PRETREATMENT TARGETS FOR SALT 

RECOVERY FROM MARCELLUS SHALE 

GAS PRODUCED WATER 

James Silva, Rachel Gettings, 

William Kostedt, and Vicki Watkins 

IWC-13-38 

1mog1nOtlon ot work 
ACKNOWLEDGEMENT 

Funding for t his project is provided by RPSEA through the {/UltraDeepwater and Unconventional Natural Gas and Other Petroleum 

Resources" program authorized by the U.S. Energy Policy Act of 2005. 

RPSEA (www.rpsea.org) is a nonprofit corporation whose mission is to 

provide a stewardship role in ensuring the focused research, 

development and deployment of safe and environmentally responsible 

technology that can effectively deliver hydrocarbons from domestic 

resources to the citizens of the United States. RPSEA, operating as a 

consortium of premier U.S. energy research universities, industry, and 

independent research organizations, manages the program under a 

contract with the U.S. Department of Energy's National Energy 

Technology Laboratory. 

IN TER NA TIO NA L WAT£R CO N FERE N CE 2013 
Marcellus Shale Gas Water Management 

-Growing produced water (PW) supply 

-Reuse dominates .. .for now 

-Increasing PW TDS 

-PW supply eventually exceeds demand 

... water and salt recovery required 

30 ~--~--~--~----~--~ 

25 

Qj 20 ..... 

~ 

15 15 

:2: 

:2: 

10 

: : 

Pennsylvania Marcellus .•.•. ·l-· .•.. . .•. . . . ..•. . • ...... ..•• . . • . .•.• .....•.... . 

• Produced (total) 

• Reuse (hydrofractunng) 

• Deep-well lriection ............... ": . . . . ... . . . . .. .. . . ....... ' ... : .. " ......... . . . . . . . . . 

............... ~ ................. ~ .............. . 

: . ........... ·-r .............. ! ... : . . . 

5 .... . . ...... , ...... ...... .. , : : : . : : . . 

0 '-------'-----'-

2008 2009 

Objective: Define pretreatment specs for salt recovery 
Process Roadmap 

Produced Water Composition 

1 

Salt Dispojal Options 

NaCI Product Specifications 

Ba, ppm pCi 226Ra/gm 

RCRA-D Disposal (nonhazardous waste) 2100 (TCLP) 

Beneficial Reuse (e.g. road deicing salt) < rock salt (-5) < rock salt (-0.02) 

Produced Water Pretreatment Specifications 

I N TER NA TIO N AL A CO N fERE N CE 20 1 3 
PA Marcellus Produced Water Composition 

Component 

Na, mg/L 

Mg 

Ca 

Sr 

Ba 

TDS 

226Ra, pCi/L 

Design 

Case-1 

35,000 

800 

9,500 

2,500 

6,200 

132,000 

5,000 

Design 

Case-2 

52,000 

1,900 

25,000 

6,100 

8,200 

242,000 

12,500 

Design 

Case-Expt 

51 ,000 

1,800 

19,000 

1,700 

6,200 

200,000 

6,900 

Maximum Water Recovery(%) 

Evap Only 55 20 33 

Evap + NaCI{s) 89 TBD 80 

NaCI Crystallization Required for High Water Recovery 

rER NA TIO NA L WATEA CONFERE N CE 2013 
PA Marcellus Produced Water Composition Survey 

Tioga:2 \ Bradford: 7 samples 

3.5•15K 6.6-28.8K mg/I.J '!~ 

S.S-H .

4K 4.2-12.8K pCill Ra 

, 

)>-----1~ /-;\ 

I Significant Ba, Ra throughout PA Marcellus I 

I N TE itNA TIO N A L CO CE 20 1 3 
Aspen Plus TM /OLI Evaporation/Crystallization Model 

Raw 

Produced 

Water Distilled Water 

Pretreatment f-L+I Evaporation/ 

Crystallization 

Sludge Purge 

Slurry -+l Treatment-1 

Dewater 

Purge 

Crystal Treatment Fluid 

Treated 

Treatment-2 ~----+ Crystals 

to Dryer 

I Identify Operating Boundaries, Pretreatment Requirements I 

I N TER NAT IO NA L C O N F £ 1t£ N C£ 2 013 

Model Results 

() 113 1----:::::=:!==::::r:==:::c:::;--l 

~ 112 

::J 

.... 

~ 

2t 111 

E 

Q) 

I- 110 .... 

0 

a.. 

(i) 109 

N 

tl 108 

>-

..... 

() 

107 

o 1-liter lab crystallzation 

- Aspen Plus/OLI model 

of• •••••••••••••••••••••••••••••••••• ,_...,....,. 

. 0 0 

ooo 0 oo oo: 

0 0 : 

... ,t. ·····l···· ............ +·· ............. . 0 

0 

0 

······~···· ... . ···-·· ~-- ........... . 

. . ' "'' ••••• ' ' ;, • •• ••• •• ·• ... ···I··.. . .... ....... _: ... ............... . 

i : DC- pt 

. .... ..... ... ; .................. : .. Produced Water ....... . 

~ 1 atm 

106 l...---.L.---1----.I....-----A----.J 

1 1.5 2 2.5 3 

Concentration Factor vs. Pretreated Produced Water 

-Temperature trend 

0.8 

c o0.6 ~ 

u 

~ 

u.. 

0.4 

0 .2 

--Naa Rec011ery 

--H20 Rec011ery 

--BaCI2 Rec011ery 

xW Solids XTl ML 

... ~· ..... . ...... t ............... } .......... . . . . 

DC-Expt ..... i ............ . Produced Water 

1 atm 

0 ~~~~~~~~~~~~~~ 

1 2 3 4 5 6 

Concentration Factor vs. Pretreated Produced Water 

-Predict maximum concentration factor (w/o BaCI2 coprecipitation) 

I N TE R N AT IO N A L CO N fE R E N CE 2013 
Operate Below Maximum CF 

Ba/Sr 

Ba/Ca 

Bulk Crystal Mass Ratios 

Evap Feed 

4.5 

0.34 

Crystals 

4.6 

0.34 

ratio(xtls) 

---

ratio(feed) 

1.0 

1.0 

I BaCI2 on NaCI crystals: entrained mother liquor I 

IN TER NA TIO NA L W AT£R CO N FERE N CE 2013 
Estimate Residual Ba, Ra on Treated NaCI Crystals 

-Sulfate pretreatment effective for Ba, Ra removal 

-Ra/Ba pretreated water same as raw water 

-Ra, Ba on NaCI crystals: entrained concentrate 

-NaCI crystal dewatering, treating key to achieving specifications 

Unit Operation 

Evaporation/ 

Crystallization 

Crystal 

Treatment 

Parameter Typical Values 

Pressure 1 atm 

Water Recovery 85% 

Wt fraction moisture in dewatered crystals o.q3-0.05 

Crystal treatment liquor/crystal mass ratio 0.02- 0.2 

I N TERNATIO N A L CO N FE R E N CE 2013 
E 

a. 

a. 

~1000 .!!1 

~ >-

~ 

(.) 

(.) 

co 

z 

~ 500 

0 

.!: 

co 

co 

Design Case-1 Results 

RCRA-D OK 

226Ra: 1.4 pCi/gm 

--Oewatered Crystals 

--Treatment-1 

--Treatment-2 . . . . . . ......... ; ........ ..;. . ....... •······ .. -~- ........ : ..... ............. . 

Raw 

feed 

~b±±=t=rLJ 0 1000 2000 3000 4000 5000 6000 7000 

[Ba] in Pretreated Feed (mg!L) 

I N TE RNA TIO NA L CO N rEAE N CE 2013 
i 

E 

a. 

a. 

~1000 

!!1 

~ >-

.... 

() 

() 

ro 

z 

~ 500 

0 

c: 

ro 

(]) 

Design Case-1 Results 

RCRA-D OK 

226Ra: 1.4 pCi/gm 

-Dewatered Crystals 

- Treatment-1 

- Treatment-2 

.... : ........ ~. . .... .;. ...... . 

2000 3000 4000 5000 6000 7000 

[Ba) ln Pretreated Feed (mg/L) 

50 r---,----.--~----~--,---~ 

~ 

i 40 E 

a. 

a. 

~ 

!!1 

- Dewatered Crystals 

.. - Treatment-1 

- Treatment-2 

. . . . ro 30 · 1ii 

. ............... .. ... ..... ... .. .. . ......... . 

>-

.... 

() 

() 

ro 20 ·· ··· · ·· · · 

z 

~ 

0 

c: 

ro 

(]) 

10 

50 100 150 250 300 

[Ba) in Pretreated 

Beneficial reuse OK, 226Ra 

0.004 pCi/gm 
Conclusions: 

-PA Marcellus produced water: significant Ba, Ra levels 

-Aspen Plus/OLI crystallizer model correctly predicts BaCI2 coprecipitation 

-Source of Ba, Ra in NaCI(s): concentrate entrained with NaCI crystals 

-Pretreatment and crystal treatment: significant influence on Ba, Ra in NaCI(s) 

-Design Case-1 produced water to NaCI(s): meeting NaCI(s) Ba product spec 

determines pretreatment target and extent of crystal treatment needed 

I N TER NA TIO NA L A CO N rERE N CE 20 13