nio2-wo3/usy-w中油型加氯裂解催化剂的研制.doc
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nio2-wo3/usy-w中油型加氯裂解催化剂的研制,摘要加氢裂化技术是重油深度加工的主要工艺手段之一，也是唯一能在原料轻质化的同时直接生产车用清洁燃料和优质化工原料的重要技术手段，是最有效利用原油资源的工艺。由于加氢裂化技术具有原料适应性强、产品方案灵活、液体产品收率高、产品质量好等诸多优点，不但可以直接生产汽、煤、柴等清洁燃料，而且其生产的轻、重石脑油和加氢裂化尾油还...
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摘要
加氢裂化技术是重油深度加工的主要工艺手段之一，也是唯一能在原料轻质化的同时直接生产车用清洁燃料和优质化工原料的重要技术手段，是最有效利用原油资源的工艺。由于加氢裂化技术具有原料适应性强、产品方案灵活、液体产品收率高、产品质量好等诸多优点，不但可以直接生产汽、煤、柴等清洁燃料，而且其生产的轻、重石脑油和加氢裂化尾油还是优质的化工原料，因此，近年来加氢裂化技术已逐步发展成为现代企业油、化有机结合的技术，多年来一直受到世界各国炼油企业及研究机构的重视。加氢裂化催化剂作为加氢裂化技术的核心，它的一个重要开发方向就是开发高中油选择性、高活性的加氢裂化催化剂，以最大限度的生产优质中间馏分油为目的。
中油型加氢裂化催化剂开发的技术难点主要是如何平衡中油选择性和活性，在保持相同中油选择性的前提下，进一步提高催化剂活性，降低装置能耗。通过分子筛改性、优化催化剂制备工艺、提高加氢活性组分分散度、应用新型催化材料等方法，国内外研究机构已经实现了现有加氢裂化催化剂性能的进一步提升。
本研究针对一段串联加氢裂化工艺，进行了NiO-WO3/USY中油型加氢裂化催化剂的研制工作。200ml固定床加氢装置评价结果表明，研制的加氢裂化催化剂，在控制原料>350℃馏分油转化率为75%的高转化率条件下，加氢裂化生成油C5+液收98.2m%，加氢裂化生成油中138～370℃柴油馏分的收率67.84m%，中油选择性80.2%，能满足工业装置最大量生产中间馏分油的需要，整体催化性能优于参比剂。
关键词：催化剂；加氢裂化；中间馏分油；中油选择性
Research of NiO-WO3/USY Hydrocracking Catalyst
for Maximum Middle Distillate Production
ABSTRACT
The technology of the hydrocracking is one of the main way to process heavy oil to light oil.It is the only way of producing cleanness fuel for automobile and high quality chemical raw material while hydrocracking the feeds.It is the most efficient way to utilize crude oil.It has extensive adaptability to many feeds,it can produce many products with high quality,and the yield of liquid is high,so this technology is becoming of one link between the refinery and the chemical plant.The refineries and the research institutes pay more attention on it.Hydrocracking catalyst is the core of the technology,one of the most important way is to research out a kind of catalyst with high active and selectivity to Middle Distillate.
It is important to set up a balance between the selectivity of middle distillate and the activity.It is a good catalyst which has high selectivity to Middle Distillate,and has high
activity at the same time.Now Hydrocracking catalyst is developing quickly by treating the molecular sieve,optimizing the produsing technology of the catalyst,improving the disperse
of the hydrogenation and using many kinds of new catalysis materials.
Novel hydrocracking catalyst was developed for producing more middle distillate with two reactors in series process.Evaluation of catalytic performance of the
hydrocracking catalyst was carried on a 200mL fixed-bed hydrogenation unit,the results howed that under the 75%conversion of>350℃feedstock distillate,C5 +
liquid yield of the hydrocracking product can reach more than 98.2m%,138～370℃diesel oil yield of hydrocracking product was 67.84m%,selectivity of middle distillate was 80.2%,the
catalyst can meet the need of producing more middle distillate in the industrial unit, catalytic performance of the catalyst was better than reference catalyst.
Keywords:Catalyst,Hydrocracking,Middle Distillate,selectivity of middle
Distillate
目录
前言......................................................................................................................................1
第一章概述........................................................................................................................3
1.1加氢裂化技术简介.......................................................................................................3
1.2国内外技术现状及发展趋势........................................................................................3
1.2.1加氢裂化工艺的技术现状...................................................................................3
1.2.2加氢裂化催化剂的技术现状...............................................................................4
1.2.3发展趋势...............................................................................................................6
1.3加氢裂化机理及化学反应............................................................................................6
1.3.1烷烃（烯烃）的加氢裂化反应...........................................................................6
1.3.2环烷烃的加氢裂化反应.......................................................................................7
1.3.3芳烃的加氢裂化反应...........................................................................................8
1.4本课题的主要研究内容和技术关键............................................................................9
1.5预期达到的研究成果和具体学术价值........................................................................9
1.6本课题的研究思路......................................................................................................10
第二章试验过程..................................................................................................................12
2.1主要原材料与试剂......................................................................................................12
2.2催化剂制备..................................................................................................................12
2.3分析及表征..................................................................................................................12
2.3.1比表面分析（BET）.........................................................................................12
2.3.2物相分析（XRD）............................................................................................12
2.3.3酸性表征（Py-IR）...........................................................................................12
2.3.4组成分析（XRF）.............................................................................................12
2.3.5晶型晶貌表征（SEM-EDS）............................................................................13
2.3.6原料油及产品分析.............................................................................................13
2.4催化剂性能评价..........................................................................................................13
2.4.1评价原料.............................................................................................................13
2.4.2评价氢气.............................................................................................................14
2.4.3评价装置.............................................................................................................14
2.4.4评价方法............................................................................................................14
第三章催化剂的研发..........................................................................................................16
3.1载体组分确定..............................................................................................................16
3.1.1无定形硅铝的筛选.............................................................................................16
3.1.2分子筛的筛选.....................................................................................................17
3.2活性金属组分及负载方式研究..................................................................................18
3.3催化剂制备工艺的优化及确定..................................................................................19
3.4催化剂的表征..............................................................................................................19
3.4.1物化性质..........................................................................................................19
3.4.2 BET表征.........................................................................................................20
3.4.3 SEM电镜.........................................................................................................20
3.4.4金属分散性分析..............................................................................................21
3.4.5催化剂的酸性..................................................................................................21
3.5加氢裂化性能评价.....................................................................................................22
3.5.1工艺条件考察..................................................................................................22
3.5.2 200ml评价.......................................................................................................24
3.5.3同国内外参比剂对比评价..............................................................................25
3.5.4转化率与产品分布及性质的关系..................................................................27
3.5.5催化剂耐氮性能试验......................................................................................28
3.5.6 2000小时活性稳定性试验.............................................................................28
3.6本章小结.....................................................................................................................29
第四章催化剂中试放大......................................................................................................31
4.1催化剂表征..................................................................................................................31
4.2放大催化剂的性能评价..............................................................................................32
4.2.1 200ml加氢评价...............................................................................................32
4.2.2 3L加氢评价....................................................................................................32
4.2.3 1500hr活性稳定性试验..................................................................................334.3本章小结.....................................................................................................................33
结论......................................................................................................................................35
参考文献..................................................................................................................................36
致谢....................................................................................................................................381
加氢裂化技术是重油深度加工的主要工艺手段之一，也是唯一能在原料轻质化的同时直接生产车用清洁燃料和优质化工原料的重要技术手段，是最有效利用原油资源的工艺。由于加氢裂化技术具有原料适应性强、产品方案灵活、液体产品收率高、产品质量好等诸多优点，不但可以直接生产汽、煤、柴等清洁燃料，而且其生产的轻、重石脑油和加氢裂化尾油还是优质的化工原料，因此，近年来加氢裂化技术已逐步发展成为现代企业油、化有机结合的技术，多年来一直受到世界各国炼油企业及研究机构的重视。加氢裂化催化剂作为加氢裂化技术的核心，它的一个重要开发方向就是开发高中油选择性、高活性的加氢裂化催化剂，以最大限度的生产优质中间馏分油为目的。
中油型加氢裂化催化剂开发的技术难点主要是如何平衡中油选择性和活性，在保持相同中油选择性的前提下，进一步提高催化剂活性，降低装置能耗。通过分子筛改性、优化催化剂制备工艺、提高加氢活性组分分散度、应用新型催化材料等方法，国内外研究机构已经实现了现有加氢裂化催化剂性能的进一步提升。
本研究针对一段串联加氢裂化工艺，进行了NiO-WO3/USY中油型加氢裂化催化剂的研制工作。200ml固定床加氢装置评价结果表明，研制的加氢裂化催化剂，在控制原料>350℃馏分油转化率为75%的高转化率条件下，加氢裂化生成油C5+液收98.2m%，加氢裂化生成油中138～370℃柴油馏分的收率67.84m%，中油选择性80.2%，能满足工业装置最大量生产中间馏分油的需要，整体催化性能优于参比剂。
关键词：催化剂；加氢裂化；中间馏分油；中油选择性
Research of NiO-WO3/USY Hydrocracking Catalyst
for Maximum Middle Distillate Production
ABSTRACT
The technology of the hydrocracking is one of the main way to process heavy oil to light oil.It is the only way of producing cleanness fuel for automobile and high quality chemical raw material while hydrocracking the feeds.It is the most efficient way to utilize crude oil.It has extensive adaptability to many feeds,it can produce many products with high quality,and the yield of liquid is high,so this technology is becoming of one link between the refinery and the chemical plant.The refineries and the research institutes pay more attention on it.Hydrocracking catalyst is the core of the technology,one of the most important way is to research out a kind of catalyst with high active and selectivity to Middle Distillate.
It is important to set up a balance between the selectivity of middle distillate and the activity.It is a good catalyst which has high selectivity to Middle Distillate,and has high
activity at the same time.Now Hydrocracking catalyst is developing quickly by treating the molecular sieve,optimizing the produsing technology of the catalyst,improving the disperse
of the hydrogenation and using many kinds of new catalysis materials.
Novel hydrocracking catalyst was developed for producing more middle distillate with two reactors in series process.Evaluation of catalytic performance of the
hydrocracking catalyst was carried on a 200mL fixed-bed hydrogenation unit,the results howed that under the 75%conversion of>350℃feedstock distillate,C5 +
liquid yield of the hydrocracking product can reach more than 98.2m%,138～370℃diesel oil yield of hydrocracking product was 67.84m%,selectivity of middle distillate was 80.2%,the
catalyst can meet the need of producing more middle distillate in the industrial unit, catalytic performance of the catalyst was better than reference catalyst.
Keywords:Catalyst,Hydrocracking,Middle Distillate,selectivity of middle
Distillate
目录
前言......................................................................................................................................1
第一章概述........................................................................................................................3
1.1加氢裂化技术简介.......................................................................................................3
1.2国内外技术现状及发展趋势........................................................................................3
1.2.1加氢裂化工艺的技术现状...................................................................................3
1.2.2加氢裂化催化剂的技术现状...............................................................................4
1.2.3发展趋势...............................................................................................................6
1.3加氢裂化机理及化学反应............................................................................................6
1.3.1烷烃（烯烃）的加氢裂化反应...........................................................................6
1.3.2环烷烃的加氢裂化反应.......................................................................................7
1.3.3芳烃的加氢裂化反应...........................................................................................8
1.4本课题的主要研究内容和技术关键............................................................................9
1.5预期达到的研究成果和具体学术价值........................................................................9
1.6本课题的研究思路......................................................................................................10
第二章试验过程..................................................................................................................12
2.1主要原材料与试剂......................................................................................................12
2.2催化剂制备..................................................................................................................12
2.3分析及表征..................................................................................................................12
2.3.1比表面分析（BET）.........................................................................................12
2.3.2物相分析（XRD）............................................................................................12
2.3.3酸性表征（Py-IR）...........................................................................................12
2.3.4组成分析（XRF）.............................................................................................12
2.3.5晶型晶貌表征（SEM-EDS）............................................................................13
2.3.6原料油及产品分析.............................................................................................13
2.4催化剂性能评价..........................................................................................................13
2.4.1评价原料.............................................................................................................13
2.4.2评价氢气.............................................................................................................14
2.4.3评价装置.............................................................................................................14
2.4.4评价方法............................................................................................................14
第三章催化剂的研发..........................................................................................................16
3.1载体组分确定..............................................................................................................16
3.1.1无定形硅铝的筛选.............................................................................................16
3.1.2分子筛的筛选.....................................................................................................17
3.2活性金属组分及负载方式研究..................................................................................18
3.3催化剂制备工艺的优化及确定..................................................................................19
3.4催化剂的表征..............................................................................................................19
3.4.1物化性质..........................................................................................................19
3.4.2 BET表征.........................................................................................................20
3.4.3 SEM电镜.........................................................................................................20
3.4.4金属分散性分析..............................................................................................21
3.4.5催化剂的酸性..................................................................................................21
3.5加氢裂化性能评价.....................................................................................................22
3.5.1工艺条件考察..................................................................................................22
3.5.2 200ml评价.......................................................................................................24
3.5.3同国内外参比剂对比评价..............................................................................25
3.5.4转化率与产品分布及性质的关系..................................................................27
3.5.5催化剂耐氮性能试验......................................................................................28
3.5.6 2000小时活性稳定性试验.............................................................................28
3.6本章小结.....................................................................................................................29
第四章催化剂中试放大......................................................................................................31
4.1催化剂表征..................................................................................................................31
4.2放大催化剂的性能评价..............................................................................................32
4.2.1 200ml加氢评价...............................................................................................32
4.2.2 3L加氢评价....................................................................................................32
4.2.3 1500hr活性稳定性试验..................................................................................334.3本章小结.....................................................................................................................33
结论......................................................................................................................................35
参考文献..................................................................................................................................36
致谢....................................................................................................................................381
