Well cementing

Wells and like borings into the earth's surface, especially those for the production of petroleum and gas, are very well and efficaciously cemented with cement compositions or pastes containing, as their effective gel control and cement set retardation agent, an additive that is a resulfonated, alkaline oxidized, hydrolyzed, partially desulfonated lignosulfonate product.

GENERAL BACKGROUND OF THE INVENTION 
The increased number of deep wells being drilled and the encounterments, 
during drilling, of abnormally high temperature gradients has led to the 
development of cement retarders to be used to help extend the pumpability 
of manufactured cements currently available. It is extremely desirable in 
such connection to have longer thickening times in the cementing 
compositions employed when they are used under high temperature 
conditions. These demands, oftentimes, cannot be met with presently 
available (including commercial) retarded cements (such as API Classes D 
and E). 
At the present time, very few cementing compositions are used to cement 
wells below 12,000 feet where static temperatures are in excess of 
260.degree. F., unless additional retarder is utilized. Observation of 
cementing compositions currently used in wells 10,000 feet and deeper 
indicates that a larger number of the compositions employed contain 
additives to modify the properties of the basic cement. These additives, 
in addition to retarders, can frequently be light-weight clay and 
equivalent mineral materials (such as bentonite, Diacel D, etc.) silica 
flour, heavy-weight materials (such as Hi-Dense No. 2, barite, etc.) or 
any of the many other materials and component additives available for 
altering the properties of the cement composition used. 
The selection of a retarder that will be compatible with the manufactured 
retarded cements, which in themselves usually contain a retarder, 
sometimes becomes a difficult task. Compounds such as lignins (salts of 
lignosulfonic acid), gums, starches, various weak (oftentimes organic) 
acids, and cellulose derivatives have been used in the manufacture of 
commercial retarded cements. One of the first retarders developed in the 
trade was a blend of borax, boric acid and gum arabic. Due to blending 
problems, this retarder was exceedingly difficult to handle at bulk cement 
plants. Nonetheless, much actual use has been had of such retarders for 
commercial retarded cements prior to the time that ameliorated retarders 
were developed. 
The primary factor and influence that governs the use of additional 
retarder is the temperature of the well. As the temperature increases, the 
chemical reaction between the cement and water is accelerated. This, in 
turn, reduces the thickening time or pumpability of the cement composition 
or paste. The use of additives with high water ratios also necessitates 
the use of additional retarder to obtain the desired thickening time. This 
can be due to one or both of the following fundamental factors, namely: 
(1) high surface materials, which generally have high water requirements, 
which adsorb part of the retarder leaving less to affect the retardation 
of the cement; and (2) additional water which further dilutes the 
concentration of retarder and thereby reduces its retarding potential. 
Most currently available retarders can be used with the basic cementing 
compositions containing API Class A, D, or E cements, Pozmix-Cement and 
Pozmix 140 blended with various additives. Appropriate test data available 
in the art coupled with developed laboratory observations can indicate the 
performance of cementing compositions and the like with and without 
retarder when used to depths of 12,000 feet or where static temperatures 
are in the range of 260.degree. to 275.degree. F. Where bottom hole 
conditions exceed these values, it is normally recommendable that 
thickening time tests be made, in the laboratory, on the specific 
component parts of the slurry (or paste) prior to the actual cementing 
job. Variations in thickening times are not due solely to down hole 
conditions of temperature and pressure. They frequently, pragmatically 
speaking, may be the result of irregularities in the basic cement. 
Further quite pertinent art and direction in the area of well cementing and 
the like practices includes the Report Prepared By The API MID-CONTINENT 
DISTRICT STUDY COMMITTEE ON CEMENTING PRACTICES AND TESTING OF OIL-WELL 
CEMENTS issued by AMERICAN PETROLEUM INSTITUTE (i.e., "API"), Division of 
Production, in Dallas, Texas 75201 as API Bulletin D-4, Corrected Edition 
of March 1963, entitled "The Effects Of Drilling-Mud Additives On Oil-Well 
Cements"; "API Specification For Oil-Well Cements And Cement Additives" 
(API Std 10A, Fourteenth Edition, dated April, 1969); and "API Recommended 
Practice For Testing Oil-Well Cements And Cement Additives" (API RP 10B, 
Sixteenth Edition, dated April, 1969). 
TICULARIZED BACKGROUND OF THE INVENTION 
Various and numerous sulfonated and otherwise derived lignin materials have 
already been found, known and developed and advantageously applied in well 
cement compositions as retarding agents therefor. U.S. Pat. No. 2,880,102 
is specifically illustrative of this. Considered generically, these 
lignosulfonate materials even include the alkaline oxidized, partially 
desulfonated lignosulfonates of the type prepared according to the 
teachings disclosures of U.S. Pat. No. 2,491,832 which are prepared from 
treatments of alkaline sulfite waste pulping liquor from wood conversion. 
While numerous references are available dealing in one capacity or 
discipline or another with the identity and nature of lignin, per se, and 
many of the derivatives of lignin including lignosulfonates (all of which, 
by the way, are generally relatively imprecise and not positively 
definite), preparation and multitudinous uses of the contemplated 
materials, substantial elucidation thereupon and thereof may also be 
found, by way of illustration, in U.S. Pat. Nos. 1,848,292; 2,371,136; 
2,371,137; 2,505,304; 2,576,418; 2,598,311; 2,800,449; 3,156,520; and 
3,726,850. Still additional art of interest is uncovered in U.S. Pat. Nos. 
Re. 18,268; 2,057,117; 2,104,701; 2,399,607; and 2,434,626. 
Another excellent informational source in this area is the Bulletin (No. 
131) published by AMERICAN CAN COMPANY of Greenwich, Connecticut 06830 
(U.S.A.) entitled "Chemicals From Wood". 
The alkaline oxidized, hydrolyzed, partially desulfonated lignosulfonates 
which are utilized as the starting materials to obtain the retardant 
resulfonated lignosulfonate additives used in and for well cementing 
compositions, and so forth, in practice of the present invention are, as 
indicated, usually most readily and conveniently obtained pursuant to the 
teachings of U.S. Pat. No. 2,491,832. In this patented process, especially 
if and when enhanced by-product yields of vanillin are wanted, it is 
frequently more desirable to employ a waste pulping liquor for the process 
which is derived from a totally, or at least substantially, softwood 
source -- although this is not an entirely restrictive limitation since 
hardwood starting materials may also be used. 
Using the process patented in U.S. Pat. No. 2,491,832, the degree of 
desulfonation realized is a factor of and controlled by the amount of 
caustic interjected for the reaction; the strength of the oxidation 
effected (i.e., the relative amount of air or oxygen employed -- being 
careful to avoid such severe oxidation conditions as might induce 
demethylation); the reaction time and temperature schedules followed, and 
the solids dilution, generally aqueous, of the lignosulfonate containing 
spent sulfite liquor effluent being treated (with greater dilution 
conditions tending to lead to more extensive desulfonation probably due to 
the thereby increased availability of the reacting molecules to the 
oxidizing influence applied). 
While very desirable partially desulfonated lignosulfonate materials are 
prepared with the alkaline oxidation conducted on a spent sulfite liquor 
containing, on a weight percent basis, from about 30 to 35% of dissolved 
solids, the spent liquors being cooked in the desulfonation process may 
have as little as 14-10% to as much as 40% solids content in order to 
obtain beneficial desulfonated products. 
Practically, almost any caustic alkaline solution can be employed for 
effecting the partial desulfonation reaction, although lower alkalinity 
generally results in less desulfonation. More caustic is required when 
sugars and other saccharides are present (and they are usually present 
with otherwise untreated spent sulfite liquors) in any varied or more 
substantial amounts in order to effect the decomposition of such 
saccharides. Ordinarily, very good results are achieved when sufficient 
caustic concentration is maintained throughout the desulfonating cook to 
maintain the reaction mass in the relatively high pH range of between 
about 10.5 and about 11 . For example, a quite satisfactory proportion of 
lignosulfonate solids to caustic to employ in the reaction mass involves 
use of an aqueous lignosulfonate solution of about 31-32 wt. % and having 
a specific gravity around 1.22-1.24 or so containing a caustic 
concentration in the solution of about 140 gms. NaOH/liter. 
Adequate oxidation conditions to achieve desired ranges of desulfonation of 
the lignosulfonate in the spent sulfite liquor may be achieved by 
providing, almost invariably from either air or oxygen passed through the 
cooking reaction mass, between about 20-25 or so and about 40-50 or so 
grams of elemental oxygen (i.e., O.sub.2) per each 100 grams of lignin in 
the lignosulfonate material being desulfonated. In actual practice to 
obtain a frequently more desirable range of partially desulfonated 
material, between about 27 and 35 grams of O.sub.2 per gram of lignin are 
utilized. 
While variations may be encountered, temperatures on the range of from 
about 140.degree. C. to about 170.degree. C., advantageously in the 
neighborhood of 165.degree. C., are usually most desirable to utilize. Of 
course, the reacting mass is cooked until the desired degree of 
desulfonation (or, when vanillin by-product is important, the desired 
yield of it) is obtained. Usually and at the 165.degree. C. level the 
cooking time is on the order of 45 minutes or so; the optimum time to 
employ, as will be appreciated by those skilled in the art, depending on 
reaction conditions and the particular degree of desulfonation desired in 
the resulting partially desulfonated lignosulfonate material. It is 
oftentimes most advantageous (if not literally necessary for material 
handling purposes) to terminate the cooking while some free caustic still 
remains in the reaction mass. This tends to prevent problems of 
emulsification during subsequent recovery of the partially desulfonated 
lignosulfonate. Beneficially and for the indicated purpose, the reaction 
may accordingly be finished when, say, about 4-5 gms./liter of free NaOH 
is found to remain in the reaction mass. 
Practice of the process of U.S. Pat. No. 2,491,832 yields, in effect, a 
spent oxidized liquor which, as has been disclosed and as is known, 
contains partially desulfonated, generally acid-insoluble, chemically 
altered organic lignin substances. These are usually isolated and/or 
fractionated by acid (namely, sulfuric) precipitation which eliminates 
various sludge-producing, mostly calcium-based, ingredients therein. After 
the precipation, the purified partially desulfonated lignosulfonate 
material is generally dissolved in caustic to yield a sodium salt; then 
spray or otherwise dried to yield a powder product -- although, if 
desired, it may be finally prepared and used in an undried liquified form 
or reconstituted to an aqueous liquid of any desired concentration. 
The partially desulfonated lignosulfonate material thus obtained is not 
directly procurable from original spent sulfite liquors as are the 
normally-gotten and ordinarily so-called, albeit undesulfonated, 
"lignosulfonates"(the "water soluble"calcium or equivalent lignosulfonate 
salt or lignosulfonic acid described in U.S. Pat. No. 2,880,102 being 
typical of same). To the contrary, the partially desulfonated 
lignosulfonate additive products of reference are exceptionally pure 
materials containing essentially no sugars or polysaccharides and having 
only vanishing traces, if any, of combined sulfur in sulfite form; and 
further having other inherent distinguishing features including relatively 
uniform and substantially constant relative molecular size 
characteristics. 
Although a sugar and saccharide-containing spend sulfite liquor is 
desirable to employ as the starting material for preparation of partially 
desulfonated lignosulfonates from which is resulfonated compositions used 
as cement retardants in the present invention are derived, otherwise 
treated spent sulfite liquors may equivalently be utilized. These, for 
example, may be those which have previously been treated in divergent ways 
and for other initial conversion purposes wherein the sugars and/or 
saccharides are utilized and consumed, as in the preliminary manufacture 
from raw spent sulfite liquor of yeast or alcohol or in other ways giving 
a sugar and/or saccharide --reduced or --free spent sulfite liquor. 
The alkaline oxidized, partially desulfonated lignosulfonates which are 
anionic polyelectrolytes with a relative molecular size usually on the 
order of 1,000 to 20,000 and from which the resulfonated products employed 
as cement retardants pursuant to instant practice are obtained generally 
have an organic sulfonic sulfur, i.e., --SO.sub.3, content, calculated as 
percent sulfur by weight of broadly between about 1/2and about 5 wt. %. 
More advantageously for many purposes, this sulfur range is between about 
13/4and about 31/4wt. %; while quite often it is preferable for the 
partially desulfonated lignosulfonate to contain from about 2.2 to about 
2.8 wt. % of the combined sulfur in the sulfonic form. 
A commerically available product, "MARASPERSE CB"(TM), obtainable from 
AMERICAN CAN COMPANY, is an example of an alkaline oxidized, hyrdolyzed, 
partially desulfonated lignosulfonate material useful as the starting 
material from which to derive the solubilized, re-sulfonated 
lignosulfonates cement retarding additives of the present invention. 
"MARASPERSE CB", as usually available, generally has the following typical 
analysis parameters and physical characteristics features: 
Typical analyses (moisture-Free and Wt. % Basis): 
______________________________________ 
pH - 3% Solution 8.5-9.2 
Total Sulfur as S, % 2.5-2.9 
Sulfate Sulfur as S, % 
0.1-0.25 
Sulfite Sulfur as S, % 
0-0.05 
CaO, % 0.02-0.05 
MgO, % Trace-0.03 
Na.sub.2 O, % 9.4-9.9 
Reducing sugars, % 0 
OCH.sub.3, % 12.4-12.9 
Sodium Lignosulfonate, % 
99-99.6 
Solids, % 92-94 
______________________________________ 
Ultraviolet analyses (k-value representing base line): 
______________________________________ 
Upper UV: 
K Solids at Max. (275 mu) 
29-30.5 
K OCH.sub.3 at Max. 225-250 
Differential UV: 
Max. nm 250-252 
K Solids at Max. 10-11.3 
K OCH.sub.3 at Max. 82-88 
Baseline K Solids 9.5-10.5 
Phenolic OH, % 1.8-2.1 
OH/OCH.sub.3 0.26-0.30 
______________________________________ 
Physical characteristics: 
______________________________________ 
usual Form Powder 
Moisture Content (Max., % H.sub.2 O) 
8.0 
Color Black 
Bulk Density (lbs./cu. ft.) 
43-47 
Solubility in Water (%) 100 
Solubility in Oils and 
Most Organic Solvents (%) 
0 
Surface Tension, 1% Sol'n 
(in dynes/cm) ca. 51.4 
______________________________________ 
While the known alkaline oxidized, hydrolyzed, partially desulfonated 
lignosulfonates, including such things as "MARASPERSE CB", are excellent 
surfactant, dispersant, detergent and otherwise attractively-propertied 
materials which are very good as cement retarding additives under many 
circumstances, they still have certain intrinsic inadequacies and 
limitations leaving some desiderata and unfulfilled capability for use in 
many crucial well cementing applications and for expanded applicability in 
and for this highly advantageous purpose. Noteworthy amongst these are 
difficulties in the employment of the mentioned partial desulfonated 
lignosulfonates are their relatively limited solubility in saline 
solutions plus their sometimes not totally satisfactory reliability and 
predictability as to set retarding and gel control, especially time-wise, 
of well cement compositions and pastes in which they are incorporated. 
FIELD AND OBJECTIVES OF THE INVENTION 
This invention pertains to and resides in the general field of well 
cementing in the area of new and improved cementing and the like 
compositions and their method of preparation; more particularly as to a 
greatly effective highly saline salt solution tolerant and predictable gel 
control and retardant additive agent for exceptionally beneficial and 
useful well cementing operations. The agent involved in the well cementing 
compositions and preparation thereof in practice of the present invention 
is an exceptionally pure lignosulfonate derivative of the type disclosed 
in the copending, concurrently filed Application for United States Patent 
of the present Applicants entitled "SOLUBILIZED RESULFONATED 
LIGNOSULFONATES" Having Ser. No. 671,397 filed Mar. 29, 1976. Provision of 
the vastly improved well cementing compositions and techniques (including 
preparation thereof) in and for many of a very wide gambit of well 
cementing and the like purposes as well as many other of the salient 
propensities and capabilities and satisfactory characteristics of 
presently-contemplated practice is amongst the principal aims and 
objectives of the invention.

TICULARIZED DESCRIPTION OF THE INVENTION 
Conventional oil well cements and the like comprised of hydraulic cement, 
sometimes and optionally colloidal clay or equivalent, and various 
additaments in small proportions are known. They are generally supplied as 
premixes to be slurried at the well site with water for intended usage in 
the well. 
The well cementing compositions of this invention are, basically, a 
hydraulic cement preparation (which, as may be desired, can also be 
comprised of clays and the like and/or other functional additaments) 
containing as a gel control and retardation additive agent a resulfonated 
derivative of the above-described and identified alkaline oxidized, 
hydrolyzed, partially desulfonated lignosulfonates. Besides their unique 
chemical constitution, the additive agents employed are characterized in 
having (as compared to most other so-called lignosulfonates) an evened-out 
and/or very similarly dimensioned relative molecular size range within a 
10-20% size measure from any given constant (particularly in volumetric 
comparison with the molecular size of 2-napthalene sulfonic acid); a 
solubility -- especially as regards saline solution tolerance or 
compatibility and/or in aqueous acidic media at least 10 percent and 
usually 2 or 3 times greater than that of the partially desulfonated 
lignosulfonate starting material from which the resulfonated additives 
used in the present invention are derived; and a substantially increased, 
i.e., at least 50 percent and up to 15-20 times surfactant and dispersant 
activity. 
The resulfonated additive materials for the well cements are readily 
obtained by the direct sulfonation or sulfoalkylation of the referenced 
alkaline oxidized, hydrolyzed, partially desulfonated lignosulfonate 
starting material. Ordinarily and most conveniently, this is done with 
appropriate sulfonating reagents in an aqueous solution of the starting 
material, advantageously using agitation during the reaction (which is 
better when applied vigorously and may be either by mechanical mixing or 
stirring and/or from the agitating effects of steam being pressed into the 
reaction mass when steam is used for heating), at any desired suitable 
temperature. In general, the reaction can be conducted over a temperature 
range from about 50.degree. C. to about 200.degree. C., although it is 
ordinarily desirable to run at least at the boil (i.e., about 100.degree. 
C. or so) in order to avoid unduly long reaction times. Ordinarily, a 
temperature on the order of 160.degree. C. is satisfactory for most of the 
resulfonations done. Of course, the reaction is accomplished under 
corresponding pressure when temperatures over boiling are utilized. The 
time of reaction generally varies with the temperature involved; lower 
temperatures requiring longer times. At higher temperatures the 
resulfonations can be completed in as little as 1/2 hour or so while 
temperatures at the lower end of the scale may require as much as 16 or 
more hours for completion. When conducted at about 160.degree. C., the 
resulfonation cooking is usually completed within about an hour. 
Any suitable sulfonation reagents may be used for the resulfonation 
reaction. When straight sulfonations are desired, they may be 
advantageously accomplished with an alkali metal (such as sodium) 
bisulfite or sulfur dioxide. Sulfoalkylations, as are frequently quite 
desirable, are done with mixtures of an appropriate lower alkyl aldehyde 
and a bisulfite. The sulfonate group, per se, that is attached in straight 
sulfonation is, of course, --SO.sub.3 H. The sulfoalkylates, which 
ordinarily involve 1 to 3 carbon atom alkyl units, are of the structure 
--(CH.sub.2).sub.x --SO.sub.3 H, wherein x is usually an integer from 1-3 
and when x is plural the alkyl unit may be linear in attachment or, as is 
probably the more frequent case, comprised of side-chain arrangements. 
The aldehyde utilized in at least approximative stoichiometric proportions 
with the bisulfite in the sulfoalkylations performed for the resulfonation 
is generally of the structure: RCH:O, wherein R is hydrogen or an alkyl 
group containing from 1 to 3 carbon atoms. Obviously, if desired, mixed 
aldehyde reaction systems may be utilized even though there is ordinarily 
no particular advantage in this. Usually, it is very desirable to 
accomplish the resulfonation with a sulfomethylating reaction using 
formaldehyde (CH.sub.2 O) and sodium bisulfite (NaHSO.sub.3) as reagents 
so as to make sulfomethyl (--CH.sub.2 SO.sub.3 H) attachments in the 
resulfonated product. 
As indicated, about stoichiometric relative proportions of the aldehyde and 
bisulfite reagents are employed for the resulfonation; these being used in 
amounts calculated to effect the desired extent or quantity of sulfonic 
acid units in the finally obtained resulfonated product. Actually, a plus 
or minus 20% tolerance from exactly stoichiometric ratios is tolerable. In 
sulfomethylating reactions, the amount of formaldehyde used may vary from 
about 11/2 to about 12 wt. % of the desulfonated starting material being 
resulfonated while the bisulfite can correspondingly be utilized in 
quantities, on the same basis, of between about 5 and about 40 wt.%. A 
particularly desirable resulfomethylated product containing about 51/2 wt. 
% of sulfur in organic sulfonic sulfonate form is obtained by the reaction 
in the described manner of "MARASPERSE CB" with about 15 wt. % of sodium 
bisulfite and 41/2 weight % of formaldehyde, based on "MARASPERSE CB" 
weight, cooked for one hour at 160.degree. C. 
The resulfonated products used as additives for well cementing compositions 
in practice of the present invention may, as desired, contain anywhere 
from about 11/2 wt. % to 14-15 wt. % of total sulfur in combined organic 
sulfonic sulfonate form. Advantageously the range of such sulfur is 
between about 23/4 and about 10 wt. %, with greater desirability 
oftentimes attained in the sulfur wt. % range of from about 41/2 to about 
61/2 wt. %. 
While it is not intended to be bound by any particular theory, it is 
believed that the starting alkaline oxidized, hydrolyzed partially 
desulfonated lignosulfonate material (as obtained when following the 
procedures of U.S. Pat. No. 2,491,832) has the sulfonic acid group 
attachments at least substantially if not predominantly or entirely on the 
side chains of and in the lignin molecules, this ordinarily being on the 
side chain carbons which are in the alpha position relative to the ring 
and carrying over from the initial substitutions made during the original 
sulfite pulping operations. On the other hand and surprising at it is, it 
is believed the sulfonate and/or sulfoalkyl units prepared in practice of 
the present invention are substantially if not predominantly or entirely 
positioned in ortho and/or para substitutions on the aromatic rings of the 
lignin molecules. Thus, the resulfonated product used in practice of the 
instant invention as a well cement additive is, quite obviously, a 
basically different and dissimilar lignosulfonate from and as compared to 
the lignosulfonate material found in spent sulfite liquors from which are 
obtained the starting lignosulfonates that are resulfonated in present 
practice. 
A typical resulfonation reaction for manufacture of the additives pursuant 
to the present invention may be figuratively represented by the following, 
presumed-to-be-accurate chemical reaction formulae: 
##STR1## 
The resulfonated, alkaline oxidized, hydrolyzed partially desulfonated well 
cement (or cementing paste) additives of the present invention are 
generally employed in amounts, based on total resulting composition 
weight, between about 0.05 and about 3 wt. %. More often, the additive 
concentration employed is from about 0.2 to about 1.5 wt. % while 
frequently the most desirable range is from, say, 0.3 to 1 wt. %. 
The particular quantity of additive employed generally depends in very 
large measure on the cement setting schedule (according to API criteria) 
being followed and the temperature encountered during actual setting of 
the cement composition. Usually, relatively more of the retarder additive 
is required when higher setting temperatures conditions are encountered. 
The additive resulfonated desulfonated lignosulfonates utilized in practice 
in accordance with the present invention are characterized in imparting to 
the cement compositions in which they are incorporated an excellent 
tolerance and resistance against premature settings and gellations under 
exposure to severely strong saline environments such as are frequently 
found in many wells due to the presence therein by infiltration or seepage 
of natural salt (including sea) waters. They also tend to ensure an 
uncommon and unusual accurate predictability as to cement setting 
character, speaking time-wise, in the compositions under any given setting 
temperature and schedule; this being of obviously considerable advantage 
and importance for the most effective and beneficial application and 
efficient utilization of a well cementing composition or paste. 
The compositions of the present invention are, and very desirably so, 
essentially gellation-free admixtures. In this, they avoid the frequent 
problem of gellation experienced with many cement retarder additives that 
are known and have been used in well cementing operations. As is readily 
appreciated by those skilled in the art, this is a very important factor 
especially for purposes of laboratory and other than actual usage test and 
evaluation procedures. Very beneficially in this regard, the compositions 
of the present invention invariably do not exhibit or cause with premature 
gellation any consequent and so-called pseudo false settings. 
EXEMPLIFICATION OF THE INVENTION 
The following detailed Illustrations more particularly delineate and show 
the extraordinary benefits and advantages obtained in and by practice of 
the present invention and with the exceptionally useful and versatile 
resulfonated lignosulfonate composition products involved for well cement 
additive utilizations. 
FIRST ILLUSTRATION 
Excellent quality resulfonated additives, containing about 5.5 wt. % of 
organic sulfonic sulfur (based on composition weight) are made in large 
scale preparations by the sulfomethylation of "MARASPERSE CB" containing 
about 2.6 wt. % of total sulfur measured as S according to the following 
general procedure (in which all percentages are on a weight basis): 
A. synopsis of Procedure: 
The "MARASPERSE CB" liquor is sulfomethylated by cooking one hour at 
160.degree. C. with 15% NaHSO.sub.3 and 4.5% CH.sub.2 O. 
______________________________________ 
Molecular Weights Of Particular Reagents Involved: 
______________________________________ 
Formaldehyde 
CH.sub.2 O 30 
Sodium Bisulfite 
NaHSO.sub.3 104 
______________________________________ 
__________________________________________________________________________ 
(B). Bill of Materials: 
Basis: 
Per 100 lbs. 
Basis: Approximate 6000-gallon Batch 
Finished 
Gallons 
Product In 
(U.S. 
Pounds 
Solids, 
Pounds 
lbs. Solids 
Measure) 
Liquid 
lbs./gal. 
Solids 
__________________________________________________________________________ 
"MARASPERSE CB" 
Liquor 85.50 5,400 
52,800 
3.71 20,000 
Formaldehyde 
3.85 270 2,450 
3.33 900 
Sodium Bisulfite 
12.80 3,000 3,000 
Total 102.15 58,250 23,900 
Finished Additive 
Product 100 23,400 
__________________________________________________________________________ 
C. procedure in Detail: 
I. Makeup - 
1. Pump "MARASPERSE CB" liquor to process tank (about 5500 gallons); 
2. Measure the volume in the tank; 
3. Take a pint sample; 
4. Check temperature and specific gravity of the liquor; 
5. Determine the pounds per gallon of liquor solids from the gravity 
reading; 
6. Agitate and steam the liquor to about 80.degree. C.; then 
7. Add 4.5% formaldehyde based on the "MARASPERSE CB" liquor solids (A 
490-lb. drum of formaldehyde at 37% solids containing 180 lbs. 
formaldehyde); 
8. Slowly and with good agitation, add 15% sodium bisulfite based on 
"MARASPERSE CB" liquor solids (taking into account that if this is added 
too fast, it will not mix in); then 
9. After the bisulfite is completely mixed in, continue agitation for 15 
minutes. 
II. Reaction 
1. Transfer about 1850 gallons of liquor to a feed tank for the high 
temperature, pressure reaction vessel while maintaining the temperature at 
about 80.degree. C.; 
2. dump the liquor from the feed tank to a stirred, autoclave-type, 
pressure, reactor; 
3. Steam to 160.degree. C.; 
4. cook one hour at 160.degree. C.; 
5. blow the cook slowly to avoid foaming; 
D. process Variables: 
The "MARASPERSE CB" liquor should have a gravity of 1.16 to 1.18 at room 
temperature, (3.5 to 3.9 lbs. solids/gallon) with maximum soluble lime 
less than about 0.1% CaO. The addition of the bisulfite to the liquor is 
critical. This must be done very slowly to avoid forming a crust on the 
surface, which is very difficult to break up. 
Following the preparation, the products are readily obtained in solid 
(usually powdered) alkali metal (i.e., generally sodium) salt form by 
spray or other drying procedures. 
The resulfonated lignosulfonate products obtained from the above-specified 
preparation procedure have outstanding qualities and characteristics as 
well cement retarders in all of the particulars specified in the foregoing 
"TICULARIZED DESCRIPTION OF THE INVENTION". The additives are: soluble 
in synthetic and natural (such as North Sea water) salt solutions; 
dissolvable with ease in acid media as low as pH 1.5 or so; markedly 
surfactant; and have a very close molecular size range constancy of easily 
less than a 20% measure (and usually closer to 10% and frequently much 
less in this) when collated to a given standard size of molecule such as 
2-napthalene sulfonic acid (i.e., "2-NSA") as indicatable by diffusion 
tests through micro-size porous filter media consisted of cellulose type 
cell membranes, or filters, having average pore sizes of 0.4 microns. 
The graph presented in FIG. 1 of the accompanying Drawing nicely 
demonstrates as a typical representation the very close relative molecular 
size constancy of the resulfonated lignosulfonate retarder additives 
utilized in practice of the present invention as compared to conventional 
and heretofore-known "lignosulfonate" products. As is apparent therein, 
the resulfonated desulfonated lignosulfonate additives for use in the 
present invention have (in contradistinction with normal and ordinarily 
obtained "lignosulfonates") the described relatively narrow relative 
molecular size average particulars. 
This constancy is evidenced by way of illustration in FIG. 1 with respect 
to several resulfonated desulfonated lignosulfonates coming within the 
practice of the invention; illustratively, those having a relative 
molecular size when measured by comparison with 2-naphthalene sulfonic 
acid of 2900, about 3500, and 4200. As will be evident from the drawing, 
this relative molecular size is sustained during the entire period 
provided for complete filter passage by diffusion. Conventional 
lignosulfonates, on the other hand have a relative molecular size which 
extends during the diffusion period from about 1000 to in excess of 
100,000. 
The resulfonated products obtained by the foregoing Procedure are all found 
to be extremely useful and effective retarding agents to precisely control 
and regulate the setting under high temperature and pressure conditions 
even in highly saline aqueous environments. 
Similar very good results, using appropriate reagents for the purpose, are 
realized when the resulfonated products and made by direct 
non-alkyl-group-containing sulfonations as well as for sulfoethylations, 
sulfopropylations and so forth. 
SECOND ILLUSTRATION 
Using resulfomethylated products prepared according to the First 
Illustration, a number of salt tolerance tests in extremely high 
concentration synthetic aqueous saline solution are performed. In each, 
the salt solution is made up in water to a total volume of 1 liter and is 
composed, in the water, of 50 gms. of sodium chloride (NaCl), 16.5 gms. of 
calcium chloride (CaCl.sub.2) and 15.5 gms. of magnesium chloride 
(MgCl.sub.2). About 0.50 gms. of the lignofulfonate additive material 
being tested is put into 2 fluid ounces (about 60 ml) of the solution. 
Another 50 ml. of the salt solution is then added to the mixture and the 
entire make-up manually shaken briefly to effect whatever preliminary 
dissolution can be achieved; after which it is put on a mechanical shaker 
for one hour to ensure as much solubilization as possible. Subsequent to 
that, a 10 ml. portion of the overall mixture is placed into a graduated 
container tube from a standard laboratory-type DeLaval Centrifuge and 
centrifuged for 5 minutes thereon at 20,000 RPM. The volume percent of 
sludge found after the centrifugation (based on original volume of 
centrifuged material) is then measured. In all cases, the resulfonated 
products of the First Illustration have never more than 2.0 and usually 
(at least about 9 out of 10 times) less than 1.6 volume percent of removed 
sludge after the centrifugation. In contrast and by application of the 
same saline solubility test, the general type of "MARASPERSE CB" starting 
material utilized in the First Illustration has about a 6 volume percent 
sludge level after the centrifugation analyses. 
Analogous results are obtained when the same saline solubility tests are 
repeated excepting to utilize, as the aqueous saline media; (i) 200 
grams/liter NaCl solution; and/or "North Sea" water comprised, per liter, 
of 30.0 gms. NaCl, 1.16 gms. CaCl.sub.2 and 5.54 gms. MgCl.sub.2 (giving a 
total dissolved content of 36.70 gms./liter of such salts). 
THIRD ILLUSTRATION 
A desulfonated lignosulfonate from the vanillin process containing 0.7 wt. 
% combined sulfur as organic sulfonic sulfonate was attempted, in a 5 gm. 
quantity, to be dissolved in 50 ml. of pH 1.5 sulfuric acid then filtered 
through a fine mesh filter. The attempted solution was very turbid in 
appearance and, after passage through the filter (during which it filtered 
very slowly), left 4.7 gms. of undissolved solids out on the filter paper. 
In contrast, three resulfonated or resulfomethylated products made from the 
same desulfonated starting material were subjected to the same test. 
Sample "X" of the resulfonated or resulfomethylated product contained 1.5 
wt. % combined sulfur, Sample "Y" 2.3% and Sample "Z" 2.0%. The Sample "X" 
solution was slightly turbid and filtered slowly but left only 0.2 gms. of 
undissolved solids on the filter paper. Sample "Y" was a clear brown 
liquid in the strong acid solution but filtered quite rapidly and left no 
residue (i.e., actually 0.0 gms.) on the filter paper which remained clean 
after filtration. Sample "Z" while producing a slightly turbid solution, 
also filtered rapidly and left no measurable residue on the filter paper 
which appeared only very slightly discolored after the filtration. 
FOURTH ILLUSTRATION 
A sample of "MARASPERSE CB" (2.6 wt. % S) and, for comparative purpose, a 
sample of a resulfomethylated derivative thereof made to a 51/2 wt. % S 
content according to the procedure of the First Illustration were tested 
as dispersants for Stellar clay according to the well-known, standard 
ASP-200 Stellar Clay Test using for the measurement a Fann Rotational 
Viscosimeter obtained from the Fann Instrument Company of Houston, Texas. 
Values for yield point, zero gel and Fann 600.degree., 300.degree., 
200.degree., 6.degree. and 3.degree. settings were obtained. The data 
obtained, of course, represents the force required to move a stationary 
clay system through the plug flow to plastic flow condition in a pipe with 
the numerical measurements taken in lbs./100 ft..sup.2 of pipe surface; 
lower readings indicating better dispersant effect by the additive as the 
consequence of requiring less force for the movement of the mixture 
through the apparatus. The results were as follows: 
__________________________________________________________________________ 
Yield 
Fann.degree. Zero 
Product Point 
600 300 200 100 6 3 gel 
__________________________________________________________________________ 
"MARASPERSE CB" 
69 91 80 72 63 39 34 36 
RESULFOMETHYLATED 
DERIVATIVE 16 34 25 22 18 13 13 15 
__________________________________________________________________________ 
The superiority of the additive made for retarder use in accordance with 
the present invention is easily discernible and plainly evident from the 
foregoing. 
FIFTH ILLUSTRATION 
A series which included a composition of a normal (and not resulfonated) 
desulfonated lignosulfonate (as obtained from spent oxidized liquor from 
the vanillin process generally pursuant to the above-identified U.S. Pat. 
No. 2,491,832) and resulfonated (more precisely, resulfomethylated) 
derivatives thereof prepared according to the First Illustration hereof 
were tested for their propensities and capabilities to disperse and 
control the setting retardation times of Type I cement (i.e., similar to 
that prescribed in ASTM C150 Specifications) using The Fann Viscosimeter 
Apparatus (as described in the above Fourth Illustration) to finally 
measure the results. Each of the test sample compositions was made up with 
300 gms. of the Type I cement (obtained from IDEAL CEMENT COMPANY), 25 
gms. of NaCl (giving, in effect, in the final composition about a 15 wt. 
%, based on total composition weight, aqueous salt solution), 3 gms. of 
the lignosulfonate additive and 138 ml. of distilled water. In each case, 
the composition to be tested was preliminarily prepared by adding, in a 
laboratory-style Waring Blender operated at low speed: the lignosulfonate 
dispersant to the water; then the salt; followed by the cement. Shearing 
of each constitution was done for 10 minutes at a 40 volt setting (60 
cycle AC) of the Blender. After the mixing, each sample mix was placed in 
the appropriate testing cup to each of which was added one drop (i.e., 
about 0.1 cc.) of octanol before placing each for testing in the Fann 
Viscosimeter. The results were as set forth in the following tabulation, 
wherein Sample "D" was the starting desulfonated lignosulfonate (obtained, 
as above-described, from a vanillin process) containing 0.66 wt. % of 
organically combined sulfonic sulfonate sulfur; while Samples "A", "B" and 
"C" were resulfomethylated derivatives thereof containing, respectively, 
2.10 - 2.29 - 3.65 wt. %'s of sulfonic sulfur with additional minor 
quantities of non-sulfonic sulfur contained therein (all as determined by 
the method described at pg. 850 of "Analytical Chemistry" in Vol. 32, No. 
7, for June 1960). 
__________________________________________________________________________ 
Sample 
Yield 
Fann.degree. Zero 
Setting Time 
No. Point 
600 300 200 100 6 3 gel 
To Light Gel 
__________________________________________________________________________ 
"A" 102 164 133 120 104 59 48 53 3 hrs. 
"B" 101 159 130 116 101 56 43 53 3 hrs. 
"C" 70 114 92 87 70 49 32 37 4 hrs. 
"D" 112 176 144 128 111 60 50 62 2 hrs. 
__________________________________________________________________________ 
These data very well illustrate the improvement in cement retardation 
achieved with the retarder additives employed in practice of the present 
invention. 
SIXTH ILLUSTRATION 
A resulfonated desulfonated lignosulfonate retarder additive having the 
chemical composition specified in the Fourth Illustration was added to 
five different, popular, known and commercially widely employed cements 
for well paste preparations and each tested for setting time per API 
Schedule 8 using the conventional Pan American Test Apparatus Procedure. 
Analogous compositions were prepared excepting to use as the retarding 
agent additive a well known product often employed for the purpose which 
was a partially purified, sugar-destroyed, calcium-based lignosulfonate 
obtained from AMERICAN CAN COMPANY and identified commercially as 
"MARABOND 21" (TM). 
The comparative results obtained are set forth in the graph of FIG. 2 of 
the accompanying Drawing which clearly and convincingly evidences the 
superior setting time predictability realized in use of the resulfonated 
desulfonated retarder additives of the present invention. These 
compositions, additionally, gave no gellation problems. 
SEVENTH ILLUSTRATION 
Good results are obtained when the Samples "X", "Y" and "Z" resulfonated 
desulfonated lignosulfonate materials described in the Third Illustration 
are employed as retarding agents in amounts varying from 0.2 to 1.2 wt. % 
of the composition and tested in "LONE STAR No. L" (Class H), "LONE STAR 
MT" (Class H) and "IDEAL DSU" (Class G) cements using Well Simulation 
Tests (per API RP-10B) over Schedules 4, 5, 6, 7, 7B and 8. Thickening 
times (without problems of gellation) of from about 11/2to 41/2hours are 
experienced with the various retarded cement compositions prepared and 
tested. 
EIGHTH ILLUSTRATION 
The resulfonated desulfonated lignosulfonate additive identified in the 
Fourth Illustration was tested at various concentration levels in Class H 
cement to check setting times obtained with both fresh water and salt 
water exposures. The excellent results obtained were as set forth in the 
following tabulation (with, again, no gellation experienced): 
______________________________________ 
12,000 ft. Casing Schedule - 172.degree. F 
Wt. % Retarder 
Fresh Water Time 
18% Salt Water Time 
______________________________________ 
0.2 1 hr., 47 min. 
2 hrs., 43 min. 
0.3 3 hrs., 30 min. 
3 hrs., 32 min. 
0.4 4 hrs., 5 min. 
5 hrs., 14 min. 
0.5 6 hrs., 14 min. 
6 hrs., 30+ min. 
______________________________________ 
14,000 ft. Casing Schedule - 206.degree. F 
Wt. % Retarder 
Fresh Water Time 
18% Salt Water Time 
______________________________________ 
0.3 1 hr., 58 min. 
1 hr., 44 min. 
0.4 3 hrs., 1 min. 
2 hrs., 27 min. 
0.5 3 hrs., 47 min. 
2 hrs., 45 min. 
0.6 4 hrs., 9 min. 
3 hrs., 42 min. 
0.7 5 hrs., 12 min. 
4 hrs., 33 min. 
0.8 5 hrs., 12 min. 
______________________________________ 
Equivalent good results are likewise obtainable with other of the 
above-delineated resulfonated desulfonated lignosulfonate additive 
products pursuant to the practice of the present invention including 
straight (i.e., non-alkyl-unit-containing) organically sulfonated and 
resulfonated materials and various sulfoethylated and sulfopropylated 
resulfonated desulfonated lignosulfonate derivative additives. 
Many changes and modifications can readily be made and adapted in 
embodiments in accordance with the present invention without substantially 
departing from its apparent and intended spirit and scope, all in 
pursuance and accordance with same as it is set forth and defined in the 
hereto appended Claims.