fcc汽油分娩國(guó)iv標(biāo)準(zhǔn)干凈汽油-

I

will

divide

my

presentation

into

following

5parts.4研究背景1235技術(shù)路線烯烴定向轉(zhuǎn)化/辛烷值恢復(fù)催化劑選擇性加氫脫硫催化劑組合工藝及其應(yīng)用提綱6其他相關(guān)問(wèn)題7結(jié)論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.生產(chǎn)清潔汽油的意義歐III2000歐IV2005國(guó)III2007國(guó)IV2013(預(yù)測(cè))國(guó)V(預(yù)測(cè))硫(ppmw)<150<50<150<50<10苯(v%)<1.0<1.0<1.0<1.0<1.0芳烴(v%)<42.0<35.0<35.0<35.0<35.0烯烴(v%)<18.0<18.0<25.0<28.0<25.0氧(m%)<2.7<2.3<2.7<2.3<2.3清潔汽油標(biāo)準(zhǔn)的必然發(fā)展趨勢(shì)—低烯烴和超低的硫含量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.硫我國(guó)CC汽油的組成烯烴芳烴300～600

ppmw約 40

v%10～20

v%CC36%13%國(guó)外17%34%78%5%0.5%中國(guó)14.5%36%CC汽油異構(gòu)化汽

重油整汽

油烷基化

汽油生產(chǎn)清潔汽油的意義□清潔汽油生產(chǎn)的關(guān)鍵——降低CC汽油中硫和烯烴的含量美國(guó)和中國(guó)汽油調(diào)合組分的構(gòu)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.兩種CC汽油改質(zhì)技術(shù)□催化裂化“原位”改質(zhì)技術(shù)□后加氫處理改質(zhì)技術(shù)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.化裂化原位改質(zhì)技術(shù)□降烯烴 化劑□RG,

TOM/GOR,

LBO

系列 化劑□烯烴減少6-10

v%,脫硫率20-30%□兩段提升管和輔助提升管□烯烴減少20

v%,脫硫率30%□不足□很難達(dá)到更高的脫硫率□汽油的收率有較大的損失后加氫處理改質(zhì)技術(shù)□選擇性加氫脫硫□典型工藝:Scnining,

Prime-G+,

RSDS,

RS,

OCT-M□適合于低烯烴含量的CC汽油□加氫脫硫和辛烷值恢復(fù)組合□典型工藝:Octgin,

OT,

RIDOS□適合于低到中等烯烴含量的CC汽油，具有良好的辛烷值恢復(fù)能力□不足:高脫硫率下汽油收率較低Based

on

the

above

discussion,

we

can

conclude

that

the

difficulty

inupgradingFCC

gasoline

lies

in

the

contradictions

between

gasoline

qualityspecifications

and

process

requirements.汽油質(zhì)量標(biāo)準(zhǔn) 工藝要求深度加氫脫硫矛盾保持辛烷值降烯烴矛盾保持辛烷值提高辛烷值矛盾汽油產(chǎn)率催化劑的穩(wěn)定性CC汽油加氫改質(zhì)技術(shù)開(kāi)發(fā)的難點(diǎn)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汽油改質(zhì)的技術(shù)路線目標(biāo)催化劑降烯烴和脫硫工藝相組合生產(chǎn)國(guó)IV標(biāo)準(zhǔn)的清潔汽油工藝加氫異構(gòu)化和芳 選擇性加氫脫硫構(gòu)化工藝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.加氫異構(gòu)化和芳構(gòu)化催化劑RON＝93RON＝54單支鏈異構(gòu)ctlyst＋H2芳

構(gòu)RON＞100√RON＝0加×氫飽和RON＝42雙-√或三支鏈異構(gòu)√要求:酸性:適宜強(qiáng)度，具有加氫異構(gòu)和芳構(gòu)化活性，但不至于使催化劑快速結(jié)焦失活孔徑: 足夠大，使在孔道內(nèi)能形成雙-或三支鏈異構(gòu)體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.具有加氫異構(gòu)化和芳構(gòu)化活性的復(fù)合催化劑以ZSM-5為核，SPO-11為殼的復(fù)合材料具有優(yōu)異異構(gòu)化功能的SPO-11具有優(yōu)異芳構(gòu)化功能的ZSM-5酸性較強(qiáng)容易失活孔徑較小異構(gòu)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沸石的酸性調(diào)變□水熱處理和復(fù)合酸處理相結(jié)合強(qiáng)B酸位易使催化劑過(guò)失度活水熱處理使強(qiáng)B酸進(jìn)位一步用復(fù)合酸處理，使大量減少，孔道堵塞

適度增加，孔道疏通++++++++

++++++++水熱處理+

復(fù)合酸處理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的孔徑調(diào)變0.6nm0.8~1

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

H2OSPO-11的孔徑調(diào)變傳統(tǒng)水熱合成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.飽和烴烯烴芳烴硫(ppmw)RON產(chǎn)率

(wt%)原料45.339.615.137091.5-產(chǎn)品(500

h)56.121.521.810591.098.5√優(yōu)異的降烯烴和保辛烷值能力X 較低的脫硫率—71%具有烯烴異構(gòu)和芳構(gòu)功能的復(fù)合催化劑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.高選擇性加氫脫硫催化劑金屬硫化物中心Edge位

HDS實(shí)現(xiàn)高選擇性加氫脫硫的路線：最大限度地提高Edge位的比例高分散度高活性低選擇性高堆積度高選擇性低活性協(xié)調(diào)的分散和堆積平衡選擇性和活性Rim位加氫＋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%!高選擇性加氫脫硫催化劑飽和烴烯烴芳烴硫(ppmw)RON損失原料133.649.317.1900–全餾分產(chǎn)品(500

h)41.641.217.21800.7切割-調(diào)和產(chǎn)品(500

h)40.642.117.31170.6原料245.339.615.1380–全餾分產(chǎn)品(500

h)53.331.415.3850.8切割-調(diào)和產(chǎn)品(500

h)51.133.715.2700.6烯烴飽和率

15-20%全餾分脫硫率

77-80%切割-調(diào)和脫硫率

82-87%RON損失

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?加氫異構(gòu)/芳構(gòu)化催化劑？選擇性加氫脫硫催化劑選擇性加氫脫硫催化劑加氫異構(gòu)/芳構(gòu)化催化劑工藝配置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!工藝(兩個(gè)100

mL等溫反應(yīng)器串聯(lián))飽和烴烯烴芳烴RON硫(ppmw)產(chǎn)率

(wt%)原料43.642.613.892.4403-產(chǎn)品(450

h)70.812.616.686.53998.4SelectivehydrodesulfurizationHydrogenUpgraded

productHydroisomerizationand

aromatizationFCC

gasoline烯烴過(guò)度飽和,RON損失

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!飽和烴烯烴芳烴RON硫(ppmw)產(chǎn)率

(wt%)原料44.240.815.091.8365-產(chǎn)品(1500h)53.427.019.690.64898.5HydrogenSelectivehydrodesuluriztionCCgsoline工藝(兩個(gè)100

mL等溫反應(yīng)器串聯(lián))Hydroisomeriztion

ndroUmptgirzdteidonproduct脫硫率

87%,烯烴減少14

v%,RON損失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!基于餾分切割的CC汽油加氫改質(zhì)組合工藝國(guó)IV預(yù)測(cè)國(guó)V硫(ppmw)<50<10烯烴(v%)<25<25CC汽油中硫和烯烴的分布確定合適的餾分切割溫度，對(duì)達(dá)到理想的改質(zhì)效果至關(guān)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.基于餾分切割的CC汽油加氫改質(zhì)組合工藝全餾分FCC穩(wěn)定汽油循環(huán)氫+新氫輕汽油(<65℃)國(guó)IV或國(guó)V清潔汽油調(diào)和組分切割塔重汽油選擇性加氫脫硫辛烷值恢復(fù)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.飽和烴烯烴芳烴硫(ppmw)RON產(chǎn)率

(wt%)原料43.938.717.435790.1-切割-調(diào)和產(chǎn)品

(450

h)54.424.221.42390.498.7操作條件:1st反應(yīng)器,250

oC,1.3

MP2nd反應(yīng)器,350

oC,1.3

MPH2/Oil=300,一反

3.0

h-1，二反

1.5

h-1改質(zhì)組合工藝(兩個(gè)250

mL絕熱反應(yīng)器)脫硫率

93%，烯烴減少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工藝技術(shù)：200

kt/工業(yè)裝置2009年12月在大連石化公司建立了200

kt/的工業(yè)裝置，2010年1月4日開(kāi)始全餾分CC汽油進(jìn)料運(yùn)轉(zhuǎn)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工藝技術(shù)：工藝配置由于開(kāi)工進(jìn)度要求，未能投用循環(huán)氫脫硫裝置Grdes工藝：標(biāo)定操作參數(shù)參數(shù)8

Mar.(5:00AM)8

Mar.(13:00PM)9

Mar.(5:00AM)氫/油比(v/v)423437403壓力/MPa1.731.731.731st

反應(yīng)器

進(jìn)料溫度/oC198198198空速/h-12.502.422.63壓力/MPa1.431.431.432nd

反應(yīng)器

進(jìn)料溫度/oC359359360空速/h-11.271.231.33Grdes工藝：標(biāo)定結(jié)果原料產(chǎn)品增量芳烴,v%17.122.85.7烯烴,v%43.627.1-16.5飽和,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%在循環(huán)氫中H2S未脫除的不利條件下，實(shí)現(xiàn)國(guó)IV清潔汽油的生產(chǎn)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工藝技術(shù)：循環(huán)氫脫硫裝置的投用及其效果□大連公司2010年承擔(dān)了80萬(wàn)噸京IV、滬IV汽油生產(chǎn)任務(wù)，用于催化汽油改質(zhì)的生產(chǎn)裝置僅有20萬(wàn)噸/年汽油加氫改質(zhì)工業(yè)試驗(yàn)裝置，因而主要靠調(diào)入重整汽油來(lái)滿足生產(chǎn)需求，結(jié)果導(dǎo)致汽油密度過(guò)高，影響了銷售終端效益□大連石化公司原料變動(dòng)頻繁，且無(wú)原料罐區(qū)，催化進(jìn)料每5-7天變化一次，在原料硫含量變化較大時(shí)，改質(zhì)汽油硫含量變化較大，影響產(chǎn)品調(diào)和□從2010年5月開(kāi)始，大連石化公司又承擔(dān)了粵IV汽油生產(chǎn)任務(wù)，生產(chǎn)壓力進(jìn)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工藝技術(shù)：循環(huán)氫脫硫裝置的投用及其效果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.硫裝置的投用及其效果-標(biāo)定結(jié)果項(xiàng)目原料油原料油原料油產(chǎn)品汽油產(chǎn)品汽油產(chǎn)品汽油(產(chǎn)品-原料)標(biāo)定編號(hào)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%芳烴含量(v%)15.716.416.119.719.719.53.57烯烴含量(v%)46.246.946.830.027.428.8-17.90飽和烴含量(v%)38.136.737.150.352.851.614.27干點(diǎn)溫度(℃)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.硫裝置的投用及其效果-裝置提提量量后后操操作作數(shù)數(shù)據(jù)據(jù)終餾點(diǎn)溫度

192.4℃ no

spec 已審批 合格樣品編號(hào):1438549

裝置:20萬(wàn)噸/年

汽油加氫精制裝置

采樣點(diǎn):汽加氫精油 采樣時(shí)間:2010-8-18

8:00:391.液體石油產(chǎn)品烴類芳烴體積百分含量20.8%(v/v)no

spec已審批合格烯烴體積百分含量31.4%(v/v)no

spec已審批合格飽和烴體積百分含量47.7%(v/v)no

spec已審批合格2.紫外熒光硫硫含量32.8800mg/kgno

spec已審批合格3.研究辛烷值研究法辛烷值89.9no

spec已審批合格4.硫醇硫含量硫醇性硫0.00060%(m/m)no

spec已審批合格5.GB/T6536餾程樣品編號(hào):1438548

裝置:20萬(wàn)噸/年

汽油加氫精制裝置

采樣點(diǎn):汽加氫原料 采樣時(shí)間:2010-8-18

8:00:391.液體石油產(chǎn)品烴類芳烴體積百分含量16.8%(v/v)no

spec已審批合格烯烴體積百分含量41.1%(v/v)no

spec已審批合格飽和烴體積百分含量42.1%(v/v)no

spec已審批合格2.紫外熒光硫硫含量121.9000mg/kgno

spec已審批合格3.研究辛烷值研究法辛烷值90.8no

spec已審批合格4.硫醇硫含量硫醇性硫0.00150%(m/m)no

spec已審批合格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.硫裝置的投用及其效果-裝置提提量量后后操操作作數(shù)數(shù)據(jù)據(jù)5.密度密度(20℃)

720.7kg/m3 no

spec 已審批 合格樣品編號(hào):1439706裝置:20萬(wàn)噸/年汽油加氫精制裝置采樣點(diǎn):汽加氫精油采樣時(shí)間:2010-8-20

8:00:301.液體石油產(chǎn)品烴類芳烴體積百分含量20.4%(v/v)no

spec已審批合格烯烴體積百分含量29.1%(v/v)no

spec已審批合格飽和烴體積百分含量50.6%(v/v)no

spec已審批合格2.紫外熒光硫硫含量47.0100mg/kgno

spec已審批合格3.硫醇硫含量硫醇性硫0.00048%(m/m)no

spec已審批合格4.GB/T6536餾程終餾點(diǎn)溫度191.2℃no

spec已審批合格樣品編號(hào):1439705裝置:20萬(wàn)噸/年汽油加氫精制裝置采樣點(diǎn):汽加氫原料采樣時(shí)間:2010-8-20

8:00:301.液體石油產(chǎn)品烴類芳烴體積百分含量18.7%(v/v)no

spec已審批合格烯烴體積百分含量40.8%(v/v)no

spec已審批合格飽和烴體積百分含量40.5%(v/v)no

spec已審批合格2.紫外熒光硫硫含量187.9500mg/kgno

spec已審批合格3.硫醇硫含量硫醇性硫0.00133%(m/m)no

spec已審批合格4.GB/T6536餾程終餾點(diǎn)溫度182.3℃結(jié)果<195℃已審批合格其他相關(guān)問(wèn)題□Grdes工藝對(duì)于不同催化原料的適應(yīng)性□高硫、高烯烴原料□高硫、低烯烴原料(MIP裝置和兩段提升管裝置CC汽油□Grdes與Prime-G+的對(duì)比□Grdes工藝用于國(guó)V標(biāo)準(zhǔn)清潔汽油生產(chǎn)的可能性□現(xiàn)有工藝從低硫(S<150

mg/kg)CC汽油生產(chǎn)國(guó)V標(biāo)準(zhǔn)汽油的可能性□從高硫、高烯烴含量的CC汽油生產(chǎn)國(guó)V清潔汽油Grdes工藝對(duì)于不同催化原料的適應(yīng)性山東恒源石化兩種催化汽油的改質(zhì)數(shù)據(jù)全餾分FCC穩(wěn)定汽油循環(huán)氫+新氫輕汽油(<65℃)國(guó)IV或國(guó)V清潔汽油調(diào)和組分切割塔重汽油選擇性加氫脫硫辛烷值恢復(fù)Grdes工藝對(duì)于不同催化原料的適應(yīng)性項(xiàng)目二催化三催化全餾分重餾分改質(zhì)后重餾分調(diào)和產(chǎn)品全餾分重餾分改質(zhì)后重餾分調(diào)和產(chǎn)品硫含量，μg/g505.8725.151.6346.28493.6735.534.6736.71FIA組成，v%芳烴15.6925.5930.3519.1417.6328.1129.9318.49烯烴37.7432.9414.1722.8326.3817.812.4614.87飽和烴46.5989.841.4785.9/86.5/90.055.9989.854.0886.2/85.7/90.2辛烷值(RON)(10.22)山東恒源石化兩種催化汽油的改質(zhì)數(shù)據(jù)依據(jù)汽油餾程數(shù)據(jù)，將二催化、三催化CC汽油在65℃切割為輕、重餾分，其中二催化CC汽油輕餾分占32.9wt%，重餾分占67.0

wt%，三催化CC汽油輕餾分占33.9

wt%，重餾分占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+工藝流程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+的技術(shù)特色-SHU好處：脫硫醇和雙烯選擇性加氫Prime-G+的辛烷值損失S=500

ppmS=400

ppm

RON損失1.5-3.0RON損失1.0-3.0RON損失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工藝與Prime-G+工藝的比較選擇性加氫脫硫反應(yīng)器氫氣加氫異構(gòu)/芳構(gòu)化反應(yīng)器全餾分汽油加氫改質(zhì)產(chǎn)品Grdes工藝1.全餾分2.兩個(gè)反應(yīng)器Prime-G+工藝1.餾分切割2.兩個(gè)反應(yīng)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工藝與Prime-G+的對(duì)比：工藝流程□Grdes工藝□大連石化公司：采用全餾分汽油進(jìn)料□無(wú)切割塔，兩個(gè)反應(yīng)器□Prime-G+工藝□大港石化：LCN+HCN□錦西石化：LCN+MCN+HCN□1-2個(gè)切割塔，兩個(gè)反應(yīng)器□生產(chǎn)國(guó)V標(biāo)準(zhǔn)汽油□Grdes工藝：1個(gè)切割塔，2-3個(gè)反應(yīng)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工藝與Prime-G+的對(duì)比:脫硫率Gardes全餾分，無(wú)循環(huán)氫脫硫Gardes全餾分，有循環(huán)氫脫硫Prime-G+切割(LCN+HCN)，大港Prime-G+切割(LCN+MCN+HCN)，錦西項(xiàng)目值或脫除率值或脫除率值或脫除率值或脫除率硫含量,mg/kg原料 產(chǎn)品168.1

48.07

71.38%原料 產(chǎn)品93.82

21.84

76.72%原料 產(chǎn)品122

1984.4%原料 產(chǎn)品163

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

17.1322.765.6316.3019.93.613.6813.750.07///烯烴,

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氫耗,

%

0.310.32

/

/液收,

%

99.0299.3399.6899.99標(biāo)油/t16.02

20.4626.818.99Gv%rdes工藝兩v%次標(biāo)定的脫硫率分別71.38%和76.72%，平均為74.05%PMOrN

ime-80G.9+3

工80藝.56在大港石化的標(biāo)定結(jié)果84.4%，在錦西石化的標(biāo)定結(jié)果為60%，平均值為72.2%總能耗,體kg

效果Grdes與Prime-G+的脫硫基本相當(dāng)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工藝與Prime-G+的對(duì)比:降烯烴Gardes全餾分，無(wú)循環(huán)氫脫硫Gardes全餾分，有循環(huán)氫脫硫Prime-G+切割(LCN+HCN)，大港Prime-G+切割(LCN+MCN+HCN)，錦西項(xiàng)目原料 產(chǎn)品值或脫除率原料 產(chǎn)品值或脫除率原料 產(chǎn)品值或脫除率原料 產(chǎn)品值或脫除率硫含量,mg/kg168.1硫醇,mg/kg95.93芳烴,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