stepwise liquefaction technology for fossil...

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Stepwise Liquefaction Technology for Fossil Fuels

Qiang GuoSynfuels China Technology Co., Ltd.

Email: [email protected]

2015.6.9

——Slurry-bed Hydrocracking

我们的事业能源的未来Our expertise Energy in future

Contents

1. Background

2. Project planning

3. Research of slurry-bed hydrocracking

Coals structure and pyrolysis properties

Recycling solvents

Fe based catalyst

X to liquids reaction

4. Pilot tests

1. Background

LAB1.0L

PPΦ 0.3m

DEMOΦ 5.Xm

IndustrializationΦ 10.Xm

Development of SFC F-T technologies

1. Background

Energy efficiencyProduct quality

Stepwise liquefaction

COALGasoline

Kerosene

Diesel

Solvent

…

Chemicals

DCL SEP&HYDRO

PRODUCTSUP-GRADING

GASIFACTION ICTL

O2/H2O

Recycling solvent

H2Residues

Slurry-bed hydrocracking

Technology improvement

1. Background

Features of slurry-bed hydrocracking reaction

1. Feedstocks Low-rank coals Heavy crude oil Coal tar Biomass

2. Operating pressure 30-50 bar3. Chemical structure of products Straight-chain alkanes Aromatics Cycloalkanes Isoparaffins

4. Process：Recycling solvent balance

2. Project planning

Fundamental research

Pilot plant

Technologies

Feedstocks structure and prolysis properties

Hydrogen transfer from solvents to coals

Structure and performance of Fe-based catalyst

Formation and stabilization of free radicals

Commercialization!

Preparation of high-activity Fe based catalyst

Selective hydrogenation process for H2-donor solvent

Coal slurry pretreating technology

Slurry-bed hydrocracking reaction

(10000 t/a)


Coal structure-Wiser Model

O S

H H

H

O

H

NH2

H

C

H

H

O

H

H

H

H2 HO

H2

O C

H

H

C

H

HO

C

HH

H

H

H

C H

H

HH

C H

H

H

H

H

H

H2H2

H2

HH2

CH H

CC

HH

H H

C

C

C

H

H

HH

OH

H

H2H2

H

H

H

H2 OH HH2

H2

H

H

H

H

H

H

H

H

H

C H

H

H2S

OC

OH

O

H

H

OH

H H H OH

HHHHC

H

HH

HH

HH

O

C

H H

H

H2

H2H2

H2

HO

H CH3

S

H

O

H

H

H

C

O

O

H

S

S

N OC

H

H

H

H

O

H

H

C HH

H

H

OH

N

H

××

×

×

××

×××

××

×

×

×

××

××

×

××

×CH

HO

C

HH

H

H

H

H

O

H

H

C HH

H

H

OH

N

H

CH

H

O S

H H

H

O

H

NH2

H

C

H

H

H

H

HH

H

H2H2

H

H

H

H2 OH HH2

H2OH

C HH

S H C H H O

Stabilized by hydrogen

Products：Gases

(CH4, H2S, LPG…)

Liquids

(H2O, Naphtha…)

Large molecules

(Asphaltene, Solids…)

Coal structure and pyrolysis properties



Temperature/ oC 400 420 430 440In-situ EPR Spins *1018 /g 5.16 11.63 13.69 16.43

Spins capture Spins *1021 /g 1.54 2.33 2.67 4.85

In-situ electron paramagnetic resonance (EPR) analysis

0 100 200 300 400 500 600

0

10

20

30

40

50

60

Temperature/oC

Spin

s (*1

018 )

/g

AUS coal MTH coal YZ coal

Free radicals capture


Coal GasesDry gas LPG…

Water AshChemicals

(small molecules)

+ + +


Pyrolysis

Spin capture

1

2

3

4

5

6

7

8

9

10

11

12


Chemical structureRecycling solvent Coal swelling and hydrogen donor

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27


Recycling solvent - Hydrogen transfer mechanism

SolventsDissociation energy (KJ/mol)

C-H bonds Transition statesTetralin 345.78 47.40Decalin 394.23

Dihydroanthracene 312.86 32.96Tetrahydroanthracene 340.65 45.14Hexahydroanthracene 298.57Octahydroanthracene 345.12 47.00Perhydroanthracene 399.03

Dihydrophenanthrene 348.28 46.24Tetrahydrophenanthrene 340.46 47.40Octahydro-phenanthrene 345.21 48.50Perhydrophenanthrene 394.95

Dihydropyrene 339.82 42.67Tetrahydropyrene 348.78 57.58Hexahydropyrene 340.92 49.96Decahydropyrene 337.25 46.75Perhydropyrene 398.06


Recycling solvent -Hydrogen donating ability

Solvents A B C D E F

Group compositionAlkanes 15.4 19.5 19.4 19.5 19.2 14.6

Naphthenes 13.1 25 37.6 48.1 55.1 58.6Aromatics： 71.5 55.5 43.0 32.4 25.7 26.9

monocyclics 41.4 39.9 34.5 27.3 22.0 22.1Dicyclics 25.8 13.5 8.0 4.9 3.6 4.5tricyclics 4.3 2.1 0.5 0.2 0.1 0.3

Coal liquefactionCoal conversion % 82.38 89.53 91.37 91.70 97.25 98.67

Oil yield % 43.10 61.33 64.39 65.18 71.04 72.39 >150 oC 4.29 4.02 4.69 4.28 5.97 3.99

150-370 oC -1.97 16.58 37.36 23.43 25.02 26.98 370-520 oC 1.75 17.94 2.89 15.80 18.15 20.80

H2O yield % 14.38 16.62 16.22 16.16 15.80 16.17


Catalyst structure

0.1 1 10

0

2

4

6

8

10

12

14

Pa

rticle

size

dist

ribut

ion

/%

Paritcle size /µm

121 141 142 143


0.0

0.5

1.0

1.5

2.0

2.5

dca

Cons

umpt

ion

(t/10

0t co

al

）

b

Catalyst

Catalyst performance

0

10

20

30

40

50

60

DCB

naph

thale

ne co

nver

sion

/%

A

Catalyst

Samples MTH-coal M-152 M-255 M-296 M-325

Real density 0.691 0.714 0.713 0.712 0.724Particle size(μm) 17.01 19.29 32.90 32.79 18.27

200 400 600 800 1000-2.0

-1.5

-1.0

-0.5

0.0

DTG

(%/m

in)

Temperature (oC)

MTH-coalM-152M-255M-296M-325H-230H-300

New coal-slurry pretreatment technology


0 20 40 60 80 100

0.000

0.005

0.010

0.025

0.030

0.035

dV/d

log(

w) P

ore V

olum

e (cm

3/g)

Average Width (nm)

MTH-coal M-152 M-255 M-296 M-325

New coal-slurry pretreatment technology

72

74

76

78

80

82

Oil y

ield

(%)

M-123 M-325M-269M-255M-152As-prepared

Oil yield Coal conversion

Pretreatment time (s)

Coal

conv

ersio

n (%

)

56

58

60

62

64

66

68


Influence of pretreatment of coal liquefaction

X to liquid reaction


—Low-rank coals

Samples AUS YL HM MTHIndustrial analysis

M ad % 11.18 4.56 15.17 5.67A ad % 1.27 3.96 3.98 5.00V ad % 45.22 43.81 41.15 33.14

Test resultsConversion daf(%) 97.25 95.95 87.69 80.01Oil yield daf(%) 71.04 74.09 66.08 66.08H2O yielddaf(%) 15.8 11.45 8.26 5.8LPG daf(%) 3.09 2.8 2.66 2.76520oC daf(%) 21.9 15.33 27.86 22.31

（Pressure：30bar）



—Heavy crude oil

API gravity 11

Carbon residue wt% 13.66

C /wt% 86.08

H /wt% 11.01

H/C /mol 1.53

N /wt % 0.937

S /wt% 0.439

IBP oC 201.4

370oC % 11.4

520oC % 35.3

720oC % 63.6

Dry gas (%) 4.79

LPG (%) 3.83



—Coal tarsSamples YD HM JN CZ DB

Analysis Density (20oC,g/cm3) 1.0415 1.1136 1.1136 1.0902 0.9415

Coal dust % 4.79 0.7 10.96 6.01 1.78Asphaltene % 0.91 0.24 13.12 21.10 0.79

H/C mol 1.18 1.37 1.22 0.72 1.44O/S/N wt% 7.13 9.15 9.39 2.23 3.01

X to liquid reaction —Products


Samples Naphtha DieselDensity (20oC), g/cm3 0.7743 0.8493distillation range：

5% 91.2 oC 135.2oC50% 118.4oC 264.2oC95% 166.0oC 347.8oC

S, ppm 8.02 7.17N, ppm 15.00 13.20Octane value(RON) 82.6group composition, m%

Alkanes 1.9 12.3Naphthenes 88.4 60.8Aromatics： 9.7 26.9Monocyclics 9.6 24.5

Dicyclics 0.1 2.4tricyclics 0 0

4. Pilot tests

20,000 t/a pilot plant

4. Pilot tests

Feedstocks Heavy crude oil Coal tar

Capacity 1.7t/h 2.0t/h

Operating conditions

Temperature 445oC 435oC

Pressure 4.5MPa 4.5MPa

Main Products

LPG 5.04% 1.70%

Naphtha 17.23% 15.93%

Diesel 59.39% 69.94%

Total 81.66% 87.57%

Fe catalyst consumption 1.0% 0.9%

H2 consumption 2.14% 3.82%

Pilot test results

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幻灯片编号 1幻灯片编号 21. Background1. Background1. Background2. Project planning3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking3. Research of slurry-bed hydrocracking4. Pilot tests4. Pilot tests幻灯片编号 23

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