eder associates consulting engineers, p. c, · eder associates consulting engineers, p.c. samples...

e eder associatesconsulting engineers, p. c,

November 10, 1993File #497-14

Mr. Mike GiffordUnited States Environmental Protection AgencyRegion VHS RW-6J77 West Jackson StreetChicago, IL 60604

Re: Revised Antidegradation Demonstration for National Presto Industries, Inc.

Dear Mike:

Enclosed are two copies of our revised antidegradation demonstration for National PrestoIndustries, Inc.'s (NPI's) treated groundwater discharge at the Riverview Park. The reviseddemonstration incorporates the changes which you requested in your November 1, 1993, letterto Mr. Rich Nauman of NPI.

Please call me if you have any questions.

Very truly yours,

EDER ASSOCIATES CONSULTING ENGINEERS, P.C.

Bruce A. Fenske, P.E.

BAF/skkEnc.

cc w/ enc: D. Hantz (WDNR)S. Thon (WDNR)R. Riedl (WDNR)J. Schmidt (WDNR)R. Nauman (NPI)D. Kugle (Eder)W. Warren (Eder)G. Rozmus (Eder)

BAF\4L497-14.002 11/10/93

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eder associates consulting engineers, p.c.

CHAPTER NR 207 ANTTOEGRADATION INFORMATION REQUEST

NATIONAL PRESTO INDUSTRIES, INC.3925 N. Hastings WayEau Claire, WI 54703

If you request an increase in any of your permit effluent limitations, you must provide allor part of the following information as required by Wisconsin Administrative Code,Chapter NR 207, Water Quality Antidegradation. You are advised to contact the permitdrafter who is identified in the cover letter that accompanies this permit reissuance packagebefore you begin work on this information request. The permit drafter will verify whatinformation you must provide, identify the classification of your receiving water, provideyou with a list of water quality indicator parameters if necessary and verify that significantlowering of water quality will or will not occur. All requirements of Ch. NR 207 must besatisfied before the Department can issue a permit containing an increased effluentlimitation.

If your facility discharges to a receiving water that is classified as Exceptional ResourceWaters, Great Lakes Waters or Fish and Aquatic Life Waters and you are proposing anincreased discharge (as defined in Ch. NR 207), you must document the following:

I. An assessment of existing treatment capability which demonstrates:

A. Any of the following:

1. Your monthly average discharge equals or exceeds 85% of yourmonthly average permit limitation for 3 consecutive months;

2. Your daily discharge equals or exceeds 85% of your daily maximumpermit limitation 5 or more times during a calendar year; or

3. Exceedances of any daily maximum, weekly average or monthlyaverage permit limitation;

In a memorandum dated April 20, 1993, the Wisconsin Department of

Natural Resources (WDNR) Bureau of Water Resources Management

recommended a weekly average effluent limitation for cadmium of 0.035

Ibs/day. At a maximum groundwater discharge rate of 380 gpm, the

concentration limitation would be 7.7 ng/t. The WDNR calculated the

BAFX4L497-14.002 1 11/10/93


weekly average limitation based on one-third of the Chippewa River's

assimilative capacity at a river flow of 370 cfs. Because NPI needs a

cadmium effluent limitation based on the full assimilative capacity of the

Chippewa River, an antidegradation demonstration is required according

to Chapter NR 207, Wisconsin Administrative Code.

Eder Associates Consulting Engineers, P.C.'s (Eder's) calculations

indicate that a weekly average effluent limitation for cadmium would be

49 fJ.g/1, if the full assimilative capacity of the Chippewa River and an

updated Federal Energy Regulatory Commission (FERC) relicensing flow

of 785 cfs for the Chippewa Falls Dam were used. The new FERC flow

will become effective January 1, 1994. Without the antidegredation

demonstration, NPI would be entitled to a weekly average cadmium

effluent limitation of 16 ng/t, which is based on one-third of the

Chippewa River's assimilative capacity at a river flow of 785 cfs.

To characterize water quality for the discharge, Eder did a 48-hour

pumping test of recovery wells EW-3 and EW-4 from November 17

through November 19, 1992; a 14-day pumping test of recovery well EW-

4 from March 3 through March 19, 1993; and a 44-hour pumping test of

recovery wells EW-1 and EW-2 from April 14 through April 16, 1993.

Cadmium levels in the samples collected from recovery well EW-3 ranged

up to 19.6 fj.g/1. Cadmium levels in the samples collected from recovery

well EW-4 ranged up to 49 /*g/£. Cadmium was not detected in the

BAF\4L497-14.002 2 11/10/93


samples collected from EW- 1 and EW-2 at or above the method detection

limit of 0.23

Based on these cadmium results, Eder calculated an expected average

cadmium concentration of about 18 pg/t in the combined discharge from

all four recovery wells. Because the expected discharge concentration is

based on limited data, the long-term weekly average discharge

concentration under continuous pumping conditions cannot be determined

with statistical certainty. The weekly average cadmium concentration may

at times be significantly greater than the expected average concentration

of 18 fj.g/L A weekly average concentration at or above 18 /xg/7 would

exceed the 16 pglt limitation which is based on only one-third of the

river's assimilative capacity. NPI needs a weekly average effluent

limitation based on the full assimilative capacity because of the potential

for exceeding the 16 /xg/f limitation.

B. The treatment facilities were maintained in good working order;

A cascade aerator will be used to remove VOCs from the pumped groundwater

before discharge to the Chippewa River. This system will not have any moving

parts; therefore, it will continue to operate in good working order. The cascade

aerator cannot remove cadmium. Treatment to reduce cadmium levels is not

feasible due to the low levels and no cost effective treatment alternatives (see

Appendix A).

BAF\4L497-14.002 3 11/10/93


C. The treatment facilities were operated and maintained as efficiently aspossible; and

Operation and maintenance of the cascade aerator will be performed according to

the USEPA approved plan submitted with the Interim Remedial Action Design

package. Although operation and maintenance will maintain the VOC removal

efficiency, it will not affect the cadmium level.

D. The conditions documented in A, above were not due to temporary upsets.

The conditions documented in A are not related to potential upsets in the cascade

aerator VOC removal system, which is not subject to breakdown. The conditions

of an exceedance of cadmium permit limits would be caused by potential

variations in cadmium levels in the groundwater discharge and the lack of an

applicable cost effective cadmium reduction technology to meet the proposed

Limitation. Cadmium levels in the discharge are not related to an "upset" of the

treatment system.

II. A demonstration that the proposed increased discharge will accommodate importanteconomic or social development in any of the following ways:

A. You will be increasing your employment.

B. You will be increasing your production level.

C. You will be avoiding a reduction in your employment level.

D. You will be increasing your efficiency.

E. There will be industrial, commercial or residential growth in the community.

BAF\4L497-14.002 4 11/10/93


F. You will be providing economic or social benefit to the community.

G. You will be correcting an environmental or public health problem.

The pumping, treatment, and discharge of groundwater from the NPI site is

consistent with the Interim Action Record of Decision issued by the USEPA on

September 30, 1991, and the Remedial Design Package approved by the USEPA

on June 10, 1993. Because this on-site interim remedial action will result in the

removal of volatile organic compounds (VOCs) in the groundwater at the NPI

site, an environmental problem will be corrected by this action.

HI. The following demonstration is optional. If you do not provide the informationrequested below, however, the Department will assume that your proposed increaseddischarge will significantly lower water quality and must comply with FV, below.

A. The expected levels of the indicator parameters in the discharge.

The expected concentration of cadmium in the treated groundwater discharge will

be 18 fj.g/t, although this concentration may vary under continuous pumping

conditions.

B. The existing levels of the indicator parameters upstream of, or adjacent to,the discharge site using applicable procedures in Chs. NR 102 and NR 106or specified by the Department if none of those procedures apply. Existinglevels shall be based on the earliest source of data after March 1, 1989 unlessa demonstration is made that there has been a change in existing levelsresulting in a change in the assimilative capacity of the receiving water, inwhich case the existing levels shall be based on the data used in thedemonstration.

BAF\4L497-14.002 5 11/10/93


In WDNR's April 20, 1993, memoranda recommending effluent limitations for

the proposed discharge of treated groundwater by NPI, the background level of

cadmium in the Chippewa River at Eau Claire was listed as 0.01 /xg/f.

C. A calculation of expected levels in the receiving water of the indicatorparameters as a result of the proposed increased discharge. In calculatingexpected levels in the receiving water, the following shall be used:

1. Applicable design low flow rates or dilution ratios for the receivingwater. In chs. NR 102 or NR 106 or specified by the Department ifnone of those rates or ratios apply.

2. The yearly average discharge loading rates for the increased portionsof the discharge.

NPI will discharge between 330 and 380 gpm of treated groundwater to

the Chippewa River. The Federal Energy Regulatory Commission

regulated low flow of the Chippewa River will be 785 cfs as of January

1, 1994. Eder estimates that the yearly average cadmium discharge

loading rate will be approximately 30 Ibs per year (0.547 mgd x 0.018

mg/£ x 8.34 x 365 days/year) based on a discharge rate of 380 gpm and

an average effluent concentration of 18 ng/t. Based on the short term

pumping test results, the yearly maximum cadmium discharge loading rate

could be as much as 81.6 Ibs/year (0.547 mgd x 0.049 mg/t x 8.34 x 365days/year) based on a discharge rate of 380 gpm and a maximum effluentconcentration of 49

D. A comparison of the expected levels in the receiving water of each indicatorparameter as calculated in C, above to:

1. The assimilative capacity multiplied by one-third for all indicatorparameters except dissolved oxygen; or

BAFX4L497-14.002 6 11/10/93


2. The sum of the existing level multiplied by two-thirds and the waterquality criterion multiplied by one-third for dissolved oxygen.

Based on the new FERC flow of 785 cfs, one-third of the assimilative

capacity of the Chippewa River for cadmium is 27.2 Ib per year. The

total assimilative capacity of the Chippewa River for cadmium is 81.6 Ib

per year (0.25 x 785 cfs x 0.646 mgd/cfs x 0.22 jzg/f x 8.34 x 365

days/year).

E. For discharges to Great Lakes Waters, an indication of whether the dischargeof any substance that has a bioaccumulation factor greater than 250 will beinitiated or increased.

The NPI treated groundwater discharge to the Chippewa River is not in the Great

Lakes basin. The Chippewa River flows into the Mississippi River which flows

to the Gulf of Mexico.

FV. If your increased discharge is found to result in a significant lowering of waterquality or if you have waived the demonstration for the lowering of water qualityas outlined in ffl, above, then you must demonstrate the following:

A. The proposed significant lowering of water quality cannot be prevented in acost effective manner by the following types of pollution control alternatives:

1. Use of conservation measures.

The 380 gpm treated groundwater discharge rate cannot be reduced using

conservation measures because a lower pumping rate would not effectively

prevent the off-site migration of contaminated groundwater from the

Melby Road Disposal Site and the southwestern portion of the NPI site.

BAF\4L497-14.002 7 11/10/93


2. Use of recycling measures.


recycling measures because NPI does not have a need at its facility for

this volume of water.

3. Use of other applicable wastewater treatment process or operationalchanges.


applicable wastewater treatment processes, (See Nora Brew memoranda

to Dennis Kugle, dated April 16, 1993, and to Bruce Fenske, dated July

14, 1993, included in Appendix A for a discussion of treatment processes)

without reducing the groundwater recovery system's ability to prevent off-

site migration of contaminated groundwater from the Melby Road

Disposal Site and the southwestern portion of the NPI site.


operational changes because the discharge is unrelated to NPI

production/manufacturing and does not result from NPI

production/manufacturing related activities.

4. Use of source reduction measures.


source reduction because the discharge does not result from process

operations and there is not a "source" to reduce. The discharge results

BAF\4L497-14.002 8 11/10/93


from an on-site interim action to maintain groundwater plume

contamination.

B. If your proposal includes an expansion of your wastewater treatment plant,demonstrate whether or not there are alternative wastewater treatmenttechnologies that:

1. Have documented performance levels for similar wastewatercomposition;

2. Have capital costs less than 110% of the capital costs (or presentworth less than 115% of the related total present worth value) foralternative achieving the water quality based effluent limitations ortreatment technology (categorical) effluent limitations, as appropriate;and

3. Would prevent a significant lowering of water quality.

Manufacturers of cadmium removal technology have not demonstrated that

their equipment is capable of consistently meeting a cadmium effluent

limitation of 16 ugll. The preliminary cost estimates for a treatment

system that may be able to meet a 16 pg/t limitation range from $0.2 to

$1.1 million with annual operating and maintenance costs between $0.3

and $0.4 million (see Appendix A). These capital cost estimates greatly

exceed 110 percent of the on-site interim action groundwater remediation

system. This system consists of two cascade aerators at a capital cost of

$10,000.

C. Demonstrate whether or not there are other discharge locations oralternatives which would meet the conditions of B.2 and 3., above.

The discharge location in the main channel of the Chippewa River off Riverview

Park provides the greatest assimilative capacity for cadmium of the possible

BAF\4L497-14.002 9 11/10/93


discharge locations. The other two locations discussed with WDNR staff are the

backwater area of the Chippewa River in Riverview Park, and near the Highway

124 Bridge. These alternate locations would result in weekly average cadmium

effluent limitations of approximately 0.23 pg/t and 2.3 pg/t, respectively.

Significant lowering of water quality could not be prevented at these alternate

discharge locations. The main channel of the Chippewa River provides the

discharge location with the greatest ability to assimilate the treated groundwater

discharge from the NPI site.

Discharge to the city of Eau Claire sanitary sewer is not an option because of the

likelihood the cadmium levels in NPI's treated groundwater discharge would

cause the city to exceed the cadmium limitation in its WPDES permit. The city's

discharge ranged between five and six mgd with an average cadmium level of

0.58 ng/t for the February to July 1993 period. Monthly monitoring results

ranged up to 2.2 /xg/f , nearly equaling the city's 2.4 pg/t weekly average

cadmium limitation. On the average, NPI's discharge could not exceed 22 pg/t

without causing the city to violate its effluent limitation. An NPI discharge above

4.6 fig/t would have caused the city to violate its effluent limitation in the month

of its maximum observed discharge. With NPI's average discharge of 18 ng/t

and with discharge levels up to 49 p g / l , the city could not accept the NPI

discharge without expecting to violate its cadmium effluent limitation.

BAF\4L497-14.002 10 11/10/93


APPENDIX A

BAF\4L497-14.002 11/10/93


MEMORANDUM

TO: Bruce Fenske File #497-14Doc. tfTG3076

FROM: Nora Brew

DATE: July 14, 1993

RE: National Presto Industries, Inc.Revised Cadmium Treatment Technologies and Costs

This memorandum supplements my April 16, 1993 memorandum to DennisKugle. Based on currently available data, Eder Associatesestimates that groundwater recovered at the southwestern portion ofthe NPI site under the interim response action will containapproximately 49 ppb cadmium. The WPDES permit cadmium limitationfor discharge to the main channel of the Chippewa River would be 16ppb if WDNR does not approve an antidegradation demonstration. Wecontacted the vendors who provided the conceptual cadmium treatmentschemes and costs, which are summarized in the April 16 memo, toobtain updated information based on the revised projections.

John Eason of NAPCO indicated that a system employing double passreverse osmosis followed by metal selective ion exchange wouldprobably achieve the desired cadmium removals. The distillationstep described in NAPCO's April 7, 1993 letter would be eliminated.The estimated capital equipment costs for this treatment scheme areapproximately $700,000 to $1.1 million. The estimated annualoperating and maintenance costs for this system are approximately$175,000 to $250,000. The treatability study that would berequired to confirm that the desired effluent levels could beconsistently met and to refine the cost estimates would costapproximately $19,000. This information is summarized in a July 1,1993 letter from NAPCO (attached).

-1-


MEMO TO:DATE:

Bruce FenskeJuly 14, 1993

Stanley Karrs of U.S. Filter Corporation indicated that the desiredcadmium removals could probably be achieved using their sorptionfilter technology, eliminating the need for an ion exchange system.Treatability testing would be required to confirm this and torefine cost estimates. The estimated capital equipment costs forthe sorption filter system are approximately $250,000. Thisinformation is summarized in a July 12, 1993 letter from U.S.Filter Corporation (attached).


-2-

NAPCOPlymouth Industrial ParkTerryville. Connecticut 06786203-589-7800 • FAX: 203-589-7304 July 1, 1993

Eder Associates480 Forest Avenue -__Locust Valley, NY 11560

,; OTHERAttention: Ms. Ellen Beacon

Reference: NAPCO Waste Treatment Proposal No. WA/13699

Dear Ms. Beacon:

I have reviewed this project based upon the new influent andeffluent numbers of 49 PPB and 16 PPB respectively. Based uponthis data it appears the best treatment method would still be 1or 2 pass R.O. The reject would then be treated with metalselective ion exchange. The ion exchange stream would berecombined with the R.O. product water prior to discharge.

The ion exchange regenerate solution could be evaporated to aconcentrated brine or batch chemically treated.

This treatment would eliminate the need for distillationequipment on the R.O. reject stream. This would significantlylower the unit operating costs. The estimated capital costswould also be reduced by $400,000.00 - $500,000.00.

The treatability work should still include R.O. testingutilizing a 1 GPM bench scale system. Metal selective ionexchange would be evaluated in the laboratory. Wasteconcentration and treatment options would also be evaluated. Byeliminating the distillation evaluation the treatability testingwould be reduced 30% resulting in a new price of $18,500.00.

I would be happy to meet with you and the client to reviewthis project.

Sincerely,

form Eason'Senior Product ManagerWaste Treatment

JE:11cc: L. Dallaire

M O N 1 0 : 5 1

U.S.FILTER

LANCY;-rivs i ci,. •••;--'81

E^OHE PA -TEL <i2

July 12, 1993

Eder Associates480 Forest AvenueLocust Valley, New York 11560

Attention: Ms. Ellen Beacon

Reference: Job No. 497-14

Dear Ellen:

This confirmatory letter is being written to follow-up our phone conversation of June 29,1993. In that conversation you mentioned there had been a change in your influent feedon this project to 49 ppb and that your effluent limits were now 16 ppb.

At that effluent level, our sorption filter technology would be applicable. This streamwould still require testing since we have so little data on it, but it's in the range wheresorption filtration is suitable. The total equipment cost for the filter would beapproximately $250,000. This would include a sludge holding tank and a small filterpress to dewater the solids. Enclosed is a brochure on the filter which describes it.

Yours very truly,

UNITED STATES FILTER CORPORATION

Stanley R. r^LrrsDirector of Process Engineering

SRK/mn

Enclosure

cc: ILS, FilterMr. Thomas J. Whalen

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ApplicationsThe Lancy Sorption Filter is designed (ortreatment of segregated and non-segregatedstreams, stand alone treatment, polishingtreatment, and retrofitting or upgrading ofexisting treatment systems. It, consistentlyremoves heavy metals to meet extremely toweffluent levels for:• contaminated groundwater applications• electronics manufacturing (printed circuit

board)• metal finishing operations• landfill leachate• stream dischargers.

Design CriteriaLancy Sorption Filter units are designed toremove low levels of total suspended solidsand heavy metals. Typical maximumincoming loadings are as follows:Total heavy metals:0-50 ppm total metals>60 pom, pre-trealment is requiredTotal suspended solids:0-100 ppm>100 ppm. pre-treatment is requiredTotal acidity.Less than 100 ppm expressed as CaCO3The influent should be essentially free ofemulsified oil and grease which drasticallyincreases media consumption. Typicaly lessthan 10 ppm oil and grease is tolerable.Separate equipment can be provided lopretreat such streams.All chemical feed concentrations andchemical feed pump rates are based onthese parameters. Consult the factory lor

Features• Removes chelated and non-chelaied heavy

metals from segregated or mixed wastestreams

• Specialized proprietary filter media forremoval of heavy metals and residualsoluble sulfides

• Patented sulfide control• Pre-piped and pre-wired skidded unit with

built in chemical feed modules• Fully automatic end continuous operation

for four standardized sizes: 20, 80, 160,240 gpm

• No internal moving parts• PLC controlled operation• Unique backwash system which utilizes

compressed air to drive filtered water backthrough the filter tubes

Benefits• Zinc, silver, copper, lead, cadmium can be

reduced to < 0.05 ppm and other metalsto < 0.1 ppm

• Mercury can be reduced to < 20 ppb• Continuously recycles and reuses the

media for maximum solids handlingcapacity

• Easy installation• Minimal operator attention required• Can be designed into new or existing

treatment systems• No additional solids ere added to the

waste stream to remove heavy metals• Low sludge generation• Capital end operating costs are typically

lower than cross flow microfilters• Process guarantees are provided based

on treatatxlity

Sludge Comparison GraphExample: Removal of 1 b. of coppe/ metal

UK. ofSWgeFormed

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INFLUENTLANCY SORPTION FILTERFLOW SCHEMATIC

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Process DescriptionThe Sorplion Filter process uses sodiumsulfide chemistry to precipitate heavy metalsto most very low effluent limits.Wastewalers to be treated by the LancyScrption Filter are directed to the integral pHadjustment - sulfide reactor. Here the pH israised automatically by caustic addition.Simultaneously, sodium sulfide is added via apatented suifide sensing device to thewastewater. Safety interlocks are included toinsure that the pH is a minimum of 95 beforesulfide can be added.The wastewater then overflows to theretention tank, which serves as a pumpdowiT/holding vessel. From (he retentiontanks, the wastewater is pumped to the filterbody where K is filtered through a proprietaryreactive media which performs two functions.First, it filters out the fine, ccfloidal metalsulfide precipitate formed in the reactionmodule. Second, it absorbs any residualsoluble metals and unreacted sulfidesremaining in the solution.

Sizing ChartFlow Rate Filter Area

gpm sq. ft.2080160240

Overall SystemL x W x H

40160320480

18' x BVi' x 13'Multiple skidsMultiple skida

Equipment arrangement Is flexible andcan. rf required, be supplied to fit otherequivalent plan area dimensions.

As the liquid passes through the numerousfilter tubes contained in the filter body.suspended solids and metals are depositedon the outside of the tubes. Filtrate passesup through theinside diameterof the tubes, intoth,e filtrateheaders and onto the mainoutlet.At the end of thefilter cycle, airtrapped in thelop of the filtercap is releasedcausing the filter tubes to expand and"bump" the fitter cake along the entire lengthof the tube Filtered liquid is forced backthrough the tubes, carrying the accumulatedsolids and liquid to waste in a matter ofseconds. At this time, the solution in the filtersystem is recycled back through a separateprecoat lank until the media is recoated onthe filter fingers, therby exposing new sitesfor filtration and adsorption.While the tiller precoats, the incoming wasteis accumulated in the retention tank. After theprecoat cycle is completed, the filter resumesprocessing of the accumulated wastewater.

M O H 10 : 5 5 R .

CapabilitiesWhether you are integrating a Lancy SorptionFitter into a new or existing treatment design.<y depending on the sorption filter toconsistently perform as a siand-alonetreatment process. US Fitter has the in-housecapabilities to help.Based on conclusive laboratory (reatabilitywork as well as our experience withhundreds of applications, US Filter willprovide in writing, a straight forwardperformance guarantee in addition <o ourmechanical warranty.Once s/zing is confirmed, you get equipmentthat performs reliably for years. The reliabilitystarts with professional start-up assistanceand continues with uninterrupted customerservice. If you prefer; we can also install anyof the equipment we supply. Our installationexperience includes hundreds of turnkey andequipment supply projects. By choosing USFrier, you get more than a good piece ofequipment, you get professional, experiencedassistance with your treatment solution.

With environmental regulations continuing tobecome more stringent, the Lancy SorptionFilter effectively reduces heavy metals in acontaminated stream to the part per billionrange The Lancy Sorption Filter provides anexceptionally efficient method for thecontinuous removal of both chelated and-non-chelated he^vy metals using provensuif.de chemistry and specialized adsorptionmedia.

Options1. Stainless steel filter body2. 3-channel chart recorder3. Materials of construction for piping • PVC,

CPVC4. Alternate medias including diatomaceous

earth and ceflufose fiber5. Sludge handling equipment6. Pre-treatment equipment

Efl Lancy Systems and Equipment181 Thorn Hill


MEMORANDUM

TO: Dennis Kugle File $497-14Doc. IMW2460

FROM: Nora Brew cc: R. Nauman

DATE: April 16, 1993

RE: Cadmium Treatment TechnologiesNational PrestSeL Industries, Inc.

Based on the November 1992 48-hour pumping test results, EderAssociates estimates that 180 gpm of groundwater containing 10 to30 ppb cadmium will be recovered at the southwestern portion of theNPI site under the interim response action. Groundwater dischargedto the backwater area of the Chippewa River would be subject to a0.23 ppb WPDES limit on cadmium, with no dilution allowed. Thismemorandum summarizes Eder's evaluation of the cadmium removaltechnologies available to achieve the 0.23 ppb discharge limit.

Eder searched USEPA's RREL Treatability Program Data base toidentify technologies that could be used to remove cadmium fromgroundwater. Most of the cadmium treatability information in thisdata base is for treatment of wastewaters with influent cadmiumlevels significantly greater than the influent levels expected atNPI. Therefore, the cadmium removal efficiencies for varioustechnologies presented in USEPA's data base cannot be directlyapplied to NPI.

Eder contacted USEPA's Risk ^eVjctior. Engineering LaboratorySuperfund Technology Demonstrather. Division for recommendations oncadmium removal technologies. Doug Grosse (USEPA) suggested cationexchange and in-situ precipitation. Mr. Grosse indicated that ionexchange could achieve the 0.23 ppb discharge limit if a resin thatselectively binds cadmium is used. This is a costly technology.Mr. Grosse suggested that Eder contact vendors such as Rohm & Haas

-1-

___ w ___ is the two units together ie. UFwPAC -Ultrafiltration using Powdered ActivatedCarbon.

___(B) is batch instead of continuous flow.

Scale

B - Bench Top P - Pilot Plant F - Full Scale

Number after letter refers to the plant number in a specificreference (ex. F7 - plant 7 is the seventh full scale plantin the indicated report).

Matrix

C - Clean water (ex. distilled)D - Domestic wastewaterGW - GroundwaterHL - Hazardous leachateI - Industrial wastewaterML - Municipal leachateRCRA - RCRA listed wastewaterS - Synthetic wastewaterSF - Superfund wastewaterSP - SpillT - Tap waterTSDF - Commercial treatment, storage and disposal

facility - liquidsW - Surface water

SIC (Standard Industrial Classification) Codes

For industrial wastewaters a 2 digit SIC code will be givenfollowing the letter designation, i.e. I 22 is a Textile MillProducts wastewater. If the SIC code is unknown a U will beshown, I U.

10 - Metal mining12 - Coal mining13 - Oil and gas extraction20 - Food and kindered products22 - Textile mill products24 - Lumber and wood products26 - Paper and allied products except computer equipment27 - Printing and publishing28 - Chemicals and allied products29 - Petroleum refining and related30 - Rubber and misc. plastic products31 - Leather and leather products33 - Primary metals industries34 - Fabricated metal produces except machinery & transportation

equip.36 - Electronic and electric equipment37 - Transporation Equipment39 - Misc. manufacturing industries

47 - Transportation services49 - Electric, gas, and sanitary99 - Nonclassifiable establishments industries

Effluent Concentration

Effluent concentration will be given as a arithmetic mean to twosignificant figures. The number of samples used to calculate themean is given after concentration as (n) (ex. 13 (5) - 13 is themean of 5 sample values).

% Removal

Percent removal will be calculated on a concentration basis.If data are available, it will also be calculated on a massbasis for physical/chemical systems. Those values calculatedon a mass basis will be noted by a (m). An example would be:

% Removal: 99.95 99.95 is based on concentration98 (m) 98 is based on mass

Influent - Effluentwhere % Removal = ————————————

Influent

Reference Quality Codes

A - Papers in a peer reviewed journal.B - Government report or database.C - Reports and/or papers other than in groups A or B notreviewed.D - Group C papers and/or reports which have been given a "good"quality rating by a selected peer review.E - Group C papers and /or reports which have been given a "poor"quality rating by a selected peer review. These data willonly be used when no other data are available.

Additional Codes Following Reference Codes

V - Volatile emissions data available in ReferenceS - Sludge data available in Reference$ - Costs data available in Reference

Physical/Chemical Properties Data

(c) - Values presented are values that were reportedcalculated in the reference as is and are only usedwhere measured are not available.NA - Values for the particular property have not been foundin literature to date.

NATIONAL PRESTO INDUSTRIES, INC. SITE - CADMIUM TREATABILITY INFO

Rev. No. 4.01 RREL TREATABILITY PROGRAM 06/10/93

RREL TREATABILITY PROGRAM

Treatment Technologies

AAS - Activated Alumina SorptionAFF - Aerobic Fixed FilmAL - Aerobic LagoonsAPI - API Oil/Water SeparatorAS - Activated SludgeAirS - Air StrippingAlkHyd - Alkaline HydrolysisAnFF - Anaerobic Fixed FilmAnL - Anaerobic LagoonsBGAC - Biological Granular Activated CarbonCAC - Chemically Assisted ClarificationChOx - Chemical Oxidation (Parantheses shows oxidation

chemical ie. ChOx(Oz) is ozone, ChOx(Cl) is chlorine,ChOx(Sur) is surfactant, and ChOx(H202wOz) is peroxidewith ozone.)

ChOx/Pt - Chemical Oxidation/PrecipitationChPt - Chemical PrecipitationChRed - Chemical ReductionDAF - Dissolved Air FlotationED - ElectrodialysisFil - FiltrationGAC - Activated Carbon (Granular)IE - Ion ExchangeKPEG - Dechlorination of Toxics using an Alkoxide (Formed, by

the reaction of potassium hydroxide with polyethyleneglycol (PEG400))

PACT - Powdered Activated Carbon Addition to Activated SludgeRA - Resin AdsorptionRBC - Rotating Biological ContactorRO - Reverse OsmosisSBR - Sequential Batch ReactorSCOx - Super Critical OxidationSed - SedimentationSExt - Solvent ExtractionSoft - Water SofteningSS - Steam StrippingTF - Trickling FilterUF - UltrafiltrationUV - Ultraviolet RadiationWOx - Wet Air Oxidation

NOTES:___ + ___ is the first process unit followed in process

train by the second ie. AS + Fil - ActivatedSludge followed by Filtration.

P R — 1 - * — 9 3 W E D 1 2 : 0 0 P i S T D ^ l - P l N C Y P . O S

Eder Associates April 14,1993Attention: Ms. Nora Brew Page 2 of 2

If you have any questions, please feel free to call me at (412) 772-1265.

Sincerely,

U.S. FILTER, INC. WARRENDALE, PA

Stanley R. KarrsDirector, Process and Application Engineering

cc: John W. LowryG. Kent PetersonThomas J. Whalen

PR.— 1 - * — - 3 3 U E D 1 2 : 0 0 f t S T D - ^ l _ « M C Y R . O 2

U.S.FILTERVN(TtD JTAW f ll«» COM (XATtON

April 14,1993id THORN HIU.RQAD

WARRENDALE. PAT,J A . , TEL <12-7Laer Associates FAx<i480 Forest AvenueLocust Valley, New York 11560(516)671^440

Attention: Ms. Nora Brew

Reference: Job No. 497-14

Dear Mfl. Brew:

After reviewing the revised influent and effluent numbers and flow data receivedon April 6, 1993, we still feel that an ion exchange approach would be best (foreither scenario) to reach the very low cadmium number you wish to achieve.

As mentioned in our September 2, 1992 letter to Mr. Valenti, we still need moredetailed analytical Information (i.e., a balanced water analysis for all inorganics,residual levels of organics present, plus total dissolved solids and total suspendedsolids levels).

If we were to assume there are no organics and no suspended solids and that allmetals are soluble, a duplex set of chelating resin columns with counterflowregeneration and the use of our sorption filter to treat the regenerant may beadequate to meet both scenarios. The cost of equipment only for this type of systemwould be between $650,000 and $700,000.

If there are organics present and suspended metals are present but total dissolvedsolids are low (<200 ppm) we would suggest microfiltration, cation and anioncolumns with counterflow regeneration followed by a polishing mixed bed unit.The regenerant would again be run through a sorption filter and blended with theeffluent from the mixed bed unit. Equipment only for this type of system wouldcost between $1,200,000 and $1,300,000.

As you can see, more information would be helpful. In any event, with effluentlimits this low, a treatability study would be required to determine whether theselimits could be reliably met, In <?r<;ler to propose treatability at a reasonable cost,more information is needed.

94/67/93 14 1 3 7 8 263 569 7384 NQPCO INC. 62

WA/13699April 7, 1993Pago 2

II. DISTILLATION EVALUATION

Samples of the raw well water and the R.O. reject wouldbe distilled in the laboratory to determine the minimumwaste concentration attainable without contaminating thedistillate with cadmium. A larger scale vaporcompression still would then be tested to verify thedistillation results on an energy efficient system. Thiswould also allow direct scale up of the component sizing,

III. "HASTE CONCENTRATION

The still bottoms would be treated with metal selectiveion exchange, and by chemical methods to determine iffurther waste concentration was possible.

The coat for the treatability study would be as follows:

Labor & ExpensesEquipment ( RentalsAnalytical

Total

$ 14,250.00$ 6,370.00$ 5.700.00

$ 26,320.00

The estimated capital cost of a complete system is $1.2 - 1.5million. This cost would be further defined along with systemoperating costs, and presented in the treatability report.

It may be possible to do a laboratory evaluation of thedistillation and R.O. technologies for less money if financing thetreatability phase is a problem. This data would still have tobe tested at the pilot plant level to have validity.

Please let me know if you have any questions.

S:.nee rely,

Jj>hn EasonSenior Product ManagerWaste Treatment

JEillcc: L. Dallaire


MEMO TO: Dennis KugleDATE: April 16, 1993

to obtain additional information on ion exchange systems. As analternate, Mr. Grosse suggested an innovative in-situ metalsprecipitation approach. This approach injects chemicals into theaquifer to precipitate metals which then bind onto clay particlesor other aquifer heterogeneities. Mr. Grosse indicated that in-situ precipitation of chromium has been tested, but cadmiumprecipitation has not yet been attempted.

Eder contacted Rohm & Haas and Bill Waitz said that they havelittle experience in cadmium removal. The majority of Rohm & Haas'ion exchange systems were used to treat aqueous streams with muchhigher influent concentrations of metals than the NPI groundwater.Therefore, Mr. Waitz indicated that he was uncomfortable with NPI'scadmium treatment requirements and did not wish to develop aconceptual ion exchange system.

Eder described NPI's treatment needs to Napco. Napco was surprisedat the low influent cadmium levels expected and the degree ofremoval required, and indicated that it was very difficult toaccurately measure levels of cadmium below 1 ppb. John Easonindicated that a system employing double pass reverse osmosisfollowed by distillation and ion exchange would probably achievethe desired cadmium removals. However, Mr. Eason said that anextensive treatability study (estimated cost = $30,000) would berequired to confirm that the desired effluent levels could beconsistently met and to refine the system installation costs andoperating and maintenance costs. Napco's proposal is attached.Napco submitted a preliminary estimate indicating that the capitalequipment costs for the proposed treatment scheme would be between$1.2 and $1.5 million. Based on information obtained from Napco,

-2-


MEMO TO:DATE:

Dennis KugleApril 16, 1993

Eder estimates that the annual operating and maintenance costs forthis system would be between $400,000 and $500,000.

Eder also received conceptual cadmium treatment information fromU.S. Filter Corporation. Stanley Karrs indicated that an ionexchange approach would be appropriate to achieve the 0.23 ppbcadmium discharge limit. Mr. Karrs recommended using a duplex setof chelating resin ion exchange columns if the groundwater containsonly soluble metals and no organics or suspended solids. Mr. Karrsestimated that the equipment cost would be between $650,000 and$700,000. If the groundwater contains organics, suspended metals,and less than 200 ppm total dissolved solids, Mr. Karrs suggestsusing microfiltration, cation and anion exchange. The estimatedequipment cost would be between $1.2 and $1.3 million. Mr. Karrssaid that a treatability study would be required to determinewhether the cadmium discharge limit can be reliably met and torefine equipment and operating and maintenance costs.

The cadmium levels detected in groundwater at the NPI site arelower than levels typically encountered in industrial applications.Eder has evaluated similar cadmium removal problems for otherfacilities that have been required to meet stringent metalsdischarge limits based on surface water standards. In thesesituations, many vendors are reluctant to discuss possibletreatment scenarios to achieve these low levels cf cadmium andother metals when the influent concentrations are so low. None ofthe vendors that Eder contacted would guarantee that their systemscould meet the 0.23 ppb discharge limits for cadmium. Full scaleapplication of ion exchange or other technologies suggested by thevendors and USEPA may or may not consistently achieve the desired

_ -3 _


MEMO TO: Dennis KugleDATE: April 16, 1993

levels, thus the costs required to implement these options cannotbe justified.


-4-

' 67 '93 M I 5 6 8 283 589 7 3 8 4 H R P C O INC.

NAPCOrmbuth Induitrial Perkrryyillo, Connecticut 067M3-589-7800 • FAX: 203-589-7304

Po«Mt~ brtnd fax tranamfflal nwrw 7871

April 7f 1993

Eder Associate*480 Foreat AvenueLocust Valley, NY 11560

Attention: Ms. Nora Brew

Reference: NAPCO Waste Treatment Proposal No. WA/13699

FAX: (516) 671-3349

Dear Msi Brewt

The technology exists to meet the 0.23 ppb cadmium limit forthe ground water stream in question.

We would propose to use double pasa R.O. to purify the mainstream. Approximately 20% of the initial stream would be rejectedcontaining the cadmium. The stream would be distilled with thecadmium and other metals concentrating in the still bottoms. Itmay then be possible to further concentrate the waste streamusing metal selective ion exchange or chemical treatment.

NAP<pO proposes to perform a treatability test to allow propersizing of the system and to identify the operating costs. Thetreatability work would consist of the following:

I. R.O. EVALUATION

A stream from the well would be passed through a doublepass R.O. system. The system would be sized to processabout 1 GPM of feed water. Samples of the permeate wouldbe collected and tested for cadmium to determine theminimum concentration attainable. Sufficient testingwould be performed to determine what the minimum rejectvolume would be and approximate system operating costs.This work could be performed at the site or in thelaboratory.

CADMIUM

AQUEOUS TREATMENT TECHNOLOGY DATA

TECHNOLOGY

ALASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASASAS+FilAS+FilCACChPtChPtChPt

SOURCEMATRIX

DDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDDD

SCALE

FF2F3F4FFlF2FlF3F28FlF36F4F17F37F19FlF2F5F58F2F38F4F4F3F10F5FlFF2FibFlaF2bF2aF6F5F7PFlF7F4F2F3aF3bF4F2FlF

INFLUENT CONCENTRATION: 0-100 ug/L

EFFLUENTCONCENTRATION( ug/L )

0.20 (36)0.31<1<7 (16)1.0<0.1 (7)<0.1 (7)5.5 (7)7 (6)<16 (6)<0.1 (7)5 (6)<3 (6)<2 (6)<5 (7)<2 (7)<2 (6)3 (6)1<2 (6)<10 (3)1.8 (23)1.9 (23)10 (2)<20 (2)5 (23)80.6 (23)<0.95 (24)<0.58 (22)4.0 (23)4.4 (15)5.5 (23)0.9 (23)0.6 (23)7.9 (14)1 (30)10 (2)5 (1)10 (4)<0.75 (22)<0.50 (12)5 (1)8.7 (9)2.0 (32)2.7 (106)

PERCENTREMOVAL

1790.997.8>90.9>3085>99.47>99.416886>95.240>95.882>95.5>80>58>60>676293.3>87>0777575>0323886>89>90.4827591.3255062670050>90.0>91.107492.382

REFERENCE

54E ——243A-S-167E-S-167E-S-201B-S-243A-S-234A ——234A ——234A ——1B-S-

167E-S-1B-S-

234A ——1B-S-1B-S-1B-S-1B-S-1B-S-1B-S-1B-S-

167E-S-1B-S-35E-S-52A ——o A~""~"""35E-S-35E-S-52A ——59E ——52A ——67B ——67B ——67B ——67B ——52A ——52A ——52A ——16A-S-35E-S-35E-S-31B ——35E-S-67B ——67B ——31B ——

1682B ——1682B ——1830B ——

FilFilROSedSedSedSedSedSedSedSedSedTFTFTFTFTFGAGAnFFGAGGAGGAGCAC (B)ChOx (Cl)ChPtChPtChPtChPtChPtChPtChPtChPtChPtChPtChPtChPtChPtChPtChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+Fil

DDDDDDDDDDDDDDDDDGWIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII

1028312849283434343436363434343434343434343434343434343436363434343634343434

FFPIF12F3F10F5PFilF2F7FlF37F17F8F9F3F2BFFlF9B2F34B21B74B59B51BlB4B31B56B34B61B24B71B54B64B72B35B55B52B57B73B60B65B2B3B22B32B33B5B25B23B75B63

66.3<1.2 (35)0.6 (23)5 (3)0.8 (23)20 (2)0.86 (3)1.0 (23)20 (4)10 (2)3 (30)16 (6)<2 (6)0.8 (23)1.2 (23)3 (3)<4 (1)5 (5)5.316 (1)<1 (D70 (1)<3 (1)3 (1)<5 (1)1 (D15 (1)2 (1)1 (D27 (1)20 (1)25 (1)21 (1)<3 (1)7 (1)11 (D1 (D12 (1)20 (1)7 (1)8 (1)1 (D<5 (1)1 (D1 (D<1 (D<1 (D<3 (1)16 (1)22 (1)<1 (D<3 (1)<3 (1)<5 (1)1 (D

2549>90.9143820503600505076>92.6116240>4358440>800>2567>91.497.067758864416738>67887697.07974848297.0>91.497.097.0>88>88>677971>88>69>67>91.497.0

59E——33D-S-18B——52A——35E-S-52A——35E-S-44E-S-52A——35E-S-35E-S-35E-S-1B-S-1B-S-52A——52A——35E-S-87B——45E——393A——31B——32B——638B——-87B——29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B~$29B—$29B--$29B—$29B—$29B—$29B—S29B-29B—*T29B—$29B—$58B—$29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B—$29B--S

ChPt+FilChPt+FilChPt+FilChPt+FilChPt+Fil (B)FilFilPACTRA (B) + FILSExtSExt (B)SSSSSSAnFFChPtASAPIASAirSDAFFilFilFilGACGACGAC

I 34I 34I 34I 34I 10I 28I 33I 31I 28 'I 28I 28I 28I 28I 28MLMLSSFSFSFSFSFSFSFSFSFSF

B62B57B53B58B2P7PFlF20F8F32F33F7F6PFBF3F6F4F3F8F2F3F2F4F8

21 (1)20 (1)20 (1)1 (D<10 (1)34 (13)3416 (1)<4 (1)8 (2)12 (2)4 (1)<4 (1)12 (3)19 (8)22 (21)4.7 (5)<3.7 (1)<5 (1)<4.3 (2)5 (1)8 (4)13 (1)<3.7 (1)<3.7 (1)9 (2)<5 (2)

38415697.0>674000>3800r\,

>L,0305958>20>17>19000>26>230>23

29B — $29B — $29B — $29B— $66B ——

254B ——53B— $31B ——87B ——87B ——87B ——87B ——87B ——87B ——41A-S-36E— $25A-S-245B ——245B ——245B ——245B ——245B ——245B ——245B ——245B ——245B ——245B ——

CADMIUM

AQUEOUS TREATMENT TECHNOLOGY

TECHNOLOGY

ASASASSedALASCAC (B)ChPtChPtChPtChPtChPt

ChPtChPtChPtChPt (B) + FILChPt+FilChPt+Fil

SOURCEMATRIX

DDDDI 28I 28I 49I 33I 34I 10I 99I 99

I 34I 34I 34I 28I 99I 34

DATA

SCALE

F12F57FFFilF3BlPB9PIPIP2

B19B16B6F19PIBIO

INFLUENT


15 (6)96 (6)12250<40 (1)2830 (1)20140 (1)10 (12)97110

55 (1)98 (1)180 (I)6.5 (1)3119 (1)

CONCENTRATION:

PERCENTREMOVAL

91.290.195.141>75777594.14898.97671

86763399.2892.292.9

>100-1000

REFERENCE

1B-S-1B-S-33D-S-33D-S-87B ——975B— $638B ——53B— $29B-- $51B ——7E ——7E ——

29B— $29B — $29B— $87B ——7E ——29B— $

ChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+Fil (B)ROIE

I 34I 34I 99I 34I 34I 34I 10I 10W

B8B20P2B18B17B7BlP2P

23 (1)29 (1)2516 (1)11 (D22 (1)60 (1)3 (4)2 (3)

91.492.893.396.097.291.87699.649S.07

29B — $29B— $7E ——29B— $29B— $29B— $66B ——51B ——42A ——

CADMIUM


TECHNOLOGY

ASChPtROROROChPtChPtChPtChPt + Fil (B)ChPt + Fil (B)ChPt+FilChPt+FilChPt+FilChPtChPt

SOURCEMATRIX

DDDDDI 34I 34I 34I UI 28I 34I 34I 34SFSF

DATA

SCALE

F6P2P2P4P3B69B66FB3B2B70B67B68F2F8

INFLUENT


65 (6)18160 (4)1,700 (7)620 (7)73 (1)430 (1)93 (15)20 (1)20 (1)66 (1)360 (1)70 (1)13 (1)6 (5)

CONCENTRATION:

PERCENTREMOVAL

94.199.3085818694.86995.798.498.495.37495.099.3199.70

>1-10 mg/L

REFERENCE

1B-S-55E ——18B —— "18B ——18B ——29B— $29B— $89B— $88E ——88E ——29B— $29B— $29B--$245B ——245B ——

CADMIUM


TECHNOLOGY

ChOx/Pt (B)ChOx/Pt (B)ChPtChPtChPtChPtChPt+FilChPt+FilChPt+FilChPt+FilChPt+FilChPt+Fil

SOURCEMATRIX

I 34I 34I 33I 34I 34I 33I 33I 34I 33I 34I 33I 34

DATA

SCALE

B2F3B39B49B46B36B37B50B38B48B40B47

INFLUENT


900 (1)13,00050 (1)26 (1)1,100 (1)80 (1)7 (1)<10 (1)4 (1)<10 (1)2 (1)920 (1)

CONCENTRATION:

PERCENTREMOVAL

91.37299.6799.95598.099.4799.953>99.98399.973>99.98399.98798.4

: >10-100 rag

REFERENCE

248A ——62E ——29B— $29B— $29B— $29B— $29B— $29B— $29B— $29B— $29B— $29B— $

CADMIUM


TECHNOLOGY

ChPt (B)ChPt (B)Fil+GAC

SOURCEMATRIX

SSTSDF

DATA

SCALE

BlB2F3

INFLUENT


240 (1)<50 (1)690 (3)

CONCENTRATION:

PERCENTREMOVAL

98.4>99.6796.5

: >10-100 mg

REFERENCE

43E ——43E ——28BVS-

CADMIUM

AQUEOUS TREATMENT

TECHNOLOGY

ChOx/Pt (B)ChOx/Pt (B)RO

TECHNOLOGY DATA

SOURCEMATRIX

III

343433

SCALE

BlB4P

INFLUENT

EFFLUENTCONCENTRATION( mg/L )

0.8 (1)6.3 (1)0.007

CONCENTRATION: >100-1000

PERCENTREMOVAL

99.6596.199.996

REFERENCE

248A ——37E— $39E ——

J

MERCURY REMOVALIn the early "70's Akzo ChemicalsCo. of the Netherlands developeda process for the removal ofmercury using Duolite GT-73*.The process, which has been welldocumented in the literature1'5involves the following steps;

was then called Invac TMR. Rohmand Kaas offers Dvofitc CT-73 commercially andAlizo licences « technology paciL*c« 'or mercuryrecovery. Tho*e writhing lo purchase a technologypada^e should com ao:Akxo Zout ChemieBoortorenwet 2O7SJ4RSHen«elo(0)The rather lands

(a) Oxidation-Duolite GT-73reacts only with ionic mercury,therefore any metallic mercurymust be converted to the ionicform. This is readily accomplishedby chlorination with the pH of thesolution maintained at 3 to preventiron from precipitating. In order toprevent clogging of the down-stream resin beds, a good filtrationsystem is essential. Metalhydroxides and unreacted mercuryare readily filtered using eithersand or doth filters.(b) Dechlorination—The thiolgroups of Duolite GT-73 arereadily oxidized. Therefore,removal of chlorine introduced instep (a), or from other sources isessential in order to retain resinactivity. The Akzo process employsa two stage dechlorination, firstreaction with NaHSCb, NaiSOjor SOi, then passage through aspecial activated carbon. Thecarbon is housed in a columnhaving the same dimensions as theion exchange columns.(c) Ion Exchange—Two beds areused in series operating in acounter-current mode. One bedacts as a roughing unit and theother as a scavenger.A schematic representation of theprocess is shown in Rgure 1.

b>

€

INTRODUCTIONDuolite GT-73 is a macroporousion exchange resin based on acrosslinked polystyrene matrix.The functionality of this resin isprovided mainly by the thiol (-SH)group, with minor quantities ofsulfonic acid groups.It has long been recognized thatthe mercury-sulfur bond is a verystrong one, and, in fact, organicspecies that contain -SH groupsare named mercaptans which arisesfrom the Latin mercurium captans,"seizing mercury." Because DuoliteGT-73 contains -SH functionalgroups it has a very high selectivityfor mercury and also a hightendency to bind certain metal ionssuch as copper, silvo; cadmiumand lead. The selectivity sequenceis: Hg> Ag> Cu> Pb> Cd> Ni>Co> Fe> Ca> Na.

€

ION EXCHANGE WITHDUOLITEGT-73Ik-cause the thiol (-SH) groups inDuolitc GT-73 form such a strongbond with ionic mercury, even verystable complexes such as HgCI =can be removed because they existin equilibrium with the preferredions, HgCI* andHg' ' as out-lined below:

2 a ••

CAPACITYDuolile GT-73 has .1 total capacityof at least 1.2 eq/lilcr of -SH unitsand more typically 1.4 cq/lilcr. Tl\cequilibrium capacity of DuolitcGT-73 is dependent on mercuryconcentration in the liquid phasebut is independent of pH (between1 and 13) and NaQ concentration(between 0 and 310 grams ofNaQ/1). Figures 2 and 3 illustrateDuolitc GT-73 capacity formercury at various concentrations.

In the treatment of chlor-alkaliwaste water, it has been demon-

Figure 1Akzo Process for Mercury Removal

Figure 2Capacity ol Ouolitc GT-73 Rclntivc lo (lieConcentration ol Mercury in "ic Feed

Figure 3Equilibrium Curve of Ouotitc GT-73

iplc

sii.iicJ 111.11 IM.III it eii.nu c n:llowi.ilc.it 10 Ivil volume^ :vrhour (1.25 v,pm/l t' | u ill p.-. .',iu<.«.in diluent with .1 mercury v on-cenlr.ilion well In-low 5 p|v.- ,.\lypic.il l'ie.iklhrou};h cum •-presenletl in l:ij;ure -1.

SELECTIVITYIlic .illinily ol Duolilc G I-~.mel.il ions parallels llie soli::"ptxxliK.1 of (lie mel.il sullidc-tncl.il with (lie lowest sullici-.hilily product li.is I lie hij'Jic-:.illinily lor (lie resin. l\>r ex.- :ivheti .1 solution coiil.iiiun;: .e.ich ol I I;;. ( u. I'h.nul ( <:is [i.isseil lhroii;;li Duohle C; !mercury bre.iks through \\'.the oilier mel.ils. I his is ;;r.villuslr.ilcil in I i:-.iiie :•

REGENERATIONDuolile ( i }'•'/'.\ is iv.idilyre);ener.itv\i with miiu-i.il .1. >sucii .is I 1C I. A iypic.il rej;e:' .ill.-curve is presenleil in l'i};ure •„•

RESIN LIR:Clicniic.il d.im.i;;c lo Duolilt v.i 1-7is ex|Kx1iil in the lorm of ovJ.iliool -SI I groups. This c.m K-

such .is chlorine .ind oilier >:ro';>;<ixid.inls.iloii}; with oxygen .:-. tinpri-seni'e ol lernc ions. 1 he •• > id.i-lion pr<Hceils .is lolloxvs:Ml^ KM I • ..M.l.1,11 ^± NS Sf :lli.'lAU. S'.K i ..V.,|.IMI ^

Reaction 1 is cosily reversiblewhereas reaction 2 is not. AkzoZout Chcmic offers a proprietaryreactivation procedure whichreverses reaction 1 and thereforeextends resin life. Figure 7 showsresin life to be highly dependent onwhether a reactivation procedureis employed. Reduction of thedisulfide linkage is well docu-mented in the literature withreducing agents such astriphenylphosphinc6-7,1-4-dithio-threitol,* strong aJkali,9 sodiumhydrosulfitc,10 sodium bisulfitc,"and sodium sulfitc.':

OTHER METALSThe high selectivity of DuoliteGT-73 for various metals is shownin Figure 6 as a function of pH.All data were determined in a INsolution of NaNO . The resin hasa pronounced preference forcopper, lead and cadmium ions,which are removed in considerablequantities even from solutionscontaining only 1 mcq/1 of metaland a large excess of Na * ions.The data indicate the possibilityof selective separation of thesemetals.

Examples:1. Removal of lead from waste

water.InfluentCompositionPb" " 6 ppmSb' ' ' 0.3 ppm .Ma" 100 ppmpH = 2.5

The solution is passed througha column of Duolitc GT-73 al allowr.ilc of 15 m/h (6.1 Rpm/ft:)

Figure 4Typical breakthrough curveChlor-alkflli plant brine. pH 2.mercury concentration in Iced 20 SO nig/I.

5000

1000

1000 5000 10.000

Figure 5Replacement ot the ions of Cd, Pb and Cuby Hg-ions when percolating a solutioncontaining 10 ppm ot each specimen

1000 5000 10,000

The effluent contains loss th.in001 ppm Pb. After pass.i^c of700 liters (185 t;al) of ihc solu-tion through 1 liter of rcsm theeffluent composition wns si ill

Kq;cncrnlion \\ i lh .1 nilru .KH!soluhon piovoil successful \vi l l ioul di'tiT 101 .1! 1011 of llu- i CMII

Figure 6Regeneration o( Ouolite GT-73 withconcentrated Hd. Regeneration rate1 m1 HCJ/m' resin hourMercury concentration o( resin prior toregeneratkxi 35 g Hg/liler resin

1 2 3 4 5 6

Figure?Change of Doodle GT-73 operatingcapacity as • function of time

300

2. Removal of copper from nickelsolutionInfluentCompositionCu* * 100 ppmNi4 + 40g/lNa* 40g/lHowrate 15 m/h (6.1 gpm/ft1).The effluent contains less than0.25 ppm Cu after passage of 200liters (53 gal) solution/liter ofresin. After 250 liters (66 gal),of solution the leakage hasincreased to 5 ppm Cu.

3. Ag removal from fixing-bathsolution.InfluentCompositionAg 10g/l(NH4)2S20, 150 g/1Row rate: 3 m/h (1.2 gpm/ft1)EffluentComposition: Ag 25 ppm

RgureSDuottte GT-73 Ion Exchange Equilibria in 1 N. NaNO, SolutionMetal concentration: 1 meq/l metal ions.

isoo

woo

operational W«of t e«n io yean

Table #1 lists the basic character-istics of Duolite GT-73. figure 9and 10 show the hydraulicexpansion and pressure drop.

SAFE HANDLINGINFORMATION:A Material Safety Data Sheet isavailable for Duolite GT-73. Toobtain a copy, contact your Rohmand Haas representative.

CAUTION:Acidic and basic regenerant solu-tions are corrosive and should behandled in a manner that willprevent eye and skin contact.Nitric acid and other strongoxidizing agents can cause explo-sive type reactions when mixedwith ion exchange resins. Properdesign of process equipment toprevent rapid buildup of pressureis necessary if use of an oxidizingagent such as nitric acid is contem-plated. Before using strongoxidizing agents in contact withion exchange resins, consult sourcesknowledgeable in the handling ofthese materials.

€TABLE 1DUOLTTE GT-73*CHARACTERISTICSResin Characteristics:

Chemical Structure

Particle size distributionDensity as shippedDelivery formTotal capacitypH-rangeMoisture contentSwelling:H ——> NaH —» CuH — > H g

Recommended Operating Conditions:Recommended flow rateBackwash flow rateBed depthOperating capacity

Regeneration

'Formerly known as Imac TMR and Imac GT-73

macroporous polystyrene beads withweakly acidic active sites0.3-1.2 mmSOOg/lfSOlbs/ft3)H*1.4 eq/1 (30.6 Kgrs as CaCO./ft-')1-1350-60%

40%5%5%

5-20 m/h (2-8 gpm/ft2)10-12 m/h (4-5 gpm/ft1)0.5-1.75 m (1.6-5.7 ft)300-1000 meo/1, dependent on applicationconditions (65 to 21.8 Kgrs as CaCo,/ftJ)Mineral acids (HC1, H,SO4)

Figure 9HYDRAULIC EXPANSIONOuolitc GT-73

Bl

Figure 10Pressure DropOoofiteGT-73 REFERENCES

1. "Akzo Zout Chemie, technicalliterature. The Akzo ImacTMR process for the removalof mercury from waste water."

2. M.D. Rosenzweig, ChemicalEngineering, 82.60 (1975).

3. GJ. Dejong and CJ. N. Rickers.J. Chromatography, 102,443(1974).

4. C Calmort, "Ion Exchange andPollution Control", Chapter 16,pg. 201 (1979).

5. J.H. Vis, Chemical Age of India,31,481(1980).

6. B.J. Sweetman, Tex. Res. J.,36,1096, (1966).

7. B.J. Sweetman, Aust. J. Chem.,19 (12), 2347 (1966).

8. H.D. Weigmanrv Journal ofPblym. Sc., 6 (8), 2237, (1968).

9. M. Wronski, Lodz. TawarzNauk. Wydaal III, Acta.Chirru, 10,11, (1965).

10. L Bemisek, Czech. Pat.129,460.

11. J.B. Speakman, J. Tex. Inst.,32.T83.

12. LJ. VJblfram, Tex. Res. J., 36(11), 947 (1966).

tcrFUDW RATE IN GPM/FP

ROHMmflfls. PA. 19105

Ovolite if m fn»*4<m«ri;«f RoAm «*«< !(«•« Company The Cot«fMf:y*J ftoiicy « to nrj itrr i«J J«*c*4>t-fcVlk<rrGy«inT - - - « - - - • ' • --* ^ •- « - * - . _ - . _ « - . . .

TKcvr »ucXCt<*oA< and dita arc ba»cd on information **< bcUcw Co be rc*i*Wc. They arr olfcrcd i«K<>odfaiiK. but wfeKout fuaranlev. a« coodi<io«« a<vj method* of MX of o«*r fwo<J*>ct* arc- bryond <HK«*«<col.W< rtcocntncnd lka4 (Kc pcocpcctivc w*er dctcrmwx (Kc ftufcabitar of (Hjr malcriali a«sd twKCcU«»mbefore adopcinc them on a commercial tcale.Su(ccsl*ont for utct of our prod wet t or the inc1u«>o«\ of dc*crirxiv< mJicrul from pu tents and the citationof specific p*t*t**« in this publication cKould not be undcrMood as recommending the u*< at *HH proJ«>d«in vtoUtion of any palrnl or at permtsiion or license (o trie any rutenli of the RnKm and 1 (4" Com(v»ny.

IE-0-297 AUJUSU9W

ROHM RND HflRS COMPRNYPHILADELPHIA, PENNSYLVANIA 191O5

FLUID PROCESS CHEMICALS

AMBERLITE DP-1Amberlite DP-1 is a macroreticular weakly acidic cation exchange resin based upon a crosslinkedmethacrylic acid copolymer structure. Its unusually high exchange capacity is derived from car-boxylic acid groups. Amberlite DP-1 effectively removes soluble iron and other metal cations frompotable water and is essentially free of taste, odor, and colorthrow.

IMPORTANT FEATURES OF AMBERLITE OP-1;STABILITY—Amberlite DP-1 has exhibited excellent resistanceto physical attrition and is stable in the presence of strongalkalies and acids, aliphatic and aromatic solvents. On pro-longed contact with certain organic solvents, the resin swells tosome extent, but no breakage of the beads has been observed.SELECTIVITY—In the sodium form, Amberlite DP-1 softenswater in the same manner as does a strongly acidic cationexchanger. The selectivity of Amberlite DP-1 for hardnes^ ionsis, however, considerably greater than that of the sulfonic acidcation exchange resins such as Amberlite IR-120. The hydro-lytic behavior of the sodium salt of Amberlite DP-1; its selec-tivity for divalent cations, and the ease with which the sodiumsalt of this resin reacts with hydrogen ions to neutralize water

are the keys to the unique behavior of this product for waterconditioning.HIGH CAPACITY—With an acid-alkali regeneration, AmberliteDP-1 has an operating exchange capacity of over 40 kgr/ft3

(91 g/1). For convenience, Amberlite DP-1 can be regeneratedwith a mixture of sodium citraie, sodium hydrooride and sodiumchloride to yield a softening capacity of approximately 17 to 21kgr/ft5 (39 to 48 p/1). The neutralization capacity of AmberliteDP-1 is far superior to a sulfonic acid cation exchanger.STABLE OVER THE ENTIRE pH RANGE

INSOLUBLE IN ALL COMMON SOLVENTS

HYDRAULIC CHARACTERISTICSPRESSURE DROP—The approximate pressure drop for each footof Amberlite DP-1 bed depth, in normal downflow operation, atvarious water temperatures and rates of flow is shown in thegraph below.

BACKWASH—After each service cycle. Amberlite DP-1 shouldbe backwashed with water for approximately 10 minutes topurge the bed of any suspended insoluble material that mayhave collected on the resin. The resin bed shocdd be expanded aminimum of 50% during backwash.

OLrCLOCCQUJIED

CLa.

40 F|4'C)

WF (IS'Cl

-80T(27C»

-10O-F(3« C)

t I ' I » -0

FLOW RATE IN GPM/FT'

GPM'M' k3 U tv - CPU II' • ? <PSI H W MH,O M rt-W" PS I 1 «

CXMHydraulic EJcp*rtsJoo

CttcKim or Sodium Form

GPMtt'

APPLICATIONS"MYSlCAt FORM—White opaque spherical particles shipped in

iium form in a moist condition.. .nrriNG WEIGHT—46 lba/fl3 (736 g/1)MOISTURI CONTENT—60 to 70%*

R E E N G R A D I N G (WET)—16 to 50 mesh (U.S. SUndard Sieves)FICTIVE SIZE—0.45 mm*

SWELLING—100% (hydrogen to sodium)

SUGGESTED OPERATINGCONDITIONS -^ -i^

pH range* "irimum Temperature

inimum Bed Depthttackwash Flow RateService Flow Rate

^generation LevelRegeneration Flow Rate

nse Flow Rate

Rinse Water Requirements

cchange Capacity

4.5-14250*F(121*C)24 in. (0.61 m)See detailed information2-4 gpm/ft3

(16 to 32 1/hr/l)See detailed information0.25-0.50 gpm/fts(2.0 to 4.0 1/hr/l)Same as regeneration flowrat* initially, then 2 gpm/ft3

(16 1/hr/l)25-50 gal/ft*(3.35 to 6.7 1/1)See detailed information

EXCHANGE CAPACITYAND REGENERATION -

mberlite DP-1, which contains slightly ionized carboxylic acidoups, shows a very high affinity for hydrogen ions. Conse-

xjently, complete regeneration of this resin may be accom-plished with the following low levels of acids.

taooftAdd Obs/tt>)

HCI 6.25H,SO, 8.4

*jno««t(tA)

100134

Conctttntio*(X uArtios)

5.0%2.0%

' convert the resin back to the sodium form, 6 Ibs of NaOH/ft3

6 g/1) as a 4% solution are required.For a water containing 500 ppm hardness at 75*F (24*C), flowingat 2 gptn/ft3 (16 1/hr/l), a capacity of over 40 kgr (91 g/1) can be

pected when using Amberlite DP-1 in the sodium form. A.ver temperature or higher flow rate will decrease the capacity

u. Amberlite DP-1.

applications where it is not desirable to use acid regenera-m, such as in home water softeners, Amberlite DP-1 can be

regenerated with a 9% solution of sodium chloride, sodiumhydroxide and sodium citrate. Capacities for several solutions

e shown below.

Sotatio* CocnpoiitkM (/I of rtiaiItn rueoexinVtt' nun) Na' Cl HaOH Ki, Citrate KaCI IUOH Crtratt

Total tefMerant(Itrs/ U/1 t< Capaotjrt>) rtiiil (ktrm1) dCaCO/)

71010

5.5.5

112

112 8160 8160 8

161632

811.12

5.55

136184200

171821

.3

.7

.4

394249

6.8.0

SOFTENING—Amberlite DP-I in the sodium form has proven tobe effective in softening waters for home and industrial use. Inindustrial and domestic exchange tank applications, AmberliteDP-1 offers a very high capacity when acid-alkali regenerationis used. For automatic home water softening and neutralization,regeneration is conveniently accomplished with a 9% aqueoussolution containing sodium citrate, sodium chloride and sodiumhydroxide.DEALKALIZATION—The reduction of bicarbonate and carbon-ate concentrations and the removal of alkaline metals, particu-larly from waters having a hardness to alkalinity ratio greaterthan unity, may efficiently and economically be accomplishedby utilizing Amberlite DP-1 in the hydrogen form. In the hydro-gen form, Amberlite DP-1 converts bicarbonate salts to carbonicacid, which breaks down to yield carbon dioxide and water. Onceformed, the carbon dioxide may be removed with simpleaeration.WASTE CONTROL—Amberlite DP-1 effectively removes manytrace metals such as zinc, copper, cobalt, chromium and cad-mium from municipal and industrial waste streams. These met-als are removed while permitting alkali metals and alkalineearths to remain in solution. The resin is then regenerated witha dilute acid solution to yield a concentrated waste more amen-able to disposal or, in some cases, recovery of the metals.FOA—When employing Amberlite DP-1 in the processing orproduction of any food material which is to be consumed bynumans or animals, precautions must be taken to avoid con-tamination that may result from extractables, bacterial actionor introduction of extraneous poisonous materials. Precondi-tioning treatment is necessary to reduce the extractables tolevels complying with Food and Drug Administration Regula-tion 21CFR173.25. A suggested preconditioning treatment is tosubject the resin to at least three cycles of exhaustion using 150gal (568 1) of a 0.5% solution of sodium hydroxide per cubic footof resin (28.3 11 Following each of the three preconditioningexhaustion steps, the resin should be regenerated with 35 gal f(132 1) of a 5.0% sulfuric acid solution per cubic foot of resin f(28.3 IXThisprecondiUoningtreatraentwillputtheresininthe Vhydrogen form. If operation in the sodium form is desired, theresin must be regenerated with sodium hydroxide.S A F E H A N D L I N G I N F O R M A T I O N — A Material Safety DataSheet is available for Amberlite DP-1. To obtain a copy contactyour Rohm and Haas representative.CAUTION—Acidic and basic regenerant solutions are corrosiveand should be handled in a manner that will prevent eye andskin contact.Nitric acid and other strong oxidizing agents can cause explo-sive-type reactions when mixed with ion exchange resins.Proper design of process equipment to prevent rapid buildup ofpressure is necessary if use of an oxidizing agent such as nitricacid is contemplated. Before using strong oxidizing agents incontact with ion exchange resins, consult sources knowledge-able in the handling of these materials.

AMBERUTT a a trademark of Rohm and Haai Company or afitt tubfidianei oraffUialei. Tht Company's policy u to register Us trademark! where productsdesignated thereby are marketed by the Company, its subsidiariei or a/fUiales

These sugges t i ons and data are based on I n f o r m a t i o n we believe lo ber e l i a b l e . They are offered In food f o l t h . bul wi thout juarantee. as con-d i t i o n s »nd methods of UK of our products are beyond our control Werecommend t h a t the prospective user determine the s u i t a b i l i t y of ourm a i e r l a l j and luggetl loni befoie adop t ing them on a commercial scaleSuete t t loni for ujei of our products or the Inclusion of d e s c r i p t i v em a t e r i a l f r o m patents and the c i t a t i o n of specific pa ten ts In th i s publ l c i i lon should not be understood as recommending the use of ourproduc t s In v i o l a t i o n of any pa ten t or as permission or license lo useany p a l e n t s o f (he Rohm and Haas C o m p a n y .

fl

ApplicationsThe Lancy Sorption Filter is designed fortreatment of segregated and non-segregatedstreams, stand alone treatment, polishingtreatment, and retrofitting or upgrading ofexisting treatment systems. It consistentlyremoves heavy metals to meet extremely loweffluent levels for:• contaminated groundwater applications• electronics manufacturing (printed circuit

board)• metal finishing operations• landfill leachate• stream dischargers.

Design CriteriaLancy Sorption Filter units are designed toremove low levels of total suspended solidsand heavy metals. Typical maximumincoming loadings are as follows:Total heavy metals:0-50 ppm total metals>50 ppm. pre-treatment is requiredTotal suspended solids:0-100 ppm>100 ppm, pre-treatment is requiredTotal acidity:Less than 100 ppm expressed as CaC03The influent should be essentially free ofemulsified oil and grease which drasticallyincreases media consumption. Typically lessthan 10 ppm oil and grease is tolerableSeparate equipment can be provided topretreat such streams.All chemical feed concentrations andchemical feed pump rates are based onthese parameters. Consult the factory foralternatives if these loadings are exceeded.

Features• Removes chelated and non-chelated heavy

metals from segregated or mixed wastestreams

• Specialized proprietary filter media forremoval of heavy metals and residualsoluble sulfides

• Patented sulfide control• Pre-piped and pre-wired skidded unit with

built in chemical feed modules• Fully automatic and continuous operation

for four standardized sizes: 20, 80, 160,240 gpm

• No internal moving parts• PLC controlled operation• Unique backwash system which utilizes

compressed air to drive filtered water backthrough the filter tubes

Benefits• Zinc, silver, copper, lead, cadmium can be

reduced to < 0.05 ppm and other metalsto < 0.1 ppm

• Mercury can be reduced to < 2.0 ppb• Continuously recycles and reuses the

media for maximum solids handlingcapacity

• Easy installation• Minimal operator attention required• Can be designed into new or existing

treatment systems• No additional solids are added to the

waste stream to remove heavy metals• Low sludge generation• Capital and operating costs are typically

lower than cross flow microfilters• Process guarantees are provided based

on treatability

INFLUENT

pH/SULFIDECONTROL

r

LANCY SORPTION FILTERFLOW SCHEMATIC

MEDIA DISCHARGEREAGENT TANKS SULRDE REACTOR RETENTION

TANK •PATEKTED

Process DescriptionThe Sorption Filter process uses sodiumsulfide chemistry to precipitate heavy metalsto meet very low effluent limits.Wastewaters to be treated by the LancySorption Filter are directed to the integral pHadjustment - sulfide reactor. Here the pH israised automatically by caustic addition.Simultaneously, sodium sulfide is added via apatented sulfide sensing device to thewastewater. Safety interlocks are included toinsure that the pH is a minimum of 9.5 beforesulfide can be added.The wastewater then overflows to theretention tank, which serves as a pumpdown/holding vessel. From the retentiontanks, the wastewater is pumped to the filterbody where it is filtered through a proprietaryreactive media which performs two functions.First, it filters out the fine, colloidal metalsulfide precipitate formed in the reactionmodule. Second, it absorbs any residualsoluble metals and unreacted sulfidesremaining in the solution.

As the liquid passes through the numerousfilter tubes contained in the filter body,suspended solids and metals are depositedon the outside of the tubes. Filtrate passesup through theinside diameterof the tubes, intothe filtrateheaders and onto the mainoutlet.At the end of thefilter cycle, airtrapped in thetop of the filtercap is releasedcausing the filter tubes to expand and"bump" the filter cake along the entire lengthof the tube. Filtered liquid is forced backthrough the tubes, carrying the accumulatedsolids and liquid to waste in a matter ofseconds. At this time, the solution in the filtersystem is recycled back through a separateore-ma* tank until the media is recoated onthe iiiter fingers, therby exposing new sites•or filtration and adsorption.While the filter precoats. the incoming wasteis accumulated in the retention tank. After theprecoat cycle is completed, the filter resumesprocessing of the accumulated wastewater

CapabilitiesWhether you are integrating a Lancy SorptionRlter into a new or existing treatment design,or depending on the sorption filter toconsistently perform as a stand-alonetreatment process, US Filter has the in-housecapabilities to help.Based on conclusive laboratory treatabilitywork as well as our experience withhundreds of applications, US Filter willprovide in writing, a straight forwardperformance guarantee in addition to ourmechanical warranty.Once sizing is confirmed, you get equipmentthat performs reliably for years. The reliabilitystarts with professional start-up assistanceand continues with uninterrupted customerservice. If you prefer, we can also install anyof the equipment we supply. Our installationexperience includes hundreds of turnkey andequipment supply projects. By choosing USRlter, you get more than a good piece ofequipment, you get professional, experiencedassistance with your treatment solution.

With environmental regulations continuing tobecome more stringent, the Lancy SorptionRlter effectively reduces heavy metals in acontaminated stream to the part per billionrange The Lancy Sorption Filter provides anexceptionally efficient method for thecontinuous removal of both chelated andnon-chelated heavy metals using provensulfide chemistry and specialized adsorptionmedia.

Options1. Stainless steel filter body2. 3-channel chart recorder3. Materials of construction for piping - PVC,

CPUC4. Alternate medias including diatomaceous

earth and cellulose fiber5. Sludge handling equipment6. Pre-treatment equipment

U.S.UNITED STATES FILTER CORPORATION

Lancy Systems and Equipment181 Thorn Hill RoadWarrendale. Pennsylvania 15086-7527(412) 772-0044 Fax: (412) 772-1360

_L OF C O N T E N T S

NTRODUCTION 1

I EXCHANGE PROCESS.^ELOPMENT 2

OPERATING COST" NSIDERATIONS 3

,CAL REPLACEMENTRESIN SERVICE 4

INTENANCEANOLD SERVICE 7

OTHER IWT SERVICES 8

Increased volumes and higher punty levelsof water and other liquids are the result of acontinuous effort lo achieve higher productquality and greater cost effectiveness mindustry today.

Ion exchange is the primary process lorproducing high purity water and its use hasgrown dramatically Its cost effectiveness hasimproved through equipment innovations,resin improvements, system selection andapplication, and maintenance services. Thecost of ion exchange resins typically repre-sents less than 10% of the total operating costto produce high purity water and other liquids;whereas, the remaining 90% is consumed inchemicals, labor, water, power, sewer, andmaintenance costs. Like any other servce theselection, application, and supplying of ionexchange resins must result in cost savingsthat make the service a good value Manyvariables affect the ability at a resin to performefficiently in any system. IWT, as a leader in thewater and liquid treatment industry, combinesequipment design and operating experiencewith resin evaluation expertise to assist cus-tomers m identilying these variablesThis publication describes the (actors to beconsidered for the cost-effective selection andapplication of ion exchange resins. Informa-

tion is also provided on the many supportservices available from IWT for optimizingyour system's performance

ION EXCHANGE-A VERSATILE TOOLWhat is (he significance o( the number00000000017 This number is the allowablefraction of sodium contamination in the feed-water to a utility nuclear steam generator It isequivalent to 01 parts-per-txllion In terms ofthe proverbial needle in the haystack, if theneedle were 1/32" in diameter and 2" inlength, the haystack would have to be 20' indiameter and over 40' tall to achieve this concentration level How is it possible to achievethis stringent sodium concentration level? It isaccomplished through modern technologicaladvancements and the phenomenal capabili-ties ol a process called ion exchange.

This illustrates /ust one of hundreds of appli-cations where ion exchange has beenapplied by IWT In addition to removingionized minerals to extremely low levels, theporosity and electro-chemical characterisesof the ion exchange copolymers have wideapplication lor the separation and purificationof various food products and organic chemi-cals including high fructose corn syrup, highpurity dextrose, phenols, armno acids, vita-mins, hormones, and various petroleum frac-tions Ion exchangers can remove specificionic species selectively, such as gold,platinum, and palladium, so that thesevaluable minerals can be recovered andrecycled. Variations of ion exchange resinshave also been used to adsorb toxic chemi-cals, such as herbicides, so that they can beconcentrated and recycled within the produc-tion process

Since the synthesis of ion exchange resins byAdams and Holmes m 1935. the list of appli-cations has grown continuously for the highlyversatile ion exchange resin in its many forms.even more rapidly today than in past yearsThe selection of the optimum resm for a givenapplication and geographic! location requires expert consultation because o! theexpanding applications for ion exchangeresm technology and the more than 100commercially available resins being marketedtoday IWT welcomes the opportunity todiscuss your application requirements andhow our Total System method can benefit you

Om

OmmCO

CO

COmiomCO

I EXCHANGE PROCESSVELOPMENT

in the 1930's. Illinois Water Treatment Com-iy was founded for the purpose of produc-chemicals and eventually evolved into a

manufacturer of water treatment systems. In1935. an innovative chemical development

k place in England. It was demonstrated_t catioruc (positive) and anionic (negative)

functional groups could be chemicallynded onto synthetic polymers—termedms These materials were originally

pioduced m granular forms; spherical resinswere developed later. It was further demon-

ited that through a combination o( ion:hange and sorption. nearly all of the

dissolved salts contained in water could*>» removed by simply passing the water

xigh columns filled with ion exchange,_ .ins, thus, avoiding more expensive dis-tillation processes. The ion exchange resins

jld also be rejuvenated for continued'. after exhaustion by treatment with acids

and alkalies."^cognizing the potential for this process,

r developed the capability to design andi. _nufaclure the equipment needed to pro-duce high quality water in commercial quan-

•s. As far as it is known, the first commercialonizing unit in the United States was built

by IWT and installed in a plant in Rockford,Illinois. During World War II. many industries

:uired water of high quality and. as early as

1942. IWT already had installed over 50deionizers throughout the United States. Overthe years, many important contributions havebeen made to expand the application of theion exchange process. Resin manufacturershave made available a wide variety of ionexchange materials in each of the lour majorclassifications of strong acid, weak acid,strong base, and weak base resins. Theseresins have been used in various combina-tions and in numerous system configurationsto economically achieve a given quality orcharacteristic of end product. Since the com-pany's beginning. IWT has made significantcontributions in the development of a numberof techniques which have upgraded thequality of treated solutions and improved theoperational efficiencies of the ion exchangeprocess. Some of the major patents that havebeen issued to IWT that have greatly impactedthe treatment of water and other liquids are:

Patent # Title2.605,084 Method of Mixing Granular

Materials (for mixed beddeiorwzers)

2.615,924 Method of Purifying Glycerin2.771,424 Process for Regenerating

Ion Exchange Material2.891,007 Method of Regenerating

Ion Exchangers

3,382.169 Process lor DeionizingAqueous Solutions

3.617,558 Layered Ion Exchange Process4.193.817 Production of Bottler's Liquid

Sugar4,204.041 High Loading of Immobilized

Enzymes on Activated CarbonSupports

4,316.802 Filter

To meet the expanding treatment require-ments of industry, IWT's product line hasgrown over the years to include not only ionexchange systems, but clarification, filtration,ultrafiltration. reverse osmosis, adsorption,waste treatment, and pollution control sys-tems, as well as systems lor the recovery ofvaluable chemicals and precious metals fromsolutions.IWT has applied ion exchange and relatedprocesses to the treatment of water suppliesfor power generation and the production ofelectronic components, chemicals, pharma-ceuticals. cosmetics, and food products, toname a few. Today, ion exchange is the pre-ferred method lor treatment of water suppliesfor industries all over the world. By incor-porating the specialized skills of chemists,biologists, engineers, and technologists. IWTcan provide the expertise necessary to sol veany liquid treatment problem.

OPERATING COST CONSIDERATIONS

Efficient, economical operation of ion ex-change systems and auxiliary equipment hasbecome an increasingly important considera-tion m the processing of various products Asignificant cost associated with the operationof these systems is (he chemical regenerationof the resin that is required to restore them toa service condition. This includes not only thecost of the regenerant chemical, but also thelabor cost, neutralization cost, and sewersurcharges or waste treatment costs requiredto meet discharge limitationsProper selection and application of ionexchange resins can be a major contributorto the cost-effective operation of any ionexchange system. The cost of resin typicallyrepresents less than 10% of the total operat-ing cost to produce high purity water andother liquids; whereas, the remaining 90% iscomprised of chemicals, labor, water, power,sewer, and maintenance costs, etc. Manyvariables affect the ability of the resins toperform efficiently in any system. IWT com-bines equipment design and operating ex-perience with resin evaluation expertise lohelp identify these variables and optimizeequipment performanceThe overwhelming cost of chemicals, water,and labor as compared to the cost of ionexchange resin associated with the operationof a typical two bed baler feedwater make-updeminef alizer is illustrated in Chart 1. The cost

CttartlOperating Co«t of t lypfcal IWo Bed BoilerFeedwater Make-up OeminerdlzerEven considering regional cMlerences n the variablesused lo devetop Ihs cnafl. the cost of resin replacementis minor compared to the total system operating costs

of replacing the resin is small, but the savingsof the other operating costs can be significantYou can get the most for your money bypurchasing resins from a supplier with theexpertise to address this important issue

Every ion exchange system has its unique"Optimum Replacement Point" (ORP). It isIWT's goal, as a leader in the replacementresin market, to help our customers prolongthe useful life of their resin and move the 'ORP(as illustrated in Graph A) as far to the right aseconomically feasibleProper resin selection will contribute to im-proving the *ORP by reducing

The frequency of regenerations- Irreversible fouling- Premature chemical degradation- The effects of inadequate equipment design- The effects of variations in feedwater and

regenerant characteristicsOther ways to reduce chemical, water, andlabor consumption are by:- Adding pretreatment equipment to protectthe resin

- Optimizing regenerant quality- Optimizing equipment design- Improving operator knowledge

IWT can assist you in determining where the'ORP is for your system and can recommendsteps which can be taken to optimize yoursystem's performance.

GraphAOptimum Replace ment Point (*ORP)Tha graph iKostraies the 'OOP s lor l«o demineralizatcnsystems When the percent increase in operating costsbecomes greater than the cost ot the resin as a percent oloperating cost, < e more economical lo replace the resin

. JTAL REPLACEMENT RESIN SERVICE

Responslveness And Reliabilityte o> the largest inventories of ion exchangew in the United States and an experienced

start of chemists, chemical engineers, factory(--•ned service personnel, and local represen-

ves allow IWT to provide customers witho»l. dependable resin replacement service.I WT's extensive inventory of cation and anion

un meets the needs of a wide variety oflustnes and applications including

• RWR Condensate Polishingonvendonal Condensate Polishing

Hadwastenoiler Make-up

Dfterwng• Pharmaceutical" jgar Demmeralization

ator CoolingMetal Recovery" ation Conductivity

JtalystsDealkalization

ectromcsjlp and Paper

Deoxygenation

Resin Processing For Special NeedsHigh purity resins require special processmg to ensure high degrees ol conversionand low levels of impuniies Resins as listedin Chart 2. are made m IWT's facility to meetstringent industry specifications, such asthose recommended for nuclear units byGeneral Electric and Wesnnghouse and theultrapure water quality requirements ol theelectronics industry IWT's facility is designedspecifically for these high purity applicationsand many other customer requirements.such as:- Cleaning and sterilizing louled and con-taminated resinsCustom Wending of resins

- Resizing and regenerating chromato-graphic resins

- Pick up and delivery of resins in a slurry- Custom packaging of resinsCross regenerating of resins including resinsfor food and pharmaceutical applications

IWT has a resin reprocessing service forsalvaging fouled and/or exhausted resinwhen it is not feasible or economical todo so at the jobsite The resn can be trans-ported to and from the jobsite m our tanktrucks. 55 gallon steel drums, or standard fiberdrums. Hydraulic transfer ol the resin toand Irom our tank trucks minimizes fieldlabor and downtime This service has helpedsave some of our customers thousands ofdollars worth ol replacement resin and otherassociated costs

Chart 2Nuclear Grade, Semiconductor, andSpecially ResinsName Ionic Farm Description and Application

Hydrogen Nuclear grade gel type cation resinwith a high degree of conversionand low levels ol metallic impuritiesand sodium Applications includecondensate polishing, radwasle.and high punty systems

Hydroxide Nuclear grade gel type anionresinwith a high degree of conversionand low levels of impurities Apptications nclude condensate polishing. radwaste, and high puritysystems.

Hydrogen/ Nuclear grade mixed bed resin lorHydroxide use in condensate polishing.

radwasle, and high purify systemsHydroxide Nudear grade porous gel type

anion resin with a high degree olconversion and low levels ofimpurities. Applications ncludecondensalepofehmg. radwasle.and high punty systems

Hydrogen Nudeaf grade high crosstinked geltype cation resin with a high degreeof conversion and low levels ofmetallic impurities and sodium Applications nduoe condensatepolishing, radwasle. and high puritysystems

Hydrogen Self-indicating cation resm used ncartridge systems and lor eatenconductivity determination m theutility industry

Sutlite High purity oxygen removal[resinSuflate High purity jnion resin specially

treated for taste and odor tree loodand pharmaceutical appficaiions.

Hydrogen/ High purity mixed bed resinHydroxide specially treated lor task and odor

free food and pharmaceuticalapplications

High purity semiconductor resins are specially tested to ensurethe required effluent guarantee

RESIN INVENTORY RESIN PROCESSING FACILITY RESIN TRANSPORT SERVICE

Research And Development SupportServicesAchieving optimum performance Irom ademineralizer system is enhanced by periodicanalysis of the ion exchange resin IWT'sextensive analytical capabilities are used byanalysts and chemists in determining resinquality, as well as diagnosing unit operatingproblems and evaluating new ion exchangeproducts for conventional and special liquidprocessing applicationsInstrumentation such as the HIAC particlecounter used to measure particle size and dis-I nbution o( ion exchange resi n beads and anAVC-80 microwave moisture analyzer used inthe determination o< solids content of resinbeads are two examples ol the state-of-the-artequipment available for accurate evaluationof ion exchange resin characteristics. Otherinstruments include two Perkm-Elmer atomicabsorption spectrophotometers. two Hewlett-Packard gas chromatographs. a DohrmannEnvtrotech total organic carbon analyzer.a Waters Associates liquid chromatograph.and a Dionex ion chromatograph Theseinstruments and their uses are described

ATOMIC ABSORPTIONSPECTROPHOTOMETER

in the "IWT Research And Development"bulletinTests measuring the capacity percent conversion. moisture content, particle size distnbudon. bead strength, impurities, extractacJes.and kinetics are used in varying degrees toevaluate the suitability o( new and used ionexchange resns for specific applcadons Testresults ol field resin samples are comparedwith the original manufacturing speoficaiionswith the aid of a computer program, resultingm a detailed report that can be used as avaluable trouble-shooting tool

Presently, over 100 ion exchange resins arecommercially available: many have uniquefeatures for specialized applications Modidcations m bead size and uniformity, betterresistance to osmotc shock, and the development of the inert resin system are some of Ihemost recent advancements in the industryIWT's pilot plant coupled with extensiveanalytical capabilities is used in its ResinEvaluation Program to evaluate new andimproved products. IWT is qualified to recommend and provide the resins and servces thatwill help achieve the most cost-effective operation of your demineralizer system

MICROWAVE MOISTURE ANALYZER

MAINTENANCE ANDFIELD SERVICE

VT LIQUID TREATMENT SYSTEM

Preventative maintenance is essential to cost-effective and reliable operation of ion ex-change systems. Resins can become pre-maturely fouled or oxidized having a sig-nificant effect on effluent quality and runlength It is also possible that by-productsfrom oxidized resin can foul other resinsdownstream.IWT recommends frequent sampling andanalysis of resins to identify premature orexcessive degradation. Analyses of your resinsamples will report any significant losses incapacity or changes in other resin charac-teristics that could indicate a potential prob-lem A trend analysis of resin characteristicskept by the customer from accumulated resintest data can also be used to more closelymonitor performance. Resin analyses can besupplemented with leedwater. product wattand regenerant chemical analyses if indicated"by operating experience. In addition, IWTprovides recommendations for restoring theresin through special cleanup procedures,minimizing further deterioration through addi-tional pretreatment or operational modifica-tions, and resin replacement when necessaryAlthough the optimum frequency of resmanalysis varies with operating conditions. IWTrecommends a minimum of once a year andpreferably every six months to assure trouble-free operation.Service contracts are available '3 providecustomers with a cost-effective v.ay of as-suring reliable performance c heir ionexchange and auxiliary equipment. IWTservice contracts can be custom designrto include operation records analysis, wa,and resin analyses, equipment maintenanceevaluations, operator training, and resinreplacement

OTHER IWT SERVICES

WT's liquid treatment capabilities are the;sult of forty-seven years o< experience in

providing service and equipmeni to clients inall maior industries

h rough the years, a wide variety o( productsand processes has been developed andimproved by IWT experts Now. the companys applying its extensive knowledge in thispecialized technology to major research,

engineering, technical service, and manufac-turing programs aimed at developing lower:ost. higher performance systems.

Key liquid treatment related servicesState-ol-the-art analytical and pilot plantcapabilities are available lor process feasi-bility testing, laboratory simulations, and pilotlest programs.

; Equipment design, evaluation, and opera-tion training can be conducted tor engineersand operators. Custom designed trainingprograms can also be held at the customer'sjobsite.IWT can provide assistance in specificationpreparation lor both ion exchange resinsand equipment Many ol these specifica-tions are modularized on IWT's computer.Market test samples of various purifiedproducts, such as sugar solutions, fruitjuices, bottled water, pharmaceutical gradewater, and other solutions, can be producedm IWT's semi-works facility and shippedin drums or lank car quantities tor userevaluation.Equipment designed for specific customerapplications is available for lease Completeoperating systems can be provided on alease, option to purchase, or rental basis

• Field pilot plants are available for optimizingprocess parameters and can include com-plete start-up and operating service

- Qualified and experienced chemists, chemi-cal engineers, mechanical and electricalengineers, biologists, and environmental

engineers can assist customers with const*ing services These services indude struc-tural analysis, control panel layout, controlsoftware design, process and instrumentdiagrams, and detailed mechanical andelectrical drawings.Replacement distribution, sight strainers,conductivity instrumentation, support beds,and membranes are a few ol the more criti-cal spare and replacement items that can bereadily supplied by IWT.IWT can contract turn-key installations forentire liquid treatment plants including allauxiliary and waste treating equipment. Thisservice provides unified responsibility andavoids contractor-supplier conflicts.The Total CostThe development of an optimum liquid treat-men! system is a team effort that requires bothIhe intimate knowledge of the owner-user'sumque operating methods and conditions, aswell as the broad knowledge when is pro-vided by a quality equipment supplierThe total cost of a liquid treatment plant ismade up of many cost factors—including thecost of reliability, chemicals, waste water treat-ment, maintenance, operating labor, power,ion exchange resin and other media replacements. initial equipment capital, etc. It hasbeen demonstrated that the operating, main-tenance, and reliability costs associated witha liquid treatment plant usually exceed theinitial cost of the plant over its useful lifeby two to one or three to one: and yetthese cost factors do not always receive aproportionale amounl ol attention and in-vestment To ensure cost effectiveness, aprogram of operator training, maintenance,and performance monitoring should beestablished at the time the equipmeni ispurchased Contact IWT for more informalion on how our Total System method canbenefit you

*f^* cm

UNITED S T A G E S F ' L T E R C O R P O R A ! , c :

(Illinois Water Treatment products and systems)4669 Shepherd Trail, P.O. Box 560Rockford, IL 61105-0560Tel: ( 8 1 5 ) 877-3041 Fax: (815) 877-0172

9

ION EXCHANGE IN HEAVY METALSREMOVAL AND RECOVERYWilliam H. Waitz. Jr.

Editor's Note

Amber-hi-Lites has now completed 30 years of con-tinuous publication. This milestone is a tribute to theefforts of Dr. Robert Kunin, who wrote the first issueand nearly every one since, and continues to be theprincipal contributor. We want publicly to acknowl-edge our debt to him for his guidance and hard workDr. Kunin joined the Research Division of Rohm andHaas Company in 1946 and was employed there until1970 when he became a member of the marketing staffIn this new capacity he served as technical consultantto the company's ion exchange sales and marketingpersonnel throughout the world. He retired from Rohmand Haas in 1976 and established a private consultingpractice. Throughout his association with Amber-hi-Lites, his fertile imagination, his encyclopedic knowl-edge of the chemical industry and his prolific pen haveenabled this publication to grow and develop. We aregrateful to him, and look forward to his futurecontributions.

The first issue of Amber-hi-Lites was dated April.1949, and differed considerably from our current issue.Ther;; were several short items on the front page, cover-ing var-ous news items of interest to the ion exchange"industry." The second and third pages contained threeshort articles on Protein Purification, Silica Sorptionand Bacteria Binding as well as several abstracts ofarticles on ion exchange taken from the current litera-ture The back page was devoted to an advertisemenl(or two new ion exchange resins, Amberlite IRC-50andAmberlite IRA-400

There was a short note on the bottom of the (rontpage which read:

"Every publication must have a motive, a plan, a rea-son (or existence And Amber-hi-Lites is no exceptionIt will report all the news ot ion exchange that it can

hold, so that you who now employ adsorption tech-niques, and you who search for efficient process short-cuts, and you who have only an academic interest in ionexchange phenomena may run and read and file to readagain."

This statement of objective is as valid today as it wasthen. The technology of ion exchange has increased inscope and complexity, and the length and depth ofAmber-hi-Lites have both increased accordingly. Shortitems have given way in this publication to longer, moreinvolved treatises on a single phase or use of ionexchange. Amber-hi-Lites has provided a forum forpresentation of new ideas, new products and new con-cepts, and it has occasionally been the starting pointfor spirited discussions on various aspects of the artand science of ion exchange between people whoseviews might differ from those expressed in these pages

This issue of Amber-hi-Lites features an article onadsorption of heavy metals, written by William H Waitz.Jr Mr. Waitz is Market Planning Manager for IndustrialChemicals-North America, located in Rohm and HaasCompany's Home Office in Philadelphia. He has hadextensive marketing experience, most recently in thefield of waste control and sugar processing applica-tions of ion exchange resins

Gerald D. Button6dit')r

INTRODUCTIONInterest in the removal and/or recovery of heavy

metals from industrial waste streams continues toincrease as discharge limitations become more restr ic-t ive Pre-treatment of wastes prior to discharge tomunicipal sewage treatment plants is now a reality Inthe past, it has frequently been possible to comply wi ththe limitations through the use of precipitation sys-tems However, as permissible discharge limits are

lowered, precipitation will not meet these lower limitsIn addition, when working at the usual low concentra-tions encountered in industrial waste streams, exces-sive amounts of chemicals are required to effectprecipitation and large lagoons are necessary to settleout the resulting sludge As inflation increases thevalue of metals, recovery begins to look more attrac-t i ve Consequently, there is increasing interest in ionexchange as a part of industrial waste treatmentsystems

Ion exchange has been used widely for a number ofyears in the recovery of gold (rom plating wastes andfor the rejuvenation of chrome plating baths by theremoval of Fe° and Cr'3 The chrome plating installa-tions also use anion exchange resins to recover CrO< J

ions from the rinse water for return to the platingbaths ' Recovery of Na2CrO< from cooling tower blow-down for return to the system is another applicationbeing used in several large scale operations.2

in designing an ion exchange system to removeobjectionable ions from waste streams, one must, ofcourse, consider the selectivity of the resins for variousions Fo r tuna te l y , the natura l se lect iv i ty of ionexchange resins favors the larger ions with higher va-lence Ai low concentrations, therefore, both weaklyand strongly acidic cation exchange resins willexchange ions of alkali metals and alkaline earths forheavy metal ions The weakly and strongly basic anionexchange resins have an aff ini ty for the large heavymetal anion complexes such as Fe(CN)6 V3

The major exceptions to this preference for largerions with higher valence are that weakly acidic cationexchange resins prefer to be in the acid (hydrogen ion)lorm and weakly basic anion exchange resins prefer tobe m the free base form rather than a salt form. As aresult , weakly acidic cation exchangers prefer hydro-gen ions to all other cations and weakly basic anionexchange resins will shift preferentially to the free baseform m the presence of hydroxide ions

The resm choice m designing an ion exchange sys-tem for heavy metals removal or recovery is. ot course,dependent uponthegoalof the install at ion If the remov-al of a single species is required, then a resin that isprimarily selective lor that ion. such as a "chelatingresm." is called for If. on the other hand, a variety ofheavy metals must be removed, this can often beaccomplished with a weakly acidic resin m the sodiumform which will replace all the heavy metal ions withsodium ions Where deionizmg and recycling of wastewater is of interest, a strongly acidic cation exchangeresm in the hydrogen form must be used since it willrelease hydrogen ions to replace all other cations in thes t ream

if one or more of the heavy metals to be removed ispresent as an amomc complex, an anion exchanger esm usual ly m the sal t fo rm, s selected This resm willadsorb only those metals which are nrosent as anions.an o thers oresenl as ca t ions wi l l oass i> i rough the resmtied loialiy unadsorbed

CHELATING RESINAmberh le I R C - 7 18 is a maC 'Ore t iC ' j l a r chelat ing resm

spec i f i ca l l y designed for the removal ol ce r ta in heavy

R A m O e r • hi • h ies C 1 0 4 March 1968R A r r s e ' - h M e s s l S 1 May 19'6N L 3": <3 '.Vaii; 'A1 M A T b e r h i - m e s

metals For most applications, it must be operated inthe sodium form and. therefore, cannot be used m totaldeiomzation. However, because of its high affinity forCu'2 and Fe'3. it can be operated in the hydrogen lormwhen being used to remove these ions.

The selectivity, relat ive to calcium, of Ambwiile IRC-718 for various cations at pH 4. determined in columnexperiments under laboratory conditions, is shown inTable I (as below) These values will, of course, bea f f e c t e d by both the con cent ration of metals and the pHof the st ream being treated, as well as by changes ine lec t ro l y te and background metal concentrationsNote the resin's much greater selectivity for heavymetals than for calcium

The selectivity of Amberiite IRC-718 was also investi-gated in an ammoniacal s t ream (pH=9) containing 200g/l (NH4)2SO«. The results are given in Table II

Amberhte IRC-718 can be regenerated e f f i c i e n t l yith a 4 to i 0% so iu t iO" of a s i rong acid Capac i t i es tor

a - i o u s heavy m e i a i s under a v a ' . e t y of co id i t ic -s are. v e ~i n T a b l e !'i

Table IV and Figure I compare the effectiveness ofthe hydrogen and sodium forms of Amberhte IRC-718for removing copper from a stream containing SOppmof Cu'J and 1.000 ppm CaCI? at pH 4

j 0 -^ Infant

Cu" » P0«"Ct" '000 PC*

f.O. «•!. ID .X 't 0 —

»„».«.,. i«C

J 10-1

FIGURE I

EFFECT OF pH ON C A P A C I T YT h e e l f e c ' o f p H o n t h e c a o a C ' ! ' . o f

!s dramahc Because of i ts a ' lthe resm s capac i t y for most o'ly De'ow DH 4 F ; Q u r e II coAmberhie I R C - 7 1 8 when usedpresence of caicujm ch lo r ide IpH 2 and pH 4 The daia snc* \ iha' gocc remcr e a l i z e d 'or 200 bed vo lumes i ' ?00 Qano^s cubicf r e s ' n ) when t r e a t i n Q i he sues "!i 3\ PH 4 we reasleakage occurred at PM ."> ,s "i the cu rve b'es h a - p i y m less than SO bed •. r i .mes

C 'j pr ic 3 rid I e r ' ic 0 n s 3 ' C ' " •' •' > c >• P ' >o ^^- ! ' h '~- ,

i iy ior nya -ogener ions 'a i ls o f f s t

a r e s i ^ e c a p a c ^ io remove n i cke l \

m process s t r e ame

718 both m the sodium form, for ihe removal ol zmcfrom a solution containing 50 ppm of Zn'3 and 1.000ppm ot CaCI? at a pH o*7 0 The How rate was 8 bedvolumes per hour Of 1 gpm/tt3 and removal was essen-tially the same (or bolh resins except that AmberliteIRC-718 showed a sharper break m the leakage curveaf ter 250 bed volumes

Table VI ana Figure IV i l lus t ra te Ihe elution curves forzmc f rom Amberh le lRC-7 i8and Amberlite DP-1 with a10% HCl regenerant at a f low ra te of 8 bed volumes perhour or 1 gpm/ft3 It can be seen that Amberlite DP-1gives a sharper elulion curve and is. therefore, the bet-ter choice under these particular circumstances

FIGURE II

CHELATING RESIN VERSUS WEAKLYACIDIC CATION EXCHANGE RESIN

Although Amberlite IRC-718 is often required toachieve efficient heavy metals removal. Amberlite DP-1. a weakly acidic cation exchange resin in the sodiumform, sometimes exhibits equal or superior capacityand regeneration efficiency when treating wastestreams containing heavy melals. In addition, this resinis less costly than Amberlite IRC-718 Table V and Fig-ure III compare Amberlile DP-1 with Amberlite IRC-

..-I

FIGURE III

Bed Volume*

FIGURE IV

'n Table VII and Figure V Amber l i te I R C - 7 1 B ancAmberhte DP-1 are compared lor Pb'2 removal In t h 'Sw a s t e s t ream the concent ra t ion o< Pb' was 50 ppm mthe presence of 1.000 ppm ot CaCi? and at a pH ol 4 0The How rate through the ies>r' was 8 bed volumes per

hou' ot 1 gpn-vtl3 The da ta sno'-% !he s i g n i f i c a n t a d v a "!.iqe o f Amber l i te D P - 1 ovrr A • • ' • f e r i i t e i R C - ' ' 6 "^ tn!'.';: it: a I ion

u

lion ol lead nitrate since it had removed more lead in theloading cycle Amberllte DP-1 is the better choice tor awaste stream ol this type Extreme care should be exer-cised when contacting resins with nitric acid Oxidationol the resin may occur with gas evolution and potentialpressure build up The reader is referred to Amber-hi-Lites *153 Fall/Winter 1976

Amberllte IRC-718. on ihe other hand, was found tobe Ihe preferred resin when t rea t ing a stream contain-ing copper wi th an ammonium su l fa te backgroundTable VII I and Figure VII show the advantages ofAmberllte IRC-718 over Amberl l te DP-1 for removingcopper in the presence ol a high concentration olammonium sul late As the table shows, at lower con-centrat ions of ammonium sul late. the performance ofthe Amberllte DP-1 is greatly improved, but AmberllteIRC-718 sti l l oul performs it

FIGURE V

Elution of lead from both resins is shown in Figure VI10% nitric acid was used at a flow rate of 8 bed volumesper hour or 1 gpm/fp Both resins readily released thelead but the Amberllte DP-1 gave the higher concentra-

100.000

80.000 —

Elution of Pb*"" FromAmbcrlite OP-t andAmberllte IRC-718

Regenennl 10% HNO,Flow Rite 8 bv/hr

—•— Amberlne DP 1

-*-Amberlits IRC-718

1 2 3

Bed Volumes of Eluate

FIGURE VI

FIGURE VII

EFFECT OF pH ON CAPACITYFigure vn I i l l us t ra tes the e f f e c t o tpH on tne capac i ty

of Anberliie DP-1 and Amberllte IRC-718 when theseres ins are used for removal of cadmium at pH 2 1 andpH 8 0 in this work . Cd'? was preseni at a concent ra -t i on cl 50 ppm wi th 1.000 ppm of calcium chloride At af l o w ra te of 8 bed voimes per hour (1 gpm/ l t 3 ) bothr es i t s showed sharp leakage c u r v e s w i th end points atess ' ^ a n 100 bed voKjmPs ,11 pH ? 1 A! pH 8 0 and the

« JLmtytrt*. OP-1

CtO,

«flib««ta DP-1 H< 107. AmfcirtX MC-711 pH 107. AmbxINt DP-1 p« 10. A/nbtt«t« IRC-711 pH 10

I100»»d Yokmxt

MO 400

FIGURE VIII

same (low rate, however, Amberlite IRC-718 showedless than 0.1 ppm leakage (or 350 bed volumes whileleakage (rom the Amberlite DP-1 remained under 0.1ppm (or 520 bed volumes.

EFFECT OF FLOW RATE ON CAPACITYFlow rate also has a major effect on the capacity of

both Amberlite IRC-718 and Amberlite DP-1. Figure IXshows a comparison of these resins removing cadmiumat flow rates of 8 bed volumes per hour and 16 bedvolumes per hour or 1 and 2 gpm/ftJ. The stream beingtreated contained 50 ppm of Cd*J and 1.000 ppm ofcalcium chloride. Both resins showed greater capacityat 8 bed volumes per hour with the capacity of Amber-lite DP-1 affected more by an increase in (low rate thanthe capacity of Amberlite IRC-718.

t to—

1000 n>™

Amtmtte DP-< I IV4*.Amb««> DP-1 K IV/Hr.Xm6«<*« WC-7K I IVA*.ArnbxHM MC-7U K §Vi«r

100 MOtod Vo4um«

FIGURE IX

RECOVERY OF CHROMIUM FROM COOLINGTOWER SLOWDOWN

In ion exchange systems that recover chromate fromcooling tower blowdown. Amberlite IRA-94 is used torecover CrO/? for recycling This process is described

in Amber-hi-Lites «151.z To meet most present NPDESpermits, it is also necessary to remove Cr° (ro'm theblowdown. Again, this can be accomplished usingeither Amberlite IRC-718 or Ambeflite DP-1, butAmberlite DP-1 shows twice the capacity and is therecommended resin. Figure X represents a comparisonof Amberlite DP-1 and Amberlite IRC-718 in the treat-ment of a stream containing 50 ppm of Cr° and 1,000ppm CaCI?at apH4. At a (low rate of 8 bed volumes perhour (1 gpm/ft5). Amberlite IRC-718 reaches break-through at 100 bed volumes while Amberlite DP-1 curvebreaks at about 200 bed volumes.

I ,-

IRC-711 n Amb*<«t> OP-1InflutmCr" SO ppmCaO, 1000 ppmPH4.0Flow FUt* I b«4 vo4um««/T>our———•——— AmbxKte DP-1——•——Am6«ftlt« IRC-»U

I100&*d Votunvit

FIGURE X

1900

A CASE HISTORYThere have been several interesting commercial

applications of metal recovery technology using ionexchange. In one case Amberlite DP-1 was used to treata waste water lagoon from an abandoned plating oper-ation containing a variety of heavy metals

This lagoon held one million gallons of acidic wastewater with the following composition:

displaced by the heavy metals so that after 100 bedvolumes of throughput calcium leakage had reachedthe concentration of the calcium m the influent Leak-age data for this la bora lory experiment are presented mTable X

A composite of the eff luent ol the f i r s t 175 bedvolume from this run gave the following analysis.

The principal amon was sul fate. although quantitiesof chloride and bicarbonate were also present Totaldissolved solids were 3550 ppm and the pH was 4 7During ra instorms this lagoon would over f low into alocal s t ream and the owner of the land was ordered totake action to abate water pollution

Deionization in a situation like this, is of course, eco-nomically impractical Therefore, tests were run t reat-ing the lagoon water with Amberlite DP-1 which wouldexchange sodium ions for the polyvalent ions presentm the water, thereby making it suitable for use in sprayirrigation

Laboratory column experiments demonstrated that itwas possible, through the use of Amberlite DP-1, toremove the heavy metals such as zinc and cadmiumwithout removing the alkaline earths such as calciumEarly m the column run, calcium was exchanged forsodium by the resin However, this calcium was then

Regeneration of the loaded Amberlite DP-1 withhydrochloric acid is shown m Table XII Bed volumes 1through 4 were 1NHCI B e d v o i u m e s S t h r o u g h S w e r edeionized water

-f

After pilot work was completed, twenty-eight cubicfeet of Ambertite DP-1 were installed. Each cycle con-sisted of 125 bed volumes of 26.000 gallons. Conse-quently. 38 cycles were needed to treat the entire 1million gallon lagoon. This required 40 days. The acidwaste regenerant was treated with lime to precipitatethe heavy metals as insoluble hydroxides and oxides. Inthis case the lime dosage had to be sufficient to reach apH of greater than 10 to effect the maximum precipita-tion of zinc and cadmium. The supernatant liquid fromthe precipitation step was recycled to the waste lagoonsince the zinc concentration exceeded 0.5 ppm. Thesludge was buried in a suitable landfill.

Ion exchange resin and equipment costs for thisoperation were less than $3,000. Regenerant require-ments were 200 pounds of acid per cycle with 225pounds of sodium hydroxide per cycle required toreturn the resin to the sodium form.

The entire operation was carried out without incidentat a cost that was less than $10.000 in 1975 exclusive oflabor. This included equipment start-up costs and therequired analytical work.

CONCLUSIONThe proper choice of an ion exchange process for

treating any stream containing heavy metals mustbegin with a careful analysis of the stream so that ajudgment can be made as to the ionic state of the metalsto be removed and the probable effect of backgroundelectrolytes. This knowledge will lead to a decision as

to whether anion or cation exchange is more likely to besuitable and whether a strong or weak electrolyteexchanger, or a chelating structure, is indicatedLaboratory experiments are then essential in order todefine operating conditions, leakage values and capac-ities under the conditions as they exist and under con-ditions which have been altered within economic limits.Comparisions of two or more resin types may be neces-sary where the exact nature of the various solutes is notknown.

The data presented in this issue of Amber-hi-Litesindicate what can be accomplished under the condi-tions as described here. The circumstances of eachstream are unique, and operating performance in anyspecific situation cannot usually be predicted with pre-cision unless laboratory effort, as described above, iscarried out.

The results presented here, and a steadily growingnumber of commercial installations, point to anexpanding use of ion exchange resins to solve difficultseparations in the field of waste control, particularlythose involving heavy metals.

CREDITSThe author gratefully acknowledges the efforts of Or.

Guenter R. Ackermann, Mr. Claude A. Bevan. Dr. Fred-erick P. Hinz, Mr. James T. McNulty. and Mr. Daniel J.Raab in producing the technical information containedin this paper.

Correspondents <n other countries lie nwfed lo address inquiries lo our subsidiaries

ARGENTINA—flohn and Haas Argentina SAC ICjsiOa de Correo No 5388. Correo CentralBuenos AiresAUSTRALIA—Room and Haas Australia Ply. Lid"ttrer House. 26 Cotlins Street Melbourne Victoria1000AUSTRIA—Rohm and Haas GmbH AustriaEltsabethstrasse 22. A-1010. Vienna•JELGIUM—flohm and Haas Belgium SA0 Place Stephanie. 1050 Brussels

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• Manse Road. West Hill. OntarcXILE—Induslrias Quimicas Chile. Llda

Cjs*a 13607 Correo 21. SantiagoCOLOMBIA—Rohm and Haas Colombia. SA\partado Aereo 90606. Bogota:OSTA RICA—Rohm and Haas Centre America SA.panado 3906. San Jose

DOMINICAN REPUBLIC—Rohm and Haas Canbe. IncP O Bo« 203-2. Santo Domingo

ENGLAND—Rohm and Haas (UK ) LimitedLenrag House. 2 Mason's Avenue. CroydonCR93N6FRANCE—Rohm and Haas France SALa Tour de Lyon. 185 rue de Bercy. 75579 PansCedex 12GERMANY-flohm and Haas Deutschland GmbHD-6000 Frankfurt/Mam Rhemsttasse 29GREECE—Rohm and Haas Greece LtdXemas 32. Athens (621)INDIA—Rohm and Haas Asia IncPO Bon 9112. Or Annie Besani RdBombay 400025(TALY—Rohm and Haas Italia S p ACaseHa Postal 1792. MilanJAPAN—Rohm and Haas Asa IncKaisei Bk3g . 4th Floor. Azabu P 0 Box 22 8-10Aiabudan l-clxxne Mmato-ku. Tokyo 106MEXICO—Rohm and Haas Mexico S A de C VApartado Postal 12. 1129. Mexco 12 OF

NETHERLANDS—Rohm and Haas Nederland B VStatenplem 56 DordrechtNEW ZEALAND—Rohm and Haas New Zealand LtdPO Box 22-220. OtahuhuPERU—Rohm and Haas Peru S AP 0 Box 6062 LimaPHILIPPINES-Rohm and Haas Philippines. IncPO Box 263 Makan Rizal 0-708PUERTO RICO—Rohm and Haas CoPuerto Rco Brancn Office PO Box 2019Hato Rey 00919SINGAPORE—Rohm and Haas Asia IncPO Box 581 Singapore 2SOUTH AFRICA—Rohm and Haas South Atrica LtdPO Box 78 125 Shepstone RoadNew Germany. NaiaiSPAIN—Rohm and Haas Espana S AProverua 216 Barcelona 11

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ROHMIHHflSP H I L A D E L P H I A . PA 19105

ACRYSOL. AMBERLITE. AMBERLYST. LYKOPON. MONOBEO. PRlMAFLOC. STRATABEO and TRITON a'etrademarks ol Rohm and Haas Company, or ol rts subs<Jiaries or affiliates The Company s policy rs to register MStrademarks where products designated thereby are markeled by the Company its subsidiaries or affiliates

These suggestions and data are based on information we believe to be reliable They are offered m good faun Ouiwithout guarantee, as conditions and methods ol use of our products are beyond our control We recommend matthe prospective user determine the suitability of our materials and suggestions before adopting them on acommercial scale

Suggestions to' uses ol out prooucis or the inclusion o' descriptive maie'iai I'om patents and tne oia'ion o'specific patents m m.s publication should not be understood as recommending me use o' our products m violationol any patent o< as permission or license to use any patents ol tne Ronm and Haas Company

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