Ceramic Particles With Controlled Pore and/or Microsphere Placement and/or Size and Method Of Making Same

• US 20110160104A1
• Filed: 12/23/2010
• Published: 06/30/2011
• Est. Priority Date: 12/31/2009
• Status: Active Grant

• Current Assignee: Halliburton Energy Services Incorporated (Halliburton Company)
• Original Assignee: Oxane Materials, Inc.
• Inventors: Wu, Shanghua, Xie, Yuming, Coker, Christopher E., Chatterjee, Dilip
• Granted Patent: US 8,728,991 B2
• Time in Patent Office: Days
• US Class Current: 507/269
• CPC Class Codes: C04B 2235/3206 Magnesium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3225 Yttrium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3229 Cerium oxides or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3463 Alumino-silicates other than clay, e.g. mullite
• CPC Class Codes: C04B 2235/3481 Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
• CPC Class Codes: C04B 2235/3826 Silicon carbides
• CPC Class Codes: C04B 2235/48 Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
• CPC Class Codes: C04B 2235/483 Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
• CPC Class Codes: C04B 2235/528 Spheres
• CPC Class Codes: C04B 2235/5409 expressed by specific surface values
• CPC Class Codes: C04B 2235/5427 millimeter or submillimeter sized, i.e. larger than 0,1 mm
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/5445 submicron sized, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 2235/5463 Particle size distributions
• CPC Class Codes: C04B 2235/6581 Total pressure below 1 atmosphere, e.g. vacuum
• CPC Class Codes: C04B 2235/6584 at an oxygen percentage below that of air
• CPC Class Codes: C04B 2235/6585 at an oxygen percentage above that of air
• CPC Class Codes: C04B 2235/96 Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
• CPC Class Codes: C04B 35/185 Mullite 3Al2O3-2SiO2
• CPC Class Codes: C04B 35/195 Alkaline earth aluminosilicates, e.g. cordierite or anorthite
• CPC Class Codes: C04B 35/62204 : using waste materials or refuse clay-wares containing waste materials C04B33/132
• CPC Class Codes: C04B 35/62605 : Treating the starting powders individually or as mixtures
• CPC Class Codes: C04B 35/62695 : Granulation or pelletising devices for shaping artificial aggregates from ceramic mixtures B28B1/004
• CPC Class Codes: C04B 35/64 : Burning or sintering processes C04B33/32 takes precedence ; powder metallurgy B22F
• CPC Class Codes: C04B 35/645 : Pressure sintering
• CPC Class Codes: C04B 38/0635 : Compounding ingredients C04B38/0615 takes precedence
• CPC Class Codes: C04B 38/08 : by adding porous substances
• CPC Class Codes: C04B 38/10 : by using foaming agents C04B38/02 takes precedenceor by using mechanical means, e.g. adding preformed foam
• CPC Class Codes: C09K 8/80 : Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
• CPC Class Codes: C09K 8/805 : Coated proppants
• CPC Class Codes: E21B 43/04 : Gravelling of wells
• CPC Class Codes: E21B 43/26 : by forming crevices or fractures
• CPC Class Codes: E21B 43/267 : reinforcing fractures by propping

Abstract

The present invention relates to lightweight high strength microsphere containing ceramic particles having controlled microsphere placement and/or size and microsphere morphology, which produces an improved balance of specific gravity and crush strength such that they can be used in applications such as proppants to prop open subterranean formation fractions. Proppant formulations are further disclosed which use one or more microsphere containing ceramic particles of the present invention. Methods to prop open subterranean formation fractions are further disclosed. In addition, other uses for the microsphere containing ceramic particles of the present invention are further disclosed, as well as methods of making the microsphere containing ceramic particles.

Claims

1. A method for producing a microsphere and/or pore containing ceramic particle, said method comprising

a. forming a green body from a green body material that comprises at least one ceramic or ceramic precursor and at least one microsphere and/or pore former, wherein a majority of said microsphere and/or pore formers are distributed in said green body such that the majority of said microsphere and/or pore formers are not in contact with each other, and said microsphere and/or pore formers have a substantially uniform shape and size;

b. sintering said green body under sintering conditions to form a sintered body having a plurality of microspheres and/or pores contained therein, and wherein said microspheres and/or pores are optionally at least partially surrounded by at least one glassy compound, and a majority of said microspheres and/or pores are not in contact with each other.

2. The method of claim 1, wherein said ceramic or ceramic precursor comprises cordierite, mullite, bauxite, silica, spodumene, silicon oxide, aluminum oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, lithium oxide, iron oxide, spinet steatite, a silicate, a substituted alumino silicate clay, an inorganic nitride, an inorganic carbide, a non-oxide ceramic or any combination thereof.

3. The method of claim 1, wherein said ceramic or ceramic precursor has a particle size distribution, d_gs, from about 0.5 to about 15, wherein, d_gs={(d_g90−

d_g10)/d_g50} wherein d_g10 is a particle size wherein 10% of the particles have a smaller particle size, d_g50 is a median particle size wherein 50% of the particles have a smaller particle size, and d_g90 is a particle size wherein 90% of the particle volume has a smaller particle size.

4. The method of claim 1, wherein said ceramic or ceramic precursor comprises from about 90% by weight to about 99.9% by weight of said green body.

5. The method of claim 1, wherein said microsphere and/or pore former is capable of forming said glassy compound and said gas.

6. The method of claim 1, wherein said microsphere and/or pore former comprises a carbide, a nitride, an oxynitride, a sulfide, a halide, a boride or any combination thereof.

7. The method of claim 1, wherein said microsphere and/or pore former comprises an organometalic compound or a composite.

8. The method of claim 1, wherein said microsphere and/or pore former comprises a metallic alloy with at least one metal capable of forming an oxide vapor.

9. The method of claim 1, wherein said microsphere and/or pore former is silicon carbide.

10. The method of claim 5, wherein said glassy compound is silicon dioxide.

11. The method of claim 1, wherein said microsphere and/or pore former comprises a combustible inorganic or organic material.

12. The method of claim 1, wherein said microsphere and/or pore former at least partially decomposes to generate a gas.

13. The method of claim 1, wherein said microsphere and/or pore former has a particle size distribution, d_fs, from about 0.5 to about 5.0, wherein, d_fs={(d_f90−

d_f10)/d_f50} wherein d_f10 is a particle size wherein 10% of the particles have a smaller particle size, d_f50 is a median particle size wherein 50% of the particles have a smaller particle size, and d_f90 is a particle size wherein 90% of the particles have a smaller particle size.

14. The method of claim 1, wherein said microsphere and/or pore former comprises from about 0.01% by weight to about 10% by weight of said green body.

15. The method of claim 1, wherein the green body material further comprises at least one sintering promoter comprising a sintering aid, a glassy phase formation agent, a grain growth inhibitor, a ceramic strengthening agent, a crystallization control agent, or phase formation control agent, or any combination thereof.

16. The method of claim 1, wherein said green body material further comprises yttrium oxide, cerium oxide and any combination thereof.

17. The method of claim 1, wherein said green body further comprises a hollow template.

18. The method of claim 1, wherein said sintering is performed in the presence of a gas.

19. The method of claim 18, wherein said gas comprises from about 100 ppm to about 100% by weight oxygen.

20. The method of claim 1, wherein said sintering is performed under a pressure of from about 1×

10⁵ Pa to about 5×

10⁵ Pa.

21. The method of claim 1, wherein said sintering creates reactive diffusion or local melting of said ceramic or ceramic precursor in said green body.

22. The method of claim 1, wherein said sintering is performed at a temperature from about 500°

C. to about 2500°

C. and said pressure is from about 0.1 MPa to about 200 MPa for about 1 hour to about 20 hours.

23. The method of claim 1, wherein at least 80% by total number, of said microspheres are not in contact with each other.

24. The method of claim 1, wherein said microsphere and/or pore containing ceramic particle has a specific gravity of from about 1.8 to about 2.25, a microsphere placement and/or size of from about 1% to about 10%, a crush strength of from about 10 MPa to about 300 MPa, and a four point bending strength of about 50 MPa to about 400 MPa.

34. The method of claim 1, wherein said ceramic or ceramic precursor comprises at least one sedimentary material or at least one synthetically produced material or both.

25. A microsphere and/or pore containing ceramic particle comprising a sintered body having a plurality of microspheres and/or pores contained therein, and wherein said microspheres and/or pores are optionally at least partially surrounded by at least one glassy compound, and a majority of said gas microspheres and/or pores are not in contact with each other.

26. The microsphere and/or pore containing ceramic particle of claim 25, wherein said sintered body comprises at least in part cordierite, mullite, bauxite, silica, spodumene, silicon oxide, aluminum oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, lithium oxide, iron oxide, spinet steatite, a silicate, a substituted alumino silicate clay, an inorganic nitride, an inorganic carbide, a non-oxide ceramic or any combination thereof.

27. The microsphere and/or pore containing ceramic particle of claim 25, wherein said sintered body surrounds or encapsulates a cenosphere, a micro glass bead, a synthetic cenosphere, a polymer bead or any combination thereof.

28. The microsphere and/or pore containing ceramic particle of claim 25, wherein said microsphere and/or pore containing ceramic particle has a specific gravity of from about 0.8 to about 3.5, a microsphere and/or pore total volume of from about 1% to about 49%, a crush strength of from about 10 MPa to about 300 MPa, and a four point bending strength of about 50 MPa to about 400 MPa.

29. The microsphere and/or pore containing ceramic particle of claim 25, wherein said microsphere and/or pore containing ceramic particle has a specific gravity of from about 1.8 to about 2.25, a microsphere and/or pore total volume of from about 1% to about 10%, a crush strength of from about 10 MPa to about 300 MPa, and a four point bending strength of about 50 MPa to about 400 MPa.

30. The microsphere and/or pore containing ceramic particle of claim 25, wherein said microsphere and/or pore containing ceramic particle has d_ps from about 0.4 to about 1.0, wherein d_ps=(d_p90−

d_p10)/d_p50 and wherein d_p10 is a particle size wherein 10% of the particles have a smaller particle size, d_p50 is a median particle size wherein 50% of the particles have a smaller particle size, and d_p90 is a particle size wherein 90% of the particles have a smaller particle size.

31. The microsphere and/or pore containing ceramic particle of claim 25, wherein R_p is from about 0.01 to about 0.1, wherein R_p=d_v50/d_p50 wherein d_v50 is a median microsphere and/or pore size where 50% of the microspheres and/or pores of the distribution has a smaller microsphere and/or pore size and D_p50 is a median particle size where 50% of the particles of the distribution have a smaller particle size.

32. A method to prop open subterranean formation fractures comprising introducing a proppant formulation comprising the microsphere containing ceramic particle of claim 25 into a subterranean formation.

33. A method of treating a subterranean producing zone penetrated by a well bore comprising the steps of:

a. preparing or providing a treating fluid that comprises a fluid, energized fluid, foam, or a gas carrier having the microsphere containing ceramic particle of claim 25 suspended therein, and

b. pumping said treating fluid into said subterranean producing zone whereby said particles are deposited therein.

35. The microsphere and/or pore containing ceramic particle of claim 25, wherein said sintered body comprises at least one material derived from at least one sedimentary material or at least one synthetically produced material or both.

36. A method for producing proppants, wherein said method comprises filtering by membrane filtration one or more of the starting materials that form said proppant, and then forming a green body from said starting materials that have been filtered by membrane filtration and then sintering said green body to form a sintered body.

37. The method of claim 36, wherein said membrane filtration is a cross flow membrane separation.

38. The method of claim 36, wherein said membrane filtration is a dead end filtration.

39. A method for producing microsphere and/or pore formers comprising the steps of

a. producing microsphere and/or pore former templates of a predetermined size, and

b. selecting a subset of said sized microsphere and/or pore former templates, and

c. coating said selected subset of said sized microsphere and/or pore former templates with inorganic or organic materials.

40. The method of claim 39, wherein said selecting a subset of said sized microsphere and/or pore former templates is produced by means comprising screening, filtration, air separation, sedimentation, impingement, flotation, and any combination thereof.

41. A microsphere and/or pore former comprising a microsphere former template with an organic or inorganic coating and having a select average particle size and select particle size distribution.

42. The microsphere and/or pore former of claim 41, wherein said inorganic material comprises, oxides, nitrides, borides, carbides halides, metals, metal oxides or any combination thereof.

43. The microsphere and/or pore former of claim 41, wherein said organic material is a polymer comprising polymethyl methacrylate, polystyrene, polyolefins, polycarbonate, silicone polymers and any combination thereof.

44. A method for producing a glass-ceramic, ceramic, metal or combinations thereof article, said method comprising

a. forming a green body from a green body material that comprises at least one ceramic or ceramic precursor and said microsphere and/or pore former of any preceding or following embodiment/feature/aspect, wherein a majority of said microsphere and/or pore formers are distributed in said green body such that the majority of said microsphere and/or pore formers are not in contact with each other, and said microsphere and/or pore formers have a substantially uniform shape and size;

b. sintering said green body under sintering conditions to form a sintered body having gas bubbles contained therein, and wherein said gas bubbles are at least partially surrounded by at least one glassy compound which forms a microsphere and/or pore in situ in said glass-ceramic, ceramic, metal or combinations thereof particle.

45. A glass-ceramic, ceramic, metal or combinations thereof article comprising a sintered body having gas bubbles contained therein, and wherein said gas bubbles are optionally at least partially surrounded by at least one glassy compound forming in situ microspheres and/or pores, and a majority of said in situ microspheres and/or pores are not in contact with each other.

46. The glass-ceramic, ceramic, metal or combinations thereof article of claim 45, wherein said sintered body comprises at least in part cordierite, mullite, bauxite, silica, spodumene, silicon oxide, aluminum oxide, sodium oxide, potassium oxide, calcium oxide, zirconium oxide, lithium oxide, iron oxide, spinel, steatite, a silicate, a clay, a substituted alumino silicate clay, an inorganic nitride, an inorganic carbide, a non-oxide ceramic or any combination thereof.

47. The glass-ceramic, ceramic, metal or combinations thereof article of claim 45, wherein said sintered body surrounds a cenosphere, a micro glass bead, a synthetic cenosphere, a polymer bead or any combination thereof.

48. The glass-ceramic, ceramic, metal or combinations thereof article of claim 45, wherein said glass-ceramic, ceramic, metal or combinations thereof article has a specific gravity of from about 1.8 to about 2.25, a porosity of from about 1% to about 10%, a crush strength of from about 10 MPa to about 300 MPa, and a four point bending strength of about 50 MPa to about 400 MPa.

49. The glass-ceramic, ceramic, metal or combinations thereof article of claim 45, wherein said in situ formed microspheres and/or pores contain whiskers or fibers.

50. The glass-ceramic, ceramic, metal or combinations thereof article of claim 45, wherein said sintered body contains whiskers or fibers.

51. The glass-ceramic, ceramic, metal or combinations thereof article of claim 45, wherein the interface between said sintered body and said microsphere contains whiskers or fibers.

52. A microsphere and/or pore containing ceramic proppant having one or more of the following characteristics:

a) a majority of pores and/or microspheres in said proppant (excluding any optional central void) have a size of less than 50 cubic microns,

b) a population of proppants (based on a 50 gram sample of proppants) have a specific gravity variance of ±

0.8 or less,

c) a total porosity of 5% to 33% by volume of proppant (excluding any optional central void), wherein a majority of the pores/microspheres are not in contact with each other,

d) the pores/microspheres are uniformly distributed in the proppant such that the pore/microsphere density is about the same throughout the proppant.

53. The microsphere and/or pore containing ceramic material of claim 52, wherein said majority is 50% to 95% based on a count of total pores/microspheres present in said proppant excluding any central voids optionally present.

54. The microsphere and/or pore containing ceramic material of claim 52, wherein said proppant has a crush strength of at least 2,000 psi.

55. The microsphere and/or pore containing ceramic material of claim 52, wherein said proppant has a crush strength of at least 5,000 psi.

56. The proppant of claim 52, wherein said pore/microsphere density is such that a sector of said proppant has a density of within ±

25% compared to a different sector of said proppant.

57. The proppant of claim 52, wherein said proppant has a specific gravity of 1.0 to 2.6.

58. The proppant of claim 52, wherein said specific gravity variance is ±

0.3 or less.

59. The proppant of claim 52, wherein said proppant has all of said characteristics.

60. The proppant of claim 52, wherein a) is present in said proppant and said size is less than 20 microns.