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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2018, Vol. 12 Issue (4) : 867-877    https://doi.org/10.1007/s11705-018-1768-x
REVIEW ARTICLE
Research and development of hydrocracking catalysts and technologies in China
Chong Peng1, Yanze Du1, Xiang Feng2(), Yongkang Hu1, Xiangchen Fang1
1. Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian 116000, China
2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, China
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Abstract

Hydrocracking of petroleum feedstock represents a compelling route for the production of industrial clean fuels, which has triggered the continuous research and development of core technology related areas such as catalysts, reaction engineering and engineering design. This review particularly focuses on the research and development of catalysts and catalytic processes for hydrocracking of petroleum feedstock in China. Hydroprocessing technologies of China keep pace with the up-to-date progress of the world, and some of the technologies have achieved leading role in the world. It is noted that China Petroleum and Chemical Corporation has a full range of hydroprocessing technologies and provides corresponding “tailor-made” catalysts. Through the efforts of several generations, 20 categories of the catalysts including more than 60 brands have been developed, among which more than 40 brands have been successfully applied for more than 130 times. Importantly, the pivotal technical improvements including the deep drawing vacuum gas-oil (VGO) and de-asphalting oil hydrocracking technology to improve material adaptability, the high value-added hydrogenation technology to convert high aromatic diesel conversion to naphtha, the hydrocracking technology using VGO-catalytic diesel blends, the Fushun Research Institute of Petroleum and Petrochemicals’ diesel to gasoline and diesel hydrocracking technologies, and the Sheer hydrocracking technology to reduce energy are reviewed.
Keywords hydrocracking      process      catalyst      China     
Corresponding Author(s): Xiang Feng,Xiangchen Fang   
Just Accepted Date: 09 August 2018   Online First Date: 17 December 2018    Issue Date: 03 January 2019
 Cite this article:   
Chong Peng,Yanze Du,Xiang Feng, et al. Research and development of hydrocracking catalysts and technologies in China[J]. Front. Chem. Sci. Eng., 2018, 12(4): 867-877.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1768-x
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I4/867
Fig.1  Composition of hydrocracking catalysts [19,20]
Catalysts FC-14/FC-16 Catalyst abroad FC-14/FC-16 Catalyst abroad
Feed oil VGO:heavy diesel= 82:18 VGO
Inlet pressure /MPa 18.0 18.4 18.0 18.1
WTAB /°C 372.6 401.1 373.3 404.0
LHSV /h?1 0.94 1.06 0.89 1.02
Jet fuel /% 45.29 33.91 39.96 33.10
Diesel /% 27.79 31.30 29.21 29.29
Unconverted oil/% 3.36 9.37 7.35 10.00
Jet fuel and diese l/% 73.08 65.21 69.17 62.39
Hydrogen consumption /(Nm3·t−1) 239 259 211 244
Jet Fuel
Dry point /°C 276 263 270 263
Freezing point /°C <?50 <?50 <?50 <?50
Silver corrosion /level 1 1 1 1
Diesel
Flash point /°C >90 >90 >90 >90
Solidification point /°C ?17 +1 ?18 +1
Tab.1  Comparison between FC-14 and the catalysts abroad
Name of feedstock Deep drawing VGO Experiment conditions
Density at 20°C/(g·cm−3) 0.9101 Process, One through single-stage
Distillation /°C Catalyst, FF-36/FC-32/FF-36
IBP /10% 331/385 Total pressure, 16.4 MPa
50% /90% 463/562 Total LHSV, 0.61 h?1
93% 571 Average reaction temperature, 385°C
S/(µg·g−1) 11900 Chemical hydrogen consumption, 2.38%
N/(µg·g−1) 1022
BMCI 41.7
Tab.2  Hydrocracking of pilot scale test conditions
Name of feedstock Deep drawing VGO Name of feedstock Deep drawing VGO
Yield of main products and properties Density at 20°C/(g?cm−3) 0.8125
Heavy naphtha Cetane number index (ASTM 4737-96a) 73.3
Yield/% 28.16 Freezing point°C ?25
Aromatic potential/% 52.1 S/(µg·g−1) <10
Kerosene Residue (>250°C)
Yield /% 19.83 Yield /% 44.07
Density at 20°C/(g·cm−3) 0.8029 Density at 20°C/(g·cm−3) 0.8318
Freezing point /°C <?60 BMCI 11.2
Yandian /mm 28 Residue (>350°C)
Aromatic /v-% 5.5 Yield /% 30.29
Light diesel Density at 20°C/(g·cm−3) 0.8403
Yield /% 13.78 BMCI 10.2
Tab.3  Hydrocracking results of pilot scale test
Name of feedstock Deep drawing VGO
Density at 20°C/(g·cm−3) 0.9101
Distillation /°C 331–600
S /(µg·g−1) 11900
N /(µg·g−1) 1022
BMCI 41.7
Experiment conditions
Catalyst FZC and FF-36/FC-14 and FF-36
Total pressure/MPa 16.5
Total LHSV (for fresh feed) /h?1 0.43
Hydrogen /oil ratio 1000/1200
Process One through single-stage Partial cycle single-stage Full cycle single-stage
Average reaction temperature /°C 393/403 388/398 393/403
Chemical hydrogen consumption /% 2.15 2.09 2.13
Tab.4  Hydrocracking of pilot scale test conditions
Name of feedstock Deep drawing VGO
Process One through single-stage Partial cycle single-stage Full cycle single-stage
Yield & properties of main products
Heavy naphtha
Yield /% 17.97 16.22 20.74
Aromatic potential /% 47.0 49.5 45.1
Kerosene
Yield /% 36.25 35.08 41.03
Density at 20°C/(g·cm−3) 0.8010 0.8025 0.7994
Freezing point/°C <?50 <?50 <?50
Yandian /mm 30 30 30
Aromatic /v-% 4.3 4.1 3.4
Diesel
Yield /% 24.14 30.01 30.90
Density at 20°C/(g·cm−3) 0.8302 0.8329 0.8324
Cetane (practical) 59.2 60.5 59.5
Freezing point /°C ?29 ?26 ?47
S /(µg·g−1) <5 <5 <5
Residue (back oil)
Yield /% 15.28 14.20 0
Density at 20°C /(g·cm?3) 0.8559 0.8523 0.8547
Viscosity index 116 108 105
Freezing point /°C ?36 ?14 ?29
Tab.5  Hydrocracking results of pilot scale test
Feed DAO VGO Mix oil 1 Mix oil 2 Mix oil 3
DAO blending ratio /% ? ? 10 20 30
Density at 20°C /(g·cm−3) 0.9580 0.9111 0.9165 0.9221 0.9255
Distillation /°C ? ? ? ? ?
IBP /10% 365/424 335/385 340/387 345/388 344/387
30% /50% 477/543 406/443 419/448 423/451 427/455
70% /90% ?/? 470/504 476/515 479/533 488/?
95% /EBP (T56%:560) 516/530 (T93%:560) (T92%:542) (T88%:542)
Residue carbon /% 3.80 0.09 0.31 0.52 0.94
Paraffin /% 13.1 21.9 19.7 18.9 18.5
Cycloparaffin /% 20.8 33.5 32.7 32.4 31.4
Aromatic /% 62.0 44.6 45.6 46.5 46.4
Resin /% 4.1 0 2.0 2.2 3.7
S /% 1.52 1.26 1.29 1.30 1.32
N /(µg·g−1) 2428 1352 1473 1601 1732
Ni /(µg·g−1) 6.74 <0.01 0.68 1.33 2.00
V /(µg·g−1) 6.85 0.04 0.71 1.40 2.08
Tab.6  Properties of feedstock
Feedstock Mix oil 1 Mix oil 2 Mix oil 3
Catalyst FF-36/FC-32 FF-36/FC-32 FF-36/FC-32
Reaction temperature Benchmark a/Benchmark b Benchmark a+7/ Benchmark b+5 Benchmark a+18/ Benchmark b+12
Yield of light naphtha /% 3.58 3.78 4.08
Heavy naphtha
Yield /% 19.93 20.06 20.98
Aromatic potential /% 59.9 60.0 62.0
Kerosene
Yield /% 21.92 21.34 21.94
Yandian /mm 21 21 20
Aromatic /v-% 7.6 7.9 11.6
Diesel
Yield /% 21.92 21.34 21.94
Cetane number 61.2 60.0 60.0
Residue
Yield /% 39.80 40.00 38.20
Viscosity index 152 137 159
Tab.7  The experiment results of FHC technology
Feed Middle east VGO Catalytic diesel Mix feedstock
Density at 20°C /(g·cm−3) 0.9160 0.9350 0.9195
Distillation /°C 332?504 183?393 176–506
S:N /% 1.72/0.14 0.38/0.07 1.29/0.11
C:H /% 85.69/12.45 89.44/10.11 87.05/11.55
BMCI 39.4 75.2 56.9
Tab.8  Properties of feedstock
Feed Mix feedstock
Catalyst FF-46/FC-32
Total pressure /MPa 15.3
Total LHSV /h−1 0.61
Average reaction temperature /°C 378
Main products distribution
Light naphtha 3.50
Heavy naphtha 23.62
Kerosene 34.58
Diesel 25.23
Residue 12.42
Tab.9  Main process conditions
Properties of main products Value
Heavy naphtha
Aromatic potential /% 66.7
Kerosene
Density at 20°C /(g·cm−3) 0.8080
Yandian /mm 23
Aromatic /v-% 10.5
Diesel
Density at 20°C /(g·cm−3) 0.8204
Freezing point /°C ?40
S:N /(µg·g−1) <10/<?2
Residue
BMCI 13.1
Yield of liquid C5+ 99.35
Chemical hydrogen consumption 2.97
Tab.10  Properties of products
Fig.2  Process flow diagram of 2.0Mt/a Sheer hydroprocessing unit
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