烷基化工艺技术
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– Polymerization 聚合 – Hydrogen Transfer 氢转移 2C3H6 C6H12 2 i-C4H10 + C5H10 C8H18 + C5H12
2,2,4-trimethylpentane i-C7 i-C9
– – – –
Disproportionation 歧化 2 C8H18 C7H16 + C9H20 Cracking 裂解 C12H26 C7H14 + C5H12 Esterification 酯化 2 C4H10 + H2SO4 di-butyl sulfate Formation of Acid Soluble Oil (ASO) 形成酸溶性油（ASO）
Acid-HC Settlers
Spent Acid
A World of Solutions
Effluent PostTreatment
Fresh Acid Waste Water
n-Butane
Alkylate
9
Conventional Sulfuric Acid Alkylator 传统硫酸法烷基化技术的反应器
A World of Solutions
3
Why Alkylation? 烷基化的意义
Alkylate is an excellent high octane gasoline blendstock 烷基化油是理想的高辛烷值调和组分 Alkylate contains mostly branched paraffins (no olefins, no aromatics) which are clean burning 烷基化油所含的大多为支链烷烃（没有烯烃、没有芳烃）， 是清洁燃料 Alkylate has low RVP 烷基化油蒸汽压低 Alkylation allows upgrading C4s to gasoline value increasing pool volume 烷基化使得C4升值为汽油，并增加了汽油产量
– Lower operating temperature improves alkylate quality 低温反应改善烷基化油的质量 – Lower operating temperature increases hydrocarbon-acid emulsion viscosity making mass transfer more difficult 低操作温度提高烃-酸乳液的粘性阻碍质量传递 – At low temperature, the power requirement for mixers increases tremendously 在低温下操作，搅拌器的所需的功率急剧增大
Acid–HC liquid contact is achieved by mechanical mixers 酸、烃两相的混合靠机械搅拌完成
A World of Solutions
10
Problems with Conventional SA Alkylation 传统的硫酸法烷基化技术的问题 Inability to operate at low temperature for optimal performance 不能利用对反应性能最理想的低温
Undesirable feed impurities 要避免的杂质
– Butadiene, Mercaptans, Water, Oxygenates (DME, MTBE) 丁二烯、硫醇、水、含氧化合物（如二甲醚、MTBE）
A World of Solutions
7
Conventional Sulfuric Acid Alkylation 传统硫酸法烷基化技术
Large Droplets
Droplet Size
Elaborate effluent treatment required 反应生成物的后处理复杂
– Acid wash required after settler on hydrocarbon phase 沉降后要对烃（油）相进行酸洗 – Caustic wash necessary to neutralize the residual SA 要用碱水洗涤以对废酸进行中和 – Water wash to remove residual caustic 水洗以去除残存的碱
Requires high maintenance and frequent downtime 需要大量的维护并会频繁停车
– Corrosion and plugging equipment downstream of caustic wash 碱洗下游的设备发生腐蚀和结垢堵塞 – Alkylator mixer and seals need frequent attention 反应器搅拌器及密封需要频繁的维护
A World of Solutions
Conventional SA Process 传统的硫酸法技术
Байду номын сангаас
Refrigeration
Olefin Feed
Propane
Isobutane Make-up
Alkylation Contactor
Water Caustic
iC4 recycle
Fractionation
A World of Solutions
2
What is Alkylation 什么是烷基化？ Alkylation 烷基化
– Alkylation is the process of reacting iso-butane with light olefins, primarily butene, to produce a longer branched chain paraffin called alkylate 烷基化是让异丁烷和轻质烯烃（主要是丁烯）反应生成长链、带支链的 烷烃（即烷基化油）的反应过程
Several mechanical mixers (several contactors) are needed to ensure good mixing 需要若干台反应器（搅拌器）
A World of Solutions
11
Problems with Conventional SA Alkylation 传统的硫酸法烷基化技术的问题 Difficult separation of hydrocarbonacid emulsion 很难分离烃-酸乳液
Corrosion 腐蚀 Water carryover from water wash causes corrosion issues 水洗所对来的夹带水造成腐蚀问题
A World of Solutions
12
Problems with Conventional SA Alkylation 传传统的硫酸法烷基化技术的问题
A World of Solutions
6
Sulfuric Acid Alkylation Chemistry 硫酸法烷基化的化学反应机理 Alkylation 烷基化 i-C4 + C4H8 i-C4 + C3 H6 i-C4 + C5 H10 Side reactions 副反应
High energy input for mixer 搅拌器能耗高
– High intensity mechanical mixing necessary to create good contact between acid and hydrocarbon 为了实现酸和烃之间的良好混合，需要强劲的机械搅拌
High acid consumption 酸耗高
– Often significantly over 70 kg acid/ ton of alkylate 每吨烷基化油的酸耗经常超过70 kg – Acid regeneration costs are high 酸再生的费用高
Multiple contactors required due to size limitation 单台反应器的处理量受到尺寸限制，所以需要多台反应器
A World of Solutions
5
Alkylation in China 中国的烷基化情况
Alkylate is an ideal blendstock to meet China’s clean energy needs 烷基化油在中国是一股理想的汽油调和组分来满足中国的 能源需求 Chinese gasoline pool is very deficient in alkylate 中国的汽油池中烷基化油所占比重严重不足 Spread developing b/w gasoline and LPG makes alkylation economical! 汽油与LPG的价差使得烷基化项目具有经济效益
CDAlky® Advanced Sulfuric Acid Alkylation 先进的低温硫酸法烷基化工艺
1
A World of Solutions
Agenda 提纲 Alkylation Overview 烷基化概貌 Conventional Sulfuric Acid Alkylation 传统硫酸法烷基化工艺 CDAlky Technology Overview CDAlky工艺技术简介 CDAlky Commercialization Status CDAlky工艺技术工业化状态
Same catalyst (sulfuric acid), same reaction chemistry 相同的催化剂（硫酸），同样的化学反应机理 Breakthrough reactor technology that eliminates mechanical mixers 反应器技术的突破，去除机械搅拌
Solid Acid Alkylation 固体酸烷基化
– Safer but expensive alternative; Yet to find industry acceptance 安全但是投资大、操作成本高；尚未工业化
SA Alkylation
硫酸法烷基化 – Alkylation technology of choice for refiners 当今炼油企业所选择的烷基化技术 – Most optimal choice in balancing the safety/operability issues with benefits of high quality alkylate 在安全性和可操作性之间取得最佳平衡，并生产高质量的烷基化油
A World of Solutions
4
Future of Alkylation 烷基化的前景 HF Alkylation 氢氟酸法烷基化
– High quality alkylate, low acid consumption, more feedstock flexibility 产生高质量的烷基化油，酸耗低，适合多种原料 – Extremely hazardous; not preferred anymore 极大的安全隐患，市场上不再推行
A World of Solutions
13
® CDAlky Advanced Sulfuric Acid Alkylation 先进的低温硫酸法烷基化工艺
A World of Solutions
Well Understood Principles of CDAlky Process CDAlky的反应机理
– Fine emulsion necessary for mass Wt% of transfer requires long settling period droplets and large settlers 为了实现良好的质量传递而形成的酸 乳液需要很长的沉降时间和大型的沉 降器
Small Droplets
2,2,4-trimethylpentane i-C7 i-C9
– – – –
Disproportionation 歧化 2 C8H18 C7H16 + C9H20 Cracking 裂解 C12H26 C7H14 + C5H12 Esterification 酯化 2 C4H10 + H2SO4 di-butyl sulfate Formation of Acid Soluble Oil (ASO) 形成酸溶性油（ASO）
Acid-HC Settlers
Spent Acid
A World of Solutions
Effluent PostTreatment
Fresh Acid Waste Water
n-Butane
Alkylate
9
Conventional Sulfuric Acid Alkylator 传统硫酸法烷基化技术的反应器
A World of Solutions
3
Why Alkylation? 烷基化的意义
Alkylate is an excellent high octane gasoline blendstock 烷基化油是理想的高辛烷值调和组分 Alkylate contains mostly branched paraffins (no olefins, no aromatics) which are clean burning 烷基化油所含的大多为支链烷烃（没有烯烃、没有芳烃）， 是清洁燃料 Alkylate has low RVP 烷基化油蒸汽压低 Alkylation allows upgrading C4s to gasoline value increasing pool volume 烷基化使得C4升值为汽油，并增加了汽油产量
– Lower operating temperature improves alkylate quality 低温反应改善烷基化油的质量 – Lower operating temperature increases hydrocarbon-acid emulsion viscosity making mass transfer more difficult 低操作温度提高烃-酸乳液的粘性阻碍质量传递 – At low temperature, the power requirement for mixers increases tremendously 在低温下操作，搅拌器的所需的功率急剧增大
Acid–HC liquid contact is achieved by mechanical mixers 酸、烃两相的混合靠机械搅拌完成
A World of Solutions
10
Problems with Conventional SA Alkylation 传统的硫酸法烷基化技术的问题 Inability to operate at low temperature for optimal performance 不能利用对反应性能最理想的低温
Undesirable feed impurities 要避免的杂质
– Butadiene, Mercaptans, Water, Oxygenates (DME, MTBE) 丁二烯、硫醇、水、含氧化合物（如二甲醚、MTBE）
A World of Solutions
7
Conventional Sulfuric Acid Alkylation 传统硫酸法烷基化技术
Large Droplets
Droplet Size
Elaborate effluent treatment required 反应生成物的后处理复杂
– Acid wash required after settler on hydrocarbon phase 沉降后要对烃（油）相进行酸洗 – Caustic wash necessary to neutralize the residual SA 要用碱水洗涤以对废酸进行中和 – Water wash to remove residual caustic 水洗以去除残存的碱
Requires high maintenance and frequent downtime 需要大量的维护并会频繁停车
– Corrosion and plugging equipment downstream of caustic wash 碱洗下游的设备发生腐蚀和结垢堵塞 – Alkylator mixer and seals need frequent attention 反应器搅拌器及密封需要频繁的维护
A World of Solutions
Conventional SA Process 传统的硫酸法技术
Байду номын сангаас
Refrigeration
Olefin Feed
Propane
Isobutane Make-up
Alkylation Contactor
Water Caustic
iC4 recycle
Fractionation
A World of Solutions
2
What is Alkylation 什么是烷基化？ Alkylation 烷基化
– Alkylation is the process of reacting iso-butane with light olefins, primarily butene, to produce a longer branched chain paraffin called alkylate 烷基化是让异丁烷和轻质烯烃（主要是丁烯）反应生成长链、带支链的 烷烃（即烷基化油）的反应过程
Several mechanical mixers (several contactors) are needed to ensure good mixing 需要若干台反应器（搅拌器）
A World of Solutions
11
Problems with Conventional SA Alkylation 传统的硫酸法烷基化技术的问题 Difficult separation of hydrocarbonacid emulsion 很难分离烃-酸乳液
Corrosion 腐蚀 Water carryover from water wash causes corrosion issues 水洗所对来的夹带水造成腐蚀问题
A World of Solutions
12
Problems with Conventional SA Alkylation 传传统的硫酸法烷基化技术的问题
A World of Solutions
6
Sulfuric Acid Alkylation Chemistry 硫酸法烷基化的化学反应机理 Alkylation 烷基化 i-C4 + C4H8 i-C4 + C3 H6 i-C4 + C5 H10 Side reactions 副反应
High energy input for mixer 搅拌器能耗高
– High intensity mechanical mixing necessary to create good contact between acid and hydrocarbon 为了实现酸和烃之间的良好混合，需要强劲的机械搅拌
High acid consumption 酸耗高
– Often significantly over 70 kg acid/ ton of alkylate 每吨烷基化油的酸耗经常超过70 kg – Acid regeneration costs are high 酸再生的费用高
Multiple contactors required due to size limitation 单台反应器的处理量受到尺寸限制，所以需要多台反应器
A World of Solutions
5
Alkylation in China 中国的烷基化情况
Alkylate is an ideal blendstock to meet China’s clean energy needs 烷基化油在中国是一股理想的汽油调和组分来满足中国的 能源需求 Chinese gasoline pool is very deficient in alkylate 中国的汽油池中烷基化油所占比重严重不足 Spread developing b/w gasoline and LPG makes alkylation economical! 汽油与LPG的价差使得烷基化项目具有经济效益
CDAlky® Advanced Sulfuric Acid Alkylation 先进的低温硫酸法烷基化工艺
1
A World of Solutions
Agenda 提纲 Alkylation Overview 烷基化概貌 Conventional Sulfuric Acid Alkylation 传统硫酸法烷基化工艺 CDAlky Technology Overview CDAlky工艺技术简介 CDAlky Commercialization Status CDAlky工艺技术工业化状态
Same catalyst (sulfuric acid), same reaction chemistry 相同的催化剂（硫酸），同样的化学反应机理 Breakthrough reactor technology that eliminates mechanical mixers 反应器技术的突破，去除机械搅拌
Solid Acid Alkylation 固体酸烷基化
– Safer but expensive alternative; Yet to find industry acceptance 安全但是投资大、操作成本高；尚未工业化
SA Alkylation
硫酸法烷基化 – Alkylation technology of choice for refiners 当今炼油企业所选择的烷基化技术 – Most optimal choice in balancing the safety/operability issues with benefits of high quality alkylate 在安全性和可操作性之间取得最佳平衡，并生产高质量的烷基化油
A World of Solutions
4
Future of Alkylation 烷基化的前景 HF Alkylation 氢氟酸法烷基化
– High quality alkylate, low acid consumption, more feedstock flexibility 产生高质量的烷基化油，酸耗低，适合多种原料 – Extremely hazardous; not preferred anymore 极大的安全隐患，市场上不再推行
A World of Solutions
13
® CDAlky Advanced Sulfuric Acid Alkylation 先进的低温硫酸法烷基化工艺
A World of Solutions
Well Understood Principles of CDAlky Process CDAlky的反应机理
– Fine emulsion necessary for mass Wt% of transfer requires long settling period droplets and large settlers 为了实现良好的质量传递而形成的酸 乳液需要很长的沉降时间和大型的沉 降器
Small Droplets