The concept is simple really.
"Waste" describers material that was not used for its intended purpose or
unwanted material produced as a consequence of another process. In the chemical
industry, waste is either considered inert or contaminated. Inert waste can be
recycled or released into the environment. Malformed polymer or leaking steam may be
considered inert wastes, although they are not chemically inert. Wastewater is a
type of contaminated waste that needs to be treated before the components can be recycled
or released to the environment. No matter what type of waste you have, waste
costs money. Malformed polymer is either sold as scrap for much less than the
properly formed parts or it has to be reprocessed. Either scenario costs a company
money. Treating wastewater is certainly an expensive endeavor. In short, there
is much motivation to minimize waste in the chemical and other industries.
Recovering Materials
Technology
Description
Economics
Types of
Waste
Example
Applications
Gravity Settling
Tanks or ponds
provide hold-up time allowing solids to settle
Relatively inexpensive; dependent on particle
size and settling rate
Slurries or streams with suspended solids
Industrial wastewater treatment
Filtration
Collection devices
such as screens, cloth, or other; liquids pass and solids are retained
Labor intensive, relatively inexpensive,
additional energy needed for pumping
Aqueous solutions with finely divided solids
Polymer filtration, wastewater, etc.
Floatation
Air bubbled liquid to
collect fine solids that rise to surface with bubbles
Relatively inexpensive
Aqueous solutions with finely divided solids
Refinery oil/water mixtures, paper wastes;
mineral industry
Flocculation
Agent added to
aggregate solids to together to facilitate separation
Relatively inexpensive
Aqueous solutions with finely divided solids
Refinery oil/water mixtures, paper wastes;
mineral industry
Centrifugation
Spinning of mixtures
and centrifugal force causes separation by differences in densities
Competitive with filtration
Liquid/liquid or liquid/solid separations
Paints
Distillation
Boiling off materials
by taking advantage of differences in boiling points
Energy intensive
Organic liquids
Solvent separations
Evaporation
Solvent recovery by
boiling off the solvent
Energy intensive
Organic/Inorganic aqueous streams
Rinse waters from metal plating waste
Ion Exchange
Waste streams pass
through resin bed where ionic materials are selectively removed
Relatively high costs
Heavy metal aqueous solutions
Metal plating solutions
Ultrafiltration
Separation of
molecules by size using membrane
Relatively high costs
Heavy metal aqueous solutions
Metal coating applications
Reverse Osmosis
Separation of
dissolved materials from liquid through a membrane
Relatively high costs
Heavy metals; organics, inorganic aqueous
solutions
Seldom used industrially
Electrolysis
Separation of
positively charged materials by application of electric current
Dependent on concentrations
Heavy metals; ions from aqueous solutions;
copper recovery
Metal plating
Carbon absorption
Dissolved materials
selectively absorbed in carbon
Relatively costly thermal regeneration needed;
energy intensive
Organic/inorganics from aqueous solutions with
low concentrations
Metal plating
Solvent
Extraction
Solvent used to
selectively dissolve solid or extract liquid from waste
Relatively high costs
Organic liquids, phenols, acids
Recovery of dyes
Precipitation
Chemical reaction
caused formation of solids which settle
Relatively high costs
Lime slurries
Metal plating wastewater treatment
Electrodialysis
Separation based on
differential rates of diffusion through membranes
Moderately expensive
Separation/concentration of ions from aqueous
streams
Separation of acids and metallic solutions
Chlorinolysis
Pyrolysis in
atmosphere of excess chlorine
Insufficient U.S. market for carbon
tetrachloride
Chlorocarbon wastes
Carbon tetrachloride manufacturing
Reduction
Oxidative state of
chemical changed through chemical reaction
Inexpensive
Metals, mercury in dilute streams
Chrome plating solutions and tanning operations
Thermal Oxidation
Thermal conversion of
components
Relatively high costs
Chlorinated organic liquids; silver
Recovery of sulfur, hydrochloric acid
Batch Operations
When you think of a batch operation, you may not think
that these smaller units produce much waste. To the contrary, batch operations
produce much more waste per unit product than do continuous processes.
Traditionally, manufacturers using batch operations could afford this high waste content
thanks to the high value of their products. In recent years, waste has become more
and more expensive to deal with while competition has forced product value down.
What has raised the cost of waste "production"? Increased solvent prices
and fees for environmental permitting and monitoring emissions.
Each run of a batch process differs in many aspects. Waste
generation is no exception. For example, one run may yield 1.5 lbs. of unwanted
by-product while a small pressure variation in the next run causes 1.7 lbs. of waste to be
produced. Waste handling equipment must be designed to handle the worst case
scenario waste production conditions. Careful control of reaction conditions can
help minimize waste in such applications. Reactor loading and unloading are also
opportunities to minimize waste.
During reactor loading, add solids before liquids. This will
minimize the amount of time that a most likely volatile liquid is in contact with the
atmosphere. If possible, use a solvent with a lower vapor pressure to minimize
evaporation losses. Consider using a hopper specific to your solids. Some
hoppers allow locking of the process vessel to minimize vapor losses. Also, some
hoppers are available to open and distribute solids packaged in bags (cut-in hoppers).
During batch reactor operations, consider using a vapor recycling
system if necessary. The cumulative effects can be well worth the investment.
Install gaskets on all vessel openings. Use statistical process control (SPC) to
regulate reactions rather than using intermediate testing. When discharging the
reactor, try to allow the reactor to cool as much as possible to limit volatile organic
compounds from leaking.
Process Modifications
Raw Materials
Feed quality is very important in waste minimization. Working
with suppliers to improve feed quality reduce waste dramatically. Even small
impurities can lead to giant amounts of waste. For example, a specific feed impurity
may speed up catalysts degradation which in turn produces waste that must be separated
from final products. Even if these impurities are not a compromise of your quality
and are left in the product, it may increase the waste in your customer's process.
Raw materials can also be evaluated for reduction or elimination. Consider a company
that uses algae inhibitor in their cooling tower. By shielding their tower from the
sun, they quickly found that they could reduce their inhibitor use by half.
Reactors The transition from laboratory to industrial scale can sometimes see
a drastic change in product yield if proper mixing is not employed. By using static
mixers before the reactor, by-product yield can be minimized. Constant searching for
better catalyst materials can also help a reactor operate at peak efficiency.
Consider a separate, smaller reactor for recycle streams. Optimum conditions for
recycle streams can vary from those used for fresh feeds. A separate reactor allows
these different, optimum conditions to be used.
Distillation Columns Distillation columns contribute to waste by allowing
impurities to remain in the product. The solutions to this problem include ways to
better separations. It is critical that engineers analyze the cost of waste
treatment and the additional energy costs required for better separations. At times,
the additional energy may be much more expensive than waste treatment. Separations
can be bettered by the following methods:
1. Increased reflux ratio
2. Additional trays
3. Changing feed location
4. Insulating column
5. Pre-heating column feed
6. Increasing size of vapor lines
Columns can also produce significant waste due to inadequate
condensation. The vapor can find its way to a vent or flare and add to atmospheric
pollution and result in costly fines. Be sure your condenser is operating properly.
Specific Examples
Acrylonitrile Acrylonitrile production in the U.S. was 1.45 million metric tons in
1995. Each metric ton of acrylonitrile manufactured requires 400 metric tons of
cooling water for process use. Typically, about 0.5% of cooling water is discarded
to prevent buildup of slime and solids during recirculation. This discarded water
(called blowdown) contains toxins used as bactericides and fungicides and should be
considered hazardous. For every 400 metric tons of cooling water used (per ton of
product), 2 metric tons of wastewater are generated. That's a total of about 2.9
million metric tons of wastewater produced from the acrylonitrile industry in the U.S.
alone.
Assuming a waste treatment cost of $0.08 per gallon, the waste
treatment costs per ton of product are:
(2000 kg water) x ($0.08/gallon water) / (3.785 kg/gallon water) = $42 per ton of product
A closed loop refrigerant system could perform the necessary cooling duty for around $17
per ton of product.For a 100,000 ton/year facility, this could
result in a saving of around $2.5 million annually. Assume a total plant cost of
$400 million. The cooling water system would cost 2% of the total plant cost while
the refrigeration system would cost twice as much. This puts the refrigeration
system cost at $16 million. It's likely that over the life of the plant (especially
with tightening regulations), the refrigeration system will easily pay for itself.
Not to mention that is helps keep waste generation to almost nothing.
Paint Stripping The U.S. Air Force spends much of their time stripping paint from
equipment and repainting. Typically, a methylene chloride solvent is applied,
followed by scraping, washing with water (contaminating thousands of gallons), hand
sanding, and buffing.
Hill Air Force Base in Ogden, Utah decided to try a different way.
They use tiny plastic beads in a blasting technique (similar to sandblasting) to
remove the paint. The only waste is pulverized paint, while the plastic beads can be
separated and recycled. Below we'll compare the costs associated with
stripping one F-4 aircraft.
Chemical Stripping
Plastic bead stripping
Waste solids generated
9767 lbs sludge
320 lbs dry waste
Waste water generated
200,000 gallons
---
Hazardous solid disposal
$967
$32
Waste water treatment
$1,485
---
Investment
N/A
$647,389
Raw material costs
$5,422
$346
Energy costs
$231
$127
**Payback occurs after approximately 80 similar sized
aircrafts have been stripped
PVC Manufacturing During the production of polyvinylchloride (PVC), waste streams of
HCl are produced. These streams are traditionally handled in one of two ways.
Chlorinolysis uses the HCl stream to produce carbon tetrachloride. This process
requires high temperature and pressure as well as significant capital investments.
In the past, this investment could be justified through the revenue produced by selling
carbon tetrachloride. As the carbon tetrachloride market has grown weaker, the HCl
has become more valuable as a reactant in the PVC process rather than the carbon
tetrachloride reaction. Thus most plants utilizing the oxychlorination method of PVC
production are using catalytic fluidized bed reactors to recycle the HCl to the process.
This is a perfect example of how the chemical market can influence waste
minimization.
Sulfuric Acid Reduction at Standard Uniform
Services Standard Uniform sought a cost effective replacement for
sulfuric acid used to adjust the pH of its wastewater to levels required by discharge
permits. One of Standard Uniform's customers in the industrial gas business
suggested using carbon dioxide to alter the pH. Below the economics over a 10 year
period are shown: