Polymer non-dispersed drilling fluids
United States Patent [1 1 1111 3,880,764 Donham 1 1 Apr. 29, 1975 15 1 POLYMER NON-DISPERSED DRILLING 3.346.488 10/1967 FLUIDS 3.434.970 3/1969 3.472.325 10/1969 [75] Inventor: James E. Donham. Houston. Tex. 3 ,54 51 4 1973 [73] Assignee: Amoco Production Company, Tulsa. FOREIGN PATENTS OR APPLICATIONS Okla- 717.460 9/1965 Canada 252/85 A [22] Filed: Nov. 6, 1972 Primary Examiner-Benjamin R. Padgett [211 App! 304027 Assistant Examiner-E. A. Miller Attorney, Agent, or Firm-Paul F. Hawley; Arthur [52] U.S. Cl. 252/8.5 A; 252/85 B; 252/85 C; McIlroy 175/65 [51] Int. Cl ClOm 3/40 57 ABSTRACT [58} Field of Search 175/65; g Polymer non-dispersed low solids drilling fluids can be prepared to tolerate high calcium and salt concentrations by incorporating therein an effective amount of [56] References Cited triamino dihexylene pentakis phosphonic acid, tet- UNITED STATES PATENTS ramino trihexylene hexakis methylene phosphonic 3.081.260 3/1963 Park 252/85 A acid, salts thereof, or mixtures of the acids or salts. 3.323.603 6/1967 Lummus et all. 252/85 C 3.338.320 8/1967 Gilson ct a1 252/35 c 10 Clam, 2 Drawmg Flgures (ll LOW SOLIDS-AVG. MUD WT. 8.5 (2) ADDITIVE ADDITIONS-AVG. MUD WT. 8.6 (3) ADDITIVE TREATED INTERVAL-AVG. MUD WT. 8.7 (4) SODA ASH TREATED INTERVAL- AVG. MUD WT. 9.0 (5) DISPERSED-AVG. MUD WT.&#39;9.3  
  INTERVALI |NT.2 INTERVAL3 l INTERVAL4 INTERVAL 5 9.6  
 p g 8.8 z  
 8.0 I l 1 r l 0 2 4 6 8 IO l2 I4 16 DEPTH I000 POLYMER NON-DISPERSED DRILLING FLUIDS The present invention relates to novel drilling fluids and to their use in environments previously considered unsuitable for such fluids. More particularly, it relates to use of amino alkyl phosphonic acids in conventional weighted or unweighted polymer non-dispersed drilling fluids to render the latter useful in the presence of high calcium and salt concentrations.  
 BACKGROUND OF THE INVENTION The use of low solids polymer non-dispersed muds is widely accepted as a valuable adjunct to optimized drilling techniques to allow optimum hydraulics, borehole stability and maximum penetration rates.  
  Polymer non-dispersed muds are applicable to a wide range of conditions encountered in drillng, both in weighted and non-weighted systems. Their unique dril ling properties are due to the maintenance of low drilled solids content and optimum flow characteristics, allowing maximum advantage to be realized from computerized hydraulic programs, bit weight-rotary speed calculations and optimized bit selection. The desired properties are obtained by utilizing the chemical and physical characteristics of high molecular weight. long chain organic polymers. These polymers are used to simultaneously extend the use of bentonite and flocculate drilled solids, and to lower the fluid loss and alter drilling fluid flow properties without dispersing the drilling fluid.  
  The long chain high molecular weight polymers perform a dual function extension of bentonite and flocculation of drilled solids and accordingly are referred to as dual-action polymers.&#34; Bentonite extension, or increasing the viscosity of a bentonite suspension. is achieved by the active charged sites on the polymer chain reacting with charged sites on bentonite platelets and creating a large polymer-clay structure that is more viscous than an equivalent amount ofbentonite without the polymer. Drilled solids flocculation is carried out by the active sites on the polymer chain reacting with the less highly charged (compared to bentonite) drilled solids and gathering them into a dense mass that is much larger than the individual particles. This denser structure settles according to Stokes Law. A typical slurry of 7 lbs/barrel bentonite and 0.025 lb/barrel of the polymer in water will yield more viscosity than 14 lbs/barrel bentonite without the polymer. This allows a drilling fluid to be formulated with a lower solids content, thereby increasing the drilling rate without sacrificing the hole-cleaning due to viscosity and yield value of the drilling fluid. The effective size of the particles in the drilling fluid is much larger due to the presence of the polymer-clay structure, rather than dispersed bentonite platelets of colloidal size. Selective flocculation of drilled solids by the polymer also prevent their buildup in the system. The absence of colloidal solids is the reason for the much higher drilling rates obtained with polymer non-dispersed muds.  
  lt is well known that colloidal solids are detrimental to penetration rate. Colloidal solids of less than 1 micron in size are the worst offenders because of their property of forming an instantaneous fllter cake along the fracture planes induced by the bit striking the formation. This filter cake effectively seals the crevice surrounding the freshly broken chip and prevents entry of the turbulent flow of drilling fluid jetting from the bit.  
 The chip hold-down pressure is sufficiently strong (due to pressure caused by hydrostatic differential) to prevent the chip being washed away by the fluid stream. The chip must be struck again and fractured into smaller particles before being swept away by the jet stream. Cuttings size is smaller. The drilling fluid weight increases, also reducing drilling rates.  
  The contribution of these smaller solids to plastic viscosity, yield values and gel strength is disproportionally large and also exerts a drastic reduction in penetration rate; so maintenance of the drilling fluid in a nondispersed, low-solids state is highly advantageous to the drilling of the well.  
  A typical low solids non-dispersed mud contains the following ingredients:  
 1. Sodium montmorillonite (bentonite) 2. Alkali metal salt (preferably sodium, potassium or ammonium) of a high molecular weight (1 to 12 million) partially hydrolyzed polyacrylamidepolyacrylate copolymer for selectively flocculating drilled solids and exerting some effect on viscosity properties; usually lower gel strength and yield points; 0.0l0.5 lbs/bbl.  
 3. Alkali metal salt of a high molecular weight 3l2 million mole weight polyacrylate for extending the bentonite viscosity -0.0l0.5 lbs/bbl.  
 4. A low molecular weight polyacrylic acid, or an alkali salt of a low molecular weight polyacrylate (usually less than 100,000 mole weight) for controlling fluid loss and assisting in controlling high viscosities, yield values, and gel strengths contributed by the bentonite and by the bentonitepolymer structure 0.25 5.0 lbs/bbl.  
 5. Fresh water.  
 Note: Items 2 and 3 may be added as a blend of the two polymers to simultaneously achieve both bentonite extension and solids flocculation; 2 may be added alone in areas where natural bentonite deposits being drilled would cause viscosities to be too high when the extending polymer is added.  
  The general practice of the industry is to use these polymer non-dispersed muds in as many areas as possible to decrease drilling costs, contingent upon a favorable drilling environment for utilizing this type of drilling fluid.  
  Low solids non-dispersed polymer muds have some limitations in areas of use. High calcium content, e.g., in excess of about ppm, has an adverse effect, because of formation of calcium bentonite and reacting with the polymer. High chloride content, e.g., in excess of about 5,000 ppm, has a detrimental effect due to dehydration of the polymer-clay structure. The practice is to treat out calcium with soda ash, caustic, or barium carbonate, and pre-hydrate the polymer-bentonite slurry when high salt conditions are encountered. lf salt and calcium is too high, then the system is usually dispersed or converted to a salt water mud, thereby losing the high penetration rates and other advantages offered by polymer non-dispersed muds.  
  Naturally occurring formations of bentonitic shales also normally limit the use of low solids non-dispersed muds, particularly in combination with anhydrite or other calcium-containing strata. When these formations are drilled they usually cause a rapid buildup of solids in the drilling fluid, which do not settle out and are reground into colloidal size. Anhydrite formations often underlie these. and the calcium contamination then causes excessive viscosity. These adverse conditions are particularly detrimental to a polymer nondispersed mud that has been weighted with barium sulfate.  
  The addition of barite to increase drilling fluid weight adds inert solids that can alter the flow properties of the system. Yield values and gel strengths may be higher than desired, particularly in the presence of calcium contamination, mud-making shales, and salt. These viscosity problems have been reported in driling fluids using the high molecular weight polyacrylate and partially hydrolyzed polyacrylamide-acrylate copolymer blend previously referred to, but can occur in polymer non-dispersed muds using other polymers for bentonite extension.  
  When these problems occur, the practice is to add a dispersant or thinner to achieve manageable lower viscosities, yield values, and gel strengths. This is a self defeating mechanism, because the dispersion of the small particles into even smaller ones makes their removal even more difficult, increases the chip holddown and keeps the cycle going. The only way to handle the situation then is to run large quantities of water, add large amounts of bentonite to maintain desired properties, and use enough dispersant or thinner to reduce yields and gel strength caused by the drilled solids and added bentonite. Sodium hydroxide and sodium carbonate are added to react with and treat out the calcium contamination. A thinner or dispersant functions by adsorbing onto exposed edges of clay lattices and neutralizing attraction of edge valances between particles. Flocculated clumps are broken up and new surfaces are created by separating aggregated or stacked sheets of clay. The number of individual clay particles is increased and particle size is decreased, resulting in increased plastic viscosity and lower drilling rates. Phosphates, tannins, and lignosulfonates are commonly employed as the thinner or dispersant. The addition of a dispersant results in decreased yield values and gel strength, but increased plastic viscosity due to breaking up aggregates and flocculated clumps of clay into colloidal particles. Since there are many areas in which the previously described conditions prevail, the use of low solids polymer non-dispersed muds has been limited to only those areas favorable to their use.  
 DESCRIPTION OF THE DRAWINGS FIG. 1 of the drawings is a plot showing the difference in drilling rates in formations containing bentonitic shales and high concentrations of calcium and salt. The dashed line represents the drilling rate obtained using a dispersed mud, while the solid line indicates the results obtained with the drilling fluid of my invention.  
  FIG. 2 is a plot involving the same well as represented by the solid line in FIG. 1, indicating the mud weight during the drilling operation. The additive (a mixture of triamino dihexylene pentakis methylene phosphonic acid and a tetramino trihexylene hexakis methylene phosphonic acid in which the former was present in a ratio of 3 moles to 1 mole of the latter) was employed in a polymer non-dispersed, low solids drilling fluid for the major portions of intervals 2 and 3. The well using the drilling fluid claimed herein and whose drilling rate is shown by the solid curve in FIG. 1 demonstrated a striking increase in penetration rate due entirely to the ability to maintain a polymer non-dispersed mud in this field where previously it had been impossible to use this type of fluid. Protection of the system through most of intervals 2 and 3 as shown in FIG. 2 was made possible by use of the additive during drilling of the troublesome shale and anhydrite formations. In this operation, viscosities, yield strengths, solids content and mud weight were almost optimum for a non-dispersed mud and well below those of a typical dispersed mud.  
 SUMMARY OF THE INVENTION I have now discovered an additive for polymer nondispersed muds capable of rendering them useful in drilling types of formation previously regarded by the industry to be unsuitable for such muds. I have further observed that when this additive is present in these muds and used in areas in which they previously have been considered inoperable, said muds still retain all the desirable features of low solids drilling fluids. Specifically, I have found that the addition of a mixture of certain amino methylene phosphonic acids or alkali metal salts thereof to a typical polymer non-dispersed mud, the latter generally containing a clay such as bentonite, polyacrylates and a dual-action polymer or the equivalent, results in a system that is highly resistant to the ordinary harmful effects of calcium and salt contamination, and reduces viscosity buildup due to drilled solids. As previously mentioned, dispersed muds are normally used where substantial calcium and salt concentration are anticipated. This, together with the fact that conventional polymer non-dispersed systems are ordinarily unstable in such an environment. renders totally unexpected the application of the drilling fluids of my invention in high calcium and/or salt systems. The effect of my new additive in a typical low solids drilling fluid is to lower viscosities, yield values and gel strengths without dispersing or deflocculating the system.  
  Since polymer low solids non-dispersed muds depend upon the maintenance of clay-polymer structures or aggregates and controlling the attractive forces between these structures, a thinner, dispersant or deflocculant will render the non-dispersed mud ineffective and change it to a dispersed state.  
  The additives of my invention neither disperses nor deflocculates the polymer non-dispersed mud. Although the mechanism is not exactly known, laboratory data indicate that my additive functions by destroying the attractive forces between the polymer-clay aggregates without affecting the integrity of the polymer chain-bentonite platelet structure. The organic high molecular weight phosphonate is of sufficient ionic strength to neutralize the edge valence attractions on the exposed bentonite platelets. but is not of sufficient strength to displace the bentonite platelets from the polymer chains. The phosphonate molecule is of sufficient length to align itself along the polymer-clay structure, and neutralize several edge valences.  
  The new structure, composed of the polymerbentonite platelet chain aligned with a molecule of my additive, is highly resistant to invasion by calcium ions into the polymer-clay structure. The molecular size of this additive is too great to diffuse into the interplanar area of the clay molecule. It ionizes to give H ions; these displace some monoand di-valent cations inside the clay lattice, thereby giving lower viscosity by decreasing the inter-planar distances and reducing the standoff distance; this releases water from the clay/- polymer aggregate and lowers viscosity. The polymer/- clay aggregates bind more water than clay alone. There is no breakup of polymer/clay aggregates, as is true with a thinner or dispersant. The effect is to lower gel strength by reducing inter-aggregate attractiverepulsive forces, destroying the equilibrium condition.  
 ture, such as for example, the mixture described in US. Pat. No. 3,472,325.  
  As a substitute or equivalent of the combination polyacrylate salt and partially hydrolyzed polyacrylatem F W lowered because h particle Size 5 polyacrylamide for flocculation and bentonite extenmbutlon 15 Shlfted tPWard larger p l A dlspersam sion, 1 may use other materials known to possess similar acts the Opposhe mahheh Yleld Values characteristics such as, for example, the vinyl maleic changed or lowered y yi because attracvvefl copolymer described in US. Pat. No. 3,070,543 for l l l fcrces between mdlvldual y Platelets are such uses. Such substances are genereally referred to as re ahve y hhdffected&#39; dual-action polymers,  
  As previously stated, the add1t1ves of my mvent1on Th 1k 1 h h It th f may be used in combination with any conventional 8 mfnmo y p h ergo polymer-non-dispersed low solids muds, and preferably sul e or use.m h i e n mg s o my m&#39; vent1on are trlammo dihexylene pentakls methylene are used 1n comb1nat1on wlth a relatlvely low molecular h h d t t t 1 h weight polyacrylate for best results as will be com- 15 i f n 2 s mented on in more detail below. The polyacrylates emp 1 S ployed for fluid loss prevention may be any of those or- .zj i q to 2 uce t nove. dinarily used for this purpose. However, in general l 0 my mvhntlon er to emp 0y a.mlx.ure O these two wherem a ma or amount of the triammo deprefer those havmg a molecular weight not in excess of i t f r Xam 16 in a ratio Offrom about about 100.000-for example, from about 50,000 to Z0 fwd we is presen p 1 l00,000. These materials, which are generally prefera- 3 h of the f to about 1 mole of h i bly used in the form of their alkali metal salts, may also ramlho compouhd&#39; Thls group of Compounds be employed in the form ofthe corresponding free acid cloed h N h a memo? for and produce optimum results. insofar as concerns yield prlifamhoh gweh therem&#39; w h quhhhty of values, gel strengths and fluid loss, in concentrations of addmve m accordance wlth my mvenuon i from about 0.1 to 3.0 lbs/barrel of drilling fluid. vary generally Prefer to employ It In the drilling fluid systems contemplated, I may use cohcehfmhohsfahgmg to about 1 lb/bfm a combination of materials for obtaining proper solids mammal pheferably added to the Clrculahhg flocculation, control of yield values and gel strengths m and geherahy at rate Such that the on the one hand, and for extending the Viscosity of the s1red concentration 15 obtained 1n the system after not clay material, such as bentonite, on the other. Thus, for more than about f&#34; threfle homplete ch&#39;culrihohs&#39; solids flocculation and control of yield values and gel For the purpose of i hh h h refernhg 9 strengths 1 may employ a high molecular weight, e.g., these COmPQuhdS as h addmve or an addmve 2 million partially hydrolyzed polyacrylamide such term is intended to include each one of the abovepolyacrylate copolymer alkali metal salt, also preferahamedpompouhds separately 1h combmahoh the bly in concentrations ranging from 0.005 to 0.5 lb/bbl free held or form In prepanhg latter any Ohthe of mud The partially hydrolyzed polyacrylamide common amines such as ethanol amme, ethyl amine, polyacrylate copolymer while it may Vary in ratio of butyl amme, hexyl amme, etc., may be used in add1t1on free acid groups to amide groups, the polyacrylamide to Shhable alkah metal compounds preferably has from about 2 to 10 percent of its amide 40 The properties of typical polymer non-dispersed low groups hydrolyzed. For bentonite extension I may use solids muds with and without the additive claimed a high molecular weight, e.g., ll2 million, polyacrylherein are shown in the Table I below and were deterate alkali metal salt or the corresponding polyacrylic mined from a 15 lb non-dispersed laboratory mud conacid in amounts ranging, typically, from about 0.005 to taining about 335 lbs of bariet/bbl and other ingredi- 0.5 lb/barrel. A synergistic blend of the copolymer and ents in the amount shown below, and a 10.5 lb field polyacrylate may be employed as a dual-action mixmud- TABLE I Blend of Partially Hydrolyzcd Copolymcr of Polyacrylatc- Polyacrylumide* and Sodium System Sodium Polyaerylate Polyacrylatc*** Additive Bentonite l .l l5 lh/bbl 0 0 9.0 lb/bbl 2 ,I I5 lb/bbl 2 lb/bbl 0 9.0 lb/bhl 3 .l 15 lb/bbl 3 lb/bbl 0 9.0 lb/bbl 4 .l 15 lh/hbl 2 lh/bbl 0.25 lb/bbl 9.0 lh/hbl 5 .1 l5 lb/bbl 3 lb/bhl 0.25 lb/bbl 9.0 lb/bbl 6 ),1 l5 lh/bhl 0 0.25 lh/bbl *Mol weight about 2-4 million **Mol weight about 12 million ***Mol weight about 100,000  
 Mud Properties:  
  Apparent Plastic Yield Gel Fluid Cake System Viscosity Viscosity Point Strength Loss 32nd&#34; pH From the above Table it can be observed that the adtrol. Maintaining solids content at a low level had been dition of sodium polyacrylate increases plastic viscosi ible in the past, the muds were dispersed and atity, yield values and gel strengths (Systems 2 and 3). tempts to use apolymer non-dispersed m d b The addition of the additive lowers plastic viscosity, doned. These problems were due to the extremely unyield Values and g Strengths y m 6). When the adfavorable environment a layer of bentonitic mudditive 1S incorporated in a system containing sodium making shales interspersed with layers of anhydrites. y ly (lower molecular W elght) the Pldstic The well was spudded and surface pipe set. Drilling cosity is reduced A dispersant thinner invariably ra s out ofsurface was commenced four days later with gel the plastic viscosity. It will be seen that the use of the wawp High molecular Weight million) copolymer f j alone (system 6 System 1) reduces plasnc additions were begun at a depth of 1,855 feet in order vllscoslty by 4 or by about f lncorpom&#39; to maintain low drilled solids. An aqueous solution of non of the additive to a system containing 2 lbs/barrel the copolymer was added directly downstream of the of the lower molecular welght Sodlum polyacrylate shale shaker prior to entering the reserve pit. The  
 (System 2 v. System 4) reduces plastic viscosity by 16 dF or abqut 23 l to a System 15 tion of around .01 lb/bbl. Solids flocculation occurred taming 3 lbs/barrel of such sodi umpoly acrylate (Sysimmediately with large flocs forming and settling tom 3 v. System 5) reduces plastic viscosity by 24 units idly. Mud weight at the pump Suction was 84 lbs/gab or by 25 percent. Since the addition of increments of lon- Soda ash was also added during this period down polyacrylate increases plastic viscosity, the observed to a depth M6 399 feetto Control Calcium contaminw increased percent reduction is unique and unexpected. 20 tion The Calcium Content was maintained at 2O 40 The effect 9 pomt also l 36 ppm. Plastic viscosity and yield values ranged from 46 cent reduction with 2 lbs/barrel of sodium polyacrylate and respectively in this fast drming mud making and 37 percent ip wlth 3 lbs/balm of sfldium intervaldNo materials were added at this stage to conpiflyucrylate&#39; The neghglble effectpn fluld l Wlth trol fluid loss with rates running from 32.8 cc/ mindium polyacrylate and the actual increase in System 6 25 Utes API at 2 695 feet down to 14 0 BO minutes API v. System l illustrates the true non-dispersive nature of at 6,000 feet. A mixture of high molecular weight (2-4 the additive of my invention, i.e.. it reduces plastic vis- I million) partially hydrolyzed polyacrylamidecosity. yield values and gel strengths without dispersing or thinning the mud polyacrylate copolymer and sodium polyacrylate (moamount of copolymer added resulted in a concentra- 2 0.04 lbs/bbl 0.2 *Made from 10.5 lb field mud. Ward County, Texas, containing about 72 lhs/hbl harite, 15 lbs/hhl hcntonite.  
  Apparent Plastic Yield Gel System Viscosity Viscosity Point Strength Fluid Loss Cake pH 1 14.5 10 9 25/40 NA NA 9 2 l0 8 4 2/18 NA NA 9 From Table No. 11 it can be observed that the addilecular weight 10-12 million) in an amount sufficient tion of the additive to a field mud results in lower plast produce a concentration in the mud after one circutic viscosity, yield value. and gel strength without dislation of from about .025 to about .05 lb/barrel was persing, whereas a dispersant would have increased the added at a depth of 4,431 feet to reduce bentonite replastic viscosity while lowering the gels and yield value. quirements. The mud weight was maintained at 8.6 to 8.8 pounds per gallon, with a solids content of from /2 ix gg iig s OF THE to 2 /2 percent. Penetration rates were high during this interval, with an average rate of 27.3 feet/hour in the The following examples illustrate in further detail the 5,869 f t interval between surface and 6,399 feet. effectiveness of the use of my additive in polymer non- Thi compared to an 8.8 foot/hour average rate at approximately the same depth for the well wherein the drilling rate is shown in the dashed line of FIG. 1 in which a dispersant was being used.  
 EXAMPLE 1 Some tight hole problems were encountered at 6,061  
 After laboratory testing was completed a full-scale feet and the mud was turned to the steel pits. Weight test well was obtained to determine the effectiveness of per gallon increased to 9.0 pounds and plastic viscosity the additive in rendering polymer non-dispersed muds d yield value increased to 16 and 8. re pec i ly. resistant to calcium and/or salt concentration. The test Befltomte addltlOn W115 ntmued. at WhlCh time th dispersed low solids muds in environments previously considered unsuitable for such drilling fluids. 55  
 well selected was located in the South Elk Basin field. mud mmained pp m y 20 s/ a l- Add ions Park County, Wyoming. Previous wells drilled in this of high molecular weight copolymer were increased to area attempting to use polymer non-dispersed muds improve flow properties, i.e., the plastic viscosity-yield had been beset with problems caused by calcium convalue ratio. and lower the solids content. The hole con tamination and high solids content. The shales encounditions cleared up and circulation through the reserve tered are bentonitic in nature and very difficult to conpit was resumed. During the time that circulation was in the steel pits, addition of the additive (in a ratio of 3 moles of the triamino dihexylene pentakis methylene phosphonic acid to 1 mole of the tetramino trihexylene hexakis methylene phosphonic acid) was begun to pre condition the system prior to drilling the calciumcontaining formations known to cause problems. Addition of the additive to the mud was begun at a depth of about 6,200 feet and incorporated therein at a rate such that after one complete circulation the system contained .21 lb/barrel. Gel strengths had begun to climb up to this point gel strengths were O-initial and -2 10 min. Prior to conditioning the system with the additive, gel strengths had climbed to 4-initial and 27 10 min with soda ash treatment. After incorporating the additive into the mud system, the weight came back down to 8.6 lbs/gallon. The plastic viscosity range was 8-10 and yield values ran 4-10. The calcium content ranged from 80-340 ppm, with no attempt to remove it. During the depth illustrated by interval 2, FIG. 2, no fluid loss control agent was added. Fluid loss ranged from 12-20 cc/30 min API.  
  At a depth of 7,500 feet. additions of the additive were discontinued, at which time the system contained .2 lb/barrel. During this 1,300-foot interval the maintenance of flow properties and fluid loss was achieved without addition of soda ash (although 5 sacks were inadvertently added at one point) and no sodium polyacrylate addition. Even after discontinuing the addition of the additive, the system remained in good condition up to a depth of about 9,500 feet. This will also be seen from the curve in FIG. 2 where the mud weight ranged from 8.6 lbs/gallon at 6,200 feet to about 8.8 lbs/gallon at 9,500 feet. The calcium content varied from 150 to 350 ppm. with no attempt being made to remove it, during which time the pH ranged from 7.8 to 8.0.  
  At a depth of 8,845 feet. low molecular weight (not in excess of 100,000) sodium polyacrylate treatment was begun, with fluid loss being reduced from 13.2 cc/30 min down to 6.4 cc/30 min API and was maintained below cc. At 9,930 feet soda ash treatment was begun (mostly interval No. 4 shown in FIG. 2) and a conventional low solids non-dispersed mud was maintained from this point to a depth of 13,246 feet with mud weight averaging 9.0 lbs/gallon. Fluid loss was controlled 8-10 cc/30 min, with low molecular weight sodium polyacrylate. The concentration of additive at this time in the system was less than .05 lb/barrel. The pH was allowed to increase to 9.5 and ranged from 8-10.  
  The solids content increased from 3 percent for the additive treated fluid in interval 3 of FIG. 2 to 5-6 percent for interval 4 (FIG. 2) for the soda ash treated interval. Mud weight increased from an average of 8.7 lbs/gallon to an average of 9.0 lbs/gallon during the soda ash treated interval. The use of soda ash to treat out calcium is a common practice. Addition of soda ash precipitates calcium as an insoluble, inert carbonate as shown by the equation:  
 Na CO CaSO, CaCO;, Na- SO The sodium sulfate acts as a dehydrating agent the same as sodium chloride; sodium carbonate increases pH. Both of these factors tend to interfere with the stability of the polymer-clay structure that is the backbone of a polymer non-dispersed mud. Use of the additive in this system did not contribute to the problem. The additive does not raise the pH or react to form an inorganic salt. It stabilizes the polymer-clay structure by displacing cations from the polymer chain and bentonite platelets and forming a protective layer&#34; adjacent the polymer-clay structure. By modifying electrical charges and releasing some water of hydration at the interface between polymer-clay structures, reduction in gel strengths, yield values and plastic viscosity was achieved without dispersing, and plastic viscosityyield value ratios were maintained at optimum levels.  
  A conventional dispersant such as, for example, a lignosulfonate, added to a non-dispersed polymer mud destroys the clay-polymer structure by neturalizing all the charges along the polymer backbone&#34; and on the bentonite platelets. The plastic viscosity increases, yield point drops drastically and solids buildup almost invariably occurs. Fluid loss is lowered considerably by dispersing all the large structures to colloidal, submicron-sized particles. This phenomenon was strikingly evident when the mud system in the test well (see FIG. 2) was dispersed at 13,246 feet. Plastic viscosity had been running from 19-25, averaging around 20 and the plastic viscosity-yield value ratio was about 1:1 in the interval (3) preceding the dispersed interval (4, FIG. 2). Gel strengths were 2-inital and 10-25 10 mins. Solids content averaged 5 percent, with mud weight at 8.8 to 9.0 lbs/gallon.  
  After dispersing, the plastic viscosity went to 36 and averaged around 35. The plastic viscosity-yield value ratio rose to around 2:1 and gel strengths were Z-initial and 5-10 10 min. Solids content rose to 9 percent and averaged 8.5 percent. Mud weight climbed to 9.3 lbs/gallon, accompanied by a decline in drilling rate from 5.6 to 3.5 feet/hour. A computerized run was made and predicted that during the 1,284-foot dispersed interval, a penetration rate of 3.71 feet/hour could have been realized if the mud had not been dispersed instead of the actual rate of 3.09 feet/hour. The savings would have been $5.17/foot or $6,803.60 for the interval, a 15.7 percent reduction in cost.  
 EXAMPLE 2 After completion of the well involved in Example 1, another test was made to evaluate the effectiveness of the additive in a weighted (15 lbs/gallon) nondispersed mud. This well was drilled in West Texas in an area where it had been determined that the use of the polymer blend for bentonite extension resulted in excessive yield points and gel strengths. Previous attempts with such treatment had resulted in failures. Initially the drilling fluidemployed consisted essentially of fresh water, bentonite l0 lbslbarrel), a polymer blend of partially hydrolyzed polyacrylamide-polyacrylate copolymer (molecular weight 2-4 million) and high molecular weight (10-12 million) polyacrylate (.2 lb/barrel) and a low molecular weight (75.000) polyacrylate (1 lb/barrel).  
  The well was watched closely and additive was incorporated in the drilling fluid whenever gel strengths rose to undesirable levels. Usually the additive was em ployed in concentrations of about .2 to .25 lb/barrel. On incorporation of the additive into the system. the gel strength would decrease to a manageable level and no further additive was used until gel strengths increased again whereupon the procedure was repeated.  
  The result was that no problems occurred and the weighted non-dispersed mud was run with good results in an area where previous attempts to use the polymer blend to maintain non-dispersed properties had failed.  
  From the foregoing description it will be apparent to those skilled in the art that the use of the additive of my invention in polymer non-dispersed drilling fluids, weighted or unweighted, will retain their desirable characteristics in drilling environments previously considered unsuitable for such muds and thus permit their use on a greatly enlarged scale by the industry.  
  The term alkali metal salts as used herein is intended to include the ammonium or amine salts of the acid involved. Also it is to be understood that I consider the free acid in the case of the additive, the fluid loss control material (sodium polyacrylate) and the flocculant (high mol wt polyacrylate copolymer) to be equivalent to the corresponding alkali metal salts.  
 1 claim:  
  1. A conventional polymer non-dispersed low solids aqueous drilling fluid having incorporated therein an additive selected from the group consisting of triamino dihexylene pentakis methylene phosphonic acid and tetramino trihexylene hexakis methylene phosphonic acid, the alkali metal salts of said acids and mixtures thereof, said additive being present in an amount effective to render said fluid stable to contamination by soluble calcium and salts.  
  2. The drilling fluid of claim 1 in which an alkali metal salt of a low molecular weight polyacrylate (not more than about 100,000) is employed as a fluid loss control material.  
  3. The drilling fluid of claim 2 wherein said additive is employed in a concentration of from about 0.05 to 0.5 lb/barrel.  
 4. The drilling fluid of claim 2 wherein said additive LII is a mixture of the two acids having a larger amount of the triamino dihexylene pentakis methylene phosphonic acid.  
  5. The drilling fluid of claim 3 wherein said additive contains the two acids in a ratio of from about 3 moles of the triamino dihexylene pentakis phosphonic acid to about 1 mole of the tetramino trihexylene hexakis methylene methylene phosphonic acid.  
  6. The drilling fluid of claim 2 in which said alkali metal salt is present in an amount corresponding to from about 0.1 to about 2.0 lbs/barrel.  
  7. A method of drilling a well in a formation containing components that normally impart abnormal viscosity to conventional polymer non-dispersed low solids mud, comprising circulating in said well, while drilling, the drilling fluid of claim 1.  
  8. A method of drilling a well in a formation containing anhydrite and inorganic chlorides in an amount sufficient to produce an abnormally high viscosity in a conventional polymer non-dispersed low solids drilling fluid, comprising circulating in said well, while drilling, the drilling fluid of claim 2.  
  9. A method of drilling a well in a formation containing anhydrite and inorganic chlorides in an amount sufficient to produce an abnormally high viscosity in a conventional polymer non-dispersed low solids drilling fluid, comprising circulating in said well, while drilling, the drilling fluid of claim 4.  
  10. A method of drilling a well in a formation containing anhydrite and inorganic chlorides in an amount sufficient to produce an abnormally high viscosity in a conventional polymer non-dispersed low solids drilling fluid, comprising circulating in said well, while drilling, the drilling fluid of claim 5.  
  UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 3,880,764  
 DATED April&#39; 29, 1975 |NVENT0R( James E. Donham It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 1, line 17, the word &#34;drillng&#34; should read -drilling-.  
 Column 6, line 15, before the word &#34;phosphonic&#34; insert -methylene-.  
 Coluntn l2, Claim 5, line 6, before the word &#34;phosphonic&#34; insert methylene--; line 8, delete &#34;methylene&#34; (first occurrence).  
 Signed and Scaled this fourth Day Of November 1975 [SEAL] Arrest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oflalems and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,880,764  
 DATED April 29, 1975 |NVENTOR(5) 1 James E. Donham It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 1, line 17, the word &#34;drillng&#34; should read drilling-.  
 Column 6, line 15, before the word &#34;phosphonic&#34; insert methylene- Column 12, Claim 5, line 6, before the word &#34;phosphonic&#34; insert -methylene-; line 8, delete &#34;methylene&#34; (first occurrence).  
 Signed and Scaled this fourth Day Uf November 1975 [SEAL] Arrest:  
 RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj&#39;Parenrs and Trademarks