Hydroprocessing 美国科罗拉多矿业大学
合集下载
- 1、下载文档前请自行甄别文档内容的完整性，平台不提供额外的编辑、内容补充、找答案等附加服务。
- 2、"仅部分预览"的文档,不可在线预览部分如存在完整性等问题,可反馈申请退款(可完整预览的文档不适用该条件!)。
- 3、如文档侵犯您的权益，请联系客服反馈,我们会尽快为您处理(人工客服工作时间：9:00-18:30)。
• Pressure swing adsorption (PSA) • Membrane separation
• FCCU Offgas
5 vol% hydrogen with methane, ethane & propane Several recovery methods (can be combined)
Hydroprocessing: Hydrotreating & Hydrocracking
Chapters 7 & 9
Gases
Polymerization Sulfur Plant
Sulfur
Gas
Sat Gas Plant
LPG Butanes Alkyl Feed
Alkylation
Fuel Gas LPG
8
Sources of Hydrogen in a Refinery
By‐product from other processes Manufactured
• Catalytic Reformer
Most important source of hydrogen for the refiner Continuously regenerated reformer: 90 vol% Semi‐continuously regenerated reformer: 80 vol%
• Hydrotreating
Desired function
• Cobalt molybdenum – sulfur removal & olefin saturation • Nickel molybdenum – nitrogen removal & aromatic saturation
5
Characteristics of Petroleum Products
Hydrotreating: just enough conversion to remove undesirable atoms; hydrogen addition for atom removal
Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000
Lubricant Greases Waxes
Waxes
Coking
Light Coker Gas Oil
Coke
2
Purpose
•Hydrotreating
Remove hetero atoms & saturate carbon‐ carbon bonds
• Sulfur, nitrogen, oxygen, & metals removed • Olefinic & aromatic bonds saturated
• Downflow fixed bed – temperature to control final sulfur content • First bed may guard bed for nickel, vanadium, & arsenic
o o
Feed stock must first be hydrotreated Catalysts deactivate & coke does form even with hydrogen present
• Steam‐Methane Reforming (SMR)
Most common method of manufacturing hydrogen 90 – 95 vol% typical purity
• Gasification / Partial Oxidation
Produce synthesis gas (syngas) Hydrogen recovery
Gas Separation & Stabilizer
Light Naphtha
Isomerization
Polymerization Naphtha
Isomerate
Alkylate
Reformate Heavy Naphtha
Atmospheric Distillation Naphtha Hydrotreating Naphtha Reforming
Aviation Gasoline Automotive Gasoline Solvents
Naphtha
Crude Oil
Kerosene
Desalter
Jet Fuels Kerosene
Hydrocracking
Distillate AGO
Gas Oil Hydrotreating Fluidized Catalytic Cracking
• Hydrocracking
Crystalline silica alumina base with a rare earth metal deposited in the lattice
• Platinum, palladium, tungsten, and/or nickel
Reactor configuration
Cat Naphtha
Solvents
Distillate Hydrotreating Treating & Blending
Heating Oils Diesel
LVGO
Vacuum Distillation
Cat Distillates Fuel Oil Cycle Oils
HVGO
Residual Fuel Oils
• Driven by several factors
Increased use of hydrodesulfurization for low sulfur fuels Heavier & higher sulfur crudes Reduction in demand for heavy fuel oil More complete protection of FCCU catalysts Demand for high quality coke Increased production of diesel
6
Characteristics of Petroleum Products
Hydrocracking: hydrogen addition to minimize coke formation
Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000
7
Hydroprocessing Trends
• Hydrogen is ubiquitous in refinery & expected to increase
Produces higher yields & upgrade the quality of fuels
• The typical refinery runs at a hydrogen deficit – “hydrogen short” vs. “hydrogen
Handbook of Petroleum Refining Processes, 3rd ed. Ed. Robert A. Meyers, McGraw‐Hill, 2004
4
Typical Hydrogen Usage
Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000
DAO
Solvent Deasphalting
Coker Naphtha
SDA Bottoms
Naphtha
Asphalts
Visbreaking
Vacuum Residuum
Heavy Coker Gas Oil
Distillates Fuel Oil Bottoms Lube Oil
Solvent Dewaxing
Convert benzene in gasoline blend stocks
Minimal craห้องสมุดไป่ตู้king Minimal conversion – 10% to 20% typical Products suitable for further processing or final blending
long”
As hydroprocessing becomes more prevalent, this deficit will increase As hydroprocessing progresses in severity, the hydrogen demands increase dramatically
• Hydrocrackers require periodic regeneration of the fixed bed catalyst systems • Channeling caused by coke accumulation a major concern • Can create hot spots that can lead to temperature runaways
• Cryogenic • Pressure swing adsorption (PSA) • Membrane separation
More expensive than steam reforming but can use low quality by‐product streams
9
Hydroprocessing Catalysts
• Reforming, catalytic cracking, hydrocracking
3
Hydroprocessing Objectives
Feedstocks Naphthas Desired Products Catalytic reformer feed LPG Atmospheric gas oils Diesel Jet Ethylene feedstock Naptha Vaccum gas oils LSFO FCC feed Diesel Kerosene/jet Naptha LPG Ethylene feedstock Lube oil base stock Residuum LSFO FCC feedstock Coker feedstock Diesel Process Objectives Removal of S, N, & olefins Hydrocracking Removal of S, aromatics, & n‐paraffins Removal of S & aromatics Removal of aromatics Hydrocracking Removal of S Removal of S, N, & metals Removal of S & aromatics Hydrocracking Removal of S & aromatics Hydrocracking Hydrocracking Hydrocracking Removal of aromatics Hydrocracking Removal of S, N, & aromatics Hydrocracking Removal of S Removal of S, N, CCR, & metals Removal of S, CCR, & metals Hydrocracking
o
• Hydrocracking
Severe form of hydroprocessing
• Break carbon‐carbon bonds • Drastic reduction of molecular weight
Reduce average molecular weight & produce higher yields of fuel products 50%+ conversion Products more appropriate for diesel than gasoline
• FCCU Offgas
5 vol% hydrogen with methane, ethane & propane Several recovery methods (can be combined)
Hydroprocessing: Hydrotreating & Hydrocracking
Chapters 7 & 9
Gases
Polymerization Sulfur Plant
Sulfur
Gas
Sat Gas Plant
LPG Butanes Alkyl Feed
Alkylation
Fuel Gas LPG
8
Sources of Hydrogen in a Refinery
By‐product from other processes Manufactured
• Catalytic Reformer
Most important source of hydrogen for the refiner Continuously regenerated reformer: 90 vol% Semi‐continuously regenerated reformer: 80 vol%
• Hydrotreating
Desired function
• Cobalt molybdenum – sulfur removal & olefin saturation • Nickel molybdenum – nitrogen removal & aromatic saturation
5
Characteristics of Petroleum Products
Hydrotreating: just enough conversion to remove undesirable atoms; hydrogen addition for atom removal
Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000
Lubricant Greases Waxes
Waxes
Coking
Light Coker Gas Oil
Coke
2
Purpose
•Hydrotreating
Remove hetero atoms & saturate carbon‐ carbon bonds
• Sulfur, nitrogen, oxygen, & metals removed • Olefinic & aromatic bonds saturated
• Downflow fixed bed – temperature to control final sulfur content • First bed may guard bed for nickel, vanadium, & arsenic
o o
Feed stock must first be hydrotreated Catalysts deactivate & coke does form even with hydrogen present
• Steam‐Methane Reforming (SMR)
Most common method of manufacturing hydrogen 90 – 95 vol% typical purity
• Gasification / Partial Oxidation
Produce synthesis gas (syngas) Hydrogen recovery
Gas Separation & Stabilizer
Light Naphtha
Isomerization
Polymerization Naphtha
Isomerate
Alkylate
Reformate Heavy Naphtha
Atmospheric Distillation Naphtha Hydrotreating Naphtha Reforming
Aviation Gasoline Automotive Gasoline Solvents
Naphtha
Crude Oil
Kerosene
Desalter
Jet Fuels Kerosene
Hydrocracking
Distillate AGO
Gas Oil Hydrotreating Fluidized Catalytic Cracking
• Hydrocracking
Crystalline silica alumina base with a rare earth metal deposited in the lattice
• Platinum, palladium, tungsten, and/or nickel
Reactor configuration
Cat Naphtha
Solvents
Distillate Hydrotreating Treating & Blending
Heating Oils Diesel
LVGO
Vacuum Distillation
Cat Distillates Fuel Oil Cycle Oils
HVGO
Residual Fuel Oils
• Driven by several factors
Increased use of hydrodesulfurization for low sulfur fuels Heavier & higher sulfur crudes Reduction in demand for heavy fuel oil More complete protection of FCCU catalysts Demand for high quality coke Increased production of diesel
6
Characteristics of Petroleum Products
Hydrocracking: hydrogen addition to minimize coke formation
Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000
7
Hydroprocessing Trends
• Hydrogen is ubiquitous in refinery & expected to increase
Produces higher yields & upgrade the quality of fuels
• The typical refinery runs at a hydrogen deficit – “hydrogen short” vs. “hydrogen
Handbook of Petroleum Refining Processes, 3rd ed. Ed. Robert A. Meyers, McGraw‐Hill, 2004
4
Typical Hydrogen Usage
Refining Overview – Petroleum Processes & Products, by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD‐ROM, 2000
DAO
Solvent Deasphalting
Coker Naphtha
SDA Bottoms
Naphtha
Asphalts
Visbreaking
Vacuum Residuum
Heavy Coker Gas Oil
Distillates Fuel Oil Bottoms Lube Oil
Solvent Dewaxing
Convert benzene in gasoline blend stocks
Minimal craห้องสมุดไป่ตู้king Minimal conversion – 10% to 20% typical Products suitable for further processing or final blending
long”
As hydroprocessing becomes more prevalent, this deficit will increase As hydroprocessing progresses in severity, the hydrogen demands increase dramatically
• Hydrocrackers require periodic regeneration of the fixed bed catalyst systems • Channeling caused by coke accumulation a major concern • Can create hot spots that can lead to temperature runaways
• Cryogenic • Pressure swing adsorption (PSA) • Membrane separation
More expensive than steam reforming but can use low quality by‐product streams
9
Hydroprocessing Catalysts
• Reforming, catalytic cracking, hydrocracking
3
Hydroprocessing Objectives
Feedstocks Naphthas Desired Products Catalytic reformer feed LPG Atmospheric gas oils Diesel Jet Ethylene feedstock Naptha Vaccum gas oils LSFO FCC feed Diesel Kerosene/jet Naptha LPG Ethylene feedstock Lube oil base stock Residuum LSFO FCC feedstock Coker feedstock Diesel Process Objectives Removal of S, N, & olefins Hydrocracking Removal of S, aromatics, & n‐paraffins Removal of S & aromatics Removal of aromatics Hydrocracking Removal of S Removal of S, N, & metals Removal of S & aromatics Hydrocracking Removal of S & aromatics Hydrocracking Hydrocracking Hydrocracking Removal of aromatics Hydrocracking Removal of S, N, & aromatics Hydrocracking Removal of S Removal of S, N, CCR, & metals Removal of S, CCR, & metals Hydrocracking
o
• Hydrocracking
Severe form of hydroprocessing
• Break carbon‐carbon bonds • Drastic reduction of molecular weight
Reduce average molecular weight & produce higher yields of fuel products 50%+ conversion Products more appropriate for diesel than gasoline