μm tested by dynamic light scattering instrument. The formation of liquid crystal in the system can help to improve the stability of CLA.
It is observed by optical microscopy that the effect of catalyst material dispersed to base oil in form of micro-foam is better than traditional forms. The result of autoclave reaction showed that compared to traditional dispersion technology, slurry-bed hydro-processing coke yield of Liao-he residual oil dispersed by CGA reduced from 1.25% to 0.98%, coke yield of Venezuela residual oil reduced from 1.31% to 1.06%, coke yield of Liao-he residual oil dispersed by CGA reduced from 2.39% to 1.67%, coke yield of Venezuela residual oil reduced from 2.78% to 2.05%; with yield of light oil increased to some extent.
引文
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