������������4,������2 ������������4 ������2 ������������4
C4xH8x+2
H2SO4 + CxHy (ASO) 2H2O + SO2 + CxHy-2
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Sulfuric Acid Alkylation Fundamentals 硫酸法烷基化基本原理
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Sulfuric Acid Alkylation Chemistry 硫酸法烷基化化学反应机理
Alkylation Reactions
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2 i-C4H10 + C5H10 2 C8H18 CxH2x+2
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C8H18 + C5H12
C7H16 + C9H20 CyH2y + Cx-yH2(x-y)+2
– Contaminants, i.e. Butadiene, Mercaptans, Oxygenates 杂质，如丁二烯，硫醇，氧化物
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California CaRFG3 加州标准
Euro 5 欧五
Sulfur, ppm 硫 Olefins, % 烯烃 Aromatics, % 芳烃 O + A, % 烯烃+芳烃 Benzene, % 苯 RVP, kPa Winter/Summer 蒸汽压 冬季/夏季 Effective 生效日期
Boiling Point, oF
Reference: Mr. Bill Piel, Tier Associates, USA
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Gasoline Specs 汽油标准
Olefins are among the most photo-chemically reactive components of automotive emissions with great ozone forming potential 汽车尾气中，烯烃的光化学反应活性最高、臭氧生成潜势 （OFP）最高 Light olefins and heavy aromatics present the biggest ozone yield contributing to SMOG and Greenhouse Effect 轻质烯烃和重质芳烃的高臭氧生成潜势使其成为雾霾和温 室效应的主要推手 Olefins are also known to cause carbon deposit/gum in car engines 烯烃会造成燃烧室积碳
i-C4+C4H8
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224TMP, 233TMP & 234TMP
– Olefin Ranking: B2≥B1>IB>C3~C5 烯烃对目标产物选择性的排名
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Sulfuric Acid Alkylation Chemistry 硫酸法烷基化化学反应机理
10
Olefins
Aromatics
5
Lt. FCC gasoline
Hvy. Reformate
Oxygenates
Toluene
2
ETBE Isomerate Ethanol Alkylate
1
N butane MTBE
0.5
High RVP increases Evaporative Emissions
8
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
Advances in Alkylation
Breaking the Low Reaction Temperature Barrier with CDAlky ® Technology
CDAlky®____克服低温反应束缚的先进烷基化技术
Information contained herein is confidential and/or proprietary to Lummus Technology Inc. and/or its affiliates. All such information is protected by the relevant agreements, including confidentiality and limited use agreements, between you, your employer and/or its affiliates, and Lummus Technology Inc. or its affiliates. The information herein may only be used in accordance with those agreements, and is not to be disclosed to unauthorized parties without permission of Lummus Technology, Inc.
Side Reactions 副反应
– Polymerization 聚合反应 – Hydrogen Transfer 氢转移 – Disproportionation 歧化 – Cracking 裂化 xC4H8
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C4xH8x+2
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Outline 提纲
Why Alkylate 烷基化油的意义
Sulfuric Acid Alkylation Fundamentals 硫酸法烷基化基本原理
CDAlky® Key Advantages CDAlky®技术的优势 CDAlky® Commercial Experience CDAlky®技术的工业应用业绩
4
Contribution to Ozone Formation 不同碳氢化合物生成臭氧的能力
Ozone Reactivity and Boiling Temperatures of Gasoline Alternatives
Paraffins
Ozone Yield ( gm Ozone / gm VOC )
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500
35
150
30
50
28
10
25
10
15
4
10
24
18
40
40
40
-
40
25
22
35
China VI?
60 1 2.5 1 1 1 1 7.0 psi ~48 kPa Jan. 1, 2017 0.7 7.0 psi ~48 kPa Jan. 1, 2012 1
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PM2.5 Contributors in Beijing 北京地区PM2.5的来源
Catering, automobile repair, Livestock and Poultry breeding, Construction and others 餐饮、汽车修 理、畜禽养殖、 建筑涂装等其…

By-Products 副产品
– Formation of Acid Soluble Oil (ASO) 酸溶性油的生成 • Esterification 酯化反应 • Polymerization 聚合反应 – SO2 2 C4H10 + H2SO4 mono & di-butyl sulfate 单丁基硫酸酯和二丁基硫酸酯 xC4H8
烷基化反应
– Exothermic Process 放热反应 – Sulfuric Acid = Catalyst 硫酸作催化剂 – Reaction of C4 Olefins with iC4 to Produce Trimethylpentane (TMPs) 碳四烯烃与异丁烷反应生成三甲基戊烷
50 100
Ideal Boiling Temperatures
Higher Temperatures increases Cold Cycle Exhaust HC's
250 300 350
150 200 Boiling Temperature ( F )
CARB & CEC "created" a low cost, external supply of Lt. Alkylate to replace Oxygenates in RFG
88/74 Jan. 1, 2000
88/72 Jan. 1, 2010
85/68 Jan. 1, 2014
85/65 June 1, 2012
85/65 Jan. 1, 2016
60 Jan. 1, 2009
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Gasoline Blending Components in China 中国汽油池组成