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Residue Hydrotreating Technology

General situation
  
FRIPP has been involved itself in the development of residue hydrotreating technology since 1980s and had successfully developed S-RHT whole set technology, FZC-XX series catalysts for vaccum residue (VR) hydrotreating and FZC-XXX series catalysts for atmospheric residue (AR) hydrotreating. All these provide most effective solutions for refiners to process and utilize heavy residue reasonably. Up to now, FRIPP¨s VR hydrotreating catalysts and AR hydrotreating catalysts as well as S-RHT technology had been well served the relevant units of Shengli Refinery, Maoming Petrochemical Company (S-RHT unit) and Dalian West Pacific Refining Co. Ltd. and achieved successful run. The capacities of these units are added up to 5.5 Mt/a, which has brought a great amount of economic and social benefits.

Catalysts
  Coping with the reactions of residue hydrotreating process, FRIPP successfully developed two series, four category catalysts: guard catalysts, hydrodemetallization (HDM) catalysts, hydrodesulphurization (HDS) catalysts and hydrodenitrogenation (HDN) catalysts in which FZC-XX series are specified for VR hydrotreating and FZC-XXX series are specified for AR hydrotreating.

Characteristics and functions of FZC-XX series catalysts

Category

Catalysts

Characteristics

Functions


Guard catalyst


FZC-1X series

 
Large pore volume and big pore size

Remove Ni, V, Ca and impurities, protect post-catalysts from coking and decelerate bed-pressure drop going up quickly.

HDM

FZC-2X series

Large pore volume and big pore size

Maximally remove nickel and vanadium

HDS

FZC-3X series

Stronger acidity, smaller pore size, bigger surface area

HDS, HDN

HDN

FZC-4X series

Strongest acidity, small pore, biggest surface area, high metal content

High HDN activity, hydroconversion

  FZC-XX series include four categories, sixteen catalysts, which had been successfully commerciallized in Qilu Petrochemical Company in 1995 and Maoming Petrochemical Company S-RHT unit in 1999.

  FZC-XXX series include three categories (HDM, HDS and guard catalysts) five catalysts, which had been successfully commerciallized in Dalian West Pacific Refining Co. Ltd. in November 1999.

Characteristics and functions of FZC-XXX series catalysts

Category

Catalysts

Characteristics

Functions

Guard cat.

FZC-100

High void rate

HDM, remove impurities, protect post-catalysts from coking and decelerate bed-pressure drop going up quickly

 

FZC-101

 

FZC-102

 

FZC-103

HDM

FZC-201

High pore volume and big pore size and larger void

Maximally remove nickel and vanadium

HDS

FZC-301

Smaller pore size, bigger surface area and larger void

High HDS activity, hydroconversion

 

Commercial S-RHT unit
  A 2.0MT/a S-RHT unit loaded with FZC-XX series catalysts was designed and constructed in Maoming Petrochemical Company in recent years. The unit was aiming at pretreating VR and providing feed for RFCC.

Feedstock, operating conditions and impurity removals

Feedstock

  

  Density20kg/m3

976.9

  viscosity100mm2/s

94.57

  Sm%

3.52

  N, m%

0.26

  CCR, m%

12.64

  Ni+V, μg/g

84.0

Operating conditions

  

  run timehr

5800

  reaction temperature,

380

  hydrogen partial pressureMpa

15.3

  LHSV, h-1

0.20

  gas/oil ratio of first reactorv/v

800

Impurity removals

  

  HDS%

90.86

  HDN%

66.58

  HDCCR%

65.58

  HDMNi+V%

87.48

Properties of main products

Naphtha

  

  Sμg/g

15

  Nμg/g

2

  Boiling range

43~159

Diesel oil

  

  Sμg/g

250

  Nμg/g

120

  Boiling range

197~361

  Cetane number

48

Hydrotreated AR

  

  Density, (20), kg/m3

938.1

  Sm%

0.37

  N, m%

0.10

  CCR, m%

5.00

  Ni+ V, μg/g

12.1

  The data show that the impurities such as sulphur, nitrogen and metal in residue have been effectively removed in Maoming S-RHT unit. The unit contributes not only small amount of naphtha and some high quality light diesel oil with low sulphur, but also about 90% yield of hydrotreated atmospheric residue that is qualified RFCC feedstock. Therefore, S-RHT combined with RFCC has effectively achieved full conversion of sour residue.

Commercial atmospheric residue hydrotreating unit
  
FZC-XXX series catalysts were put into commercial application in Dalian West Pacific Refining Co. Ltd. ARDS unit in November 1999. The unit has A and B two trains of reactors. A train was loaded with imported catalysts and B train with catalysts developed by FRIPP.

Feedstock

density20kg/m3

955.1

viscosity100mm2/s

24.95

Sm%

2.91

N, m%

0.18

CCR, m%

8.19

Ni+V, μg/g

37.21


Properties of hydrotreated AR and impurities removal

Run timehr

7200

Train

A

B

Catalyst

from other provider

FZC-XXX series

AR properties

  

 

  density, (20)kg/m3

0.9219

0.9158

  Sm%

0.45

0.33

  N, μg/g

1307

1098

  CCR, m%

4.29

3.73

  Ni+ V, μg/g

12.39

12.40

Impurity removal

  

 

  HDS%

87.2

96.0

  HDN%

40.3

49.6

  HDCCR%

56.7

62.4

  HDMNi+V%

72.5

72.48

  The data show that the HDS, HDN and HDCCR activities of FZC-XXX series catalysts are better than that of the imported one and the HDM activity of the two trains are almost the same.

  

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