Analytical Procedures

225.020

Analytical & Materials QC

Gravimetric Solubility

Gravimetric Solubility
Procedure No.: WM-GL-HES-QM-225.020

Description
This procedure is designed to measure the solubility of formation samples, wellbore deposits, produced solids, and fracturing proppants in acids and other treatment fluids. Solubility data obtained from this analysis supplement X-ray diffraction data and are of interest for well treatment designs. Several different acids may be tested, but 15% hydrochloric acid (HCl) and a mixture of 12% HCl with 3% hydrofluoric acid (HF) are standard. American Petroleum Institute procedures for testing gravel-pack sands and proppants may differ slightly. Consult these procedures when necessary.

Equipment and Reagents

Item Analytical balance Vacuum oven Desiccator Requires a storage cabinet large enough to handle the expected sample load 15% solution HCl at 12% and HF at 3% Nalgene 130-4045 set including a 115-mL capacity plastic funnel with filtrate receiver and 0.45-mm filter 250 mL with watch glass or plastic lids to cover the top Specifications Quantity 1 1 1

Water bath Hydrochloric acid (HCl) Mixture of hydrochloric acid (HCl) and hydrofluoric acid (HF) Disposable filter assemblies

1 As needed As needed One set

Glass and polyethylene beakers Buchner funnel with Whatman filter paper

As needed One set

Procedure
Summary
Testing various formation samples for solubility yields important information for well treatment design processes. Samples are dried, ground to pass through a 100-mesh sieve, weighed, and then immersed in test fluid either for 60 minutes at 65C (150F) or for the specified time and temperature. At the end of the time period, the remaining sample is cooled, filtered, and dried, and finally weighed. Gravimetric solubility is calculated from the weight lost relative to the original sample weight.

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Analytical & Materials QC

Gravimetric Solubility

Analytical Procedures
225.020

Sample Handling
NoteSamples should have a consistently low moisture content. Oily or paraffin-coated samples do not wet properly. Clean them with solvents before drying. 1. Clean oily or paraffin-coated samples with chloroform, acetone, or methanol with one of the following methods: a. Rinse the sample with 25 to 50 mL of each solvent in a Buchner funnel on Whatman filter paper. b. Shake the sample with a 50-mL aliquot of each solvent in a centrifuge tube, spinning the solids between each step and discarding solvents in an appropriate disposal container. 2. The cleaning procedure should yield 10 g for the solubility test. Dry the sample at 65C (150F) in an oven for at least one hour. Store the dried sample in a desiccator.

CautionWear safety glasses when handling acids. Wear gloves and a laboratory coat or apron to protect clothing, especially when handling hydrofluoric acid (HF).

Standards Preparation
1. To prepare 15% HCl solution, dilute 800 mL of concentrated, reagent grade HCl to 2 L with deionized (D.I.) water in a volumetric flask. This dilution is convenient to store and is ready to use. To prepare 12% HCl-3% HF mixture, do the following: a. Dilute 594 mL of concentrated reagent grade HCl with D.I. water. b. Add either 100 mL of 52% concentrated HF or 92.6 g of ammonium bifluoride (ABF) solid reagent. c. Dilute the sample to 2 L with D.I. water.

2.

Main Procedure
1. 2. 3. 4. Dry a Nalgene disposable filter at 65C (150F) for 30 minutes. Cool the filter to room temperature in a desiccator and weigh it to the nearest 0.0001 g with an analytical balance. Store in a desiccator until used. Lightly grind the sample with a mortar and pestle until it is able to pass through a 100-mesh sieve screen. Store it in a desiccator until it is weighed. Using an analytical balance, weigh the sample to the nearest 0.0001 g into a tared 250-mL beaker. When testing with 15% HCl use a glass beaker; for HCl and HF, use a plastic beaker. Add approximately 5 mL of methanol to the sample to promote wetting of the entire sample and add 100 mL of the acid or acid mixture. Cover the beaker with a watch glass or plastic lid.

5.

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Analytical Procedures
225.020

Analytical & Materials QC

Gravimetric Solubility

7. 8.

Remove the beaker from the water bath and filter the sample with the dried and weighed Nalgene assembly (see Step 1) connected to a vacuum line through a trap. Rinse the beaker with up to 50 mL of D.I. water or until all the residue has been transferred to the filter. When filtration is complete, detach the filter from the vacuum and pour the filtrate back into the beaker for disposal or additional testing. The filtrate may be used to determine the percentage of soluble iron. Dry the filter and filtered sample in a vacuum oven at 65C (150F) for at least 4 hours. Leave the oven vent valve open slightly to allow airflow through the oven and to prevent condensation.

9.

10. Transfer the dry filter and residue to the desiccator and allow to cool to room temperature. 11. Weight the filter and residue to the nearest 0.0001 g.

Data Interpretation
Use the following equation to calculate the gravimetric solubility from the initial sample weight (Step 6), filter weight (Step 4), and the combined filter and insoluble residue weight (Step 13):

wt filter + residue wt filter % weight soluble = 1 100 sample wt

References
1. 2. 3. Evaluation of Sand Solubility in Acid, RP 56, Recommended Practices for Testing Sand Used in Hydraulic Fracturing Operations, API, Section 6 (1983). Evaluation of Sand Solubility in Acid, RP 58, Recommended Practices for Testing Sand Used in Gravel Packing Operations, API, Section 6 (1986). Acid Solubility Considerations, RP 60, Recommended Practice for Testing High Strength Proppants Used in Hydraulic Fracturing Operations, API, Section 6 (1989).

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