Resilient Cement

[0001] The present embodiment relates generally to a composition for sealing a subterranean zone penetrated by a well bore.

[0002] In the drilling and completion of an oil or gas well, a composition is often introduced in the well bore for cementing casing or pipe strings. In this process, known as primary cementing, a composition is pumped into the annular space between the walls of the well bore and the pipe string. The composition sets in the annular space, supporting and positioning the pipe string, and forming a substantially impermeable barrier which divides the well bore into subterranean zones. After primary cementing, the undesirable migration of fluids between zones is prevented. Likewise, compositions are often subsequently introduced into a subterranean zone for remedial operations to recover circulation or to plug the well bore. Most remedial operations comprise introducing a composition into the well bore to reestablish a seal between the zones.

[0003] Previously, a variety of cement compositions have been used for cementing. However, cement is undesirable for use with expandable casing. After the expandable casing is placed down hole, a mandrel is run through the casing to expand the casing, and expansions up to twenty five percent are possible. As cement is incompressible, expansion of the casing can lead to crushing of the cement, and consequent loss of effectiveness regarding the zones. Therefore, a composition with comparable strength to cement, but greater elasticity and compressibility is required for cementing expandable casing.

[0004] A sealing composition according to the present embodiment basically comprises a mixture of latex, dithio carbamate, zinc oxide, and sulfur, for sealing a subterranean zone penetrated by a well bore. The sulfur containing component vulcanizes the latex to form a solid mass which seals the zone.

[0005] In a first embodiment, the composition comprises a mixture of latex, dithio carbamate, zinc oxide, and sulfur. Preferably, the amount of latex is maintained at a 41-90 percent ratio by weight of the composition. The dithio carbamate is preferably present in an amount that is 0.1-2 percent of the latex by weight. The zinc oxide is preferably present in an amount that is 2-5 percent of the latex by weight. The sulfur is preferably present in an amount that is 1-4 percent of the latex by weight.

[0006] The composition may further comprise stearic acid. The stearic acid is preferably present in an amount that is 0.1-2 percent of the latex by weight.

[0007] The composition may further comprise a weighting agent. The weighting agent is preferably present in an amount that is 0.1-150 percent of the latex by weight.

[0008] The composition may further comprise acetylenic alcohol for defoaming, such as is available from Halliburton Energy Services of Duncan, Okla., under the trademark D-AIR3. The acetylenic alcohol is preferably present in an amount that is 0.001-0.2 percent of the latex by weight.

[0009] In a second embodiment, the composition comprises a mixture of latex, dithio carbamate, zinc oxide, sulfur, and a foaming agent, wherein the mixture is foamed. Preferably, the amount of latex is maintained at a 41-90 percent ratio by weight of the composition. The dithio carbamate is preferably present in an amount that is 0.1-2 percent of the latex by weight. The zinc oxide is preferably present in an amount that is 2-5 percent of the latex by weight. The sulfur is preferably present in an amount that is 12 percent of the latex by weight. The foaming agent is preferably present in an amount that is 2-4 percent of the latex by weight.

[0010] The composition may further comprise stearic acid. The stearic acid is preferably present in an amount that is 0.1-2 percent of the latex by weight.

[0011] The composition may further comprise a weighting agent. The weighting agent is preferably present in an amount that is 0.1-150 percent of the latex by weight.

[0012] As will be understood by those skilled in the art, the latex for either embodiment may be any of a variety of well known rubber materials commercially available which contain unsaturation in the backbone of the polymer. These include natural rubber (cis-1,4-polyisoprene), modified types thereof, synthetic polymers, and blends of the foregoing. The synthetic polymers include styrene/butadiene rubber, cis-1,4-polybutadiene, neoprene rubber, acrylonitrile styrene/butadiene rubber, and cis-1,4-polyisoprenerubber.

[0013] For either embodiment, the composition preferably includes a latex comprising a styrene/butadiene copolymer latex emulsion prepared by emulsion polymerization. The weight ratio of styrene to butadiene in the latex can range from 10:90 to 90:10. The emulsion is a colloidal dispersion of the copolymer. The colloidal dispersion includes water from about 40-70% by weight of the emulsion. In addition to the dispersed copolymer, the latex often includes small quantities of an emulsifier, polymerization catalysts, chain modifying agents and the like. Also, styrene/butadiene latexes are often commercially produced as terpolymer latexes which include up to about 3% by weight of a third monomer to assist in stabilizing the latex emulsions. Non-ionic groups which exhibit stearic effects and which contain long ethoxylate or hydrocarbon tails can also be present.

[0014] Most preferably for either embodiments, the composition includes a latex with a styrene/butadiene weight ratio of about 25:75, with the styrene/butadiene copolymer suspended in a 50% by weight aqueous emulsion, available from Halliburton Energy Services of Duncan, Okla., under the trademark LATEX 2000.

[0015] The weighting agent for either embodiment may be silica flour, such as is available from Halliburton Energy Services of Duncan, Okla., under the trademark SSA-1. Alternatively, the weighting agent may be manganese oxide weighting additive, available from Halliburton Energy Services of Duncan, Okla., under the trademark MICROMAX.

[0016] Alternatively, the weighting agent may be crystalline silica with an average particle size of 10 microns, available from Halliburton Energy Services of Duncan, Okla., under the trademark MICROSAND.

[0017] Dithio carbamate for either embodiment is available from Halliburton Energy Services of Duncan, under the trademark FLEXCEM COMPONENT L.

[0018] The foaming agent for the second embodiment may be an ethoxylated alcohol ether sulfate surfactant, which is available from Halliburton Energy Services of Duncan, under the trademark ZONE SEAL 2000 . The ZONE SEAL 2000 surfactant is the subject of U.S. Pat. No. 6,063,738, the entire disclosure of which is incorporated herein as if reproduced in its entirety. Alternatively, the foaming agent may be an amidopropylbetaine surfactant, which is available from Halliburton Energy Services of Duncan, under the trademark HC-2. The HC-2 surfactant is discussed in U.S. Pat. No. 5,588,489, the entire disclosure of which is incorporated herein as if reproduced in its entirety.

[0019] The following examples are illustrative of the methods and compositions discussed above.

[0020] To test curing properties of the first embodiment, 450 grams of LATEX 2000 latex, and components in the amounts listed in TABLE 1 were added to form three batches. Each of the batches was mixed in a Waring blender. The batches were poured into receptacles and incubated at the temperatures listed.

TABLE 1
Component	Batch 1	Batch 2	Batch 3
FLEXCEM COMPONENT	5.6 g	5.6 g	4.5 g
L dithio carbamate
Zinc Oxide	9 g	9 g	22.5 g
Sulfur	9 g	9 g	13.5 g
Stearic acid		9 g	4.5 g
D-AIR3 acetylenic	14.6 g	14.6 g	3 g
alcohol
SSA-1 silica flour	600 g	600 g
Comments	No Set;	Set;	Set;
	48 hr at 80 F.	48 hr at	5.5 hr at
		150 F.	150 F.

[0021] TABLE 1 shows that the second and third batches set.

[0022] To test curing properties of the first embodiment with a different weighting agent, 100 grams of LATEX 2000 latex (with the exception of Batch 8), and components in the amounts listed in TABLE 2 (including a C₁₅ alcohol ethoxylated with 15 moles of ethylene oxide, which is available from Halliburton Energy Services of Duncan, under the trademark 434B) were added to form eight batches. Each of the batches was mixed in a Waring blender. The batches were poured into receptacles and incubated at the temperatures listed.

TABLE 2
								Batch 8
								(500 g
Component	Batch 1	Batch 2	Batch 3	Batch 4	Batch 5	Batch 6	Batch 7	latex)
FLEXCEM	5.6 g	5.6 g	0.75 g	0.75 g	4.5 g	4.5 g	1.5 g	2 g
COMPONENT
L dithio
carbamate
Zinc Oxide	9 g	9 g	14 g	14 g	22.5 g	22.5 g	14 g	15 g
Sulfur	9 g	9 g	9 g	9 g	13.5 g	13.5 g	9 g	10 g
Stearic acid			4.5 g
D-AIR3	14.6 g	14.6 g	3 g	3 g	3 g	3 g		5 g
acetylenic
alcohol
MICROMAX	600 g	600 g	400 g	400 g	400 g	400 g	400 g	400 g
manganese
oxide
(15.3 lb/gal)
434B		45 g	45 g	45 g	45 g	45 g	26 g	10 g
ethoxylated
alcohol
Comments	Latex	No set;	No set;	No set;	Set;	No set;	No set;	No set;
	inverted	48 hr at	24 hr at	24 hr at	48 hr at	48 hr at	24 hr at	72 hr at
		80 F.	140 F.	140 F.	140 F.	200 F.	200 F.	200 F.

[0023] TABLE 2 shows that the fifth batch set without stearic acid.

[0024] To test curing properties of the second embodiment, LATEX 2000 latex in the amounts listed in TABLES 3A and 3B, were mixed with components in the amounts listed in TABLES 3A and 3B (including a C₁₅ alcohol ethoxylated with 40 moles of ethylene oxide, which is available from Halliburton Energy Services of Duncan, under the trademark 434C; a sodium salt of alpha-olefinic sulfonic acid surfactant which is discussed in U.S. Pat. No. 5,588,489, the entire disclosure of which is incorporated herein as if reproduced in its entirety, and is available from Halliburton Energy Services of Duncan, under the trademark AQF-2; an alcohol ether sulfate surfactant which is discussed in U.S. Pat. No. 5,588,489, the entire disclosure of which is incorporated herein as if reproduced in its entirety, and is available from Halliburton Energy Services of Duncan, under the trademark HOWCO SUDS; and ammonium decasulfate, which is available from Halliburton Energy Services of Duncan, under the trademark CFAS) were added to form twelve batches. Each of the batches was mixed in a Waring blender with a sealable metal canister. The batches were poured into receptacles and incubated at the temperatures listed.

TABLE 3A
Components	Batch 1	Batch 2	Batch 3	Batch 4	Batch 5	Batch 6	Batch 7
LATEX 2000	450 g	450 g	450 g	450 g	450 g	600 g	600 g
latex
FLEXCEM	5.6 g	5.6 g	5.6 g	5.6 g	5.6 g	6 g	6 g
COMPONENT
L dithio
carbamate
Zinc Oxide	9 g	9 g	9 g	9 g	9 g	30 g	30 g
Sulfur	9 g	9 g	9 g	9 g	9 g	18 g	18 g
Stearic acid	9 g	9 g	9 g	9 g	9 g
D-AIR3	14.6 g	14.6 g
acetylenic
alcohol
SSA-1 silica	600 g	600 g
flour
ZONE SEAL	9 g	18 g		20 g	20 g
2000
surfactant
MICROSAND			600 g	600 g	600 g
crystalline silica
434C			45 g	45 g	45 g
ethoxylated
alcohol
AQF-2			9 g
surfactant
HC-2			4.5 g			10 g	5 g
surfactant
HOWCO							10 g
SUDS
surfactant
CFAS
ammonium
decasulfate
Comments	Unstable	Unstable	Unstable	Unstable	Unstable	Unstable	Unstable
	foam	foam	foam	foam	foam	foam	foam

[0025]

TABLE 3B
Components	Batch 8	Batch 9	Batch 10	Batch 11	Batch 12
LATEX 2000	600 g	600 g	600 g	600 g	675 g
latex
FLEXCEM	6 g	6 g	6 g	6 g	8.4 g
COMPONENT
L dithio
carbamate
Zinc Oxide	30 g	30 g	30 g	30 g	13.5 g
Sulfur	18 g	18 g	18 g	18 g	13.5 g
Stearic acid					13.5 g
D-AIR3
acetylenic
alcohol
SSA-1 silica
flour
ZONE SEAL					20 g
2000
surfactant
MICROSAND			200 g	200 g	600 g
crystalline silica
434C
ethoxylated
alcohol
AQF-2	10 g
surfactant
HC-2	5 g	5 g	12 g	20 g
surfactant
HOWCO
SUDS
surfactant
CFAS		10 g
ammonium
decasulfate
Comments	Unstable	Unstable	Unstable	Foamed and	Foamed and placed in
	foam	foam	foam	placed in cell	cell; heated to 190 F.
				for 48 hours at	for 2 hours; sand
				150 F.; set	settled from top 1-2
				stable foam	inches of 8 inch column

[0026] TABLES 3A and 3B show that the eleventh and twelfth batches set.

[0027] To test curing properties of the first embodiment, 300 grams of LATEX 2000 latex, 2 grams D-AIR3 acetylenic alcohol, and components in the amounts listed in TABLE 4 were added to form eight batches. Each of the batches was mixed in a Waring blender. The batches were poured into receptacles and incubated in a 150 F. water bath.

TABLE 4
	Batch	Batch	Batch	Batch	Batch	Batch	Batch	Batch
Component	1	2	3	4	5	6	7	8
FLEXCEM	3 g	3 g	3 g					3 g
COMPONENT
L dithio
carbamate
Zinc Oxide		15 g	15 g	15 g	15 g
Sulfur	9 g		9 g	9 g		9 g
Stearic acid	3 g	3 g		3 g			3 g
Comments	No	No	Set	No	No	No	No	No
	set	set		set	set	set	set	set

[0028] TABLE 4 shows that the fourth batch set.

[0029] To test shear bond properties of the first embodiment, 450 grams of LATEX 2000 latex, 1.5 grams of FLEXCEM COMPONENT L dithio carbamate, 2 grams of D-AIR3 acetylenic alcohol, and components in the amounts listed in TABLE 5 were added to form eight batches. Each of the batches was mixed in a Waring blender. The batches were poured into receptacles and incubated before having their shear bond strengths tested. Batches 1-4 were tested after incubation for 48 hours at 200 F. Batches 5-8 were tested after incubation for 12 days at 200 F.

[0030] In a conventional shear bond test, the batches were placed in metal cylinders with a metal bar disposed in each of the cylinders. Once a batch set, the bar was supported and positioned by the composition. Shear bond strength was determined by the force required to push the bar out of the cylinder. The shear bond testing method is conventional, and is described in a paper by L. G. Carter and G. W. Evans entitled A Study of Cement-Pipe Bonding, presented at the Society of Petroleum Engineers California Regional Meeting, held in Santa Barbara, Calif., on Oct. 24-25, 1963.

TABLE 5
	Batch	Batch	Batch	Batch	Batch	Batch	Batch	Batch
Component	1	2	3	4	5	6	7	8
Zinc Oxide	13.5 g	13.5 g	27 g	27 g	13.5 g	13.5 g	13.5 g	13.5 g
Sulfur	9 g	18 g	9 g	18 g	9 g	9 g	9 g	9 g
SSA-1	600 g	600 g	600 g	600 g		200 g	400 g	600 g
silica flour
Shear bond	21 psi	14 psi	26 psi	22 psi	11 psi	28 psi	34 psi	34 psi

[0031] TABLE 5 shows that all the batches bond to metal. Batch 1 also shear bond strengths of 40 psi at 72 hours, 38 psi at 96 hours, and 55 psi at 30 days.

[0032] To test thickening times (TT) for reaching viscosities of 70 BC for the first embodiment, 600 grams of LATEX 2000 latex, 3 grams of D-AIR3 acetylenic alcohol, and components listed in the amounts listed in TABLE 6 were added to form ten batches. Each of the batches was mixed in a Waring blender. The batches were poured into receptacles and incubated at the temperatures listed in TABLE 6.

TABLE 6
	Bat.	Bat.	Bat.	Bat.	Bat.	Bat.	Bat.	Bat.	Bat.	Bat.
Component	1	2	3	4	5	6	7	8	9	10
FLEXCEM	6 g	0.75 g	0.75 g	1.1 g	0.75 g	1 g	1 g	2 g
COMPONENT
L dithio
carbamate
Zinc Oxide	30 g	3 g	6 g	12 g	18 g	18 g	18 g	18 g	18 g	18 g
Sulfur	18 g	12 g	12 g	12 g	12 g	12 g	12 g	12 g	12 g	12 g
Stearic acid	6 g	6 g	6 g	6 g	6 g	12 g			12 g
TT (hr:min) at	1:39;	12	10:26	8:20	7:37	7:44	6:00	3:39
150 F.	1:53
TT (hr:min) at						1:59	1:45	1:35	6:42	11
200 F.

[0033] TABLE 6 shows that the set up times can be controlled by varying the amounts of components.

[0034] To test applied pressure for the first and second embodiments, LATEX 2000 latex, and components listed in the amounts listed in TABLE 7 were added to form three batches. Each of the batches was mixed in a Waring blender.

[0035] The first batch, representing the first embodiment, was poured into a test cell, which was sealed and heated to 200 F. for 72 hours. After 72 hours, a valve positioned under a 325 mesh screen on the bottom of the test cell was opened, and a force of 1000 psi was applied to the test cell via a piston from the top of the cell. After approximately an hour, the volume of the batch had reduced by an amount listed in TABLE 7.

[0036] The second batch, representing the second embodiment, was poured into a test cell, which was sealed and heated to 170 F. After 48 hours, a force of 1000 psi was applied to the test cell via a piston, and the volume of the batch had reduced by an amount listed in TABLE 7. After seven days, pressure was released, and the volume of the batch returned to 85% of its original size.

[0037] The third batch, representing the second embodiment, was poured into a test cell, heated to 170 F., and thereafter, a force of 1000 psi was applied to the test cell via a piston. The t* volume of the batch was reduced by an amount listed in TABLE 7. After twenty four hours, pressure was released, and the volume of the batch returned to its original size. Thereafter, a force of 1000 psi was applied again and the volume of the batch was reduced by an amount listed in TABLE 7. After twenty four hours, pressure was again released, and the volume of the batch returned to 88% of its original size.

TABLE 7
	Batch 1	Batch 2	Batch 3
	Non-foamed	Set Foamed	Liquid Foam
Component	Latex	Latex	Latex
LATEX 2000 latex	450 g	600 g	600 g
FLEXCEM	1.5 g	6 g	6 g
COMPONENT L
dithio carbamate
Zinc Oxide	13.5 g	30 g	30
Sulfur	9 g	18 g	6 g
HC-2 surfactant		20 g	20 g
SSA-1 silica flour	400 g
Volume reduction	30%	40%	36%

[0038] TABLE 7 shows that the first embodiment is compressible in its set state when placed against a porous geological formation, and the second embodiment is compressible in both set and unset states when placed in a sealed system.

[0039] Although only a few exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciate that many other modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the following claims.