CA1163090A

CA1163090A - Fluid loss control in saturated salt cement slurries

Info

Publication number: CA1163090A
Application number: CA000381631A
Authority: CA
Inventors: Jiten Chatterji; Bobby G. Brake
Original assignee: Halliburton Co
Current assignee: Halliburton Co
Priority date: 1980-07-14
Filing date: 1981-07-13
Publication date: 1984-03-06
Also published as: IT1138054B; DE3126489C2; BR8104405A; AU7280081A; NO812339L; NL8103326A; GB2080812A; IT8122930A0; GB2080812B; AU547062B2; DE3126489A1

Abstract

Abstract of the Disclosure Salt water cement slurries having low water loss when in contact with water permeable earth formations and additives for reducing water loss from salt water cement slurries are provided. The additives are comprised of very low molecular weight carboxymethylhydroxyethylcellulose polymers. Methods of using the additives are also provided.

Description

3 0~ ~) In the drilling and completing of oil, gas and water wells, cement slurries are commonly utilized for carrying out cementlng procedures such as cementing casings in the well bores, sealing subterranean zones penetrated by the well bores, etc~ In most cases, the cement slurries are pumped into the well bores and allowed to harden once in place in the well bores or desired zones in formations.
A variety of additives have been developed and utilized heretofore for improving the properties of cement slurries and bringing about desired results including addi-tives for reducing water loss from such slurries while or after the slurries are placed. Excessive water loss from cement slurries can prevent proper hydration of the cement, and in cementing wells, excessive water loss while the slurries are being flowed through well bores can result in dehydration o~ the slurries to the point where bridging of the cement and other solids takes place in the well bores preventing completion of cement displacement, etc. While the water loss reducing additives utilized heretofore are effec-tive in cement slurries formed with fresh water or water con-taining very low concentrations of salts therein, such addi-tives are substantially ineffective in cement slurries con-taining high concentrations of salts, and particularly, in cement slurries which are saturated with salts. For example, a number of cellulose derivatives have been utilized to con-trol fluid loss from cement slurries containing little or no salts. However, such heretofore used cellulose derivatives are substantially ineffective in reducing water loss from salt water cement slurries. In addition, other heretofore used fresh water cement slurry water loss reducing additives, such as polyacrylamides, polyethylene imines mixed with naphthalene sulfonic acid and poly-2-acrylamide-3-propylsulfonic - 1 - ~

~, `i ~ 63~0 acid salts are not effective in reducing water loss from salt water cement 9 lurries.
By the present invention, water loss reducing addi-tives for salt water cement slurries are provided which are effective in reducing water loss from the slurries over a broad temperature range. In addition, methods of using the additives and salt water cement slurries containing the addi-tives are provlded. The term "salt water" is used herein to mean sea water, brines and other aqueous solutions of salts including ammonium, alkali metal and alkaline earth metal halides, and nitrates having salt concentrations therein up to saturation. Salts other than those mentioned above can be tolerated in the cement slurries of this invention to some extent even though they may react with or alter the performance of the slurries, e.g., bicarbonates, phosphates and sulfates.
The term "salt water cement slurry" is used herein to mean a cement slurry comprised of water, cement, one or more salts and other components or additives to bring about desired slurry properties or use results. The salt amounts or con-centrations in the cement slurries set forth hereinafter areexpressed in percentages by weight of the water in the cement slurries. The amounts of water loss reducing additives in the cement slurries set forth hereinafter are expressed in percentages by weight of dry cement in the slurries.
The water loss reducing additives for salt water cement slurries of the present invention are comprised of very low molecular weight carboxymethylhydroxyethylcellulose polymers. More specifically, the particular car~oxymethyl-hydroxyethylcellulose polymers which are useful in accordance with this invention have a carboxymethyl degree of substitu-tion (D.S.) in the range of from about 0.1 to about 0.7 and a ratio of moles of ethylene oxide to anhydroglucose unit (M.S.) i ~30~) in the range of from about 0.6 to about 2.8.

The carboxymethylhydroxyethylcellulose polymers axe derived from the cellulose class represented as a series of anhydroglucose units as follows:

t ~ o H~ O 1 C n ~ le portion of the above structural formula in brackets constitutes two anhydroglucose units, each having three reactive hydroxyl groups. n is an integer which gives the desired polymer molecular length. When the polymer is treated with sodium hydroxide and reacted with chloroacetic acid and ethylene oxide under controlled conditions, carboxy-methylhydroxyethylcellulose is produced shown as follows:

CEI OH H OH

H ~ \ ~
_ ~ ~H o ~ + _ L 2-CH2-H OEI2-o=~E2-C-O Na .
The sodium salt of carboxymethylhydroxyethylcellulose shown above has one of the side hydroxyl groups substituted by carboxymethyl, and therefore, the carboxymethyl degree of sub-stitution (D.S.) is 0.5 per anhydroglucose unit. As stated .. above, the preferred carboxymethyl degree of substitution for the carboxymethylhydroxyethylcellulose used in accordance with this invention is in the range of from about 0.1 to about 0.7. At a carboxymethyl D.S. of less than about 0.1, the carboxymethylhydroxyethylcellulose has limited solubility in water and at a carboxymethyl D.S. above about 0.7, the carboxy-methylhydroxyethylcellulose has too much anionic characteristic and causes a precipitate to be formed when combined with a o a cement slurr~.
The above structural formula also shows that the ratio of moles of ethylene oxide to anhydroglucose unit (M.S.) is 1 mole for two units or 0.5~ The preferred ethylene oxide M.S. for the carboxymethylhydroxyethylcellulose used in accordance with this invention is in the range of from ahout 0.6 to about 2.8. Carhoxymethylhydroxyethylcellulose having an ethylene oxide M.S. outside the range given above does not give adequate water loss reducing properties to a salt water cement slurry.
The molecular length of the carboxymethylhydroxyethyl-cellulose polymers, i.e., the molecular weight of the polymers, must be very low in order to impart a low viscosity to a salt water cement slurry with which the polymers are combined.
More specifically, the carboxymethylhydroxyethylcellulose polymers suitable for use in accordance with this invention have a very low molecular weight whereby a 1% by weight aqueous solution of the carboxymethylhydroxyethylcellulose at a tem-perature of 78F has a viscosity in the range of from about 10 20 to about 225 centipoises measured on a FAN~ viscometer at 300 rpm using a ~o~ 1 spring, standard bob and standard sleeve.
At molecular weights higher than those falling within the above given range, the viscosity of the salt water cement slurry to which the carboxymethylhydroxyethylcellulose is combined is too high whereby the resulting slurry cannot be pumped or otherwise handled. The FAN~ viscometer referred to herein is a FANN Model 35 viscometer manufactured by Fann Instrument Co. of Houston, Texas.
While the carboxymethylhydroxyethylcellulose polymers described above are effective in reducing water loss from salt water cement slurries, when the concentration of salts in the slurries is above about 18% by weight of water, ~;;
~1. ' `.

3~ 0 the effectiveness of the polymers by themselves decreases.
However, when a hydroxycarboxy acid is combined with the carboxymethylhydroxyethylcellulose polymers, the resulting additive is highly effective in reducing water loss from salt water cement slurries having high salt concentrations. More specifically, for salt water cement slurries having salt con-centrations therein in the range of from about 18% by weight of water to saturation, an additive comprised of the carboxy~
methylhydroxyethylcellulose polymers described and a hydroxy-carboxy acid present in the additive in an amount of about50% of the weight of carboxymethylhydroxyethylcellulose in the additive is utilized. Particularly suitable hydroxycarboxy acids which can be used are gluconic acid, tartaric acid, lactic acid, citric acid, maleic acid and mixtures of such acids. Of these, gluconic acid, tartaric acid and citric acid are preferred with citric acid being the most preferred.
A preferred water loss reducing additive for salt water cement slurries having salt concentrations below about 18% by weight of the slurries is comprised of carboxymethyl hydroxyethylcellulose having a carboxymethyl D.~. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8 and a molecular weight such that a 1% by weight aqueous solution of the carboxymethyl-hydroxyethylcellulose at a temperature of 78F has a viscosity .in the range of from about 10 to about 225 centipoises measured on a FA~N viscometer at 300 rpm using a ~o. 1 spring. The most preferred additive of this type is comprised of carboxymethyl-hydroxyethylcellulose having a carboxymethyl D.S. of about 0.~, an ethylene oxide ~.S. of about 2.0 and a molecular weight wherein the viscosity of a 1% by weight aqueous solution is in the range of from about 10 to about 200.

63~s~

~ preferred water loss reducing additive for salt water cement slurries having salt concentrations thereln in the range of from about 18% by weight of water to saturation is comprised of carboxymethylhydroxyethylcellulose having a carboxymethyl D.S. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8, and a molecular weight such at a 1% by weight aqueous solution of said carboxymethylhydroxyethylcellulose at a temperature of 78F has a viscosity in the range of from about 10 to about 225 centipoises measured on a FANN
viscometer at 300 rpm using a No. 1 spring, and a hydroxy-carbo~y acid selected from the group consisting of gluconic acid, tartaric acid~ lactic acid, citric acid, maleic acid and mixtures of such acids present in the additive in a weight amount of about 50% of the weight of carboxymethylhydroxy-ethylcellulose in the additive.
The most preferred additive of this type is comprised of carboxymethylhydroxyethylcellulose having a carboxymethyl D.S. of about 0.4, an ethylene oxide M.S. of about 2.0 and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78F has a viscosity in the range of from about 10 to about 200 centipoises measured on a FANN
viscometer at 300 rpm using a No. 1 spring, and citric acid present in the additive in an amount of about 50% of the weight of carboxymethylhydroxyethylcellulose in the additive.
A preferred salt water cement slurry having low water loss when in contact with permeable earth formations of this invention is comprised of salt water, cement and a water loss reducing additive comprised of carboxymethylhydroxy-ethylcellulose having a carboxymethyl D.S. in the range offrom about 0.1 to about 0~7, an ethylene oxide M.S. in the ~range of from about 0.6 to about 2.8 and a molecular weight `~ :I B3~

such that a 1% by weight aqueous solution thereof at a temperature of 78F has a viscosity in the range of from about 10 to about 225 centipoises measured on a FANN visco-meter at 300 rpm using a No. 1 spring.
Another preferred salt water cement slurry having low water loss when in contact with permeable earth forma-tions is comprised of salt water, cement, a water loss re-ducing additive comprised of carboxymethylhydroxyethylcellulose having a carboxymethyl D.S. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8 and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78F has a viscosity in the range of from about 10 to about 225 centi-poises measured on a FA~N viscometer at 300 rpm using a No. 1 spring, present in the slurry in an amount in the range of from about 0.2% to about 2~0% by weight of dry cement in the slurry, and a hydroxycarboxy acid selected from the group consisting of gluconic acid, tartaric acid, lactic acid, citric acid, maleic acid and mixtures of such acids present in said slurry in an amount in the range of from about 0.1%
to about 1.0% by weight of dry cement in the slurry.
The most preferred salt water cernent slurry having low water loss is comprised of salt water, cement, and a water loss reducing additive comprised of carboxymethylhydroxyethyl-cellulose having a carboxymethyl D.S. of about 0.4, an ethylene oxide M.S. of about 2.0 and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78F
has a viscosity of from about 10 to about 200 centipoises measured on a FANN viscometer at 300 rpm using a No. 1 spring, ~` 30 the carboxymethylhydroxyethylcellulose being present in the ` slurry in an amount in the range of from about 0.25% to about 1.8% by weight of dry cement in the slurry, and citric acid .` ~

3 0 ~ 0 present in the slurry in an amount in the range of from about 0.1% to about 0.9% by weight of dry cement in the slurry.
In use of the water loss reducing additives of the present invention for reducing water loss from a salt water cement slurry used in cementing wells, the additive is com-bined with the salt water cement slurry prior to the use thereof. Preferably, the water loss reducing additive is dry blended with other dry components and added to the mixing water used to prepare the cement slurry. If the mixing water does not already contain salts, the salt or salts used are preferably also dry blended with other dry components and the mixture then combined with the mixing water. Once the slurry is thoroughly mixed, it is introduced into a well bore and/or subterranean formations penetrated thereby and allowed to set into a hard permeable mass. The water loss reducing additives and cement slurries including such addi-tives are effective in substantially reducing water loss at temperatures over a broad temperature range, i.e. from about 100F to about 360~.
As is well understood by those skilled in the art~
the salt water cement slurries of this invention can include a variety of other components and additives to bring about desired results including solid fillers such as sand, set time retarders, accelerators, etc.
In order to facilitate a clear understanding of the additives, salt water cement slurries and methods of the - present invention, the following examples are given.
Example 1 Cement slurries are prepared using fresh water containing various concentrations of sodium chloride, cement and water loss reducing additives of this invention comprised ; ~ - 8 -~ 1~30~

of very low molecular weight carboxymethylhydroxyethylcellulose polymers (D.S. of 0O~ M.S. of 2.0, and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78F has a viscosity of from about 10 to about 200 centi-poises measured on a FA~N viscometer at 300 rpm using a No. 1 spring) and tartaric acid. The slurries and additives are mixed in a Waring Blender for 35 seconds at high speed. The surface mixing viscosities of the slurries are determined at 100F, 120F, 150F and 190F using a Halliburton consisto-meter as described in U.S. Patent No. 2,122,765.
Fluid loss properties of the slurries are determinedin accordance with API standard methods (API RP-lOB) on a 326 mesh screen at 1000 psi at 100F, 120F, 150F and 190F.
The results of these tests are given in Table I
below.

,~,. _ g _ .~ I ~ 6~090 ~o r~ 0 ~ a~ D ~ ~ ~ 0 ~ 0 ~ ~1 O O ~) 0 0 ~9 U') I` In Lr~ d' ~ d' d' Ll'~
H 1~ 1 V
a a :~
C~
Zi .~, o H :~ ~ U U~ d' 0 ~ 0 0 ~ (S) C5~ ~ ~ 0 C~
æ a ~ 1 U
H H ~> O m o U~ ~ ^
C) o ~ ~
u~ ~a ~ ~;
H ~Ll Q) ~1 1:4 ~; E~ Q, u~ o O O O O O O O O O O O O O O O O
P~ ~ E~ o o o o o (~
~ 3 E~ O
H
æ
~o ~ ~
o p~ >1 3 ; ~ ~ _ ~) ~) .i~ .L~
~rt rl ~ P~ ~ ~ ~ o u o c~ ~ o ~ o ~ o o In o oo u~
E~ ~ S:: ~I h t~ ~1 ~1 ~ ~1 ~ ~1 ~ ~ ~1 r1 3 ~ ~ ~ ~1 a) _~ ~ ~ 3 V7 S~
~ a u~ ~E~ ~ ~ . ' ~ rl o ~ ~ ,~ a H U~O ~ E~
IX O rl ~ q) ~7 ~ U C) .
~ U ~,C . ~ . . . . . . . . . . . . . .
O ~ .~ O O O O O O O O O O O O O O O O
~ 1 a) l ~ U~ 3 H
~ ,~
O O ~~1 1 ~ o e ~Q
~ >1 ~ C~ 0 0 0 0 0 00 ~D ~
I ~ ~ ~r~ ~ d' d~ 1 Ln 0 0 0 0 0 0 0 r--l ~ r l >1 O O O O OO O O O O O O O O O O Q) r~ . 3 ~; c~ u~ 3 E~ ~
r~
1~ ~ C.) X
~ ~ U~ .~
U~
(D r-~ a O ~) t~l N N N N NN N N N N N N N N t~l C /~
r~ ~
,., ~) t O

r ~ C 3 X X
~' ...' oq u~
cl U~ Cq tq tQ tQU~ U~ r--l r-l ri r--¦ r--l r-J r-¦ U~
r~ ¦ r-¦r-¦ r--¦ r~ ¦r--¦ r--l ) C) ~ h r~
a 11) ~) >-~ ) (U
u~
G~ r~ ~r~ ~r~ r~ r~ r~ rl r~
D
Q~ ~rl r~ -r~r~ r~ ~r~r~ ~1 ~/ ~ C
h h ~ h ~ O O O O O O O U~

ii 3 ~30~() From Table I it can be seen that the carboxymethyl-hydroxyethylcellulose-tartaric acid additives produce good surface mixing viscosities and fluld loss reduction in cement slurries containing various quantities of salts.
Example 2 The procedure of Example 1 is repeated using water loss reducing additives comprised of the low molecular weight carboxymethylhydroxyethylcellulose polymers described and various hydroxycarboxy acids.
The results of these tests are given in Table II
below.

'~``

~ -- 11 -~ `3~30~JO

O ~ ~ O ~ r~ ~D 0 0 ~D ~ O ~ ~ ~D O C~ D t` O ~ O ~ ~ O O C
O ~ ~D a ~ ~ ~ ~ ~ ~ ~ ~ o ~ ~ Ln ~ ~ ~ ~, ~ o ~ ~ ~ ~r ~ ~ r~ ~ ~ r~
~ o ~; Ln ~ ~ ~ Ln ~ In .. ~
~ o ~n .,~ o o o Ln o o o o CO
~ ~ O ~ ~ Ln Ln ~ r~ ~ ~ ~ Ln ~ Ln ~ ~D ~ ~ o~ oD a: C

U~ ~ ~
~ oooooooooooo ooooooooo ooooooooOoo E~ a) ~n O o o o o Ln Ln Ln Ln Ln Ln Ln Ln Ln IS) ~ ~ ( ~ O C~
E~ O

h ~ ra ~a :~ ~ ~ a.) a) aJ ~ ~ ~IJ a ~ C~ ~ h h ~/ ~1 h SJ h 51 u:~ ~ ~
U~ ~ ~1 0 ~ ~ ~ ~) .IJ .1_) .1_) ~) ~) O ~ ,~ ~ ~: o o0 Ln ~ ri Ln ta c~ o~ o c0 c~ Ln ~a (a o o~ Ln ~ ~ ~d ~ ~ o O Lr ~1~1~ ~q ~ ~ u~ ~ ~1 o O Ln ~ ~ ~ ~ u~ ~ O o Ln ~1~1 .' '~
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O 1-~ 0 ~ o~ ~ X ~ C X ~ $ ~ X ~
. ~ ~ ~q ~q U) ~q U~ V~ ~q V~ ~q U~ ~q U) V~ V~ ~q ~q ~q U~ q V~ V~ V~ V~ q U~ V~ V~
H ~ ~ td U~ V~ q U~ tq ~q U~ ~q U~ ~q 11~ q ~q U~ ~q ~q 0~ ~q U~ ~q U~ ~q Lq ~q V~ ~q V~ V~

D ~ h h h ~ h ~ ~ ~ h ~ h )~

~ u a) u ~ a a~ a ~ c c a~ ~ a) u a) u ~ a~ a~ a~ a) a) ~ a) a) a CCCCCCCCCCC~ ~:CC~CC~C C~C~C~.CCCCCC
o ~o ~ o ~ ~ ~ ~ o ~ ~ ~o o o ~ ~ o ~ ~ o ~ ~ ~o ID
n o~
O U~ N N
H ~ O --1 ~1 ~1 a) ~ ~ O N ~ ~') ~i S-l .' ~ ~ ~ ~ ~ ~
~ :~ '' ~

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o,~ , ooo ~ u u ~ ~
` ~ ~ ~o ~' v ~
~ ~ ~ ~q ~q ~ ~
~o~ ~ 0 : ~ o . ~ ~ ~ ~ ~ rl u ~
O ;~ r -t ~ O O OJ ~ ~ C C
C ~ ~ d ~ 0 11~ 'O a) - H l ~d 0~ I ~ O
1--/ H ~1 ~rl ~ 0 1~ r~l ~) ~1 . . . H 0~ ~ cd U~ o~ 0 ~ ~) , p ~d 3 G3 ~; r l r-~ ri ~ ~rl ~rl h g ~ C.) U ~ a) 3 3 E-l ~ ~ . 1~ h S-l a 3 3 $
a~ a) a) ,'' ~ o~
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From Table II it can be seen that good fluid loss reduction is obtained using the additives of this invention at temperatures of from 100F to 360F. Further, it can be seen that additives including hydroxycarboxy acids are more effective in salt water cement slurries containing salt con-centrations above about 18% by weight o~ water than those con-taining CMHEC alone.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-

1. A water loss reducing additive for use in salt water cement slurries containing high concentrations of aqueous solu-tions of salts in amounts above about 18% by weight of water present comprising carboxymethylhydroxyethylcellulose having a carboxymethyl D.S. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8 and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78°F has a vis-cosity in the range of from about 10 to about 225 centipoises measured on a FANN viscometer at 300 rpm using a No. 1 spring and a hydroxycarboxy acid selected from the group consisting of gluconic acid, tartaric acid, lactic acid, citric acid, malic acid and mixtures of such acids.

2. The additive of claim 1 wherein said carboxymethyl-hydroxyethylcellulose has a carboxymethyl D.S. of about 0.4, an ethylene oxide M.S. of about 2.0 and a molecular weight such that said viscosity is in the range of from about 10 to about 200 centipoises.

3. A water loss reducing additive for use in salt water cement slurries containing high concentrations of aqueous solutions of salts in amounts above about 18% by weight of water present comprising carboxymethylhydroxyethylcellulose having a carboxymethyl D.S. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8 and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78°F has a viscosity in the range of from about 10 to about 225 centi-poises measured on a FANN viscometer at 300 rpm using a No. 1 spring, and a hydroxycarboxy acid selected from the group consisting of gluconic acid, tartaric acid, lactic acid, citric acid, malic acid and mixtures of such acids, said acid being present in said additive in an amount of about 50% of the weight of carboxymethylhydroxyethylcellulose in the addi-tive.

4. The additive of claim 3 wherein said carboxymethyl-hydroxyethylcellulose has a carboxymethyl D.S. of about 0.4, an ethylene oxide M.S. of about 2.0 and a molecular weight such that said viscosity is in the range of from about 10 to about 225 centipoises, and said hydroxycarboxy acid is citric acid.

5. The cement slurry of claim 3 wherein said carboxy-methylhydroxyethylcellulose is present in said cement slurry in an amount in the range of from about 0.2% to about 2.0%
by weight of dry cement in the slurry.

6. The cement slurry of claim 5 wherein said hydroxy-carboxy acid is present in said slurry in an amount in the range of from about 0.1% to about 1.0% by weight of dry cement in said slurry.

7. A method of reducing the water loss from a salt water cement slurry containing high concentrations of aqueous solu-tions of salt in amounts above about 18% by weight of water present used in cementing a well comprising combining a water loss reducing additive with said salt water cement slurry prior to using said slurry, said additive being comprised of carboxy-methylhydroxyethylcellulose having a carboxymethyl D.S. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8 and a molecular weight such that a 1% by weight aqueous solution thereof at a temp-erature of 78°F has a viscosity in the range of from about 10 to about 225 centipoises measured on a FANN viscometer at 300 rpm using a No. l spring and a hydroxycarboxy acid select-ed from the group consisting of gluconic acid, tartaric acid, lactic acid, citric acid, malic acid, and mixtures of such acids.

8. The method of claim 7 wherein said carboxymethylhy-droxyethylcellulose has a carboxymethyl D.S. of about 0.4, an ethylene oxide M.S. of about 2.0 and a molecular weight such that said viscosity is in the range of from about 10 to about 200 centipoises.

9. The method of claim 8 wherein said hydroxycarboxy acid is combined with said slurry in an amount of about 50%
of the weight of carboxymethylhydroxyethylcellulose combined with said slurry.

10. A method of reducing the water loss from a salt water cement slurry containing high concentrations of aqueous solu-tions of salts in amounts above about 18% by weight of water present used in cementing a well comprising combining a water loss reducing additive with said salt water cement slurry prior to using said slurry, said additive being comprised of carboxy-methylhydroxyethylcellulose having a carboxymethyl D.S. in the range of from about 0.1 to about 0.7, an ethylene oxide M.S. in the range of from about 0.6 to about 2.8, and a molecular weight such that a 1% by weight aqueous solution thereof at a temperature of 78°F has a viscosity in the range of from about 10 to about 225 centipoises measured on a FANN viscometer at 300 rpm using a No. 1 spring, said carboxymethylhydroxyethyl-cellulose being combined with said slurry in an amount in the range of from about 0.2% to about 2.0% by weight of dry cement in said slurry, and a hydroxycarboxy acid selected from the group consisting of gluconic acid, tartaric acid, lactic acid, citric acid, malic acid, and mixtures of such acids, said acids being combined with said slurry in an amount in the range of from about 0.1% to about 1.0% by weight of dry cement in said slurry.

11. The method of claim 10 wherein said carboxymethylhy-droxyethylcellulose has a carboxymethyl D.S. of about 0.4, an ethylene oxide M.S. of about 2.0 and a molecular weight such that said viscosity is in the range of from about 10 to about 200 centipoises and said hydroxycarboxy acid is citric acid.