DECOMPOSITION OF METAL SULFATES DECOMPOSITION OF METAL SULFATES A SO - - PowerPoint PPT Presentation

▶
decomposition of metal sulfates decomposition of metal
SMART_READER_LITE
LIVE PREVIEW

DECOMPOSITION OF METAL SULFATES DECOMPOSITION OF METAL SULFATES A SO - - PowerPoint PPT Presentation

Jan 14, 2024 27 likes •367 views

DECOMPOSITION OF METAL SULFATES DECOMPOSITION OF METAL SULFATES A SO 2 -SOURCE FOR SOURCE FOR A SO 2 - SULFURIC ACID PRODUCTION SULFURIC ACID PRODUCTION Dr. Jrg Hammerschmidt Agenda Agenda 2 Introduction Short description of the

slide-1
SLIDE 1

DECOMPOSITION OF METAL SULFATES DECOMPOSITION OF METAL SULFATES A SO A SO2

2 -

  • SOURCE FOR

SOURCE FOR SULFURIC ACID PRODUCTION SULFURIC ACID PRODUCTION

  • Dr. Jörg Hammerschmidt
slide-2
SLIDE 2

2

Agenda Agenda

Introduction Short description of the Fluid Bed Technology Scale-up - From test plant to production size Influence factors for the Decomposition regarding Thermodynamic and Kinetic Outotec’s Roasting & Acid Plant Concept for the Decomposition-Process

slide-3
SLIDE 3

3

Decomp Decomp. . – – SO SO2

2-

  • Source for Acid

Source for Acid

Metal- Sulfate Decomposition MeSO4MeO2+SO2

slide-4
SLIDE 4

4

Process Options for Decomposition Process Options for Decomposition

Three Process Alternatives Multiple Hearth Furnace Rotary Kiln Fluid Bed Technology

slide-5
SLIDE 5

5

Process Process-

  • parameters

parameters -

  • for Calcium Sulfate

for Calcium Sulfate

Feedmaterial Raw Material/ Residues 200.000 t/a Old Acid 20.000 t/a Combustables 40.000 t/a Products Cement 100.000 – 130.000 t/a Sulfuric Acid 70.000 – 100.000 t/a

Rotary Kiln Rotary Kiln – – M Mü üller K ller Kü ühne hne

slide-6
SLIDE 6

6

Process Process-

  • parameters

parameters – – for Iron Sulfate for Iron Sulfate

Number of salt feed points 2 Bed cross section area 20 m² Bed height 1.4 m Temperature 800 - 900°C Number of oil feed points 15 - 20 Fuel oil consumption 2 000 kg/h Fluidizing air 13.000 Nm³/h Cinders 4 t/h Steam 8 t/h

FB FB-

  • Technology

Technology

slide-7
SLIDE 7

7

FeSO FeSO4

4-

  • Decomposition Plant

Decomposition Plant

slide-8
SLIDE 8

8

References for FB References for FB-

  • Decomposition

Decomposition

Spent Acid 435 t/day Germany/ Leverkusen Lanxess Spent Acids; FeSO4, Pyrite 600 t/day Germany/ Krefeld Kerr McGee Spent Acids; Sulphates 2000 t/day Germany/ Sachtleben Sachtleben Chemie Spent Acids 650 t/day Germany/ Worms Röhm - Hüls Spent Acids 400 t/day Germany/ Wesseling Röhm - Hüls Ferrous Sulphates/ Coal 270 t/day France/ Calais Tioxide Ferrous Sulphate, Pyrite 235 t/day Slovenija/ Celje Cincarna Feedstock Capacity t/day (100%-H2SO4) Country/ Town Company

slide-9
SLIDE 9

9

Agenda Agenda

Introduction Short description of the Fluid Bed Technology Scale-up - From test plant to production size Influence factors for the Decomposition regarding Thermodynamic and Kinetic Outotec’s Roasting & Acid Plant Concept for the Decomposition-Process

slide-10
SLIDE 10

10Which is the right Fluidized Bed System?

Which is the right Fluidized Bed System?

Stationary Fluidized Bed characterised by:

Low gas velocities Bubbling bed with defined bed surface Limited solids carry over Low slip velocity Number of plants: 264

Circulating Fluidized Bed is characterised by:

Higher gas velocity Increased solids entrainment Intensive internal and external recycle of solids Maximum slip velocity Very intensive mixing Excellent heat and mass transfer rates Number of plants: 172

Transport Reactor characterised by:

Very high gas velocities Minimum slip velocity

Bubbling fluidized bed (FB) Circulating fluidized bed (CFB) Transport or flash reactor (FR)

Gas

Velocity

Solids

Increasing solids density

Stationary Fludized Bed Circulating Fluidized Bed Flash Reactor

Increasing Expansion

slide-11
SLIDE 11

11 Why using the CFB

Why using the CFB-

  • Technology ?

Technology ?

Operation at high slip velocity,

high specific throughputs and small unit sizes resulting in lower capital cost.

Across the entire reactor system an improved control and uniformity of the operating temperature with high throughput.

ensures an uniform decomposition reaction of the material. constant Gas condition/composition in the roaster system and its uniformity.

Variation of solid residence time,

potential to improve decomposition efficiency. possibility to run with part load and load changes according to the concentrate composition.

slide-12
SLIDE 12

12 Why using the CFB

Why using the CFB-

  • Technology ?

Technology ?

Suitability for exothermic and endothermic (=decomposition) processes. Acceptance of feed material variations in chemical composition and particle size distribution ranges. Main limitations are the subsequent process steps like gas cleaning or sulphuric acid plant. Suitability to operate with oxygen enriched roasting air. Suitability for direct fuel injection like coal addition into the reactor. Reduction of heat losses.

slide-13
SLIDE 13

13

Agenda Agenda

Introduction Short description of the Fluid Bed Technology Scale-up - From test plant to production size Influence factors for the Decomposition regarding Thermodynamic and Kinetic Outotec’s Roasting & Acid Plant Concept for the Decomposition-Process

slide-14
SLIDE 14

14 Basis for the CFB

Basis for the CFB-

  • Design Data

Design Data

Laboratory Pilot-Test Work Vast Experiences in FB-Technology-> Scale-up Models for Thermo- dynamic and Fluidization CFB Design-Basis

slide-15
SLIDE 15

15 Vast Experience

Vast Experience

Alumina calcining plants 51 units Gold ore roasting plants 5 units Power plants* 82 units Calcining of clay/lime 3 units Sulphur adsorption 16 units Fluorine adsorption 10 units Further Processes 5 units total 172 units

Coal based reduction; Gas based reduction (Circored), Ore preheating (Circoheat) etc.

*no longer part of Outotec’s offer

slide-16
SLIDE 16

16

Particle size and density Retention time Process temperature Process energy requirement Production rate Demand on product quality

Vast Experience in design criteria Vast Experience in design criteria

Laboratory Pilot-Test Work Vast Experiences in FB-Technology-> Scale-up Models for Thermo- dynamic and Fluidization CFB Design-Basis

slide-17
SLIDE 17

17 Pilot

Pilot plants plants -

  • study phases

study phases

50 mm 80 mm 160 mm 200 mm 700 mm 350 mm DTA* Basic Investigations (batch) Continuous Pilot Plant Operation Semi-Industrial Pilot Plant Operation Scale Up Data Achievable

* Differential Thermal Analysis

Laboratory Pilot-Test Work Vast Experiences in FB-Technology-> Scale-up Models for Thermo- dynamic and Fluidization CFB Design-Basis

slide-18
SLIDE 18

18 50mm FB laboratory apparatus

50mm FB laboratory apparatus

slide-19
SLIDE 19

19

200 mm CFB pilot plant 200 mm CFB pilot plant

Gas Conditions:

  • xidizing or reducing

Temperature: up to 1050 °C Pressure: atmospheric/pressurized

slide-20
SLIDE 20

20Scale up figures of former Outotec

Scale up figures of former Outotec projects projects

Process From pilot To industrial Scale up plant size plant size factor Al calcination, 1,000 mm/ 3,600 mm/ 1:20 24 t/d 500 t/d Coal combustion, 360 mm/ 5,000 mm/ 1:1,000 20 kg/h 500 t/d Gold ore roasting, 200 mm/ 3,800 mm/ 1:4,000 22 kg/h 2,000 t/d

slide-21
SLIDE 21

21

Agenda Agenda

Introduction Short description of the Fluid Bed Technology Scale-up - From test plant to production size Influence factors for the Decomposition regarding Thermodynamic and Kinetic Outotec’s Roasting & Acid Plant Concept for the Decomposition-Process

slide-22
SLIDE 22

22

Influencefactors regarding Thermodynamic and Kinetic

For Thermodynamik Temperature Atmosphere – SO2 – O2 - CO Type of Metalsulfate – Impurities For Kinetik (Mass- and Heat transport) – beside the above mention criteria…. Specific Surface Gas flow at Sulphate Surface

slide-23
SLIDE 23

23

Fe Fe2

2(SO

(SO4

4)

)3

3-

  • Decompostion

Decompostion Depending Depending on

  • n Temperature

Temperature (Air) (Air)

400 500 600 700 800 900 1000 10 20 30 40 50 60 70 80 90 100 File: C:\HSC6\Gibbs\FeSO42.OGI C kmol Temperature SO2(g) Fe2O3(H) Fe2(SO4)3 SO3(g) FeSO4 FeO

slide-24
SLIDE 24

24

Temperature and Atmosphere Temperature and Atmosphere

slide-25
SLIDE 25

25 Atmosphere

Atmosphere

20 40 60 80 100 Time /min 50.00 60.00 70.00 80.00 90.00 100.00 TG /% 200 400 600 800 1000 1200

  • Temp. /°C

180 ml/min Air +20ml/min N2 200 ml/min N2 Mass Change: -44.09 % Mass Change: -44.11 % End: 938 °C End: 914 °C

200 ml/min N2 End: 915°C 180 ml/min Air + 20 ml/min N2 End: 938°C

Decomposition of Decomposition of MnSO MnSO4

4 ·

· H H2

2O

O

slide-26
SLIDE 26

26

Influence of type of Influence of type of Metalsulfate Metalsulfate @ 850 @ 850°C

slide-27
SLIDE 27

27

Kinetic = fast Kinetic = fast Masstransport Masstransport

SO2/SO3 Gas Film Fluidising medium Fluidising medium saturated with SO2/SO3 Sulphate particle

Specific Surface Gas flow at Sulphate Surface

slide-28
SLIDE 28

28 Decomposition of

Decomposition of MnSO MnSO4

4 ·

· H H2

2O

O in N in N2

2 at different N

at different N2

2-

  • Flow

Flow

20 40 60 80 100 Time /min 50.00 60.00 70.00 80.00 90.00 100.00 TG /% 200 400 600 800 1000 1200

  • Temp. /°C

20ml/min N2 200ml/min N2 Mass Change: -44.12 % Mass Change: -44.13 % End: 915 °C End: 932 °C

200 ml/min N2 End: 915°C 20 ml/min N2 End: 932°C

  • Mass. Change –44,13%
  • Mass. Change –44,12%
slide-29
SLIDE 29

29

Agenda Agenda

Introduction Short description of the Fluid Bed Technology Scale-up - From test plant to production size Influence factors for the Decomposition regarding Thermodynamic and Kinetic Outotec’s Roasting & Acid Plant Concept for the Decomposition-Process

slide-30
SLIDE 30

301

1st

st Concept = CFB + Recuperator

Concept = CFB + Recuperator

Off-Gas Recycling- material Concentrate + Coal Calcine Air

CFB Recuperator

Air

slide-31
SLIDE 31

31

Advantage of 1 Advantage of 1st

st Concept

Concept

Energy Recovery from the Off-Gas stream in the recuperator and reducing the fuel consumption in the CFB Reducing of the off-gas volume stream and decreasing

  • f the equipment size.

Increasing the SO2-concentration in the off-gas stream Higher flexibility in the concentrate composition.

slide-32
SLIDE 32

322

2nd

nd Concept = CFB + Venturi Dryer

Concept = CFB + Venturi Dryer

Concentrate Off-Gas Recycling- material Coal Air Air

CFB Venturi Dryer

Calcine

slide-33
SLIDE 33

33

Advantage of 2 Advantage of 2nd

nd Concept

Concept

Energy recovery from the Off-Gas stream in the Venturi-Dryer. Saving coal consumption for drying the wet concentrate in the CFB. Saving additional equipment cost for the recuperator and Dryer. Reducing the volume of the off-gas stream and increasing the SO2-concentration in the off-gas stream. High flexibility in the concentrate composition.

slide-34
SLIDE 34

DECOMPOSITION OF METAL SULFATES DECOMPOSITION OF METAL SULFATES A SO A SO2

2 -

  • SOURCE FOR

SOURCE FOR SULFURIC ACID PRODUCTION SULFURIC ACID PRODUCTION

  • Dr. Jörg Hammerschmidt