fcc汽油分娩国iv标准干净汽油-

I

will

divide

my

presentation

into

following

5parts.4研究背景1235技术路线烯烃定向转化/辛烷值恢复催化剂选择性加氢脱硫催化剂组合工艺及其应用提纲6其他相关问题7结论To

control

air

pollution

caused

by

more

and

more

gasoline

powered

vehicles,

China

government

has

speeded

up

the

pace

to

update

theregulations

on

transportation

fuels

in

recentyears.

According

to

the

Environmental

Protection

Agency

of

China,

by

the

end

of

2010,

the

standard

China

IV

thatis

almost

equivalent

to

EuroIV

will

be

enacted,

and

then

China

V

will

follow

very

quickly.

Generally

speaking,

producing

gasoline

with

low

olefin

and

sulfur

contents

will

be

an

inevitable

trend.生产清洁汽油的意义欧III2000欧IV2005国III2007国IV2013(预测)国V(预测)硫(ppmw)<150<50<150<50<10苯(v%)<1.0<1.0<1.0<1.0<1.0芳烃(v%)<42.0<35.0<35.0<35.0<35.0烯烃(v%)<18.0<18.0<25.0<28.0<25.0氧(m%)<2.7<2.3<2.7<2.3<2.3清洁汽油标准的必然发展趋势—低烯烃和超低的硫含量The

difficulty

for

most

of

the

Chinese

refineries

to

producing

clean

gasoline

lies

in

that

FCC

gasoline

takes

ashare

of

about

80%in

commercialgasoline

pool.

In

typical

FCC

gasoline,

sulfur

content

is

as

high

as

300-600

ppm,

olefin

content

is

as

high

as

40%!

So,

reducing

the

sulfur

andolefin

contents

of

FCC

gasoline

is

the

main

focus

of

clean

gasoline

productions.硫我国CC汽油的组成烯烃芳烃300～600

ppmw约 40

v%10～20

v%CC36%13%国外17%34%78%5%0.5%中国14.5%36%CC汽油异构化汽

重油整汽

油烷基化

汽油生产清洁汽油的意义□清洁汽油生产的关键——降低CC汽油中硫和烯烃的含量美国和中国汽油调合组分的构成For

this

purpose,

many

processes

have

been

developed.

These

processes

can

be

divided

into

two

types,

i.e.,

in-situ

FCC

upgrading

and

post-hydrotreatment

upgrading.两种CC汽油改质技术□催化裂化“原位”改质技术□后加氢处理改质技术By

using

speciallydesigned

catalysts

suchRFG,

TOM/GORand

LBO

or

revamping

FCC

units

by

implementing

another

riser

reactor,

in-situupgrading

can

decrease

olefin

content

by

15-20

v%and

remove

about

30%

sulfur

in

FCC

gasoline.The

shortages

of

the

various

in-situupgrading

technologies

are:

difficult

to

achieve

higher

desulfurizationand

withlarge

loss

in

gasoline

yield.化裂化原位改质技术□降烯烃 化剂□RG,

TOM/GOR,

LBO

系列 化剂□烯烃减少6-10

v%,脱硫率20-30%□两段提升管和辅助提升管□烯烃减少20

v%,脱硫率30%□不足□很难达到更高的脱硫率□汽油的收率有较大的损失后加氢处理改质技术□选择性加氢脱硫□典型工艺:Scnining,

Prime-G+,

RSDS,

RS,

OCT-M□适合于低烯烃含量的CC汽油□加氢脱硫和辛烷值恢复组合□典型工艺:Octgin,

OT,

RIDOS□适合于低到中等烯烃含量的CC汽油，具有良好的辛烷值恢复能力□不足:高脱硫率下汽油收率较低Based

on

the

above

discussion,

we

can

conclude

that

the

difficulty

inupgradingFCC

gasoline

lies

in

the

contradictions

between

gasoline

qualityspecifications

and

process

requirements.汽油质量标准 工艺要求深度加氢脱硫矛盾保持辛烷值降烯烃矛盾保持辛烷值提高辛烷值矛盾汽油产率催化剂的稳定性CC汽油加氢改质技术开发的难点To

overcome

the

above

difficulty,

we

developed

a

combined

process

consisting

of

a

hydroisomerization

and

aromatization

catalyst

for

reducingolefincontent

and

recovering

octane

and

a

selective

hydrodesulfurizationcatalyst.

Our

aim

is

to

develop

a

process

for

producing

China

IV

cleangasoline

from

FCC

gasoline

with

high

olefin

and

sulfur

content.CC汽油改质的技术路线目标催化剂降烯烃和脱硫工艺相组合生产国IV标准的清洁汽油工艺加氢异构化和芳 选择性加氢脱硫构化工艺How

to

reduce

olefin

content

of

FCC

gasoline

without

causing

octane

loss?

The

key

is

to

maximize

catalyst

hydroiosmerizationand

aromatizationactivity

to

transfor

olefins

into

two-

or

three-branched

isoalkanes

and

aromatics

while

minimizing

the

saturation

of

olefins.

This

requires

that

thecatalyst

to

have

suitable

acidity

to

provide

both

hydroisomerization

and

aromatization

activity

and

pore

size

large

enough

for

the

formation

of

two-orthree

branch

isomerization.加氢异构化和芳构化催化剂RON＝93RON＝54单支链异构ctlyst＋H2芳

构RON＞100√RON＝0加×氢饱和RON＝42双-√或三支链异构√要求:酸性:适宜强度，具有加氢异构和芳构化活性，但不至于使催化剂快速结焦失活孔径: 足够大，使在孔道内能形成双-或三支链异构体Bycombining

ZSM-5

that

has

excellent

aromatizationactivityand

SAPO-11

that

has

excellent

hydroisomerization

activity,

we

obtained

acompsoite

catalyst.

As

expected,

this

catalyst

shows

good

isomerization

and

aromatizationactivity,

but

suffers

fromquick

deactivation

because

ofthe

too

strong

acidity

of

the

ZSM-5

and

weaker

hydroisomeization

activity

because

of

smaller

pore

size

of

SAPO-11.具有加氢异构化和芳构化活性的复合催化剂以ZSM-5为核，SPO-11为壳的复合材料具有优异异构化功能的SPO-11具有优异芳构化功能的ZSM-5酸性较强容易失活孔径较小异构活性差Later

on,

we

developed

a

combined

steamingand

organic

acid

treatment

method

to

adjust

the

acidity

of

the

ZSM-5

zeolite

in

the

composite.First,

we

use

steamingto

dealuminate

the

zeolite,

but

steamingisasevere

operation

and

thus

can

excessively

reduce

strong

B

acid

sites

and

theresulting

extraframework

aluminium

species

causes

blockage

of

zeolite

pore

channels.

So,

we

further

treat

the

zeolite

with

an

organic

acid

torecover

partof

B

acid

sites

and

clean

the

pore

channel.

As

I

will

introduce,

the

modified

ZSM-5

shows

excellent

aromatization

activity

andstability.ZSM-5沸石的酸性调变□水热处理和复合酸处理相结合强B酸位易使催化剂过失度活水热处理使强B酸进位一步用复合酸处理，使大量减少，孔道堵塞

适度增加，孔道疏通++++++++

++++++++水热处理+

复合酸处理framework

Siframework

Al+

extraframework

Alrealuminated

AlTo

enlarge

the

pore

size

of

SAPO-11

in

the

composite,

we

developed

a

novel

alcohol-thermal

method

to

synthesize

SAPO-11

instead

of

theconventional

hydrothermal

synthesis.

Byadjusting

the

alcohol-water

ratio,

we

can

control

the

hydrolysis

degree

of

TEOS.

Bythis

way,

TEOS

isincorporated

into

the

zolite

framework

withdifferent

numbers

of

organic

groups

and

thus

the

average

pore

diameter

of

the

resultingSAPO-11

canbe

tuned

from

0.6

nmto

0.8-1.0

nm.SPO-11的孔径调变0.6nm0.8~1

nmH2OSi(C2H5O)4Si(C2H5O)n(OH)4-nC2H5OH

H2OSPO-11的孔径调变传统水热合成Si(C2H5O)4

Si(OH)4水-醇合成TEOS正硅酸乙酯(TEOS)After

modification

with

the

above

two

methods,

the

composite

derived

catalyst

show

interesting

upgrading

performance.

It

decreases

the

olefincontent

of

FCC

gasoline

by

18

v%

and

the

gasoline

yield

is

as

high

as

98%.

Moreover,

these

results

are

achieved

with

only

small

loss

in

gasolineresearch

octane

number.

However,

The

desulfurization

ratio

is

not

so

high,

with

the

sulfur

content

of

the

upgraded

gasoline

being

as

high

asregulated

by

China

IV.So,

the

question

how

to

further

decrease

sulfur

contentof

FCC

gasoline

arises.饱和烃烯烃芳烃硫(ppmw)RON产率

(wt%)原料45.339.615.137091.5-产品(500

h)56.121.521.810591.098.5√优异的降烯烃和保辛烷值能力X 较低的脱硫率—71%具有烯烃异构和芳构功能的复合催化剂As

we

know,

olefin

saturation

and

hydrodesulfurizationreactions

take

place

on

metal

sulfide

particles

supported

on

alumina.

The

rim

sites

areactive

for

both

hydrogenation

ofolefins

and

hydrodesulfurization

of

sulfur-containing

compounds,

while

edge

sites

are

only

active

for

HDS.Obviously,

the

route

to

achieve

highly

selective

HDS

is

to

maximizing

the

ratio

of

edge

sites.

Increasing

the

stacking

of

metal

sulfide

is

good

forselectivity,

but

gives

rise

to

lower

activity;

increasing

the

dispersion

of

metal

sulfide

gives

highactivity,

but

results

in

lower

selectivity.

This

suggeststhat

to

achieve

both

higher

desulfurizationratio

and

higher

selectivity,

there

must

be

a

compromise

between

dispersion

and

stacking

of

metalsulfide.高选择性加氢脱硫催化剂金属硫化物中心Edge位

HDS实现高选择性加氢脱硫的路线：最大限度地提高Edge位的比例高分散度高活性低选择性高堆积度高选择性低活性协调的分散和堆积平衡选择性和活性Rim位加氢＋HDS

l2O3The

resulting

catalyst

shows

very

good

selective

HDS

performance

for

bothfull

range

FCC

gasoline

and

heavier

fraction

after

cutting,

giving

aHDS

ratio

of

77-80%

for

full

range

FCC

gasoline

and

a

HDS

ratio

of

82-87%

for

heavier

fraction,

while

the

olefin

saturation

ratio

is

only

15-20%!高选择性加氢脱硫催化剂饱和烃烯烃芳烃硫(ppmw)RON损失原料133.649.317.1900–全馏分产品(500

h)41.641.217.21800.7切割-调和产品(500

h)40.642.117.31170.6原料245.339.615.1380–全馏分产品(500

h)53.331.415.3850.8切割-调和产品(500

h)51.133.715.2700.6烯烃饱和率

15-20%全馏分脱硫率

77-80%切割-调和脱硫率

82-87%RON损失

0.6-0.8After

obtaining

the

two

catalyst,

the

remaining

work

is

how

to

configure

the

process,

i.e.,

put

which

catalyst

in

the

first?加氢异构/芳构化催化剂？选择性加氢脱硫催化剂选择性加氢脱硫催化剂加氢异构/芳构化催化剂工艺配置Using

a

full

range

FCC

gasoline

as

feedstock

and

putting

the

hydroisomerization

catalyst

in

the

first

reactor

and

the

selective

hydrogenationcatalyst

in

the

second

reactor,

we

found

that

while

having

surprisingdesulfurizationability,

the

process

suffers

froma

big

loss

inRON

because

ofthe

excessive

saturation

of

olefins!工艺(两个100

mL等温反应器串联)饱和烃烯烃芳烃RON硫(ppmw)产率

(wt%)原料43.642.613.892.4403-产品(450

h)70.812.616.686.53998.4SelectivehydrodesulfurizationHydrogenUpgraded

productHydroisomerizationand

aromatizationFCC

gasoline烯烃过度饱和,RON损失

5.9!However,

if

we

put

the

selective

catalyst

in

the

first

reactor,

the

results

are

much

better.

Particularly,

the

desurization

ratio

is

as

high

as

87%,

butthe

RON

loss

is

still

a

little

bit

large!饱和烃烯烃芳烃RON硫(ppmw)产率

(wt%)原料44.240.815.091.8365-产品(1500h)53.427.019.690.64898.5HydrogenSelectivehydrodesuluriztionCCgsoline工艺(两个100

mL等温反应器串联)Hydroisomeriztion

ndroUmptgirzdteidonproduct脱硫率

87%,烯烃减少14

v%,RON损失1.2Whythe

direct

upgrading

of

full

range

FCC

gasoline

cannot

give

satisfactory

results?By

analyzing

the

distributions

of

sulfur

and

olefins

in

the

full

range

FCC

gasoline,

we

found

that

sulfur

mainly

exists

in

the

heavier

fraction

with

itsinitial

boiling

point

higher

than

70

oC,

while

the

lighter

fraction

with

its

boilingpoint

belowis

almost

sulfur

free.

This

means

that

it

is

unnecessary

tohave

the

light

fraction

hydrotreated.

Otherwise,

agreat

loss

in

RON

will

happen.However,

for

the

heavy

fractions,

the

olefin

content

is

comparable

to

that

regulated

by

China

IV,

but

its

sulfur

content

is

very

high.

Of

course,

itmust

be

deeply

desulfurzied

to

remove

the

excessive

sulfur.

However,

this

will

cause

theObviously,

to

achieve

better

upgrading

performance,

we

need

to

split

full

range

FCC

gasoline

into

a

light

fraction

and

a

heavier

farction!基于馏分切割的CC汽油加氢改质组合工艺国IV预测国V硫(ppmw)<50<10烯烃(v%)<25<25CC汽油中硫和烯烃的分布确定合适的馏分切割温度，对达到理想的改质效果至关重要Based

on

the

above

discussion,

finally

we

proposed

a

FCC

hydro-upgrading

process.

The

first

step

is

to

split

full

range

FCC

gasoline

intoalightfraction

and

heavier

fraction.

For

the

former,

no

further

treatment

is

needed.

However,

the

heavier

fraction

should

be

treated

using

the

selectiveHDS

catalyst

in

the

first,

and

thenfurther

treated

using

the

hydroisomerization

and

aromatizationcatalyst.

Finally,

the

untreated

lighter

fraction

andthe

treated

heavier

fraction

are

blended.Here,

we

must

point

out

that

this

process

configurationis

different

from

the

commercial

processes

that

usually

put

the

hydrodesulfurizationreactorafter

the

hydroisomerization

and

aromatization

reactor.基于馏分切割的CC汽油加氢改质组合工艺全馏分FCC稳定汽油循环氢+新氢轻汽油(<65℃)国IV或国V清洁汽油调和组分切割塔重汽油选择性加氢脱硫辛烷值恢复With

the

first

reactor

being

operated

at

250

oC

and

1.0

MPa,

second

reactorat

350

oC

and1

MPa,

the

volumetric

H2

to

oil

ratio

at

300,andtotalweight

hourly

superficial

velocity

at

1.05,

the

process

gota

desulfurization

ratio

of

93%,

olefin

reduction

of

14.5%.

Most

importantly,theproduct

RON

increases

by

0.4%!Byblending

the

lighter

fraction

and

the

treated

heavier

fraction,

we

got

a

product

olefincontentof

24.2%,

sulfur

content

of

23

wppm,

which

arefully

in

compliance

with

the

specifications

of

China

IV

standard.饱和烃烯烃芳烃硫(ppmw)RON产率

(wt%)原料43.938.717.435790.1-切割-调和产品

(450

h)54.424.221.42390.498.7操作条件:1st反应器,250

oC,1.3

MP2nd反应器,350

oC,1.3

MPH2/Oil=300,一反

3.0

h-1，二反

1.5

h-1改质组合工艺(两个250

mL绝热反应器)脱硫率

93%，烯烃减少14.5

v%，RON增加0.3On

the

basis

of

the

above

results,

a200

kt/per

annumindustrial

unit

was

set

up

inDalianPetroChemical

Companyin

the

end

of

2009

under

thesupport

of

PetroChina

and

has

been

put

into

operation

since

the

4th

of

this

January.

This

is

the

full

view

of

the

unit.Grdes工艺技术：200

kt/工业装置2009年12月在大连石化公司建立了200

kt/的工业装置，2010年1月4日开始全馏分CC汽油进料运转This

slide

shows

the

schematic

of

the

process.

The

process

takes

full-range

FCC

gasoline

as

feedstock.

Before

entering

into

the

1st

reactor,

thefeed

is

preheated

by

the

streamcoming

out

from

the

2nd

reactor,

then

hydrodesulfurized

in

the

1st

reactor,

goes

into

the

2nd

reactor

for

octanerecovery.Grdes工艺技术：工艺配置由于开工进度要求，未能投用循环氢脱硫装置Grdes工艺：标定操作参数参数8

Mar.(5:00AM)8

Mar.(13:00PM)9

Mar.(5:00AM)氢/油比(v/v)423437403压力/MPa1.731.731.731st

反应器

进料温度/oC198198198空速/h-12.502.422.63压力/MPa1.431.431.432nd

反应器

进料温度/oC359359360空速/h-11.271.231.33Grdes工艺：标定结果原料产品增量芳烃,v%17.122.85.7烯烃,v%43.627.1-16.5饱和,v%39.350.110.8硫,mg/kg1704871.7%RON92.5791.63-0.93MON80.9380.57-0.37硫醇,mg/kg95.98.491.2%在循环氢中H2S未脱除的不利条件下，实现国IV清洁汽油的生产This

slide

shows

the

schematic

of

the

process.

The

process

takes

full-range

FCC

gasoline

as

feedstock.

Before

entering

into

the

1st

reactor,

thefeed

is

preheated

by

the

streamcoming

out

from

the

2nd

reactor,

then

hydrodesulfurized

in

the

1st

reactor,

goes

into

the

2nd

reactor

for

octanerecovery.Grdes工艺技术：循环氢脱硫装置的投用及其效果□大连公司2010年承担了80万吨京IV、沪IV汽油生产任务，用于催化汽油改质的生产装置仅有20万吨/年汽油加氢改质工业试验装置，因而主要靠调入重整汽油来满足生产需求，结果导致汽油密度过高，影响了销售终端效益□大连石化公司原料变动频繁，且无原料罐区，催化进料每5-7天变化一次，在原料硫含量变化较大时，改质汽油硫含量变化较大，影响产品调和□从2010年5月开始，大连石化公司又承担了粤IV汽油生产任务，生产压力进一步增大This

slide

shows

the

schematic

of

the

process.

The

process

takes

full-range

FCC

gasoline

as

feedstock.

Before

entering

into

the

1st

reactor,

thefeed

is

preheated

by

the

streamcoming

out

from

the

2nd

reactor,

then

hydrodesulfurized

in

the

1st

reactor,

goes

into

the

2nd

reactor

for

octanerecovery.Grdes工艺技术：循环氢脱硫装置的投用及其效果This

slide

shows

the

schematic

of

the

process.

The

process

takes

full-range

FCC

gasoline

as

feedstock.

Before

entering

into

the

1st

reactor,

thefeed

is

preheated

by

the

streamcoming

out

from

the

2nd

reactor,

then

hydrodesulfurized

in

the

1st

reactor,

goes

into

the

2nd

reactor

for

octanerecovery.硫装置的投用及其效果-标定结果项目原料油原料油原料油产品汽油产品汽油产品汽油(产品-原料)标定编号8.16.6:008.16.14:008.17.6:008.16.6:008.16.14:008.17.6:00-辛烷值(RON)9191.191.39090.190.3-1.00辛烷值(MON)79.779.879.879.479.679.6-0.23硫含量(mg/kg)86.8989.517721.6718.7214.179%硫醇硫(%,m/m)0.001510.001140.001320.000310.000360.0003873%芳烃含量(v%)15.716.416.119.719.719.53.57烯烃含量(v%)46.246.946.830.027.428.8-17.90饱和烃含量(v%)38.136.737.150.352.851.614.27干点温度(℃)185.6185.4184.5192.4189.1194.56.83This

slide

shows

the

schematic

of

the

process.

The

process

takes

full-range

FCC

gasoline

as

feedstock.

Before

entering

into

the

1st

reactor,

thefeed

is

preheated

by

the

streamcoming

out

from

the

2nd

reactor,

then

hydrodesulfurized

in

the

1st

reactor,

goes

into

the

2nd

reactor

for

octanerecovery.硫装置的投用及其效果-装置提提量量后后操操作作数数据据终馏点温度

192.4℃ no

spec 已审批 合格样品编号:1438549

装置:20万吨/年

汽油加氢精制装置

采样点:汽加氢精油 采样时间:2010-8-18

8:00:391.液体石油产品烃类芳烃体积百分含量20.8%(v/v)no

spec已审批合格烯烃体积百分含量31.4%(v/v)no

spec已审批合格饱和烃体积百分含量47.7%(v/v)no

spec已审批合格2.紫外荧光硫硫含量32.8800mg/kgno

spec已审批合格3.研究辛烷值研究法辛烷值89.9no

spec已审批合格4.硫醇硫含量硫醇性硫0.00060%(m/m)no

spec已审批合格5.GB/T6536馏程样品编号:1438548

装置:20万吨/年

汽油加氢精制装置

采样点:汽加氢原料 采样时间:2010-8-18

8:00:391.液体石油产品烃类芳烃体积百分含量16.8%(v/v)no

spec已审批合格烯烃体积百分含量41.1%(v/v)no

spec已审批合格饱和烃体积百分含量42.1%(v/v)no

spec已审批合格2.紫外荧光硫硫含量121.9000mg/kgno

spec已审批合格3.研究辛烷值研究法辛烷值90.8no

spec已审批合格4.硫醇硫含量硫醇性硫0.00150%(m/m)no

spec已审批合格This

slide

shows

the

schematic

of

the

process.

The

process

takes

full-range

FCC

gasoline

as

feedstock.

Before

entering

into

the

1st

reactor,

thefeed

is

preheated

by

the

streamcoming

out

from

the

2nd

reactor,

then

hydrodesulfurized

in

the

1st

reactor,

goes

into

the

2nd

reactor

for

octanerecovery.硫装置的投用及其效果-装置提提量量后后操操作作数数据据5.密度密度(20℃)

720.7kg/m3 no

spec 已审批 合格样品编号:1439706装置:20万吨/年汽油加氢精制装置采样点:汽加氢精油采样时间:2010-8-20

8:00:301.液体石油产品烃类芳烃体积百分含量20.4%(v/v)no

spec已审批合格烯烃体积百分含量29.1%(v/v)no

spec已审批合格饱和烃体积百分含量50.6%(v/v)no

spec已审批合格2.紫外荧光硫硫含量47.0100mg/kgno

spec已审批合格3.硫醇硫含量硫醇性硫0.00048%(m/m)no

spec已审批合格4.GB/T6536馏程终馏点温度191.2℃no

spec已审批合格样品编号:1439705装置:20万吨/年汽油加氢精制装置采样点:汽加氢原料采样时间:2010-8-20

8:00:301.液体石油产品烃类芳烃体积百分含量18.7%(v/v)no

spec已审批合格烯烃体积百分含量40.8%(v/v)no

spec已审批合格饱和烃体积百分含量40.5%(v/v)no

spec已审批合格2.紫外荧光硫硫含量187.9500mg/kgno

spec已审批合格3.硫醇硫含量硫醇性硫0.00133%(m/m)no

spec已审批合格4.GB/T6536馏程终馏点温度182.3℃结果<195℃已审批合格其他相关问题□Grdes工艺对于不同催化原料的适应性□高硫、高烯烃原料□高硫、低烯烃原料(MIP装置和两段提升管装置CC汽油□Grdes与Prime-G+的对比□Grdes工艺用于国V标准清洁汽油生产的可能性□现有工艺从低硫(S<150

mg/kg)CC汽油生产国V标准汽油的可能性□从高硫、高烯烃含量的CC汽油生产国V清洁汽油Grdes工艺对于不同催化原料的适应性山东恒源石化两种催化汽油的改质数据全馏分FCC稳定汽油循环氢+新氢轻汽油(<65℃)国IV或国V清洁汽油调和组分切割塔重汽油选择性加氢脱硫辛烷值恢复Grdes工艺对于不同催化原料的适应性项目二催化三催化全馏分重馏分改质后重馏分调和产品全馏分重馏分改质后重馏分调和产品硫含量，μg/g505.8725.151.6346.28493.6735.534.6736.71FIA组成，v%芳烃15.6925.5930.3519.1417.6328.1129.9318.49烯烃37.7432.9414.1722.8326.3817.812.4614.87饱和烃46.5989.841.4785.9/86.5/90.055.9989.854.0886.2/85.7/90.2辛烷值(RON)(10.22)山东恒源石化两种催化汽油的改质数据依据汽油馏程数据，将二催化、三催化CC汽油在65℃切割为轻、重馏分，其中二催化CC汽油轻馏分占32.9wt%，重馏分占67.0

wt%，三催化CC汽油轻馏分占33.9

wt%，重馏分占Finally,

I’d

like

to

thank

the

long-term

support

from

the

Ministry

of

Science

and

Technology

of

China,

National

Natural

Science

FoundationofChina,

China

Petroleum

Corporation,

Dalian

Petrochemical

Company,

and

China

University

of

Petroleum.

Also,

I’d

like

to

thank

my

colleaguesand

graduate

students

atboth

Ph.D.

and

Master

levels.Prime-G+工艺流程Finally,

I’d

like

to

thank

the

long-term

support

from

the

Ministry

of

Science

and

Technology

of

China,

National

Natural

Science

FoundationofChina,

China

Petroleum

Corporation,

Dalian

Petrochemical

Company,

and

China

University

of

Petroleum.

Also,

I’d

like

to

thank

my

colleaguesand

graduate

students

atboth

Ph.D.

and

Master

levels.Prime-G+的技术特色-SHU好处：脱硫醇和双烯选择性加氢Prime-G+的辛烷值损失S=500

ppmS=400

ppm

RON损失1.5-3.0RON损失1.0-3.0RON损失0.5-1.5S=300

ppmBase

one

the

above

introduction,

we

can

draw

the

following

conclusions:UpgradingFCC

gasoline

withhigher

sulfur

and

olefin

contents

is

challenging

China

refining

industry.Direct

hydro-upgrading

of

full

range

FCC

gasoline

is

difficult

to

simultaneously

satisfy

product

specifications

and

process

requirements.

Cuttingfull

range

FCC

gasoline

into

a

lighter

fraction

and

heavy

fraction

and

then

further

treating

the

latter

one

provides

a

feasible

solution

to

thisproblem.The

combined

hydrodesulfurizationand

hydroisomerization/aromatization

process

is

suitable

for

upgrading

FCC

gasoline

with

higher

olefin

andsulfur

content;

the

resulting

product

is

fully

in

compliance

with

the

China

IV

standard.Grdes工艺与Prime-G+工艺的比较选择性加氢脱硫反应器氢气加氢异构/芳构化反应器全馏分汽油加氢改质产品Grdes工艺1.全馏分2.两个反应器Prime-G+工艺1.馏分切割2.两个反应器Base

one

the

above

introduction,

we

can

draw

the

following

conclusions:UpgradingFCC

gasoline

withhigher

sulfur

and

olefin

contents

is

challenging

China

refining

industry.Direct

hydro-upgrading

of

full

range

FCC

gasoline

is

difficult

to

simultaneously

satisfy

product

specifications

and

process

requirements.

Cuttingfull

range

FCC

gasoline

into

a

lighter

fraction

and

heavy

fraction

and

then

further

treating

the

latter

one

provides

a

feasible

solution

to

thisproblem.The

combined

hydrodesulfurizationand

hydroisomerization/aromatization

process

is

suitable

for

upgrading

FCC

gasoline

with

higher

olefin

andsulfur

content;

the

resulting

product

is

fully

in

compliance

with

the

China

IV

standard.Grdes工艺与Prime-G+的对比：工艺流程□Grdes工艺□大连石化公司：采用全馏分汽油进料□无切割塔，两个反应器□Prime-G+工艺□大港石化：LCN+HCN□锦西石化：LCN+MCN+HCN□1-2个切割塔，两个反应器□生产国V标准汽油□Grdes工艺：1个切割塔，2-3个反应器Base

one

the

above

introduction,

we

can

draw

the

following

conclusions:UpgradingFCC

gasoline

withhigher

sulfur

and

olefin

contents

is

challenging

China

refining

industry.Direct

hydro-upgrading

of

full

range

FCC

gasoline

is

difficult

to

simultaneously

satisfy

product

specifications

and

process

requirements.

Cuttingfull

range

FCC

gasoline

into

a

lighter

fraction

and

heavy

fraction

and

then

further

treating

the

latter

one

provides

a

feasible

solution

to

thisproblem.The

combined

hydrodesulfurizationand

hydroisomerization/aromatization

process

is

suitable

for

upgrading

FCC

gasoline

with

higher

olefin

andsulfur

content;

the

resulting

product

is

fully

in

compliance

with

the

China

IV

standard.Grdes工艺与Prime-G+的对比:脱硫率Gardes全馏分，无循环氢脱硫Gardes全馏分，有循环氢脱硫Prime-G+切割(LCN+HCN)，大港Prime-G+切割(LCN+MCN+HCN)，锦西项目值或脱除率值或脱除率值或脱除率值或脱除率硫含量,mg/kg原料 产品168.1

48.07

71.38%原料 产品93.82

21.84

76.72%原料 产品122

1984.4%原料 产品163

65.860%硫醇,mg/kg95.938.3691.3%16.384.1269.83%16.5//34.46//芳烃,

17.1322.765.6316.3019.93.613.6813.750.07///烯烃,

43.6

27.06 -16.54

45.3

29.4 -15.9

35.95

33.45 -2.5

31.8029.65-2.15RON

92.56

91.63 -0.93

91.1

90.1 -1.0

91.58

91.05 -0.53

87.1586.20-0.95-0.37

79.77

79.53 -0.24

79.8

80.15

0.35

78.15

77.70 -0.45氢耗,

%

0.310.32

/

/液收,

%

99.0299.3399.6899.99标油/t16.02

20.4626.818.99Gv%rdes工艺两v%次标定的脱硫率分别71.38%和76.72%，平均为74.05%PMOrN

ime-80G.9+3

工80艺.56在大港石化的标定结果84.4%，在锦西石化的标定结果为60%，平均值为72.2%总能耗,体kg

效果Grdes与Prime-G+的脱硫基本相当Base

one

the

above

introduction,

we

can

draw

the

following

conclusions:UpgradingFCC

gasoline

withhigher

sulfur

and

olefin

contents

is

challenging

China

refining

industry.Direct

hydro-upgrading

of

full

range

FCC

gasoline

is

difficult

to

simultaneously

satisfy

product

specifications

and

process

requirements.

Cuttingfull

range

FCC

gasoline

into

a

lighter

fraction

and

heavy

fraction

and

then

further

treating

the

latter

one

provides

a

feasible

solution

to

thisproblem.The

combined

hydrodesulfurizationand

hydroisomerization/aromatization

process

is

suitable

for

upgrading

FCC

gasoline

with

higher

olefin

andsulfur

content;

the

resulting

product

is

fully

in

compliance

with

the

China

IV

standard.Grdes工艺与Prime-G+的对比:降烯烃Gardes全馏分，无循环氢脱硫Gardes全馏分，有循环氢脱硫Prime-G+切割(LCN+HCN)，大港Prime-G+切割(LCN+MCN+HCN)，锦西项目原料 产品值或脱除率原料 产品值或脱除率原料 产品值或脱除率原料 产品值或脱除率硫含量,mg/kg168.1硫醇,mg/kg95.93芳烃,v%17.1348.0771.38%93.8221.8476.72%1221984.4%16365.860%8.3691.3%16.384.1269.83%16.5//34.46//22.765.6316.3019.93.613.6813.750.07///27.06-16.5445.329.4-15.935.9533.45-2.531.8029.65-2.1591.63-0.9391.190.1-1.091.5891.05-0.5387.1586.20-0.95MON

80.9380.56 -0.37

79.77

79.53 -0.24