埃克森美孚甲醇制汽油技术
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SynGas and MeOH Generation
MTG
14,500 BPD plant in New Plymouth New Zealand. Plant ownership 75% NZ Government and 25% ExxonMobil. 新西兰新普利茅斯甲醇制汽油工厂日产汽油 14,500桶。 新西兰政府拥有75%的股份，剩余25%由埃克森美孚占有。
Methanol
甲醇
•
水
Water
• •
Gasoline 汽油
5
MTG REACTION PATH 甲醇制汽油技术的化学反应
2 CH3OH
Methanol 甲醇
CH3OCH3 + H2O
Di-Methyl Ether 二甲醚 Light Olefins 低碳烯烃 C5+ Olefins Paraffins Naphthenes Aromatics
2005 Summer 2005 Winter MTG Gasoline US Regulation
API Gravity Aromatics (%Vol) Olefins (%Vol) RVP (psi) T50 (F) T90 (F) Sulfur (PPM) Benzene (%Vol)
58.4 27.7 12 8.3 211.1 330.7 106 1.21
甲醇合成 甲醇制汽油
Gasification
MeOH Synthesis FischerTropsch Synthesis
费托合成
MTG
Gasification
Refining
精炼
Coal
Gasification
Liquid Fuels
H2
燃料油
Direct Liquefaction
直接液化
Refining
Percent of Feed Percent of Hydrocarbon Product
MTG GASOLINE PROPERTIES/COMPOSITION
Octane, RON Octane, MON (R+M)/2 Paraffins, vol%
92 82 87 53 12 9 26 0.3 nil
• The New Zealand MTG experience demonstrated MTG to be a robust technology 新西兰甲醇制汽油经验证明EMRE甲醇制汽油技术成熟、可靠 • Daily gasoline yield and octane indicated a very consistent process performance 汽油日产量及辛烷值结果表明工艺过程稳定，产品变数很小 • After start up the unit ran reliably with an on-stream factor greater than 96% 工厂启动后运行可靠性高达96% 以上
• MTG Gasoline is completely compatible with conventional gasoline MTG 汽油和常规汽油完全匹配 • MTG Gasoline contains essentially no sulfur and low benzene MTG 汽油不含硫、苯含量低
7
Gas
1% 5% 38% 56%
2% 11% 87% -
LPG
Olefins, vol% Napthenes, vol%
Gasoline
Aromatics, vol% Benzene, vol%
H2O
Sulfur
MTG GASOLINE VS. U.S. CONVENTIONAL GASOLINE MTG 汽油和美国市场上常规汽油的比较
烷烃、环烷烃、芳烃
CH3OH, CH3OCH3
Methanol, Di-Methyl Ether Light Olefins
+ H2O
C5+ Olefins
Gasoline 汽油
6
MTG YIELDS AND PROPERTIES/COMPOSITION 甲醇制汽油工艺的产量、特性及成分
MTG GASOLINE YIELDS
直接液化
“F-T Crude”
费托产品
Direct 直接
Direct Liquefaction H2
“Synthetic Crude”
合成油
Coal Gasification: Syngas: H2 O2 H2O CO2
3
OPTIONS FOR COAL TO LIQUID TRANSPORTATION FUELS 煤转运输燃料油的途径
9
EMRE MTG PROCESS FLOW DIAGRAM EMRE 甲醇制汽油工艺流程
MTG Reactor System (Multiple)
Purge Gas C2LPG Light Gasoline
Blending
甲醇制汽油 反应器（多个）
ห้องสมุดไป่ตู้LPG
Finished Gasoline
Methanol
11
NEW ZEALAND PLANT OPERATING EXPERIENCE 新西兰甲醇制汽油工厂的操作经验
95 90
Rx Stream Factor GASOLINE YIELD WT% OF HC
Initial Startup: October, 1985 > 96% Stream Factor over 7 year period
精炼
4
EXXONMOBIL MTG TECHNOLOGY 埃克森美孚甲醇制汽油技术
• MTG reactions de-hydrate methanol and convert carbon and hydrogen into various hydrocarbons 化学反应将甲醇脱水并使之转化为烃类 The “Shape Selective” MTG catalyst limits the synthesis reactions to 10 carbons 甲醇制汽油工艺 “构型选择性”催化剂将烃类产 物碳链限制在十个碳以内 The result is sulfur free gasoline MTG 产物为不含硫的常规汽油 The first MTG plant was operated in New Zealand from 1985 to 1997 第一个甲醇制汽油工厂建于新西兰，并在1985 年到1997年间运行
Heavy Gasoline Stabilized Gasoline
Treated Gasoline
H2O
Raw Gasoline
Stabilizer DeEthanizer
稳定器
Splitter
HGT Reactor HGT 反应器
Stabilizer
乙烯去除器
分馏塔
稳定器
10
NEW ZEALAND MTG FACILITY: NEW PLYMOUTH NZ 新西兰甲醇制汽油工厂：新西兰新普利茅斯
100% 95% 90% 85% 80% 75% 70% 0 360 720 1080 1440 1800 2160 2520 2880 Elapsed Time, Days
85 96 94 92 90
1st Calendar Year
GASOLINE OCTANE, RON
1st Calendar Year
埃克森美孚在催化剂研发和生产 领域处世界领先地位
ExxonMobil is the world leader in catalyst development and manufacture
JAMG MTG PLANT IN SHANXI CHINA 中国山西晋城煤业集团的甲醇制汽油项目
ExxonMobil Methanol To Gasoline (MTG) Technology
埃克森美孚甲醇制汽油技术
Zhiguo Hou ExxonMobil Research & Engineering (EMRE) July 26, 2011
AGENDA
• Coal to Liquid Fuels Background 煤转燃料油的背景 • EMRE Methanol to Gasoline Technology EMRE 甲醇制汽油技术 • MTG and Fischer-Tropsch Comparative Analysis 甲醇制汽油技术与费托液化技术的比较分析 • EMRE MTG Licensing – The MTG Advantage EMRE 甲醇制汽油技术转让 - 技术工艺优势
61.9 24.7 11.6 12.12 199.9 324.1 97 115
61.8 26.5 12.6 9 201 320 0 0.3 30 1 (0.62)
8
EMRE MTG PROCESS EMRE甲醇制汽油工艺
• Methanol is fed to a fixed bed reactor system where all of the methanol is converted to hydrocarbon and water 甲醇被送入一个固定床反应系统，在那里被全部转化为烃类和水 • MTG reactor effluent is separated into gas, raw gasoline and water 反应器流出物被分离成燃气、液态烃（粗汽油）和水 • Raw gasoline is separated into LPG, light gasoline & heavy gasoline 粗汽油被进一步分馏成 LPG （液化石油气）、轻汽油和重汽油 • Heavy gasoline is hydro-treated to reduce durene content 重汽油组分经过温和的水整理工艺以除去四甲基苯 • Heavy and light gasoline are re-combined into finished MTG gasoline 水整理后的重汽油与轻汽油再混合，成为甲醇制汽油过程的最终产物
2
OPTIONS FOR COAL LIQUEFACTION 煤液化的途径
甲醇合成
O2
H2O
CO2
Methanol Synthesis
费托合成
CH3OH
甲醇
Coal Gasification: Syngas: CO + 2H2
Coal
Indirect 间接
FischerTropsch Synthesis
12
KEY MTG FEATURES 甲醇制汽油的主要特点
• Operability 可操作性
– Gas phase conventional fixed bed reactors 传统的气相固定床反应器 – On-stream MTG catalyst regeneration and replacement 在线催化剂再生、更换 – Gasoline production is de-coupled from syngas generation and methanol synthesis -- Improves on-stream factor vs. direct coupled operation 汽油生产与煤气化及甲醇合成步奏分离，进一步提高了工厂整体在线运行的 可靠性
• Constructability 建造可行性
– Parallel reactor design provides reactor size flexibility 平行反应器设计增加了反应器尺寸的灵活度 – New Zealand experience demonstrated constructability in remote locals 新西兰的商业经验证实了在边远地区建造甲醇制汽油项目的可行性
13
NEW GENERATION MTG TECHNOLOGY 新一代甲醇制汽油技术
• • • 第二代甲醇制汽油技术设计基于新西兰工厂十来年的操作经验 2nd generation Design based on 10 years learning's from New Zealand operation 工艺热整合进一步优化 / 工艺流程效率进一步提升 Improved heat integration / process efficiency 新一代高寿命、高选择性催化剂 New generation catalyst development
MTG
14,500 BPD plant in New Plymouth New Zealand. Plant ownership 75% NZ Government and 25% ExxonMobil. 新西兰新普利茅斯甲醇制汽油工厂日产汽油 14,500桶。 新西兰政府拥有75%的股份，剩余25%由埃克森美孚占有。
Methanol
甲醇
•
水
Water
• •
Gasoline 汽油
5
MTG REACTION PATH 甲醇制汽油技术的化学反应
2 CH3OH
Methanol 甲醇
CH3OCH3 + H2O
Di-Methyl Ether 二甲醚 Light Olefins 低碳烯烃 C5+ Olefins Paraffins Naphthenes Aromatics
2005 Summer 2005 Winter MTG Gasoline US Regulation
API Gravity Aromatics (%Vol) Olefins (%Vol) RVP (psi) T50 (F) T90 (F) Sulfur (PPM) Benzene (%Vol)
58.4 27.7 12 8.3 211.1 330.7 106 1.21
甲醇合成 甲醇制汽油
Gasification
MeOH Synthesis FischerTropsch Synthesis
费托合成
MTG
Gasification
Refining
精炼
Coal
Gasification
Liquid Fuels
H2
燃料油
Direct Liquefaction
直接液化
Refining
Percent of Feed Percent of Hydrocarbon Product
MTG GASOLINE PROPERTIES/COMPOSITION
Octane, RON Octane, MON (R+M)/2 Paraffins, vol%
92 82 87 53 12 9 26 0.3 nil
• The New Zealand MTG experience demonstrated MTG to be a robust technology 新西兰甲醇制汽油经验证明EMRE甲醇制汽油技术成熟、可靠 • Daily gasoline yield and octane indicated a very consistent process performance 汽油日产量及辛烷值结果表明工艺过程稳定，产品变数很小 • After start up the unit ran reliably with an on-stream factor greater than 96% 工厂启动后运行可靠性高达96% 以上
• MTG Gasoline is completely compatible with conventional gasoline MTG 汽油和常规汽油完全匹配 • MTG Gasoline contains essentially no sulfur and low benzene MTG 汽油不含硫、苯含量低
7
Gas
1% 5% 38% 56%
2% 11% 87% -
LPG
Olefins, vol% Napthenes, vol%
Gasoline
Aromatics, vol% Benzene, vol%
H2O
Sulfur
MTG GASOLINE VS. U.S. CONVENTIONAL GASOLINE MTG 汽油和美国市场上常规汽油的比较
烷烃、环烷烃、芳烃
CH3OH, CH3OCH3
Methanol, Di-Methyl Ether Light Olefins
+ H2O
C5+ Olefins
Gasoline 汽油
6
MTG YIELDS AND PROPERTIES/COMPOSITION 甲醇制汽油工艺的产量、特性及成分
MTG GASOLINE YIELDS
直接液化
“F-T Crude”
费托产品
Direct 直接
Direct Liquefaction H2
“Synthetic Crude”
合成油
Coal Gasification: Syngas: H2 O2 H2O CO2
3
OPTIONS FOR COAL TO LIQUID TRANSPORTATION FUELS 煤转运输燃料油的途径
9
EMRE MTG PROCESS FLOW DIAGRAM EMRE 甲醇制汽油工艺流程
MTG Reactor System (Multiple)
Purge Gas C2LPG Light Gasoline
Blending
甲醇制汽油 反应器（多个）
ห้องสมุดไป่ตู้LPG
Finished Gasoline
Methanol
11
NEW ZEALAND PLANT OPERATING EXPERIENCE 新西兰甲醇制汽油工厂的操作经验
95 90
Rx Stream Factor GASOLINE YIELD WT% OF HC
Initial Startup: October, 1985 > 96% Stream Factor over 7 year period
精炼
4
EXXONMOBIL MTG TECHNOLOGY 埃克森美孚甲醇制汽油技术
• MTG reactions de-hydrate methanol and convert carbon and hydrogen into various hydrocarbons 化学反应将甲醇脱水并使之转化为烃类 The “Shape Selective” MTG catalyst limits the synthesis reactions to 10 carbons 甲醇制汽油工艺 “构型选择性”催化剂将烃类产 物碳链限制在十个碳以内 The result is sulfur free gasoline MTG 产物为不含硫的常规汽油 The first MTG plant was operated in New Zealand from 1985 to 1997 第一个甲醇制汽油工厂建于新西兰，并在1985 年到1997年间运行
Heavy Gasoline Stabilized Gasoline
Treated Gasoline
H2O
Raw Gasoline
Stabilizer DeEthanizer
稳定器
Splitter
HGT Reactor HGT 反应器
Stabilizer
乙烯去除器
分馏塔
稳定器
10
NEW ZEALAND MTG FACILITY: NEW PLYMOUTH NZ 新西兰甲醇制汽油工厂：新西兰新普利茅斯
100% 95% 90% 85% 80% 75% 70% 0 360 720 1080 1440 1800 2160 2520 2880 Elapsed Time, Days
85 96 94 92 90
1st Calendar Year
GASOLINE OCTANE, RON
1st Calendar Year
埃克森美孚在催化剂研发和生产 领域处世界领先地位
ExxonMobil is the world leader in catalyst development and manufacture
JAMG MTG PLANT IN SHANXI CHINA 中国山西晋城煤业集团的甲醇制汽油项目
ExxonMobil Methanol To Gasoline (MTG) Technology
埃克森美孚甲醇制汽油技术
Zhiguo Hou ExxonMobil Research & Engineering (EMRE) July 26, 2011
AGENDA
• Coal to Liquid Fuels Background 煤转燃料油的背景 • EMRE Methanol to Gasoline Technology EMRE 甲醇制汽油技术 • MTG and Fischer-Tropsch Comparative Analysis 甲醇制汽油技术与费托液化技术的比较分析 • EMRE MTG Licensing – The MTG Advantage EMRE 甲醇制汽油技术转让 - 技术工艺优势
61.9 24.7 11.6 12.12 199.9 324.1 97 115
61.8 26.5 12.6 9 201 320 0 0.3 30 1 (0.62)
8
EMRE MTG PROCESS EMRE甲醇制汽油工艺
• Methanol is fed to a fixed bed reactor system where all of the methanol is converted to hydrocarbon and water 甲醇被送入一个固定床反应系统，在那里被全部转化为烃类和水 • MTG reactor effluent is separated into gas, raw gasoline and water 反应器流出物被分离成燃气、液态烃（粗汽油）和水 • Raw gasoline is separated into LPG, light gasoline & heavy gasoline 粗汽油被进一步分馏成 LPG （液化石油气）、轻汽油和重汽油 • Heavy gasoline is hydro-treated to reduce durene content 重汽油组分经过温和的水整理工艺以除去四甲基苯 • Heavy and light gasoline are re-combined into finished MTG gasoline 水整理后的重汽油与轻汽油再混合，成为甲醇制汽油过程的最终产物
2
OPTIONS FOR COAL LIQUEFACTION 煤液化的途径
甲醇合成
O2
H2O
CO2
Methanol Synthesis
费托合成
CH3OH
甲醇
Coal Gasification: Syngas: CO + 2H2
Coal
Indirect 间接
FischerTropsch Synthesis
12
KEY MTG FEATURES 甲醇制汽油的主要特点
• Operability 可操作性
– Gas phase conventional fixed bed reactors 传统的气相固定床反应器 – On-stream MTG catalyst regeneration and replacement 在线催化剂再生、更换 – Gasoline production is de-coupled from syngas generation and methanol synthesis -- Improves on-stream factor vs. direct coupled operation 汽油生产与煤气化及甲醇合成步奏分离，进一步提高了工厂整体在线运行的 可靠性
• Constructability 建造可行性
– Parallel reactor design provides reactor size flexibility 平行反应器设计增加了反应器尺寸的灵活度 – New Zealand experience demonstrated constructability in remote locals 新西兰的商业经验证实了在边远地区建造甲醇制汽油项目的可行性
13
NEW GENERATION MTG TECHNOLOGY 新一代甲醇制汽油技术
• • • 第二代甲醇制汽油技术设计基于新西兰工厂十来年的操作经验 2nd generation Design based on 10 years learning's from New Zealand operation 工艺热整合进一步优化 / 工艺流程效率进一步提升 Improved heat integration / process efficiency 新一代高寿命、高选择性催化剂 New generation catalyst development