Development of technology of methane combustion on granulated catalysts for environmentally friendly...

Development of technology of methane combustion on granulated catalysts

for environmentally friendly gas turbine power plant

Z.R.Ismagilov, N.V.Shikina, S.A.Yashnik, A.N.Zagoruiko

M.A.Kerzhentsev, V.A.Ushakov,S.R.Khairulin, V.A.Sasonov,

V.N.Parmon Boreskov Institute of Catalysis,

Novosibirsk, Russia

V.M.Zakharov, B.I.Braynin, G.K.Vedeshkin, E.D.Sverdlov, O.N.Favorski Central Institute of Aviation Motors, Moscow, Russia

The Baranov Central Institute of Aviation Motors (CIAM) is leading establishment of the Russia aviation engine - building for provision of world-level basic and applied research, creation of scientific and technological base for development of new "critical" technologies – gas turbine power units.

Development advanced environment friendly gas turbine with

catalytic combustion chamber

The Boreskov Institute of Catalysis (BIC) is one of the largest research centers worldwide specialized in catalysis. The BIC’s R&D activities span the areas from fundamental problems of catalysis to development of new catalysts and catalytic technologies, including catalytic combustion.

D-30KP

A-50 (powered by D-30KP) IL-78 (powered by D-30KP)

Airplane engines designed at CIAM

CIAM – the only research organization realizing integral scientific studies and development in the field of aero engines - from fundamental studies of physical processes up design of new engines, certification, as well as scientific support of their operation by reliability and failures. Practically all Soviet (Russian) aircraft engines were created under direct participation of Institute and passed upgrading at CIAM facilities.

Large scale engine and turbine testing facilities of CIAM

Moscow (CIAM)

St-Petersburg

Omsk

Novosibirsk (BIC)

RUSSIAVolgograd

UIC

BIC and CIAM in Russia

The goalDevelopment of catalyst and catalytic combustion chamber for small gas turbine power plants for decentralized power supply

Approach- Regenerative turbine technology- Low temperarue turbine- Granulated catlyst for stationary turbine loading

Key steps

1) development and study of advanced granulated catalysts with low Pd content, providing minimum emissions of NOx (<5ppm), CO (<5ppm) and HC (5ppm)

2) modeling of the processes in a catalytic combustor

3) design of a model catalytic combustion chamber and pilot testing

4) design and testing of a prototype catalytic combustion chamber

Catalysts for high-temperature combustion of hydrocarbon fuel

Catalysts based on

noble metals

Pd

Catalysts based on transition

metal oxides

MnOx

MnLaAl11O19

The thermal stability of MnOx/Al2O3 catalysts can

be increased (up to 1300oC) by doping with La, Mg or

Ce oxidesZ.R.Ismagilov, Patent RU 2185238(2002)

For oxidation of methane, MnOx/Al2O3 and hexaaluminates

are less active at low temperature than Pd/CeO2-Al2O3 catalysts

The properties of these two catalyst-types will be used for development of the combined catalytic package with reduced

Pd content for combustion chamber,

Most active in deep oxidation of methane,

CO, unsaturated hydrocarbons

Stable to thermal sintering in the

oxidizing environment

J.J.Spivey, J.B.Butt Catal. Today. 11 (1992) 465.

The upper temperature limit of their use is

about 800-900°C

PdO Pd

R.J.Farrauto, et.al. Appl. Catal. A 81 (1992) 227.

Very expensive

Low light-off temperature

MnLaAl11O19 has high thermal stability

Inexpensive

1. 2.

Pd CeO2

• Pd 0.1 - 2 wt.% • CeO2 3 - 12 wt.%

Preparation conditions

• H2PdCl4

• Pd(NO3)2

• Pd(CH3COO)2

•Pd(NH3)4(NO3)2

•Pd(NH3)4(Cl3)2

Catalytic activity in methane oxidation• Space velocity: 1000 and 24000 h-1

• Temperature: 200 – 700oC• Feed composition: 1 vol.% in air

5. Characterization

XRD

TPR-H2

X-ray microanalysis

Pd Catalysts supported on -Al2O3

1. Type of active component

2. Loading of active component

3. Precursor

• 800 оС – 1100оС4. Calcination temperature

1.1. Development of catalyst with low ignition temperature

MnOx and MnLaAl11O19 Pd and MnOx, MnLaAl11O19

• Pd 0.1 - 2 wt.%• MnO2 - 3 -11 wt.%

•La2O3 - 5 -22 wt.%

• 900 оС – 1100оС

Preparation conditions

• H2PdCl4

• Pd(NO3)2

• Pd(CH3COO)2

Catalytic activity in methane oxidation• Space velocity: 1000 and 24000 h-1

• Temperature: 200 – 700oC• Feed composition: 1 vol.% in air

5. Characterization

XRD

TPR-H2

X-ray microanalysis

1.2. Development of catalyst with high thermal stability

Oxide and mixed Catalysts supported on -Al2O3

1. Type of active component

2. Loading of active component

3. Precursor

• 900 оС – 1100оС

4. Calcination temperature

• Mn(NO3)3

• Mn(CH3COO)2

Properties of granulated catalysts

Catalyst Tcalc. Physico-chemical properties after calcination

oC Loading

wt.%

XRD composition Ssp

m2/g

V,

cm3/g

strength

MPa

IC-12-60-2Pd-Ce-Al2O3

1000 Pd- 2.1Ce- 10.1

-Al2O3

CeO2 D~ 200Å(S33=1100)*

PdO D~ 180 and 250Å (S39=480)*

74 0.26 2.4

ICT-12-40MnOx-Al2O3

900 Mn – 6.9 (+)-Al2O3 and -Al2O3

Mn2O380 0.23 2.3

IC-12-61Mn-La-Al2O3

1100 Mn-6.9La-10.1

MnLaAl11O19 (S37=60)*

LaAlO3

-Al2O3

43 0.18 3.4

IC-12-62-2Pd-Mn-LaAl2O3

1000 Pd -0.65 Mn-7.1La- 9.4

MnLaAl11O19 (S37 = trace)*

**-Al2O3 (а – 7.937 А)

PdO D~400 Ǻ (S39 - 70)

48 0.18 2.5

Ring size: Length – 7.5 mmOD– 7.5 mmID – 2.5 mm

Development of catalyst with low ignition temperature

The catalyst IC-12-60 based on Pd-CeO2-Al2O3 was selected as a catalyst with low ignition temperature:

• the methane ignition temperature on the catalyst is 240С, the combustion products do not contain CO and NOx

• the active component is highly dispersed PdO particles which provide high activity at low temperatures

This catalyst can be used in the upstream section of combustion chamber for initiation of fuel combustion

200 300 400 500 6000

20

40

60

80

100

Temperature, oC

CH

4 c

on

vers

ion

, %

1000 h-1

24000 h-1

48000 h-1

GHSV

Pd-CeO2-Al2O3

1 vol.% CH4 in air, GHSV

100 200 300 400 500 600 700 800

0

20

40

60

80

100

T50%

=325oC

T50%

=415oC

T50%

=370oC

Temperature, oC

CH

4 co

nv

ers

ion

, %

1 vol.% CH4 in air, 24000 h-1

MnLaAl11O19

Pd/Al2O3 (1200oC)

• At the same Pd loading (1.5 wt.%) the magnitude of the synergetic effect depends on the palladium precursor: acetate, nitrate or chloropalladic acid.

• The Pd loading (0.5 wt.%), Pd precursor (nitrate) and calcination temperature (1000oC) were optimum for Pd-Mn catalysts

Pd precursorPd(CH3COO)2

Pd(NO3)2

H2PdCl4

1.5 %Pd/MnLaAl11O19 (1200oC)

Catalytic activity of Pd-Mn catalyst: Effect of Pd precursor

1.2. Optimization of catalyst with high thermal stability

• The catalysts IC-12-61 containing Mn-La hexaaluminate structure exhibits high stability at high temperatures.

• Doping of Mn-La catalyst (IC-12-62) with Pd to 0.5 wt.% allows a decrease of ignition temperature by 100C and reduction of CO content in the reaction products

• These catalysts can be used in the downstream section of the combustion chamber for high temperature fuel combustion

Stability of Mn-La and Pd-Mn-La catalyst at high temperature

1.2. Optimization of catalyst with high thermal stability

3 vol.% CH4 in air, 10000 h-1 and 930oC

0 50 100 150 200260

280

300

320

340

360

Igna

tion

tem

pera

ture

, o C

Duration time, h

0 50 100 150 200

0

20

40

60

80

100

CO

con

cent

ratio

n, p

pmDuration time, h

IC-12-62 IC-12-62, 0-5 ppm

IC-12-61, 12-86 ppm

IC-12-61

T = 100oC

360-365oC

265-275оC

2. Modeling of processes in a catalytic combustor2.1. Calculation of kinetic parameters from experimental data

,exp)ε1(0

CH0 4

P

PC

RT

Ekw

k0 – pre-exponential factor of rate constant (s-1), E – activation energy (J/mol), R – absolute gas constant (J mol-1 K-1), Т – reaction temperature (К), – part of free volume in catalyst bed, CCH4 – methane concentration (mole fraction), Р –pressure (atm), Р0 – standard pressure (1 atm).

Total rate of methane oxidation

Catalyst k0, s-1 E, kJ/mol

IC-12-60 (Pd-Ce-Al2O3) 4.36 . 107 81.4

ICT-12-40 (Mn-Al2O3) 1.09 . 105 71.2

IC-12-61 (Mn-La-Al2O3) 1.09 . 105 71.2

IC-12-62 (Pd-Mn-La-Al2O3) 3.29. 10563.8

Kinetic parameter of deep methane oxidation

2.2. Design of catalyst packages in the combustion chamber

Uniform catalyst package

Combined catalyst packages

CH4 + air CH4 + airCH4 + air

2.2 Modeling of methane combustion process on uniform catalyst package

Catalyst package: ICT-12-40 (MnOx-Al2O3) or IC-12-61(Mn-La-Al2O3)

(Ссн4- 1.5 - 5.0 vol.%, GHSV - 7000 - 40000 h-1, P – 1 atm)

Combustion efficiency as function of methane concentration and GHSV

1.5% CH4

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

5000 10000 15000 20000 25000 30000 35000 40000 45000

GHSV, 1/час

Ко

нв

ерси

я 450

500

550

600

Co

nve

rsio

n, %

GHSV, h-1

1.5 % CH4

3.6% CH4

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

5000 10000 15000 20000 25000 30000 35000 40000 45000

GHSV, 1/час

Ко

нв

ерси

я 450

500

550

600

Co

nve

rsio

n,

%

GHSV, h-1

3.6 % CH4

2% CH4

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

5000 10000 15000 20000 25000 30000 35000 40000 45000

GHSV, 1/час

Ко

нв

ерси

я 450

500

550

600

Co

nve

rsio

n, %

2.0 % CH4

GHSV, h-1

5% CH4

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

5000 10000 15000 20000 25000 30000 35000 40000 45000

GHSV, 1/час

Ко

нв

ерси

я 450

500

550

600

Co

nve

rsio

n, %

5.0 % CH4

GHSV, h-1

The methane combustion efficiency

increases with the increase of the

temperature and with methane concentration

2.3. Modeling of methane combustion process on combined catalyst package

Catalyst package: IC-12-60 (Pd-Ce-Al2O3)- 20 mm + IC-12-61(Mn-La-Al2O3)-180 mm

Temperature profile in the catalyst bed and methane conversion profile as function of GHSV

Загрузка 20/180 мм

400

450

500

550

600

650

700

750

800

850

900

0 0,2 0,4 0,6 0,8 1

Относительная длина слоя

Температура,С

10000 1/час

40000 1/час

граница слоев

Te

mp

era

ture

, oC

Relative bed height

Beds border

1000 1 / h40000 1/h

Загрузка 20/180 мм

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 0,2 0,4 0,6 0,8 1

Относительная длина слоя

Конверсияметана

10000 1/час

40000 1/час

граница слоев

Met

han

e c

on

ver

sio

n, %

Relative bed height

Beds border

h

h

• The temperature growth in catalyst bed and the methane conversion growth are higher in IC-12-60 catalyst bed than in IC-12-61 catalyst bed

Catalytic package: IC-12-60 (2%Pd-Ce-Al2O3) + IC-12-62 (0.5%Pd-Mn-La-Al2O3)

Effect of ratio of heights of IC-12-60 and IC-12-62 catalyst beds and GHSV on methane conversion

Inlet temperature - 450ºС,Inlet methane concentration - 1.5 vol.%, pressure – 1 atm


20/180 мм

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

0 0,04 0,08 0,12 0,16 0,2

Высота слоя, м

Ко

нв

ер

сия

мет

ан

а

10000 1/час

40000 1/час

60000 1/часMet

han

e c

on

ver

sio

n, %

Bed height, m

10000 h-1

40000 h-1

60000 h-1

20 / 180 mm40/160 мм

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1

0 0,04 0,08 0,12 0,16 0,2

Высота слоя, м

Ко

нв

ерси

я м

етан

а10000 1/час

40000 1/час

60000 1/час

Met

han

e c

on

ver

sio

n, %

Bed height, m

10000 h-1

40000 h-1

60000 h-1

40 / 160 mm

• The methane combustion takes place mainly in IC-12-60 catalyst bed • This tendency becomes stronger with the decreasing space velocity and the

increasing of the height of IC-12-60 catalyst bed

10000 20000 30000 400000.0

0.2

0.4

0.6

0.8

1.0

Me

tha

ne

co

nve

rsio

n

GHVS, h-1


Catalyst package: IC-12-60 (Pd-Ce-Al2O3) + IC-12-61(Mn-La-Al2O3)

Combustion efficiency as function ofratio between height of the catalyst bed and GHSV

CCH4 1.5 vol. %, P – 1 atmIC-12-60 / IC-12-61 40 / 160 mm 30 / 170 mm 20 / 180 mm

CCH4 3.6 vol. %, P – 1 atmIC-12-60 / IC-12-61 20 / 180 mm

The methane combustion efficiency increases with the increase of the height of IC-12-60 catalyst bed and with methane concentration

Catalytic package: IK-12-60 (2%Pd-Ce-Al2O3) + IK-12-62 (0.5%Pd-Mn-La-Al2O3)

Effect of height ratio of IC-12-60/IC-12-62 catalyst beds on parameters of methane combustion

The methane combustion efficiency and temperature in catalyst bed increase with the increase of the height of IC-12-60 catalyst bed

2.3 Modeling of methane combustion process on combined catalyst package

Inlet temperature - 450ºС,Inlet methane concentration - 1.5% vol., pressure – 1 atm

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000 20000 30000 40000 50000 60000

Объемная скорость, 1/час

Ос

тато

чн

ое

со

де

рж

ан

ие

ме

тан

а,

рр

м

0/200

20/180

40/160

200/0

Res

idu

al m

eth

ane

con

ten

t, p

pm

GHSV , 1/h

600

650

700

750

800

850

900

950

1000

10000 20000 30000 40000 50000 60000


Мак

с.те

мп

.кат

али

зато

ра,

С0/200

20/180

40/160

200/0

GHSV , 1/h

Max

imu

m c

atal

yst

tem

per

atu

re, o

C

0,95

0,96

0,97

0,98

0,99

1

10000 20000 30000 40000 50000 60000


Ко

нв

ерси

я м

етан

а

6.5x6x2 mm

7x7x2 mm

7x7x3 mm

15x15x4 mm

0

0,5

1

1,5

2

2,5

3

3,5

4

10000 20000 30000 40000 50000 60000


Гид

р.с

оп

р.,

атм

6.5x6x2 mm

7x7x2 mm

7x7x3 mm

15x15x4 mm

GHSV, 1/h

Pre

ssu

re d

rop

, atm

GHSV, 1/h

Met

han

e co

nve

rsio

n

Catalyst package: IC-12-60 (2%Pd-Ce-Al2O3)-20 mm + IC-12-62 (0.5%Pd-Mn-La-Al2O3)-180 mm

Effect of shape and size of catalyst granules on parameters of methane combustion process


Inlet temperature - 450ºС, inlet methane concentration - 1.5% vol., pressure – 1 atm

The methane combustion efficiency and the pressure drop in catalyst bed increase with the decrease of the granule size

Granule shape - ring

Met

han

e co

nve

rsio

n

3. Design of catalyst packages in the combustion chamber

Uniform catalyst package

Combined catalyst packages

CH4 + air CH4 + airCH4 + air

«high temperature region» thermostable oxide catalyst, Mn-La-Al2O3, provides stable methane combustion at high temperatures

«ignition region»

Pd-catalyst with low light-off temperature - 240ºС initiates methane oxidation and provides outlet temperature sufficient to start methane combustion on the oxide catalyst

200 300 400 500 6000

10

20

30

40

50

60

70

80

90

100

110GHSV- 48000h-124000h-1

1000h-1

Temperature, oC

CH

4 co

nvers

ion

, %

Pd-Ce-Al2O3-catalyst

Schematic view of two-step methane oxidationin catalytic combustion chamber

200 300 400 500 600 700

0

20

40

60

80

100

CH

4 c

on

ve

rsio

n, %

Temperature, oC

Mn-La-Al2O3-catalyst: - initial; □- after 30 h; ○ - 50 h; ▲ - 100 h testing at 930oC

Catalytic activity in methane conversion

3. Design of catalyst packages in the combustion chamber

CH4+air

Т=1200K

Т<1000K

4. Tests in a model catalytic combustion chamberScheme of the model catalytic combustion chamber (BIC)

Thermocouples Sampling pipes

Fuel/Air mixture

Reactionproducts

4. Testing of uniform catalytic package in the model catalytic combustor

0 20 40 60 80 100 120

97.5

98.0

98.5

99.0

99.5

CH

4 co

nve

rsito

n,

%

Time duration, h

• The Mn-La catalyst which contains hexaaluminate structure exhibits higher stability at high temperatures than MnOx-Al2O3 catalyst

• Doping of Mn-La catalyst with palladium to 0.5 wt.% allows an increase of methane combustion efficiency (from 99.3 to 99.5%) and a decrease of inlet temperature (from 600 to 575oC)

GHSV - 15000 h-1, - 6.8-7.0, CH4 – 1.5 vol.%

T inletICT-12-40, 580oCIC-12-61, 600oCIC-12-62, 575oC

200 300 400 500 600

0

20

40

60

80

100

T50%

-340-350oC

T50%

-420oC

CH

4 con

vers

ion,

%

Temperature, oC

T50%

-385oC

GHSV - 1000 h-1, CH4 – 1.5 vol.%

80-120 hours of testing

Fresh – close symbolSpent – open symbol

4. Testing of combined catalytic package in the model catalytic combustor

0 20 40 60 80 100 120 140

98,0

98,5

99,0

99,5

100,0

CH

4 co

nve

rsito

n,

%

Timeon stream, h

GHSV - 15000 h-1, - 6.8-7.0, CH4 – 1.5 vol.%

Catalyst and T inletICT-12-62, 580oCIC-12-62, ring+sphere, 580oCIC-12-61 (ring)+IC-12-62(sphere), 575oC

Catalyst package formed by two beds of catalysts of the same chemical composition: the upstream bed of large rings and the downstream bed of smaller beads (with different void volumes) allows a considerable increase of combustion efficiency

4. Testing of combined catalytic package in amodel catalytic combustor

GHSV - 15000 h-1, - 6.8-7.0, CH4 – 1.5 vol.%

T inletICT-12-61, 600oCIC-12-60+IC12-61, ring, 580oCIC-12-60, IC-12-61 (ring)+IC-12-62(sphere), 470oC

0 10 20 30 40 50 60 70 80 9097.5

98.0

98.5

99.0

99.5

100.0

CH

4 co

nve

rsito

n,

%

Time duration, h

Composing the catalyst package by three catalysts with different chemical compositions and different shapes:

• IC-12-60 (ring) with low ignition temperature

• IC-12-61 (ring) with high thermal stability

• IC-12-62 (sphere) smaller granules and high activity

allowed us to achieve high combustion efficiency at a low inlet temperature 470оС

Scheme of the model catalytic combustion chamber (CIAM)

T2P2

P1

80

L =

100

- 3

80 м

мT1

1

2

8

34

7

5

6

9

Продукты сгорания

Х

Х=0

Sampling

Combustion Products

Air + CH4

1 – catalytic combustion chamber 2 – thermal shield 3 – air electric heater4 – compensating lattice5 – electric heater 6 – «guard» electric heater7 – thermal protection of frame8 – mixer9 – hot probe

4. Tests in a model catalytic combustion chamber

Design of catalytic combustion chamber

Catalyst bed height – 300 mm

Combination of beds: IC-12-60 (Pd-Ce-Al2O3) - 20mm

Inert material – 20 mm

IC-12-61 (Mn-La-Al2O3) - 260mm

Temperature profile through catalyst bed (=6.68-10)

Outlet concentrations of CH, CO, NOx (=6.68-10)

Tinlet – 840 KGair – 4.5 g/s

Reaction

CH4 + 2O2 = CO2 + 2H2O

4

4

221,0)100(

CH

CH

CC

The layer of inert material acts as a heat shield. At differrent methane concentrations and low air/fuel eqivalence ratio ( = 6.7), the Pd-catalyst is not overheated above 1000К ( 730ºС )

Concentrations of emissions at the outlet of the catalytic combustion chamber areNOx 0-1 ppm; CO < 4 ppm; CH <10 ppm

4. Testing of combined catalytic package in the model catalytic combustion chamber

Exhaust

AirP = 3,8 - barT = K

5540 - 850

M ethane

Catalystm odule

Preheatingcham ber

Methane

Schematic view and main characteristics of the prototype catalytic combustor for a 125 kW gas turbine

5. Testing of the prototype catalytic combustion chamber

Diameter 0.6 m

Height 1.65 m

Catalyst loading 70 kg (87 dm3)

Temperature at the combustor inlet

830 K

Temperature at the combustor outlet

1180 K

Pressure 5 atm

Air velocity at the combustor inlet

950 g/s (2640 nm3/h)

Photos of the prototype catalytic combustor for a 125 kW gas turbine


Design of catalytic combustion chamber

Catalyst: ICT-12-40 (Mn-Al2O3)Catalyst bed height – 450 mmCatalyst bed volume – 87 dm3

Granule shape - ringGranule size - 7.5 x 7.5 x 2.5 mm

Test conditions

Temperature at the combustor inlet 850 KPressure at the combustor inlet 5 atmAir flow velocity at the combustor inlet

830 g/s (2310 nm3/h) Methane flow velocity in the preheating chamber

0-0.9 g/s (0-4.5 nm3/h) Methane flow velocity in the combustor

6,9-7.5 g/s (34.8-37.5 nm3/h) GHSV 19000 - 31200 h-1

Results of the tests of the prototype catalytic combustor

Temperature at the combustor inlet 850 K

Pressure at the combustor inlet 5.0 atm

Air flow velocity at the combustor inlet 830 g/s (2310 nm3/h)

Methane flow velocity in the preheating chamber 0-0.9 g/s (0-4.5 nm3/h)

Methane flow velocity in the combustor 6.9 g/s (34.5 nm3/h)

GHSV 27000 h-1

Temperature at the catalyst bed inlet 835 - 860 K

Temperature at the catalyst bed outlet 1145-1160 K

Concentrations at the combustor outlet

HC 18-20 ppm

CO 4.2-6 ppm

NOx 0 ppm



СО, NOx and CH4 concentrations (ppm) at the outlet of the catalytic combustion chamber

CO

, N

O c

on

cen

trat

ion

, p

pm

5 – 6 ppm CO

0 ppm NOx

Time duration, s

Time duration, s

CH

4 c

on

cen

tra

tio

n,

pp

m

18-20 ppm CH4

Temperature at the combustor inlet 840 K

Pressure at the combustor inlet 5.0 atm

Air flow velocity at the combustor inlet 960 g/s (2670 nm3/h)

Methane flow velocity in the preheating chamber 0.89 g/s (4.5 nm3/h)

Methane flow velocity in the combustor 7.45 g/s (37.5 nm3/h)

GHSV 31200 h-1

Temperature at the catalyst bed inlet 880 K

Temperature at the catalyst bed outlet 1145 K

Concentrations at the combustor outlet

HC 6 ppmCO 4.2 ppmNOx 4.6 ppm

5. Testing of the modified prototype catalytic combustion chamber

36

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