SPE 140751

Enhancing Production by Removing Zinc Sulfide Scale From an Offshore Well: A Case History

Authors: Sandra L. Berry, Joel L. Boles, Amit Singh, Baker Hughes, Imran Hashim, Newfield Exploration

Presentation Outline
Scale Mineralogy and Chemistry Acid Solubility Studies Oxidizing Agent Treatments Scale Reprecipitation Study Well Acid Treatment Acid Flowback Sample Analysis Conclusions

Factors That May Affect The Dissolution Rate of the Scale in The Well
 Downhole temperature and pressure  Pressure changes  H2S scavenger concentration and type  Ratio of acid volume to scale weight  Scale pre-treatment with oxidizers

Scale Mineralogy and Chemistry

Zinc Sulfide Solids From Bailer Runs

Mineralogy XRD Results

Minerals 1st Run Drive Bailer (10011 ft) 2nd Run Drive Bailer (10011 ft) 3rd Run After Spot 20 Gals 15% HCL Pump Bailer (10011 ft) Major Minor

Wurtzite(ZnS) Major Iron sulfide Major =>20% Minor =5-20% Trace =<5% Minor

Major Minor

Zinc Sulfide Scale Chemistry

Wurtzite Hexagonal form

Sphalerite Cubic Form

Reference: Encyclopedia of Materials: Science and Technology

Acid Solubilities At 150F With Atmospheric Pressure

 Approximately 5.0 grams of scale was placed in 50 mls of each tests acid.  #1-10% HCl + 10 gpt ACI +10 gpt Intensifier + 1 gpt
Surface Tension Reducer + 2 gpt Flowback Additive + 26 gpt Acetic Acid + 100 pptg Iron Control #1 + 25 pptg Iron Control #2 + 15 gpt Hydrogen Sulfide Scavenger #2 + 2 gpt Clay Stabilizer
  

#2-15% HCl #3 -15% HCl + 15 gpt HS #2 # 4 -15% HCL + 15 gpt HS #3

Pounds of Zinc Sulfide Scale Dissolved Per Gallon Of Acid At 150F For One Hour At Atmos. Pressure
Pounds Of Zinc Sulfide Dissolved Per Gallon Of Acid
3.50 # of Zinc Sulfide Dissolv 3.00 2.50 2.00 1.50 1.00 0.50 0.00
10% HCl (#1) 10% HCl (#2) 10% HCl (#3) 10% HCl Theor. 15% HCl (no 15% HCl + 15 15% HCl + 15 HS) gpt HS-2 gpt HS-3 15% HCl Theor.

3.47

2.27

0.83 0.34 0.35 0.35

0.73

0.79

Test Acid #

Acid Solubility Tests With Excess Zinc Sulfide Scale At 150F/AP and 220F/1000 psi Nitrogen Pressure For Two Hours
 Second set of solubility tests  Excess zinc sulfide scale (45 grams/100 mls acid)  Acid blends:
1) 15% HCl with no additives 2)15% HCl + 10 gpt ACI + 10 gpt Intensifier + 5 gpt HS#3 + 50 pptg Iron Control #1

 Compare the solubility of 15% HCl with/without additives as well as the effects of pressure on the solubility of zinc sulfide in 15% HCl.

Pounds of Zinc Sulfide Scale Dissolved With Excess Zinc Sulfide Scale Present
#of Zinc Sulfide Dissolved Per G

Pounds of Zinc Sulfide Dissolved With Excess Zinc Sulfide Scale Present
2 1.8 1.6 1.4 of Acid 1.2 1 0.8 0.6 0.4 0.2 0 15% HCl (No Additives) 15% HCl (Additives) 15% HCl (No Additives) 15% HCl (Additives)
220 F with 1000 psi Nitrogen Pressure 150F With Atmospheric Pressure

1.9 1.71

0.871 0.699

Acid Syste ms With/Without Pre ssure

Zinc Sulfide Scale Solubilities With Excess Acid at 150F/AP and 220F/1000 psi Nitrogen Pressure and Varying Concentrations of HS#3 Third set of tests 5X excess acid ratio to scale solid Solubility test at AP and HT/HP Conditions Varying concentrations of HS#3 Acid blends:
#1 15% HCl + 10 gpt ACI + 10 gpt Intensifier + 5 gpt HS#3 + 50 pptg Iron Control Agent. #2 15% HCl + 10 gpt ACI + 10 gpt Intensifier + 10 gpt HS#3 + 50 pptg Iron Control Agent #3 15% HCl + 10 gpt ACI + 10 gpt Intensifier + 15 gpt HS#3 + 50 pptg Iron Control Agent #4 15% HCl + 10 gpt ACI + 10 gpt Intensifier + 50 gpt HS#3 + 50 pptg Iron Control Agent #5 15% HCl + 10 gpt ACI + 10 gpt Intensifier + 100 gpt HS#3 + 50 pptg Iron Control Agent

Solubility Tests with 5X Excess Acid Versus Previous Solubility Tests

Test # 1 2 Conditions 150F/Atmospheric Conditions Scale to Acid Volume Ratio 45.0 grams in 100 mls of acid % Solubility Efficiency 54.7% Solubility Efficiency 25.1% Solubility Efficiency

220F/1000 psi nitrogen pressure 45.0 grams in 100 mls of acid

3 4

150F/Atmospheric Conditions

4.50 grams in 100 mls

86.0% Solubility Efficiency 78.1% Solubility Efficiency

220F/1000 psi nitrogen pressure 4.50 grams in 100 mls of acid

Solubility Tests with 5X Excess Acid and Varying Concentrations of HS-3

Zinc Sulfide Dissolved In 15% HCl cid Versus Concentration of HS-3 t tmospheric and HTHP Conditions
# of Zinc Sulfide Dissolved Per Gallon of 15% HCl

0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0

220F With 1000 psi Nitrogen Pressure 150F With Pressure tmospheric

5 gpt 10 gpt 15 gpt 50 gpt HS-3 HS-3 HS-3 HS-3

100 gpt HS-3

5 gpt 10 gpt 15 gpt 50 gpt HS-3 HS-3 HS-3 HS-3 cid

100 gpt HS-3

Concentration Of HS-3 (gpt) in 15% HCl

Oxidization Agent Studies

 Reported to increase acid solubility  Oxidization agents treatments
-5% Sodium hypochlorite -3% Hydrogen peroxide -Concentrated oxidizer formulation

 Treatment reacts for one hour at 150F  Ratio of 22.4 grams of scale with 50 mls acid  Acid : 15% HCl + 10 gpt ACI + 10 gpt Intensifier
+ 5 gpt HS#3+ 50 pptg Iron control agent

Acid Solubility of Scale After Treatment With Oxidizing Agents

Dissolution Rate of Zinc Sulfide Scale In 15% HCl Acid After Treatment With Oxidizers
#Of Zinc Sulfide Scale Dissolved Per Gal. of 15% HCl Acid 4 3.5 3 2.5 2 1.5 1 0.5 0

Theoretical Solubility

72F/Atmospheric 220F/1000 psi Nitrogen

F# 1

et ic al

2O

aO

aO

2O

Th eo r

3%

5%

Oxidizer Treatm ent

5%

3%

F# 1

Acid Solubility of Zinc Sulfide After Oxidizing Agents

Test # Scale Treatment Test Conditions Acid Treatment Pounds of Zinc Sulfide per Gallon of Acid % Increase In Acid Solubility Over Untreated Scale 14.9% 1 5% Sodium Hypochlorite 720F Atmospheric Pressure 720F Atmospheric Pressure 720F Atmospheric Pressure 15% HCl + Additives 2.235

3% Hydrogen Peroxide

15% HCl + Additives

2.335

18.6%

Concentrated Oxidizer Formulation #1

15% HCl + Additives

1.861

0%

4 5 6

5% Sodium Hypochlorite 3% Hydrogen Peroxide Concentrated Oxidizer Formulation #1

2200F/1000 psi nitrogen pressure 2200F/1000 psi nitrogen pressure 2200F/1000 psi nitrogen pressure

15% HCl + additives 15% HCl + additives 15% HCl + additives

1.158 1.198 1.086

24.7% 27.2% 19.7%

Zinc Sulfide Reprecipitation Tests

Conduct zinc sulfide scale dissolution tests 22.4 grams of scale in 50 mls of 15% HCl Filter solution to collect acid effluent Initial acid effluent pH of 0.35 Aliquots were taken out and pH was adjusted to 1.0, 2.0, 3.0, 4.0, 5.0 with 0.2N NaOH  Fluids were observed for precipitation

    

HCl Acid Effluent With pH Adjustment By Addition of 0.2 N NaOH

Concern about maintaining pH of acid solution below 3.0 to prevent reprecipitation in the formation or wellbore.

Well Treatment
Acid scale treatment designed from lab tests to determine acid strength, additive package, and proper acid to scale ratio Recommended acid formulations:
15% HCl Formulation: 15% HCl + 20 gpt Acid Corrosion Inhibitor + 20 gpt Intensifier#1 + 20 gpt Intensifier#2 + 1 gpt Flowback Additive + 50 pptg Iron Control Agent#1 + 25 pptg Iron Control Agent#2 + 10 gpt HS#3 + 2 gpt HS#22 + 0.5 gpt Clay Control 7.5% HCl Formulation: 7.5% HCl + 10 gpt Acid Corrosion Inhibitor + 10 gpt Intensifier#1 + 1 gpt Surface Tension Reducer + 26 gpt Acetic Acid + 10 pptg Iron Control Agent #1 + 50 pptg Iron Control Agent #2 + 25 pptg Iron Control Agent#3 + 10 gpt HS#3 + 2 gpt HS#22 + 2 gpt Clay Control.

Well Treatments
 Treatment thru coiled tubing  1st treatment -12 bbls of mixed solvent (remove hydrocarbons from scale)  2nd treatment -12 bbls of 15% HCl acid spotted in four stages of 3.0 bbls each across the sliding sleeve, screen and perforation area.  Soaking time of 15 minutes at each stage

Well Treatments
 Acid circulated from bottoms up  Fresh treatment of solvent to remove hydrocarbons from formation  Followed by 53 bbls. of 7.5% acid and 30 bbls. of 5% KCl with N2 Foam diversion treatment in 3 stages  Utilized to dissolve scale from formation pore throats. Acid flowed back after a 12-hour soak period.  Acid flowback samples of the 15% circulated acid and the 7.5% injected acid were collected and analyzed.  Corrosion inhibitor slugs were pumped ahead of the acid treatment to better protect the coiled tubing string from the stronger 15% HCl acid system.

Treatment Plot For Acid Spot Across Sliding Sleeve, Screen And Perforations
10000 5000 tart I lug Start Sol e nt Start 15% l I Slug on zone 4000

Solvent - Acid Soak

10

2000

irculate out 15%

l to surface

Start 5% K l flush Sol e nt on zone ( irl) Sol e nt (inje ct) 15% l (inje ct) Pump Rate ( pm) l (1 - cirl) 15% l (2 15% irl) l (3 irl) 5

1500

i)

Well ead (

2000 15% l (4 irl)

500 1000

0 100 Elapse d ime (min) 200

0 240

N2 Rate (

5000

Annulus ( si)

3000

15%

1000

f/ i )

Treatment Plot For Acid Spot With N2 Across Formation

A cid / N 2 In je ctio n
10000 5000 Start Sol e nt Start 4000 .5% l-1 Start K l/N2 - 1 Sol e nt on zone Start .5% l-2 Start K l/N2-2 W ell ead (psi) Annulus (psi) 3000 5 2000 .5% l - 2 on zone K l/N2 - 2 on zone Start .5% l-3 Start K l slug 7.5% l - 3 on zone Start K l flush 10 2000

1500

Pump Rate ( pm)

5000

1000

500 1000

0 250

300

350 Elapse d ime (min)

400

0 450

N2 Rate (scf/min)

Acid Flowback Samples

 Four acid flowback samples collected
1)Sample #1 First spot treatment (15% HCl circulated) 2)Sample #2 First spot treatment (15% HCl circulated) 3)Second Injection Flowback Sample #1(7.5% HCl injected) 4)Second Injection Flowback Sample #2(7.5% HCl injected)

Samples analyzed for elemental composition/physical characteristics.

Acid Flowback Samples Physical Parameters and Elemental Composition

Parameter 10-28-09 11:30 am First Spot Treatment Sample #1 (15% HCl Circulated) Black with solids Rotten egg odor 0.79 20% 80% 10-28-09 11:35 am First Spot Treatment Sample #2 (15% HCl Circulated) Black with solids Rotten egg odor 0.74 30% 70% 10-28-09 11:00 pm Second Injection Sample #1 (7.5% HCl Injected) 10-28-09 11:05 pm Second Injection Sample #2 (7.5% HCl Injected)

Appearance Smell pH % Solvent % Aqueous Elemental (mg/l) Calcium Barium Magnesium Iron Potassium Sodium Boron Copper Manganese Molybdenum Phosphorus Silica Strontium Zinc Aluminum Sulfur Chromium

Black with solids Rotten egg odor 4.9 5% 95%

Black with solids Rotten egg odor 4.2 5% 95%

14,690 ND 1,523 7,224 8,287 6,929 10 ND 92 ND 87 38 44 3,673 4,208 671 568

546 ND 311 12,060 7,422 6,261 <10 ND 66 ND 39 37 ND 15,358 97 606 2297

41 ND 38 366 841 285 ND ND 3 ND 12 5 ND 258 ND 294 15

20 ND 26 699 735 269 ND ND <5 ND 40 7 ND 1,079 15 855 127

Conclusions
 Solubility of the submitted zinc sulfide is much lower in 15% HCl than the calculated theoretical value.  Increased pressure significantly decreases the solubility of zinc sulfide scale in 15% HCl

Conclusions
 Solubility tests with 5x the theoretical amount of 15% HCl acid showed the maximum dissolution of this scale.  Study shows the importance of treating scale with excess acid volume to increase the scale dissolution rate at increased pressure and to ensure the removal of all the scale.

Conclusions
 Adding HS#3 to the acid enhanced the acid dissolution rate up to a concentration of 10 gpt . However, above this concentration the scale dissolution rate begins to decline and a secondary precipitation begins to develop in the solution.  Study with pre-treatment of the zinc sulfide scale with an oxidizing agent to try to increase the dissolution rate show that 3% H2O2 was the most effective oxidizing agent.

Conclusions
 Laboratory analysis is critical to maximizing the efficiency of zinc sulfide scale removal operations to properly identify scale form and combinations of additives that will best ensure removal.

Questions?