vacumme

2015 CHINA-KOREA-JAPAN PETROLEUM TECHNOLOGY CONGRESS
Research for the EB hydrocracking of residue
and its UCO upgrading
Wu qing
CNOOC Oil & Petrochemicals Co. Ltd.
Beijing
China
OCT. 2015
三
1
FEEDSTOCKS CHARACTERIZATION AND PILOTING CONDITIONS
2
EBULLATED-BED HYDROCRACKING PILOT TESTING RESULTS AND DISCUSSION
3
4
PILOT TESTING FOR THE UPGRADING OF UCO FROM EB HYDROCRACKING PROCESS
TECHNICAL AND ECONOMIC ANALYSIS FOR COMMERCIAL EB PROCESS UNIT
 POOR QUALITY HEAVY OIL OR RESIDUE：
 TRENDS
 FUEL OIL、SOLVENT DEASPHALT PROCESS、DELAY COKE、FCC、
VRDS……
 EB、SLURRY/VCC OR……
 EB HYDROCRACKING PROCESSING：
 RELIABILITY & PRACTICABILITY
 CONVERSION
 UCO DISPOSING
 INVESTMENT & ECONOMY
PREFACE

CNOOC OIL & PETROCHEMICALS CO.LTD.：

CRUDE FROM CNOOC：MOST OF THEM ARE HEAVY CRUDE

HUIZHOU REFINERY 1ST PHASE: DELAYED COKE ( 4200kt/a )

HUIZHOU REFINERY 2nd PHASE: VRDS ( 4000kt/a )+FCC((4800kt/a )
 EB HYDROCRACKING PROCESS：

OPTIMIZATION FOR THE OVERALL PROCESS INTEGRATION OF 1 ST PHASE AND 2ND PHASE OF
HUIZHOU REFINERY IN THE DAYA BAY PETROCHEMICAL INDUSTRY ZONE

KEY DESIGN DATA SUCH AS CONVERSION,YIELD , PRODUCT DISTRIBUTION AND QUALITY, CATALYST
CONSUMPTION

UCO DISPOSE, EXISTED UNIT REVAMP, EB UNIT CAPACITY AND INVESTMENT ……
 PILOT TESTING

EB PILOT TESTING FOR RESIDUE IN USA

PILOT TESTING FOR UCO FROM EB UNIT IN CHINA
 COMMERCIAL EB PROCESS UNIT

INVESTMENT & ECONOMY
4
1、FEEDSTOCKS CHARACTERIZATION AND PILOTING CONDITIONS
1.1、FEEDSTOCKS FOR PILOT TESTING：
 RESOURCES：MIXED HEAVY OIL FROM VACUUME RESIDUE、FCC SLURRY、VGO OF
THE 3RD DRAW OUT LINE FROM VACUMME TOWER
 SAMPLING DATE：JULY,3-4,2013
 MIXED CRUDE ：PENLAI：PAZFLOR：NEW WENCHANG：VAN GOGH=45%：30%：15%：
10%
 THE OIL SAMPLES WERE SHIPPED TO USA AT 15,JULY,2013
1.2 、CATALYST SELECTION
 THE ORIGINAL CATALYST WAS “A*31” RECOMMENDED BY “A” COMPANY IN
CASE STUDY OF THE PROPOSAL
 ANOTHER CATALYST TYPE NAMED AS “A**20PEM”WAS SELECTED TO REPLACE THE
ORIGINAL ONE IN ORDER TO
THE MORE HIGHER METAL CONTENT FEEDS.
5
1、FEEDSTOCKS CHARACTERIZATION AND PILOTING CONDITIONS
1.3、 FEEDSTOCK COMPARSION BETWEEN SAMPLES FOR PILOT TESTING AND PROPOSAL
ITEMS*
API GRAVITY
H
N
S
CCR
METAL
CONTENTS：
Ca
Ni
V
Na
∑(sum)
ASPHALTENE
(C7 INSOLUBLE)
UNIT
w%
w%
w%
w%
ppm
SAMPLES FOR PILOT
TESTING
9.9
11.5
1.02
0.61
14.95
COMMERCIAL EB UNIT
PROPOSAL
12.4
11.08
0.85
0.46
16.2
321
55
9.4
5.7
391
12.8
78.9
2.8
10
104.5
2.43
1.2
w%
•
Very high content of
nitrogen( >1%),that means very
difficulty for cracking
•
Very high content of
Calcium(321ppm)，that means it
will have negative effects on the
catalyst performance and
consumption
*DETAILED ANALYSIS WERE ALSO CARRIED OUT
1.4、PILOTING UNIT

A EBULLATED-BED PILOT UNIT

TWO-STAGRE EBULLATED BED CONFIGURATION WITH INTERSTAGE
SEPARATION

THE VOLUM OF EACH REACTOR IS 3 LITRE

THE LOADING QUANTITY OF EACH REACTOR IS 1.5 LITRE
6
CNOOC OIL & PETROCHEMICALS CO.LTD.
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.1、RESULTS AND DISCUSSION
Expected
R1 WABT R2 WABT conversion Actual
Condition
Days
%slurry
LHSV
1A
1-2
10
0.38
413
413
50
40
1B
4-6
10
0.38
419
424
62
47
2
8-9
10
0.31
427
432
65
64
2B
11-12
15
0.31
427
432
65
64
3
4
14-16
18-20
10
10
0.28
0.245
424
427
429
432
75
75
64
71
CONDITION 1 (1A & 1B):
THE MEASURED CONVERSION WAS MUCH LOWER THAN EXPECTED
SO THE OPERATION CONDITIONS WERE MODIFIED
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.2、RESULTS AND DISCUSSION
 CONDITION 2( 2 & 2B)
• Higher reaction temperature, Lower LHSV(0.31) ,Conversion reached 64%，
operation went very well but more coke
• For condition named 2B, The slurry rate was increased from 10% to 15% in an
attempt to mitigate the sediments increase while the vacuum residue feed
rate wan decreased to keep the same total LHSV as 0.31h-1
Condition
Days
% slurry
LHSV
h-1
R1 WABT R2 WABT Actual
°C
°C
conversion
1A
1-2
10
0.38
413
413
40
1B
4-5-6
10
0.38
419
424
47
2
8-9
10
0.31
427
432
64
2B
11-12
15
0.31
427
432
64
3
14-16
10
0.28
424
429
64
4
18-20
10
0.245
427
432
71
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.3 RESULTS AND DISCUSSION
•
•
•
•
CONDITION 3
Compared to the condition 2, at the same conversion( that is 64%), a
longer residence time in the reactor can lead to a lower sediments
concentration.
The sediments were at 0.55%,to be compared with 0.60% in condition 2A.
That means that the effect of a longer residence time is limited.
The slurry rate was back to 10%,because of the reason having in our mind
that it could not be available is so much large quantities in the future
commercial unit.
Condition
Days
% slurry
LHSV
h-1
R1 WABT R2 WABT
Actual
°C
°C
conversion
1A
1-2
10
0.38
413
413
40
1B
4-5-6
10
0.38
419
424
47
2
8-9
10
0.31
427
432
64
2B
11-12
15
0.31
427
432
64
3
14-16
10
0.28
424
429
64
4
18-20
10
0.245
427
432
71
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.4 RESULTS AND DISCUSSION
•
•
•
Condition 4
The objective of this condition was to achieve the minimum
conversion at 70%.
The LHSV of 0.245h-1 was the minimum space velocity that can be
operated in the pilot unit .
Condition
Days
% slurry
LHSV
h-1
R1 WABT R2 WABT Actual
°C
°C
conversion
1A
1-2
10
0.38
413
413
40
1B
4-5-6
10
0.38
419
424
47
2
8-9
10
0.31
427
432
64
2B
11-12
15
0.31
427
432
64
3
14-16
10
0.28
424
429
64
4
18-20
10
0.245
427
432
71
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.6、RESULTS FOR HDS AND HDN
2.5、RESULTS FOR THE CONVERSION OF VR AND CCR
90.00
80.00
540C+ Conversion
80.00
CCR Conversion
70.00
70.00
60.00
%
%
60.00
50.00
HDS
50.00
HDN
40.00
30.00
40.00
20.00
10.00
30.00
0
5
10
Period
15
0
20
•
AT LOWER CONVERSION LEVEL：THE CCR
CONVERSION IS REMARKABLY HIGHER THAN
THE VR CONVERSION；
•
AT HIGHER CONVERSION LEVEL：THE TWO
•
•
CONVERSIONS ARE ABOUT AT THE SAME LEVEL
•
THAT MEANS THE INTEGRATED PROCESS OF EB
AND DELAYED COKE IS VERY FAVORABLE FOR
REFINERY (!!!)
•
5
10
Period
15
20
EXCELLENT FOR HDS :ABOUT 88 %
A WEAK DEACTIVATION OF CATALYST:
COMPARED TO THE HIGHER METAL
CONTENTS FEED ( CLOSE TO 400
WPPM), THE DEACTIVATION IS QUITE
MODERATE!
HDN, ABOUT 20-40%
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.7、RESULTS FOR HDM ( METALS REMOVAL)
2.8、RESULTS FOR CHEMICAL HYDROGEN CONSUMPTION
90.00
80.00
70.00
HDNi
HDCa
%
60.00
50.00
40.00
30.00
20.00
0
•
•
•
5
10
Period
15
20
EXCELLENT FOR NICKEL REMOVAL: THE HDNi IS
ABOUT 80% ( FROM APPROXMIATELLY 75 TO 82
WT%) , ABOUT 15 WT% HIGHER THAN OTHER
TYPICALLY FEEDS .
THE CALCIUM REMOVAL IS LOWER: THE HDCa IS
FROM 45% OF STARING TO THE 25%, AVERAGE IS
ONLY ABOUT 35%；
THE MAJORRITY OF CALCIUM REMAINS IN THE
UNCONVERTED OIL! That may corroborate the
result of that the catalytic deactivation is smaller
than suspected.
•
•
•
The chemical hydrogen consumption is
approximately from 1.5 TO 2.0 WT% ( or
equivalently 168 to 224 NM3/M3)
The higher conversion , the higher
chemical hydrogen consumption
The higher slurry rate , also the higher
chemical hydrogen consumption
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.9、RESULTS FOR THE SEDIMENTS COMPARED TO THE CONVERSION
(PRODUCT STABILITY)
80.00
0.80
540C+ Conversion
70.00
0.70
IP-375
60.00
0.60
%
50.00
3
2
40.00
0.50
4
0.40
2B
30.00
0.30
20.00
0.20
1A/B
10.00
0.10
0.00
0.00
0
•
•
•
•
CONDITION
CONDITION
CONDITION
CONDITION
5
10
Period
15
20
2: HIGHER SEDIMENTS
2B：LOWER SEDIMENTS WHILE HIGHER SLURRY RATE
3 : LOWER SEDIMENTS,LOWER LHSV
4: HIGHER SEDIMENTS, HIGHER CONVERSION( about 71%)
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.10、RESULTS FOR ASPHALTENE CONVERSION


LEFT:
•
•
C5 asphaltene conversion is consistently higher than C7’s (around 50wt% to 40wt%)
The asphaltenes will concentrated in the unconverted products, so it is not favourable
behaviour for the product stability.
RIGHT:
• There is a good correlation between nitrogen and C7 asphaltenes reduction
• Most difficult nitrogen is concentrated in the heavy asphaltenes
• A higher nitrogen content feed, a necessarily lower conversion of asphaltenes.
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.11、RESULTS FOR THE YIELDS OF NORMALIZED
50.0
45.0
VGO
40.0
35.0
Resid
Yield
30.0
25.0
20.0
15.0
Diesel
10.0
5.0
Naphtha
0.0
30.0
40.0
50.0
Conversion
60.0
70.0
 The yields of H2S, NH3 and H2O are calculated based on the difference in the level
of S,N and O in the liquid products and feed.
 The liquid yields correlate well with the level of conversion.
 when the conversion is around 70%, the liquid products of naphtha, diesel and VGO
are 9%,27% and 38%,respectively.
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.12、RESULTS FOR OTHERS
TOTAL SEDIMENTS BY
HOT FILTRATION
VR
SLURRY
TOTAL
FEED
（VR+SLURRY+HVGO）
BOTTOM
OF
SEPARATOR
<0.01
0.32（ash:cat
fines）
0.03
0.6
PENTANE
INSOLUBL
ES
9.56
12.5
HEPTANE
INSOLUBL
ES
2.43
10.8
TOLUENE
INSOLUBLE
S
0.01
0.39
9.38
3.11
5.0
2.4
FEED
VGO
UCO
17.9
50.2
29.3
AR
30.0
38.1
29.1
0.04
RE
44.7
9.5
32.1
0.25
AS
2.1
2.2
8.8
LOSS
5.4
2.2
0.7
FEED
COLLOIDAL INDEX
0.25
SA
UCO
1B
0.56
2
0.59
2B
0.57
4
0.62
 TBP ANALYSIS, SEDIMENTS, SARA, COLLOIDAL INDEX FOR STABILITY
 The colloidal index is one kinds of indicator for the product stability
 The higher colloidal index, the lower the product stability
 Colloidal index = ( saturates + asphaltenes ) / ( aromatics + resins )
 CATALYSY SELECTION AND ANALYSIS
 FRESH CAT ( PHYSICAL AND CHEMICAL PROPERTIES)
 SPENT CAT (SEM,ETC)
2、EBULLATED-BED HYDROCRACKING PILOT TESTING：
RESULTS AND DISCUSSION
2.13、SUMMARY
 Special feed: higher contents of nitrogen and calcium , more difficultly for
cracking or to be converted.
 Catalyst selection must be taken into account of the negative effect of
higher calcium and nitrogen contents in the feeds.
 Main parameters such as HDS, HDN, HDCCR could reach to 80-90%,
40% and 65%,respectively,and there are higher than suspected.
 The minimum CCR removal of 60% could be reached by controlling the
rate of catalyst consumption or replacement.

Recommendation:
 slurry rate 10%; LHSV 0.25 h-1；Suited other operation conditions:
 Conversion is setted at 70% and the chemical hydrogen consumption is 1.6%, the liquid
product yields of naphtha, diesel and VGO could reach at 9%,27% and 38%,respectively.
3、PILOT TESTING FOR THE UPGRADING OF UCO
FROM EB HYDROCRACKING PROCESS
OBJECTIVE：TO SEEKING THE VARIETIES OF THE YIELDS AND QUALITY OF THE
PRODUCTS FROM DELAYED COKING UNIT BY USING VR MIXED WITH UCO FROM EB
UNIT AS FEEDSTOCK
3.1 FEEDS：
 VACUUM RESIDUE FROM HUIZHOU
REFINERY：
 Sampling Date：March,24,2014
 Mixed Crude Processed：
Penlai:Pazflor:New
wenchang:New
xijian=38%:25%:15%:10%
 UCO：Be shipped back from EB Unit
in USA to China at the data of
March ,18,2014.
 3.2 Piloting process unit:
 Two Heating Furnace – one Tower 18
 Capacity: 1-4 kg/hr
3、PILOT TESTING FOR THE UPGRADING OF UCO FROM EB
HYDROCRACKING PROCESS
3.3、Feeds characterization compared
density，g/cm3
Element analysis,%
C
H
N
S
CCR,%
Metal contents, ppm
Ni
V
Fe
Ca
SARA composition
S%
A%
R%
A%
3.4、Delayed Coke Piloting Unit :Operation Conditions
VR
UCO
1.001
0.997
87.33
11.50
1.02
0.61
14.95
87.28
11.26
1.49
0.195
18.32
55
9.4
6
321
34
7.0
21
742
9.56
30.0
44.7
2.1
29.3
29.1
32.1
8.8
Pressure/MPa
Heating
/℃
Furnace
0.17
Temp(outlet)
495
Preheating Temp of the Feed /℃
350
Coking Tower Temp(inlet)/℃
495
Feed Rate /g•h-1
2000
Water rate (per total feeds)，%
5~6
19
3、PILOT TESTING FOR THE UPGRADING OF UCO FROM EB
HYDROCRACKING PROCESS
3.5、YIELDS：(4 sets data corresponding to different
UCO concentrations of 0%,15%,25%,35%,respectively)
FEEDS
100%VR
85%VR+15%UCO
DRY GAS
3.77
4.15
LPG
2.70
2.83
C5～180℃
13.79
17.18
180℃～350℃
30.13
30.84
＞350℃
29.35
24.31
COKE
20.24
20.59
LOSS
0.02
YIELDS,m%
SUM
100.00
0.09
100.00
C5～350℃Yields，m%
43.92
48.02
C5+ Yields，m%
73.27
72.33
20
3、PILOT TESTING FOR THE UPGRADING OF UCO FROM EB
HYDROCRACKING PROCESS
3.6、Quality and Conclusion
QUALITY COMPARED
UCO%
0
15
25
35
CONCLUSION:
1、NAPHTHA:
DENSITY （ 20 ℃ ）
0.7371
0.7328
0.7448
0.7405
SULFUR/gg-1
1097
795
786
739
NITROGEN/gg-1
164.6
184.5
204.9
225.7
RON
66.6
66.2
64.8
61.2
0.8531
0.8509
0.8499
0.8438
SULFUR/gg-1
2800
2500
1941
1698
NITROGEN/gg-1
1876
1703
1696
1612
C.I.
49.6
53.3
53.8
47.5
/g.cm-3
 UCO IS ONE KIND OF GOOD FEEDS FOR DCU
 UCO WILL IMPROVE THE BEHAVIOUR OF 100% VR
IN DELAYED COKING PROCESS.
 THE INTEGRATED PROCESS OF EB
2、LCO：
HYDROCRACKING AND DELAYED COKE IS A
DENSITY （ 20 ℃ ）
/g.cm-3
OPTIMIZED PROCESS ,AND ALSO, A POTENTIAL
EMULATIVE PROCESS FOR HEAVY OIL UPGRADING
3、COKE：
WATER/wt%
0.78
0.76
0.71
0.64
CARBON/wt%
89.5
90.3
89.9
90.9
2
1
4
1
VOLATILITY/wt%
8.88
8.23
8.42
7.86
DENSITY/gcm-3
1.38
1.38
1.38
1.38
ASH/wt%
0.99
0.84
1.09
0.69
SULFUR/wt%
0.59
0.54
0.50
0.46
21
4、 TECHNICAL AND ECONOMIC ANALYSIS FOR COMMERCIAL EB PROCESS UNIT
4.1、OVERLOOKING：
4.2、OPERATION CONDITIONS
MAIN DESIGNING CONDITIONS：
 2200KT/a（2000kt/a VR+200kt/a
ITEMS
REACTORS
FCC SLURRY）
 CONVERSION FOR VR:68%
 SINGLE TRAIN
 RUNNING CYCLE:4 years /cycle
2
0.25
SPACE VELOCITY，LHSV,hr-1
432
AVE.TEMP OF 1ST REACTOR，WABT ,℃
 ANNUALLY OPERATION TIMES: 8400
hours per year
PARAMETERS
437
AVE.TEMP OF 2ND REACTOR,WABT, ℃
18.2
PRESSURE（INLET OF 1ST REACTOR），MPag
MAIN CONSTITUENT PARTS： REACTION
SECTION、FRACTION SECTION、CATALYST
DISPOSING UNIT,ETC.
68
CONVERSION (545℃+) ，wt%
HDS，wt%
79.8
HDN，wt%
37.6
HDCCR，wt%
60.0
ENERGY CONSUMPTION： 26kg EO/t
GENERAL LAYOUT： 26760 m2
0.50
CATALYST DISPLACEMENT,KG/T
22
3.18
CATALYST CONSUMPTION, T/DAY
入
方
出
方
4、 TECHNICAL AND ECONOMIC ANALYSIS FOR COMMERCIAL EB PROCESS UNIT
4.4、PRODUCTS QUALITY
4.3、MATERIAL BALANCE
MATERIALS
NAME
CAPACITY
KT/a
w%
VACUMME
RESIDUE
2000.00
90.91
FCC SLURRY
200.00
9.09
44.2
2.01
2244.2
102.01
21.1
0.96
HYDROGEN
SUM
H2S+NH3
FUEL GAS （
+LPG)
105.1
4.78
PURPOSE OR
OUTLET
RANGE(TBP), ℃
DENSITY(20℃), g/cm3
176.2
8.01
LIGHT
HYDROCARBO
N RECOVERY
UNIT
360〜540
>540
738.0
871.0
950.0
998.0
0.2
25.7
CETANE NUMBER
43
S, w%
80μg/g
200μg/g
800μg/g
0.40
N, w%
150μg/g
1500μg/g
0.6
1.58
12.0
11.4
62
V, μg/g
＜1
7
Ca, μg/g
20
799.5
36.34
2ND FCC UNIT
1ST DELAY
COKING UNIT
102.01
175〜360
2
VGO,360-545℃
2244.2
C5〜175
Ni, μg/g
29.30
SUM
UCO
H, w%
644.6
22.62
VGO
UNIT
1ST PHASE
HYDROTREATING
UNIT
497.6
DIESEL
HYDROTREATING
Diesel,175360℃
UCO,545℃+
NAPHTHA
CCR, w%
1ST PHASE
Naphtha,C5175℃
ITEMS
23
900
4、 TECHNICAL AND ECONOMIC ANALYSIS FOR COMMERCIAL EB PROCESS UNIT
4.5 THE FINANCIAL INDEX ANALYSIS FOR 2200KT/a EB PROCESSING UNIT
ITEMS
UNIT
NO PROJECT
HAVING PROJECT
DELTA
REMARKS
一
FINANCE EVALUATING
PARAMETERS
1
TOTAL INVESTMENT
10K YUAN
5364796
5591538
226742
2
Total investment for App.
10K YUAN
4556380
4780338
223958
4
SELLING INCOME
10K YUAN
15821479
16020005
198526
AVE.
5
TAX AND PLUS
10K YUAN
1525939
1569598
43659
AVE.
6
ADDED-VAULE TAX
10K YUAN
876942
901479
24537
AVE.
7
TOTAL COST
10K YUAN
12841876
12906339
64463
AVE.
8
TOTAL PROFIT
10K YUAN
576722
642590
65867
AVE.
9
INCOME TAX
10K YUAN
144181
160647
16467
AVE.
10
PROFIT AFTER TAX
10K YUAN
432542
481942
49401
AVE.
11
COMPLETE OPERATION COST
YUAN/T
325.04
338.87
13.84
AVE.
12
CASH COST
YUAN/T
161.55
168.76
7.20
AVE.
13
PROFIT PER FEED OF TON
YUAN/T
191.94
213.84
21.90
AVE.
二
PROJECT ECONOMIC INDEX
1
IRR
％
10.01%
10.54%
23.81%
AFTER INCOME TAX
2
NPV
10K YUAN
-895279
-767969
127311
24
IBID,DISCOUNT13%
IBID(contain 3 years of
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