Journal of Materials Science

, Volume 51, Issue 16, pp 7585–7597 | Cite as

Study of 4, 4′-methylenebis-cyclohexanamine as a high temperature-resistant shale inhibitor

  • Hanyi Zhong
  • Zhengsong Qiu
  • Zhichuan Tang
  • Xin Zhang
  • Jiangen Xu
  • Weian Huang
Original Paper


In order to develop high-performance water-based drilling fluid with the aim of meeting the increasing requirement of drilling industry, highly inhibitive and high-temperature-resistant shale inhibitors are essential. In this study, 4, 4′-methylenebis-cyclohexanamine was introduced as a potential shale inhibitor. The inhibitive properties of the amine compound in comparison with currently available polyether diamine inhibitor were evaluated using bentonite inhibition test, shale cuttings hot-rolling dispersion test, linear swelling test, and pressure transmission test. The inhibitive mechanism was investigated with zeta potential measurement, X-ray diffraction analysis, and contact angle measurement. The results indicated that 4, 4′-methylenebis-cyclohexanamine can inhibit shale hydration and dispersion effectively, and prevent pressure transmission to a certain extent, performing better than that of polyether diamine. Furthermore, the new diamine provides reliable thermal stability as high as 220 °C, preserving the benefits of high-temperature wells application. This novel diamine inhibits shale hydration and dispersion with the combination of chemical inhibition and physical plugging. The intercalation into the interlayer of clay with monolayer collapses the hydrated clay structure and expels the water molecules. After adsorption, clay surface became more hydrophobic, which prevents the imbibition of water. The variation of solubility separates the compound from the solution, which can plug the micro-pores of shale and prevent fluid invasion.


Shale Contact Angle Interlayer Spacing Drilling Fluid Clay Surface 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work was financially supported by National Science Foundation of China (Nos. 51374233 and 51474236), Application and basic research Project of Qingdao (15-9-1-43-jch), and the Fundamental Research Funds for the Central Universities (16CX02023A).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Chen G, Chenevert ME, Sharma MM, Yu M (2003) A study of wellbore stability in shales including poroelastic, chemical, and thermal effects. J Pet Sci Eng 38(3–4):167–176CrossRefGoogle Scholar
  2. 2.
    Zeynali ME (2012) Mechanical and physic-chemical aspects of wellbore stability during drilling operations. J Pet Sci Eng 82:120–124CrossRefGoogle Scholar
  3. 3.
    Shadizadeh SR, Moslemizadeh A, Dezaki AS (2015) A novel nonionic surfactant for inhibiting shale hydration. Appl Clay Sci 118:74–86CrossRefGoogle Scholar
  4. 4.
    Zhong H, Qiu Z, Huang W, Sun D, Zhang D, Cao J (2015) Synergistic stabilization of shale by a mixture of polyamidoamine dendrimers modified bentonite with various generations in water-based drilling fluid. Appl Clay Sci 114:359–369CrossRefGoogle Scholar
  5. 5.
    Van Oort E (2003) On the physical and chemical stability of shales. J Pet Sci Eng 38(3):213–235CrossRefGoogle Scholar
  6. 6.
    Caenn R, Chillingar GV (1996) Drilling fluids: state of the art. J Pet Sci Eng 14:221–230CrossRefGoogle Scholar
  7. 7.
    Patel A, Stamatakis E, Young S, Cliffe S (2002) Designing for the future: a review of the design, development and testing of a novel, inhibitive water-based drilling fluid. In: AADE-02-DFWM-HO-33, AADE 2002 Technical Conference, Texas, 2–3 AprilGoogle Scholar
  8. 8.
    Gomez S, Ke M, Patel A (2015) Selection and application of organic clay inhibitors for completion fluids. In: SPE 173731. SPE International Symposium on Oilfield Chemistry, Texas, 13–15 AprilGoogle Scholar
  9. 9.
    Schlemmer R, Patel A, Friedheim J, Young S, Bloys B (2003) Progression of water-based fluids based on amine chemistry—can the road lead to true oil mud replacements? In: AADE-03-NTCE-36, AADE 2003 National Technology Conference, Texas, 1–3 AprilGoogle Scholar
  10. 10.
    Patel A, Stamatakis E, Young S, Friedheim J (2007) Advances in inhibitive water-based drilling fluids—can they replace oil-based muds? In: SPE 106476, SPE International Symposium on Oilfield Chemistry, Texas, 28 Feb–2 MarchGoogle Scholar
  11. 11.
    Balaban RDC, Vidal ELF, Borges MR (2015) Design of experiments to evaluate clay swelling inhibition by different combinations of organic compounds and inorganic salts for application in water base drilling fluids. Appl Clay Sci 105:124–130CrossRefGoogle Scholar
  12. 12.
    Suter JL, Coveney PV, Anderson RL, Greenwell HC, Cliffe S (2011) Rule based design of clay-swelling inhibitors. Energy Environ Sci 4:4572–4586CrossRefGoogle Scholar
  13. 13.
    Hodder M, Cliffe S, Greenwell C, Williams P, Coveney P (2010) Clay Swelling inhibitors-computer design and validation. In: AADE-10-DF-HO-32, AADE Fluids Conference and Exhibition, Texas, 6–7 AprilGoogle Scholar
  14. 14.
    Mao H, Qiu Z, Shen Z, Huang W (2015) Hydrophobic associated polymer based silica nanoparticles composite with core-shell structure as a filtrate reducer for drilling fluid at ultra-high temperature. J Pet Sci Eng 129:1–14CrossRefGoogle Scholar
  15. 15.
    Zhao C, Tong K, Tan J, Liu Q, Wu T, Sun D (2014) Colloidal properties of montmorillonite suspensions modified with polyetheramine. Coll Surf A 457:8–15CrossRefGoogle Scholar
  16. 16.
    Shan W, Tao S, Fu F, Yue W, Zhao Z (2014) Research on the drilling fluid technology for high temperature over 240°C. Proced Eng 73:218–229CrossRefGoogle Scholar
  17. 17.
    Zhong H, Sun D, Huang W, Liu Y, Qiu Z (2015) Effect of cycloaliphatic amine on the shale inhibitive properties of water-based drilling fluid. Open Fuels Energy Sci J 8:19–27CrossRefGoogle Scholar
  18. 18.
    An Y, Jiang G, Ren Y, Zhang L, Qi Y, Ge Q (2015) An environmental friendly and biodegradable shale inhibitor based on chitosan quaternary ammonium salt. J Pet Sci Eng 135:253–260CrossRefGoogle Scholar
  19. 19.
    Khodja M, Canselier JP, Bergaya F, Fourar K, Khodja M, Cohaut N, Benmounah A (2010) Shale problems and water-based drilling fluid optimization in the Hassi Messaoud Algerian oil field. Appl Clay Sci 49:383–393CrossRefGoogle Scholar
  20. 20.
    Zhang S, Qiu Z, Huang W, Cao J, Luo X (2013) Characterization of a novel aluminum-based shale stabilizer. J Pet Sci Eng 103:36–40CrossRefGoogle Scholar
  21. 21.
    Liu J, Qiu Z, Huang W (2015) Novel latex particles and aluminum complexes as potential shale stabilizers in water-based drilling fluids. J Pet Sci Eng 135:433–441CrossRefGoogle Scholar
  22. 22.
    Zhong H, Qiu Z, Zhang D, Tang Z, Huang W, Wang W (2016) Inhibiting shale hydration and dispersion with amine-terminated polyamidoamine dendrimers. J Nat Gas Sci Eng 28:52–60CrossRefGoogle Scholar
  23. 23.
    Alemdar A, Güngör N (2005) The rheological properties and characterization of bentonite dispersions in the presence of non-ionic polymer PEG. J Mater Sci 40:171–177. doi: 10.1007/s10853-005-5703-4 CrossRefGoogle Scholar
  24. 24.
    Moslemizadeh A, Shadizadeh SR, Moomenie M (2015) Experimental investigation of the effect of henna extract on the swelling of sodium bentonite in aqueous solution. Appl Clay Sci 105–106:78–88CrossRefGoogle Scholar
  25. 25.
    Abu-Jdayil B (2011) Rheology of sodium and calcium bentonite–water dispersions: effect of electrolytes and aging time. Int J Miner Process 98(3–4):208–213CrossRefGoogle Scholar
  26. 26.
    Luckham PF, Rossi S (1999) The colloidal and rheological properties of bentonite suspensions. Adv Colloid Interface Sci 82(1–3):43–92CrossRefGoogle Scholar
  27. 27.
    Kelessidis VC, Christidis G, Makri P, Hadjistamou V, Tsamantaki C, Mihalakis A, Papanicolaou C, Foscolos A (2007) Gelation of water–bentonite suspensions at high temperatures and rheological control with lignite addition. Appl Clay Sci 36:221–231CrossRefGoogle Scholar
  28. 28.
    Amanullah M, Al-Arfaj M, Al-Ansari A (2015) Method for prediction of inhibition durability index of shale inhibitors and inhibitive drilling mud systems. US 9164018Google Scholar
  29. 29.
    Ewy RT, Morton EK (2009) Wellbore-stability performance of water-based mud additives. SPE Drill Complet 24(3):390–397CrossRefGoogle Scholar
  30. 30.
    Wang L, Liu S, Wang T, Sun D (2011) Effect of poly(oxypropylene)diamine adsorption on hydration and dispersion of montmorillonite particles in aqueous solution. Coll Surf A 381(1–3):41–47CrossRefGoogle Scholar
  31. 31.
    Lin JJ, Chen YM, Yu MH (2007) Hydrogen-bond driven intercalation of synthetic fluorinated mica by poly(oxypropylene)-amidoamine salts. Coll Surf A 302(1–3):162–167CrossRefGoogle Scholar
  32. 32.
    Takahashi T, Yamada Y, Kataoka K, Nagasaki Y (2005) Preparation of a novel PEG-clay hybrid as a DDS material dispersion stability and sustained release profile. J Control Release 107(3):408–416CrossRefGoogle Scholar
  33. 33.
    Yalçin T, Alemdar A, Ece ÖI, Güngör N (2002) The viscosity and zeta potential of bentonite dispersions in presence of anionic surfactants. Mater Lett 57(2):420–424CrossRefGoogle Scholar
  34. 34.
    Duman O, Tunç S, Çetinkaya A (2012) Electrokinetic and rheological properties of kaolinite in poly(diallyldimethylammonium chloride, poly(sodium 4-styrene sulfonate) and poly(vinyl alcohol) solutions. Coll Surf A 394:23–32CrossRefGoogle Scholar
  35. 35.
    Wang J, Liu G, Wang L, Li C, Xu J, Sun D (2010) Synergistic stabilization of emulsions by poly(oxypropylene) diamine and laponite particles. Coll Surf A 353(2–3):117–124CrossRefGoogle Scholar
  36. 36.
    Mohan KK, Fogler HS (1997) Effect of pH and layer charge on formation damage in porous media containing swelling clays. Langmuir 13:2863–2872CrossRefGoogle Scholar
  37. 37.
    Ritter AJ, Geraut R (1985) New optimization drilling fluid programs for reactive shale formations. In: SPE 14247, 60th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers, Las Vegas. 22–25 SeptGoogle Scholar
  38. 38.
    Zhong H, Qiu Z, Huang W, Cao J (2011) Shale inhibitive properties of polyether diamine in water-based drilling fluid. J Pet Sci Eng 78:510–515CrossRefGoogle Scholar
  39. 39.
    Siguín D, Ferreira S, Froufe L, Garcia F (1993) The relationship between isomorphic substitutions and swelling in montmorillonites. J Mater Sci 28:6163–6166. doi: 10.1007/BF00365038 CrossRefGoogle Scholar
  40. 40.
    Lu S, Chung DDL (2014) Effect of organic intercalation on the viscoelastic behavior of clay. J Mater Sci 49:3189–3195. doi: 10.1007/s10853-014-8022-9 CrossRefGoogle Scholar
  41. 41.
    Zaltoun A, Berton N (1992) Stabilization of montmorillonite clay in porous media by high-molecular-weight polymers. SPE Prod Eng 7(2):160–166CrossRefGoogle Scholar
  42. 42.
    An Y, Jiang G, Qi Y, Ge Q, Zhang L, Ren Y (2015) Synthesis of nano-plugging agent based on AM/AMPS/NVP terpolymer. J Pet Sci Eng 135:505–514CrossRefGoogle Scholar
  43. 43.
    Akhtarmanesh S, Ameri Shahrabi MJ, Atashnezhad A (2013) Improvement of wellbore stability in shale using nanoparticles. J Pet Sci Eng 112:290–295CrossRefGoogle Scholar
  44. 44.
    Mittal V (2008) Effect of the presence of excess ammonium ions on the clay surface on permeation properties of epoxy nanocomposites. J Mater Sci 43:4972–4978. doi: 10.1007/s10853-008-2732-9 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Hanyi Zhong
    • 1
  • Zhengsong Qiu
    • 1
  • Zhichuan Tang
    • 1
  • Xin Zhang
    • 1
  • Jiangen Xu
    • 1
  • Weian Huang
    • 1
  1. 1.School of Petroleum EngineeringChina University of PetroleumQingdaoChina

Personalised recommendations