Zimpro® Wet Air OxidationZimpro® Wet Air Oxidation · Zimpro® Wet Air OxidationZimpro® Wet Air...
-
Upload
trinhquynh -
Category
Documents
-
view
221 -
download
1
Transcript of Zimpro® Wet Air OxidationZimpro® Wet Air Oxidation · Zimpro® Wet Air OxidationZimpro® Wet Air...
Zimpro® Wet Air OxidationZimpro® Wet Air OxidationEnviroArabia 2007
Chad Felch
Dr. Michael Howdeshell
Water TechnologiesProtection notice / Copyright noticeFor internal use only / Copyright © Siemens AG 2006. All rights reserved.
Introduction / Contents
OverviewDescription of the Zimpro® WAO processp p pDescription of spent caustic samplesTest ProceduresResultsFull-Scale Zimpro® WAO CasesConclusions
Water TechnologiesProtection notice / Copyright notice
D i ti f Zi ® W t Ai O id tiDescription of the WAO Process
Description of Zimpro® Wet Air Oxidationp
Water TechnologiesProtection notice / Copyright notice
Wet Air Oxidation –Typical Process Flow Diagram
Water TechnologiesProtection notice / Copyright notice
W t Ai O id tiWet Air Oxidation
Process Variables
Oxidation temperature and pressureHydraulic detention timeHydraulic detention timeOxidant – typically air or oxygenFlow configuration gCatalyst
Water TechnologiesProtection notice / Copyright notice
Wet Air Oxidation For Hi h St th I d t i l W t tHigh Strength Industrial Wastewaters
D i f ifi iDestruction of specific constituentsPretreatment for biological polishingGross reduction in COD loadingGross reduction in COD loading
Repsol POSM, Tarragona, Spain
Water TechnologiesProtection notice / Copyright notice
p g p
Wet Air Oxidation –Hi h St th I d t i l W t tHigh Strength Industrial Wastewaters
Typical Industrial Wet Air Oxidation Feed Characteristics
Fl 1 t 50 3/hFlow range: 1 to 50 m3/h
COD range: 10,000 mg/l to 100,000 mg/l
Temperature Range: 150 to 320°C
Pressure range: 5 to 225 barg
Water TechnologiesProtection notice / Copyright notice
Description of Spent Caustic Streams
Spent Caustic Waste Streams
Water TechnologiesProtection notice / Copyright notice
Cl ifi ti f S t C tiClassification of Spent Caustics
Type Principle COD Source Source
Sulfidic Sulfides and/or mercaptans
Ethylene orLPG Scrubbersmercaptans LPG Scrubbers
Phenolic compounds and Scrubbing or FCCCresylic Phenolic compounds and reduced sulfur
Scrubbing or FCC gasoline washes
Naphthenic Naphthenic compounds and reduced sulfur
Scrubbing kerosene, diesel, and jet fuel
Water TechnologiesProtection notice / Copyright notice
Issues With Spent Caustic Produced in the P t h i l I d tIssues With Spent Caustic Produced in the P t h i l I d tPetrochemical IndustryPetrochemical Industry
Odors caused by sulfides mercaptansOdors caused by sulfides, mercaptans and volatile organicsHazards associated with toxicityHi h h i l d dHigh chemical oxygen demandTendency to foamCorrosivePotential inhibitory or toxic effects in biological treatment
Water TechnologiesProtection notice / Copyright notice
R ti D i WAO f S t C tiReactions During WAO of Spent Caustics
Sulfide
NaHS + 2 O2 + NaOH => Na2SO4 + H2O
MercaptanMercaptan
NaSR + 3/2 O2 => RSO3-Na
CresylicC6H5O-Na + 7 O2 + 11 NaOH => 6 Na2CO3 + 8 H2OC6H5O-Na + 51/2 O2 + 83/4 NaOH => 41/2 Na2CO3 + 3/4 CH3COO-Na + 53/4 H2O
NaphthenicNa-C12H22O2 + 163/4 O2 + 23 NaOH => 12 Na2CO3 + 221/2 H2ONa-C12H22O2 + 131/4 O2 + 173/4 NaOH => 81/2 Na2CO3 + 13/4 CH3COO-Na + 171/4 H2O
Water TechnologiesProtection notice / Copyright notice
Laboratory Testing Objectives andLaboratory Testing Objectives and Procedures
Laboratory Testing Objectives and Procedures
Water TechnologiesProtection notice / Copyright notice
St d Obj tiStudy Objectives
1 To investigate the effect of temperature on the destruction of1. To investigate the effect of temperature on the destruction of chemical oxygen demand in different types of spent caustic streams.
2 T i ti t th bi d d bilit f ffl t f t i id ti f2. To investigate the biodegradability of effluent from wet air oxidation of spent caustic at various WAO oxidation conditions.
Water TechnologiesProtection notice / Copyright notice
T t A tTest Apparatus
Laboratory WAO testing wasLaboratory WAO testing was performed in autoclaves constructed from nickel 200 or Inconel 600
The volume of the autoclaves ranged between 500 ml to 750 ml
Water TechnologiesProtection notice / Copyright notice
T t A tTest Apparatus
The autoclave reactor is l d d i tloaded into a shaking heaterassembly for mixing and temperature pcontrol
Water TechnologiesProtection notice / Copyright notice
D t i ti f Bi d d bilitDetermination of Biodegradability
Biodegradability was monitored in two waysBiodegradability was monitored in two ways
1. BOD to COD Ratio (BOD/COD > 0.4 is considered readily1. BOD to COD Ratio (BOD/COD 0.4 is considered readily biodegradable)
2. An analytical investigation of the types of organics present in the oxidized effluent samplespresent in the oxidized effluent samples.
Water TechnologiesProtection notice / Copyright notice
Laboratory Test ResultsLaboratory Test Results
Results From Laboratory Testing
Water TechnologiesProtection notice / Copyright notice
R lt S lfidi S t C tiResults – Sulfidic Spent Caustic
Sulfidic Spent CausticSulfidic Spent CausticMeasured Chemical Oxygen Demand and Biological
Oxygen Demand%
40000
50000>99% Reduction
in COD at all temperatures
t t d
20000
30000
40000 tested
10000
20000BOD (mg/L)COD (mg/L)
Feed 200°C 240°C 260°C
BOD (mg/L)COD (mg/L)0
Water TechnologiesProtection notice / Copyright notice
260 C
R lt S lfidi S t C tiResults – Sulfidic Spent Caustic
Sulfidic Spent Caustic
0 50.60.70.8
OD
0.20.30.40.5
B
OD
/CO
0.4
00.1
200°C 240°C 260°C
Temperature (°C)
Water TechnologiesProtection notice / Copyright notice
R lt C li S t C tiResults – Cresylic Spent Caustic
C li S t C tiCresylic Spent Caustic Measured Chemical Oxygen Demand and
Biological Oxygen Demand
30000
g yg%COD Reduction
200°C 54%
220°C 57%
15000
20000
25000 240°C 60%
260°C 64%
5000
10000
15000BOD (mg/L)COD (mg/L)
Feed 200°C 220°C 240°C 260°CBOD (mg/L)
COD (mg/L)0
Water TechnologiesProtection notice / Copyright notice
260 C
R lt C li S t C tiResults – Cresylic Spent Caustic
Cresylic Spent Caustic
0.600.700.80
D
0 200.300.400.50
BO
D/C
OD
0.40
0.000.100.20
Feed 200°C 220°C 240°C 260°CFeed 200 C 220 C 240 C 260 C
Temperature (°C)
Water TechnologiesProtection notice / Copyright notice
R lt N hth i S t C tiResults – Naphthenic Spent Caustic
Naphthenic Spent CausticMeasured Chemical Oxygen Demand and
Bi l i l O D d
3000035000
Biological Oxygen Demand%COD Reduction
200°C 60%
200002500030000 220°C 62%
240°C 68%
260°C 75%
50001000015000 BOD (mg/L)
COD (mg/L)
Feed 200°C 220°C 240°C 260°CBOD (mg/L)
COD (mg/L)0
Water TechnologiesProtection notice / Copyright notice
260 C
R lt N hth i S t C tiResults – Naphthenic Spent Caustic
Naphthenic Spent Caustic
0.80
0.60
0.70
0 80
0 30
0.40
0.50
BO
D/C
OD
0.40
0.10
0.20
0.30B
0.00Feed 200°C 220°C 240°C 260°C
Water TechnologiesProtection notice / Copyright notice
TOC I ti tiTOC - Investigation
Sulfidic Cresylic NaphthenicReported As Units
Oxidation Temperature °C 200 240 260Retention Time min 60 60 60Retention Time min 60 60 60TOC C mg/L 3370 2420 2770
Acetic Acid CH3COOH mg/L 5650 1720 3190Formic Acid HCOOH mg/L 760 1910 2820Fumaric Acid HOOCCH=CHCOOH mg/L 11 9 <1
P i i A id CH CH COOH /L 620 250 100Propionic Acid CH3CH2COOH mg/L 620 <250 <100
Succinic Acid HOOCCH2CH2COOH mg/L 940 360 599Oxalic Acid HOOCCOOH mg/L 560 1610 1560Oxalic Acid HOOCCOOH mg/L 560 1610 1560
Acetone CH3COCH3 mg/L --- --- 202% Recovery of TOC % 97.8 73.0 101
Water TechnologiesProtection notice / Copyright notice
y
Full Scale WAO Case StudiesFull Scale WAO Case Studies
Full-Scale WAO Case Studies
Water TechnologiesProtection notice / Copyright notice
F ll S l WAO C St d S lfidiFull Scale WAO Case Study - Sulfidic
Data From A Full Scale WAO Unit Treating Sulfidic Spent Caustic
Temperature - 200°C Retention Time - 60 minutes
Feed EffluentFeed Effluent
Analysis Units
COD mg/L 10880 2410COD mg/L 10880 2410
TOC mg/L 1060 930
S lfid S /L 3380 1Sulfide-S mg/L 3380 <1
Thiosulfate-S mg/L 1790 34
There are currently >30 full scale WAO systems treating sulfidic spent caustic
COD Destruction % --- 77.8TOC Destruction % --- 12.3
Water TechnologiesProtection notice / Copyright notice
There are currently >30 full scale WAO systems treating sulfidic spent caustic. There have been no reported issues with biodegradability of the oxidized effluent.
F ll S l WAO C St d C liFull Scale WAO Case Study - Cresylic
Data From A Full Scale WAO Unit Treating Cresylic Spent CausticData From A Full Scale WAO Unit Treating Cresylic Spent CausticTemperature - 260°C Retention Time - 60 minutes
Feed EffluentFeed EffluentAnalysis UnitsCOD mg/L 71200 15400COD mg/L 71200 15400TOC mg/L 20800 5790Sulfide-S mg/L 2870 <1Thiosulfate-S mg/L 520 <30BOD mg/L --- 7900BOD/COD --- --- 0.51COD Destruction % --- 78.4TOC D t ti % 72 2
Water TechnologiesProtection notice / Copyright notice
TOC Destruction % --- 72.2
F ll S l WAO C St d N hth iFull Scale WAO Case Study - Naphthenic
Data From A Full Scale WAO Unit Treating Naphthenic Spent CausticTemperature - 250°C Retention Time - 90 minutes
Feed EffluentAnalysis UnitsCOD mg/L 62600 9750TOC mg/L 12000 3250Sulfide S mg/L 6820 <1Sulfide-S mg/L 6820 <1Thiosulfate-S mg/L 1610 <40BOD mg/L --- 5710BOD mg/L 5710BOD/COD --- --- 0.59COD Destruction % --- 84.4
Water TechnologiesProtection notice / Copyright notice
TOC Destruction % --- 73.0
C l iConclusions
1 COD destruction increased with oxidation temperature1. COD destruction increased with oxidation temperature
2. WAO was effective at eliminating compounds responsible for causing d i h lfid d todor issues such as sulfide and mercaptans.
3. WAO increased the BOD/COD ratio
4. Majority of the TOC present in oxidized spent caustic samples was small chain organic acids.g
Water TechnologiesProtection notice / Copyright notice
C t tContact
Dr. Michael HowdeshellResearch & Development DirectorSiemens Water Technology
Chad FelchDirector of Technical ServicesSiemens Water Technology
301 W Military RdRothschild, WI 54474
301 W Military RdRothschild, WI 54474
Phone: (715) 355-3450
i h l h d h ll@ i
Phone: (715) 355-3237
h d f l h@ [email protected] [email protected]
Water TechnologiesProtection notice / Copyright notice
Th k !Thank you!
Water TechnologiesProtection notice / Copyright notice