conference10-15

8/16/2019 conference10-15

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Naphthenic Base Lube Oil Manufacture

Via Hydrogenation Process

Naphthenic Base Lube Oil Manufacture

Via Hydrogenation Process

Reporter ： ZHEN Xinping ,ZHANG Hong

Written by：ZHEN Xinping, ZHANG Hong, QIN Benji, LI Rong

Reporter ： ZHEN Xinping ,ZHANG Hong

Written by：ZHEN Xinping, ZHANG Hong, QIN Benji, LI Rong


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Foreword

Characteristics of naphthenic heavy oil from Karamay

To manufacture transformer oils via hydrotreatingcombined process

To manufacture rubber oil and bright stock oil via highpressure hydrogenation process

Commercialized

1

2

3

4

5


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.

稀油探明面

积

稠油探明面

积

In 1980‘s, about 0.6 billion tons of

reserves of naphthenic base heavy

oil was been discovered in

Karamay.

Naphtenic base heavy oil and

paraffinic base oil distribute

crossly under ground, and lack of

efficient way to separate them.

How to get pure naphthenic base

heavy oil is the most important

precondition for process these two

kinds of crude oil efficiently.


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Naphthenic base heavy oil is high in Acid number, low in yield of its light fraction , and

makes equipment corrosive so bad, makes refinery long time operation not safe, lower

economic benefit, even make lower percentage in refined crude oil.

Pure naphthenic heavy oil is low in solidifying point, is high in cycle-alkane content, is

suitable to manufacture special lube oil. To process naphthenic heavy oil at local field is

easier to make resource utilization effectively.

High-end

PropertiesNaphthenic Heavy

Oil

Da QingCrude

Oil

Density at 20℃, kg/L 0.939 0.861

Acid Value ,mgKOH/g 9.33 0.03

CCR, m% 5.78 3.2

Colloid, m% 19.11 10.22

Wax, m% 2.38 26.14

Ca, µg/g 212


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In Karamay Oil Field, about two thousands sets of mining system

and 6 sets of transporting system to ensure naphthenic base

crude oil mined, transported and refined separately in large scale.

Refining

separately

Storing

separately

Transporting

separately

Mining

separately

High-end

special lube oil

汽油

P ar af f i ni c

b a s e c r u d e

煤油

Naphthenic

base crude oil

Paraffinic

F or N a

ph t h eni

c

Collect

crude

Collect

crude

F or

paraf f i

.


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Foreword




Commercialized

1

2

3

4

5


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Properties

From 9th

district inKaramay

No. 3 Crude oil

in Karamay

Huan Xiling

heavy crude

From Suizhong

361

Merey Crude

oil inVenezuela

Oil classificationHeavy

naphthenic

Medium

naphthenic

Heavy

naphthenic

Heavy

naphthenic

Heavy

naphthenic

Density at 20℃

,kg/m3 928.8 883.4 943.4 943.4 959.3

Viscosity at

50℃, mm2/s229.1 33.01 679 560 206.8

Solidifying point,

℃ -21 -54 -20 -2 -12

Acid value,

mgKOH/g4.72 1.82 3.71 3.33 1.24

Sulfur, % 0.1 0.12 0.26 0.39 2.49

Nitrogen, % 0.1 — 0.41 0.53 0.5

CCR, % 5.5 3.8 4.8 9.1 11.5

Wax, % 1.42 1.05 2.2 1.32 2.4

Colloid, % 23.5 13.3 20.5 21.8 —

aramay


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• Karamay naphthenic crude oil is very typically, a kind of

heavy oil with low sulfur content, high viscosity, high acidvalue, and special in low asphaltene content.

2. Characteristics of Naphthenic Heavy Oil from Karamay

2 Ch t i ti f N hth i H Oil f K


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Distillations from Karamay naphthenic crude oil compared with Huan Xinlinand Suzhong 361 heavy crude oil in viscosity and solidifying point

2. Characteristics of Naphthenic Heavy Oil from Karamay


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Aromatic Hydrocarbons in Karamay naphthenic heavy crude oil islower, equal to the half of the two others, and is suitable to manufactur

.

Distillations from Karamay naphthenic crude oil compared with Huan Xinlinand Suzhong 361 heavy crude oil in CA


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Foreword




Commercialized

1

2

3

4

5

C bi d P


12/30

Combined Process

PCA is transformed to ideal component via HydrotreatingCombined Process

C bi d P


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1. Variation Law about how hydrocarbons generate hydrogen and

effects oxidation resistance in high voltage electric field, that work

as important guideline to design catalyst and combined process

H2 evolution，

μL/minoxidation stability (RBOT)

min

alkane +40（emit） 300

alkane+10% mono-aromatic +30（

emit）

200

alkane+1% di-aromatics -10（

absorb）

280

alkane+1% tri-aromatics +35（emit） 180

alkane+1% tetra-aromatics +34（emit） 150

Combined Process

C bi d P


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lkanes Low

clane High

no-aromatics Moderate

aromatics ModerateA Low

oling, Insulation,

imate adaptation, Longriod operation,

formation carrier, HSE

Combined Process

C bi d P


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2. Modified catalyst used under medium pressure, select Aluminawith suitable pore size as carrier, use Ni-W active component,

increase acidity in catalytic, to improve transformed yield about

aromatics.

Ideal component

Combined Process

Combined Process


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propertiesHydrotreating

combined process

Solvent refining

processimprovement（%）

Mono-aromatic，% 22.6 8.5 +166

Di-aromatics，% 7.0 1.6 +338

H2 evolution，μL/min -25（absorb） +20（emit） +225

3. Hydrotreating combined process to manufacture transformer oil, by means

of opertimizing process condition, controlling hydrotreating reaction extent to

improve mono-aromatics and di-aromatics contents about 2 times to solventrefining process.

Compared data about Aromatic contents and hydrogen evolution intransformer oil made by different process

Combined Process

Combined Process


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Aromatic content in transformer base oil will be controlled effectivelyvia combining this two process; 12 types of products were passed

SIEMENS 、 ABB examination and got their certification.

Combined Process


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Foreword




Commercialized

1

2

3

4

5

high-pressure hydrogenation process


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high pressure hydrogenation process

RHW process is a kind of all hydrogen type high pressure

hydrogenation technique to manufacture naphthenic base lube oil

low aromatic, which can be used to control aromatics saturated and

hydrogenation extent flexiblely.



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1.RHW process integrate advantages from combined catalytic to

process different raw materials. Its turn round period is more than 3

years.

H2

high pressure hydrogenation process



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-

1. Invent catalyst RDW-1 used to hydrotreating de-wax, design Molecular

Sieve Pretreatment process to remove alkanes with large molecule, develop

catalyst formed technique to improve its strength, add active metal in catalyst to

enhance its carbon deposition resistance.

D=0 54nm

0 51 0 57nm

g p y g p



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2. Based on reaction chemical mechanism, saturate aromatics at suitablereaction condition, to get rubber oil and maximum yield.

PropertiesVacuum Dist

line 2 KN4006

Vacuum Distline 3

KN4010

VI 2 25 43 1

ν40℃，mm2/s 51 41 45 88 301 6 143 6

ν100℃，mm2/s 5 648 5 549 13 58 9 866

Flash point，℃ 192 195 214 220

Pour point，℃ 21 < 33 0 7 24

Nitrogen，μg/g 267 8 12 9 733 6 7 1

Sulfur，μg/g 52


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2. More than 20 kinds of rubber oil have been developed successfully,

which PCA is lower than the most strict limitation of I grade (< 0.2mg/kg)

from EU. And Karamay Petrochemical Co. become famous long-term

appointed rubber oil supplier for rubber manufacturer.

独山子石化

SN Products SN Products SN Products

1 K6H 9 KNH4008 17 KGN3510

2 K10H 10 KNH4010 18 KFN3506

3 YT-6 11 KPH6006 19 KFN3508

4 YT-10 12 KPH6008 20 KFN3510

5 KN4006 13 KPH6010 21 KJN360

6 KN4010 14 KP6030 22 KZ50

7 KN4012 15 KP6035 23 KZ160

g p y g p



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3. Based on reaction chemical mechanism, control the extent of reaction, make

aromatic saturated and rings opened to get 150 BS with high viscosity and

viscosity index at same time.

properties DAO 150BS

VI 54 83

ν100℃，mm2

/s 74.19 32.25Flash point (O)，℃ 288 281

Pour point，℃ 3 -12.5

Nitrogen，μg/g 948.8 5.6

sulfur，μg/g 1144 5.7

Saturated

hydrocarbons,% 66.84 92.86

Aromatics,% 33.16 7.14Rotating bomb/min - 360

g y g



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3. In 2010 year, 119 thousands tons of Bright Stock (API II) wasmanufactured and salt out to produce high grade lube oil as important

mixture .


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Foreword




Commercialized

1

2

3

4

5

.


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d i s t i l l a t e

S D A

H y d r o t r e a t i n g

c om b i n e

H yd ro genat

e

Mix &

modified

T r an s f or m er

oi l

R u b b er

oi l

B

ri gh t

st ock

as

ph al t

A complete industrial chain has been formed in Karamay , from

- – .


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Got CHINA PRODUCT QUALITY

ASSOCIATION awards!

In 2003 year, got Quality prizemedal for naphthenic rubber oil

In 2005 year, got the Qualityfor prize medal road asphalt

.


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哈尔滨

长春

沈阳

呼和浩特

天津

银川太原

西宁

拉萨

兰州西安

石家庄

郑州

济南

成都

南京合肥

武汉

上海

杭州南昌长沙贵阳

昆明

福州

广州

香港

南宁台北

海口

乌鲁木齐克拉玛依石化公司

哈萨克斯坦

吉尔吉斯斯坦

巴基斯坦

印度

非洲

越南柬埔寨

韩国

日本

美国

SN High-end special lube oil

Outputs of 2010

（thousands ton）

Global

ranking Data from

1 White naphthenic rubber oil 3401

Nynas

2 Transformer oil 174 2 Doble in USA


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