重油悬浮床加氢高周转频率溶液催化剂体系的构筑及其应用基础

Slurry bed hydro cracking technology is one effective method to process high carbon residue, high metal content of inferior oil, trace catalyst dissolved in heavy oil will be brought out by the product after completing the service mission in a bubble reactor, which can avoid the problem of blocking coke formation in the fixed bed when heavy oil was processed. At present, the problems of limiting its large-scale industrial application are that the low temperature performance of the catalyst is poor, the turnover frequency is not high enough and the consumption amount is very large. In this project, we will design and synthesize mixed active metal oxygen cluster inorganic -organic complexes and construct high turnover frequency (TOF) solution catalyst to play synergistic and micro scale effects in heavy oil catalytic hydroconversion process. The oil solubility and dispersity of the catalyst will be improved by introducing the lipophilic groups in the molecular structure of the solution catalyst, and the homogeneous catalytic advantage of the process will be enhanced too. The mechanism of solution catalyst and the coalescence settlement separation characteristics of decomposed catalyst particles in heavy oil system will be studied, in addition, high voltage and high frequency pulse dynamic desalting and desolid separating technology will be developed. This project obtain the relevant application foundation knowledge of heavy oil slurry bed hydro cracking catalyst solution system, by studying transformation rule of model molecules or heavy oil fractions resin, asphaltene and heteroatom organics in the catalytic environment, to establish the science and technology foundation for the development of efficient solution catalyst system and promote the heavy oil slurry bed hydro cracking process scale application.

悬浮床加氢工艺是处理高残碳、高金属含量劣质油的有效手段之一，溶解于重油中的微量催化剂在鼓泡反应器内完成服役使命后随产物带出，有效避免采用固定床加工重油带来的结焦结垢堵塞床层问题。目前，限制其大规模工业应用的问题是催化剂的低温性能差、周转频率(TOF)低、用量大。本项目通过设计合成混合活性金属氧簇无机-有机复合物以及构筑高TOF的溶液催化剂来发挥其在催化重油加氢转化中的协同效应和微尺度效应；通过在溶液催化剂分子结构内引入亲油性基团，改善催化剂的油溶性和分散性，强化过程的均相催化优势；研究溶液催化剂的作用机理和退役催化剂颗粒在重油体系中聚并、沉降等分离特性，发展高压高频脉冲动态电脱盐脱固分离技术；通过研究模型分子或重油组分中胶质、沥青质及其杂原子有机物在催化环境下的转化规律，获得重油悬浮床加氢溶液催化过程的应用基础知识，为发展高效溶液催化剂体系和推进重油悬浮床加氢工艺的规模化奠定科学技术基础。

项目针对重油浆态床加氢转化高性能催化剂的低成本制备与规模化应用过程关键科学问题，系统研究和诠释了重油加氢溶液催化剂的全生命周期，包括服役过程中的构效关系和退役催化剂的分离策略。取得如下成果：.利用小尺寸多酸簇，采用离子组装-限域硫化策略，发展了超分散油溶性溶液催化剂的制备方法。研究了加入第二金属对催化剂加氢转化性能的协同作用，包括制备不同第二金属单原子协同的杂多酸簇XMo6（X=Fe, Co, Ni）前驱体，详细比较不同第二金属的协同作用；采用低温固相合成策略，利用金属阴离子簇与表面活性剂阳离子的静电作用，实现了活性金属组分表面性质从亲水性到亲油性的转变。研究表明，表面活性剂的空间位阻、金属阴离子簇尺寸和所带电荷量对催化剂的合成与性能具有较大影响。.针对重油中固体颗粒粒径小、分散程度高等特点，从表面性质调控的角度提出基于电场和旋流离心力场耦合的油中固体颗粒的强化分离方法。通过研究固体颗粒不同亲水性及水滴捕获固体颗粒液滴粒径的动态变化以及脱固效率，包括基于实验结果改进剪切作用对载固颗粒液滴的粒径分布的预测模型。从单液滴在剪切条件以及液滴旋转条件下的捕集特性入手，分别研究了液滴对固体颗粒的捕集效率，包括针对捕集后载固颗粒的液滴，研究了剪切流条件下液滴的动力学行为和剪切条件下载固颗粒液滴的曳力预测模型。建立了电场和旋流离心力场耦合作用油/水/固三相分离过程的数值模型。研究结果表明，提出的方法合理、有效，实验结果表明油/固两相分离效率高达90%以上。 .相关研究工作已经申请发明专利5项，在国内外学术期刊上发表论文5篇；培养博士研究生1人，硕士研究生3人,在读博士生2人，硕士生2人。