SIMPLIFIED

 “FLOTATION  DE-­‐INKING”  OF  NEWSPAPER

NAUMAN  MITHANI  (CHEM  317  -­‐  2010  SPRING)

1
 PURPOSE
• de-­‐ink  newspaper  as  per  the  technique  of  flota%on  de-­‐inking

• scaled  down  &  adapted  for  lab  environment                                  improvised  equipment

• focus  on  op#misa#on  of  variables:

✓ duraAon  of  flotaAon

✓ concentraAon  of  flotaAon  agent

if   -­‐ temperature
possible
-­‐ consistency  (cs.  %)

2
 BACKGROUND:    paper   facts

• paper,  a  ubiquitous  material

recovered
• a  disposable  material un-recovered

• 33%  to  50%  of  solid  municipal  waste* 100

paper (million tonnes)

➡ a  crucial  parameter  in  the  long-­‐term  environmental   75 50
sustainability  of  a  large  populaXon  centre

50
✤ so  it  must  be  recycled,  which  in  turn  consumes...

✤ water 25 50
4.5
✤ electricity 13.5
0
✤ &  other  (environmental)  resources USA (2004) Canada (2006)

✤ sustainability  &  expansion  if:

✤ high  performance  &  high  quality  of  recycled  paper

* Nie et al. Environmental Engineering and Policy (1998) vol. 1 (1) pp. 47-58 3
 INTRO:  chemical  composiXon  of  paper

• Paper,  essenXally,  is  a  felted  sheet  of  cellulose  fibres

• actually,  it  is  a  complex  mixture  of    chemical  addiXves,  fillers,  bonding  agents  (upto  ~40  %  weight)

• Cellulose:  (C6H10O5)n
• bears  a  surfeit  of  O-­‐  and  OH  groups                  network  of  H-­‐bonds
• highly  hydrophilic
• zero  water-­‐contact  angle

hydrophilic and hydrophobic surfaces. The contact angle

is measured from the surface through the liquid to the
Hydrophilic Hydrophobic tangent of the liquid surface as indicated by the arrows.

4
 INTRO:  the  ink  (toner)
• Ink  applies  to  paper...
• ...  by  absorpXon  which  then  dries/sets  in  the  fibre
• ...  OR...  by  fusing  which  then  cools  and  bonds  to  the  fibre

• different  composiXon  for  different  printed  materials:

• NEWSPRINT  INK:  mineral/vegetable  oil  (45  -­‐  60%)  and  resin  (5  to  35%)

• the  oil  serves  as  the  vehicle  for  the  pigment

• black:  inorganic  carbon  (graphite)  blacks
• colours:  organic  pigments

• immiscible  oil  +  (co)polymer  resin  +  carbon  black                          ink  is  H-­‐phobic

• water  contact  angle  is  >80°.
hydrophilic and hydrophobic surfaces. The conta
is measured from the surface through the liquid t
Hydrophilic Hydrophobic tangent of the liquid surface as indicated by 5the a
 INTRO:  flotaXon  de-­‐inking
• (froth)  flotaXon  de-­‐inking  is  the  more  popular  de-­‐inking  method
• bejer  than  wash  de-­‐inking  (laundry-­‐esque)  since  it  can  also  remove  larger  parXcles:  10  -­‐  
400  μm  (diameter)  in  addiXon  to  fine  ink  &  filler  parXcles.

• overall:  lesser  quanXXes  of  water  needed

• overall:  higher  quality  of  recycled  paper

• schemaXc  below  shows  industrial  de-­‐inking  plant  setup

source: Wikipedia
6
 INTRO:  the  flotaAon  de-­‐inking  process
• first  step  -­‐  pulping:  the  paper  is  disintegrated  in  water  to  form  a  pulp  slurry

• collector  (foaming  agent  +  surfactant)  is  added  to  pulp  slurry

• air  (bubbles)  is  introduced

• the  H-­‐phobic  ink  binds  to  collector  +  air  bubble • actuality:  conXnuous  FEED  of  pulp  slurry  
+  collector  mixture  into  such  a  chamber  
• carried  to  the  surface  -­‐  REJECT  stream where  air  is  con#nuously  supplied

• forms  “contaminant”-­‐laden  foam/froth

• which  is  then  removed  or  scraped-­‐off

• the  flotaXon  is  only  1  in  a  series,  there  are  2  series

• only  1  improvised  flota#on  cell  shall  be  used  here

source: Wikipedia 7
 analyzed for ink concentration and for fiber content.

Tubing
Foam laden with ink
Air Pump Dispersed Figure
Wastepaper
Large Plastic Tray experi

Figure 1. Schematic Drawing of the Laboratory Flotation Experiment.

schemaXc  of  the  improvised  flotaXon  cell  
Common, inexpensive equipment and no chemicals (other than a surfactant to enhance foaming) are ne

for the exercise. The experiment is useful for middle/high school science courses or introductory level

college environmental, chemical engineering, or chemistry courses in need of a simple experiment that

schemaXc  of  industrial  flotaXon  cell  setup

EWFTiBook:Users:fedosky:Desktop:_Online:JCE May 2004:JCE0504_Web Supplements:JCE2004p0693W.doc
2

photo  of  the  improvised  flotaXon  cell 6

photo  of  an  industrial  flotaXon  cell  using  “surface  surfactant  spray”

source: Deng et al. “SURFACTANT SPRAY”...Georgia Institute of Technology (2004)

8
 INTRO:  flotaAon  de-­‐inking  performance
dry mass of accepted solids
• fibre  yield,  Y  (%):   dry mass of total solids fed into process × 100

• based  on  the  law  of  mass  conservaAon:  (F)EED    =    (A)CCEPT  +  (R)EJECT

A
• fibre  yield  based  on  (F)EED  and  (A)CCEPT  stream:     YFA (%) = × 100
F

F−R
• fibre  yield  based  on  (F)EED  and  (R)EJECT  stream:   YFR (%) = × 100
F

A
• fibre  yield  based  on  (A)CCEPT  and  (R)EJECT  stream: YAR (%) = × 100
A+ R

• contaminant  removal  OR  cleanliness  efficiency:

• based  on  the  contaminant  or  ink  spec  count  of  the  (F)EED  and  (A)CCEPT  streams:
FEED count - ACCEPT count
cleanliness efficiency = × 100
FEED count

9
EXPERIMENTAL:  notable  MATERIALS  (common,  inexpensive)
• household  blender

• generic  1  litre  aqua#c  tank  pump  coupled  with  an  air  diffuser

• Paper:  same  pages  from  mulXple  copies  of  a  standard  newspaper  (SFU  Peak)  printed  on  
52/75  e-­‐brite  paper  (NORPAC,  Burnaby,  BC)

• Ink:  standard  newspaper  ink  (Sun  Chemical,  Richmond,  BC)  -­‐  exact  formulaXon  could  not  be  
known

• foaming  agent  (collector):  “BRD2345”,  a  proprietary  foaming  agent  (Buckman  Laboratories,  

Memphis,  USA)

• microscope  &  soQware  for  ink  spec  size  and  density  characterisaXon:  

• MoAc  B-­‐5  Professional  Series  with  MoAc  images  Advanced  3.0  by  Micro-­‐OpXc  Industrial  
group  (Richmond,  BC)
10
EXPERIMENTAL:  METHOD  (overview)

1. cut  2.25g  worth  of  paper  into  3  ×  3  cm  squares  and  place  them  in  blender  with  400  mL  of  tap  water  (pH:  6.51)  of  
desired  temperature

2. blended  for  3  min.

3. added  desired  amount  of  foaming  agent  to  the  pulp  slurry  and  sXrred  gently  at  length  (>  5  min.)

4. divided  the  pulp  slurry  into  two  beakers  labelled  FEED  stream  &  ACCEPT-­‐to-­‐be  stream

5. filled  the  ACCEPT-­‐to-­‐be  stream  beaker  to  desired  volume  (maintained  temperature)  to  control  consistency  (cs.  %)

6. placed  the  ACCEPT-­‐to-­‐be  stream  into  a  relaXvely  large  plasXc  tray

7. the  air  diffuser  connected  to  the  air  pump  (by  tubing)  was  placed  into  the  beaker

8. the  pump  was  turned  on  to  mark  the  start  of  the  flotaXon

11
 eq. 2: Cleanliness efficiency = " 100
Associate Professor FEED count
North Carolina State University

EXPERIMENTAL:
Department of Wood and Paper Science

 METHOD  (overview)
It has been found that the operational parameters of a flotation de-inking process must balan
Raleigh NC, 27695-8005
Telephone: (919) 515-6185
Fax: (919)fibre
515-6302
Email: richard_venditti@ncsu.edu
(contd.)
yield and high cleanliness efficiency: if a high fraction of the FEED is subjected to rejection then
the (processed) sample may be very clean; naturally, the down side is low fibre yield; and vice versa

Lab Summary
• Experimental overview
9. the  generated  foam  wFlotation
as  periodically   scraped  
de-inking is used in paperorecycling
ff  (REJECT   stream)
processes to preferentially remove hydrophobic contaminants
This series of experiments seeks to build upon the paper on lab-scale flotation de-inking by V
such as inks and toners
Chem. from a slurry
Ed. 81(5), 693]:of “A
fibers in an aqueous
Simple phase.
Flotation In the process,
De-Inking fine air bubbles
Experiment for theareRecycling of Paper” [9]. The ex
10. arer  a  certain,  desired   Xme  into
introduced the  
thepsuspension
ump  was  
and turned   off  to  contaminants
the hydrophobic mark  the  epreferentially
nd  of  the  attach
flotaXon
to the bubble-water
overview is cited as follows:
interfaces and float to the surface. The foam on the top of the surface laden with contaminant is skimmed
11. the  contents  of  the  away
plasXc   tray  in(REJECT  
resulting stream),  the  remnants  in  the  ACCEPT-­‐to-­‐be  beaker  (now  the  ACCEPT  stream)  
the separation.
“This paper describes a laboratory exercise for the flotation de-inking of wastepaper. The exercise consists
&  the  contents  of  the  FEED  stream  were  filtered  (Whatman  1:  110  mm)
printed wastepaper in a blender and then removing the ink or toner contaminants by pumping air bubble
suspension
This paper describes usingexercise
a laboratory an aquarium pumpde-inking
for the flotation or otherofsource of airThe
wastepaper. bubbles.
exerciseFoam is
consists taken off the top of the cont
12. the  contents  of  each  stream  were  dried  overnight  at  105  °C
inkprinted
of disintegrating (the reject sample)
wastepaper while the
in a blender and cleaned fiber the
then removing remains in thecontaminants
ink or toner container by
(the accept sample). After the expe
reject samples
pumping air bubbles aresuspension
through the analyzedusing
for ink concentration
an aquarium and for
pump (Figure fiber
1) or content.
other source of air
13. the  mass  of  the  contents  (fibres)  
Common, of  each   stream  w
inexpensive as  measured
equipment and no chemicals (other than a surfactant to enhance foaming) are need
bubbles. Foam is taken off the top of the container that is rich in ink (the reject sample) while the cleaned
exercise.” [9]
fiber remains in the container (the accept sample). After the experiment the accept and reject samples are
14. contaminant  (ink  spec)  characterisaXon  was  ajempted  using  the  microscope  setup
analyzed for ink concentration and for fiber content.

Tubing
Foam laden with ink
Air Pump Dispersed Figure 3: A schematic drawing of the
Wastepaper
Large Plastic Tray experiment.

Figure 1. Schematic Drawing of the Laboratory Flotation Experiment.

• a  schemaXc  of  the  experimental  setup  is  shown  here

12
RESULTS  &  DISCUSSION:   INK  SPEC  COUNT  FAILURE

• the  ink  specs  were  too  small  &  numerous  for  the  naked  eye

• could  not  carried  out  with  the  microscope:  two  sample  photos  from  different  experiments  are  shown  below

• even  at  10X,  the  specs  are  too  small  and  numerous  for  a  manual  count  -­‐  the  sorware  did  not  have  the  
ability  to  conduct  a  parXcle/spec  count

• at  >10X,  there  was  insufficient  light  for  any  viewing 13

 RESULTS  &  DISCUSSION:   effect  of  CS.  %

• consistency,  cs.  %  is  defined  as:          cs.      )    =        mass

       (    %                of
       solids
                   (grams)
                         ×      100
                         where  ρ(water)  =  1  g /mL
volume of water (mL)

vol. conc. time avg. Y

T (°C) cs. (%) σ (%)
(mL) (mL/g) (min.) (%)

23 0.296 5.00 2.22 10.0 48.9 4.7

23 0.468 5.00 2.22 10.0 28.5 19.2

average Y (%) vs. cs. (%) • as  the  cs.  %  is  raised  by  58%,  the  yield  falls  by  
60 the  same  number:  ΔY(%)  /  Δcs.(%)  =  1

50
• expectedly,  since  there  is  a  greater  
40 amount  of  fibre  per  unit  volume  of  
avg. Y (%)

water...
30

20 • ...  there  is  more  that  may  be  carried  off  

into  the  REJECT  stream.
10

0 • results  are  inconclusive  since  there  are  

0.20 0.26 0.32 0.38 0.44 0.50 insufficient  data  points.
cs. (%)
14
 RESULTS  &  DISCUSSION:   effect  of  TEMPERATURE

vol. conc. time avg. Y σ (%)

T (°C) cs. (%) (mL) (mL/g) (min.) (%)

23 0.468 5.00 2.22 10.0 28.5 0.6

35 0.468 5.00 2.22 10.0 21.2 20.5

average Y (%) vs. temperature (°C)

50
• as  the  temperature  is  raised  by  52%,  the  
fibre  yield  falls  by  26%:                                                                      
40
ΔY(%)  /  ΔT  (°C)  =  0.5
avg. Y (%)

30
• expectedly,  as  there  is  greater  convecXon  and  
20
greater  thermal  moXon...

10 • ...  there  is  a  greater  amount  that  goes  up  &  

out  as  REJECT  stream
0
20 25 30 35 40
• results  are  inconclusive  since  there  are  
temperature (°C)
insufficient  data  points

15
 RESULTS  &  DISCUSSION:   effect  of  TIME   (min.)

vol. conc. time avg. Y

T (°C) cs. (%)
(mL) (mL/g) (min.) (%)
σ (%) • downward  trend  is  expected

23 0.468 5.00 2.22 10.0 28.5 19.2 • trend  is  exponenXal:  as  Xme  goes  by...
23 0.468 5.00 2.22 5.0 35.8 18.4
23 0.468 5.00 2.22 3.0 40.9 31.1
23 0.468 5.00 2.22 2.0 51.6 20.6
• ...  fibre  +  water  are  REJECTED
23 0.468 5.00 2.22 1.5 54.4 15.1
23 0.468 5.00 2.22 1.0 64.2 0.2 • the  layer  of  foam  becomes  thicker  &  
thicker  -­‐  reaches  deeper  into  the  beaker
average Y (%) vs. time (min.)
80 • acts  as  physical  filter/barrier  for  
70
remaining  fibres...

60
• ...  slows  further  fibre  REJECTION
50
avg. Y (%)

40
• as  per  the  trend,  ideal  flotaXon  
30
R² = 0.99 duraXon:  0  <  t  (min.)  ≪  1  -­‐  unrealisXc
20

10 • table  shows  a  significant  increase  

0
below  3  min.  -­‐  the  1.5  -­‐  2.0  min.  region
0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
time (min.)
16
 RESULTS  &  DISCUSSION:  effect  of  CONCENTRATION  of  FOAMING  AGENT
T (°C) cs. (%)
vol. conc. time avg. Y
σ (%)
• fibre  yield  is  not  affected  by  
(mL) (mL/g) (min.) (%)
concentraXon  of  foaming  agent
23 0.468 5.00 2.22 1.5 54.7 15.3
23 0.468 4.00 1.78 1.5 58.8 0.2
• a  volume  as  low  as  0.25  mL  in  240  mL  
23 0.468 3.00 1.33 1.5 58.2 0.8
23 0.468 2.00 0.89 1.5 48.9 4.7 of  water  may  be  sufficient  for  
23 0.468 1.00 0.44 1.5 58.3 5.8 flotaXon
23 0.468 0.50 0.22 1.5 53.8 41.5
23 0.468 0.25 0.11 1.5 57.2 40.9

• 1:1000  of  foaming  agent:water

Y (%) vs. vol. of BRD2345 foaming agent
100 • lower  cost  of  operaXon
90
80
70
avg. Y (%)

60
50 R² = 0.0001
40
30
20
10
0
0 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00
volume of BRD2345 (mL) 17
FURTHER  DISCUSSION
• individual  high  error  margins:  fibre  loss

• wet  fibre  sXcks  to  every  container/vessel  -­‐  difficult  to  wash  down  -­‐  scrubbing  down  is  not  possible  during  an  
experiment

• ∴  fibre  loss  in  every  transfer/step  e.g.  division  into  separate  FEED  and  ACCEPT  streams

• compounded  with  each  subsequent  step  -­‐  the  further  a  step  is  from  the  FEED  stream,  the  higher  the  loss  (reason  for  
the  significantly  different  YFR)

• suggesAon:  use  a  flotaXon  vessel  with  rough  interior  walls  or  Teflon

• other  a^empts  at  ink  spec  count:  failure

• pulped  and  intact  squares  were  placed  in  various  solvents  to  ajempt  a  leeching-­‐out  for  subsequent  UV-­‐Vis  
spectroscopic  analysis

• ...  benzene,  toluene,  xylenes,  DMSO,  acetonitrile,  polypropylene  glycol,  glycerol,  methanol  &  ethanol...

• graphite  is  virtually  insoluble  -­‐  all  ajempts  failed

• suggesAon:  dedicated  system  e.g.  flatbed  scanner/CCD  camera  +  image  analysis  sorware  e.g.  Apogee  Spec*Scan  2000

18
CONCLUSION
• cs.  %:  higher  fibre  loss  with  higher  cs.  %

• temperature:  higher  fibre  loss  with  higher  temperature

• dura#on:  a  realisXc  opXmum  of  1.5  min.  was  determined  with  a  fibre  yield  of  54.4%

• concentra#on  of  foaming  agent  BRD2345:  has  no  effect  on  fibre  yield

• suitable  concentraXon:  1:1000  in  water

• results  are  only  par#ally  valid:  only  one  of  two  performance  criteria  could  be  obtained

• effect  of  experimental  variables  on  contaminant  count  could  not  be  ascertained

• dedicated,  proper  equipment  is  needed

19
ACKNOWLEDGEMENTS
• Dr.  Richard  Vendie  of  the  Wood  &  Paper  Science  Dept.  of  North  Carolina  State  University  for  his  
guidance  and  provision  of  the  foaming  agent  BRD2345.

• Dr.  Dev  Sharma,  for  his  general  assistance

• SFU  Dept.  of  Chemistry  for  their  generous  funding  and  making  this  only  a  2-­‐credit  course

• Tahir,  for  his  ears

• Jasbir,  for  his  complete  experimental  failure  thereby  reassuring  my  that  parXal  failure  is  not  so  
bad

• Yuen,  for  never  being  here  -­‐  the  extra  benchspace  was  invaluable

• Neil  Draper,  for  reminding  me  that  pH  of  water  slowly  decreases  in  open  air

• ...  Dr.  Goyan,  for  the  ?-­‐grade...

20
REFERENCES
• [1]   Breedlove.  The  analysis  of  ball-­‐point  inks  for  forensic  purposes.  Journal  of  chemical  educa#on  (1989)  vol.  66    (2)  pp.  170

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