# 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 h is project is provided by RPSEA through the {/Ultra Deepwater and Unco nventiona l Natural Gas and Other Petroleum Resources" program authorized by the U.S. Energy Policy Act of 2005 . RPSEA (www . rp sea.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 techno l ogy that can effectively deliver hydrocarbons from domest i c resources to t h e citizens of the United States. RPSEA, operating as a consortium of premier U.S. energy research universities, industry, and independent research organ i zat i ons, 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 wate r (PW) s uppl y -Reu se dominates .. .for now -Increasing PW TDS

- P W supp ly eventually exceeds demand

. ..water and sa lt recovery required**30 ~--~--~--~----~--~**  

### 25 Qj 20


### .....

## ~ 15 15 :2: :2: 10 : : Pennsy lva n ia M arcellus .•.•. ·l-· .•. . . . •. . . . .. •. . • ..... . .. • • . . • . . •.• .. .. . •... . . • Produced (tot al ) • Reuse (hydrofractunng) • Deep-well l riectio n
. ....... . . . .... ": . . . .... . ... .. .. . . ....... ' ... : . . " ......... . . . . 

### . . . . .

.... . ....... . ..**~** . .. ....... . . . . .. .**~** . . .... . .. . .. . . .
: . 

# ........... ·-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 

### 226 Ra/gm R C RA-D Di sposa l ( n onhazardous waste) 2100 (TCL P ) Beneficia l Reuse (e.g. road deic i ng sal t ) < rock sal t (-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 N a, mg/ L Mg Ca Sr Ba TDS 226 

### Ra , 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 E vap 

### + NaCI {s) 

### 89 TBD 

### 80 

# NaCI Crystallization Required for High Water Recovery
rER NA TIO NA L WATEA CONFERE N CE 2013

# PA Marcellus Produ c ed Water Composition Survey

Ti oga: 2 \ B radf o rd : 7 samples 3 . 5• 15 K 6 . 6 -28 . 8K mg /I.J

**'! ~**  S . S- H .4 K 4 . 2- 1 2 . 8K pC ill Ra ,



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



# I Significant Ba , Ra throughout PA Marce llus 

# 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 Crysta l 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- 1 10 

## .... 0 a.. (i) 109 N tl 108 >- ..... () 107 o 1-liter lab crystallza tion

- Aspen Plus/OLI model of• •••••••••••••••••••••••••••••••••• ,_...,....,.
. 0 0 ooo 0 oo oo: 0 0 : 

# ...

,t. ·····l···· ............ 

## +·· ............. . 0 0 0

**······~····** ... . ···-··

**~--** ............

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

### i :

**DC- pt** 

. .... ..... ... ;..................:.. Pr od u ce d W at er .. .. .. ..

**~** 1 atm 106 l...---.L.---1----.I....-----A----.J 1 1 .5 2 2 .5 3 Concentrati on Factor vs . Pretreated P roduc ed Wate r



### - T e mp e rature trend 0 . 8
c o0 .6

**~** u

**~** u.. 0.4 0 .2 -- Naa Rec011ery

-- H20 Rec011ery

-- BaC I2 Rec011 ery xW Solids XTl ML



## ...

**~·** 

## ..... . ......t ............... } .......... . . . .

DC- Expt ..... 

### i............ . Produced W a t e r 1 atm 0

**~~~~~~~ ~~~~**  **~~~** 1 2 3 4 5 6 Co ncentra t i on Fa ctor vs . Pretreated P r od u ced W ater 

### -Predict maximum con centrat ion f actor (w /o BaCI 2 

### co pre ci p i ta t i on ) I N TE R N AT IO N A L CO N fE R E N CE 2013

# Operate Below Max imum CF

Ba/S r Ba/Ca B ulk C r ystal M ass Ratios Evap Feed 

### 4 . 5 0 . 34 Crystals 

### 4 .6 0.34 ratio(xtls)

--- 

### ratio(feed) 

### 1.0 1 . 0 

## I 

# BaCI 2 

# on NaCI c rystals: e ntrained 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 co ncentrate -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 /crys tal mass ratio 

## 0 . 02- 0.2

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

**~1000** .!!1



### ~ >-

**~** (.) (.) co 

### z

**~** 500 0

. !: co 

### co 

## Design Case-1 Results RCRA-D OK 226 Ra: 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 Pre t reated 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 226 

### Ra : 1.4 pCi/gm -Dewatered Crysta ls

- Treatment-1

- Treatment-2

.... : ........

**~.** 

### . .... .;. .......

2000 3000 4000 5000 6000 7000 [Ba) l n 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 , 226 

### Ra 0 .004 pCi/gm

# Conclusions: -PA Marcellus produced water: significant Ba , Ra levels -Aspen Plu s/O LI crystallize r model correctly predicts BaCI 2 

### coprecipitation -Source of Ba, Ra in NaC I( s

) : concentrate entrained with NaCI crysta ls -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