salinitymigaonforpotashminesites · 2016. 5. 20. · salinitymigaonforpotashminesites!...

Salinity Mi*ga*on for Potash Mine Sites Synergis)c Ca)on and Anion Removal Using a Dual-‐Adsorbent

2016 FCS Na+onal Workshop | Montréal, Québec | Sec+on C – Remedia+on

Nick Gibb B.Sc., M.Sc. Candidate

Department of Civil and Geological Engineering University of Saskatchewan

Supervisor: Dr. Wonjae Chang, P.Eng.

Sodium •  Soil structure degrada+on. •  Mobiliza+on of contaminants from soil ion-‐exchange sites.

The Problem Chloride

•  Toxic at high concentra+ons. •  Corrodes equipment and infrastructure.

Fig. 1: Sodic Soil Fig. 2: Chloride-‐damaged leaves 3

4

Increased saliniza-on can impact drinking water through leaching of contaminants in soils, sediments, and water infrastructure.

Kaushal, S. S., Increased Saliniza3on Decreases Safe Drinking Water. Environmental Science & Technology 2016.

Salinity Mi+ga+on for the Potash Industry: Adsorp+on of Sodium Chloride Onto Geomaterials

Desalinized groundwater

Adsorp*on: the binding of molecules to a surface.

Salinized groundwater

Process Schema*c

6

General structure of LDH Fig. 3: R. Salomão et al, Hydrotalcite synthesis via co-‐precipita)on reac)ons using MgO and Al(OH)3 precursors, Ceramics Interna+onal 37 (2011) 3063-‐3070.

Anion (Cl-‐) adsorbent: Layered double hydroxide (LDH)

Cl-‐ adsorp3on mechanism: the memory effect

1.  Thermal treatment (calcina+on) of LDH:

Mg6Al2(OH)16CO3 ! Mg6Al2O9+CO2+8H2O

2.  Contact the calcined LDH with saline water:

Mg6Al2O9+2Cl-‐ + 9H2O ! Mg6Al2(OH)16Cl2 + 2OH-‐

CLDH

CLDH Cl-‐LDH

CO3-‐LDH

Fig. 4: Calcina+on at 500°C for 1 hour is sufficient

8

Ca+on (Na+) Adsorbent Natural Zeolite • Naturally-‐occurring aluminosilicate mineral. •  Isomorphous subs+tu+on: Al3+ for Si4+. • Porous structure holds loosely-‐held, exchangeable ca+ons. • Commonly used adsorbent.

9 Fig. 6 Fig. 5 Fig. 5

Ca+on (Na+) Adsorbent Acid-‐ac*vated Zeolite •  Strips pre-‐exis+ng ca+ons (Ca, Mg, K); subs+tuted by H+. • Weakening of Al-‐O bonds causes dealumina+on. •  Enlarges the surface area.

10 Fig. 6 Fig. 5 Fig. 5

11

Natural zeolite Surface area: 39.6 m2/g

Fig. 7

Zeolite modified with 1 M H2SO4 Surface area: 63.5 m2/g

Increased Surface Area in Ac*vated Zeolite

Objec3ve 1:

Determine the op3mal CLDH dose

12

13 V = 25 mL; [Cl]ini+al = 1542 mg/L; Contact +me: 24 hours; experiments in triplicate

Chloride Percent Removal Vs. CLDH Dose

Selected CLDH pre-‐treatment dose: 2.25 g/100 mL

Objec3ve 2:

Determine the op3mal degree of zeolite acid-‐ac3va3on 0, 0.1, 1, and 2 molar sulfuric acid

14

V = 25 mL; [Na]ini+al = 1000 mg/L; Contact +me: 24 hours; experiments in triplicate 15

0 1 2 3 40

20

40

60

80

100

NZ-Nadc

Zeolite Dose (g)

Na+ %

Rem

oval

Effect of Acid Strength Na+ Percent Removal vs. Zeolite Dose

-‐Nadc indicates that the zeolite was used aCer CLDH pre-‐treatment (i.e. Cl-‐ removal) Natural Zeolite


0 1 2 3 40

20

40

60

80

100

AZ(0.1 H2SO4)-NadcNZ-Nadc

Zeolite Dose (g)

Na+ %

Rem

oval

AZ(0.1 H2SO4) indicates natural zeolite which has been acid-‐ac+vated with 0.1 M H2SO4



0 1 2 3 40

20

40

60

80

100

AZ(1 H2SO4)-NadcAZ(0.1 H2SO4)-NadcNZ-Nadc

Zeolite Dose (g)

Na+ %

Rem

oval



0 1 2 3 40

20

40

60

80

100

AZ(2 H2SO4)-NadcAZ(1 H2SO4)-NadcAZ(0.1 H2SO4)-NadcNZ-Nadc

Zeolite Dose (g)

Na+ %

Rem

oval

1M = 2M > 0.1 M > natural


19

0 1 2 3 40

2

4

6

8

10

12

NZ-NadcAZ(0.1 H2SO4)-NadcAZ(1 H2SO4)-NadcAZ(2 H2SO4)-Nadc

Zeolite Dose (g)

Fina

l pH

Selected acid concentra*on: 1 M

V = 25 mL; [Na]ini+al = 1000 mg/L; Contact +me: 24 hours; experiments in triplicate

Effect of Acid Strength pH Trends

Objec3ve 3:

Determine the op3mal type of acid hydrochloric, nitric, sulfuric

20

21

0 1 2 3 40

20

40

60

80

100

AZ(1 H2SO4)-Nadc

Zeolite Dose

Na+ % R

emov

al


22

0 1 2 3 40

20

40

60

80

100

AZ(1 H2SO4)-Nadc

AZ(1 HNO3)-Nadc

Zeolite Dose

Na+ % R

emov

al


23

0 1 2 3 40

20

40

60

80

100

AZ(1 HNO3)-NadcAZ(1 H2SO4)-NadcAZ(1 HCl)-Nadc

Zeolite Dose

Na+ % R

emov

al Acid Type Not Important


24

1.  CLDH pre-‐treatment dose: 2.25 g / 100 mL

2.  Degree of zeolite acidifica+on: 1 M

3.  Acid type: any strong acid

Op*miza*on Summary

Objec3ve 4:

Removal Efficiency and pH Trends CLDH+AZ Dual Adsorbent Vs. Controls

25

0 1 2 3 4 50

20

40

60

80

100

NZ-NaCl

Zeolite Dose (g)

Na+ Percent Rem

oval

26

-‐NaCl indicates 0.043 M NaCl solu+on; no CLDH pre-‐treatment

Na+ Removal Percentage Vs. Zeolite Dose


27

0 1 2 3 4 50

20

40

60

80

100

NZ-Nadc

NZ-NaCl

Zeolite Dose (g)

Na+ Percent Rem

oval



28

0 1 2 3 4 50

20

40

60

80

100

NZ-NadcAZ(1 HCl)-NaClNZ-NaCl

Zeolite Dose (g)

Na+ Percent Rem

oval



29

0 1 2 3 4 50

20

40

60

80

100

AZ(1 HCl)-NadcNZ-NadcAZ(1 HCl)-NaClNZ-NaCl

Zeolite Dose (g)

Na+ Percent Rem

oval



Na+ adsorp*on enhanced by: 1. CLDH pre-‐treatment 2. Zeolite acid-‐ac*va*on

0 1 2 3 4 50

2

4

6

8

10

12 NZ-NaCl

Zeolite Dose (g)

Fina

l pH

30

Natural zeolite alone: the pH stays neutral, but Na+ uptake is low and there is secondary pollu*on.

Final pH Vs. Zeolite Dose


31

0 1 2 3 4 50

2

4

6

8

10

12 NZ-NaClAZ(1 HCl)-NaCl

Zeolite Dose (g)

Fina

l pH

Ac*vated zeolite alone: very acidic and unsuitable for environmental applica*ons.



32

0 1 2 3 4 50

2

4

6

8

10

12 NZ-NaClNZ-NadcAZ(1 HCl)-NaCl

Zeolite Dose (g)

Fina

l pH

Natural zeolite aZer CLDH: cannot neutralize pH.



33

0 1 2 3 4 50

2

4

6

8

10

12 NZ-NaClNZ-NadcAZ(1 HCl)-NaClAZ(1 HCl)-Nadc

Zeolite Dose (g)

Fina

l pH

Ac*vated zeolite aZer CLDH: By adjus*ng the dose, pH

can be neutralized.



Secondary Pollu*on

34

Natural Zeolite CLDH

Ca2+

Ca2+ K+

Mg2+ Ca2+

Na+

K+ OH-‐

OH-‐

OH-‐ OH-‐ Cl-‐

Na+ Cl -‐

K+

Hard, basic water

Mg2+

Mg2+ K+ Ca2+

Natural zeolite and CLDH

Ac*vated Zeolite CLDH

H+

H+

H+ H+

H+

Na+

H+ OH-‐

OH-‐

OH-‐ OH-‐ Cl-‐

Na+ Cl -‐

OH-‐ H+

H2O

Ac*vated zeolite and CLDH

35

Desalina*on of Potash Brine Impacted Groundwater

Fig. 7

Groundwater-‐brine Bicarbonate 194 Carbonate <1 Chloride 1657 pH 8.15 Sum of ions 3593 Total hardness 517 Nitrate 0.18 Calcium 65 Magnesium 78 Potassium 440 Sodium 673 Aluminum 0.05 Iron <0.01 Sulfate 400 SAR 113

Units: mg/L, except EC (μS/cm), pH and SAR

Groundwater was spiked with potash brine to simulate real-‐world contamina+on

Process Schema*c

37

Groundwater-‐brine Aser CLDH Bicarbonate 194 <1 Carbonate <1 144 Chloride 1657 203 pH 8.15 12.38 Sum of ions 3593 2287 Total hardness 517 141 Nitrate 0.18 0.07 Calcium 65 3 Magnesium 78 <1 Potassium 440 460 Sodium 673 750 Aluminum 0.05 0.15 Iron <0.01 <0.01 Sulfate 400 4 SAR 113 866


Groundwater-‐brine Aser CLDH Aser CLDH and AZ Bicarbonate 194 <1 27 Carbonate <1 144 <1 Chloride 1657 203 219 pH 8.15 12.38 7.31 Sum of ions 3593 2287 391 Total hardness 517 141 99 Nitrate 0.18 0.07 0.55 Calcium 65 3 20 Magnesium 78 <1 10 Potassium 440 460 13 Sodium 673 750 86 Aluminum 0.05 0.15 0.86 Iron <0.01 <0.01 0.52 Sulfate 400 4 6 SAR 113 866 31


40

1.  Increasing the stability of ac+vated zeolite

2.  Regenera+ng or repurposing the saturated adsorbents

Current Work

RESEARCH IN PROGRESS

Poten+al Applica+ons For Environmental Remedia+on

•  Essen+ally anything ionic (e.g. Pb, As, Cd, Se, Ba, Cr, P, NH4, NO3, certain

pes+cides and dyes, etc.).

•  Further research and pilot studies are needed.

Removal of pollutants from water:

Fig. 8 41

Poten+al Applica+ons For Environmental Remedia+on

•  E.g. process water from steam-‐assisted gravity drainage (SAGD) opera+ons.

•  Could be a pre-‐treatment for reverse osmosis desalina+on (to decrease

energy requirements and alleviate the problem of membrane scaling).

Reducing the TDS of produced water:

Fig. 15 42

Fig. 9

Poten+al Applica+ons For Environmental Remedia+on: Pump-‐and-‐Treat System

Fig. 10

43 Introduction to Environmental Engineering, First Edition Richard O. Mines and Laura W. Lackey

Copyright ©2010 by Pearson Education, Inc. Upper Saddle River, New Jersey 07458 All rights reserved

PW Reservoir

Reservoir Dam

Zeolite Treatment System

Monitoring Sta+ons

Fig. 11: Coalbed methane waste stabiliza+on and treatment pond (Powder River Basin, MT)

Poten+al Applica+ons For Environmental Remedia+on: Treatment Pond

44

•  Groundwater saliniza+on is a problem at potash mines. •  A highly-‐efficient dual-‐adsorbent has been developed to remove ca+ons and anions from contaminated water.

•  The dual-‐adsorbent has been characterized and evaluated with both NaCl solu+on and natural groundwater spiked with potash brine.

•  Na+ uptake onto the modified zeolite has been increased by a factor of 2-‐3. •  The treated water is pH-‐neutral and there is no secondary pollu+on. •  The two adsorbents are low-‐cost and can be regenerated. •  This technology has poten+al applica+ons for environmental remedia+on.

Email [email protected] [email protected]

Presenta*on Summary

Figure Credits 1.  Peggy Greb, USDA (D186-‐10). Dried-‐out sodic soil. 2.  University of Maryland. Chloride-‐damaged plant. 3.  R. Salomão, L.M. Milena, M.H. Wakamatsu, V.C. Pandolfelli, Hydrotalcite synthesis via co-‐precipita3on reac3ons using MgO and Al(OH)3

precursors, Ceramics Interna3onal 37 (2011) 3063-‐3070. 4.  Guruleninn (2012). High temperature muffle furnace (1473 K). Wikipedia Commons. 5.  Bear River Zeolite (2011). Mineral and mine photos. 6.  Mills, B. (2006). Zeolites. Wikipedia Commons. Zeolite-‐ZSM-‐5-‐3D-‐vdW.png. 7.  California Department of Water Resources (2016). Groundwater Informa3on Center. 8.  Envirocon (2016). Environmental Remedia3on. 9.  Harvest Energy. Steam-‐Assisted Gravity Drainage Overview. 10.  Introduc3on to Environmental Engineering, First Edi3on Copyright ©2010 by Pearson Educa3on, Inc. Upper Saddle River, New Jersey 07458 All

rights reserved 11.  Richard O. Mines and Laura W. Lackey, Montana Board of Oil & Gas Conserva3on (Billings, MT) and ALL Consul3ng.

46

Research Steering Commicee Richard Weishaupt, Agrium Kathlene Jacobson, Mosaic Jeff Meadows, PotashCorp

R&D Panelists John Sundquist, Agrium Murray Schultz, Mosaic Craig Funk, PotashCorp

Acknowledgements

IMII Team Al Shpyth

Marylou Langridge

Selected References (1/2) Belbase, S., Urynowicz, M.A., Vance, G.F., Dangi, M.B., 2013. Passive remedia3on of coalbed natural gas co-‐produced water using zeolite. Journal of environmental management 131, 318-‐324.

Ganjegunte, G.K., Vance, G.F., Gregory, R.W., Urynowicz, M.A., Surdam, R.C., 2011. Improving saline–sodic coalbed natural gas water quality using natural zeolites. Journal of environmental quality 40, 57-‐66.

Goh, K.-‐H., Lim, T.-‐T., Dong, Z., 2008. Applica3on of layered double hydroxides for removal of oxyanions: a review. Water research 42, 1343-‐1368.

Hutcheson, M.S., 1983. Toxicological effects of potash brine on bay of Fundy marine organisms. Marine Environmental Research 9, 237-‐255.

Kameda, T., Miyano, Y., Yoshioka, T., Uchida, M., Okuwaki, A., 2000. New Treatment Methods for Waste Water Containing Chloride lon Using Magnesium-‐Aluminum Oxide. Chemistry Leners, 1136-‐1137.

Kameda, T., Yoshioka, T., Watanabe, K., Uchida, M., Okuwaki, A., 2007a. Dehydrochlorina3on and recovery of hydrochloric acid by thermal treatment of a chloride ion-‐intercalated hydrotalcite-‐like compound. Applied Clay Science 37, 215-‐219.

Kameda, T., Yoshioka, T., Watanabe, K., Uchida, M., Okuwaki, A., 2007b. Dehydrochlorina3on behavior of a chloride ion-‐intercalated hydrotalcite-‐like compound during thermal decomposi3on. Applied Clay Science 35, 173-‐179.

Liang, X., Zang, Y., Xu, Y., Tan, X., Hou, W., Wang, L., Sun, Y., 2013. Sorp3on of metal ca3ons on layered double hydroxides. Colloids and Surfaces A: Physicochemical and Engineering Aspects 433, 122-‐131.

Lv, L., He, J., Wei, M., Evans, D., Duan, X., 2006. Uptake of chloride ion from aqueous solu3on by calcined layered double hydroxides: equilibrium and kine3c studies. Water Research 40, 735-‐743.

Misaelides, P., 2011. Applica3on of natural zeolites in environmental remedia3on: A short review. Microporous and Mesoporous Materials 144, 15-‐18. 48

Selected References (2/2) Pless, J.D., Philips, M.L., Voigt, J.A., Moore, D., Axness, M., Krumhansl, J.L., Nenoff, T.M., 2006. Desalina3on of brackish waters using ion-‐exchange media. Industrial & engineering chemistry research 45, 4752-‐4756.

Rives, V., 2001. Layered double hydroxides: present and future. Nova Publishers.

Theiss, F.L., Couperthwaite, S.J., Ayoko, G.A., Frost, R.L., 2014. A review of the removal of anions and oxyanions of the halogen elements from aqueous solu3on by layered double hydroxides. Journal of colloid and interface science 417, 356-‐368.

Wajima, T., 2013. Ion exchange proper3es of Japanese natural zeolites in seawater. Analy3cal Sciences 29, 139-‐141.

Wajima, T., 2014. Desalina3on Behavior of Calcined Hydrotalcite From Seawater for Prepara3on of Agricultural Cul3va3on Solu3on Using Natural Zeolite. Energy and Environment Research 4, p3.

Wajima, T., Shimizu, T., Yamato, T., Ikegami, Y., 2010. Removal of NaCl from seawater using natural zeolite. Toxicological & Environmental Chemistry 92, 21-‐26.

Wang, X., Nguyen, A.V., 2016. Characterisa3on of electrokine3c proper3es of clinop3lolite before and aper ac3va3on by sulphuric acid for trea3ng CSG water. Microporous and Mesoporous Materials 220, 175-‐182.

Wang, X., Ozdemir, O., Hampton, M.A., Nguyen, A.V., Do, D.D., 2012. The effect of zeolite treatment by acids on sodium adsorp3on ra3o of coal seam gas water. Water research 46, 5247-‐5254.

Zhao, H., Vance, G.F., Ganjegunte, G.K., Urynowicz, M.A., 2008a. Use of zeolites for trea3ng natural gas co-‐produced waters in Wyoming, USA. Desalina3on 228, 263-‐276.

Zhao, H., Vance, G.F., Urynowicz, M.A., Gregory, R.W., 2009. Integrated treatment process using a natural Wyoming clinop3lolite for remedia3ng produced waters from coalbed natural gas opera3ons. Applied Clay Science 42, 379-‐385.

49

BACKUP SLIDES For Q&A

50

Synergis*c Effects

51

Zeolite performs much bewer under the basic condi+ons (pH ~12.5) generated by CLDH

Fig. 6

–AOH + OH-‐ ! –AO-‐ +H2O (where A can be either Al or Si)

Hydroxide generated from anion removal using CLDH

Nega+ve charge enhances ca+on

adsorp+on

pH neutraliza+on

Zeolite is amphoteric – it can take on an extra H+ or lose the one it has to develop charge

Treatment Sequence

52

CLDH 1st, ac*vated zeolite 2nd:

Ac*vated zeolite 1st, CLDH 2nd: LDH is unstable under the acidic condi)ons (pH ~2.5) generated by ac)vated zeolite.

Ac)vated zeolite performs very well under the basic condi)ons generated by CLDH

pH ↑

pH ↓

pH ↑

pH ↓

53

Na+ Adsorp*on Isotherm

54

Isotherm Models

Zeolite Freundlich Model Langmuir Model 𝐾↓𝐹  (mg/g)

(mg/l)n 1/𝑛 R2 𝑞↓𝑚𝑎𝑥 

(mg/g) 𝐾↓𝐿 

(1/mg) R2

NZ-‐NaCl 0.0081 1.01 0.9938 n/a

NZ-‐Nadc 0.2469 0.5767 0.979 19.5 0.00179 0.9951

AZ(1 HCl)-‐NaCl 0.0722 0.7284 0.9875 16.7 0.00134 0.9819

AZ(1 HCl)-‐ Nadc 0.5450 0.5374 0.9458 28.6 0.00276 0.986

55

CLDH Regenera*on •  Thermal treatment of Cl-‐LDH •  Regenerates CLDH •  Concentrated HCl by-‐product; it can be sold or used to regenerate the zeolite.

•  Highly efficient; minimal waste.

Re-‐purposing the Saturated Adsorbents

LDH Selec*vity

CO32− > Naphthol Yellow2-‐ > HPO4

2-‐ > HAsO42-‐ > CrO4

2-‐

> SO42− > MoO4

2-‐ > OH− > F− > Cl− > Br− > NO3− > I−

Clinop*lolite Zeolite Selec*vity

Cs+ > Rb+ > K+ > NH4+ > Ba > Sr2+ > Na+ > Ca2+ > Fe3+ > Al3+ > Mg2+ > Li+

•  Cl-‐LDH could be used for adsorp+on of hazardous materials, e.g. uranium oxyanions, fluoride, heavy metals, oxyanions, dyes, etc.

•  Similarly, the Na-‐zeolite can be re-‐purposed, e.g. removal of heavy metals.

Note: these selec+vity sequences are not complete.

Miyata 1983

Zhao et. al. 2009

56

salinitymigaonforpotashminesites · 2016. 5. 20. · salinitymigaonforpotashminesites!...

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