United States
Environmental Protection
Agency
Municipal Environmental Research EPA-600/2-80-096
Laboratory          August 1980
Cincinnati OH 45268
Research and Development
Evaluation of Hot
Acid Treatment for
Municipal Sludge
Conditioning


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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional  grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.  Environmental Health  Effects Research
      2.  Environmental Protection Technology
      3.  Ecological Research
      4.  Environmental Monitoring
      5.  Socioeconomic Environmental Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

This report has  been assigned  to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                             ADDENDUM
               EVALUATION  OF HOT ACID TREATMENT FOR
       HOT ACID TREATMENT  FOR MUNICIPAL SLUDGE CONDITIONING

                        (EPA-600/2-80-096)
After completion of this report, the U.S. Environmental
Protection Agency (EPA) had an engineering assessment made of
the Wai den hot-acid process for removal of heavy metals from
municipal sludge.  The results of this assessment will
eventually be available as an EPA report.  In the interim, an
abstract of the report can be obtained from:

          R. V. Villiers, Project Officer
          Municipal Environmental Research Laboratory
          U.S. Environmental Protection Agency
          Cincinnati, Ohio  45268

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                              EPA-600/2-80-096
                              August 1980
  EVALUATION OF HOT ACID TREATMENT FOR
     MUNICIPAL SLUDGE CONDITIONING
                 by
          Kenneth J.  McNulty
           Ann T. Malarkey
         Robert L. Goldsmith
     Wai den Division  of Abcor,  Inc.
    Wilmington, Massachusetts  01887

           Henry A. Fremont
   Champion International  Corporation
            Knightsbridge
         Hamilton, Ohio 45020
        Contract No.  68-03-2459
            Project Officer

          Roland V. Villiers
      Wastewater Research Division
Municipal Environmental Research Laboratory
         Cincinnati, Ohio  45268
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
         CINCINNATI, OHIO  45268

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                                  DISCLAIMER


     This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publi-
cation.  Approval does not signify that the contents necessarily reflect
the views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.

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                                  FOREWORD
     The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health
and welfare of the'American people.  Noxious air, foul water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.

     Research and development is that necessary first step in problem solu-
tion and it involves defining the problem, measuring its impact, and
searching for solutions.  The Municipal Environmental Research Laboratory
develops new and improved technology and systems for the prevention, treat-
ment, and management of wastewater and solid and hazardous waste pollutant
discharges from municipal and community sources, for the preservation and
treatment of public drinking water supplies, and to minimize the adverse
economic, social, health, and aesthetic effects of pollution.  This publica-
tion is one of the products ,of that research; a most vital communications
link between the researcher and the user community.

     Land application is an attractive method for final disposal of sludge
solids.  However, this method has not been fully exploited because of the
potential environmental risk certain concentrations of heavy metals in
sludge present.  In some cases, the concentrations of heavy metals must be
reduced to acceptable levels prior to land disposal.  This report presents
an investigation of a process designed to remove heavy metals from sludge.
The process involves both acidification and heating of the sludge.  Results
show that the process has potential for good solubilization and removal of
toxic heavy metals and, in addition, destroys essentially all pathogens and
improves the dewaterability of the sludge.  A preliminary economic analysis
of the process indicates that it is quite cost-competitive with alternative
stabilization/conditioning processes.
                                        Francis T. Mayo, Director
                                        Municipal Environmental Research
                                        Laboratory
                                    m

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                                  ABSTRACT


     Bench-scale tests were conducted to evaluate the technical  and economic
feasibility of the hot acid process for stabilization/conditioning of
municipal sewage sludge.  This process involves acidification of the sludge
(pH 1.5-3) and heating to temperatures below boiling (^95°C).  Test results
indicate that the process improves the dewaterability of the sludge, destroys
essentially all pathogens, and preferentially solubilizes certain heavy
metals relative to nitrogen and organics.  The process demonstrated the
potential for good solubilization and removal of toxic heavy metals including
cadmium, zinc, and nickel with minimal solubilization of nitrogen.  Thus the
hot acid process improves the desirability of sludge solids for land
application.  A preliminary economic analysis of the process indicates  that
it is quite cost-competitive with alternative stabilization/conditioning
processes.

     Thts report was submitted i;n fulfillment of Contract No. 68-Q3-2459
by the Walden Division of Abcor, Inc. under the sponsorship of the U.S.
Environmental Protection Agency.  This report covers the period  of Sept-
ember 26, 1976 to February 11, 1979 and work was completed as of April  6,
i y / y *
                                     IV

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                                 CONTENTS
Foreword ..	     iii
Abstract			'.     iv
Fi gures	     vi
Tables	     ix
Acknowl edgment	.	     xi i

     ,1.   Introduction	      1
     2.   Conclusions	      4
     3.   Recommendations	      7
     4.   Bench-Scale Process Studies 	      8
     5.   Comparison with Alternative Conditioning Processes         87
     6.   Optimization for Removal of Heavy Metals 	    105
     7.   Specification of Solids-Separation Equipment 	 '   123
     8.   Specifications for Pilot System	    126
     9.   Energy and Economic Analyses	    133

References	      150
Appendi ces	

     A.   Verification of Selected Analytical Results	      153
     B.   Laboratory Report on Centri fugation Tests	      156

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                                   FIGURES
Number
Page
  1    Digestion apparatus	  10

  2    Filtration test system	  11

  3    Centrifugation apparatus  	  12

  4    Effect of stirring speed  during digestion  on  the
       sett!ing rate of hot-aci d treated WAS	  18

  5    Effect of oxygen sparging during digestion on the
       sett!ing rate of hot-acid-treated WAS  	  19

  6    Effect of the concentration of added acid  on  the
       settling rate of hot-acid-treated WAS  	  21

  7    Variation of WAS pH with  time  for various  storage
       conditions	  23

  8    Variation of WAS TOC  with time for various
       storage conditions 	  24

  9    The effect of pH on the settling rate  of WAS
       digested at 95°C for  30 minutes	  27

  10   The effect of pH on the filtration rate  of WAS
       digested at 95°C for  30 minutes	,	  28

  11   The effect of pH on the centrifugation rate of
       WAS di gested at 95°C  for  30 mi nutes	  29

  12   Acid demand vs. pH for various  sludges (sludge
       solids basis)  	  32

  13   Acid demand vs. pH for various  sludges (wet sludge
       basis)	  33
  14   Effect of treatment conditions  on settling rate for
       Brockton WAS	  39

  15   Effect of treatment conditions  on filtration  rate
       for Brockton WAS	•	o	  49

  16   Effect of treatment conditions  on centrifugation rate
       for Brockton WAS	  41

  17   Effect of treatment conditions  on settling rate for
       Fitchburg WAS   	  44

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FIGURES (Continued)
Number
18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36
37
38

Effect of treatment conditions on filtration rate for
Fitchburg WAS 	 	 	 	
Effect of treatment conditions on centrifugation rate
for Fitchburg WAS 	 	
Effect of treatment conditions on settling rate for
Brockton pri mary pi us WAS 	 	 	 • 	
Effect of treatment conditions on filtration rate for
Brockton primary pi us WAS 	 	 • 	
Effect of treatment conditions on centrifugation rate
for Brockton primary pi us WAS 	 	 	
Effect of treatment conditions on settling rate for
Fi tchburg primary pi us WAS 	 • • • • 	
The effect of time and temperature on the degree of
suspended solids solubilization for Fitchburg WAS 	
Effect of treatment conditions on the degree of COD
solubilization for Fitchburg WAS 	 	
Effect of treatment conditions on the degree of zinc
solubilization for Fitchburg WAS 	 	 	 	
Effect of treatment conditions on the degree of COD
solubilization for Brockton primary plus WAS 	 	 	
Effect of treatment conditions on the degree of COD
solubilization for Fitchburg primary plus WAS 	
Effect of ferric chloride dosage on the filtration rate
of hot-acid-treated WAS 	 . ... 	 •
Effect of ferric chloride dosage on the centrifugation
rate of hot-acid- treated WAS 	 	 •
Effect of polymer dosage on the filtration rate of hot-
acid-treated WAS 	 	 	
Effect of polymer dosage on the centrifugation rate of
hot-acid-treated WAS 	
Comparison of filtration rates for WAS treated by
various conditioning processes 	 	 •
Comparison of centrifugation rates for WAS treated by
various conditioning processes 	 • 	 	 	
Schematic diagram of digestion apparatus used to re-
evaluate heavy metals solubilization 	 ...
Cadmium solubilization as a function of pH 	 	 .-
Cadmium solubilization as a function of acid usage .....
Zinc solubilization as a function of acid usage 	 	
Page

46

47

50
I" T
51

53

56

64

65

67

70

75

. . . 89

, , , 90
•• f**t '
91
••
92
f\f\
93
f\ r~ "
95
....-' , -
•'/.,. 106
112 :
,., 114
115
        VI1

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                                FIGURES  (Continued)
Number
  39   Nickel solubilization as a function of acid usage	,
  40   Chromium solubilization as a function of acid usage . „	,
  41   Solids solubilization as a function of acid usage	,
  42   COD solubilization as a function of acid usage	„	,
  43   Process flow schematic for 5 gpm hot acid treatment	
  44   Simplified flow schematic of hot acid sludge treatment
       process 	.•	
  45   Material balance results for full-scale hot acid treatment
       system	
  46   Energy balance results for full-scale hot acid treatment
       system	„	
  47   Operating and maintenance cost as a function of plant capa-
       city for various sludge treatment alternatives	
Page
116
117
118
119
127

134

137

138

148
                                    vm

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                                    TABLES
Number
                                                                   Page
  1    Assays and Procedures 	.	    ^
  2    Solids Concentrations as a Function of Sludge
       Age and Storage Conditions ••	    "

  3    Acid Requirements as a Function of pH for
      • Brockton and Fitchburg Sludges 	    6l
  4    Test Matrix for Evaluation of Primary Variables	    35

  5    Effect of Treatment Conditions on Solid-Liquid
       Separation Rates for Brockton WAS	    36

  6    Analysis of Variance Results fipr Solids Separation
       Tests (Brockton Waste Activated Sludge) 	    37

  7    Effect of Treatment Conditions on Solid-Liquid
       Separation Rates for Fitchburg WAS 	    4^

  8    Analysis of Variance Results for Solids Separation
       Tests (Fitchburg Waste Activated Sludge) • • •	    43
  9    Effect of Treatment Conditions on Solid-Liquid
       Separation Rates for Brockton Primary PI us  WAS 	    48

  10   Analysis of Variance Results for Solids Separation
       Tests (Brockton Primary PI us WAS)	    49

  11   Effect of Treatment Conditions on Solid-Liquid
       Separation Rate for Fitchburg Primary PI us  WAS 	    54

  12   Analysis of Variance Results for Solids Separation
       Tests (Fitchburg Primary PI us WAS)	    55

   13   Effect of Treatment Conditions on Solubilization of
       Sludge Constituents for Brockton WAS  	    58

   14   Analysis of Variance Results for Solubilization
       Tests (Brockton WAS)	• •    60
   15   Effect of Treatment  Conditions on  Solubilization
       of SIudge Constituents  for Fitchburg  WAS 	    6^

   16   Analysis of Variance Results for Solubilization
       Tests (Fitchburg WAS)	    63

   17   Effect of Treatment  Conditions on  Solubilization of
       Sludge Constituents  for Brockton Primary Plus WAS  	   68

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                               TABLES (Continued)
Number
  18
      Analysis of Variance Results for Sol utilization Tests
      (Brockton Primary Plus WAS)  	  59
      Effect of Treatment Conditions on Sol utilization of
      Sludge Constituents for Fitchburg Primary Plus WAS «•••	  72
      Analysis of Variance Results for Solubilization Tests
      (Fitchburg Primary PI us WAS)	  73
      Summary of Metals Solubilization for Brockton WAS 	  76
      Bacterial Assays for Raw and Hot-Acid-Treated Sludges	  78
      Summary of Optimization Tests for Solid-Liquid Separation..  81
      Summary of Solubilization Results for Optimization
      Tests 	  82
      Effect of Time and Temperature on the Survival  of
      Typical  Pathogens Found in Sludge	  85
      Potential Advantages  and Disadvantages  of Hot Acid
      Treatment  	  86
      Solubilization of Solids  and Organics  for Various
      Treatment Processes  	  96
      Comparison of  Solubilization for the Hot-Acid and
      Thermal  Conditioning  Processes  	  97
      Estimated Chemical Conditioning Dosages  for
      Vacuum Filtration	 100
      Comparison of  Supernatant  Quality for Various Sludge
      Treatment Techniques  	„	 101
      Comparison of  Sludge Conditioning Alternatives  		 104
      Effect of Treatment Conditions  on the Degree of Solubil-
      ization of Heavy Metals and  Other Sludge  Constituents 	 108
33    Solubilizations obtained for Sludges from Various Cities
      at Preferred Operating Conditions	 121
34    Specification  for Centrifuges to Dewater  Brockton WAS
      FolTowing Hot  Acid Treatment	 125
35    Specification  of Pilot System Components	 130
36   Assumptions and Design Bases for Economic Analysis 	 135
37    Purchased Equipment Cost for Hot Acid Treatment 	 140
38    Capital Costs  for Hot Acid Treatment 		 141
39   Operating and Maintenance Costs for Hot Acid Treatment
      ($/Dry Metric Ton Sol ids)  	 142
40   Capttal and Operating Costs for Anaerobic Digestion 	 144
  19

  20

  21
  22
  23
  24

  25

  26

  27

  28

  29

 30

 31
 32

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                               TABLES (Continued)
Number
                                                                     Page
  41   Capital and Operating Costs for Aerobic Digestion 	 145
  42   Capital and Operating Costs for Lime Treatment 	 146
  43   Capital and Operating Costs for Heat Treatment 	 147
                                     XI

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                               ACKNOWLEDGMENTS
     The authors gratefully acknowledge the following contributors to this
program.

     -- Leah B. Daniel of the Walden Division of Abcor, Inc.  for conducting
        many of the bench-scale experiments and for providing technical
        input on the experimental aspects of the program.

     -- Tim Murphy and John Tanzi of the Brockton Wastewater  Treatment
        Plant, Rich Willians of the Fitchburg Wastewater Treatment Plant,
        and Richard Manthe of the Milwaukee Sewage Commission for providing
        samples of sewage sludge.

     — Adam Nisbet, Jim Gibbs, and staff of Bird Machine Company for
        conducting bench-scale and pilot-scale centrifugation tests.

     — John R. Harland of the Walden Division of Abcor, Inc. for providing
        engineering assistance on the plant design and economic analysis
        for the process.

     Financial support for this program was provided through  the Municipal
Environmental  Research Laboratory of the U.S. Environmental Protection
Agency.  The support and technical assistance of the Project  Officer,
Mr. R.V. Villiers, and the Director of the Ultimate Disposal  Section,
Dr. J.B. Parrel!, are gratefully acknowledged.
                                   xn

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                                  SECTION 1

                                 INTRODUCTION
     The disposal of sludge from municipal  wastewater treatment plants  is  a
problem of increasing complexity and magnitude.   The amount of sewage sludge
produced in the United States is expected to increase over the next several
years because of increases in the sewered population and the upgrading  of
existing wastewater treatment plants.  Simultaneously, environmental  re-
strictions are decreasing the options available  for sludge disposal.  At
present, four techniques for sludge disposal are in general  use 0-):
          —• sanitary landfill,
          — ocean disposal,
          — incineration with
          -- land application.
landfill  of ash and scrubber sludge,  and
Of these, ocean disposal is being phased out by 1981.

     Of the various options listed above, land application is the only option
that utilizes sludge in a beneficial manner.  When applied to land, sludge
provides an excellent soil conditioner and results in the conservation and
reuse of organic matter, nitrogen, phosphorus, and certain trace elements,
all of wfifdT are necessary plant nutrients.  At present, only about 25% of
the sludge produced is applied to land(2), and only part of that is applied
to cropland.  On a national basis there is more than enough cropland available
to accomodate all of the sludge produced; however in the Northeast the
percentage of the cropland required for land application of sludge is higher
than the national average.  (In New Jersey, for example, it is projected
                                                                     appears
 to  be  the most  promising technique presently available for utilization/
 disposal of  sludge.
      The  land  application of sludge, however, does have some potential
 limitations  particularly where the land is to be used for food-chain crops.
 Of particular  concern  is the uptake of heavy metals such as cadmium, zinc,
 nickel, copper,  and molybdenum which can accumulate in plants and may pose a
 hazard to plants,  animals, or humans^2).  Of these potentially hazardous
 metals, cadmium  is the metal of greatest environmental concern.  The daily
 dietary intake of  cadmium for U.S. adults approximates the total tolerable
 daily intake proposed  by the Food and Agriculture Organization and the World

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Health OrganizationC3).  Because of the potential of certain food-chain crops
to accumulate significantly increased cadmium levels from sewage sludge applied
to land, rules have been proposed(^) for limiting and monitoring the land
application of cadmium bearing sludges to food-chain crops.

     In addition to heavy metals, the presence of pathogens  and pesticides
(and other persistant organics) in the sludge are also of concern(4).
Pathogens may create a public health hazard, and pesticides  and heavy metals
could be ingested directly if the sludge is applied in such  a way as to
adhere to the edible portion of the crops.  While lead is not a potentially
hazardous metal with respect to plant uptake, the direct ingestion of lead
(in addition to cadmium) should be avoided because of the proximity of the
current daily intake to the proposed tolerable level(3).

     While there are many municipal sludges that, when stabilized, are suit-
able for direct application to land, many others contain high concentrations
of cadmium or other heavy metals.  None of the sludge stabilization
processes in current use (e.g. anaerobic digestion, aerobic  digestion,
thermal treatment (190°C), Time treatment, pasturization (70°C), etc.) is
capable of removing significant quantities of heavy metals.   Thermal treat-
ment, for example, has been shown to remove approximately 72% of the nitrogen
content from sludge solids but it does not remove significant quantities of
heavy metals (5,6,7).  Thus thermal treatment is detrimental  to the soil
conditioning value of the sludge solids.

     The objective of this program was to evaluate and develop a new process
for the treatment of municipal wastewater sludge.  This process was invented
by Champion International Corporation (patent applied for ),  and Abcor, Inc.
has an option to negotiate an exclusive liscense for its commercialization.
In brief, the process consists of acidifying the sludge (pH  approximately 1.5
to 3) and heating it to a temperature below boiling (80 to 100°C) for a
relatively short time (10 to 60 minutes).  This "hot acid treatment"
process:

          1.  improves the dewaterability of the sludge,
          2.  destroys essentially all pathogens, and
          3.  preferentially solubilizes heavy metals relative
              to nitrogen and organics.

     The preferred application for this new process is for stabilization/
conditioning of thickened waste activated sludge (WAS) or mixtures of primary
sludge and thickened WAS.  Following hot acid digestion, the  solids would be
separated from the liquor using appropriate dewatering equipment.  Neutrali-
zation of solids (possibly by impregnation with anhydrous ammonia to simultan-
eously increase nitrogen levels) may be required prior to land application.
The liquor from the hot acid digestion would be treated with  lime to pre-
cipitate the solubilized heavy metals before recycling the liquor to secondary
treatment.  The heavy metal  sludge would be dewatered and disposed of in  a
secured landfill or by other appropriate techniques.

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     Ideally, the hot acid process would be similar in concept and application
to the thermal conditioning process.  Both would stabilize the sludge and
condition it for dewatering in a single operation.   However, the unique
advantage of the hot acid process would be its ability to solubilize heavy
metals to a much greater degree than organics and nitrogen.  This process, if
successfully developed to commercialization, could provide economical sludge
stabilization while upgrading the quality of solids for disposal by land
application, and could make land application a viable utilization/disposal
option for many municipalities where high levels of heavy metals currently
necessitate disposal by other alternatives.

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                                  SECTION 2

                                 CONCLUSIONS
     Bench-scale tests were conducted to evaluate the effects of the primary
process variables, pH, temperature, and time, on the performance character-
istics of the hot acid process.  These variables were investigated over the
ranges of:  pH 2 to 3, temperature 80 to 95°C, and digestion time 10 to 60
minutes.  Four sludges, two waste activated sludges and two primary-WAS
mixtures, were evaluated during these tests.  The following conclusions are
based on the results of these tests.

     1.   Within the ranges investigated, the pH had the most significant
          influence on the rate of solid-liquid separation following hot
          acid treatment.  For all sludges the optimum pH for solids sep-
          aration was 2.5.  The preferred temperature level was 95°C, but
          digestion time, within the range investigated, did not have a
          pronounced influence on the solids separation rate.

     2.   The amount of concentrated sulfuric acid required to reduce the
          pH of the sludge to 2.5 was 70-100 kg/dmt (dry metric ton).  At
          an acid usage of 100 kg/dmt the cost for acid would be $4.95/dmt
          ($4.50/dst (dry short ton)) of sludge solids.  The acid costs for
          the process are therefore quite reasonable and operation at even
          lower pH's cannot be ruled out on the basis of acid cost.

     3.   The primary process variables did not appear to have a significant
          influence on the solubilization of suspended solids.  Over the
          range of variables investigated the average solubilization of
          suspended solids ranged from 6.2% to 10.6% for the four sludges
          tested.

     4.   The pH and temperature had a significant effect on the degree of
          organics solubilization, as determined by COD.  Lower pH and
          higher temperature promoted greater COD solubilization.   Within
          the range of variables investigated the degree of COD solubili-
          zation was generally <10%.

     5.   The pH was the only variable which had a significant influence on
          zinc solubilization.  Lower pH's resulted in greater solubili-
          zation.   Solubilizations as high as 80% were determined for zinc
          during these tests.   On the other hand, solubilizations of copper
          at the conditions investigated during these tests were negligible.

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     6.   Bacterial assays confirmed the expectation that the hot acid
          process destroys essentially all pathogens.

  ,   Bench-scale tests were also conducted with WAS to directly compare the
hot acid treatment process with thermal treatment and chemical  conditioning
(ferric chloride and polymer addition).  Thermal treatment produced the
greatest improvement in sludge dewaterability.  The improvement in sludge
dewaterability for hot acid treatment was at least as great as  for chemical
conditioning.  The hot acid process solubilized significant quantities of
zinc, cadmium, and nickel while thermal treatment produced no significant
solubilization of heavy metals, with the possible exception of nickel.  On
the other hand, the hot acid treatment solubilized only 8% of the COD
compared to 27% for thermal treatment and solubilized only 10%  of the
nitrogen compared to 76% for thermal treatment.  Thus the sludge from hot
acid treatment should be much more desirable for land application than
sludge from a thermal treatment process.

     Additional bench-scale tests were conducted to define the  factors re-
sponsible for solubilization of heavy metals and to optimize the hot acid
process for heavy metals removal.  Consistent correlations were obtained
between the degree of solubilization and the acid usage in kg of concentrated
H2S04 per dmt.  These correlations indicate a rapid increase in the degree
of solubilization of cadmium, zinc, nickel, and chromium over the range of
100 to 200 kg/dmt and-of copper (based on limited data) over the range of
250 to 300 kg/dmt.  The correlation of metals solubilization with acid usage
was found to be more consistent than correlation with pH.

     Tests conducted with fresh WAS samples from various municipalities
indicated excellent solubilizations of cadmium (88-100%), zinc  (82-100%), and
nickel (73-100%) at acid usages >200 kg/dmt.  Only moderate solubilization
of chromium (M5%) was obtained, and appreciable copper solubilization (^80%)
required a higher acid usage (>300 kg/dmt).  For these tests, average solids,
COD, and TKN solubilizations were 24, 16, and 28%, respectively.

     An acid usage of 200 kg/dmt was selected as the optimum for heavy metals
solubilization.  This is two to three times as great as the acid usage re-
quired for optimum dewatering (70-100 kg/dmt to achieve pH 2.5).  However,
the cost for acid at a usage of 200 kg/dmt is still <$10/dmt ($9/dst) and is
considered to be quite acceptable for the levels of solubilization obtained.

     Bench-scale and pilot-scale centrifugation tests were conducted in order
to specify full-scale dewatering equipment for the hot acid process.  The
pilot tests indicated good cake solids concentrations (18-36% solids), but
solids recoveries were low.  The use of a flocculant was recommended to
improve the recovery of solids.                   :

     Preliminary designs and specifications were developed for a pilot-scale.
and various-capacity, full-scale, hot-acid-treatment plants.  For a full-
scale plant with a feed capacity of 20 dmtpd  (dry metric tons per day) of
                                      5

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solids at a consistency of 3%, the total  capital  investment is  estimated  at
$250,000 for hot acid treatment alone and at $647,000 for hot acid  treatment
plus solids separation and liquor treatment.  Depending upon the  amount of
acid added, the process can be optimized  either for dewaterability  (MOO  kg/
dmt) or for metals sol utilization (^200 kg/dmt).   The operating and mainten-
ance costs, including the cost of capital, for a  20 dmtpd plant are:
                                  Hot Acid
                               Treatment Alone
Optimum Dewatering

Optimum Metals Removal
$/dmt

19.00

24.00
($/dst)

(17.25)

(21.79)
Hot Acid Treatment,
Solids Separation, &
  Liquor Treatment

$/dmt       ($/dst)
29.90

37.71
(27.15)

(34.24)
     Total operating and maintenance costs, including cost of capital, were
compared for various stabilization/conditioning processes:  hot acid treat-
ment, thermal treatment, anaerobic digestion, aerobic digestion, and lime
treatment.  The comparison did not include the cost of dewatering and
supernatant (or liquor) treatment.  The estimated treatment costs for a
20 dmtpd plant decreased in the order:  anaerobic digestion ($74/dmt),
aerobic digestion ($47/dmt), thermal treatment ($39/dmt), hot acid treatment
($19-247dmt), and lime treatment  ($16/dmt).

     Based on the results of this program it is concluded that the hot acid
process is a highly promising technique for the treatment of municipal sludge
It has been shown that this process:

     — substantially improves sludge dewaterability,
     — destroys essentially all  pathogens,
     — has the potential to solubilize significant quantities
        of heavy metals including cadmium,
     ~ preferentially solubilizes heavy metals rather than
        nutrients such as organics and nitrogen, and
     ~ is highly cost-competitive with alternative stabilization/
        conditioning processes.

-------
                                  SECTION .3

                                RECOMMENDATIONS
     The bench-scale tests have indicated that the hot acid process is a
highly promising technique for sludge stabilization/conditioning,  and further
development of the process is recommended.  The next step in development of
the process should be the design, fabrication, and testing of continuous-
flow, transportable, pilot system similar to that described in Section 8.
This system should be installed and operated at various municipal  treatment
plants in order to evaluate the process under dynamic flow conditions with
fresh sludge.

     Rather than designing and building an entire pilot system at  the outset,
it is recommended that only the hot acid treatment portion be.built initially.
Field operation of this portion of the pilot plant will permit an  evaluation
of the operating characteristics and control methodology for hot acid treat-
ment.  In addition, an assessment should be made of alternative techniques
for dewatering the hot-acid-treated sludge and for treating the liquor
remaining after separation of the solids.  When the preferred techniques
have been identified, the pilot system should be modified to include all unit
processes and the performance of the integrated system should be,-demonstrated.
Sufficient information should be obtained from operation of the pilot system
to permit an accurate assessment of the process economics.

-------
                                  SECTION 4

                         BENCH-SCALE PROCESS STUDIES
     Bench-scale tests were conducted in order to characterize and optimize
the performance of the hot acid process.  Specific objectives of these tests
were:

     — to evaluate the process with various secondary sludges and
        and various mixtures of primary and secondary sludge;
     — to determine the acid requirements for the various sludges;
     — to optimize the process with respect to pHs
        temperature, and reaction time; and
     — to evaluate alternative solid-liquid separation techniques.

METHODS AND MATERIALS

Sludge Identification

     Tests were conducted,with sludge from two municipalities in eastern
Massachusetts:  Brockton and Fitchburg.  At both locations samples of primary
sludge and waste activated sludge (WAS) were obtained.  Tests were conducted
either with WAS alone or with an equal-volume mixture of primary and WAS.
The individual sludges were stored separately and the primary WAS mixtures
were prepared just before the tests in which they were used.   Samples were
obtained in 5-gal polyethylene carboys and refrigerated immediately upon
arrival at Walden.  The samples were used within 7 days of the date on which
they were obtained.

     Samples of Brockton waste activated sludge were obtained after dissolved-
air-flotation thickening.  No chemicals were added prior to the thickener.
The Fitchburg waste activated sludge was obtained following dissolved-air-
flotation thickening which was preceeded by the addition of polymer (Nalco
7120 or Calgon 2620).  The total solids (TS) concentrations of the sludges as
received were:
                                      Range of Total
             Sludge                     Solids "
     Brockton WAS
     Brockton primary & WAS
     Fitchburg WAS
     Fitchburg primary & WAS
2.5
4.0
4.0
4.2
4.9
4.5
4.1
6.8
                                      8

-------
Bench-Scale Test System

Digestion—
     The system used for hot acid digestion of the sludge is  shown in
Figure 1.  The acidified sludge was contained within a one-liter graduated
cylinder wrapped with heating tape, and the power input to the heating tape
was controlled by a variable transformer.  The contents of the cylinder was
agitated at a speed of about 60 rpm to provide good heat transfer from the
walls of the container.  Agitation was provided by a Phipps and Bird stirrer
(Model 7790-300) which was modified for use with graduated cylinders as shown
in the "Stirrer Detail" of Figure 1.  A dial thermometer was  attached to the
shaft of the stirrer to indicate the sludge temperature.  Three one-liter
samples of the sludge were treated simultaneously.

Settling--
     Settling tests were conducted in the same graduated cylinders as used
for digestion (Figure 1).  Following the digestion period the stirrers were
removed from the cylinders, the power to the heating tapes was turned off,
and the sludge-water interface was recorded as settling occurred.

Filtration—
     The filtration test system is shown in Figure 2.  Samples of treated
sludge were filtered through Whatman #1 filter paper which was supported in
a Buchner funnel.  A,tubular plexiglass extender was used to permit the
entire 45 ml sludge sample to be poured into the funnel at one time.
Filtrate was produced under a controlled vacuum of 51 cm (20 inches) of
mercury and was collected in a.250 ml graduated cylinder-

Centrifugation—   , ,
     The apparatus^ shown in Figure 3 was used to centrifuge samples of the
treated sludge.  The centrifuge tube was a plastic graduated cylinder (10 ml)
with the base removed, and a slot was machined in the metal tube shield.  A
stroboscope was used to  "stop" the rotation of the centrifuge so that the
interface height could be recorded as a function of time without stopping
and removing the tubes.  The centrifuge  (Clay Adams Model 0101) was
operated at 2,600  rpm which provided an average centrifugal acceleration of
750 G's.

Experimental Procedures

     The refrigerated carboy containing the sludge was agitated to mix the
sludge before removing samples.  Three one-liter samples were placed in
beakers for pH  adjustment and a fourth sample was set aside for analysis.
The three one-liter samples (generally adjusted to different pH's) were
treated simultaneously.  The pH was adjusted to the desired level by addition
of concentrated (96%) reagent-grade sulfuric acid.  The  samples were then
poured into the graduated cylinders of the  apparatus shown in Figure 1 and
heated to the desired temperature.  The  time required to heat the sludge was
generally in the range of 10-20 minutes with the longer  times required for

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samples exhibiting a greater tendency to foam.   Samples were held at the
desired temperature for the desired time by manually controlling the power
input to the heating tapes.

     Following digestion, 45 ml of the sludge from each of the three
cylinders was poured into each of the three corresponding filters, and 10 ml
from each of the three cylinders was poured into the three corresponding
centrifuge tubes.  The settling tests were conducted with the remaining
sludge (~ 900 ml in each cylinder) by recording the interface height as a
function of time over a 1-hour period.  The filtration and centrifugation
tests were conducted simultaneously as soon as possible after placing the
samples in the respective test equipment.  For filtration, the volume of
filtrate was recorded as a function of time over a period of one hour, while
for centrifugation, the interface height was recorded as a function of time
over a period of 10 minutes.

Sampling and Analysis

     Following the settling test, the contents of each graduated cylinder was
thoroughly mixed and divided into two portions.  One of the two portions  was
retained for analysis; the other was filtered through Whatman fl filter paper,
and the filtrate was retained  for analysis.  Similar samples (unfiltered and
filtrate) of the raw sludge, which had been set aside at the outset of the
test, were also retained for analyses.

     The assays performed and  the analytical procedures used are listed in
Table 1.

     Samples of sludge and sludge filtrate which had been subjected to the
hot acid treatment were preserved by refrigeration prior to analysis.  It
was believed that the low pH of the samples  (generally 2-3) along with
refrigeration would sufficiently arrest  any  biological activity.  On the
other hand samples of the raw  sludge were  chemically preserved  in addition to
refrigeration.  Samples for total solids analyses were preserved by the
addition of formaldehyde  (to 1% by weight).  The formaldehyde was assumed to
vaporize during evaporation of the sample  prior to the gravimetric determin-
ation of total  solids.  Samples for COD  and metal analyses were preserved by
reducing the pH  to  1.0 with I-^SO^..

Data  Reduction

      In  general  the  calculational procedures used in reducing the data were
straight  forward and require  no special  explanation.   However,  the  rationale
and  the  procedures  used  to  calculate  the percent of  various  sludge  con-
stituents  solubilized  by  the  hot  acid process  are  not  directly  obvious and
deserve  further clarification. For each set of three  hot-acid-treated
samples,  a sample of  raw sludge was  obtained and  analyzed as  the  control  to
which the  hot-acid-treated samples  were  to be  compared.   Thus for a  hot-
acid test at given conditions  the analytical  results obtained for sludge
 constituent M (e.g.  a  heavy metal  or COD)  were:
                                       13

-------
                          TABLE 1.   ASSAYS  AND PROCEDURES
Assay
Total solids
Volatile solids
BOD
COD
TOC
Zinc
Copper
Cadmi urn
Nickel
Chromium
Lead
Total phosphorus
TKN
Fecal coli form
Fecal streptococcus
Procedure
Gravimetric - total residue
dried at 103°C - 105°C
Gravimetric - at 550°C
5 day incubation, electrode
Di chroma te reflux
Combustion - membrane detection
Dohrmann Envirotech T.O.C.
Analyzer
Atomic absorption
Atomic absorption
Atomic absorption
Atomic -absorption
Atomic absorption
Atomic absorption
Persulfate digestion
Ascorbic Acid Method
Kjeldahl, selective ion electrode
Fecal coli form membrane
filter procedure
Membrane filter technic
Reference*
SM208A
SM208E
SM507
SM508
EPA, p.
SM301A
SM301A
SM301A
SM301A
SM301A
SM301A
SM425C,
EPA, p.
SM909C
SM910B




236t






425F
175t


Standard Methods for the Examination of Water and Wastewater.   Fourteenth
edition.  American Public Health Association, Washington,  D.C.   1976.

Methods for Chemical Analysis of Water and Wastes.  EPA-625/6-74-003.  U.S.
Environmental Protection Agency, Office of Technology  Transfer,  Washington,
D.C., 1974.
                                   14

-------
     1.   Total concentration ' of M -in raw sludge (unfil te red) = (TM)raw

     2.   Total concentration of M in raw sludge filtrate == (DM).,.',..,, '..."'
                                                                i dw
     3.   Total concentration of M in treated sludge (unfiltered)  =

          (TM) treated                                         .....    '
     4.   Total concentration of M in treated sludge filtrate =

          ^treated

     The concentration of suspended constituent M in the raw and treated
samples is then:
(SM>
                  = <™
                         aw
    treated
                            treated ' (DM)treated
The simplest procedure for calculating the percent of constituent M
solubilized by the treatment process is:
% Solubilized =
                          
                    raw
                                        treated
                                 (SM)
                                                 x'100%
                                                          (1)
                                     raw
The use of Equation (1) to calculate the percent solubilized resulted in
numerous inconsistent and widely scattered results.  For example, for one
set of analyses the percent COD solubilized was -7% as calculated by
Equation (1) even though the COD of the treated filtrate was nearly 8 times
as great as the COD of the raw filtrate.

     A careful inspection of the data indicated that the results calculated
by Equation (1) are strongly influenced by inaccuracies in obtaining
representative samples of sludge.   Because of the heterogeniety of the raw
sludge, two samples taken from the'same container of sludge could have
significantly different concentrations of suspended constituents (solids,
COD, metals) although the dissolved constituents would be expected to be
homogeneously distributed for all samples.  These sampling-related differences
in suspended constituents for two samples (one,to be treated, one to remain
untreated) can have a large influence on the percent solubilization
calculated byEquation (1).              ,

     A second source of inaccuracy in the use of Equation (1) is that any
constituents that are volatilized by the hot acid process (e.g. carbonates
-»• carbon dioxide) are calculated as being solubilized.  Thus in many, cases
the calculated degree of solubilization using Equation (1) indicates much
higher dissolved concentrations in the filtrates than are actually present.

     In order to reduce the effects of sampling inaccuracies and volatili-
zation on the calculated percent solubilization, the amount of suspended
constituent in the raw sludge was calculated from the treated sample:
(SM>
    raw
                        treated ' (DM)raw
                                                          (2)
                                      15

-------
Then (SM)*aw was used in Equation (1)  in
procedure gave quite consistent results,
calculated.
                               place  of (SM)raw.  This
                               and  no negative  solubilizations
                                                                 calculational
                                                                        were
     The degree of suspended solids sol utilization was calculated by a  similar
procedure except that Equation (2) was modified to take into account the
sulfate added with the sulfuric acid during acidification of the sludge.   Thus
Equation (2) becomes:
          (SS>raw = ^treated - (DSVaw ' Padded
                                                          (3)
where:
          (SS)
              raw
              treated
          (TS(Vadded
               calculated suspended  solids  concentration of raw
               sludge

               total  solids  concentration of  treated sludge

               dissolved solids  concentration of  raw sludge

               total  concentration of sulfate added to  the raw
               sludge
The amount of sulfate added was calculated from the known volume of concen-
trated H?S04 added to the sample, the concentration of the acid (96%),  its
density (1.83 g/cc), and its SOzj: content.  The concentration of suspended
solids in the treated sludge was calculated by:
(SS>
    treated
                      = ^
                            treated
                                          treated
                                                                    (4)
No correction for sulfate is required since both the total  and dissolved
solids analyses for the treated sample include the added sulfate,  which is
assumed to remain dissolved.  Equations (3) and (4) were then used in
Equation (1) to calculate the percent sol utilization of suspended  solids.

RESULTS AND DISCUSSION

     Tests were conducted to characterize and optimize the  hot acid process
with respect to the important performance criteria for sludge conditioning.
Results are presented below for the acid requirements of the process, the
solid-liquid separation rates, the solubilization of various sludge
constituents, and the destruction of pathogens.

Preliminary Tests

     Preliminary tests were conducted at the outset of the  program in order  to
evaluate the effect of several process variables believed to be of minor im-
portance and to determine the range of interest of the process variables
believed to be of primary importance (pH, temperature, and  digestion time).
The minor process variables investigated were:

     1.   Stirring speed during digestion
     2.   Aeration during digestion
     3.   Concentration of ^SCvj. added to the raw sludge
                                      16

-------
     4.   Sludge age and storage conditions
     5.   Ferric chloride or polymer addition to the treated sludge.
The ranges of major process variables investigated were:
     pH
     Digestion Temperature
     Digestion- Time
1.5 - 4.0
80 - 95°C
10-60 minutes
     All preliminary tests were conducted with Brockton WAS using the
procedures described above.  Unless otherwise specified, the minor process
variables were investigated at a pH of 2, a temperature of 95°C,  and a
digestion time of 30 minutes.

Stirring Speed During Reaction—
     Different stirring speeds were investigated during digestion to determine
if the stirring speed affects the solid-liquid separation rate or the degree
of TOC solubilization.  Two samples of sludge were acidified to pH 2 and
digested at 95°C for 30 minutes using a stirring speed of 60 rpm.  One of
the samples was then subjected to high shear by mixing in a Waring blender
for two minutes.

     Settling curves for the two samples are shown in Figure 4.  The height
of the interface (as indicated by the ml graduations on the graduated
cylinder) is plotted as a function of settling time.  The sample  subjected
to high shear settled much slower than the sample subjected to low shear.
This suggests that floes formed during digestion may have been broken up
by the intense mixing in the blender.

     Since homogenization is used in many biological investigations to
induce lysis'of cellular materials, it was anticipated that high-shear
mixing would increase the TOC of hot-acid-treated sludge.  However, the TOC
of the filtrate of the high-shear sample (1140 mg/1) was slightly lower
than the TOC of the filtrate of the low-shear sample (1250 mg/1).  This
indicates that cell lysis was not significant at the stirring speeds used.
It was concluded that the stirring speed should be adjusted to the minimum
speed that maintains a reasonably uniform temperature profile throughout
the sludge during digestion.  In all subsequent tests with this apparatus a
stirring speed of 60 rpm was used.  (Tests at a higher stirring speed
using a different apparatus are described in Section 6).

Aeration During Reaction--
     Aeration during digestion was investigated to determine whether or not
it had any effect on the solids separation rate or the degree of  TOC
solubilization.  Two samples were digested at identical conditions except
that oxygen was sparged into one of the samples during digestion.

     The settling curves are shown in Figure 5 for both the oxygen-sparged
sample and the control.  The oxygen-sparged sample settled more slowly than
the control.  This may be the result of oxygen-entrainment in the sparged
sludge which would reduce its density and inhibit settling.
                                      17

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     There was no significant difference in the concentrations  of  soluble
TOG for the two samples (1500 mg/1  for the oxygen-sparged sample,  1540 mg/1
for the control).

     Based on these results, air sparging would appear to have  no  beneficial
effects on the hot-acid process.  The evaluation of air sparging to  improve
the sol utilization of heavy metals  is considered in Section 6.

Concentration of Sulfuric Acid--
     The effect of acid concentration of process performance was investigated
using three different acid concentrations:

     1.   concentrated H2S04 (96% by weight)
     2.   concentrated 1^04 diluted with an equal  volume of water (50:50)
     3.   concentrated H2S04 diluted with three times its volume of
          water (25:75)

Settling curves are shown in Figure 6 for digested  samples acidified with
the three different concentrations  of acid.  The samples treated with the
two higher acid concentrations gave similar settling curves,, and,  except for
the last 15 minutes of the test, both settled more  rapidly than the  25:75
samp!e.

     The effect of the concentration of added acid  on the solubilization of
organics (here, measured as soluble TOC) was investigated.  The TOC  values
of the filtrates for the concentrated 50:50 and 25:75 concentrations were
1760, 1850, and 2120 mg/1, respectively.  This is interesting,  since it was
expected that the higher concentrations would solubilize more organics.
Although the explanation of this behavior is not apparent, it can  be con-
cluded that concentrated acid should be used in the process.

Sludge Age and Storage Conditions--"1
     Sludge age and storage conditions were investigated in order  to
determine whether a new supply of sludge was required each day, or whether
sludge could be stored for a certain period of time without significant
deterioration with respect to evaluating process performance.

     The three storage conditions examined were: 1) room temperature
(biologically active sludge), 2) formaldehyde treatment, 1% by  volume
(biologically inactive), and 3) refrigeration (biologically arrested).

     Each working day during a six-day period, a sample of each of the three
sludges was acidified and digested, and settling curves, as well as  TOC and
solids data, were generated.  The interface height  after 30 minutes  of
settling time is shown below as a function of sludge age and storage
condition.  (The interface height is given, in terms of the volume  of sludge
remaining out of an initial volume  of TOGO ml.)
                                     20

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                                              21

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 Time
(days)

 0.25
 1.1
 4
 5
 6
                 Sludge volume remaining after 30 minutes of settling (ml)
Room temperature

    810
    760
    810
    820
    820
Refrigerated

    810
    700
    820
    790
    790
Formal dehyde

    920
    815
    960
    930
    930
From these data it is apparent that the room temperature and refrigerated
samples settle at approximately the same rate after hot acid treatment, but
the formaldehyde-treated sample settles significantly slower following hot
acid treatment.  This result rules out the use of formaldehyde for sludge
preservation.  Comparing the settling rates observed on the first day with
those observed on the sixth day, the results appear to lie within the
experimental precision of the test.

     The pH of the sludge was measured each day during storage and is shown
in Figure 7.  The curves all have the same general  shape and indicate a
decrease in pH with storage time.  The pH change — from 6.0 to 5.5 over
six days — is considered tolerable.

     The soluble TOC concentrations of the three sludge samples are shown
in Figure 8 as a function of storage time.  The soluble TOC of the refriger-
ated sludge remained fairly constant throughout the six-day period (160 mg/1
± 25), while both the HCHO-treated and room-temperature sludges showed
constant increases in soluble TOC (80 and 60 mg/l-day, respectively).  TheSe
increases may be due either to cell autolysis which occurs during endogenous
respiration (in the case of room-temperature sludge) or to the loss of cell
membrane semi-permeability (in the case of the HCHO-treated sludge).  The
TOC values for the HCHO-treated sludge are much larger than the values for
the other two sludges because the formaldehyde contributes to the total
organic carbon concentration.

     The total solids and dissolved solids concentrations of the three
sludge samples are shown as a function of sludge age in Table 2.  Although
there is some variability in the total solids analyses, there is no
consistent trend to higher or lower total solids concentrations with storage
time.  The scatter in the total solids data is probably the result of the
heterogeniety of the sludge which made it difficult to obtain a truely
representative sample.

     The dissolved solids in the raw sludge account for only about 5% of the
total solids.  There appears to be a consistent increase in dissolved solids
during the first day of storage, but thereafter the dissolved solids concen-
trations remain reasonably constant.  The scatter in the dissolved solids
data could be the result of analytical errors since only a rather small
volume of sample was submitted for analysis.
                                      22

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3000
O  Room Temperature
Q  Formaldehyde-Treated
/\  Refrigerated
2500
2000
1500
1000
 500
                       L..
                        -.-.O
             •-:-'-.4	A
                             TIME,  DAYS
        Figure 8.  Variation of WAS  TOC with time for various
                  storage conditions.
                               24

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-------
Ferric Chloride or Polymer Addition—
     Ferric chloride and various polymers were evaluated to determine whether
or not their use in conjunction with the hot acid process would produce a
substantial improvement in the solid-liquid separation rates.   For each set
of tests three samples were compared:  the first was hot acid  treated without
additives, the second was hot acid treated with the additive added before
digestion, the third was hot acid treated with the additive added after
digestion.  Ferric chloride was added as a 10%-by-weight solution in
sufficient quantity to reduce to pH of the raw sludge to 3.0.   Several  types
of acrylami de-based polymers were evaluated (Allied Colloids'  Percol 720,
725, 726, and 728) each at a dosage of 50 ppm based on the weight of the wet
siudge.

     It was concluded on the basis of settling, filtration, and centri-
fugation tests that the addition of ferric chloride or polymer at the
conditions investigated did not substantially improve the solid-liquid
separation rates for the hot acid process.  Although minor improvements were
observed in some cases, the improvements were not considered sufficient to
justify the additional cost of the additive.

Selection of Ranges for Major Process Variables--
     Tests were conducted to identify the ranges of pH, temperature, and time
for which the hot acid process produced the best performance.   The pH was
studied over a range of 1.5-4.0; the temperature, over a range of 80-95°C;
and the time, over a range of 10-60 minutes.  For the tests at various pH 's
all samples of Brockton waste activated sludge (2.7% solids) were digested at
95°C for 30 minutes.  The settling, filtration, and centrifugation curves
are shown in Figures 9, 10, and 11, respectively.  For settling the interface
height (calculated as the percent of initial sludge volume remaining) is
plotted against settling time.  The sludge samples digested at pH 2.5 settled
most rapidly followed by the sludge settled at pH 2.0.  For filtration
(Figure 10) the volume of filtrate collected out of an initial volume of
45 ml is plotted against filtration time.  The sludge samples  digested at
pH 2.5 and 3.0 filtered the most rapidly.  For centrifugation  the interface
height (calculated as the volume of sludge remaining from an initial volume
of 10 ml) is plotted against the centrifugation time.  The sample adjusted to
pH 4 centrifuged least rapidly, but all of the other samples appeared to
centrifuge at about the same rate.  Based on these tests it was concluded
that the optimum pH range for the hot acid process is 2.0 to 3.0.

     Tests conducted at temperatures of 80, 90, and 95°C (at pH 1.5 and
45 min digestion time) indicated better solid-liquid separation at a
digestion temperature of 95°C.  Since higher temperatures are  ruled out by
the boiling point of water and lower temperatures give  lower  solid-liquid
separation rates, it was concluded that the optimum temperature range for
solid-liquid separation is 80-95°C.
                                     26

-------
10A 1VI1INI  JO  %  '1H  3DWH31NI
                27

-------
                                          pH 1.5

                                          pH 1.8

                                     A   pH 2.0
       10
20         30         40

        TIME, MINUTES
                                                  50
60
Figure 10.  The effect of pH  on the filtration rate of WAS
            digested at  95°C  for 30 minutes.
                             28

-------
     ()
  3.5
  3;0
  2.5
§2.0
  1.5
0
         O pH 1.5

         Q pH 1.8

         A PH 2.0


         O PH 2.5


         O PH 3.0



         0 PH 4-°
                                                          -JO
                                                           10
                               TIME, MINUTES
                                                                      I
      Figure 11.   The effect of pH on  the centrifugation  rate of
                   WAS digested at 95°C for 30 minutes.
                                   29

-------
     Two different sets of tests were conducted to evaluate the variable of
time.   In the first, three samples were digested at pH 1.5, a temperature of
95°C and times of 30, 45, and 60 minutes, respectively.  In the second set,
three samples were digested at pH 2.5, a temperature of 95°C, and times of
10, 20, and 30 minutes, respectively.  From these tests the solid-liquid
separation rates did not appear to be strongly dependent on digestion time,
and a range of 10 to 60 minutes was selected as the preferred range of
digestion times for the hot acid process.

Acid Requirements

     Concentrated sulfuric acid was added to the sludge before heating, and
the volume of acid required to adjust the sludge to the desired pH was
recorded for each test.  Table 3 summarizes the acid requirements determined
during  the program for the tests of primary importance.  A series of tests
were conducted with the first four sludges listed in Table 3 resulting in 9
separate tests for each sludge at each pH.  The acid requirements Were cal-
culated both on a solids basis (kg acid per metric ton of solids) and on a
wet sludge basis (kg acid per metric ton of wet sludge).  For each sludge at
a given pH, the acid requirement should be the same for each of the 9 tests.
In general, there is some scatter about the mean as indicated by the
standard deviation, but the standard deviation (relative to the mean) is con-
sistently less when the acid requirement is calculated on a wet sludge basis
rather  than a sludge solids basis.  This implies that the liquid fraction of
the sludge exerts a greater acid demand than the solid fraction.  On the other
hand, comparison of the acid requirements for sludges obtained on different
dates (e.g. results for Brockton WAS at pH 1.5) suggests a better correlation
on a sludge solids basis.

     Figures 12 and 13 present the average acid demand as a function of pH
on a sludge solids basis and a wet sludge basis, respectively.  The points
in each figure indicate the average of the means listed in Table 3 for the
indicated pH.  (In calculating this average all means of Table 3 were
weighted equally even through some means are more uncertain than others.)
The relationship between acid demand and pH is approximately linear over the
range of pH 2 to 3 but begins to increase rapidly below a pH of 2.  It is of
interest to note that at pH 2.0 the acid demand of all  the sludges are about
the same.  At this pH the approximate acid requirement is 110 kg/dmt solids
or 4.4 kg/ wmt sludge.   Of the sludges tested the Fitchburg WAS required
the most acid to achieve the desired pH levels.

Solid-Liquid Separation

     For each of the four sludges, a full-factorial  experimental  design was
used to evaluate the effects of the major-process variables (pH,  temperature,
and time) on solid-liquid separation and on solubilization of various sludge
constituents.   In the full-factorial  design, all  combinations of the three
"factors" (pH, temperature, and time)  at each of three  levels (27 tests per
sludge)  were tested.   The levels investigated were:
                                     30

-------
            TABLE 3.   ACID REQUIREMENTS AS  A FUNCTION OF PH  FOR
                        BROCKTON AND FITCHBUR6 SLUDGES
Sludge , >
sample la)
B-2° (2-28)


F-2° (3-15)


B-l°+2° (3-28)


F-10«° (4-11)


B-2° (2-14)


B-2° (2-22)





8-2° (4-26)





F-2° (5-10)





8-10*20 (5-3)





•6-2° (5-19)
8-2° (5-26)
B-l°+2° (5-27)
' F-2° (6-3)
F-10+20 (6-7)
B-2° (8-17)




Total solids(b)
(t by weight)
n Mean std. dev. pH
9 4.21


9 4.02


9 4.53


9 4.22


6 3.98


3 2.53





3 3.53





2 4.06





2 4.11





3.21
2.51
4.00
4.06
6.78
4.90 ,




a. Sludge Identification; example
b. Total solids concentration of
Std. Oev. - standard deviation
c. Gives the
j «_j_i 	
0.51 2.0
2.5
3.0
0.16 2.0
2.5
3.0
0.42 2.0
2.5
3.0
1.18 2.0
2.5
3.0
0.19 1.5
2.0
2.5
0.22 1.5
1.8
2.0
2.5
3.0
4.0
0.95 2.0
2.3
2.5
2.6
2.8
3.0
0.05 2.0
2.3
2.5
2.6
2.8
3.0
0.24 2.0
2.3
2.5 9
2.6
2.8
3.0
2.5
2.5
2.5
2.5
2.5
1.0
1.2
1.5
2.0
2.5
: B-lo+2° (3-28) stands
raw si udge . n = number
" of6' (m
tests Hean
9
9
9
9
9
9
9
9
9
9
9
9
7
10
1
2
1
1
4
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1





1
1
1
1
2.38
1.68
0.87
2.57
1.94
1.07
2.48
1.90
0.90
2.43
1.91
0.82
4.23
?.26
2.0
2.2
2.4'
1.8
1.2
0.7
0.5
2'.7
2.2
1.65
1.3
1.0
0.9
2.8
2.6
2.4
2.2
2.0
•1.8
2.5
2.0
1.6
1.3
'1.1
0.9
1.8
1.8
1.9
2.2
2.3
13.5
10.3
5.5
3.2
2.3
Std. dev.
0.15-
0.26
0.09
0.07
0.05
0.17
0.04
0.00
0.00
0.07
0.03
0.07
0.21
0.14
—
0.00
—
..
0.00
._
—
_.
~_ '
0.07
..
..
—
._
..
..
..
- ._
—
	
J. •
..
..
..
—
—
	
—
—
	
r..
..
._
..
. '•
Acid required * '
(kg/dmt solids)
Hean Std. dev.
100
70.9
36.6
112
84.8
46.6
98.8
74.1
35.1
112
87.9
38.7
186
101
82.5
219
156
117
92.2.
53.8
38.4
15S
128
78.7
781Q
60 .ft
54.0
120
112
103
96.2
87.4
78.7'
111
89.2
71.4
53.4
45.2
36.9
98.5
12.6
83.4
95.2
59.6
484
369
197
115
82.5
'15.2
15.7
5.5
5.5
3.8
7.6
7.4
6.3
3.0
43.5
34.2
10.2
2.1
3.4
—
7.0
—
..
0.0
..
—
..
.-
14.2

.-
—
	
._
..
.•.
._
—
._
._
._
„_
._
—
—
	
—
	
	
„
..
..
._
—
Acid required ^ '
(kg/writ sludge)
Hean Std. dev.
4.18
2.95
1.52
4.51
3.42
1 .88
4.35
3.34
1.58
4.28
3.36
1.44
7.43
3.97
3.51
5.80
4.22
2.99
2.11
1.23
0.88
4.74
3.86
2.90
2.28
1.76
1.58
4.92
4.57
4.22
3.86
3.51*
3.16
4.39'
3.51
2.81
2.28
1.93
1.58
3.16
3.16
3.34
3.86
4.04
23.7
18.1
9.66
5.63
4.04
for Brockton primary plus secondary sludge (WAS) obtained on February 28,
of independent sanple/analyses on the sludge, mean = arithmetic average,
0.26
0.46
0.15
0.12
0.09
0.29
0.07
0.00
0.00
0.12
0.06
0.12
0.37
0.24
—
0.00

__
0.00
—
—
	 : .
.-
0.13
—

—
..
.;_
..
"_;.
	
—
„ .
._
	

	
	
—
	

	

•
__
._
	
—
1977.
ml. of 96% HjSOfl added to 1 liter of sludge. • '
d.  Acid requirement calculated on a. 100% H2S04 basis per dry mstric ton (dmt) or wet metric ton (wmt).
                                            31

-------
    600
    500
    400
CO
o
    300
o
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HH
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    200
   100
      O  Brockton WAS

      A  Fitchburg WAS


      D  Brockton Primary plus WAS


         Fitchburg Primary plus WAS
                  1.0
2.0
                                  PH
3.0
4.0
5.0
      Figure 12.  Acid demand vs. pH for various sludges  (sludge
                  solids basis).
                                 32

-------
    30
    25
    20
cs
o
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CO
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    15
o
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               O  Brockton WAS
               A  Fitchburg WAS
               ^  Brockton Primary  plus  WAS
                  Fitchburg Primary plus WAS
                  1.0
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                •-  pH   ^
4.0
5.0
      Figure 13.
Acid demand vs. pH for various sludges (wet sludge
basis).
                                  33

-------
          PH
          Temperature
          Time
2.0, 2.5, and 3.0
80, 90, and 95°C
10, 30, and 60 minutes
These levels were selected on the basis of the preliminary tests  described
above.  For the most part, all of the 27 tests for a particular sludge  were
completed within one week in order to limit the extent of changes in  the
nature of the sludge.  In addition, the order in which the variables  were
investigated was randomized so that if the age of the sludge had  an effect
on performance, the effect would not be misinterpreted as arising from  the
variation of one of the factors being investigated.  The test matrix  for the
optimization tests is given in Table 4.  In general, a fresh sample of  sludge
was obtained on Monday morning, and the first set of tests was conducted in
the afternoon.  On subsequent days, two sets of tests were conducted.  For
each set, three samples, adjusted to the three different pH levels, were
digested simultaneously at the temperature and time indicated in  Table  4.

Brockton Waste Activated Sludge--
     Table 5 gives the results for solid-liquid separation rates  following
hot-acid treatment of Brockton WAS.  As indicated in Table 3, the average
total solids content of this sludge was 4.21 % by weight.  Because of the
large number of tests, it is not feasible to present rate curves  for  each
test and each solid-liquid separation technique.  Instead, the rates  of
solid-liquid separation are indicated in Table 5 by a single parameter  for
each technique.  These parameters are:
     for settling:
     for filtration:
the volume of sludge remaining after 30 minutes
settling time (calculated as a percentage of the
initial volume of sludge which was ~ 900 ml).

the volume of filtrate collected after 20 minutes
of filtration (from an initial volume of 45 ml).
     for centrifugation: the volume of sludge remaining after 10 minutes
                         of centrifugation (from an initial  volume of
                         10 ml).

     In order to determine which factors have a significant influence on the
solids separation rate, a 3-way, 3-level analysis of variance was performed
using standard statistical techniques (" '.  The "F-Test" was used to
determine, with 95% confidence, whether or not there was a difference in
solids separation rates at different levels of a given factor.  The results
of the analysis of variance for solids separation are shown in Table 6.
The first column gives the main effect or interaction for which the variance
of test results is to be analyzed.  The three-way interaction between time,
temperature, and pH was assumed to be negligible and was therefore used  as
an estimate of the experimental error.  For each solids separation technique
the test F, calculated from the experimental  data, and the tabulated F for
the 95% confidence level (Fn^) are given.  If the test F is greated than
Fg.95 the main effect or interaction is significant.  The third column
under each solids separation technique indicates whether the factor (or
interaction) is significant ("yes") or not ("no").
                                     34

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     The results of Table 6 indicate that the temperature and pH have a
significant effect on the rate of solids separation for all  three solids
separation techniques.  Of the various main effects and interactions
evaluated, the pH had the most significant effect on solids  separation rates.
The effect of time, on the other hand, was not significant.   The results of
Table 6 also indicate that there were no significant two-way interactions
between the factors of time, temperature, and pH.

     Since the time was not a significant variable in these  tests, results
obtained at different times can be averaged to give a more precise indication
of the effects of temperature and pH.  The results for settling, filtration,
and centrifugation are shown in Figures 14, 15, and 16, respectively.  In
these three figures, each data point represents the average  of three tests
at the three different digestion times for the indicated pH  and temperature.
The experimental error for these data is indicated by the standard deviation
bar which was calculated in accordance with standard statistical procedures
by taking the square root of the mean square of the time x temperature x pH
interaction.

     As shown in Figure 14, the settling rate increased (30-min sludge volume
decreased) with digestion temperature, and at the highest temperature,
appeared to go through a maximum (minimum) at pH 2.5.  However, the absolute
rate of settling was low.  At the optimum conditions, the sludge settled to
only about 87% of its initial volume in 30 minutes.

     The filtration rate (shown in'Figure 15) also increased with digestion
temperature, and at all temperatures, the maximum filtration rate occurred
at a pH of 2.5.

     The centrifugation rate (Figure 16) also increased (10-min sludge volume
decreased) with digestion temperature, and the best centrifugation rates were
again obtained in the vicinity of pH 2.5.

     Based on the settling, filtration, and centrifugation results, the
optimum treatment conditions appear to be pH 2.5 and 95°C.  Since time was
not a significant variable over the range investigated, the minimum time of
10 minutes would be selected as the optimum digestion time.

Fitchburg Waste Activated Sludge-

     Similar tests were conducted for Fitchburg WAS (4.0% solids), and results
of the solid-liquid separation tests are presented in Table 7.

     The results of the analysis of variance for the solid-liquid separation
data are given in Table 8.  For filtration the results indicate that pH is the
only significant variable.  For settling all  three variables (time, temper-
ature, and pH) and all three interactions (time x temperature, time x pH, and
temperature x pH) are significant.  For centrifugation, all  three variables
and one interaction (time x temperature) are significant.

     For settling, in which all three variables and interactions are signifi-
cant, Figure 17 gives the volume of sludge remaining after 30 minutes
settling time (calculated as a percentage of the initial 900 ml volume of
sludge) as a function of pH for various digestion times and  temperatures.
                                      38

-------
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   95
   90
   85  i—
    80  L
               2.0
                                     Digestion Temperature
                                              80°C
                                           O 95°C
                               ~T~ Estimate of

                               _J_ Standard Deviation
                     2.5
3.0
                                    PH
Figure 14.
Effect of treatment conditions on  settling rate for

Brockton WAS.
                              39

-------
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pH
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Figure 15.   Effect of treatment conditions on filtration rate
             for Brockton WAS.
                              40

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  PH
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Figure 16.  Effect of treatment conditions on centrifugation rate

            for Brockton WAS.
                                41

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     In examining  Figure 17  for  the optimum treatment conditions with respect
to settling, it can be seen that the point at pH 2.5y90°C/60 minutes gave the
minimum interface height after 30 minutes.  The next lowest point is at
pH 2.5/95°C/60 minutes, so that the optimum conditions for settling appear to
be pH 2.5/90-95°C/60 minutes.

     For filtration, only one variable --pH-- was significant.   The filtration
results (volume of filtrate collected after 20 minutes from an  initial volume
of 45 ml) is shown in Figure 18.   Each of the points shown in Figure 18  was
determined by averaging the filtrate volume over time and temperature at each
pH (average of nine points).  The optimum filtration rate occurs at a pH of
2.5.

     For centrifugation, all three variables (time, temperature, and pH) were
significant, as well as the time x temperature interaction.  The centrifu-
gation results (sludge volume remaining after 10 minutes of centrifugation
from an initial volume of 10 ml)  are shown in Figure 19 as a function of pH
for'various times and temperatures.  From these data it appears that the
optimum conditions for centrifugation are pH 2.5/95°C/60 minutes.

     Based on the above solid-liquid separation tests the preferred treatment
conditions for Fitchburg WAS are a pH of 2.5, a temperature of 95°C, and a
digestion time of 60 minutes.

Brockton Primary Plus Waste Activated Sludge--
     A 50:50 mixture of Brockton primary and WAS containing 4.5% total  solids
was tested using the same full-factorial experimental design as for the
secondary sludges.- Results for the solid-liquid separation rates as a
function of treatment conditions are given in Table 9.

     The analysis of variance for the solid-liquid separation data is given
in Table 10.  For settling, all three of the factors (time, temperature, and
pH) are significant and one interaction (time x temperature) is significant.
However, the time factor and the interaction are only marginally significant
since the Test F is close to the Fo.95.  For filtration, only the pH has a
significant influence on the rate, and for centrifugation, only pH and
temperature have a significant effect on the solid-liquid separation rate.

     Results for settling at various treatment conditions are shown in
Figure 20.  In general the settling rate passed through a maximum at pH  2.5,
and at this pH, the most rapid settling occurred for a digestion time of
10 minutes and a temperature of 90 or 95°C.  The digestion time had an
inconsistent effect on settling rate giving rise to the significant time x
temperature interaction:  at 80°C a digestion time of 60 minutes gave the
best settling rate while at 95°C it gave the worst settling rate.

     For filtration, only pH was significant, and at each pH the data for
different times and temperatures were averaged (9 tests at each pH) and
plotted in Figure 21.  The filtration rate passes through a maximum at a
pH of 2.5.
                                     45

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               Effect of treatment conditions on filtration
               rate  for Fitchburg WAS.
                               46

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rate for Brockton primary plus WAS.
                             51

-------
     Figure 22 gives the results for centrifugation as a function of the
significant variables (pH and temperature).  Results at pH 2.0 and 2.5 are
essentially identical.  The centrifugation rate appears to pass through a
maximum at 90°C, but the results at 90 and 95°C are nearly, the same.  In  fact,
considering the magnitude of the standard deviation, there is little
difference between the three temperatures.  This is consistent with the
results of the analysis of variance (Table 10) which indicated that temper-
ature is only a "marginally significant" variable at the 95% confidence level.

Fitchburg Primary Plus Waste Activated Sludge-
     Similar tests were conducted with a 50:50 mixture of Fitchburg primary
and WAS.  As shown in Table 3, the mean total solids concentration of this
sludge was 4.22% with a rather large standard deviation of 1.18%.  The 95%
confidence interval on the mean is from 3.3% to 5.1% total solids.  The
problem of obtaining a representative sample of sludge was particularly
evident during these tests.  The primary sludge contained some rather large
clumps and the distribution of clumps between samples could not be controlled.
The centrifugation results were particularly erratic, probably because of the
small sample size.  The sludge centrifuged quite rapidly reaching its
maximum compaction within 30 seconds.  However the volume of sludge remaining
after maximum compaction was reached was much more dependent on the distri-
bution of solid "clumps" between centrifuge tubes than on the hot-acid
treatment conditions to which the samples were subjected.  After reviewing  the
data it was decided that the centrifugation results were not amenable to  a
detailed analysis.

     Table 11 gives the results for settling and filtration as a function of
treatment conditions, and the analysis of variance results are given in
Table 12.  For filtration, no variables or interactions were found to be
significant.  This could be the result of uncontrolled solids distribution
when the treated samples are poured into the filters.  Since the filtrate
volume was only 45 ml, these tests could be subject to the same type of
errors as the centrifugation tests.
     For settling, a large volume was
homogeneous distribution of suspended
of the analysis of variance indicate
and the time-temperature interaction
and time-temperature interactions are
confidence level, and considering the
producible results with this sludge,
for testing significance may be justi
significant.
 used and could have resulted in a more
 solids between samples.   The results
that pH and time are significant factors
is also significant.  However, the time
 only marginally significant at the 95%
 problems encountered in  obtaining re-
the use of a higher confidence level
fied.  In this case, only the pH would be
     Figure 23 gives the settling rate for Fitchburg primary plus WAS as a
function of pH.  Each point indicates the average of nine tests conducted at
various times and temperatures at the indicated pH.  The rate of settling is
greatest following treatment of this sludge at pH 2.5.
                                      52

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                                         90
                                        °C
                 80          85
                           TEMPERATURE,
         Figure  22.   Effect of treatment conditions on
                     centrifugation rate for Brockton
                     primary plus WAS.
95
                             53

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                              56

-------
Solubili'zation of Sludge Constituents

     One of the important aspects of the hot acid process is the extent to
which it solubilizes various constituents of the sludge.   Using the
sampling, analysis, and data reduction procedures described above (Methods
and Materials), the degree of solubilization was determined for suspended
solids, suspended COD, and suspended metals.  More detailed and better
controlled experiments to specifically evaluate the solubilization of heavy
metal were subsequently conducted, and results from these tests are presented
and discussed in Section 6.

Effect of Process Variables on Degree of Solubilization—-
     In order to determine the effect of the major process variables on the
degree of solubilization of various sludge constituents,  samples were obtained
and analyzed during the full-factorial experiments described above.  Samples
were analyzed for total solids, COD, zinc, and copper.  Because of the large
number of tests, analyses were not performed for other metals during the full-
factorial experiments.  Zinc and copper were selected for analysis in order to
indicate the range of expected heavy-metals solubilization:  zinc is rela-
tively difficult to solubilize.  The results of these tests confirm the
difficulty of copper solubilization:  under all conditions covered by the full-
factorial experiment, there was virtually no solubilization of copper.  There-
fore only the zinc results are presented below for these tests.  While cadmium
would have been a more interesting metal than copper to follow, the cadmium
concentrations in some samples of the sludges was judged to be too close to
the detection limit (0.2 mg/1) to give meaningful results in all cases.

     Brockton Waste Activated Sludge—The solubilization results for
Brockton WAS are shown as a function of treatment conditions in Table 13.
All of the sludge samples listed in Table 13 were obtained from the same
batch of Brockton waste activated sludge.  With each set of three tests, a
sample of raw sludge  (indicated in Table 13 by "no treatment") was analyzed.
The mean concentrations and standard deviations for the nine raw sludge
samples are given below.
 Total  Solids  (mg/1)
 Dissolved  Solids  (mg/1)
 Total  COD  (mg/1)
 Dissolved  COD (mg/1)
 Total  Zinc (mg/1)
 Dissolved  Zinc (mg/1)
Mean Concentration

     42,100
      1,500
     53,600
      2,790
         60
          0.39
Standard Deviation

     5,100
       490
     5,440
     1,550
        14
         0.26
 The  largest standard  deviations  (relative  to  the mean) were obtained for
 dissolved  solids,  dissolved COD  and  dissolved zinc.  If the samples are
 placed in  chronological  order  according  to Table 4» there is a general
 increase  in the  dissolved  constituents with sludge age.  For example the
 dissolved  COD  of the  fresh sludge was 325  mg/1, but after 4 days of re-
 frigerated storage it h*ad  increased  to 4,480  mg/1.  Because of the low
                                      57

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concentrations of dissolved zinc,  it is likely that experimental  errors  in
the analysis also added to the scatter of the data.  These  changes  in  dis-
solved concentrations with time were assumed to have no effect on the  ease
of solubilization of suspended material, and, if an effect  did occur,  the
randomization of the tests was designed to preclude misinterpretation  of
aging effects for the effects of the primary variables  being investigated.

     In order to determine the factors which have a significant influence on
the degree of solubilization., an analysis of variance was performed on the
solubilization data of Table 13.  The results are given in  Table 14.   For
suspended solids, none of the factors investigated had  a significant in-
fluence on the degree of solubilization within the ranges investigated.
Furthermore, none of the interactions between factors were  significant.
Therefore all 27 data points were  averaged to give a mean percent solids
solubilized.  The mean solubilization and 95% confidence interval are:

          Percent Solids Solubilized = 10.6% ± 1.6%

     For COD, the results of Table 14 indicate that, of the factors and
interactions evaluated, only the pH has a significant effect on the degree
of solubilization.  Thus the results at different times and temperatures
can be averaged to give the percent COD solubilized at  each pH.  The mean
percent solubilization (average of 9 tests at each pH)  as a function of
pH is:
          fiH
          3.0
          2.5
          2.0
 Mean Percent
COD Solubilized

      3.9
      5.2
      8.0
95% Confidence
   Interval

    ± 0.5
    ± 1.0
    ± 3.7
It is apparent from these data that the percent solubilization of COD
increases as the pH decreases.

     Results for zinc sol utilization are also shown in Table 14.   As was the
case for COD solubilization, the pH is the only factor which influences the
degree of zinc solubilization.  The analysis of variance also indicates a
significant interaction between time and temperature.  However, neither the
main effect for time nor the main effect for temperature is significant, and
the Test-F for the interaction is only slightly greater than FQQ^.   There-
fore, the interaction was neglected, and the mean percent solubinzation of
zinc (average of 9 tests at each pH) as a function of pH is:
          3.0
          2.5
          2.0
  Mean Percent
Zinc Solubilized

      5.4
     23.9
     55.2
95% Confidence
   Interval
    ± 3.1
    ± 7.4
    ±15.1
As for COD, the degree of zinc solubilization increases with decreasing pH.
                                     59

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     Fitchburg Waste Activated Sludge—Table 15 gives the analytical  and
solubilization results as a function of treatment condition for Fitchburg
WAS.  The average concentration and standard deviation for the nine raw
sludge samples are given below.
Total Solids (tng/1)
Dissolved Solids (mg/1)
Total COD (mg/1)
Dissolved COD (mg/1)
Total Zinc (mg/1)
Dissolved Zinc (mg/1)
Mean Concentration

     39,600
      2,240
     41,600
      4,910
         25
          0.7
Standard Deviation

     1,600
       250
     2,600
       930
         3
         0.2
Compared to the Brockton WAS, this sludge exhibited much less change in
dissolved solids concentrations with storage time as evidenced by the much
smaller standard deviations (relative to their respective means) for the
dissolved constituents.

     Table 16 gives the results of the analysis of variance for the
Fitchburg WAS.  For suspended solids, none of the factors investigated
appeared to have a significant effect on solubilization within the
ranges investigated.  However, the interaction between temperature and time
was determined to be significant.  The temperature-time interaction is shown
in Figure 24 where the percent suspended solids solubilization is plotted
against temperature for various digestion times.  Each data point represents
the mean of the results obtained at the three different pH levels.  The fact
that the curves are not parallel indicates an*interaction between temperature
and time, and the analysis of variance indicates that this interaction is
statistically significant.  The interaction appears to indicate that the
degree of solubilization is relatively low either at low temperature and low
digestion times or at high temperature and high digestion times.  This result
is unexpected.  The significance of the interaction depends largely on the
high solubilities obtained during the set of three tests conducted at 80°C
and 60 minutes.  Further tests should be conducted to reproduce this result
before concluding that it is real.

     The mean solubilization and 95% confidence interval for the Fitchburg
WAS are:                   ...                                    -x

          Percent Solids Solubilized =10.1% ± 1.8%"

This value is in very good agreement with the corresponding value (10.6%)
determined for the Brockton WAS.

     For COD, the results of Table 16 indicate that all of the factors
investigated had a significant effect on the degree of solubilization and
that the interaction between temperature and pH was significant.  Figure 25
shows the percent COD solubilization as a function of pH for various times
                                     61

-------
TABLE  15.  EFFECT OF TREATMENT CONDITIONS ON SOLUBILIZATION OF SLUDGE  CON-
            STITUENTS FOR FITCHBUR6 WAS
Treatment conditions
Time
(min)
10


-- No



-- No



-- No
30


-- No



— No



— No
60


-- NO



— No



Temp
(°C)
80


treatment
90


treatment
95


treatment
80


treatment
90


treatment '
95


treatment
80


treatment
90


treatment
95


Concentration
Solids*
PH
2.0
2.5
3.0
--
2.0
2.5
3.0
--
2.0
2.5
3.0
—
2.0
2.5
3.0
--
2.0
2.5
3.0
—
2.0
2.5
3.0
—
2.0
2.5
3.0
—
2.0
2.5
3.0
—
2.0
2.5
3.0
-- No treatment —
Tot.
38,700
35,600
39,000
38,800
44,100
43,600
43,400
41,400
46,400
45,900
41 ,600
42,100
39,600
37,900
39,100
40,100
40,800
39,337
36,900
37,900
44,600
41 ,300
41 ,000
37,200
45,400
38,100
42,300
38,800
43,000
39,900
40,700
40,500
37,500
36,500
32,700
39,800
Dis.
7,510
7,740
6,040
1 ,872
10,270
8,570
8,320
2,480
13,560
30,520
9,000
2,270
8,740
6,420
6,340
1 ,890 ,
8,800
8,090
7,050
2,040
12,020
10,250
8,670
. .2,200
16,770
10,070
9,090
2,400
9,730
8,210
7,140
2,480
10,480
8,310
7,260
2,510
in wet sludge (mq/£)
COD
Tot.
28,700
31 ,600
31,500
,39,900
45,400
46,300
46,700
43,300
54,800
45,600
46,600
44,400
41 ,600
40,900
43,700
41,300
38,800
40,700
37,300
,37,600
46,600
50,300
42,800
43,400
47,900
36,400
42,400
44,400
31 ,200
28,600
27,800
42,500
27,400
24,700
27,000
38,000
Dis.
5,170
4,600
4,830
3,760
7,950
7,260
7,100
6,010.
9,740
8,150
6,810
5,560
6,040
5,520
6,150
4,760
5,630
4,980
5,020
3,690
9,450
8,680
7,510
5,960
8,540
7,390
6,980
5,550
7,130
6,460
5,900
4,9.90
7,150
5,820
5,510
3,950
Zinc
Tot.
32
25
22
26
26
27
26
,26
23
22
19
20
30
30
30
.30
28
30
27
25
27
27
25
25
20
19
22
21
22
22
18
24
28
27
24
26
Dis.
27
14
•9
0.8
17
15
14
0.5,
19
18
10
0.7
19
14
8
1
16
15
11
(13)
18
13
8
0.5
19
15
14
0.5
18
13
7
0.6
18
14
8
1
Solubilization (%)
Sus.
solids
1.5
8.5
4.6

8.9
7.0
10.5

17.2
11. '9
12.9

7.6
3.8
7.7

7.1
8.2
9.9

14.1
12.9
12.8
	
25.7
13.1
13.0

8.1
7.2
8.1

11.9
8.2
10.6

Sus.
COD
5.7
3.0
3.9

4.9
3.1
2.7

8.5
6.5
3.0

3.5
2.1
3.6

5.5
3.5
4.0

8.6
6.1
4.2
	
7.1
6.0
3.9

8.2
6.2
4.0

13.6
9.0
6.8

Sus.
zinc
84^0
54.5
38.9

64.7
54.7
52.9

82.1
81.2
50.8

62.1
44.8
24.1

56.0
52.4
37.7

66.0
47.2
30.6
	
94.9
78.4
62.8

81.3
57.9
36.8

63.0
50.0
30.4

  -•  Treated samples include sulfate solids  added as i.^ou*.
  (  )  Indicates  questionable value.  Average value for other untreated samples
      was used in calculating percent solubilized.
                                        62

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Figure 24.
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              the  degree of suspended solids solubilization
              for  Fitchburg WAS.
                              64

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                                         65

-------
and temperatures.  In general the degree of COD solubilization increased
with increasing time and temperature and increased with decreasing pH.
The degree of solubilization ranged from 2% at 30 minutes, 80°C, and pH 2.5
to 13.7% at 60 minutes, 95°C, and pH 2.0.

     The analysis of variance results for zinc solubilization, also shown  in
Table 16, indicate that pH, and time are significant variables and the  time-
temperature interaction is also significant.  Figure 26 illustrates the
dependence of zinc solubilization on pH and time.  Each point is the average
of the results at the three temperature levels for the indicated time and
pH.  The degree of solubilization increased linearly with decreasing pH and
reached a level of about 80% solubilization at pH 2.0.  The data appear to
indicate lower solubilization at 30 minutes digestion time than at either
10 or 60 minutes digestion time.

     Brockton Primary Plus Waste Activated Sludge--Solubilization results  for
the 50:50 mixture of Brockton primary and WAS are shown in Table 17.  The
average concentrations and standard deviations for the nine raw sludge  samples
are given below.
Total Solids (mg/1)
Dissolved Solids (mg/1)
Total COD (mg/1)
Dissolved COD (mg/1)
Total Zinc (mg/1)
Dissolved Zinc (mg/1)
Mean Concentration

     45,300
      1,290
     54,500
      2,590
         78
          0.2
Standard Deviation

    4,200
      330
    3,320
      940
        7
        0.05
The ratio of the standard deviation to the mean gives a measure of the
relative degree of scatter about the mean.  As noted for the other sludge
samples, the scatter of results is noticably greater for dissolved species
(ratios of 0.25 to 0.36) than for total species (ratios of 0.06 to 0.09).
The greater standard deviations for dissolved constituents can be attributed
to significant changes in dissolved concentrations with sludge age.  However
the changes were less than for the Brockton WAS discussed above.

     Results of the analysis of variance for the Brockton primary plus WAS
mixture are shown in Table 18.  Within the ranges investigated, none of the
variables or interactions had a significant effect on solubilization of
suspended solids.  The mean percent solubilization (average of 27 data points)
and 95% confidence interval are:
          Percent Suspended Solids Solubilized = 6.2% ± 1.1%

Thus the degree of suspended solids solubilization is significantly less for
the primary-WAS mixture than for unmixed WAS (10.6%).

     As indicated in Table 18, all three variables (time, temperature, and
pH) and time-temperature interaction had a significant effect on the degree
of COD solubilization.  Figure 27 shows' the percent COD solubilized as a
                                     66

-------
   100
    80
    60
DO
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OO
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A  30 min

    60 min
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                2.5
                 PH
3.0
                              i
Figure 26.  Effect of treatment conditions on the degree
            of zinc solubilization for Fitchburg WAS.,
                            67

-------
 TABLE  17.  EFFECT OF TREATMENT CONDITIONS ON SOLUBILIZATION  OF SLUDGE
             CONSTITUENTS FOR BROCKTON  PRIMARY PLUS  WAS
Treatment conditions
Time   Temp
(min)   (°C)     pH
Concentrations in wet sludge  (mg/&)
   Solids*          COD           Zinc
Tot.     Dis.    Tot.   Dis.    Tot.    Dis.
Sol utilization (%)
Sus.      Sus.  Sus.
solids    COD   zinc

10 80 2.0
2.5
3.0
— No treatment ~
90 2.0
2.5
3.0
— No treatment —
95 2.0
2.5
3.0
— - No treatment —
30 80 2.0
2.5
3.0
— No treatment —
90 2.0
2.5
3.0
— No treatment —
95 2.0
2.5
3.0
— No treatment ~
60 80 2.0
2.5
3.0
-- No treatment --
90 2.0
2.5
3.0
~ No t reatment —
95 2.0
2.5
3.0
— No .treatment —
f
50,300
50,300
43,400
43,200
44,300
43,200
54,600
53,200
50,400
52,000
50,900
41,100
43,900
46,800
41 ,400
44,600
44,800
47,900
50,900
51 ,200
43,300
41 ,500
42,400
46,100
43,800
41,500
42,300
41 ,700
46,400
44,800
40,500
42,800
50,200
54,500
40,900
44,000

7,750
7,326
4,170
711
8,580
6,800
5,220
1,740
9,300
7,140
5,280
1,330
8,820
6,360
5,410
1,260
10,410
8,190
4,930
1,100
6,550
6,980
5,060
1,360
7,960
5,080
4,190
1,770
9,060
6,960
5,680
1,220
10,530
8,860
5,320
1 ,090

51 ,400
53,700
55,600
53,100
55,400
54,200
51 ,800
51 ,000
57,700
57,500
59,400
61 ,400
60,500
55,500
'53,400
52,900
53,700
54,300
59,700
57,500
63,700
51 ,800
51 ,400
53,200
59,400
56,500
56,700
56,700
56,900
55,900
54,200
52,300
59,000
62,500
47,100
52,700

3
1
2

5
4
4
3
5
4
4
3
4
3
4
3
4
4
3
1
4
5
5
3
5
4
4
3
5
4
4
2
6
5
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,200
,640
,480
800
,290
,130
,570
,060
,830
,850
,750
,000
,680
,760
,340
,470
,710
,010
,540
,640
,940
,020
,180
,430
,270
,330
,540
,180
,680
,590
,500
,990
,550
,550
,100
,780

70
72
73
74
77
76
83
79
84
86
90
72
82
86
88
89
70
73
84
71
71
75
71
71
82
90
79
89
85
82
88
79
90
95
84
77.

27
20
0.8
0.1
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1.1
0.6
0.3
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0.8
0.2
0.2
14
0.5
0.3
0.2
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0.3
0.2
0.2
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0.4
0.2
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0.3
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0.2
0.2
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• 0.2
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3.4
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1.7

5.9
4.5
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2.5
3.3
3.6


3.7
2.2
2.5


5.0
3.0
3.0


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5.3
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38.5
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17.9
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16.9
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22.6
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15.6
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   * Treated samples include sulfate solids  added as
                                       ,68

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                                   70

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 function of pH for different digestion times and temperatures.  These data do
 not  indicate a consistent monotonic variation of COD sol utilization with any
 of the  three factors investigated, and the significance of all the factors
 plus one interaction may be attributable to the small estimated error
 calculated for this set of tests.  It would be advisable to repeat the
 analysis of variance using the two-way interactions in addition to the three-
 way  interaction to estimate the experimental error before testing the
 significance of the main factors.

     For zinc, only the pH was observed to have a significant effect on
 solubilization.  Therefore the results obtained at each pH for the nine
 different time and temperature combinations were averaged to give the
 following mean solubilization and 95% confidence intervals.
          EH

          3.0
          2.5
          2.0
  Mean Percent
Zinc Solubilized

      0.2
      5.2
     17.1
95% Confidence
   Interval

   ± 0.25
   ± 6.9
   ± 8.4
The  95% confidence intervals are quite large, reflecting the large range over
which  the degree of solubilization varied at each pH.  For example, the degree
of solubilization at pH 2.0 ranged from zero to 38.5 percent.  It is note-
worthy that the degree of zinc solubilization was substantially less than for
the  unmixed Brockton WAS (which gave 55% solubilized at pH 2.0).

     Fitchburq Primary Plus Waste Activated Sludge—Solubilization results for
the  50:50 mixture of Fitchburg primary and WAS are shown in Table 19.   The
average concentrations and standard deviations for the nine raw sludge samples
are:
                                   Mean Concentration    Standard Deviation
Total Solids (mg/1)
Dissolved Solids (mg/1)
Total COD (mg/1)
Dissolved COD (mg/1)
Total Zinc (mg/1)
Dissolved Zinc (mg/1)
    42,200
     2,030
    36,400
     2,920
        24
         1
    .11,800
        620
     11,000
        710
          7
          0.5
With the exception of dissolved zinc, the standard deviation relative to the
mean is approximately the same for the total  and dissolved constituents
(ratios from 0.24 to 0.30).  The scatter in results for dissolved con-
stituents can be attributed to changed during storage.   The scatter in results
for total constituents can be attributed largely to sampling inaccuracies
resulting from the presence of relatively large clumps  of solids  in this
sludge sample.  These sampling errors can occur each time a portion of a
sample of sludge is transferred from one container to another.

     The results of the analysis of variance  for the Fitchburg  primary plus
secondary sludge mixture are given in Table 20.  For suspended  solids, none
of the factors or interactions had a significant effect on the  degree of
                                       71

-------
TABLE 19.  EFFECT OF TREATMENT CONDITIONS ON  SOLUBILIZATION OF SLUDGE CON-
           STITUENTS FOR FITCHBURG PRIMARY  PLUS  WAS

Treatment conditions
Time Temp.
(min) (°C) pH
10


— No



~ No



— No
30


~ No



-- No



-- No
60


— No



-- No



-- No
80


2.0
2.5
3.0
treatment —
90


2.0
2.5
3.0
treatment —
95


2.0
2.5
3.0
treatment —
80


2.0
2.5
3.0
treatment —
90


2.0
2.5
3.0
treatment —
95


2.0
2.5
3.0
treatment —
80


2.0
2.5
3.0
treatment —
90


2.0
2.5
3.0
treatment — -
95


2.0
2.5
3.0
•treatment —
Concentrations in wet sludge
Solids* COD
Tot. Dis. Tot. Dis.
31 ,200
16,500
31,500
50,400
30,500
39,900
34,900
50,700
33,900
35,400
34,300
49,300
40,600
43,200
21 ,200
50,200
43,600
21,100
26,500
28,900
41 ,800
50,600
24,800
52,200
28,700
24,500
19,700
32,600
15,900
14,400
20,200
20,300
41,900
28,300
38,000
45,100
12,170
6,320
5', 220
1,470
6,680
6,820
4,120
2,170
7,380
5,860
3,480
1,760
6,360
6,160
3,400
1 ,820
20,600.
10,830
3,680
1,270
8,040
6,890
5,890
2,220
7,520
8,010
4,380
3,360
6,620
6,700
4,740
2,410
9,090
6,470
5,040
1,760
42,500
42,000
43,600
39,200
31,300
22,100
24,800
52,900'
39,700
33,200
52,200
43,600
51 ,800
40,700
25,300
37,100
29,200
24,400
26,400
36,400
35,200
30,000
30,900
45,800
'26,300
20,500
26,700
31 ,800
22,500
21 ,700
33,400
21,700
51,200
38,000
29,000
18,800
3,450
2,880
2,740
2,040
4,690
4,390
4,640
3,770
4,250
3,850
4,450
3,240
3,980
3,500
3,140
2,840
2,900
2,720
2,540
1,960
5,480
5,280
5,120
3,990
3,900
3,860
3,110
2,910
3,700
3,770
3,790
3,180
4,380
4,060
3,000
2,360
(mg/a)
Zinc
Tot. Dis.
25
20
20
26
22
15
15
34
18
21
21
25
29
21
15
27
18
17
16
20
28
22
19
34
20
20
13
23
19
15
15
14
24
20
14
15
18
12
10
1
12
10
2
1
12
9
2
2
11
12
2
0.7
13
12
6
0.5
19
12
3
0.8
15
14
5
1
11
7
2
1.8
16
14
4
0.9
Solubilization (%)
Sus. Sus. Sus.
solids COD zinc
24.6 .
12.1
7.1
----
1.6
4.0
1.8
	
5.3
2.7
1.1
	
1.2
2.8
3.9
	
39.4
37.9
4.4
— — — -
4.7
3.1
10.8
.'-- —
0.1
7.7
0.0
	 .
0.9
11.7
5.8
	
8.9 '
6.2
5.5

3.5
2.1
1.7
-- —
3.3
3.4
4.1
	
2.8
2.0
2.5
	 	
2.3
1.7
1.3
	
3.5
3.4
2.4
— — — —
4.8
5.0
4.2
— 	 —
4.2
5.4
0.8
— - — —
2.7
3.2
2.0
	
4.1
4.8
2.5

70.8
57.9
52.6
	
52.4
64.3
7.1
_: —
62.3
36.8
0.0
	
36.4
55.7
9.1
	
71.4
69.7
35.5
— ~ - —
66.9
52.8
12.1
— — — —
73.7
68.4
33.3
_____
53.5
• 9.1
1.5
	
65.4
65.6
23.7

    * Treated samples include sulfate solids added as
                                      72

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sol utilization.  The mean  sol utilization for suspended solids (average  of 27
data points) and 95% confidence interval  are:

         Percent Suspended Solids Sol utilized = 8.0% ± 4%

The large confidence interval reflects the wide range of values obtained and
implies a higher level of experimental error associated with the tests on this
siudge.

    For COD sol utilization, temperature,  pH, and toth the time-temperature
and the time-pH interactions were significant.  Figure 28 shows the percent
COD solutilized as a function of pH for various digestion times.  The degree
of COD sol utilization was atout the same  for toth pH 2.0 and 2.5, while
pH 3.0 gave relatively low COD sol utilizations.  In general, COD solutili-
zation increased with increasing temperature.  However, with the exception
of pH 3 and 80°C, the mean degree of COD  solutilization was tetween 3 and
4% for all conditions tested.  Thus, the  selection of conditions does not
appear to have a dramatic influence on COD solutilization.

    For zinc solutilization, pH was the only significant variable, and the
time-temperature interactions was the only significant interaction.  The
results at each pH (nine tests) were averaged to give the mean solutilization
and 95% confidence intervals shown telow.
         3.0
         2.5
         2.0
  Mean Percent
Zinc Solutilized

      19%
      53%
      61%
95% Confidence
   Interval

    ± 14%
    ± 15%
    ±  9%
The degree of zinc solutilization for this sludge sample is approximately
the same as for the sample of Fitchturg WAS at pH 2.0 and 2.5 and is
significantly greater than for the primary-WAS mixture of Brockton sludge.

Summary of Metals Sol utilizations at Various pH's—
    In addition to the matrix of tests described atove, metals sol utili-
zations were determined for various other tests.  Most of these other tests
were conducted with Brockton waste activated sludge.   As shown i.n Tatle 14,
pH is the only factor that is significant at the 95%  confidence level  for
solubilization of zinc bound by this sludge.  Therefore the results of all
the tests can te presented as a function of pH only.   Tatle 21  summarizes
the metals solutilization results for Brockton WAS.  These results include
the full factorial experiments descrited above, averaged over time and
temperature at the indicated pH.

    Of the various metals assayed, zinc was the easiest to solubilize,
chrome and lead were more difficult to solubilize, and the solubilization of
cadmium was highly variable.  In general the degree of solubilization
increased with decreasing pH, but the range of solubilization at each pH
was quite broad.  The variatility of results, particularly for cadmium led
                                     74

-------
                D
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                               Deviation
                 2.0
2.5
PH
3.0
       Figure 28.  Effect of treatment conditions on  the
                   degree of COD solubilization  for
                   Fitchburg primary plus WAS.
                             75

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76

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to questions on analytical  accuracy.  A number of samples were therefore
submitted to the Municipal  Environmental  Research Laboratory of EPA for an
independent check on the accuracy of Wai den analyses.   The results from the
two analytical laboratories are compared in Appendix A.  It is concluded that
there is, in general, good agreement between the two laboratories and that
the Wai den results are at least as consistent as those obtained by EPA.  The
broad range in the degree of solubility at a given pH is probably attributabl
to a difference between the bulk pH and the acidity at specific reaction,
sites (see Section 6.)

Destruction of Pathogens

     Several analyses were conducted to assess the extent of pathogen
destruction during hot acid treatment.  Following treatment at pH 2.5, 95°C,
and 10 minutes digestion time, samples of the treated sludge cake for each
of the four sludges tested were submitted for bacteria analyses.  Samples
of each of the raw sludges were also submitted.  Fecal coliform and fecal
streptococcus were selected as indicators of pathogenic activity.  The
analytical results, shown in Table 22, indicate essentially complete de-
struction of both fecal coliform and fecal streptococcus

ASSESSMENT OF BENCH-SCALE OPTIMIZATION TESTS

     The bench-scale process studies described above are useful for deter-
mining general process characteristics and estimating the technical and
economic feasibility of the hot acid process.  However, because of the bio-
chemical changes that can occur in sludge, it is dangerous to draw un-
qualified conclusions on the basis of bench-scale tests.  In addition, the
process may behave differently under on-site, dynamic-flow conditions as
opposed to the remote, static conditions investigated during this program.
Thus the objective of bench-scale tests should be to indicate the potential
of the process rather than to provide definitive process design data.

     One of the major cost elements for the hot-acid process is the cost of
acid required to reduce the pH of the sludge.  Based on the results of
Figure 12 and on a sulfuric acid cost of $49.50/metric ton ($45/short ton)
for concentrated (98%) acid, the approximate acid cost as a function of pH ,
would be:                  ,
          2IL
          3.0
          2.5
          2.0
          1.5
   Acid  Cost
($/dmt solids!

       2.40
       4.35
       5.80
      10.10
   Acid Cost
($/dst solids)

     2.20
     3.95
     5.30
     9.20
                                     77

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      TABLE 22.  BACTERIAL ASSAYS FOR RAW AND HOT-ACID-TREATED SLUDGES
       Sludge sample
Fecal  Streptococcus,
   counts/100 ml
Fecal Coliform,
counts/100 ml
Brockton WAS

   Raw
   Hot acid treated

Brockton primary plus WAS

   Raw
   Hot acid treated

Fitchburg WAS

   Raw
   Hot acid treated

Fitchburg primary plus WAS

   Raw
   Hot acid treated
      3.3xl06
       <100
                               9.6xl07
                                <100
   3.5xl07
    <100
                               4.2xl08
                                <100
                               2.8xl08
                                <100
                                     78

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The acid cost for operating at pH 2.0 is quite reasonable and even at pH 1.5
the cost for acid is not highly excessive.   The economics of the hot acid
process will be considered in detail in Section 9, but based on the above
costs, operation at pH's as low as 1.5 cannot be ruled out.

     The question of relative acid demand of the liquid and  solid fractions
of the sludge was not directly addressed during the tests covered in this
section.  However, during the tests described in Section 6,  a sample of
Milwaukee WAS containing 1.7% solids was acidified to pH 1.9 and a sample of
filtrate from the same sludge was acidified to the same pH.   Based on the
relative amounts of acid added, three-fourth of the acid demand was in the
liquid fraction.  For the raw sludge sample the acid demand  calculated on a
wet sludge basis (6.4 kg/wmt) is in good agreement with the  data of Figure 13,
but the acid demand calculated on a dry solids basis (375 kg/dmt) is nearly
three times as great as the data of Figure 12 would indicate.  These results
indicate an appreciable acid demand for the liquid fraction  and suggest that
the acid requirement for the process can be significantly reduced by im-
proved thickening of the sludge prior to hot acid treatment.  During the
tests described in this section, the solids concentration of the sludges
generally ranged from 2.5 to 4.5%.  Significantly higher solids concentrations
have been reported (10) for both activated (6.5%) and mixtures of activated
and primary (8.6%) sludges produced by flotation thickening  without chemical
additives.

     A  second technique that could be used to reduce acid costs is the use of
waste acid rather than commercial sulfuric acid.  Tests were conducted with
a waste pickle liquor obtained from a local galvanizing shop.  Two samples of
Brockton waste activated sludge were adjusted to pH 2.5:  one with concen-
trated  sulfuric acid, the other with waste pickle liquor.  The samples were
digested at 95°C for 10 minutes prior to determining the settling, filtration,
and centrifugation rates.  Because of the very low solids concentration for
the sludge sample tested (-1% solids) solid-liquid separation rates for the
H2S04~treated sample were quite rapid; however the waste pickle liquor appear-
ed to significantly hinder the rate of solid-liquid separation.  In addition
the waste pickle liquor contained high concentrations of some heavy metals,
e.g. 61,000 mg/1 zinc.  Considering the quantity of waste pickle liquor
required for pH adjustment (23.5 ml/liter of sludge), it is  possible to show
by calculation that the amount of zinc remaining in the dewatered sludge
(in the bound and interstitial water) is greater than the amount of zinc
bound in the raw sludge even if the treated sludge is dewatered to impossibly
high solids levels.  Thus it would be necessary to either wash the cake
solids  or to select waste pickle liquors, containing low concentrations of the
more toxic heavy metals.  Furthermore, heavy metals added with the waste
pickle  liquor would increase the cost for metals removal from the liquid
stream  prior to recycle to secondary treatment.  Other sources of waste acid
or low-cost acid .were neither identified nor evaluated; however the results
with waste pickle liquor suggest a cautious approach to the  selection of
substitute acids.
                                      79

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     The solid-liquid separation tests  provided preliminary  information on
the feasibility of three solids separation techniques  (settling,  filtration,
and centrifugation) and on the effects  of the primary  process  variables
(pH, temperature, and time) on the rates of solid-liquid  separation.   Because
of  the difficulties inherent in using bench-scale tests to predict the per-
formance of full-scale equipment, the bench-scale tests were used to select
the perferred solid-liquid separation technique.  Pilot scale tests were  then
conducted to develop quantitative design information for the selected techni-
que.  These results are presented and discussed in Section 7.

      Table  23  summarizes  the  effects of th'e  primary process variables on
 solid-liquid separation rates  for the  four sludges tested.  For each sludge
 the variables  having a significant effect, at the 95%  confidence level, on
 solids  separation rate are listed in order of decreasing  significance.  In
 general,  pH is  the variable with  greatest influence on solid-liquid
 separation  followed by temperature and then time.  It  is  also of interest to
 note that the  same variables  are, in general, significant for both settling
 and centrifugation suggesting that the mechanism of solid-liquid separation
 is similar  for these techniques and that their difference lies merely in-the
 different gravitational  accelerations  used.   The preferred  levels of the
 operating variables for solids separation are also given  in Table  23.  For
 all sludqes,  the optimum pH is 2.5. The preferred temperature level  is 90-
 95°C, with  95°C more generally appropriate,  and the preferred time, which is
 not a critical  variable,  is 10-60 minutes, with 30 minutes  representing a
 suitable  compromise.

      During the full-factorial optimization tests,  the effect of the major
 process variables on solubilization of various sludge  constituents was
 evaluated.   Table 24 summarizes the variables found to be significant at the
 95% confidence level.  The variables are listed in  order of decreasing
 significance for each sludge.

      None of the variables investigated appeared to have a  significant effect
 on the solubilization of suspended solids.  This result  is  somewhat  sur-
 prising since  the suspended solids include both organics and metals,  for
 which the variables investigated were  determined to significantly  affect
 solubilization.  That is, as the pH is lowered, the solubilization  of both
 organics and metals increase, and one  would therefore expect an  increase in
 suspended solids solubilization as the pH is lowered.  Analyses  conducted  on
 the Fitchburg secondary sludge indicated that an average of 62.5%  (range of
 9 analyses:  60.1% - 64.6%) of the total solids in  the raw  sludge  were
 volatile solids.  Assuming the volatile solids consisted primarily of organics,
 the effect of pK on suspended organics and suspended  solids should be similar.
 A possible  explanation of this apparent anomalie lies  in the  assumption  that
 the sulfate added as H2S04 remains dissolved.  If a portion of the  sulfate
 becomes bound to the solids, then the  percent solubilization  as  calculated by
 Equations (1),  (3), and (4) would be too low, and the size  of the  error  would
 increase with the amount of I^SO^ added.  This would  have the effect of
 canceling out the pH dependence for suspended solids  solubilization. The  lack
 of a pH dependence for suspended solids solubilization could also  be explained
 by postulating  that a decrease in pH increases either the volatilization or
                                    80

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 the  fixation  by  solids of  dissolved  inorganics other than sulfate.  However,
 from a  practical  point of  view,  it is really  the solubilization of organic
 solids  rather than  total soli'ds  that is  important  in assessing the additional
 loading imposed  on  the treatment system  by  recycle.  Thus the solubilization
 of inorganics could be viewed as being of little importance.

      As shown in  Table 24  the pH had a significant effect on the solubiliza-
 tion of COD and  zinc for all sludges tested.  The  temperature was a
 significant variable for COD solubilization but not for zinc solubilization,
 and  the time  was  not generally significant  for either COD or zinc
 solubilization.

      For optimum results it is desirable to minimize COD solubilization and
 maximize zinc solubilization.  However,  since the  solubilization of both COD
 and  zinc increases  with decreasing pH, some compromise must be reached.
 Determination of the preferred pH level  would require an economic optimi-
 zation  which  would  contain some  very site-specific elements (such as the
 levels  of metals  in the sludge and the cost penalty for organics recycle).

      From Table  24  it would appear that  operation  at low temperature could
 be used to minimize COD solubilization without affecting zinc solubilization.
 Although this approach may be of some use,  the solid-liquid separation
 becomes more  difficult as  the temperature is  decreased below 90°C.  Again,
 an economic optimum would  have to be defined  to properly balance tne
 opposing effects.

      The bench-scale tests were  useful in demonstrating that the hot acid
 process has the  potential  for solubilizing  significant quantities of certain
 heavy metals. As shown in Table 21, solubilization ranged up to 100% for
 zinc, 90% for cadmium, 44% for chrome, and  45% for lead at pH's of 1.5 or
 above.   In addition, results to  be presented  in Section 5 indicate good
 solubilization of nickel.  While these results demonstrate the potential of
 the  process for  heavy metals removal, the degree of removal obtained in
 these tests was  highly variable,  e.g., cadmium solubilization at pH 2.5
 varied  from 0 to  90%.  This suggests that either the characteristics of the
 particular sludge sample had a large influence on  solubilization or there was
 some uncontrolled process  variable (e.g. pH localization) responsible for the
 inconsistent  results.  Further tests were conducted to specifically evaluate
"heavy metals  solubilization, and the results  of these tests are presented and
 discussed in  Section 6.  In brief, high  and consistent solubilization of
 heavy metals  were obtained with  various  sludge samples during these latter
 tests.   These results confirm the conclusion  that  the hot acid process has
 the  potential for significant heavy  metals  removal from sludge.

      Although the number of bacterial assays  performed during the bench-
 scale tests were minimal,  they confirmed the  expectation that the hot acid
 process effectively destroys all  pathogens.   Pasteurization (exposure to
 high temperature for an adequate period  of  time) has long been recognized
                                     83

-------
and used as an effective disinfection technique.  The generally accepted
conditions for sludge pasteurization (11)are a temperature of 70°C and
holding times of 30 minutes to 1 hour.  Table 25 (12)gives the holding times
at temperatures of 70°C and below required to completely eliminate the
various types of pathogens listed.  It is evident from these data that the
temperatures and times employed in the hot acid process would be more than
sufficient to completely destroy all pathogens.  In addition, the use of low
pH should increase the rate of pathogen destruction.

     Based on the bench-scale optimization tests and the above discussion of
the state of advancement of the hot acid process, the potential advantages and
disadvantages of the process are listed in Table 26.  The unique potential
advantage of the process is its ability to remove heavy metals from the sludge
solids.  The trade-off between advantages and disadvantages must eventually
be reduced to an economic assessment of the hot acid process relative to
other acceptable alternatives.  A preliminary analysis of the process eco-
nomics is given in Section 9.

     The next step in the development of the process should be the design,
installation, and operation of a transportable pilot system at various
municipal wastewater treatment plants.  Operation of a pilot system will
provide data under dynamic flow conditions similar to a full-scale plant and
will provide data unaffected by sludge age.  The operation of a pilot system
is considered essential to the further development, optimization, and
verification of the hot acid process.
                                     84  '

-------
       .TABLE 25.  EFFECT OF TIME AND TEMPERATURE ON THE SURVIVAL OF
                   TYPICAL PATHOGENS FOUND IN SLUDGE*.'(iz)

Organism
Cysts of Entamoeba histolytica
Eggs of Ascaris lumbricoides
Bruce! la abortus
Corynebacterium diphtheria
Salmonella tyhposa
Escherichia coli
Micrococcus pyrogene var. aursus
Mycobacteri urn tubercul os i s var . promi xi s
Viruses
Temperature °C
50 55 60 65 70

5
60 7
60 3
45 4
30 4
60 5
20
20
25
*Pathogens completely eliminated at indicated time and temperature.
                                     85

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   TABLE 26.  POTENTIAL ADVANTAGES AND DISADVANTAGES OF HOT ACID TREATMENT
       Potential advantages
                                         Potential disadvantages
1.


2.


3.


4.
Improves solid-liquid separation  1
rate and cake dryness
    Solubilizes some organics
Removes toxic heavy metals from
sludge solids

Destroys all pathogens
2.  Requires heat and chemical  addition
    Requires corrosion-resistant
    materials of construction
Produces solids suitable for land
application or animal-feed supp-
1ement
                                     86

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                                  SECTION  5

                 COMPARISON WITH ALTERNATIVE  CONDITIONING  PROCESSES
      It is of interest to compare the performance of the hot acid process to
 the performance of alternative sludge conditioning processes.  Bench-scale
 tests were conducted to compare the hot acid treatment with thermal treat-
 ment, ferric chloride treatment and polymer treatment.  In addition* a
 literature review was performed to identify the characteristics of aerobic
 and anaerobic stabilization relative to the hot acid treatment process.

 BENCH-SCALE COMPARISON OF CONDITIONING ALTERNATIVES

     Bench-scale tests were conducted to directly compare various alternatives
 for conditioning the same sample of waste activated sludge.  The various
 conditioning alternatives were compared both with respect to solid-liquid
 separation rates and to solubilization of sludge constituents.

 Methods and Materials^

     The experimental apparatus and procedures for the hot acid treatment
 process were essentially identical to those described in Section 4.  A
 one-liter sample of the sludge was treated at conditions of pH 2.5, 95°C,
 and 10 minutes digestion time.

     For thermal conditioning, a 150-ml  sample of sludge was placed in a
 high-pressure, stainless-steel, gas sampling cylinder fitted with a
 pressure gauge and thermocouple.  The sealed cylinder was wrapped with
 heating tape and placed on a wrist-action shaker to provide mild agitation.
 The temperature during treatment was maintained within the range of 180-
 190°C and the time at temperature was 30 minutes.  These conditions were
 selected on the basis of typical commercial  practice (7 ) (30-40 minute
 detention time at temperatures of 170-205°C).

     Ferric chloride was added as a 10%  solution to a one-liter sample of
 raw sludge.  In order to select the preferred  dosage, preliminary tests
were conducted with the same sludge to determine the effect of dosage on
 the solid-liquid separation rate.

     A cationic polymer concentrate (Calgon  Corp. WT-2860)  was diluted to
 10% of its initial  concentration (concentrate  = 15% solids) and added to a
one-liter sample of sludge.   As for ferric chloride, the polymer dosage
was selected on the basis of preliminary tests  at various dosages.
                                     87

-------
     All  tests were conducted on a single sample of Brockton waste activated
 sludge.   The sample was obtained in the morning, and all tests were con-
 ducted during that same working day.  The total solids concentration of the
 raw sludge was 2.5%.

     The  same apparatus and procedures as described in Section 4 were used to
 determine filtration and centrifugation characteristics.  The sampling and
 analysis  procedures were also similar to those described previously.  Because
 of the small volume of sludge subjected to thermal treatment, the rates  of
 settling  after treatment were not compared.

 Results and Discussion

 Selection of Chemical Dosages-
     Figures 29 and 30 show the rates of filtration and centrifugation,
 respectively for various dosages of ferric chloride.  The dosages ranged from
 0.016 to  0.80 g FeCls/g solids.  Over this range, the rates of both filtration
 and centrifugation increased with dosage.  However, the improvement in solid-
 liquid separation rate diminished beyond a dosage of 0.16 g/g solids, which
 was therefore selected as the preferred dosage for this sludge.

     Similar tests were conducted with various polymer dosages ranging from
 0.008 to 0.4 g of polymer concentrate per g solids.  Filtration  and
 centrifugation results for the various dosages are shown in Figures 31  and
 32, respectively.  The rate of solid-liquid separation for both  filtration
 and centrifugation passed through a maximum at a dosage of 0.08  g/g solids.
This dosage was therefore selected for subsequent tests.

     It is of interest to note the chemical cost for the selected dosages of
 ferric chloride and polymer.  Assuming a cost for ferric chloride (13) Of
 $110/metric ton ($100/ton) the chemical cost corresponding to the selected
 dosage would be $17.60/metric ton of solids ($16/ton solids).  Based on a
 book price for the polymer concentrate (personal communication with Calgem
 Corp., Pittsburgh, PA, June 1978) of $1.06 kg ($0.48 Ib)  in tank truck lots,
 the cost for polymer at the selected dosage would be $85/dmt solids ($77/dst
 solids).   Because of the high cost, polymer treatment, at least  with the sel-
 ected polymer and dosage, would not be considered a viable alternative for
 the conditioning of this particular sludge.

 Comparison of Solid-Liquid Separation Rates--
     The rates of filtration following application of the various sludge
conditioning treatments are shown in Figure 33.  All of the conditioning
processes gave a substantial increase in filtration rate relative to the
untreated sludge.  The thermal conditioning process produced very rapid
filtration rates while the filtration rates for the hot acid, ferric
chloride, and polymer treatments were roughly equal* but significantly less

* It is noteworthy that the filtrate of the hot-acid-treated sample produced
  foam during this particular filtration test.  This phenominon  occurred
  sporadically from time to time and was accompanied by a significant re-
  tardation in filtration rate.   It is postulated that, in the absence of
  foaming, the hot-acid sample would have filtered at least as rapidly as
  the polymer-treated sample.

                                    88

-------
  40
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  30
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   10
                                         O 0.016 g FeCl3/g Solids
                                         A 0.032 g FeC13/Q Solids
                                         Q 0.080 g FeCl3/g Solids
                                         Q 0.160 g FeCl3/g Solids
                                         Q0.320 g FeCl3/q Solids
                                          f~] 0.800 g FeCl3/q Solids
                10
                         20         30         40
                                  TIME, MINUTES
50
60
   Figure 29.   Effect of ferric chloride dosage on the  filtration  rate of
                hot-acid-treated WAS.
                                       89

-------
  10
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O  0.016 g FeClg/g solids
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0  0.320 g FeCl3/g solids
                      0
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                              4           6
                                TIME, MINUTES
                                8
                                                          10
         Figure 30.   Effect  of  ferric chloride dosage on the centrifugation
                     rate  of hot-acid-treated WAS.
                                   90

-------
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                     O 0.008 g Polymer/g  Solids
                     A 0.024 g Polymer/g  Solids
                     D 0.08  g Polymer/g  Solids
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                     Q 0.40  g Polymer/g  Solids
 \  0s  A
                                                        10
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Figure 32.   Effect of polymer dosage on the centrifugation rate
            of hot-acid-treated WAS.
                           92

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           93

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 than  for  thermal  treatment.

      Rates of centrifugation following the various sludge treatments are
 shown in  Figure 34.  Again, all of the conditioning techniques produced a
 substantial improvement in centrifugation rate relative to the untreated
 sludge.   Thermal  treatment gave the best centrifugation rate followed by hot
 acid, polymer, and ferric chloride treatment in that order.

      From these results, it can be concluded that the hot acid process
 produced  solid-liquid separation rates which are at least as good as those
 produced  by chemical conditioning.  For centrifugation, the hot acid process
 can produce a sludge having dewatering characteristics superior to those of
 chemically conditioned sludge.

 Solubilization of Sludge Constituents—
      In addition  to the rate of. solid-liquid separation, the degree of
 Solubilization of various sludge constituents is important in comparing
 alternative sludge conditioning processes.  For sludge disposal by land
 application, the  conditioning process should, ideally, solubilize the toxic
 heavy metals without significantly solubilizing organics, phosphorus, and
 nitrogen.

     Table 27 gives the suspended solids and organics solubilizations
 obtained  with the sample of Brockton waste activated sludge.  The ferric
 chloride  and polymer treatment produced no appreciable Solubilization of
 suspended solids.  The thermal treatment solubilized one-third of the solids
 while the hot acid process solubilized about one-tenth of the solids.

     Since the supernatant from the sludge conditioning process must be
 treated,  either directly or by recycle to the secondary treatment system,
 the organic loading of the filtrate is an important parameter in judging the
 merits of alternative conditioning processes.  Both the BOD and COD of the
 various filtrates are shown in Table 27.  Of the treated samples, the organic
 loading for ferric chloride treatment was the lowest.  The higher BOD for
 the polymer-treated filtrate could have resulted from some residual  polymer
 that was  not removed with the solids.  The BOD of the hot-acid-treated
 filtrate was only slightly higher than the BOD of the polymer-treated
 filtrate.  Thermal treatment resulted in substantially greater organics
 Solubilization than for the other processes.   The high level  of organics in
 the filtrate from the thermal  process represents a significant additional
 load on the secondary treatment system.  The recycle of thermal treatment
 liquors generally results in an increase inorganic loading of approximately
 20% on the secondary treatment system (7,14).

     Table 28 further compares the solubilizations obtained with the hot acid
and thermal  processes.  (The additional analyses of Table 28 were not per-
 formed for the ferric chloride and polymer treated samples since little, if
any, Solubilization was anticipated.)  Comparing the results  for heavy metals
Solubilization,  the hot acid process solubilized significant quantities of
zinc, cadmium and nickel  but only small amounts  of lead,  chromium, and copper.
The thermal  process resulted in no significant Solubilization of heavy metals
except for nickel.  The high nickel  Solubilization for the thermal process is
questionable in  the light of the low Solubilization for other metals and in

                                     94

-------
5  6
i—i
UJ
     t
     ^i
                                 O  Hot Acid
                                 A  Fed 3
                                 O  Polymer
                                 O  Thermal
                                 O  Untreated

               \
           CN
                                                        	0  _
-   O—O--O--O—O	
                                                            -o
                                       6
                                 TIME, MIN
                                                          10
     Figure  34.  Comparison of centrifugation rates  for WAS treated by
                various conditioning processes.
                                   95

-------
TABLE 27.  SOLUBILIZATION OF SOLIDS AND ORGANICS FOR VARIOUS
           TREATMENT PROCESSES

Process
No treatment
Hot acid
Thermal
Ferric chloride
Polymer
Suspended solids
solubilization
(%)
__
11
34
1.5
1.7
Filtrate
BOD
(mg/D
310
1,300
5,600
610
1,000
Fi 1 trate
COD
(mg/D
540
2,940
11,300
830
—
COD
solubilization
(X)
__
7.8
27
0.9
—
                              96

-------
    TABLE 28.  COMPARISON OF SOLUBILIZATIONS FOR THE HOT-ACID AND
               THERMAL CONDITIONING PROCESSES


 Sludge    Process   SS  COD  Zn   Cd    Ni    Cu  Cr   Pb  P   TKN


Brockton   Hot acid  11  7.8  81   (90)   36   0   7    10  45  10
WAS

           Thermal   34  27   0.6    0   (69)  0   3     1  13  76
Milwaukee  Hot acid  11   5   47     5    79   0   1.3   0  20  8.6
WAS

*                    ~~~  ~~~~~~
  Treatment conditions for hot acid process = pH 2.5, 95°C, and
  10 min. digestion time.  Treatment conditions for thermal
  process = 180-190°C for 30 min. digestion time.

  ( ) indicates questionable or uncertain results.
                                 97

-------
the light of previous research (5) which showed no significant metals
sol utilization (including nickel) for the thermal  process.  The high
cadmium sol utilization for the hot acid process is particularly noteworthy
since cadmium is of considerable environmental concern.   However,  the 90%
cadmium solubilization was not reproducible in these tests as noted in
Section 4 (see Table 21).

     The results for phosphorus and nitrogen (total Kjeldahl  nitrogen)
solubilizations are also shown in Table 28.  For nitrogens the hot acid
process solubilized only 10% compared to 76% for the thermal  process.  The
degree of phosphorus solubilization for the hot acid process (45%) was
significantly greater for this sample than for other WAS samples tested and
was considerably greater than the degree of phosphorus solubilization for the
thermal process.

     Table 28 also shows the solubilization results for hot acid treatment of
Milwaukee WAS.  The solubilizations of suspended solids and COD were essen-
tially identical to those obtained for the Brockton sludge.  Good
solubilizations of zinc and nickel were obtained for the Milwaukee sludge,
but the solubilization of cadmium was low.  Copper, chromium, and  lead
were not solubilized.  The 20% phosphorus solubilization was more  typical
than for the Brockton sludge, and the nitrogen solubilization was  about the
same as for the Brockton sludge.

     These solubilization results indicate that the hot acid process exhibits
a number of advantages over thermal treatment.  Relative to thermal  treat-
ment, the hot acid process:

     — produces lower solubilization of solids,
     — produces lower solubilization of organics,
     — produces lower solubilization of nitrogen, and
     — has better potential for removal of toxic heavy metals.

As a result of these advantages, the sludge produced by the hot acid process
should be much more desirable for land application than sludge from a
thermal treatment process.

CHARACTERISTICS OF BIOLOGICAL STABILIZATION

     Of the various stabilization processes, anaerobic and aerobic digestion
are the most widely used.  Although experiments were not conducted with
these processes, it is possible to make some general comparisons between
these processes and the hot acid and thermal treatment processes.

Solid-Liquid Separation

     Both anaerobic and aerobic digestion improve  the dewaterability of the
treated sludge (generally a mixture of primary and waste activated sludge),
but the degree of improvement is not sufficient to permit direct dewatering
of the digested sludge.  Chemical conditioning of  digested sludge, with
lime, ferric, and/or polymer is generally required prior to dewatering.
                                     98

-------
                                   1 g
Estimates of chemical requirements (   ) (based on experience at different
treatment plants in the United States) are shown for raw and anaerobically
digested sludge in Table 29.  The chemical cost for conditioning
anaerobically digested sludge can considerably exceed that for raw sludge
because the high concentration of carbonates produced during anaerobic
digestion inhibits coagulation of the solids with ferric chloride.  Similarly,
aerobically digested sludg.es generally have been found to have poor de-
watering characteristics ('6).

Reduction of Solids

     Both anaerobic and aerobic digestion reduce the volume of solids
requiring disposal.  In anaerobic digestion organic solids are converted to
volatile organic acids which are, in turn, converted primarily to methane
and carbon dioxide.  Thus a portion of the raw sludge solids is converted
to a gas mixture which can be recovered and used for fuel (heating valued5)
5,300-7,100 kcal/m3 [600-800 Btu/ftJ]).   Anaerobic digestion can typically
achieve (on a dry basis) a 25% reduction in sludge total  solids and 35%
reduction in sludge volatile solids (15).

     Aerobic digestion also reduces the volume of solids  requiring disposal.
The primary mechanism-for solids reduction is endogenous  respiration in
which cellular matter is biologically oxidized.  Aerobic  digestion can
achieve (on a dry basis) total  solids reductions of 25%-35% with corresponding
volatile solids reductions of 40%-50% (15).

Pathogen Destruction

     Both aerobic and anaerobic digestion reduce the concentration of patho-
genic organisms.  For anaerobic digestion, digestion conditions are not
lethal  to most pathogens, but are not conductive to multiplication.  Thus
pathogen destruction appears related to a natural  die-off with time 05 ).
Anaerobic digestion has been rated (11)as "fair" (1 to 3  logs reduction) for
destruction of pathogenic bacteria (Salmonella) and "poor" (less than 1  log
reduction)  for viruses.  Aerobic digestion has been rated as "poor" for
pathogen removal;  however the potential  for virus  removal was unknown.

Supernatant Quality

     The quality of the supernatants from anaerobic and aerobic treatment 15)
are compared in Table 30.  The  variability in the  parameters listed results
primarily from differences in the digester designs  and the efficiency of
solids  separation.   For comparison purposes,  the supernatant quality from
thermal  treatment is also shown in Table  30.   In general, aerobic digestion
produces the highest quality supernatant  followed  in order by anaerobic
digestion and thermal  treatment.   Undoubetedly, much of the organic loading
of the  supernatants from biological  digestion arises from the presence of
biological  solids.   On the other hand,  the organics loading of the thermal
treatment liquor is largely dissolved (compare results of Table 27) and
represents  a much  more difficult treatment problem than the biological
supernatants.
                                     99

-------








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Heavy Metals Removal

     Anaerobic and aerobic digestion do not release any significant
of heavy metals from the sludge solids.  In fact, it has been found O7/
soluble metals are incorporated into the biomass during anaerobic digestion.
Measurements have been madeUS) on the extractability of heavy metals from
anaerobically and aerobically digested sludges using water and EDTA.  The
water extractability of cadmium, lead, and zinc remained uneffected by
anaerobic digestion, while nickel and copper became less extractable.  The
water extractability of chromium, copper, and zinc increased following
aerobic digestion, but that of cadmium, nickel, and lead remained unchanged.
However, in all cases the water extractability of metals remained low, i.e.,
at a level of less than 10 percent of the EDTA extractability of the metals.
Therefore it is concluded that neither anaerobic nor aerobic digestion result
in any significant removal of heavy metals from sludge.

DISCUSSION AND CONCLUSIONS

     The sludge treatment processes considered above fall  into four main
categories:

     — chemical treatment (polymer or inorganic chemicals),
     — biological digestion (anaerobic or aerobic),
     — thermal treatment, and
     — hot acid treatment.

These four categories are discussed below with respect to  process perfor-
mance characteristics.  The economics of the various treatment alternatives
are considered in Section 9.

     Considering current recommendations for the disposal  of wastewater
sludges (l ), it appears to be necessary to stabilize the  sludge (with
treatment equivalent to anaerobic digestion) prior to disposal  by land
application or sanitary landfill.  Since ocean dumping is  being phased out,
incineration is the only major disposal technique which does not require
prior sludge stabilization.  However, incineration is a volume reduction
technique rather than an ultimate disposal  technique and,  as such, should be
considered as a stabilization rather than a disposal process.  Thus the need
for stabilization prior to ultimate disposal appears to be quite general.
Chemical treatment, as generally practiced for dewatering, will  not produce
a disposable sludge since the process does not stabilize the sludge solids.

     As noted above, biological  digestion produces a stabilized sludge, but
the sludge cannot generally be dewatered without chemical  conditioning.
Thus biological stabilization requires chemical  conditioning, and chemical
conditioning requires biological  (or other) stabilization.  On the other hand!
both thermal treatment and, ideally, hot acid treatment produce a stabilized,
dewaterable sludge in a single processing step.   Therefore, in comparing
various sludge conditioning alternatives, three categories may be considered:

     — biological stabilization with chemical  conditioning,
     — thermal treatment, and
     — hot acid treatment.
                                     102

-------
     The performance characteristics of the above alternatives are  compared
in Table 31.  While this type of comparison can highlight general character-
istics of the alternative processes, the final  selection must be based on an
economic assessment which includes consideration of ultimate disposal.
Nevertheless it can be concluded from'Table 31  that the hot acid process
compares quite favorably to the other two alternatives.
                                     103

-------
          TABLE 31.  COMPARISON OF SLUDGE CONDITIONING ALTERNATIVES
   Performance characteristic
Biological/
 chemical
 treatment
Thermal
treatment
  Hot
  acid
treatment
Solids separation           "          Good
Pathogen destruction                  Fair
Putrefaction potential                Good
Supernatant organics (dissolved)      Good
Heavy metals removal                  Poor
Solids nitrogen                       Good
                Excellent
                Excellent
                Fair
                Poor
                Poor
                Poor
               Good (?)
               Excellent
               Fair (?)
               Fair
               Good
               Good
                                    104

-------
                                 SECTION 6

                     RE-EVALUATION OF HEAVY METALS SOLUBILIZATION
     As discussed in Section 4 and 5 the hot acid process has several
potential advantages over alternative conditioning techniques.  The most
unique advantage is its potential for sol utilization and removal of toxic
heavy metals.  Of particular importance is the removal  of cadmium because
of its tendency to accumulate in certain agricultural  crops.   The degree of
cadmium sol utilization obtained in previous tests (see Table  21) was quite
erratic, ranging from 90% in one test at pH 2.5 to essentially zero in other
tests conducted at the same pH.


     Additional tests were undertaken to  focus primarily on heavy metals
solubilization and to attempt to resolve the erratic results  observed in
previous tests.  Several variables were investigated for their effect on the
degree of solubilization.  These included:  amount of acid added, stirring
speed, heating before acidification vs. acidification before  heating, di-
gestion time, and source of sludge.  A different digestion apparatus was
used for these tests which permitted the use of larger sludge  samples, better
control of operating conditions, and wider variability of stirring speed.

METHODS AND MATERIALS

     A schematic diagram of the digestion apparatus is  shown  in Figure 35.
The digestion was conducted in a 14-liter fermenter constructed of pyrex
glass with a stainless-steel top plate and internals.   The reactor con-
tained four vertical baffles., a turbine mixer, a single orifice sparger,
pH/reference electrodes, a thermocouple well, a sample  withdrawal  tube,
and two 1000-watt Vycor immersion heaters.  With two heaters  each operated
at 110 volts, the time required to heat 8 liters of sludge to 95°C was
about 35 minutes, and rapid stirring (600 rpm) was used to prevent local
overheating of the sludge.  All tests were conducted at 959C.

     In previous tests the pH of the sludge was always  adjusted to the
desired level prior to heating; however in some of the  tests  reported in
this section, acid was added after heating to the digestion temperature.
This necessitated the measurement of pH at elevated temperatures, which
proved to be somewhat inaccurate.  For these samples the pH values reported
in this section were measured after the digested sample had cooled to room
temperature.

     Following digestion a sample of the treated sludge was obtained for
                                     105

-------
                    Stirrer Motor



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            evaluate heavy metals  sol utilization.
                              106

-------
analysis.  The sample was allowed to cool and was divided into two portions.
One portion was submitted for analysis without further treatment (treated
sludge sample).  The other sample was centrifuged and the centrate passed
through a 0.45u Millipore filter before submission for analysis (treated
sludge filtrate sample).  A similar treatment was applied to a sample of
the raw sludge to give a raw sludge sample and a raw sludge filtrate sample.
All samples were preserved by refrigeration until analysis, and analytical
work on the samples was initiated within 24 hours.  The same analytical
techniques and calculational procedures as described in Section 4 were used
for these tests.

     Fresh samples of WAS were obtained for all tests (with the exception
of a few tests conducted on Milwaukee WAS).  The samples were obtained in
the morning and the tests were conducted on the afternoon of the same day.

RESULTS AND DISCUSSION

     The experiments conducted to characterize heavy metals solubilization
were divided into two groups.  For the, first group, all tests were conducted
with fresh Brockton WAS to evaluate the effects of various operating condi-
tions.  For the second group of tests, the preferred operating conditions
were fixed and sludges from different cities were evaluated.  The detailed
test data, including test conditons, analytical results, and calculated
solubilizations, are given in Table 32.

     A number of operating variables were investigated in an attempt to
define the factors controlling cadmium (and other constituent) solubil-
izations,  these included:

     --apparatus (14-liter fermenter, designated 14-LF vs. one-liter
       graduated cylinders, designated 1-L6C and described in Section 4);
     --stirring speed (600 rpm vs. 60 rpm using 14-LF; stirring speed for
       1-LGC was 60 rpm);
     --order of acid heat addition (acid added before heating vs. heating
       before acid addition);
     --digestion time (30 min.vs. 60 min. not including heat-up time); and
     --amount of acid added.

     Tests were first conducted to compare the 14-liter fermenter (operated
at 600 rpm with  acid addition after heating and a digestion time of 30
minutes) to the one-liter graduated cylinders (operated at 60 rpm with
acid addition before heating and a digestion time of 30 minutes).  These
tests were somewhat inconclusive because of the difficulty in properly
adjusting the pH of hot sludge.  Therefore, in the first two tests the
amount of acid added per unit weight of sludge was different for the two
digesters.  This variable was determined to strongly influence the degree
of solubilization and could have hidden the effects of the other variables
such as digester configuration, degree of mixing, order of acid-heat ad-
dition, etc.  In the third test the amount of acid added to the two samples
was the same but was insufficient to produce any significant solubilization
of cadmium.  The solubilization of zinc was greater for the 14-liter fer-
                                     107

-------
TABLE  32.   EFFECT OF  TREATMENT CONDITIONS ON THE DEGREE OF  SOLUBILIZATION
              OF  HEAVY METALS AND OTHER SLUDGE  CONSTITUENTS.
Line
1
2
3
4
5
6
7
8
9
10
n
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
Date
2/28/78
2/28/78
9/5/78


9/11/78


9/19/78


9/25/78


10/2/78


10/10/78



10/16/78




10/23/78
10/30/79

11/6/78

11/14/78
Raw
* solids
Conditions (wt %)
Raw sludge f
14-LF, 600, HBA
Raw sludge
1-LGC, 60, ABH
14-LF, 600, HBA
Raw si udge
1-LGC, 60, ABH
14-LF, 600, HBA
Raw sludge
1-LGC, 60, ABH
14-LF, 600, HBA
Raw si udge
14-LF, 60 HBA
14-LF, 600, HBA
Raw sludge
14-LF, 600, ABH
14-LF, 600, HBA
Raw sludge
14-LF, 600, HBA
14-LF, 600, HBA
14-LF, 600, HBA
Raw sludge
14-LF, 600, HBA
14-LF, 600, HBA
14-LF, 600, HBA
14-LF, 600, HBA
Raw sludge
Optt( Brockton WAS)
Raw sludge
Optt(Fitchburg WAS)
Raw s 1 udge
Optt (Lawrence WAS)
Raw s 1 udge
OptJ (Milwaukee WAS)
Optf (Milwaukee WAS)
3.42
3.42
2.50
2.50
2.50
4.03
4.03
4.03
3.75
3.75
3.75
3.28
3.28
3.28
3.40
3.40
3.40
3.27
3.27
3.27
3.27
3.57
3.57
3.57
3.57
3.57
3.62
3.62
1.59
1.59
4.87
4.87
1.70
1.70
1.70
H2S04
added
(ml/1)
_
4 188
_
3.00
5.63
_
2.50
2.94
„
2.20
2.20
_
2.50
2.50
.
2.28
2.28
_
1.1
2.30
2.30
-
3.28
3.74
4.29
4.88
4.67
.
2.74
.
7.65
2.94
2.50
Acid
usage
kg/dmt
„
261
_
220
412
_
112
132
_
107
107
_
140
139
_
122
122
_
62
129
129
-
168
192
220
250
236
_
315
-
288
317
269
pH G
25°C
6.01
1.90
6.51
2.20
1.65
6.08
2.14
2.04
6.39
2.15
2.44
6.37
2.07
2.05
6.58
2.10
2.10
6.00
. 3.50
2.00
2.00
6.70
1.75
1.55
1.57
1.33
6.36
1.47
6.25
1.80
6.10
1.78
6.85
1.96
2.40
Digestion
time
(min)
„
30
-
30
30
.
30
30
.
30
30
-
30
30
-
30
30
-
30
30
60
-
30
30
30
30
60
-
60
-
60
60
60
         Condition Code:  14-LF « 14-liter ferraenter; 1-LGC - one-liter graduated cylinder;600 or 60
          stirring speed in rpm; HBA = heat before acid; ABH = acid before heat.

         ^ptiraum conditions for sludges from various cities were: use of 14-liter fermenter, 600 rpm
          agitation, acid addition before heating, and 60 minute digestion time.
                                              108

-------
TABLE  32.  EFFECT OF TREATMENT CONDITIONS ON THE DEGREE OF SOLUBILIZATION
            OF  HEAVY METALS  AND OTHER SLUDGE CONSTITUENTS    (continued)
Line
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25 ,
26
27
28
29 .
30
31
32
33
34
35
Solids**
Total Dis
34,200
34,400
25,000
39,183
30,117
40,800
41 ,053
39,786
37,500
39,953
41 ,574
32,800
49,453
37,053
34,000
39,043
37,043
32,700
36,287
35,600
- -
35,700
33,405
-
-
-
36,200
42,576
15,900
15,040
48,700
49,098
•17,000
17,888
"*
1,000
8,840
510
5,183
2,717
790
6,353
7,786
700
5,953
8,474
550
11,653
7,853
640
5,143
8,043
760
4,617
6,900
-
628
7,605
-
-
—
-624
8,776
268
4,370
1,050
14,098
1,340
4,688
"
COD
Tot 01s
-
45,100
59,700
54,100
46,700
5,200
54,100
47,700
51 ,400
56,800
55,200
57,000
53,600
40,000
45,000
46,000
38,000
42,000
43,000
-
43,000
41 ,000
-
-
•*
34,000
51 ,000
14,000
13,000
36,000
65,000
18,000
17,000
-•"
-
640
6,750
10,900
500
5,050
7,350
415
5,090
8,050
460
8,430
6,950
140
3,500
6,000
450
4,300
6,400
-
660
72,000
-
-
"*
420
7,900
79
2,500
1,800
10,000
900
3,800
"•
Concentrations in wet sludge (mg/1 )
Cadmium Zinc Nickel
Tot Dis Tot Dis Tot Dis
0.88
0.92
0.6
0.8
0.6
1.0
1.2
1.1
1.2
1.1
0.9
0.9
1.2
1.0
0.89
0.86
0.74
0.76
0.76
0.79
0.81
0.85
0.74
O.S7
0.66
0.77
0.87
0.97
<0.1
oil
0.34
0.38
2.3
2.3
3.2
<0.2
0.90
<0.2
0.3
0.7
<0 1
o'.2
0.5
<0.2
<0.2
O.2
0.2
0.5
0.4
O.2
0.7
O.2
;
-------
TABLE 32.   EFFECT OF TREATMENT CONDITIONS  ON  THE DEGREE OF SOLUBILIZATION
            OF HEAVY METALS AND OTHER SLUDGE CONSTITUENTS,  (concluded)
Line
1
£
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
Sol Ids
_
23.5
_
12.1
7.5
_
13.8
17.9
..
13.4
19.0
_
22.7
20.0
_
11.7
20.3
_
10.9
17.6
-
_
21.3
-
-
~

19.4
_
27.8
«
27.2
_
20.2
"
COO
_
-
_
10.3
19.2
_
8.8
12.8
_
9.2
13.5
_
14.1
12.2
_
7.5
12.8
„
9.3
14.0
-
_
21.3
-
-
-

14.8
_
18.7
-
13.0
_
18.0
"
Cadmium
.
97.8
_
37.5
100.0
_
12.5
41.8
_
0
0
_
41.7
40.0
_
81.4
0
.
0
0
60.5
.
81.1
64.9
100
90.9

87.6
~1ff(Jt
BDL
_
100
_
91.3
87.5
% Solubilization
Zinc
_
97.0
_
77.8
78.7
_
50.4
59.7
_
25.4
65.4
_
73.5
67.3
_
100
560
_
1.6
31.7
-
_
76.2
64.9
72.3
73.9

84.6
_
82.1
_
100
_
100
93.2
Nickel
_
100.0
_
73.9
-
_
0
0
„
68.8
0
.
81.3
80.0
_
0
62.5
_
0
0
-
_
BDL
-
-
••

72.7
_
85.5
_
100
.
90.1
74.2
Copper
.
-
_
0
9.1
..
0
0
_
0
0
.
0
0
_
0
0
.
0
0
-
_
0
•
-
~

3.1
_
81.5
.
48.3
_
78.0
0
Chromium
»
33.6
_
11.8
34.5
_
5.2
11.3
_
5.9
3.1
.
6.6
5.8
_
4.4
6.2
-
1.0
11.0
-
_
19.3
-
-
••
.
44.3
_
41.9
_
80.4
-
44.0

TKN
_
••
_
-
-
„
-
-
_
-
-
_
-
-
_
-
-
_
-
.
-
_
_
-
.
-
_
26.7
_
24.7
_
42.0
.
17.4

    BDL » Below Detectable Limit
                                    110

-------
fermenter, but the solubilization of nickel  was greater for the one-liter
graduated cylinder (see lines 10 and 11  of Table 32).

     Tests were conducted with the 14-liter fermenter  to determine the
effect of stirring speed on the degree of solubilization.   Two samples  of
the same sludge were digested sequentially under identical  conditions except
that a stirring speed of 60 rpm was used for one sample and 600 rpm was
used for the other.  The results, shown  in lines 13 and 14  of Table 32,
indicate nearly identical solubilizations for the two  samples.  It is
therefore concluded that the effect'of stirring speed  on solubilization is
not significant.

     The effect of the order in which acid and heat are applied to the
sludge is shown by lines 16 and 17 of Table 32.  Both  cadmium and zinc
were solubilized to a greater extent when the acid was added before heating
(811 and 100%, respectively) rather than after heating (0%  and 56%, res-
pectively).  This could be due in part to the longer exposure to acid when
it is added before heating.

     Comparison of lines 20 and 21 of Table 32 indicate a substantial in-
crease in the amount of cadmium solubilized when the digestion time was
increased from 30 to 60 minutes.  A sample taken after 30 minutes of
digestion indicated no cadmium solubilization while the sample taken after
an additional 30-minute digestion of the same batch of sludge indicated 60%
solubilization.  In general, however, the digestion time was much less
significant than this result would indicate.

     The above results suggest that the  conditions most conducive to heavy
metals solubilization are:

     —use of the 14-liter fermenter for digestion,
     —use of 600 rpm stirring speed (primarily to promote  good heat
       transfer and uniform conditions):,
     —acid addition before heating, and            ;
  ,   —60 minutes digestion time.

     These conditions were used in tests with sludges  obtained from various
municipal sources.

     The test results of Table 32 indicate that the variable which exerts the
greatest influence on metals solubilization is the amount of acid added.
This is in agreement with the findings reported in Section  4.  An attempt
was made to correlate the degree of solubilization as  a function of pH.
The results for cadmium are shown in Figure 36.  This  correlation indicates
a general trend toward higher solubilization of cadmium as  the pH is
decreased.  At pH's greater than 2.5, there is essentially  no solubilization
of cadmium while at pH's below about 2.0, typically 80 to 100% of the cad-
mium is solubilized.  Between pH 2 and 2.5, the data are widely scattered,
ranging from zero to nearly 90%.  These results are consistent with those
presented in sections 4 and 5 for cadmium solubilization and in particular
with the 0 to 90% solubilization range previously observed  at pH 2.5.
                                     Ill

-------
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     A somewhat better correlation was obtained by plotting the degree of
cadmium solubilization against the .acid usage in kg of concentrated sulfuricr
acid (97%) per dry metric ton of solids.   This plot is shown in Figure 37.
Below an acid usage of about 125 kg/dmt there is no significant solubil-
ization of cadmium, while above about 175 kg/dmt, 80 to 100% of the cadmium
is solubilized.  Thus the critical acid usage for good solubilization  of
cadmium is around 150 kg/dmt.

     The fact that a better correlation was obtained on the basis  of the
amount of acid added rather than pH may indicate that the bulk pH  of the
sludge is not really representative of the hydrogen ion concentration  at
the reaction sites.  This concept of a localized pH along with the steep
slope of the curve in Figure 37 could explain the "erratic" solubilizations
of cadmium noted in previous tests.

     The solubilization of zinc as a function of acid usage is shown in
Figure 38.  The shape of the curve is similar to that for cadmium.  The
solubilization increases very rapidly over the range of 100 to 150 kg  acid
per dmt.  Above this level the solubilization is generally in the  range of
75 to 100%.

     Results for nickel solubilization as a function of acid usage are
shown in Figure 39.  The degree of solubilization increases very sharply
at about 125 kg/dmt.  At higher acid usages the degree of solubilization
varies between about 70 and 100%.

     The results for chromium solubilization are shown in Figure 40.  The
degree of solubilization for chromium increases more gradually than for
cadmium, zinc, and nickel and reaches a plateau of about 40% solubilized  at
higher acid usages.

     In addition to heavy metals it is also of interest to know how the
solubilization of solids and COD vary with acid usage.  The plot for
solubilization of solids is shown in Figure 41.  The degree of solubilization
appears to gradually increase up to an acid usage of about 150 kg/dmt  but
remains approximately constant thereafter at about 25%.  The COD solubiliza-
tion increased over the same range as shown in Figure 42.  Above an acid
usage of 150 kg/dmt the COD solubilization leveled off at 15-20%.

     The results of Figures 37-40 indicate that good solubilization of the
heavy metals can be obtained at acid usages of about 200 kg/dmt and above.
This level was therefore specified for tests conducted with sludges obtained
from various municipal sources.  However, in order to add a fixed  amount  of
acid per unit of solids, it is necessary to determine the solids content
of the sludge prior to the test.  The amount of acid to be added was cal-
culated on the basis of the solids concentration as estimated by the various
municipalities at the time the sludge was obtained.  The actual solids con-
tent was not determined until after the tests were completed.  Therefore,
the acid usages for the sludges obtained from different cities varied-from
225 to 325 kg/dmt.
                                     113

-------
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-------
     Table 32 (lines 27-35) shows the degree of solubilization for various
sludge constituents as a function of acid usage at the preferred operating
conditions (14-liter fermenter, 600 rpm, acid addition before heating, 60
minute digestion time, and acid usage > 200 kg/dmt).  Tests were conducted
with samples of sludge from Brockton, MA, Fitchburg, MA, Lawrence, MA, and
Milwaukee, WI (two tests on same sample).  The mean solubilizations and
ranges obtained for the various sludges are given in Table 33.

     Excellent solubilizations were obtained for cadmium, zinc, and nickel
and moderate solubilizations were obtained for chromium and copper.  With
the exception of copper the range of solubilizations of heavy metals was
reasonably narrow indicating that at an acid usage of >200 kg/dmt the
solubilization curve has reached its plateau.  For copper, the results of
Table 32 (lines 27-35) indicate that the solubilization increases from zero
to 80% over a range of acid usage of 270 - 315 kg/dmt.  Thus copper is more
difficult to solubilize than other heavy metals and requires an acid usage
of >300 kg/dmt for good solubilization.

     Reasonably good agreement (except for copper as noted above) was ob-
tained for solubilization of a given constituent from the various sludges
as shown by the range of solubilizations in Table 33.  The sample of
Lawrence, MA sludge exhibited the best solubilizations of heavy metals (100%
for cadmium, zinc, and nickel; 80% for chromium) but also exhibited the
highest solubilization of nitrogen (42%).  This may indicate that a sig-
nificantly lower acid usage could be applied to the Lawrence sludge to
achieve acceptable solubilizations.  In general, however, the results indi-
cate that the acid usage criteria of >200 kg/dmt for solubilization of cad-
mium, zinc,- nickel, and chrome, and >300 kg/dmt for solubilization of copper
are applicable to sludges from various municipalities

     It is of interest to compare the costs of the hot acid process op-
timized for heavy metals removal to the same process optimized for de-
watering.  The major difference in operating cost will result from differ-
ences in acid usages for the two cases.  Based on the results of Section
4, optimum dewatering is obtained at a digestion pH of about 2.5.  From
Figure 12, the acid requirement to achieve a pH of 2.5 ranges from 70 to
100  kg/dmt.  For optimum metals removal  (except copper) the acid require-
ment is approximately 200 kg/dmt which is a factor of two to three times
greater than for optimum dewatering.

     Based on an acid cost of $49.50 per metric ton  ($45 per short ton)
for  concentrated sulfuric acid, the costs per ton of solids treated are:
                Process

      Optimized  for  Dewatering

      Optimized  for  Metals  Removal
Acid usage
  kg/dmt

    100

    200
   Acid cost
$/dmt      $/dst

4.95       4.50

9.90       9.00
                                     120

-------
        TABLE 33.   SOLUBILIZATIONS  OBTAINED  FOR  SLUDGES  FROM VARIOUS
                   CITIES AT PREFERRED  OPERATING CONDITIONS
    Sludge
 constituent
    Mean
sol utilization
   Range of
sol utilizations
Cadmium
Zinc
Nickel
Chromium
Copper
Solids
Organics (COD)
Nitrogen (TKN)
     92
     92
     84
     53
     53
     24
     16
     28
   88
   82
   73
   42
    3
   19
   13
   17
100
100
100
 80
 82
 28
 19
 42
                                     121

-------
Thus, for the hot acid process, the cost differential  for acidification
between optimized dewatering and optimized metals removal is only about
$5/dmt which is considered to be quite reasonable.

CONCLUSIONS

     Additional bench-scale tests were conducted to define the factors
responsible for solubilization of heavy metals and to optimize the hot acid
process for heavy metals removal.  Consistent correlations were obtained
between the degree of solubilization and the acid usage in kg of concentrated
H?S04 per dmt.  These correlations indicate a rapid increase in the degree
of solubilization of cadmium, zinc, nickel, and chromium over the range of
100 to 200 kg/dmt and of copper (based on limited data) over the range of
250 to 300 kg/dmt.  The correlation of metals solubilization with "acid
usage" was found to be more consistent than correlation with "pH".

     Tests conducted with fresh WAS samples from various municipalities
indicated excellent solubilization of cadmium (88-100%), zinc (82-100%),
and nickel (73-100%) at acid usages >200 kg/dmt.  Only moderate solubilization
of chromium (^45%) was obtained, and appreciable copper solubilization
(^0%) required a higher acid usage (>300 kg/dmt).  For these tests, average
solids, COD, and TKN solubilizations were 24, 16, and 28%, respectively.

     An acid usage of 200 kg/dmt was selected as the optimum for heavy'metals
solubilization.  This is two to three times as great as the acid usage
required for optimum dewatering (70-100 kg/dmt to achieve pH 2.5).  However,
the cost for acid at a usage of 200 kg/dmt is still <$10/dmt ($9/dst) and is
considered to be quite acceptable for the levels of solubilization obtained.
                                     122

-------
                                 SECTION 7

                   SPECIFICATION OF SOLIDS - SEPARATION EQUIPMENT
     Three techniques for solid-liquid separation:   settling,  vacuum
filtration, and centrifugation were investigated during bench-scale tests.
The solid-liquid separation tests were conducted for the purpose of iden-
tifying the effects of changes in the process variables on solids separation
rates and were not intended for generation of design data for  full-scale
dewatering equipment.  The rationale for concluding that the hot acid
process produces a sludge with adequate dewatering  characteristics is based
on:

     1) the substantial improvement in dewatering characteristics
        relative to the untreated sludge, and

     2) the results of Figures 33 and 34 which indicate that filtration
        and centrifugation rates are as favorable as for chemically
        conditioned sludge.

     Of the three solid-liquid separation techniques evaluated, settling
appeared to have the least potential applicability  to the hot  acid
treatment process.  Thickening of the sludge prior  to hot acid treatment
is very important in reducing the treatment costs.   However, for properly
thickened sludge, the hot acid process does not produce rapid  additional
settling.  As shown in Figure 14, the volume of treated sludge was reduced
by only about 10% during 30 minutes of settling following hot  acid treat-
ment.  The rate and extent of settling observed during the bench-scale tests
appeared inadequate to justify the  added cost and  complexity  of settling
before final dewatering of the sludge.

     The bench-scale filtration data can be analyzed to give the specific
resistance of the filter cake which can then be used to calculate the filter
yield'8''.  The specific resistance for raw Brockton WAS (see filtration
curve of Figure 33) was approximately 1.5x10'° sec^/g.   The hot acid process
(or chemtcal conditioning) reduced the specific resistance to  approximately
1.5x109 sec2/g.  This resistance is higher than the level  at which good
filtration results are normally obtained (108 sec2/g (15)  ).


      A number of attempts were made to obtain filtration data using a filter
 leaf apparatus.  However none of the filter materials  tried gave satis-
 factory results:  some filter materials plugged allowing no passage of
                                     123

-------
filtrate while others permitted near complete passage of both solids and
liquid.  Consequently the filter leaf tests were abandoned.

     Of the solid-liquid separation techniques evaluated, centrifugation was
selected as the preferred technique for sludge dewatering following hot
acid treatment.  This selection was based on several considerations:

          1.  The centrifugation curve for hot acid treatment
(see Figure 34) fell approximately mid-way between the curves for chemical
treatment and thermal treatment.  This was taken as an indication that
centrifugation rather than filtration was better suited for dewatering
the hot-acid-treated sludge.

          2.  The high specific resistance and problems with the filter
leaf test indicated potential problems for dewatering by vacuum filtration.

          3.  In the initial process design, the digested sludge was
dewatered before cooling (by heat exchange with the feed) in order to take
advantage of the lower viscosity of water at elevated temperatures.
Vacuum filtration was not considered well-suited for dewatering hot sludge
because of potential odor problems and potential heat loss from the
filtrate by vacuum evaporation.  (However, this process design was later
abandoned when economic calculations indicated a large energy-cost penalty
associated with failure to recover heat from the sludge solids.)

          4.  Centrifugation appeared to have certain other advantages
over vacuum filtration such as lower costs and operating .labor (&).

     Based on these advantages bench-scale and pilot-scale centrifugation
tests were conducted at Bird Machine Co.,  South Walpole, MA.   The test
results are given in Appendix B.  On the basis of the bench-scale tests it
was concluded that hot-acid-treated sludge would be a good application for
a continuous solid bowl  centrifuge, and pilot-scale tests were recommended.
However, during the bench-scale tests,  lime,  ferric chloride, and various
polymers were used to improve the solid-liquid separation.  Because of the
cost of these additives and their potential  for adsorption or precipi-
tation of solubilized heavy metals, the pilot-scale tests were conducted
without chemical  additives.   For these  tests  good  cake  solids concentra-
tions (18-36% solids) were obtained, but solids recoveries were low.  The
use of flocculents was recommended to improve the recovery of solids as
cake.  Based on these tests, the full-scale dewatering  equipment specified
by Bird Machine Co. for hot-acid-treated Brockton WAS is shown in Table 34.

     While centrifugation can be used to dewater hot-acid-treated sludge,
other solid-liquid separation devices may offer significant advantages over
centrifugation and should be evaluated.  Of particular interest is the
filter belt press which can generally produce higher cake consistencies
than centrifugation and operate with significantly lower power and
maintenance requirements
                                   124

-------
       TABLE-34,  SPECIFICATION FOR CENTRIFUGES TO  DEWATER BROCKTON WAS
                  FOLLOWING HOT ACID TREATMENT
    Centrifuge Capacity

   Solids           Liquid
kg/hr (Ib/hr)       1pm (gpm)
Description*
   68    (150)        38    (10)    One Bird Machine Co.  HB1400 or  equivalent

  680  (1,500)     - 380   (100)    One Bird Machine Co.  HB3700 or  equivalent

6,800 (15,000)     3,800 (1,000)    Three Bird Machine Co.  HB64000  or  equivalent
  All machines are horizontal, solid-bowl,  conveyor-type centrifuges.   Materials
  of construction are 300-series stainless  steel.   Centrifuges  are  of  the  low-
  speed, sludge-dewatering type which operate in the  range  of 500-800  x gravity.
                                      125

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                                 SECTION 8

                      SPECIFICATIONS FOR PILOT SYSTEM
     The process flow schematic for a 5 gpm, pilot-scale, hot-acid-
treatment system is shown in Figure 43.  Primary sludge (which has been
screened to remove gross particulates) and waste activated sludge are mixed
in the desired proportions and pass through in float control valve that
maintains a constant level in the feed tank.  The feed tank is agitated by a
0.19kw (0.25 h.p.) mixer to insure complete mixing of the two sludges, and
the 10 minutes residence time in the 0.2 m3 (50 gal) tank smoothes any
sudden changes in feed composition.

     A progressive cavity pump circulates sludge through the pilot plant.
This type of pump provides a constant flow rate with varying upstream
pressure and can pump abrasive  solids and  viscous sludges.  The flow rate
is controlled by varying the quantity of sludge returned to the pump suction
through the bypass valve.  The ultrasonic flow meter and total flow counter,
which uses the Doppler principle to measure velocity, is attached to the
outside wall of the pipe and does not contact the sludge.

     The sludge is heated in two stages.  In the first stage, the feed sludge
is heated to approximately (75°C) by exchange with the hot digested sludge;
in the second  stage steam heats the sludge to the desired digestion temper-
ature C90-95°C).  A co-axial double pipe heat exchanger is used for the first
stage since both sludge and concentrate contain solids which may settle out
unless a high velocity is maintained in both streams.  A shell and tube heat
exchanger with an area of 2.5 m2 (27 ft2) (based on an estimated overall heat
transfer coefficient, U, of 270 W/m2 °C  (50 Btu/hr-ft2-°F) is used in the
second stage with the sludge on the tube side to avoid settling.  A 68 kW
botler, capable of generating 95 kg sjteam/hour (210 Ib steam/hour), supplies
steam to the second stage at 450 kN/m  (50 psig), and the rate of steam supply
Is controlled by a temperature controller.

     The pH of the feed is adjusted to the desired level (pH 2-3) in a
0.1 m3 (25 gal) mixing tank by adding concentrated sulfuric acid at a rate of
approximately 0.1 kg acid/kg sludge solids (2 1/hr of 95% actd for sludge
With 3% solids).  A pH probe with a feedback control system regulates the
acid metering pump.  The pH is adjusted after the heat exchanger rather than
before In order to reduce corrosion and recover heat from the solids stream.
                                     126

-------
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     The hot acidified feed flows from the mixing tank over a weir to the
digester where it is held for the desired residence time.  The digester has
a total volume of 0.57 m3 (150 gallons) to provide a maximum residence time
of 30 minutes at the design flow rate of 19 1/min (5 gpm).  The tank is con-
structed of fiberglass with a 30°-slope conical bottom, a height of 2 m, and
a diameter of 0.65 m.  The volume is divided into three equal stages by two
30° conical baffles with 10-cm-diameter holes in the center of each.  This
configuration reduces axial mixing which for an unbaffled tank would result
In a poor residence time distribution.

     A variable speed mfxer (20-350 rpm) with a turbine agitator in each stage
can be used to determine the effect of agitation on performance.  The mixer
ha.s §n Independent support structure to avoid stresses in the fiberglass
digester tank.  A manhole in each digester section allows assembly of the
agitators to the mixer shaft and cleaning between the baffles (should this be
necessary).


     The level (residence time) in the digester is maintained by a differ-
ential pressure level transducer and controller that maintains a constant
preset pressure differential across the sludge by adjusting a proportional
flow control valve at the bottom of the digester.  A small air blower main-
tains a slightly reduced pressure in the digester and pH mixing tank to avoid
venting untreated gases past the agitator shaft and unsealed tank connections.
The gases from the blower are vented through a condenser and carbon adsorp-
tion column.

     Following cooling (heat recovery) in the first stage heat exchanger, the
treated sludge is centrifuged to remove solids.  (Other dewatering devices
could also be evaluated).  The solid cake is discharged; and the concentrate
flows into a 0.075 m3 (20 gallon) surge tank where the pH is adjusted by the
addition of sodium hydroxide (NaOH) or lime to precipitate heavy metals.  The
pH can be varied to determine the optimum level for maximum metals removal.
The precipitated metals are settled in a clarifier. with a surface area of
approximately 0.7 m2 (7 ft2).  It is anticipated that other suspended solids
will coagulate and settle with the metal hydroxides.  The clarified overflow
is pumped back to the secondary treatment system.  Batch tests can be
conducted to evaluate various dewatering techniques for the settled heavy
metal sludge, but it is anticipated that the flow of sludge will be too small
to allow continuous dewatering.

     Temperature (T) and pressure (P) are monitored at strategic locations
as Indicated in Figure 43.  Automatic vacuum lift samplers are used to obtain
samples of untreated sludge, dewatered sludge, and centrate.  Either time-
averaged composites or sequential samples can be collected.
                                       128

-------
     Specifications and approximate costs of the equipment  required  to build
the pilot plant are shown in Table 35.   The approximate  total  purchased
equipment cost, not including sludge dewatering, is  $40,000.   To  this cost
must be added the cost of sludge dewatering equipment, the  cost of system
design and engineering, and the cost of site preparation and  installation.
                                     129

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                                   SECTION  9

                           ENERGY  AND  ECONOMIC  ANALYSES
     A simplified flow schematic of the hot acid sludge conditioning system
is shown in Figure  44.  Thickened sludge is pumped through a heat exchanger
in which the sludge temperature is increased by heat recovered from the
treated sludge.  The sludge is then acidified with concentrated sulfuric add
(H2S04) in a flash mixing tank before entering the digester.  In the digester
the sludge is brought to digestion temperature by steam circulated through
heating coils and is retained for the desired residence time.

     After digestion the sludge is pumped back through the heat exchanger
(for energy recovery) to the centrifuge where the sludge is dewatered.
Because of the low pH, it may be necessary to neutralize the solid cake prior
to land application.  This can be accomplished by the addition of anhydrous
ammonia which will also increase the nitrogen value of the sludge.  The
liquid concentrate is returned to the secondary treatment system after pH
adjustment and settling to precipitate heavy metal hydroxides.

     Cost estimates have been developed for hot acid sludge conditioning
systems to treat 200, 20 and 2 dmtpd (dry metric tons per day) of sludge
solids.  These are the approximate quantities of primary plus waste  activated
sludge generated by wastewater treatment plants of 500, 50, and 5 m3/min
(200, 20 and 2  million gallons per day) capacity, respectively (20).  The
assumptions and design bases used to develop the cost estimates are  given
in Table 36.

     The flow rates of the various streams  in the system are shown in
Figure 45.   It is assumed that the sludge is thickened to 3% solids  prior to
conditioning, and after conditioning the Centrifuge produces a sludge cake
with 20% solids.   From Figure 12 the acid demand is taken as 0.1 kg  H?S04 per
kg of sludge  solids which should reduce the pH to 2.0 - 2.5.  As  pointed out
in Section 6, optimum metals removal would require about twice this  amount
of acid-

     The energy balance around the system is shown in Figure 46.   The
thickened sludge is initially heated to 80°C in the heat exchanger by energy
recovered from the treated sludge (approximately 80% of the heat is  re-
covered).  The sludge is further heated to 95°C in the digester by steam
passed through the heating coils.  Following digestion, during which heat
losses are assumed to be negligible, the temperature is reduced to 35°C in the
                                      133

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TABLE  36.  ASSUMPTIONS AND DESIGN BASES FOR ECONOMIC ANALYSIS

Sludge solids treated, dmtpd
Feed sludge solids concentration, percent
Feed sludge flow rate, m3/hr (gpm)
Feed sludge temperature: Entering H/E, °C
Leaving H/E, °C
Treated sludge temperature: Entering H/E, °C
Leaving H/E, °C
Overall coefficient of heat transfer- for
H/E, W/m2 °C (Btu/hr ft2 °F)
Surface area of heat exchanger, m2 (ft2)
Digestion pH
Sludge acid demand, kg acid/kg sludge solids
Acid flow rate, kg/hr
Acid price, 66°Be H2SO,(3 $/kg ($/short ton)^
Acid cost, $/hr
Overall coefficient of heat transfer
of coils in digester, W/m2 °C(Btu/hr ft2 °F)
Sludge temperature in digester, °C
Steam pressure, kN/m2 (psig)
Steam flow rate to digester, kg/hr (Ib/hr)
Energy to generate steam, :kW
Cost of No. 4 fuel oil, $/kW-hr ^
Sludge residence time in digester, min
Total pump head, m
pump efficiency, %
Miscellaneous electric power, kW
Electric power cost, $/kW-hr'b'
Labor man-days/year (conditioning)
Labor rate $/man-day (incl. fringe benefits)
Annual capital cost (20-year life, 7% per
a.nnum interest) as % of capital investment
Maintenance materials, % of total O&M cost
2
3
2.8(12.2)
20
80
95
35
575(100)
23(250)
2.0
0.1
8.3
0.05(45)
0.415
575(100)
95
450(50)
82.5(182)
48.5
0.009
30
30
70
2
0.05
200
100
9.4
5
20
3
28(122)
20
80
95
35
575(100)
230(2,500)
2.0
0.1
83
0.05(45)
4.15
575(100)
95
450(50)
825(1820)
485
0.009
30
30
70
12
0.05
275
100
9.4
5
200
3
280(1220)
20
80
95
35
575(100)
2300(25,000)
2.0
0.1
830
0.05(45)
41.5
575(100)
95
450(50)
8250(38,200)
4850
0.009
30
30
70
72
0.05
360
100
9-4
5
                            (continued)
                                 135

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                                TABLE 36.   CONTINUED
Sludge solids treated, dmtpd
20
200
Centrifuge power, kVr '
Additional labor for centrifuge, man-day/year
Lime demand, kg lime/m3 supernatant^0'
Lime flow rate kg/hr
Lime cost, $/kg ($7100 Ibs) ^
n
20
3
7.2
0.0325(1.50)
30
25
3
72
0.0325(1.50)
246
40
3
720
0.0325(1.50)
(a)   Quotation, May 1978.
(b)   Private communication with supplier.
(c)   Based on experimental dosage required to raise pH from 1.85 to 9.0.
(d)   Reference   12
                                          136

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heat exchanger before entering the centrifuge.  The sludge is dewatered after,
rather than before, heat recovery so that heat can be recovered  from the
sludge solids.  The lower sludge temperature in the centrifuge increases^
viscosity and hence the required centrifuge capacity; however, the  additional
heat recovered more than compensates for the added centrifugation costs.

     Cost estimates or quotations for all major pieces of process equipment
are given in Table 37.  All  costs are adjusted to an EPA - Sewage Treatment
Plant Construction Cost Index (EPA-STPCCI) of 288 (fourth quarter 1977).
Land costs are not included since these costs are site specific, and in an
integrated plant it is difficult to segregate the component of land cost
attributable to sludge conditioning from that attributable to other wastewater
and sludge treatment processes.

     Capital costs are shown in Table 38.  Equipment installation  is estimated
to cost 40% of the purchased equipment cost.  Installation is defined as site
preparation (assuming reasonable subsoil conditions), foundations,  and
transportation and positioning of equipment.  It does not include  equipment
hook-up which is included with piping, electrical and instrumentation.
Engineering, legal and contingency is estimated at 37.5% of the  total plant
cost  (21) and includes all costs not directly attributable to materials and
labor for plant construction, such as construction financing, contractor
fees, construction management, etc.  These cost factors are obviously
generalizations of costs which will vary with local conditions.   The overall
capital investment computed using these factors is approximately 2.4 times  the
purchased equipment cost, which  is in close agreement with other estimates
given in the  literature  (21»22).

      The capital costs are shown for both the hot acid treatment process
alone, and  hot acid treatment in conjunction with centrifugal dewatering and
supernatant treatment.   In this  way, costs can be compared directly either
with  other  conditioning  techniques or with complete  conditioning and de-
watering systems.

      Operating and maintenance  cost estimates  are shown  in Table 39.   It is
assumed  that  energy  to  heat the  sludge  is  provided  by No. 4  fuel oil at a
cost  of  $0.009/kWhr,  and that all other power would  be electrical   at a cost
of $0.05/kWhr.  Operating labor  was estimated  assuming a  fully  automatic
system requiring  only periodic  routine  checks.  The  labor rate  was  estimated
at $100  per man-day  and includes all salary  related  costs and supervision.
No attempt is made to differentiate between  operating and maintenance  labor.

      The capital-recovery-factor method (23) was  used to  determine  investor
 capitalization.   In  essence,  this  technique  calculates  the equal annual pay-
ment which must be made to yield the  same sum  at  the end of the plant life
 as if the capital  had been  invested at  compound  interest when the  plant was
 constructed.   It  is  assumed  that the  plant has  a  20 year life with no  resale
 value,  and the annual interest rate is  7%.   Under these  circumstances  the
yearly cost of financing the  construction is equal  to 9.4% of the  total
 fixed capital investment.
                                       139

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             TABLE  38.  CAPITAL  COSTS  FOR HOT ACID  TREATMENT
Plant size,  dmtpd
20
                                                                             200
                                                                  103,300
                                                                   41,300
           576,300
           230,500
                                                                   36,200    201,700
CASE I;   HOT ACID  TREATMENT ONLY
     Purchased  equipment cost  (PEC), $              25,800
     Equipment  installation (40% PEC^a')»- $         10,300
     Piping, electrical, instrumentation
       (35% PECU)),  $                               9,000
           Total plant  cost (TPC), $                45,100
     Engineering,  legal, contingency
       (37.5% TPdb))                              16,900
           Total capital investment, $              62,000
           Capital investment, $/dmtpd              31,000
           (Capital  investment, $/dstpd)           (28,100)
CASE II:   HOT ACID TREATMENT WITH DEUATERIN6 AND SUPERNATANT TREATMENT
                                                                  180,800  1,008,500
                                                                   67,800    378,200
                                                                  248,600  1,386,700
                                                                   12,400      6,900
                                                                  (11,200).    (6,300)
        Purchased equipment  cost  (PEC),$              113,800
        Equipment installation  (40% PEC^), $         45,500
        Piping,  electrical,  instrumentation
          (35% PEC(a)),  $                             39,800
              Total  plant cost  (TPC), $               199,100
        Engineering, legal,  contingency
          (37.5% TPC),  $                              74,700
              Total  capital  investment, $             273,800
              Capital  investment,  $/dmtpd             136,900
              (Capital  investment, $/dstpd)          (124,300)
280,300  1,681,300
112,100    672,500

 98,100    588,500
490,500  2,942,300

183,900  1,103,400
674,400  4,045,700
 33,700     20,200
(30,600)   (18,300)
(a)   Reference  23

(b)   Reference  21
                                          141

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TABLE  39. OPERATING AND MAINTENANCE COSTS FOR HOT ACID TREATMENT
           ($/DRY METRIC TON SOLIDS)

Plant
CASE







CASE








size, dmtpd
I: HOT ACID TREATMENT ONLY
Capital cost
Labor
Electricity
Fuel oil
Chemicals, acid
Maintenance materials
Total operating and maintenance cost
II: HOT ACID TREATMENT WITH DEWATERING AND
Capital cost
Labor
Electricity
Fuel oil
Chemicals, acid
lime
Maintenance materials
Total operating and maintenance cost
2

7.98
27.39
1.40
5.18
5.00
2.37
49.23
20

3.20
3.77
0.91
5.18
5.00
0.91
18.97
200

1.79
0.50
0.63
5.18
5.00
0.66
13.76
SUPERNATANT TREATMENT
35.25
30.13
8.00
5.18
5.00
2.80
4.39
90.75
8.68
4.11
2.71
5.18
5.00
2.80
1.43
29.91
5.21
0.55
2.1
5.18
5.00
2.80
1.04
21.88
                              142

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     The total  operating and maintainance cost for hot acid  treatment  is
$13.76, $18.97, and $49.23 per dmt solids ($12.50, $17.22, and  $44.75  per  dst
solids) for the 200, 20, and 2 dtntpd plant capacities.  Inclusion  of sludge
dewatering and supernatant treatment increases the costs to  $21.88, $29.91
and $90.75/dmt for the respective plant capacities.

     To compare the economics of hot acid treatment with other  sludge  treat-
ment techniques, cost estimates have been developed for:  anaerobic digestion,
aerobic digestion, lime treatment, and heat treatment.  The  cost estimates,
shown in Tables 40-43, respectively, are based upon capital  costs  (adjusted
to EPA-STPCCI of 288) and recently published operating and maintainance
requirements (21).  Since many operating costs (such as for  energy) have
increased at a more rapid rate than the STPCCI, care was taken  to  adjust  all
operating and maintainance costs to the same bases used to estimate the
costs of hot acid treatment given in Table 39.

     The cost estimates of Tables 40-43 are for the treatment or stabilization
process only and do not include the cost of sludge dewatering,  sludge
disposal, or supernatant treatment.  However, heat treatment and hot  acid
treatment both condition sludge for dewatering whereas anaerobic digestion,
aerobic digestion and lime treatment are principally stabilization processes
that do little to improve dewaterability.  To bring the costs to the  same
basis, the cost of chemicals which must be added to the latter group  to
prepare the stabilized sludge for dewatering has been included in the  cost
estimate.  The chemical demand of the sludges was based upon generalized
estimates given in the literature, and it should be noted that the chemical
demand may vary considerably from these estimates depending  upon the  type
of sludge and  the wastewater treatment process.

     Cost comparisons for various plant capacities are shown in Figure 47.
Lime stabilization potentially provides the lowest treatment cost per ton
of sludge because of the low capital and operating cost.  However, the high
chemical cost  to prepare the sludge for dewatering makes this process only
slightly less  expensive than the hot acid treatment process.  In addition,
sludge disposal costs (not included in this analysis) are increased by the
large  volume of lime present in the final sludge.  In addition, the lime
process does not provide metals removal.

     The principle economic advantage of hot acid  treatment over heat treat-
ment is the much lower  capital cost and operation  at  atmospheric pressure.
The advantage  of heat treatment is that  no chemical addition is required.

     Anaerobic digestion is more  costly  than aerobic  digestion because of
the higher  capital  cost resulting  from the need for odor control.  Aerobic
digestion costs are  approximately  the same as  those for hot acid treatment
for smaller plant  capacities,  but  the economic advantage of hot acid treat-
ment is greater for  larger plants.  The main  differences are the need for
more chemicals to  condition  the aerobic  sludge, and the higher capital costs
for aerobic digestion equipment.
                                      143

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-------
     For optimum removal of heavy metals, the costs presented in Table
39 and Figure 47 should be adjusted to reflect an acid usage of 200 kg/dmt
rather than 100 kg/dmt.  This will add $5/dmt for hot acid treatment only
and $7.80/dmt for hot acid treatment with dewatering and supernatant treat-
ment.  The dashed curve of Figure 47 shows the cost as a function of plant
capacity for hot acid treatment when the process is optimized for heavy
metals removal.  Total costs, including dewatering and liquor treatment and
including capital amortization, for optimized metals removal at plant capa-
cities of 2, 20, and 200 dmtpd would be $98.55/dmt, $37,71/dmt, and $29.687
dmt, respectively.

     Based on the above cost comparisons it is concluded that the hot acid
treatment process is highly cost competitive with alternative stabilization/
conditioning techniques and is particularly attractive where land application
of sludge is limited by the concentration of heavy metals in the sludge.
                                     149

-------
                                  REFERENCES
1.   Federal Register, 42 (211): 57420-57427,  Wed.,  Nov.  2,  1977.

2.   Council for Agricultural  Science and Technology.   Application of Sewage
     Sludge to Cropland:  Appraisal  of Potential  Hazards  of  the Heavy Metals
     to Plants and Animals.  EPA 430/9-76-013, U.S.  Environmental Protection
     Agency, Washington, D.C., 1976.  63 pp.

3.   Jelinek, 6.F., Health Perspectives - Sludge  Use on Land.  In:   Proceed-
     ings of 1977 National Conference on Composting  of Municipal Residues and
     Sludges, Information Transfer,  Inc., Rockville, MD,  1978.  pp 27-29.

4.   Federal Register, 43(25): 4942-4955, Mon. Feb.  6,  1978.

5.   Everett, J.6.  The Effect of Heat Treatment  on  the Sol utilization of
     Heavy Metals, Solids, and Organic Matter  from Digested  Sludge.  Water
     Pollution Control, 73: 207-209, 1974.

6.   Brooks, R.B.  Heat Treatment of Activated Sludge.  Water Pollution
     Control, 67(5): 592, 1968.

7.   Marshall, D.W. and F.C. Fiery.   Investigations  of Heat  Treatment for
     Paper Mill  Sludge Conditioning.  EPA-600/2-78-015, U.S. Environmental
     Protection Agency, Cincinnati,  Ohio, 1978.   73  pp.

8.   Vesilind, P.A.  Treatment and Disposal of Wastewater Sludges.  Ann
     Arbor Science Publishers, Inc., Ann Arbor, Michigan, 1974.  236 pp.

9.   Andersen, L.B.  Factorial Design of Experiments.   Chemical Engineering,
     70(18) :99-104, 1963.

10.  Katz, W.J.  and A. Geinopolos.  Concentration of Sewage  Treatment Plant
     Sludges by Thickening.  In:  Proceedings  of  the Tenth Sanitary
     Engineering Conference, Dept. of Civil Engineering,  University of
     Illinois, Urbana, Illinois, 1968.  pp. 33-45.

11.  Stern, G. and J.B. Farrell.  Sludge Disinfection  Techniques.  In:
     Proceedings of the 1977 National  Conference  on  Composting of Municipal
     Residues and Sludges, Information Transfer Inc.,  Rockville, Maryland,
     1977.  pp.  142-148.
                                     150

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12.




13.


14.


15.



16.



17.



18.



19.



20.


21.
22.
Black, Crow, and Eidshess, Inc.,  Process  Design  Manual  for Sludge Treat-
ment and Disposal.  EPA 625/1-74-006,  U.S.  Environmental  Protection
Agency Technology Transfer, Washington,  D.C.,  1974.   (Original  source
cited as reference 40 of Chapter  5).
Chemical Marketing Reporter, 213(24), June 12,  1978.
Co., Inc., New York, N.Y.
                              Schnell Publishing
Boyle, J.D. and D.D. Gruenwald.  Recycle of Liquor from Heat Treatment
of Sludge.  J. Water Pollution Control  Fed., 47(10):  2482-2489,  1975.

Black, Crow, and Eidsness, Inc., Process Design Manual  for Sludge Treat-
ment and Disposal.  EPA 625/1-74-006, U.S. Environmental  Protection
Agency Technology Transfer, Washington, D.C.  1974.

Cameron, J.W.  Aerobic Digestion of Activated Sludge  to Reduce Sludge
Handling Costs.  Presented at 45th Annual Conference  of the Water
Pollution Control Federation, Atlantic, Georgia, October 1972.

Hayes, T.D. and T.L. Theis.  The Distribution of Heavy Metals in
Anaerobic Digestion.  J. Water Pollution Control Fed. 50(l):61-72,
1978.

Blumfield, C. and G. Prudens.  The Effects of Anaerobic and Aerobic
Incubation on the Extract!bilities of Heavy Metals in Digested Sewage
Sludge.  Environmental Pollution 8:217-232, 1975.

Miner, R.A., D.W. Marshall, and I. Gellman.  Pilot Investigation of
Secondary Sludge Dewaterfng Alternatives.  EPA-600/2-78-014, U.S.
Environmental Protection Agency, Cincinnati, Ohio, 1978.  115 pp.
Metcalf and Eddy, Inc.
Disposal.  McGraw-Hill
 Wastewater Engineering:
Book Co., New York, N.Y.,
Collection, Treatment,
1972.  782 pp.
Metcalf and Eddy, Inc.  Assessment of Technologies and Costs for
Publically Owned Treatment Works.  Report to National  Commission on
Water Quality, Washington, D.C.  Available from National  Technical
Information Service, PB-250 690-01 through PB-250 690-03, 1976.
1401 pp.

Campbell, H.W., R.J. Rush, and R. Tew.  Sludge Dewatering Design
Manual.  Research Report No. 72, Training and Technology Transfer
Division (Water), Environmental Protection Service, Ottawa, Ontario,
1978.
                                    151

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23.  Peters, M.S. and K.D. Tinmerhaus.   Plant Design and Economics  for
     Chemical Engineers.  Second Edition.   McGraw-Hill  Book  Co.,  New  York,
     N.Y., 1968.  850 pp.

24.  Garber, W.F., G.T.  Ohara,  I.E.  Colbaugh, and  S.K.  Rakset.  Thermophilic
     Digestion at the Hyperion  Treatment Plant.  J.  Water Pollution Control
     Fed., 47(5):950-961, 1975.

25.  Notevaert, F.F., A.A. Van  Haute, and  D.A. Wilms.   Conditioning of
     Aerobically Stabilized Sludge.  Water Research  9:  1037-1046, Pergamon
     Press.  New York, N.Y.  1975.
                                    152

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                                 APPENDIX A

                 VERIFICATION OF SELECTED ANALYTICAL RESULTS
     During the course of the experimental program, questions arose concern-
ing the accuracy of analytical results, particularly those for heavy metals.
Therefore a number of samples were submitted to the Municipal Environmental
Research Laboratory of EPA (Mr. Vincent B. Sal otto) for analytical verifi-
cation.  Samples submitted to EPA were refrigerated prior to shipment and
were shipped by air freight.

     Analytical results are compared for the various samples in Table A-l.
The columns headed by "W" are the results from the Wai den Analytical
Laboratory; those headed by "E" are the results from the EPA analytical
laboratory.  In general, there is reasonably good agreement between the
results of the two laboratories.

     The cadmium results are particularly noteworthy because of the environ-
mental importance of cadmium.  One of the specific objectives of this
comparison was to verify the high cadmium solubilization (90%) reported by
the Wai den lab for Brockton WAS (first line of Table A-l).  The EPA results
do verify the high cadmium solubillzation for this test.  For the Fitchburg
and Milwaukee waste activated sludges the EPA results Indicate 50% and 84%
solubllizatlon, of cadmium respectively, while the Walden results indicate
zero percent for both-  For the sample of Brockton WAS injected at various
pH's,  good agreement was obtained between the Walden and EPA results.  It
should be noted that, for this latter sample of sludge, the heavy metals
proved to be quite difficult  to solubllize, and the results should not be
considered characteristic of  the potential of the  hot acid process to
solubilize heavy metals.

     From a comparison  of all the results of Table A-l it is concluded that
the Walden analytical results are at least as consistent as  those obtained
by EPA.  For cadmium, the EPA results suggest that solubilizations could  be
greater  than those reported on the basis  of the Walden analytical results.
                                     153

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                               154

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                                   155

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                                  APPENDIX B

                   LABORATORY REPORT ON CENTRIFUGATION TESTS

                          BIRD MACHINE COMPANY, INC.
                         SOUTH WALPOLE, MASSACHUSETTS

                          LABORATORY REPORT NO. 8876

 Customer:        Abcor, Inc.
                  Wilmington, MA

 Material:        Brockton Waste Activated Sludge
                  1599240

 Problem:          Clarification

 Test:             Preliminary

 Test date:        July 20,  1977

 Witnesses:        Dr.  Kenneth McNulty
                  Ms.  Ann Malarkey

 Sample No.  129  (Rec'd 7/20/77)

 Six  (6) liters  of a waste  activated sludge were  received in the laboratory
 for  preliminary centrifugal  testing.

 The  sludge  was  obtained  by the witnesses  from  the Brockton, MA STP and pre-
 treated before  arriving  at the laboratory.  The  sludge was identified only
 as WAS.   A  more exact definition of the sludge would be helpful; i.e., where
 the  sample  was  collected,  time of sampling.

 The  sludge  received was  still hot. The sample contained 3.59% total sol Ids bv
 weight, 2.16% dissolved  solids in the mother liquor.

 Problem

 A new sludge treatment process has been developed by Dr. Fremont of Champion
 International.   Further studies to more fully refine and design a treatment
 system are  being carried out by Abcor, Inc.

Thts new process is an acid/heat treatment for raw sludge.   Acid is added to


                                      156

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 the sludge  to  lower the  pH  to  2-3  and  the  sludge  is  heated  to  90-100°C.  Many
 of the  heavy metal  compounds dissolve  providing a solids  product which has
 better  soil  conditioning characteristics.   Improved  settling,  filtration, and
 centrifugation have been noted in  laboratory tests with treated sludge.

 Vacuum  filtration has been  ruled out as  a  means of dewatering  since  the  sludge
 is to be processed hot and  cooling would be needed prior  to filtration.

 The objective  of this test  is  to demonstrate the  ability  of a  centrifuge to
 dewater this new-type waste activated  sludge.

 A large scale  test will  be  run once the  sludge characteristics are defined.

 Test

' Spin tests were run on the sludge  as received at ?0-1006C.   The new  test tube
 spinner was used to allow for variations in centrifugal  force. The  data is
 included on pages 1-1 and 1-2.  (Note:  Huch of the  data  was given in cryptic
 notation and has not been included in  this appendix).

 Increased centrifugal force shows  a direct effect in settling out suspended
 soltds and producing a firmer cake.  The settled solids  do not have  much
 body (bulk) since a glass rod readily penetrates into 50% of the  cake.

 flocculants including alum, ferric chloride and lime were used to agglomerate
 the solids to aid in clarification.  All of the polymers  tested on the as
 received sludge showed only minimal, if any, agglomeration.  The polymers  used
 included Allied Colloids, Hercules,  and American Cyanamid.  Polymers used in
 conjunction with others of opposing charge showed no improvement in agglomer-
 ation.  A combination of lime and polymer seemed to work best in providing
 clarity and ftrm cake.  These spin tests are also included on pages 1-1  and
 1-2.   (Not  included  herein).

 Both lime and polymer used together would produce the best results as noted
 in  the spin tests.

 The batch pulp  centrifuge was also  run  at varying gravitational forces  on as
 received sludge  and  flocced slurry.

 Cake solids are  low  and  recovery  poor without pretreatment.   The  best results
 are obtained where  lime  and polymer are used together.   This  data is attached
 on pages 2-1  and  2-2.  (Not included herein).


 Conclusions

 1.  This waste  sludge or one  similar  to that tested would  be  a good  appli-
 cation for a  Bird Continuous  Solid Bowl Centrifuge.

 2.  Since  the cake product will be sold as  soil  conditioner and will probably
 need to be neutralized  to  reduce  residual  acid content,  lime  should  be  added.
                                        157

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This will  both  add  bulk  to  the  cake,  to  produce a more easily centrifuged
material,  and neutralize the acid  content of the final product.  The final
cake material would also have improved soil conditioning properties.  The
lime dosage will have to be defined more exactly in large scale tests but
would be in the range of 500-1000  IDS lime/ton dry solids of sludge.

3.  Polyelectrolytes would  be required for optimum clarification.  The pre-
liminary test indicated  about 1 Ib/ton dosage for +90% solids recovery.

4.  The expected cake product would be directly related to the amount of
lime addition.  The more lime, the drier the cake product  that would result.

5.  A large scale test would be recommended.  The amount of lime to be
allowed should be determined prior to testing.

MMangion:nt/22
NOTE:
                Allied Colloids Percol 763
                     Cost = $1.50/lb in bulk
                            $2.50/50 Ib bag for one bag only

                      1  Ib/ton  dosage  = $2.50/ton max.  cost

                Lime

                     Cost = 2<£/lb

                      500 Ib/ton  dosage =  $10/ton cost
                                    158

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                         BIRD MAGHINE COMPANY, INC.
                       SOUTH WALPOLE, MASSACHUSETTS

                  Addendum to:  Laboratory Report No.  8876
Customer:      Abcor, Inc.
               850 Main Street
               Wilmington, MA

Material:      Brockton Waste Activated Sludge

Problem:       Clarify and Dewater

Test:          6" Bird Continuous Solid Bowl Centrifuge

Test date:     April 20, 1978

Witness:       Mr. John Harland - Engineer for Abcor

Sample No. 127 (Rec'd April 20, 1978)

Two 55-gallon drums containing Brockton waste activated sludge were delivered
to the laboratory for large scale testing purposes.

Sample as received contained approximately 2.92% total solids by weight and
had a spectftc gravity of 1.01 @ room temperature.  Slurry was prepared for
testing by heating to 95° then acidifying with sulfuric acid to a pH of 1.94.


Problem

Abcor is studying a new process for waste treatment described as the "Hot
Acid Process", the principle objective being to dissolve and remove heavy
metal compounds making a solids product which has better soil conditioning
characteristics.

Pilot plant operation will require a deliquoring device which will handle 5
to 10 gallons per mtnute.

As dry a cake as possible is desired, and lime or flocculants cannot be used
as they might precipitate the solubilized metals.

Tests

Five test runs were  completed, for data obtained.  Please note data sheet
                                      159

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 appended  to  this  report.


 Variables investigated were machine speeds of 6000 and 3500 RPM, equivalent
 to 3000 x 6  and 1000 x G, respectively.
         u   Pu°LVOl^mn us?d dun'ng Run #1 was ^creased to the maximum for
 Runs n through #4 and Run #4 was made with increased cake retention time in
 an effort to produce a drier cake.


 Discussion


Test results show that acidified Brockton waste activated sludge would be a
possible application for a Bird Continuous Solid Bowl  Centrifuge.  However,
the restriction on the use of flocculants limits ability to obtain good
recovery of feed solids as cake product.


Samples of feed, cake and effluent from each run were  taken by the witness
for analysis.
                                    160

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TABLE B-l.  SOLID BOWL CENTRIFUGAL TEST DATA FOR BROCKTON WAS AT pH 1.94



                   SOLID BOWL CENTRIFUGAL TEST DATA
Customer:


Run no.
Feed: % solids
Sp. gr.
GPM
PPH solids in feed
Temp., °C
Cake: % solids
PPH wet
PPH dry
Effluent: % solids
Percent recovery
Machine RPM
Force x gravity
Materi al
Date:
1
3.64
1.0
0.73
13.29
95
36.25
2.0
0.72
2.84
23.84
3500
1000
.

2
3.
1.
P.
12.
95
17.
15.
2.
2.
25.


Abcor - Wilmington, MA
W.A.S.
4/20/78
3
64 3.64
0 1.0
70 0.695
75 12.65
95
89 25.81
0 9.33
68 2.4
85 2.47
81 35.54
6000
3000


4
3.64
1.0
0.559
10.18
95
26.88
9.33
2.5
3.0.9
17.07


                                  161

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                                    TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 1. REPORT NO.
  EPA-600/2-80-096
                                                            3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
  Evaluation of Hot  Acid Treatment for
  Municipal Sludge Conditioning
                               5. REPORT DATE
                                August  1980 (Issuing Date)
                               6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
  Kenneth J. McNulty, Ann  T.  Malarkey
  Robert L. Goldsmith,  and Henry A. Fremont
                               8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Wai den Division of Abcor,
  850 Main Street
  Wilmington, MA  01887
Inc.
10. PROGRAM ELEMENT NO.

C36B1C  Decision Unit B-121
                               11. CONTRACT/GRANT NO.

                                 68-03-2459
12. SPONSORING AGENCY NAME AND ADDRESS
  Municipal Environmental  Research Laboratory  Cin.,  OH
  Office of Research and  Development
  U.S.  Environmental Protection Agency
  Cincinnati, Ohio  45268
                               13. TYPE OF REPORT AND PERIOD COVERED
                                 Final
                               14. SPONSORING AGENCY CODE
                                 EPA/600/14
15. SUPPLEMENTARY NOTES

  Project Officer:  Roland  V.  Villiers
                 (513)  684-7664
16. ABSTRACT                                                       	~~	~—
       Bench-scale tests were conducted to evaluate  the technical and economic
  feasibility of the hot acid process for stabilization/conditioning of municipal
  sewage sludge.  This process involves acidification  of the sludge (pH 1.5-3) and
  heating to temperatures  below boiling (^95°C).  Test results indicate that  the
  process improves the dewaterability of the sludge, destroys essentially all
  pathogens, and preferentially solubilizes certain  heavy metals relative to  nitrogen
  and  organics.  The process  demonstrated the potential  for good solubilization and
  removal of toxic heavy metals including cadmium, zinc, and nickel with minimal
  solubilization of nitrogen.   Thus the hot acid process improves the desirability of
  sludge solids for land application.  A preliminary economic analysis of the  process
  indicates that it is quite  cost-competitive with alternative stabilization/
  conditioning processes.
 7.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS  C.  COS AT I field/Group
 Municipal  Sewage Sludge
 Sludge  Conditioning
 Heavy Metals Removal
                  Hot Acid  Treatment
                  Metals  Solubilization
                  Solid-Liquid Separation
                  Stabilization
                  17B
 8. DISTRIBUTION STATEMENT
  Release to Public
                                              19. SECURITY CLASS (ThisReport)
                                                UNCLASSIFIED
                                             21. NO. OF PAGES
                                                  174
                 20. SECURITY CLASS (Thispage)

                   UNCLASSIFIED
                                                                         22. PRICE
EPA Form 2220-1 (Rev. 4-77)
                                               162
                                                            U.S. GOVERNMENT PRINTING OFFICE:  1980--657-165/0105

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