1. 3/25/2017
Pollution Prevention - Fundamentals and Practice Spring Semester
Sidney Innerebner, PhD, PE, CWP
Indigo Water Group, LLC
Littleton, CO

2. Preliminaries Examples – from my background and perspective
Textbook - none
Class Structure
Guest Lecturers
Grading System
Quizzes
Buddy System!
Snow Days
Field Trips
Assignments / Web Site –
Office Hours
SOA Project
Seating Chart
Examples – from my background and perspective

3. Objective of the Course
Reorient student’s outlook to incorporate society’s interest in environmental quality and sustainability into engineering education
Encourage a stronger environmental ethic among engineering students
Understand environmental processes and their impacts.

4. “We have learned the inherent limitations of treating and burning wastes. A problem solved in one part of the environment may become a new problem in another part.
We must curtail pollution closer to its origin so that it is not transferred from place to place.”
William Reilly
former U.S. EPA Administrator
1990

5. Major Environmental Laws
1955 – Clean Air Act (CAA)
1969 – NEPA, National Environmental Policy Act
1972 – Clean Water Act (CWA)
1974 – Safe Drinking Water Act (SDWA)
1975 – HMTA, Hazardous Materials Transportation Act
1976 – RCRA, Resource Conservation and Recovery Act
TSCA, Toxic Substances Control Act
1980 – CERCLA, Comprehensive Environmental Response, Compensation, and Liability Act
1984 – EPCRA, Emergency Planning and Community Right to Know Act
1990 – Oil Pollution Act

6. 3/25/2017
Rule of Thumb 1
Your professional success rests on What you know, AND Who you know
Both are essential and equally important

7. What is Pollution Prevention?
Reducing or eliminating toxic materials
Replacing a material in the production line
Reformulating the product
Installing new or modifying existing process equipment
Closed loop (on-site) recycling
Developing new technology that helps others implement P2
Involves holistic approach

8. What P2 is NOT? End of pipe treatment Incineration or disposal
Burning waste for energy recovery
Transferring waste from one medium to another
Incorporation of waste into products or by- products

9. P2 Hierarchy
Source Reduction
Recycle / Reclaim
Treat
Dispose

10. Recycling vs. P2
EPA didn’t used to consider recycling or reprocessing as Pollution Prevention
Many States do include recycling and reuse in their definition of P2
In this course, a broader version of P2 that includes recycling and reuse of materials will be followed
Resource recovery not waste disposal!

11. ShetkaStone All Paper Recycling based in Minnesota
All types of recycled paper accepted, plants, and cloth fibers
Paper products account for 40% of solid waste in U.S.
Products produced include:
Shetkastone (countertops, benches, molding)
Ceiling Tiles
Decorative Screens
100% sustainable life cycle
Cost somewhere between Corian and Granite

12. Shetkastone A ton of paper makes 400 sf of material 1.5 inches thick
Propriety process described as:
Segregate by color
Shredding and pulping
Addition of water based polymers
Pressing and curing
Polish
Uses hydrogen bonding
No toxic glues or formaldehyde
30+ year life expectancy

13. Phosphorus U.S. has 50 to 100 year supply
U.S. supplies ~45% of world supply
Produced 29 million tons in 2007
Critical for farming
Most phosphorus is single use
Lost in run-off
Discharged to WWTP

15. Struvite Struvite is magnesium ammonium phosphate – MgNH4PO4●6H2O
Created during anaerobic wastewater treatment
A nuisance and a waste!!!
Landfill, incinerate, or land apply
Can be recovered and sold as fertilizer additive

16. P2 Rules of Thumb - Bishop
3/25/2017
P2 Rules of Thumb - Bishop
Prevent creation of the waste
Minimize handling of toxins
Operate at higher efficiency
Improve product quality
Absorb past wastes into current operations

17. What is Waste? Legally defined in RCRA
Solid product left over at the end of a process or action
Solid waste means any garbage, refuse, sludge, from a waste treatment plant, water supply treatment plant, from a waste treatment plant or air pollution control facility and other discarded material, including solid, liquid, semi-solid, or contained gaseous materials resulting from industrial, commercial, mining and agricultural activities and from community activities.
GET SOME GOOD DEFINITIONS FROM ALLEN DAVID COURSE NOTES!!

18. 3/25/2017
A waste is a resource
out of place

20. Avoiding Waste Creation
3/25/2017
Avoiding Waste Creation
Convert byproduct streams back to raw materials
Select raw materials that generate valued byproducts
Decrease energy input
Update the material balance

21. Byproducts to Raw Materials
Dezinc galvanized steel
Produce caustic from soda ash: NaOH from Na2CO3

22. Dezinc Galvanized Steel
3/25/2017
Dezinc Galvanized Steel
Zn0(s) + 2NaOH(liq) + ½ O2 -->
Na2O*ZnO(aq) + H2O(g)
Na2O*ZnO(aq) + H2O(g) + power --> Zn0 + 2NaOH (liq) + ½ O2
Zinc is stripped from steel using sodium hydroxide. End product is sodium zincate.

23. Electrowinning / Refining
3/25/2017
Electrowinning / Refining
Sodium zincate – regenerate caustic
When an electrowinning unit is in operation, the electrical potential applied to the electrodes causes dissolved metals and other positively charged ions to migrate toward and plate onto the cathodes. As metals deposit on the cathodes, the metal buildup decreases the deposition rate. When the metal deposition rate is no longer sufficient, cathodes are removed from the electrolytic cell for on-site or off-site metal recycling.

24. Tankhouse Starter Sheets

25. Rule of Thumb 2
One of the best ways to meet the best and brightest in your field is to VOLUNTEER
Moderate a session at a conference
Join a committee
Collect business cards

26. Avoiding Waste Creation
3/25/2017
Avoiding Waste Creation
Convert byproduct streams back to raw materials
Select raw materials that generate valued byproducts
Decrease energy input
Update the material balance

27. Caustic from Soda Ash CaO(s) + H2O  Ca(OH)2 + heat
3/25/2017
Caustic from Soda Ash
CaO(s) + H2O  Ca(OH)2 + heat
Na2CO3 (aq) + Ca(OH)2 (s) 
2NaOH (aq) + CaCO3 (s)
CaCO3 (s) + H2O + heat 
Ca(OH)2 (s) + CO2 (g)
Sodium hydroxide aka caustic soda typically costs more than Sodium carbonate aka soda ash. CaO is lime. Ca(OH)2 is hydrated or “slaked” lime.
At the same price, caustic has some advantages over soda ash. For one, since caustic is produced all over the US, it enjoys cheaper freight costs than soda ash, which is produced almost exclusively in Green River, Wyo. Since caustic is more soluble in water it can be more easily stored and transported in liquid form. Also, caustic is a stronger base with greater neutralizing capabilities.

28. Raw Materials Selection
3/25/2017
Raw Materials Selection
HCl from NaCl vs KCl using sulfuric acid
Neutralize with Mg(OH)2 rather than Ca(OH)2
CaSO4 is water soluble

29. Common Salt vs Potash The Mannheim Furnace
2NaCl + H2SO4 + heat -->
Na2SO4 (s) + 2HCl (gas)
2KCl + H2SO4 + heat -->
K2SO4 (s) + 2HCl (gas)
Sodium sulfate is mainly used for the manufacture of detergents and in the Kraft process of paper pulping. About two-thirds of the world's production is from mirabilite, the natural mineral form of the decahydrate, and the remainder from by-products of chemical processes such as hydrochloric acid production.
The principal use of potassium sulfate is as a fertilizer. The crude salt is also used occasionally in the manufacture of glass.

30. Mechanical rakes rotate and push H2SO4 and KCl to center of furnace
In the process, sulphuric acid reacts with potassium chloride producing potassium sulphate and a 33% hydrochloric acid solution obtained through absorption. Combustion gases, obtained as intermediate products, are used to heat up the combustion air. Producing sulphate that is free of sulphuric acid and hydrochloric acid requires equivalent amounts of acid and salt. The salt is dosaged by means of a belt weigher, the quantity of acid is measured by flow measurement and controlled by an electropneumatic positioner. Based on raw material analyses, the quantity ratio of the materials is then controlled by a human operator. The reaction between sulphuric acid and potassium chloride requires a long reaction time and a high temperature. This is achieved in a muffle furnace with a body of hearth which is heated with oil burners to 550…600°C.
The air volume/oil ratio is kept constant. The first stage of the reaction produces acidic potassium sulphate, or potassium hydrogen sulphate, which then reacts with potassium chloride during the second stage to generate the end product, potassium sulphate. Figure 36 shows the Mannheim furnace, the most important part of the production process.
According to Kemira as well as Pihkala & Salminen [222], the sulphuric acid content (H2SO4) and potassium chloride content (KCl) are used as input variables. These are added to the process at maximum feed rate, based on analysis results. Oil consumption is used as an indirect quality and quantity indicator. Mechanical rakes rotate in the muffle furnace, pushing the sulphuric acid and potassium chloride to the centre of the furnace and the produced sulphate to the outer edge. The hot, acidic, and partly caked potassium sulphate is transferred from the drop chute to a cooling and pulverizing drum where it is cooled with a water jacket. A conveyor belt then takes the ground material to subsequent treatment. Appendix 9 shows a diagram of potassium sulphate process, with the locations of field devices indicated.
The final product is neutralized and of homogeneous quality. From the cooling drum the sulphate is screened, crushed, and taken to storage by a screw conveyor. The gas released in the process is used to manufacture hydrochloric acid.
Furnace at 550 – 600 oC
Mechanical rakes rotate and push H2SO4 and KCl to center of furnace
Produced sulfate moves to outer edge
Hot, acidic, partly caked KSO4 goes from drop chute to pulverizing drum
Gas released in process is used to manufacture hydrochloric acid

31. Gypsum vs Fertilizer Ca(OH)2 + H2SO4 --> CaSO4.2H2O (s)
3/25/2017
Gypsum vs Fertilizer
Ca(OH)2 + H2SO4 -->
CaSO4.2H2O (s)
Mg(OH)2 + H2SO4 -->
MgSO4 (s) + 2H2O
MgSo4 is soluble – CaSo4 is not
The main sources of calcium sulfate are naturally occurring gypsum and anhydrite which occur at many locations worldwide as evaporites. These may be extracted by open-cast quarrying or by deep mining. World production of natural gypsum is around 127 million tonnes per annum[4].
In addition to natural sources, calcium sulfate is produced as a by-product in a number of processes:
In flue gas desulfurization, exhaust gases from fossil-fuel-burning power stations and other processes (e.g. cement manufacture) are scrubbed to reduce their sulfur oxide content, by injecting finely ground limestone or lime. This produces an impure calcium sulfite, which oxidizes on storage to calcium sulfate.
In the production of phosphoric acid from phosphate rock, calcium phosphate is treated with sulfuric acid and calcium sulfate precipitates.
In the production of hydrogen fluoride, calcium fluoride is treated with sulfuric acid, precipitating calcium sulfate.
In the refining of zinc, solutions of zinc sulfate are treated with lime to co-precipitate heavy metals such as barium.
Calcium sulfate can also be recovered and re-used from scrap drywall at construction sites.
In agriculture and gardening, magnesium sulfate is used to correct magnesium deficiency in soil, since magnesium is an essential element in the chlorophyll molecule. It is most commonly applied to potted plants, or to magnesium-hungry crops, such as potatoes, roses, tomatoes, peppers and cannabis. The advantage of magnesium sulfate over other magnesium soil amendments (such as dolomitic lime) is its high solubility.

32. Filter Encycle

33. Belt Filter Press at Parker

34. Avoiding Waste Creation
3/25/2017
Avoiding Waste Creation
Convert byproduct streams back to raw materials
Select raw materials that generate valued byproducts
Decrease energy input
Update the material balance

35. Decrease Energy Input Use only what you need
Variable frequency drives
High efficiency motors
Motion sensors for lights
Save energy and money!
Recover waste heat and use elsewhere
Flash smelting of sulfides
Production of cement

36. 3/25/2017 Flash versus reverb furnace --- huge energy savings
Reverb furnace: Furnace used for smelting, refining, or melting in which the fuel is not in direct contact with the contents but heats it by a flame blown over it from another chamber. Such furnaces are used in copper, tin, and nickel production, in the production of certain concretes and cements, and in aluminum recycling. In steelmaking, this process (now largely obsolete) is called the open-hearth process. The heat passes over the hearth and then radiates back (reverberates) onto the contents. The roof is arched, with the highest point over the firebox. It slopes downward toward a bridge of flues that deflects the flame so that it reverberates.
Flash smelting (Finnish: Liekkisulatus) is a smelting process for sulfur-containing ores [1] including chalcopyrite. The process was developed by Outokumpu in Finland and first applied at the Harjavalta plant in 1949 for smelting copper ore.[2][3] It has also been adapted for nickel and lead production.[2]
The process uses the autogenic principle by using the energy contained in the sulfur and iron for melting the ore.[4] In the process dried and powdered ore is discharged from a nozzle into a fluidized bed reactor fed with oxygen. The reduced metal melts, and drops to the bottom of a settling chamber. The flotation produces a large effective surface area of fine-grained concentrate particles.[4] The process makes smelting more energy efficient and environmentally friendly.[4] Sulfur is released mainly in its solid form, thus reducing atmospheric pollution.[1] The process is today used for 50% of the world’s primary copper production.[2] The other 50% is mainly produced from oxide ores, where the process cannot be applied.

44. P2 Rules of Thumb - Bishop
3/25/2017
P2 Rules of Thumb - Bishop
Prevent creation of the waste
Minimize handling of toxins
Operate at higher efficiency
Improve product quality
Absorb past wastes into current operations

45. Hussey Seating Company
Goal: reduce VOCs and HAPs
Two process changes
Switch to automated UV cured coating system for bleachers
Switch to aqueous based coatings for finished wood
Before switch, two coatings of polyurethane were hand applied

46. Benefits of P2 Changes VOCs reduced from 50 tpy to < 1 tpy
HAPs reduced from 10 tpy to < 1 tpy
Increased productivity
Improved on-time delivery
Before, 8 employees made 9,000 units/wk
After, 4 employees make 14,000 units/wk

47. UV system captures and recycles excess coating
Coating use increased 20%, but units produced more than doubled
Unit cost for coating decreased 17%
Easier cleanup and no solvent use
UV coating is more durable

48. Environmental Test Methods
Nessler Method for Ammonia Analysis no longer EPA approved
Alternative chemistry for COD testing
Substitute n-Hexane for Freon in FOG analysis
Recycle spent hexane with distillation
Alternate test method for nitrate – ISE versus cadmium reduction method

49. Minimize Handling of Toxins
3/25/2017
Minimize Handling of Toxins
Consumer batteries (Hg, Cd)
Freon, DDT, PCBs
Pb - paint, gasoline, ammo, solder
Hg - fungicide, coal, instruments

50. P2 Rules of Thumb - Bishop
3/25/2017
P2 Rules of Thumb - Bishop
Prevent creation of the waste
Minimize handling of toxins
Operate at higher efficiency
Improve product quality
Absorb past wastes into current operations

51. Xerox Corporation 24 Pallet Sizes 400 Suppliers
Thousands of different box sizes
$500,000 per year to send 4 million boxes to landfill
Box Reuse Program
9 Standard Box Sizes
2 Standard Pallets
Designed to fit into assembly line
60% to 80% of all parts now come in standard size boxes
Supplier agreement

52. $ Xerox Corporation Using 2.4 – 3.2 million FEWER boxes per year
Compatible with Just-in-Time delivery
Sturdier boxes
Boxes reused average of 8 times
Saved $1.5 million on pallet disposal
Efficient “cube out” = Reduced freight costs
Reduced storage costs $

53. P2 Rules of Thumb - Bishop
3/25/2017
P2 Rules of Thumb - Bishop
Prevent creation of the waste
Minimize handling of toxins
Operate at higher efficiency
Improve product quality
Absorb past wastes into current operations

54. Improving Product Quality
Longer Product Life - Cars
Grocery bags
Single use versus multiple use
Stronger to eliminate double bagging
Larger capacity means fewer bags
Bottle / Aluminum can redesign
Less material
Same product quality
Gains back up through the supply line

55. P2 Rules of Thumb - Bishop
3/25/2017
P2 Rules of Thumb - Bishop
Prevent creation of the waste
Minimize handling of toxins
Operate at higher efficiency
Improve product quality
Absorb past wastes into current operations

56. Manufacturing Cheese Curds = 15% while Whey = 85% Whey Characteristics
BOD of 30,000 – 50,000 mg/L
5% to 6% total solids
70% of solids are lactose
4% to 9% of solids are protein and minerals
Internal recycling and recovery of “waste products” for P2
Still need some wastewater treatment

57. 85% Pasturize @ 163 oF Milk Separator Cream Whey Starter/ Rennet Curds
Coagulation
Curds
Knitting & Cooking
Salt
Brining
Salt Water
Pressing
Ripen
Fines
Shred
Package
Cheese
Curd knitting

59. Cream Whey Curds Fines Salt Water
163 oF
Milk
Separator
Cream
Whey
Starter/ Rennet
Coagulation
Curds
Knitting & Cooking
Fines
Brining
Salt Water
Salt Water
Filter
Pasteurize
Chiller
Salt

60. Whey Protein Concentrate Reduced Lactose Permeate
Screen for Fines
Permeate
Separator
WheyCream
Pasteurize
Evaporator
UF Membrane
Retentate
Evaporator
Condenser
Concentrate
Crystallizer
Cow Water
Dryer
Whey Protein Concentrate
Reduced Lactose Permeate
Lactose

61. Crystalizer
Ultra-filtration membrane
Ultra-filtration membrane

62. That’s not the whole story
Clean in Place (CIP)
Nitric acid
Phosphoric acid
Sodium hydroxide
Hot water
Acids and “cow water” used multiple cycles
Eventually – all water goes to wastewater treatment plant (WWTP)
Resource recovery happens even here!

63. Rule of Thumb 3 You don’t need to know everything.
Know where to find the information.
Stay one day ahead of the client.

64. The Material Balance A prime means of enforcement
3/25/2017
The Material Balance
A prime means of enforcement
Defines rate and composition of process inputs and outputs
Interacts with the energy balance
Provides understanding of process control constraints
Helps to locate fugitive emissions and waste/lost product

65. Conversion of NH3-N to NO3-N uses 7.14 lb alkalinity per lb converted.
Bacteria convert ammonia to nitrate N2
Anoxic Tank
Aerobic Tank
NO3-N
NO3-N
NH3-N
NH3-N
NH3-N
Alkalinity
Alkalinity
Alkalinity
Bacteria convert nitrate to nitrogen gas
Conversion of NH3-N to NO3-N uses 7.14 lb alkalinity per lb converted.
Conversion of NO3-N to N2 generates 3.57 lb alkalinity per lb of N2.

66. 25 = 14 + 5 14 5 25 < 1 240 122 What has to be true?
Bacteria convert ammonia to nitrate N2
Anoxic Tank
Aerobic Tank
NO3-N
NO3-N 5 25
NH3-N
NH3-N
NH3-N
< 1
Alkalinity
240
122
Alkalinity
Alkalinity
Bacteria convert nitrate to nitrogen gas
25 =
What has to be true?

67. Analyze Background Information and Flow Diagrams
Waste types, volumes, and disposal costs
Written procedures for waste handling
Current waste reduction activities
Purchasing records and specifications
Process quality control data
Process flow diagrams

68. Painting
Inspection
Packaging
Receiving
Process Flow Diagram

69. Conduct a Facility Walk-Through
Follow the process flow diagram.
Look for sources of waste and opportunities to eliminate, reduce, reuse, or recycle.
Observe both normal operations and sporadic events such as cleanup and product changes.
Ask questions.

70. Key Questions What type of waste is it? Where did it come from?
How much of it is there?
How much do you pay to get rid of it?
If it’s raw material, how much did you pay for it?
Is it possible to reduce or eliminate it?

71. Materials In = Materials Out
Perform a Mass Balance
Materials In = Materials Out
Go back to the process flow diagram.
Move from process to process.
Identify all inputs and outputs.
Determine waste volumes and costs.
List waste reduction options.

72. Perform a Mass Balance Outputs Inputs Painted Parts Empty Drums
Air Emissions
Waste Solvent
Waste Paint
Soiled Rags
Used Air Filters
Painting
Process
Inputs
Paint
Unpainted Parts
Energy
Solvents
Rags
Air Filters

74. Prepare a Waste Assessment Report
Summarize background information.
Review waste generation and existing methods of waste management.
List waste reduction opportunities.
Include an economic assessment of current and proposed activities.

75. Evaluate Waste Reduction Options
Occupational Impacts
Initial Cost
Operating Cost
Savings
Environmental Impacts
Production Shutdown Requirements
Productivity
Impact on Quality
Energy Requirements
Facility Modifications
Maintenance Requirements

76. Homework Find 3 Unique ideas for P2 Reading assignment on website
Quiz on this week’s class next week