Robust binder, which is independent from the influence of catalytically active substances, for use in the crude oil and natural gas industry

Abstract

The invention relates to a method of stabilizing the bonding agent gelation time in the consolidation of a geological formation in the presence of one or more catalytically active substances, in which method a bonding agent is infiltrated into the formation, a portion of the infiltrated bonding agent is optionally expelled by flushing with a gas or a liquid, and the bonding agent remaining in the formation is cured. the bonding agent comprises a mixture of a) a heterocondensate, obtainable by hydrolysis and condensation of at least one hydrolyzable silicon compound and at least one metal, phosphorus or boron compound, the metal being selected from Al, Ge, Sn, Pb, Ti, Mg, Li, V, Nb, Ta, Zr and Hf, B) at least one organic polymerizable monomer or oligomer comprising a C-C double bond, and C) at least one thermal polymerization initiator without peroxide function.

Claims

1. A method of stabilizing the gelation time of a bonding agent in the consolidation of geological formations in the presence of one or more catalytically active substances, wherein the one or more catalytically active substances comprise one or both of iron ions and copper ions, and the consolidation comprises infiltrating the bonding agent into a formation, optionally expelling a portion of the infiltrated bonding agent by flushing with a gas or a liquid, and curing the bonding agent remaining in the formation, and wherein the method comprises using as bonding agent an agent which comprises a mixture of (A) a heterocondensate, obtainable by hydrolysis and condensation of at least one hydrolyzable silicon compound and at least one metal, phosphorus or boron compound, the metal being selected from one or more of Al, Ge, Sn, Pb, Ti, Mg, Li, V, Nb, Ta, Zr, Hf, (B) at least one organic polymerizable monomer or oligomer comprising at least one C-C double bond, and (C) one or more thermal polymerization initiators selected from initiators without peroxide functionality.

2. The method of claim 1, wherein the bonding agent is introduced into the formation through a steel pipe that is introduced into the geological formation.

3. The method of claim 1, wherein (C) comprises an azo compound.

4. The method of claim 3, wherein the azo compound is selected from one or more of azobisnitriles, azobiscarboxylic acid esters, azobiscarboxylic acid amides.

5. The method of claim 1, wherein (C) comprises a compound which has a C-C double bond that can be cleaved homolytically by thermal energy.

6. The method of claim 1, wherein the bonding agent further comprises one or more of a buffer, a complexing agent, a polysiloxane with at least one reactive group, and a solvent.

7. The method of claim 6, wherein the solvent is selected from alcohols, ethers, monoethers of diols.

8. The method of claim 1, wherein at least one hydrolyzable silicon compound for the heterocondensate comprises at least one non-hydrolyzable organic group which has a polymerizable group, or comprises at least one alkyl or aryl group as the non-hydrolyzable organic group.

9. The method of claim 1, wherein the heterocondensate is a metallo-, phosphoro- or borosiloxane and includes heteroatom units of at least one heteroatom selected from P, B, Al, Ge, Sn, Pb, Ti, Mg, Li, V, Nb, Ta, Zr and Hf, which are incorporated into the siloxane structure via oxygen bridges, and siloxane units in which all or a portion of the silicon atoms of the siloxane units comprise an optionally non-hydrolyzable organic group.

10. The method of claim 9, wherein the optionally non-hydrolyzable organic group is a polymerizable group or an alkyl or aryl group.

11. The method of claim 1, wherein the bonding agent is free of particles.

12. The method of claim 1, wherein at least one hydrolyzable silicon compound which comprises a non-hydrolyzable residue with at least one hydrophilic group is added to the mixture of the bonding agent.

13. The method of claim 12, wherein the at least one hydrophilic group of the non-hydrolyzable residue is a group selected from glycidyloxy, amino, polyethylene glycol, polyethylene amine, carbaldehyde, epoxy, hydroxyl, carboxy, mercapto, acid anhydride, sulfonato, and phosphonato groups.

14. The method of claim 12, wherein the non-hydrolyzable residue with at least one hydrophilic group is an alkyl group which comprises at least one hydrophilic group.

15. The method of claim 1, wherein a portion of the infiltrated bonding agent is expelled by flushing with an aqueous, salt-containing liquid.

16. The method of claim 1, wherein crude oil or natural gas is contained in the geological formation or a geological formation situated beneath it.

17. The method of claim 1, wherein the one or more catalytically active substances comprise Fe.sup.2+ions.

18. The method of claim 1, wherein the one or more catalytically active substances comprise Fe.sup.3+ions.

19. The method of claim 1, wherein the one or more catalytically active substances comprise copper ions.

20. The method of claim 1, wherein the one or more catalytically active substances comprise iron ions and copper ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Examples follow to explain the invention, which examples are in no way intended to limit it.

EXAMPLE 1

(2) 33.1 g MPTES were caused to react with 2.6 g 10 wt. % HCl. 13 g TET were added after the clear point. After the complete incorporation of the titanium alcoholate into the Si matrix, 3.1 g water were added. 51 g butanediol dimethacrylate and 4 g APTES were then added to the hydrolyzate whilst stirring in order to produce a bonding agent A.

(3) 300 mg Vazo 67 were added to 30 g of the bonding agent A produced as above and stirred at room temperature until the solid material in the bonding agent had completely dissolved.

COMPARATIVE EXAMPLE 1

(4) 30 g of the bonding agent A produced as described above in Example 1 had 600 mg Trigonox 121 added to it instead of the azo compound and were briefly stirred at room temperature.

(5) Results of the Gelation Times

(6) Different catalytically active substances were added to the bonding agents of Example 1, to which azo initiator or peroxide initiator was added, and of comparative Example 1 and the gelation times at 50 C. were examined by comparison with a reference without the addition of a catalytically active substance. Sands 1 and 2 are samples from different geological formations.

(7) TABLE-US-00001 +Fe.sup.2+ +Fe.sup.3+ +Cu.sup.2+ Sand 1 Sand 2 (50 (100 (50 Coiled (20 (20 Reference ppm) ppm) ppm) tubing wt. %) wt. %) Ex. 1 120 115 125 330 150 140 130 Azo min min min min min min min initiator Com- 125 95 90 30 60 75 105 parative min min min min min min min Ex. 1 Peroxide Initiator