油溶性催化剂和助剂在渣油悬浮床加氢裂化中的研究
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摘要
考察了不同合成条件对油溶性催化剂的影响,筛选出较好的催化剂合成条件。利用显微照片、电子扫描电镜(SEM)、X射线衍射光谱(XRD)和激光粒度等手段对硫化后催化剂进行了表征。同时,采用高压反应釜模拟悬浮床加氢裂化研究了油溶性催化剂以及助剂对渣油悬浮床加氢裂化反应的影响,并对油溶性催化剂的作用机理做了解释。
结果表明,合成油溶性Mo催化剂的优化条件为:反应物摩尔配比(化合物D:化合物E:化合物F)约为1:1:5～6左右、反应温度为220℃左右、反应时间约为4h。合成油溶性Co催化剂的优化条件为:化合物C盐溶液浓度约为15%。合成油溶性Ni催化剂合成的优化条件为:化合物A的浓度约为15%,原料配比(化合物F:化合物A)约为1:0.995、皂化反应温度约为95℃、皂化反应时间约为3h;复分解反应温度约为90℃、反应时间约为2h,复分解反应盐溶液浓度约为10%,采用逐滴滴加的方式加入。油溶性Co、Mo、Ni催化剂硫化后产物均发生了不同程度的颗粒团聚;油溶性Mo催化剂硫化后产物成微晶状态的MoS2(六方晶系)晶体;油溶性Ni催化剂硫化后产物以Ni3S2(六方晶系)晶体和微晶状态的NiS(六方晶系)晶体存在,且主要以Ni3S2晶体存在;油溶性Co催化剂硫化后产物以Co3S4(立方晶系)晶体和Co9S8(立方晶系)晶体存在,且Co9S8晶体所占比例略大于Co3S4晶体;油溶性Mo催化剂较之油溶性Co、Ni催化剂更容易硫化,在较低的温度下就能硫化。
三种催化剂的加氢活性顺序:Mo>Co>Ni。油溶性Mo催化剂处理委内瑞拉-380渣油效果较佳,且在反应过程中具有一定的抗温性。油溶性复配催化剂Mo/Ni在反应过程中都起到了一定的协同效应。Mo/Ni催化剂硫化后形成了大量的颗粒状物质,Mo以非晶体状态的硫化物存在,能够更好的分散于油样,Ni以Ni7S6晶体存在。
助催化剂单独临氢热裂化时,SA2起到一定的抑制生焦、结焦的作用;SA2与油溶性催化剂作用起到了明显的抑制结焦、生焦的作用,其最佳浓度在0.1%左右;同种类型的胺类与油溶性催化剂作用,碳链越长,壁相结焦越少。
The impact of synthesis conditions on oil-soluble catalyst was studied and the thesis screened out the better synthesis conditions. Post-sulfide catalysts were characterized by microscopic technique, scanning electron microscopy (SEM), X-ray diffraction (XRD) and laser particle. Simultaneously, effect of oil-soluble catalyst and co-catalyst on hydrocracking residue reaction was studied in autoclave simulating Slurry Phase Hydrocracking Reaction, and the mechanism of oil-soluble catalyst has been carried on the explanation.
It was inferred that, the optimality condition of oil-soluble Mo catalyst: molar ratio of reactant (compound D: compound E: compound F) is about 1:1:5~6, reaction temperature is about 220℃,reaction time is about 4h. The optimality condition of oil-soluble Co catalyst: The concentration of compound C is about 15%. The optimality condition of oil-soluble Ni catalyst: the concentration of compound A is about 15%, raw materials ratio (compound F: compound A) is about 1:0.995, the temperature of saponification is about 95℃, the time of saponification is about 3h; the temperature of the metathetical reaction is about 90℃, the time is about 2h, the concentration of solution is about 10%, and drop gradually. Most of the oil-soluble catalysts reunite themselves in varying degree. The vulcanized products of oil-soluble Mo catalyst exist as the microcrystalline state of MoS2 (Rhombohedral). The vulcanized products of oil-soluble Ni catalyst exist as the crystal of Ni3S2 (Rhombohedral) and the microcrystalline state of NiS(Rhombohedral), mainly exists as the crystal of Ni3S2. The vulcanized products of oil-soluble Co catalyst exist as the crystal of both Co3S4(Cubic)and Co9S8(Cubic) and the proportion of Co9S8 is slightly larger than the Co3S4. The oil-soluble Mo catalyst can be vulcanized more easily than Ni catalyst, and at a lower temperature sulfuration.
The order of hydrogenation activity is Mo> Co > Ni. The result is better while dealing with Venezuela-380 residue by oil-soluble Mo catalyst, and it has a certain anti-temperate during the reaction. Oil-soluble catalyst Mo/Ni have played a certain synergistic effect. Mo/Ni catalyst formed a large number of granular material in process of vulcanization. Mo catalyst existed as sulfide in non-crystalline form after vulcanizing, and could be better dispersed in the oil samples. Ni catalyst existed as Ni7S6.
SA2 played a certain role in inhibiting coke when the hydrocracking of co-catalysts were studied; SA2 and oil-soluble catalysts have played a significant role in inhibiting coke formation, the optical concentration is about 0.1%. The longer the carbon-chain, the less coking of the wall , when the same type of amine and oil-soluble catalyst co-acted.
结果表明,合成油溶性Mo催化剂的优化条件为:反应物摩尔配比(化合物D:化合物E:化合物F)约为1:1:5～6左右、反应温度为220℃左右、反应时间约为4h。合成油溶性Co催化剂的优化条件为:化合物C盐溶液浓度约为15%。合成油溶性Ni催化剂合成的优化条件为:化合物A的浓度约为15%,原料配比(化合物F:化合物A)约为1:0.995、皂化反应温度约为95℃、皂化反应时间约为3h;复分解反应温度约为90℃、反应时间约为2h,复分解反应盐溶液浓度约为10%,采用逐滴滴加的方式加入。油溶性Co、Mo、Ni催化剂硫化后产物均发生了不同程度的颗粒团聚;油溶性Mo催化剂硫化后产物成微晶状态的MoS2(六方晶系)晶体;油溶性Ni催化剂硫化后产物以Ni3S2(六方晶系)晶体和微晶状态的NiS(六方晶系)晶体存在,且主要以Ni3S2晶体存在;油溶性Co催化剂硫化后产物以Co3S4(立方晶系)晶体和Co9S8(立方晶系)晶体存在,且Co9S8晶体所占比例略大于Co3S4晶体;油溶性Mo催化剂较之油溶性Co、Ni催化剂更容易硫化,在较低的温度下就能硫化。
三种催化剂的加氢活性顺序:Mo>Co>Ni。油溶性Mo催化剂处理委内瑞拉-380渣油效果较佳,且在反应过程中具有一定的抗温性。油溶性复配催化剂Mo/Ni在反应过程中都起到了一定的协同效应。Mo/Ni催化剂硫化后形成了大量的颗粒状物质,Mo以非晶体状态的硫化物存在,能够更好的分散于油样,Ni以Ni7S6晶体存在。
助催化剂单独临氢热裂化时,SA2起到一定的抑制生焦、结焦的作用;SA2与油溶性催化剂作用起到了明显的抑制结焦、生焦的作用,其最佳浓度在0.1%左右;同种类型的胺类与油溶性催化剂作用,碳链越长,壁相结焦越少。
The impact of synthesis conditions on oil-soluble catalyst was studied and the thesis screened out the better synthesis conditions. Post-sulfide catalysts were characterized by microscopic technique, scanning electron microscopy (SEM), X-ray diffraction (XRD) and laser particle. Simultaneously, effect of oil-soluble catalyst and co-catalyst on hydrocracking residue reaction was studied in autoclave simulating Slurry Phase Hydrocracking Reaction, and the mechanism of oil-soluble catalyst has been carried on the explanation.
It was inferred that, the optimality condition of oil-soluble Mo catalyst: molar ratio of reactant (compound D: compound E: compound F) is about 1:1:5~6, reaction temperature is about 220℃,reaction time is about 4h. The optimality condition of oil-soluble Co catalyst: The concentration of compound C is about 15%. The optimality condition of oil-soluble Ni catalyst: the concentration of compound A is about 15%, raw materials ratio (compound F: compound A) is about 1:0.995, the temperature of saponification is about 95℃, the time of saponification is about 3h; the temperature of the metathetical reaction is about 90℃, the time is about 2h, the concentration of solution is about 10%, and drop gradually. Most of the oil-soluble catalysts reunite themselves in varying degree. The vulcanized products of oil-soluble Mo catalyst exist as the microcrystalline state of MoS2 (Rhombohedral). The vulcanized products of oil-soluble Ni catalyst exist as the crystal of Ni3S2 (Rhombohedral) and the microcrystalline state of NiS(Rhombohedral), mainly exists as the crystal of Ni3S2. The vulcanized products of oil-soluble Co catalyst exist as the crystal of both Co3S4(Cubic)and Co9S8(Cubic) and the proportion of Co9S8 is slightly larger than the Co3S4. The oil-soluble Mo catalyst can be vulcanized more easily than Ni catalyst, and at a lower temperature sulfuration.
The order of hydrogenation activity is Mo> Co > Ni. The result is better while dealing with Venezuela-380 residue by oil-soluble Mo catalyst, and it has a certain anti-temperate during the reaction. Oil-soluble catalyst Mo/Ni have played a certain synergistic effect. Mo/Ni catalyst formed a large number of granular material in process of vulcanization. Mo catalyst existed as sulfide in non-crystalline form after vulcanizing, and could be better dispersed in the oil samples. Ni catalyst existed as Ni7S6.
SA2 played a certain role in inhibiting coke when the hydrocracking of co-catalysts were studied; SA2 and oil-soluble catalysts have played a significant role in inhibiting coke formation, the optical concentration is about 0.1%. The longer the carbon-chain, the less coking of the wall , when the same type of amine and oil-soluble catalyst co-acted.
引文
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