Nanoparticle-assisted Biological Treatment of Petrochemical Wastewater

1
(No Transcript)
2
Nanoparticle-assisted Biological Treatment of
Petrochemical Wastewater

• Advisor
• Eunsung Kan
• GPII
• 1st semester 2009/2010

Group members Eman S. 200401039 Safa M.
200426399 Salma R. 200309192 Wafa R. 200401871
3
Introduction

• Problem Statement
• Population
• Human health
• Environment
• Purpose
• Efficient treatment of petrochemical wastewater
• Economical

4

• Project objectives
• understand the new concept of NZVI
• Impact of adding ZVI technology to current
  biological process
• practice the design of those processes
• Design Objectives
• Mass and energy balance
• MOC
• Sizing of the units optimization variables
• Comparing between a simulator results the
  manual design.

5

• Outcomes
• Design of petrochemical wastewater treatment
  process including
• ZVI dose
• Bacteria concentration
• Packing
• Reactor sizing
• Deliverables
• Design petrochemical wastewater unit
• 95 removal
• NZVI biological
• cost effective

6
Process Design
7
PFD
8

• Material Balance

Nanoparticle ZVI- driven chemical reactor Nanoparticle ZVI- driven chemical reactor Nanoparticle ZVI- driven chemical reactor
  In (g/hr) out (g/hr)
Nitrobenzene 2000.4 100.0
H 95.0 0.0
H2O 0.0 570.1
Aniline 0.0 1425.3
Total 2095.4 2095.4
Fixed film immobilized bioreactor Fixed film immobilized bioreactor Fixed film immobilized bioreactor
  In (g/hr) out (g/hr)
Nitrobenzene 100.0 100.0
H 0.0 0.0
H2O 570.1 633.1
Aniline 1425.3 71.3
CO2 0.0 3791.3
O2 4314.9 0.0
H2O 0.0 907.2
0.0 907.2
Total 6410.2 6410.0
9
Energy Balance

• Nanoparticle ZVI- driven chemical reactor

• Fixed film immobilized bioreactor

10
Potential Ethical and Environmental Issues for
nanoparticle

• Effect of nanoparticle on human health and
  environment
• The current lack of studies on the toxicity of
  all substances in all compartments makes it
  difficult to evaluate the risks to organisms.
• No specific framework is currently applicable for
  the regulation of nanoparticles in the environment

11
Proposed Process Design

• Process conditions

Symbol process condition title Value Reference
F1 water flow rate to the 1 st reactor 16.67 m3/h By our own
F2 water flow rate to the 2nd reactor 16.67 m3/h By our own
CNB Inlet concentration of NB 120 g/m3 GPI
Can Inlet concentration of aniline 114 g/m3 Assuming 95 removal efficiency
12
Proposed Process Design

• Predetermined Process variables

Symbol process variable title Value Referene
K NB chemical reaction rate constant 0.0732 min-1 Abinash, Agrawal, and Tratnyek Paul. "Reduction of Nitro Aromatic Compounds by Zero-Valent Iron Metal." Environ. Sci. Technol 1. (1995) 153-160. Web. 12 Oct 2009. lthttp//pubs.acs.orggt.
KAn specific maximum biodegradtion rate 0.63 hr-1 ALLAN KONOPKA,DEBORAH KNIGHT, AND RONALD F. TURCO. "Characterization of a Pseudomonas sp. Capable of Aniline Degradation in the Presence of Secondary Carbon Sources". Department of Biological Sciences' and Department of Agronomy,1988
KM Michaelis-Menten's constant 5 g/m3 Ref
V max Maximum biodegradation rate 63 g/m3.hr calculated by multiplying Kan with biomass concentration
13
Design Criteria

• steady state operating condition without any
  accumulation during the process.
• 95 conversion from nitrobenzene into aniline
• 95 biodegradation of aniline to carbon dioxide
  and water.
• Temperature and pressure effect are negligible in
  both units of the process.
• The nanoparticle ZVI-driven chemical reaction for
  transforming nitrobenzene into aniline is assumed
  to follow the pseudo 1st order kinetics.
• The biodegradation of aniline in the fixed film
  bioreactor is assumed to follow Michalis-Mentens
  equation.

14
Design Nanoparticle ZVI-driven chemical reactor

• Path ways of reductive degradation of NB by Fe0

15
Reaction of ZVI with NB
16

• Inlet condition

CNB 120 g/m3
Flow rate 16.67 m3/hr
P 1 atm
T 25 oC

• ZVI
• Size 30 nm
• specific surface area 18 m2/g
• Iron Loading0.1 g/L
• PH 6-7
• Packing Sand
• Size0.8 mm
• Porosity 55

17
Rate constant determination

• Rate constant kNB
• Volume

Iron Loading (g/L) 0.1
specific surface area (m2/g) 18
k (min-1) 0.0732
18
Volume and sand particles determination

• 10 allowance V12.5m3
• Height 3 Diameter
• Number of sand particles needed

19
Mass of sand and ZVI

• Mass of sand
• Mass of ZVI

20
Design Fixed film immobilized bioreactor

• inhibition of aniline

21
Specific maximum biodegradation rate determination

• Growth kinetics of Pseudomonas

22
Volume determination
kan 0.63 1/hr
biomass concentration 100 g/m3
Vmax 63 g aniline degraded/m3-hr
KM 5 g/m3
CAn 114 g/m3
FAo 16.7 m3/h
Volume 32.6m3
23
Volume determination

• Volume32.6m3
• 10 allowance V12.5m3

24
Optimization of Process Variables

• Design of the nano ZVI-driven chemical reactor at
  the pre-determined conditions

  particle size (nm) specific surface area (m2/g) rate constant (1/min) reactor volume (m3)
Proposed process 30 18 0.705 11.37
The process in the reference paper 833000 0.021 0.185 270.01
25
Effect of iron (ZVI) loading on the reactor
performance
Fe loading (g/L) specific surface area (m2/L) K (1/min) X
0.01 0.18 0.01 0.04
0.05 0.90 0.04 0.15
0.1 1.80 0.07 0.27
0.2 3.60 0.14 0.46
0.3 5.40 0.21 0.60
0.4 7.20 0.28 0.70
0.5 9.00 0.35 0.78
0.6 10.80 0.42 0.83
0.7 12.60 0.49 0.88
0.8 14.40 0.56 0.91
0.9 16.20 0.63 0.93
1 18.00 0.71 0.95
2 36.00 1.41 1.00
26
Effect of iron (ZVI) loading on the reactor
performance
27
Effect of residence time on the reactor
performance

• Residence time before optimization 40.9 minutes
• Residence time before optimization 4.25 minutes

28
Modified Re
µ fluid viscosity (1cp) ? fluid density
(1000 Kg/m3) ? fluid velocity Q/Across a
specific surface area of the bed (m-1)
a was calculated based on the sand particles
diameter a S(1-e) e fraction of the bed
volume not occupied by solid. Where S?/Dsand

?Q/Across , D
reactor0.8 m Dsand 0.8 mm
Across0.502 m2 ?0.0093 m/sec a
3375 (m-1)
29
Modified Re
1st Re
2nd Pressure drop through the porous medium
?P8.21 KPa
30
Optimization of the conditions in the fixed film
immobilized bioreactor performance

• Effect of the specific maximum biodegradation
  rate constant on the reactor
• Pseudomonas strain K1 td2.2 hr
• pseudomonas strain PN1001 td13.9 hr

K (1/hr) Vmax (g/m3.hr) right term Volume (m3) x left term calculated volume (m3)
0.63 63 32.61 0.95 32.62
0.1 10 32.61 0.16 31.86
31
Effect of biomass concentration on the bioreactor
performance
biomass concentration (g/L) Vmax (g /m3.hr) Volume (m3)
0.01 6.3 326.20
0.05 31.5 65.24
0.1 63 32.62
1 630 3.26
1.1 693 2.97
1.2 756 2.72
1.5 945 2.17
2 1260 1.63
3 1890 1.09
5 3150 0.65
32
Comparison of the model simulation with the
manual calculation
33
Capital Cost Estimation

• Purchased cost calculation (Process vessels)

Equipment Type A A k1 k2 k3 Cpo
R1 Chemical Reactor volume,m3 1.3 3.4974 0.4485 0.1074 3547.3
R2 Bioreactor volume,m3 3.6 3.4974 0.4485 0.1074 6027.5
34
Reactors Bare Module cost
Equipment Type C1 C2 C3 Fp FM FBM B1 B2 CBM
R1 Chemical Reactor - - - 1 1 - 2.25 1.82 50055.3
R2 Bioreactor - - - 1 1 - 2.25 1.82 35021.3
35
Purchased cost calculation

• Pumps cost

Equipment Type A A k1 k2 k3 Cpo
Pump 1 Centrifugal Shaft power, kW 0.05 3.389 0.0536 0.1538 1316
Pump2 Centrifugal Shaft power, kW 0.016 3.389 0.0536 0.1538 1039.2

• Bare Module cost of pump

Equipment Type C1 C2 C3 Fp FM FBM B1 B2 CBM
Pump 1 Centrifugal - - - 1 1 - 1.89 1.35 4263.84
Pump2 Centrifugal - - - 1 1 - 1.89 1.35 3367
36
Capital Cost Estimation

• Air Blower Purchased cost 89.95 from
  Cole-Parmer vender

Cost of Packing

• Cost of Nano-ZVI 2.7 /g (Sigma Aldrich,USA)
• The amount needed of ZVI 649 g

37
Cost of Packing

• The amount of Silica sand packing in the
  nanoreactor 1438 kg
• The cost of Silica sand packing

• Polyurethane packing cost15.25 /cube

38
Total Bare Module calculation
39
Manufacturing Cost Estimation
Fixed capital investment (FCI) 109,394.7
Cost of operating labor(COL) 600,000 /yr
Cost of utilities (CUT) 458.25/yr
Cost of waste treatment (CWT) -
Cost of raw materials (CRM) -
40
Comparison with Current Technology

• From communication with Petrochemical Company in
  Korea (SK Chemical, Ulsan, Korea)
• Activated sludge process cost is

Capital cost 2,000,000
Operating costs 4,670,000/yr
41
Relevant Codes of Ethics and Moral Frameworks

• Obey The Environmental Protection Agency EPA
  regulation of nitrobenzene concentration in
  treated water (amount of nitrobenzene in drinking
  water should not exceed 19.8 mg/L)
• Hold paramount the safety, health and welfare of
  the public and protect the environment in
  performance of their professional duties
• Formally advise employers or clients if they
  perceive that a consequence of their duties will
  adversely affect the present or future health or
  safety of their colleagues or the public.

42
Relevant Codes of Ethics and Moral Frameworks

• Accept responsibility for their actions, seek and
  heed critical review of their work and offer
  objective criticism of the work of others
• Act in professional matters for each employer or
  client as faithful agents or trustees, avoiding
  conflicts of interest and never breaching
  confidentiality
• Treat fairly and respectfully all colleagues and
  co-workers, recognizing their unique
  contributions and capabilities
• Continue professional development throughout
  careers, and provide opportunities for the
  professional development of those under
  supervision

43
Ethical Dilemmas

• Leak of nitrobenzene from pipes or pumps into the
  environment

44
HAZOP and Safety Studies

• A Hazard and Operability (HAZOP) study is a
  structured and systematic examination in order to
  identify and evaluate problems that may represent
  risks to personnel or equipment, or prevent
  efficient operation.
• This method is to predict the hazards and
  establish actions that may help to enhance and
  improve the safety environment of the plant.

45
HAZOP study for flow deviation
Guide Word Deviation Causes Consequences Action
No Flow Pump failure Pipe clogging by scale formation Nozzle clogging No inlet wastewater feed No production Decay of bacterial in the bio reactor Backup pump Pipe maintenance flow controller maintenance plant shut down
High Flow Pump failure due to leak. Valve failure suboptimum condition for reactions Flooding inside PBR Local y increasing pressure Leak of nitrobenzene to environment Nozzle failure High level alarm (HLA) Backup pump install Flow Control Valve (FCV) Valve maintenance Nozzle maintenance NB concentration control (analyzer installer) Isolate spill area
Low Flow Partial clogging leak in pipe Pump failure Low material flow Valve failure Low production. Channeling Leak of nitrobenzene to environment Inhibition of bacterial activity Low level alarm (LLA) Backup pump Pipe Maintenance Valve maintenance Isolate spill area
46
(No Transcript)
47
HAZOP study for temperature deviation
Guide Word Deviation Cause Consequence Action
High Temperature Hot inlet wastewater Inhibition of bacterial activity in the bioreactor above 40?C High T alarm (HTA) Cooling system before the Nano reactor
Low Temperature Cold T below 10?C Lower reaction efficiency in both reactors Poor bacterial growth Low Temperature alarm (LTA) Preheating the inlet wastewater
48
(No Transcript)
49
HAZOP study for pressure deviation
Guide Word Deviation Causes Consequence Action
High Pressure Pump failure Pump motor does not run at the rated speed Pipe clogging Optimum production not reached Less oxygen supplied to bioreactor due to back pressure of air (air blower) High pressure alarm (HPA) Back up pump Pipe maintenance
Low pressure Pump failure Inlet valve or suction line may be clogged Optimum condition not reached Low pressure alarm (LPA) Back up pump Maintain inlet valves
50
(No Transcript)
51
HAZOP study for concentration deviation
Guide Word Deviation Causes Consequence Action
High concentration High feed NB concentration Optimum production not reached Decay of bacteria in bioreactor High concentration alarm (HCA)
Low concentration Low feed NB concentration Optimum condition not reached Low concentration alarm (LCA)
52
HAZOP study for concentration deviation

• For high or low concentration of NB in feed
  wastewater a sensor should be placed.
• The only available type of NB analyzers is High
  pressure liquid chromatography that cant be used
  in this process because the lag time is high.

53
Environmental Impact of the Process

• The final product is clean water and carbon
  dioxide which is less harmful than nitrobenzene.
• Improve the treatment of toxic contaminants.
• Improve the discharged water quality in the
  environment.

54
Project Management
55
Problems faced and solutions

• No lab experiment
• No reliable software
• Difficult to predict the rate kinetics

56
Resources

• Reference papers
• Books
• Differential equation solver
• BERKELEY MADONNA Software
• Personnel
• Dr. Eunsung Kan
• Dr. Suliman AlZuhair
• Dr.Samir abu Aisha
• Websites

57
New skills learnt

• Patience
• Time management
• Build background
• Cost estimation and bio-kinetics
• Group work
• Advanced search for relevant literature

58
Way Forward

• Apply for a pilot or field demonstration
  including a laboratory test
• Enhanced by including the mass transfer
  limitations of aniline into biofilm
• Apply for nitro aromatics but it can be applied
  for chloro-aromatics pesticides and insecticides.