A New Class of Permanent Clay Stabilizers

Assem, Ahmed I. (Texas A&M University) | Nasr-El-Din, Hisham A. (Texas A&M University) | Harper, Thomas L. (Maxflo Oilfield Chemicals)



A new class of permanent clay stabilizers has been developed inorganic based on an aluminum/zirconium-based compound. The increased charge density of the molecule allows it to bind more strongly to swelling clays, while its relatively low molecular weight allows it to stabilize the clay permanently without causing formation damage by blocking the pore throats and reducing permeability.

The most commonly used clay stabilizers are organic and inorganic chloride salts including trimethylammonium chloride, potassium chloride, and choline chloride. These salts have been used for years, are effective in most wells, and are both cheap and abundant. However, their high water solubility and the relatively small size of the cation means that these products are highly mobile and thus are quickly washed away during flowback. Several chemical derivatives were made from a tri-functional amine by reacting it with organic and inorganic acids such HCl, acetic acid, and formic acid; as well as alkylating agents, including chloromethane, benzyl chloride, diethyl sulfate, and paraformaldehyde.

Certain cationic polymers have also proven useful as clay stabilizers. These much larger molecules are not as easily washed away due to steric hindrance and a much higher charge density per molecule. These products have proved useful as long-term clay stabilizers, but their high molecular weights can lead to formation damage by causing them to be filtered out on the rock face.

In this research, several laboratory tests were carried out on the new clay stabilizer. These tests included coreflood experiments conducted on Berea sandstone cores to assess the stabilizer at high temperatures and the influence of different acids on its performance. Coreflood effluent samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES) to measure the concentrations of aluminum and zirconium.

This new permanent clay stabilizer improved productivity from formations that have high clay content by minimizing clay swelling and thus preventing formation damage caused by clogged pore throats and subsequent loss of permeability. It worked well at temperatures up to 250°F and with 15 wt% HCl and regular mud acid (12 wt% HCl, 3 wt% HF).