第八讲劣质重油深加工工艺资料
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❖More residues are processed in US refineries.
during the past 10 years: API dropped 1° and sulfur content increased 0.27% coking capacity in US increased 0.27 Mt/a.
❖ Ebullated-bed hydrocracking used for handling Canada oilsand bitumen residue for decades.
Delayed Coking-Advances
❖Total capacity of delayed coking units amounting to 32%; residue processing capacity reached to 0.3 billion t/a in the world and 90 million t/a in China.
• 我国延迟焦化加工规模进展 • 2000年(1850万吨/年); • 2003年(~3000万吨/年), • 目前 (12000万吨)。
8、延迟焦化工艺制约因素
突出问题:
.
液收较低
结焦 “焦粉”淤堵
弹丸焦
9、目前我国延迟焦化存在问题
❖ 焦化液收偏低、生焦率偏高 ❖ 石油焦质量不高(粉焦、弹丸焦、粘焦) ❖ 操作周期偏短(3~12月,停工一天损失>100万元) ❖ 目前运转的装置大都不能适应劣质稠油渣油(残
Ebullated-bed hydrocracking
❖ Ebullated-bed advantage: Catalyst in reactor is continuously added and removed from the reactor
Reactor for hydrocracking
床
m%
√
<25
<7
<0.5 易加工
√
<70
<15
不难
√ 70~200 <15
稍难
√ 200~800
难加工
?
>800
极难
4、脱碳工艺对重油原料的适应性强
5、渣油深加工发展趋势
• 美国自1994年起, 减压渣油的深加工基本上围绕 延迟焦化配套相应精制系统(“Since 1994, all residue upgrading in the USA has been based on delayed coking”).
CONC. CARBON AND REMOVAL
SDA Gasification
• Old Technology • Low Liquid Yield. • High Coke Yield. • Low Investment.
• Ready for Commercial Application • High Conversion. • Suitable for the Orinoco Belt Crudes • Higher Investment.
H-Oil
415~440 13.5~21.0
— 0.4~1.3 0.35~2.1
45~85 65~82 25~45 45~75 65~90 130~300
LC-Fining
410~440 11.0~18.0 7.5~12.5
5百度文库~80 60~85
40~70 65~88 135~300
High temperature: operation temperature is almost the same with end-of-run temperature of fixed bed residue hydrogenation High pressure: To stabilize operation, maintain hydrogen partial pressure at outlet of reactor. High hydrogen consumption: For VR converted and contaminates removal.
• 目前美国、加拿大和委内瑞拉都在大力发展延迟 焦化工艺。
• 到2002年大部分流化焦化和灵活焦化装置停产或 半停产。
• 我国在大力发展渣油延迟焦化技术和加氢技术。
6、我国延迟焦化发展动力
• 原油偏重、劣质资源所占份额越来越大 • RFCC向FCC技术回归趋势(汽柴油质量要求提高) • VRDS和ARDS对原料的残炭和金属含量要求严格,
Ebullated-bed hydrocracking
Operating condition and performance of ebullated-bed hydrocracking process
Items Operating conditions
Temperature/℃ Pressure/MPa Hydrogen partial pressure/MPa Catalyst space velocity/h-1 on-line addition/withdrawal/(kg•m-3) Performance Residue conversion rate(v),% HDS (w),% HDN(w),% Carbon residue conversion rate (w),% HDM(w),% Hydrogen consumption/(m3•m-3)
Processing Technology challenges
❖ Delayed coking can process VR from Venezuela ultra-heavy oil/oilsand bitumen with technical and economic advantage.
❖ RFCC required the limit of the feedstock that carbon residue, Ni/V content is below 8%, 10ppm respectively.
❖ Fixed-bed hydrogenation requires the limits of feedstocks that carbon residue, (V+Ni) content below20%, 200ppm respectively.
ART:>50%
Criterion、Albemarle:< 50%
❖ Applied in upgrading/processing of ultra-heavy crude oil and oilsand bitumen
The first unit in oilsand improvement plant started up in 1988
❖ Temperature higher than 410℃ ❖ 16 Mpa pressure ❖ Conversion level properly controlled to avoid asphaltenes
建造与操作费用很高 • 我国重整原料和烯烃裂解原料不足 • 我国加氢的氢源不足(石脑油制氢) • 提高柴汽比的需要
7、我国延迟焦化发展趋势
• 1931年美国建立了第一套工业装置 • 目前最大装置:770万吨(Sincor,委内瑞拉) • 世界最大在建:1200万吨(Suncor,加拿大) • 我国最大: 430万吨(中海油-惠州)
炭>20)的加工
Deep Conversion Options
HYDROGEN ADDITION
FIXED BED
Hydrocracking/HDS Residfining ARDS/VRDS
FLUIDIZED BED
H-Oil LC-fining UOP Aurabon
• Commercial Technologies • Less Conversion. • Limited use Orinoco Belt Crudes • Higher Investment.
Slurry-bed hydrocracking-EST
❖ EST from ENI: Pilot experiment completed in an 1200 BPSD industrial demonstration unit at Taranto refinery.
❖ Eni's Sannazzaro refinery will host the first full scale EST industrial plant (20000 BPSD). React conditions
第八讲 劣质重油深加工工艺 I、重质油加工技术选择 II、重质油加氢工艺
I、重油深加工技术选择
一、劣质重油深加工首选工艺-热加工
1、超稠油(重油)集输对重油改质的重大需求 • 稠油管输对粘度要求严格 • 稠油船运与管输对安定性要求严格 • 稠油储存对稳定性要求严格
2、劣质渣油深加工对技术的依赖 • 高金属重油(>200ppm) • 高残炭( >17%) • 高粘度(>1000cst, 100℃)
Delayed Coking Operation
➢ Run lengths are up to 5 years with outages/partial outages for furnace decoking
➢ Cycle times are 18 hours or less
➢ Most units are being designed to minimize operator attendance on the structure to improve safety
Ebullated-bed hydrocracking
New generation catalyst
Improving process to increase impurities removal rate and capacity
Advances
Integrating ebullated-bed hydrocracking unit with downstream unit to reduce investment and operating cost
SLURRY BUBBLE
HDHPLUS™/SHP
VCC CANMET CASH (CVX) EST (ENI)
MOVING BED
Shell HDM/HYCON
CARBON REJECTION
Delayed Cocking Flexicoking Fluid Coking RFCC Visbreaking HydroVisbreaking
3、重油加工技术的选择(示意图)
20
残 15 炭 % 10
加氢处理
重油催化
5
加氢处 理
00
10
100
Ni+V ppm
热 加 工
200
3、重油加工技术的选择
重油深加工工艺
RFCC 焦化 固定 沸腾 床床
√√√ √
×√√ √
√ √&? √
√× √
★
×
渣油原料性质
悬浮 Ni+V,PPm 残碳, 硫,m% 难度
Ebullated-bed
Fixed-bed
(Ni+V) content in feed, ×10-6
>700
<200
Carbon residue in feed,%
20~25
<20
❖ Ebullated-bed hydrocracking process
LC-Fining
H-Oil
❖ Ebullated-bed hydrocracking catalyst
Champion: using anti-foulant to reduce furnace coking effectively.
Example: Unit in Delek Texas Tyler refinery went through 500 day continuous run, total estimated saving more than 2 Million $/a.
Delayed Coking-Advances
❖ Low pressure, ultra-low recycle ratio technology ❖ Larger Coke Drums applied ❖ New technology for coker furnace fouling control
during the past 10 years: API dropped 1° and sulfur content increased 0.27% coking capacity in US increased 0.27 Mt/a.
❖ Ebullated-bed hydrocracking used for handling Canada oilsand bitumen residue for decades.
Delayed Coking-Advances
❖Total capacity of delayed coking units amounting to 32%; residue processing capacity reached to 0.3 billion t/a in the world and 90 million t/a in China.
• 我国延迟焦化加工规模进展 • 2000年(1850万吨/年); • 2003年(~3000万吨/年), • 目前 (12000万吨)。
8、延迟焦化工艺制约因素
突出问题:
.
液收较低
结焦 “焦粉”淤堵
弹丸焦
9、目前我国延迟焦化存在问题
❖ 焦化液收偏低、生焦率偏高 ❖ 石油焦质量不高(粉焦、弹丸焦、粘焦) ❖ 操作周期偏短(3~12月,停工一天损失>100万元) ❖ 目前运转的装置大都不能适应劣质稠油渣油(残
Ebullated-bed hydrocracking
❖ Ebullated-bed advantage: Catalyst in reactor is continuously added and removed from the reactor
Reactor for hydrocracking
床
m%
√
<25
<7
<0.5 易加工
√
<70
<15
不难
√ 70~200 <15
稍难
√ 200~800
难加工
?
>800
极难
4、脱碳工艺对重油原料的适应性强
5、渣油深加工发展趋势
• 美国自1994年起, 减压渣油的深加工基本上围绕 延迟焦化配套相应精制系统(“Since 1994, all residue upgrading in the USA has been based on delayed coking”).
CONC. CARBON AND REMOVAL
SDA Gasification
• Old Technology • Low Liquid Yield. • High Coke Yield. • Low Investment.
• Ready for Commercial Application • High Conversion. • Suitable for the Orinoco Belt Crudes • Higher Investment.
H-Oil
415~440 13.5~21.0
— 0.4~1.3 0.35~2.1
45~85 65~82 25~45 45~75 65~90 130~300
LC-Fining
410~440 11.0~18.0 7.5~12.5
5百度文库~80 60~85
40~70 65~88 135~300
High temperature: operation temperature is almost the same with end-of-run temperature of fixed bed residue hydrogenation High pressure: To stabilize operation, maintain hydrogen partial pressure at outlet of reactor. High hydrogen consumption: For VR converted and contaminates removal.
• 目前美国、加拿大和委内瑞拉都在大力发展延迟 焦化工艺。
• 到2002年大部分流化焦化和灵活焦化装置停产或 半停产。
• 我国在大力发展渣油延迟焦化技术和加氢技术。
6、我国延迟焦化发展动力
• 原油偏重、劣质资源所占份额越来越大 • RFCC向FCC技术回归趋势(汽柴油质量要求提高) • VRDS和ARDS对原料的残炭和金属含量要求严格,
Ebullated-bed hydrocracking
Operating condition and performance of ebullated-bed hydrocracking process
Items Operating conditions
Temperature/℃ Pressure/MPa Hydrogen partial pressure/MPa Catalyst space velocity/h-1 on-line addition/withdrawal/(kg•m-3) Performance Residue conversion rate(v),% HDS (w),% HDN(w),% Carbon residue conversion rate (w),% HDM(w),% Hydrogen consumption/(m3•m-3)
Processing Technology challenges
❖ Delayed coking can process VR from Venezuela ultra-heavy oil/oilsand bitumen with technical and economic advantage.
❖ RFCC required the limit of the feedstock that carbon residue, Ni/V content is below 8%, 10ppm respectively.
❖ Fixed-bed hydrogenation requires the limits of feedstocks that carbon residue, (V+Ni) content below20%, 200ppm respectively.
ART:>50%
Criterion、Albemarle:< 50%
❖ Applied in upgrading/processing of ultra-heavy crude oil and oilsand bitumen
The first unit in oilsand improvement plant started up in 1988
❖ Temperature higher than 410℃ ❖ 16 Mpa pressure ❖ Conversion level properly controlled to avoid asphaltenes
建造与操作费用很高 • 我国重整原料和烯烃裂解原料不足 • 我国加氢的氢源不足(石脑油制氢) • 提高柴汽比的需要
7、我国延迟焦化发展趋势
• 1931年美国建立了第一套工业装置 • 目前最大装置:770万吨(Sincor,委内瑞拉) • 世界最大在建:1200万吨(Suncor,加拿大) • 我国最大: 430万吨(中海油-惠州)
炭>20)的加工
Deep Conversion Options
HYDROGEN ADDITION
FIXED BED
Hydrocracking/HDS Residfining ARDS/VRDS
FLUIDIZED BED
H-Oil LC-fining UOP Aurabon
• Commercial Technologies • Less Conversion. • Limited use Orinoco Belt Crudes • Higher Investment.
Slurry-bed hydrocracking-EST
❖ EST from ENI: Pilot experiment completed in an 1200 BPSD industrial demonstration unit at Taranto refinery.
❖ Eni's Sannazzaro refinery will host the first full scale EST industrial plant (20000 BPSD). React conditions
第八讲 劣质重油深加工工艺 I、重质油加工技术选择 II、重质油加氢工艺
I、重油深加工技术选择
一、劣质重油深加工首选工艺-热加工
1、超稠油(重油)集输对重油改质的重大需求 • 稠油管输对粘度要求严格 • 稠油船运与管输对安定性要求严格 • 稠油储存对稳定性要求严格
2、劣质渣油深加工对技术的依赖 • 高金属重油(>200ppm) • 高残炭( >17%) • 高粘度(>1000cst, 100℃)
Delayed Coking Operation
➢ Run lengths are up to 5 years with outages/partial outages for furnace decoking
➢ Cycle times are 18 hours or less
➢ Most units are being designed to minimize operator attendance on the structure to improve safety
Ebullated-bed hydrocracking
New generation catalyst
Improving process to increase impurities removal rate and capacity
Advances
Integrating ebullated-bed hydrocracking unit with downstream unit to reduce investment and operating cost
SLURRY BUBBLE
HDHPLUS™/SHP
VCC CANMET CASH (CVX) EST (ENI)
MOVING BED
Shell HDM/HYCON
CARBON REJECTION
Delayed Cocking Flexicoking Fluid Coking RFCC Visbreaking HydroVisbreaking
3、重油加工技术的选择(示意图)
20
残 15 炭 % 10
加氢处理
重油催化
5
加氢处 理
00
10
100
Ni+V ppm
热 加 工
200
3、重油加工技术的选择
重油深加工工艺
RFCC 焦化 固定 沸腾 床床
√√√ √
×√√ √
√ √&? √
√× √
★
×
渣油原料性质
悬浮 Ni+V,PPm 残碳, 硫,m% 难度
Ebullated-bed
Fixed-bed
(Ni+V) content in feed, ×10-6
>700
<200
Carbon residue in feed,%
20~25
<20
❖ Ebullated-bed hydrocracking process
LC-Fining
H-Oil
❖ Ebullated-bed hydrocracking catalyst
Champion: using anti-foulant to reduce furnace coking effectively.
Example: Unit in Delek Texas Tyler refinery went through 500 day continuous run, total estimated saving more than 2 Million $/a.
Delayed Coking-Advances
❖ Low pressure, ultra-low recycle ratio technology ❖ Larger Coke Drums applied ❖ New technology for coker furnace fouling control