\Si£F£¢g!ngtin€{S!{i!

=S:S_:`egriFifesfiIrpe

¥,r%{%grELS£±L,,£, rSF#gr;,5:fgf,# g5££g,€ffi£#j.#5;

E±I,# E\J,iIr-(a

^,¢:LRF®#nif-J

U.S. Patent 5, 217. 612 and other pat. pendg.

ACH) RECOVERY SWSThM

Function: Benefits:
Simplified, trouble~free system for efficient • Reduced acid consumption.
recovery of mineral acids, such as: Nitric, Hydro- • Reduced waste treatment and waste disposal.
fluoric, Hydrochloric, Phosphoric, and Sulfuric • Process optimization via bath stabilization.
acids. • Enhanced metal recovery ability.
• Reduced labor costs.
Application: • Reduced reporting requirements.
• Nitric acid from rack stripping, rework stripping, • Reduced liability.
and tank passivation.
• Sulfuric acid from Aluminum Anodizing, steel
Principle of Operation
pickling, or metal etching operations. The acid Recovery System utilizes proprietary ion
• Phosphoric acid from electropolishing and bright exchange membranes arranged in a stack configuration.
dipping applications. Water is used to facilitate the migration of acid molecules
• Hydrofluoric acid from stainless steel and through the membrane into a purified zone and is col-
Titanium pickling operations. lected for reuse. The remaining depleted solution con+
• Hydrochloric acid from metal cleaning baths and taining the contaminant metal is collected for metal
cation exchange regenerant solution. recovery or subsequent treatment.
 EQUIPMENT SPEcmcAmoNs
Due to the variable nature of the applicable acids, Technical Service
metal contaminants, processing volumes, concentrations Field service engineers are available for on-site start~
and processing rates, we recommend an engineering re- up assistance, operator training, and technical consulta~
view for each unique application. This review may result tion. Staff engineers are available for consultation at any
in the recommended use of a standard acid recovery time.
system, or may suggest further specific engineering.

Acid Recovery System Membrane Stack

MEMBRANE

WASTE WATER

Warranty
Zero Discharge Technologies, ]nc. warrants
against defective materials or workmanship for 6
months from the date Of the original purchase.
Parts covered under this warranty will be
replaced without charge, except for shipping and

ZEFti®
DISCHARGE
handling, upon receipt and inspection of the
defective part at our factory.
This Limited Warranty covers all defects
incurred in normal use of the equipment and does
not apply in the event of loss or damage of the
equipment due to abuse, mishandling, accident or
failure to follow operating instructions. This war.

TECENOLOGIES,INc. ranty does not cover conditions caused by lack of

reasonable and proper maintenance, or other con-
ditions beyond the control Of the sellers.
2096 \VESTOVIR ROAD No implied warrarity, including merchant-
8.4
 UCRL ID 121182

******************

Waste Acid Recycling via Diffusion Dialysis*

Ch ris steffa n i
Manufacturing and Materials Engineering Division
Lawrence Livermore National Laboratory

Inorganic acids are commonly used in surface finishing shops to remove surface
scales, produce bright surfaces, strip unwanted metals and/or coatings, and prepare
metal surfaces to receive other coatings. These acids can also be used as the
electrolyte for coatings produced by electrolytic oxidation such as anodizing. Sooner
or later the acids become unusable due to contamination with metals, the conversion
of the hydrogen ion into hydrogen gas, or they become weakened by either dragout or
dilution.

The historic way of dealing with these spent acids is either to dilute or neutralize
them and pass them into the rinse water stream or precipitate the metal component
as a hydroxide filter cake and send the metal free liquid to the POTW. The problems
with these methods are that a new bath must be made up when the old is discarded
and the cost of treatment chemicals and equipment is high. Because most acids
become contaminated with metals before the acid value is completely exhausted,
many times more acid is wasted during dilution than is used for precipitation of the
metal.

Recycling of the spent acid has been limited to use as an alkaline neutralizing
chemical during waste treatment. Diffusion dialysis equipment has provided a way to
recover the usable acid and allow separation of the metal component for recovery
and sale to refineries. This technique has been made possible by the invention of
membranes that are strong enough to withstand low pH solutions and have long life
in an industrial environment.

The process places the acid on one side of a semi-permeable membrane and de-
ionized water on the other. The exchange of ions happens due to the desire of the
two liquids to come to equilibrium. The membrane prevents the movement of the
metal ions and only allows the diffusion of the hydrogen ion. If the contact time is set
at the right interval, much of the acid crosses the membrane while the metals remain
behind. The technology is similar to that used by kidney dialysis patients when
removing waste products from their blood stream.

*This work was performed under the auspices of the U.S. Department of Energy courtesy of Lawrence
Livermore National Laboratory under contract No, W-7405-Eng-48.
The basic equipment is fairly simple: a semi-permeable membrane, two metering
pumps, de-ionized water, and some waste acid. After setting up the dialysis
equipment, the operator sets the retention time to a pre-selected value to insure
maximum acid recovery or metal rej.ection depending on the stream being recovered.
The low acid/high metal reject can then be sent to an electro winning unit, and the
recovered acid can be returned to the processing area.

Various acid solutions and mixtures of acids have been received at LLNL using this
technology. One drawback is the time involved for recovery of large volumes. The
recovery rate is dependent on the size of the membrane diffusion area. A 40 cell pair
stack, which retails for approximately $30,000.00 will recover about 10 gallons per
day (GPD), Another drawback is the recovery of mixed acids in which one of the acids
is monoprotic such as Hcl and the other diprotic such as H2S04. The difference in the
number of protons causes the rej.ection of some of the diprotic acid. In this case, a
second recovery run may have to be performed in order to recover more of the
diprotic acid. Another thing to be aware of is the doubling in size of the volume of
liquid that is being recovered. The volume of deionized water that receives the waste
acid will have to be contended with, but if electro winning is done, followed by
evaporation, this should not present any problems. The following is a compilation of
recovery values from using the equipment with assorted waste acid streams.

Test 1 was a nitric acid solution that was used to strip copper from aluminum and
SST electroforming mandrels. The stripping rate had diminished even thought the
available acid was still high. The following values represent the acid and metal
values before and after the recycling process:

(start) (finish)

4.9 N nitric acid 3.9 N Nitric acid (79.5% recovery)

60 gin/I copper metal 7.2 gin/I copper metal (88°/o rejection)

The reject solution (130 gallons) was evaporated and re-concentrated and
reprocessed through the system again. After all processing was complete, the metal
(60 lbs) was recovered by electro winning and the spent liquor was recovered by
vacuum distillation. A small amount of waste was generated from the mixing of the
liquor with the accumulation in the vacuum distillation vessel.

Test 2 was conducted on a solution used to descale steel and deoxidize copper. The
available acid was quite high, but the copper in the solution was immersion plating
on the steel, causing problems with the pre-cleaning process. An electro winning
process was attempted to remove the copper, but was not very successful because
of the large cathodes area required to reduce the copper to any acceptable level.
Also, some acid was destroyed because of the inefficiency of the process.
The following values represent the acid and metal values before and after the
recycling process:

(start) (finish)

9.4 N Muriatic acid 7.1 N muriatic acid (75,5°/o recovery)

10 gin/I copper metal 1.1 gin/I copper metal (89°/a rejection)
14 gin/I iron metal 3.1 gin/I iron metal (77.8% rejection)

The process generated 110 gallons of low acid medium metal concentration which
was vacuum distilled to re-concentrate it. It was run through the system again and
another 75% of the acid was recovered. At this point, the waste volume was only 25
gallons and it was added to the common waste from the vacuum distillation unit and
trucked off-site for treatment and disposal. The electro winning of this concentrated
metal was partially successful, but the small volume made it inefficient to recover
from this solution. If a larger waste stream had been available, then it would have
been economical to remove the metal and send it to a refiner.

Test 3 was done on a spent electrolytic activation solution. The solution again had a
very high acid value, but work processed through it started to local etch and pit
because of contamination from excess metals. The following values represent the
acid and metal values before and after the recycling process:

(start) (finish)

6.5 N sulfuric acid 5.8 N sulfuric acid (89.2% recovery)

24 gin/I nickel metal 2.6 gin/I nickel metal (91°/o rejection)
14 gin/I iron metal 3.1 gin/I iron metal (78°/o rejection)
9 gin/I chromium metal 2.2 gin/I chromium metal (76% rejection)

After recovery and adjustment to the original operating concentration, the solution
again operated as it did when it was new. The waste products were concentrated by
vacuum distillation and sent off as waste (18 gallons).

Test 4 was conducted on a waste type 11 sulfuric anodizing solution. The operating
concentration of the solution is too dilute to allow any dialysis so the solution was
distilled to 5 N from its operating concentration of 1.8 normal. The dissolved
aluminum was also concentrated and some of it was removed from the bottom of the
distillation vessel prior to acid recovery.
The following values represent the acid and metal values before and after the
recycling process:

(start) (finish)

5.1 N sulfuric acid 4.6 N sulfuric acid (90.1% recovery)

182 gin/I aluminum metal 12.1 gin/I aluminum metal (94°/o rejection)
7 gin/I copper metal .8 gin/I copper metal (89% rejection)

The recovered acid was diluted with Dl water and sent to replenish the anodizing
bath. After dilution, the aluminum content was 2.6 gin/I and the copper was only
230 PPM. The waste liquor was added to the common distillation tank and the total
waste was estimated at 10 gallons of liquid and 10 lbs. of solid waste.

Conclusions:
Diffusion dialysis a very cost effective way of recovering and separating acid
waste streams. Looking at a cost based analysis brings up the following examples.
This includes the cost of the original bath, the hydroxide used to neutralize the acid
and precipitate the metal, the disposal of the slude, and the cost to purchase the
new acid for the next bath. It does not include the cost of the labor, polymer, clarifier,
settling tank, and sludge dryer:

Hcl: $2.43/gallon x 70 gallons = $170.10

NaoH: $2.92/gallon x 23 gallons = $67.16
Disposal:
Hcl: $2.43/gallon x 70 gallons = $170.10 TOTAL = S

This shows the cost of the dialysis recovery. It too includes the cost of the original
bath but the cost of the new solution and disposal of the waste is about 10% that of
the treatment process. It does not include the cost of the recycling equipment, but it
is also much less that of a treatment systems and does not require the manpower
either. It does also not include the resale value of any reclaimed metal but that is
offset by the cost of electricity to win it back from the liquid.

Hcl: $2.43/gallon x 70 gallons = $170,10

Disposal:
Hcl: $2.43/gallon x 10 gallons = $24.30 TOTAL = S

SAVINGS OF S

F{ecovery parameters are dependent upon acid concentration, TDS, Dl water quality,
and membrane exposure times. Membrane exposure was optimized for maximum
metal rejection. These results are only meant to be representative of what your
recovery might be. To determine your actual recovery and cost you should submit a
sample of your spent acid to the manufacturer for testing.