US4582139A — Set retarded cement compositions and well cementi…

Claim 1

Independent Claim 170 words

A method of cementing a subterranean zone penetrated by a wellbore comprising the steps of: forming a pumpable set retarded thixotropic cement slurry having enhanced compressive strength development after placement across said zone or zones comprised of hydraulic cement, water, one or more retarders present in said slurry in an amount sufficient to retard the set of said slurry until after placement thereof, a crosslinkable material present in said slurry in an amount sufficient to provide thixotropic properties and gel strength development when crosslinked to said composition, and a crosslinking retarder neutralizing agent present in said slurry in an amount sufficient to crosslink said crosslinkable material and to neutralize said set retarders after placement of said slurry in said zone, said crosslinking-retarder neutralizing agent being selected from the group consisting of alkalnolamine titanium chelates and mixtures of chelates represented by the formulae: ##STR5## wherein R 1 is ethylene or isopropylene; pumping said cement slurry into said zone by way of said wellbore; and allowing said cement slurry to set therein.

Claim 2

Independent Claim 170 words

A method of cementing a subterranean zone penetrated by a wellbore comprising the steps of: forming a pumpable set retarded thixotropic cement slurry having enhanced compressive strength development after placement across said zone or zones comprised of hydraulic cement, water, one or more retarders present in said slurry in an amount sufficient to retard the set of said slurry until after placement thereof, a crosslinkable material present in said slurry in an amount sufficient to provide thixotropic properties and gel strength development when crosslinked to said composition, and a crosslinking retarder neutralizing agent present in said slurry in an amount sufficient to crosslink said crosslinkable material and to neutralize said set retarders after placement of said slurry in said zone, said crosslinking-retarder neutralizing agent being selected from the group consisting of alkalnolamine titanium chelates and mixtures of chelates represented by the formulae: ##STR5## wherein R 1 is ethylene or isopropylene; pumping said cement slurry into said zone by way of said wellbore; and allowing said cement slurry to set therein.

Claim 3

Dependent Claim 73 words

The method of claim 1 wherein said one or more retarders are selected from the group consisting of salts of lignosulfonates, organic acids and their salts, mixtures of the foregoing compounds and one or more of the foregoing compounds in admixture with one or more water soluble borates and are present in said composition in an amount in the range of from about 0.1% to about 5.0% by weight of dry cement therein.

Claim 4

Dependent Claim 54 words

The method of claim 2 wherein said crosslinkable material is selected from the group consisting of carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, a copolymer of 2-acrylamido-2-methylpropane sulfonic acid and N,N-diethylacrylamide and mixtures of these compounds present in said composition in an amount in the range of from about 0.1% to about 2.0% by weight of dry cement therein.

Claim 5

Dependent Claim 42 words

The method of claim 3 wherein R 1 of said titanium chelate is ethylene and said titanium chelate is present in said composition in an amount in the range of from about 0.1% to about 0.5% by weight of dry cement therein.

Claim 6

Dependent Claim 89 words

In a method of cementing a liner in a wellbore using a set retarded aqueous hydraulic cement slurry wherein the cement slurry is subjected to a temperature differential after placement up to about 50° F., the improvement comprising adding to the cement slurry to enhance and make uniform the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of alkanolamine titanium chelates and mixtures of such chelates represented by the formulae: ##STR6## where R 1 is ethylene or isopropylene.

Claim 7

Dependent Claim 89 words

In a method of cementing a liner in a wellbore using a set retarded aqueous hydraulic cement slurry wherein the cement slurry is subjected to a temperature differential after placement up to about 50° F., the improvement comprising adding to the cement slurry to enhance and make uniform the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of alkanolamine titanium chelates and mixtures of such chelates represented by the formulae: ##STR6## where R 1 is ethylene or isopropylene.

Claim 8

Dependent Claim 38 words

The method of claim 5 wherein said alkanolamine titanium chelate or mixture of chelates is added to said slurry in an amount in the range of from about 0.05% to about 1.5% by weight of dry cement therein.

Claim 9

Dependent Claim 52 words

The method of claim 6 wherein said cement slurry is retarded by including therein a retarder comprised of calcium lignosulfonate and potassium pentaborate in a 1:1 ratio by weight present in said slurry in an amount in the range of from about 0.1% to about 5.0% by weight of dry cement therein.

Claim 10

Dependent Claim 38 words

The method of claim 7 wherein said delayed retarder neutralizer is isopropoxytitanium triethyanolamine and is added to said slurry in an amount in the range of from about 0.1% to about 0.5% by weight of dry cement therein.

Claim 11

Independent Claim 126 words

A method of cementing a subterranean zone penetrated by a well bore comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of: a triethanolamine titanium chelate represented by one of the formula: ##STR7## wherein R is independently an alkyl or aryl group, ##STR8## wherein R 1 is independently OC 3 H 7 , OH or a halogen atom, and partially polymerized chelates produced from said triethanolamine chelates, and placing said cement slurry across said zone or zones by way of said well bore and allowing said cement slurry to set into a hard mass therein having enhanced compressive strength.

Claim 12

Independent Claim 126 words

A method of cementing a subterranean zone penetrated by a well bore comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of: a triethanolamine titanium chelate represented by one of the formula: ##STR7## wherein R is independently an alkyl or aryl group, ##STR8## wherein R 1 is independently OC 3 H 7 , OH or a halogen atom, and partially polymerized chelates produced from said triethanolamine chelates, and placing said cement slurry across said zone or zones by way of said well bore and allowing said cement slurry to set into a hard mass therein having enhanced compressive strength.

Claim 13

Dependent Claim 34 words

The method of claim 9 wherein the delayed retarder neutralizer is present in said composition in an amount in the range of from about 0.05% to about 1.5% by weight of dry cement therein.

Claim 14

Independent Claim 159 words

A method of cementing a subterranean zone penetrated by a well bore comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of: a titanium chelate represented by one of the formula: ##STR9## wherein R 1 is independently hydrogen, an alkyl group, or a hydroxyalkyl group, R 2 is independently ethylene, trimethylene or isopropylene, and R 3 is independently an alkyl or aryl group, ##STR10## wherein R 1 is independently hydrogen, an alkyl group or a hydroxyalkyl group, R 2 is independently ethylene, trimethylene or isopropylene, and R 4 is independently OC 3 H 7 , OH or a halogen atom; and placing said cement slurry across the zone or zones by way of said well bore and allowing said cement slurry to set into a hard mass therein having enhanced compressive strength.

Claim 15

Independent Claim 159 words

A method of cementing a subterranean zone penetrated by a well bore comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of: a titanium chelate represented by one of the formula: ##STR9## wherein R 1 is independently hydrogen, an alkyl group, or a hydroxyalkyl group, R 2 is independently ethylene, trimethylene or isopropylene, and R 3 is independently an alkyl or aryl group, ##STR10## wherein R 1 is independently hydrogen, an alkyl group or a hydroxyalkyl group, R 2 is independently ethylene, trimethylene or isopropylene, and R 4 is independently OC 3 H 7 , OH or a halogen atom; and placing said cement slurry across the zone or zones by way of said well bore and allowing said cement slurry to set into a hard mass therein having enhanced compressive strength.

Claim 16

Dependent Claim 34 words

The method of claim 11 wherein the delayed retarder neutralizer is present in said composition in an amount in the range of from about 0.05% to about 1.5% by weight of dry cement therein.

Claim 17

Independent Claim 163 words

A method of cementing a subterranean zone penetrated by a well bore comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of: a triethanolamine titanium chelate represented by the formula: ##STR11## wherein R is independently an oxyalkyl group, an oxyaryl group, OH or a halogen, R 3 is independently ethylene, trimethylene or isopropylene R 4 and R 5 are independently hydrogen, an alkyl group, a hydroxyalkyl group or an aminoalkyl group, R 6 is an oxyalkyl group, and R 7 is independently hydrogen, an alkyl group, a hydroxyalkyl group or an aminoalkyl group, R 7 is independently hydrogen, alkyl, hydroxyalkyl or an aminoalkyl group; and placing said cement slurry across the zone or zones by way of said well bore and allowing said cement slurry to set into a hard mass therein having enhanced compressive strength.

Claim 18

Independent Claim 163 words

A method of cementing a subterranean zone penetrated by a well bore comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance the compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of: a triethanolamine titanium chelate represented by the formula: ##STR11## wherein R is independently an oxyalkyl group, an oxyaryl group, OH or a halogen, R 3 is independently ethylene, trimethylene or isopropylene R 4 and R 5 are independently hydrogen, an alkyl group, a hydroxyalkyl group or an aminoalkyl group, R 6 is an oxyalkyl group, and R 7 is independently hydrogen, an alkyl group, a hydroxyalkyl group or an aminoalkyl group, R 7 is independently hydrogen, alkyl, hydroxyalkyl or an aminoalkyl group; and placing said cement slurry across the zone or zones by way of said well bore and allowing said cement slurry to set into a hard mass therein having enhanced compressive strength.

Claim 19

Dependent Claim 34 words

The method of claim 13 wherein the delayed retarder neutralizer is present in said composition in an amount in the range of from about 0.05% to about 1.5% by weight of dry cement therein.

Claim 20

Independent Claim 83 words

A method of cementing comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of alkanolamine titanium chelates and mixtures of such chelates represented by the formulae: ##STR12## where R 1 is ethylene or isopropylene; placing said cement slurry in a desired location and allowing said cement slurry to set into a hard mass having enhanced compressive strength.

Claim 21

Independent Claim 83 words

A method of cementing comprising: providing a set retarded aqueous hydraulic cement slurry; admixing with said cement slurry to enhance compressive strength development thereof after placement, an effective amount of a delayed retarder neutralizer selected from the group consisting of alkanolamine titanium chelates and mixtures of such chelates represented by the formulae: ##STR12## where R 1 is ethylene or isopropylene; placing said cement slurry in a desired location and allowing said cement slurry to set into a hard mass having enhanced compressive strength.

Claim 22

Dependent Claim 34 words

The method of claim 15 wherein the delayed retarder neutralizer is present in said composition in an amount in the range of from about 0.05% to about 1.5% by weight of dry cement therein.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1989-04-14	1989-10-14	1990-04-15	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1993-04-14	1993-10-14	1994-04-15	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1997-04-14	1997-10-14	1998-04-15	$7700.00	Window Closed / Lapsed

Set retarded cement compositions and well cementing methods

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