NL8105189A - Oil-based drilling packer fluids contain organophilic clays - having defined alkyl gps. as gelling agents - Google Patents

Abstract

Oil-based drilling fluids contain as gelling agent 1-50 lb/barrel of an organophilic clay (I). (I) is made by reacting a smectite clay (II) (pref. hectorite or Na bentonite) with a quaternary ammonium or phosphonium ion R1R2R3R4X(+) (III), where R1 is C6 or lower beta, gamma unsatd. alkyl and/or C2-C6 hydroxyalkyl, R2 is C8-C60 alkyl, R3 and R4 are as specified for R1 or aralkyl or C1-C22 alkyl or mixts.of these, and X is N or P. Also claimed is a process for lining a borehole by pumping such a fluid into an annular space in the hole and allowing it to gel. The oil base is pref. diesel oil. (II) has a cation exchange capacity of at least 75 milliequivalents per 100 g, and 90-140 milliequivalents of (III) are added per 100 g of (II). Where the fluid is for use as a sealant (''packer fluid''), the pref. concn. of (I) is 6-50 lb/barrel. Gel formation is effectively complete after mixing in (I) at low shear force.

Description

/ 9 H.O. 30 * 549 - 1 "

Organophilic clay products containing oil-based liquids.

The present invention relates to organophilic organic clay complexes which are dispersible in organic liquids to form a gel therein. More particularly, such gels are suitable in oil based drilling fluids and oil based fluids.

It is known that organic compounds containing a cation will react with clay products containing a negative layer lattice and exchangeable cations through the formation of organophilic organic clay products. The reaction of an organ cation containing at least one alkyl group of at least 10 carbon atoms with clay generally results in organ clay products which are swellable in certain organic liquids.

Older publications include U.S. Pat. Nos. 2,531,442 and 2 * 966,506 and the Brook "Clay Mineraly", 2nd ed., 1968 by Ralph E. Grim (MeGraw Hill Book Co., Inc.) In particular. chapter 10, Clay-Mineral-Organic Reactions biz. 356-368 Ionic Reactions, Smectite and biz. 392-501 - Organophilic Clay-Miner-20 al Complexes,

Maximum gelation (Tikkikkings) efficiency from these organoclay products is achieved by adding a polar low molecular weight organic dispersant material to the composition. Such materials are described in U.S. Pat. Nos. 2,677,661, 2,704 * 276, 2,833 * 720, 2,879 * 229, and 3 * 294 * 683. The use of such dispersion aids has been found to be unnecessary when used with particular organophilic clay products. Tan substituted quaternary ammonium ter compounds as disclosed in U.S. Pat. Nos. 50 4,105,578 and 4 * 208,218.

Older organophilic clay products have shown a limited broad range of Tan gelling utility due to Tan fluctuation in the dispersion and viscosity properties. Although the products disclosed in U.S. Pat. No. 4,105,585,555 have not shown such drawbacks, such products are difficult and expensive to prepare.

An oil-based liquid of the present invention, characterized by the presence of an organophilic gelling agent, which contains the reaction product of an oil phase and from about 2.85 to about 142.5 kg / πι - of an organic cationic compound and a smectite-type clay with a cation exchange capacity of at least 75 milliequivalents per 100 grams of clay, which organic cationic compound contains the following groups: (a) a first group selected from the group consisting of a β, β-unsaturated alkyl group with less than 7 aliphatic carbon atoms and a hydroxyl group with 2 to 6 carbon atoms and mixtures thereof, (b) a second group consisting of an alkyl group having 8 to 60 carbon atoms and (o) a third and fourth group selected from a group consisting of a β, f-unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxyalkyl group with 2 to 6 carbon atoms, an aralkyl group and an al kyl group having 1 to 22 carbon atoms and mixtures thereof, and wherein the amount of the organic cationic compound is 90 to 140 milliequivalents per 100 g clay, based on 100% active clay.

The oil-based liquid of the present invention consists of an oil phase and about 2.85 to about 142.5 kg / m 2 of an organophilic clay gelling agent. The liquid is preferably not water-containing.

A suitable oil phase of the present invention may be petroleum and fractions thereof, including but not limited to diesel oil, gasoline, fuel oil, light lubricating oil fractions and heavy naphtha with a boiling range between about 150 and 350 ° C. The most preferred product is diesel oil.

The amount of the organophilic clay used is that amount which is effective to obtain the necessary degree of gelation (thickening) of the oil-based fluid for the intended application, i.e. drilling fluid or fill fluid. The minimum concentration of organophilic clay, necessary to gel a particular liquid, depends on factors such as the type of organophilic clay used, the properties of the oil phase and possibly the emulsified water phase and the maximum temperature to which the liquid must be increased. The maximum concentration of organophilic clay is limited to that concentration, which will form a pumpable liquid.

8 105 189 3 - ά%

The concentration of organophilic clay within the range x of about 2.85 to 142.5 kg per m will generally provide a sufficient gelled liquid for wide application possibilities. Preferably, about 2.85 to 28.5 kg per m are used for the preparation of oil-based drilling fluids, while amounts of 17 to 142.5 kg per m have been found suitable for the preparation of oil-based fillers . It has been found that when the organophilic clay is mixed in the oil-based liquid, essentially complete gelation is achieved upon mixing with low shear. The resulting liquid or oil base is a stable oil based liquid at surface temperatures between -6.67 ° C and underground temperatures up to 260 ° C. The formation of a stable liquid takes place in a few minutes after addition and mixing of the organophilic clay 15 into the oil-based liquid with a slight shearing.

A filler liquid is prepared according to the present invention by adding the organophilic clay to an oil medium.

The composition of the fill liquid is controlled as described before beer for supplying a pumpable composition.

Any emulsifiers, weighting agents and flow loss control products may be added at any time. It is only necessary to obtain a stable liquid prior to use of the liquid. Once prepared, the fill fluid is transferred, such as by pumping, into a well or to pipes, at least a portion of which must be filled.

The oil-based drilling fluid can be prepared and used either before drilling begins or while drilling is in progress.

The way of adding the ingredient for the preparation of the liquid is not critical. Mixing is accomplished with conventional devices capable of applying a low shear mixing power. Greater mixing power can be used, although this is not necessary. Once prepared, the drilling fluid is transferred, such as by pumping into a borehole and circulating in circulation to the drill bit and through the bore opening in contact with its walls.

The organophilic clay products of the present invention can be prepared by mixing the clay, the quaternary ammonium compound and water together, preferably at a temperature within 40 range from 20 ° C to 100 ° C, most preferably from 35 ° C

8105189-4> V --- to 77 ° C for a sufficient period of time to allow the organic compound to react with the clay particles, followed by filtration, washing, drying. and grind. The quaternary compound is added in the desired milliequivalent ratio, preferably dispersed in isopropanol or water. When using the organophilic clay products in emulsions, the drying and grinding steps can be omitted. When the clay, quaternary ammonium compound and water are mixed in such concentrations that a slurry is not formed, the filtration and washing steps 10 can be omitted.

The organic, cationic compounds used in. The present invention are suitable can be selected from a wide range of products capable of forming an organophilic clay by exchanging cations with the smectite type clay. The organic cationic compound must have a positive charge, which is localized to only at 100 m or to a small group of atoms in the compound. Preferably, the organic cation is selected from the group consisting of quaternary ammonium salts, phosphonium salts and mixtures thereof, as well as equivalent salts. The organic cation preferably contains at least έέη group selected from each of two groups, the first group consisting of a β, onver unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxy alkyl group with 2 to 6 carbon atoms and mixtures thereof and the second group consisting of a long chain alkyl group.

A representative formula of the organic cation is the formula of the figure sheet, in which is selected from the group consisting of a β, - - unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxyalkyl group with 2 to 6 carbon atoms and mixtures thereof, Eg an alkyl group having 8 to 6: 0 carbon atoms, 30 E, and E are selected from a group consisting of a β,--un-0 4 -.

saturated alkyl group of less than 7 aliphatic carbon atoms, a hydroxyalkyl group of 2 to 6 carbon atoms, an aralkyl group, an alkyl group of 1 to 22 carbon atoms and mixtures thereof and X is phosphorus or nitrogen. .

35 E1

The β-unsaturated alkyl group can be selected from a wide range of products. These compounds can be cyclic or α-cyclic, unsubstituted or substituted. β, ^ - unsaturated alkyl groups must have less than 7 aliphatic carbon atoms 8105189-5? »Contain. The aliphatic group of the β1-unsaturated alkyl groups preferably contains less than 7 aliphatic carbon atoms. The beta-unsaturated alkyl group may be substituted with an aromatic ring which is conjugated with the unsaturation of the beta part.

The β, Y group can also be substituted with both aliphatic groups and aromatic rings.

Representative examples of eyeliache β, 5'-unsaturated alkyl groups include 2-cyclohexenyl and 2-eyclopentenyl. Representative examples of acyclic β, --unsaturated alkyl groups containing 6 or less carbon atoms include propargyl, 2-propenyl 2-butenyl, 2-pentenyl, 2-hexenyl, 3-methyl-2-butenyl, 5-methyl-2-pentenyl, 2,3-dimethyl-2-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 2,4-pentadienyl and 2,4-hexadienyl Representative examples of acyclic aromatics substituted compounds include 3-phenyl-2-propenyl, 2-phenyl-2-propenyl and 3 - (4-Methoxyphenyl) -2-propenyl. Representative examples of aromatic and aliphatic substituted products include 3-phenyl-2-cyclohexenyl and 5-phenyl-2-cyclopentenyl. The alkyl group may be substituted with an aromatic ring .

The hydroxy alkyl group can be selected from a hydroxy-substituted aliphatic group having 2 to 6 aliphatic carbon atoms, in which the hydroxyl group is unsubstituted by the carbon atom adjacent to the positively charged atom. The alkyl group can be substituted with an aromatic ring. 25 representative examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxypentyl, 6-hydroxyhexyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxypentyl, 2-hydroxyhexyl, 2-hydroxycyclohexyl, 3-bydroxycyclohexyl, 4-bydroxycyclohexyl , 2-hydroxycyclopentyl, 3-kydroxycyclopentyl, 2-methyl-2-hydroxypropyl, 3-methyl-2-hydroxybutyl and 5-30 hydroxy-2-pentenyl.

Eg

The long chain alkyl groups may be branched or unbranched, saturated or unsaturated, substituted or unsubstituted and should contain 8 to 60 carbon atoms in the straight chain portion of the group.

The long chain alkyl groups may be derived from naturally occurring oils, including various vegetable oils such as corn oil, coconut oil, soybean oil, cottonseed oil and castor oil and various animal oils and fats such as tall oil. The alkyl groups can be synthetically derived 8105139 - β -:.

. of α-olefins.

Representative examples of suitable branched, saturated alkyl groups include 12-methylstearyl and 12-ethylstearyl. Representative examples of suitable branched, unsaturated groups include 12-methyl-1-oleyl and 12-ethyloleyl. Representative examples of unbranched saturated groups include lauryl, stearyl, tridecyl, myristyl (tetradecyl), penta-decyl, hexadeeyl, hydrogenated tall oil, docosonyl. Representative examples of long-chain, straight-chain unsaturated and unsubstituted alkyl groups include oleyl, linoleyl, linolenyl, soy and tall oil.

R, and R.

3 4 R, and R are individually selected from the group consisting of 3-4 de nit 15 (a) a β, -saturated alkyl group with less than 7 aliphatic carbon atoms, as described above, (b) a hydroxyalkyl group with 2 to 6 carbon atoms as described above, (e) a cyoliso or acyclic alkyl group having 1 to 22 carbon-20 atoms and (d) an aralkyl group comprising benzyl and substituted benzyl moieties, including straight or branched chain condensed ring moieties of 1 to 22 carbon atoms in the alkyl portion of the aralkyl group.

The long chain alkyl group of R 1 and R 2 may be straight or branched, cyclic or acyclic, substituted or unsubstituted and contain 1 to 22 carbon atoms. Representative examples of suitable alkyl groups include methyl, ethyl, propyl, 2-propyl, isobutyl, cyclopentyl and cyclohexyl.

The alkyl groups may be from sources similar to the long chain alkyl groups of Rg above.

Representative examples of an aralkyl group will include benzyl and those products derived from compounds a-55 such as benzyl halides, benzhydryl halides, trityl halides, 1-halo-1-phenylalkanes, the alkyl group containing 1 to 22 carbon atoms, such as 1-halo-1-phenylethane , 1-halo-1-phenyl-propane and 1-halo-1-phenyloctadecane, substituted benzyl moieties as will be from ortho, meta and para-40 chlorobenzyl halides, para-methoxybenzyl halides, ortho, 8105189-6k - with a and para-nitrilobenzyl halides and ortho-9 meta and para-alky 1b enzyl halo, wherein the alkyls contain 1 to 22 carbon atoms and parts of the condensed ring benzyl type as will be derived from 2-halomethylnaphthene and 9-halogen -5 methyl anthracene and 9-halomethylphenanthrene, where the halogen group will be defined as chlorine, bromine, iodine or any other such group that serves as a cleavable group at the nucleof some degradation of the benzyl-type part, so that the nuoleophile replaces the splitting group with the benzyl-type part.

A quaternary compound is formed from the above-described organic cationic compound and an anionic group selected from the group consisting of chloride, bromide, nitrite, hydrozyde, acetate and mixtures thereof. Preferably, the anion is selected from the group consisting of chloride and bromide and mixtures thereof, and more preferably is chloride, although other anions such as 8105189; - *. - - 7 -.

iodide, acetate, hydroxide, nitrite, etc., may be present in the organic cationic compound to neutralize the cation.

Organic cationic salts can be prepared according to methods described in U.S. Patent Nos. 2-555-356, 2-775-617, and 3-136-819-

For convenience, it is preferred that the total organic content of the organophilic clay reaction products of the present invention be less than about 50% by weight of the organoclay product. Although larger amounts are useful, the reaction product is difficult to filter, dry and grind.

The amount of organic cation added to the clay for the purposes of the present invention should be sufficient to impart to the clay the desired improved dispersion property. This amount is defined as the milliequivalent ratio which is the number of milliequivalents (M.E.) of the organic cation in the organic clay product per 100 grams of clay based on 100% active clay. The organophilic clay products of the present invention should have a milli equivalence ratio of 90 to 140 and preferably 100 to 130. At lower milliequivalent ratios, the organophilic clay products produced are not effective gelling agents. At larger milliequivalent ratios, the organophilic clay products are poor 1 and 1. However, the milliquivalent - .25 ratio, which is preferred within the range of $ 0 to 140, will vary depending upon of the properties of the organic system to be gelled by the organophilic clay product.

The manner in which the organic cation functions in the organophilic clay reaction products of the present invention is not fully known. However, the unique properties associated with the composition of the present invention are believed to be related to the electron withdrawing and delivery portions of the cation and in particular to the essential presence of at least one long chain alkyl group. coupled with a d, β or Y unsaturated alkyl group or a hydroxyalkyl group. When bound to a positively charged atom, the long chain alkyl group appears to function as an electron donor, which contributes to the delocalization of the positive charge. More importantly, however, it allows the clay plates to be separated sufficiently to allow for further separation under medium. 8 1 0 5 1 89 - 8 - allow moderate shear conditions. In contrast, the β, X-unsaturated alkyl group appears to induce a delocalization of the positive charge, which may result in a resonance or inductive effect occurring with the unsaturated alkyl-5 group. Bit effect does not occur to any significant degree with other prior art saturated alkyl groups. The improved function of the short chain hydroxyalkyl group appears to be related to the internally covalently bonded polar activation moiety, namely the hydroxyl group if not adjacent to the positively charged atom. This effect is negated when the hydroxyl moiety is located on a carbon atom adjacent to the positively charged atom or on an alkyl carbon greater than 6 carbon atoms.

Suitable smectite-type clays exist naturally or can be prepared synthetically. Such clay products include montmorillonite, bentonite, beidelleit, hectorite, saponite and stevensite. In particular, smectite-type clays should have a cation exchange capacity of at least 75 milliequivalents per 100 g of clay.

Particularly desirable types of clay are the naturally occurring yoming varieties of bentonite and hectorite, a magnesium lithium silate clay. Suitable clay products can also be prepared by conventional methods, including puumatolytic and hydrothermal methods.

The clay products, in particular the beatonite type clay products, are preferably converted to the sodium form when they are not already in this form. This can be done inexpensively by preparing an aqueous clay suspension and passing the suspension through a bed of a cation exchange resin in the sodium form. Also, the clay can be mixed with water and a soluble sodium compound such as sodium carbonate and sodium hydroxide, followed by shearing the mixture with a clay kneader or extruder.

The cation exchange capacity of the smectite-type clays 35 can be determined by the ammonium acetate method.

The clay is preferably dispersed in water in a

A weight concentration, which ranges from about 1 to about 80%, and preferably from about 2 to about 20%, and more preferably from about 2 to about 7%. The suspension is pre-8105189

¥ Q

: - 9 - Stirred during the reaction.

The organic cationic compounds of the invention were prepared according to standard methods of the prior art from an amine having the desired number of long chain alkyl groups bound to the nitrogen atom. This long chain alkylamine was then reacted by reductive alkylation with an aldehyde or by nucleophilic replacement of an alkyl halide to form the wenated ammonium ammonium compound.

The liquid of the present invention may contain a TO aqueous phase containing aqueous solutions of inorganic suns such as sodium chloride and calcium chloride. While addition of these suns is often optional, these suns increase the osmotic pressure of the water phase to stabilize formations containing hydratable clays.

The concentration of water in the fluid is determined by photores such as fluid weight requirements, desired flow properties, subterranean temperatures and the operating requirements of drilling or nit feed. In general, the foreknowledge deserves a volume percentage. to use water ranging from about 2 to about 50%. This range makes the oil-based liquid fire resistant after exposure to temperatures which ignited the liquid. In addition, the liquid has a nit-stabbing tolerance to water contamination and the flow properties of the liquid can be controlled at values comparable to those of water-based liquids.

When using an aqueous phase in the liquid, conventional emulsifiers should be used for the water-in-oil phase. Emulsifying agents can also be used in the non-aqueous liquid. The amount of emulsifying agent used depends primarily on the amount of water present and the degree of emulsion desired. Generally, 5-7 to 85.5 kg / m 2 and, for example, 2.85 to 43 kg / m 2, have been found to be sufficient to achieve emulsion stability.

The compositions may optionally contain conventional means of heating, such as barite for controlling the liquid density between 0.9 and 2.65 kg / dm 2, as well as means for controlling the flow loss.

The smectite-type clays used in the examples were hectorite and Wyoming bentonite. The clay was dispersed in water and centrifuged to remove substantially all non-clay impurities, which can make up to 10% to about 50% of the starting clay composition. The Wyoming bentonite clay slurry was passed through a bed of a cation exchange resin to convert it to the sodium form.

The exemplary organic cationic compounds are representative of the cations of the invention and are not intended to be the only compounds useful for use.

The following examples are given to illustrate the invention, but are not intended to limit it.

10 All percentages given are by weight unless otherwise indicated. The plastic viscosity, yield strength and 10 second angels were measured according to the method described in API 1P13B, American Petroleum Institut4s Standard Procedure for Testing fluids, Pressure, April 1976

Example I

Allmethyl-di (hydrogenated tallow oil) -ammonium chloride (abbreviated AM2HT).

824.7 S methyl di- (hydrogenated tallow oil) amine, 350 ml isopropanol, 250 g NaHCO 3, 191.3 S allyl chloride and 10 g 20 allyl bromide (as catalyst) are placed in a 4 liter reaction vessel equipped with a cooler mixture is heated and refluxed. A sample was removed, filtered and titrated with HCl and ITaOH. The reaction was run completely at 0.0% amine HCl and 1.8% amine. The final analysis 25 showed an effective molecular weight of 831.17 *

Examples II-IT

A three percent clay suspension, the sodium form of

Wyoming bentonite for Examples II and III and hectorite for Example IT were heated to 60 ° C with stirring. An isopropanol solution of an organic cationic compound, etbanol-methyl-di- (hydrogenated tallow oil) ammonium chlorine [EM2HT] - (Armak Company, Division of Akzona Corp.) at an 80 percent activity in Example II and AH2HT, prepared in Example I, for Examples III and IT was added to the clay suspension and stirred for 20 min. The organoclay product was collected on a vacuum filter. The filter cake was washed with water at 60 ° C and dried at 60 ° C. The dried organic clay product was ground using a hammer mill to reduce the particle size and sieved through a sieve with a mesh size of 0.074 8105189 "- 11-Examples Y-YIII.

97.1 1 Diesel oil, 3> 6 kg emulsifier (invermul, HL Industries Inc.), 3.6 kg filtration control agent, amine lignite (Duratone HI, HI Industries Inc.), 1.8 kg lime and 17.5 1 water 5 were stirred for 20 minutes.

11.8 kg of calcium chloride, 147 kg of barite (Baroid, HL Industries Inc.) and 2.3 kg of the two bentonite clay thickeners prepared in Examples II and III in addition to two commercial products, dimethyl di (hydrogenated tall oil) ammonium chloride [2M2H1] / bentonite and benzylmethyl-di- (hydrogenated tall oil) ammonium chloride [BM2H1] / bentonite.

The mixed liquid was examined at 35.0 ° C for standard rheological data and the results are reported in Table A. None of the examples sedimented after stirring.

15 label A.

Yoorbeeld · Gelling Yloei limit 10 sec gel 10 min gel 2 2 2

Highlighter kg / on kg / out kg / cm Y EM2HT / ent oni et 88.2. 44.1 63.7 YI AM2HT / bentonite 98 53.9 68.6 20 YII 2Μ2ΞΦ / bent oni 147 78.4 9 3.1 YIII BM2HT / bent oni 107.6 68.6 88.2

The undisturbed batches of Examples Y-YIII were rolled at 60 ° C for 16 hours, and no sedimentation was observed in any of the examples. The lots were examined at 20.7 ° C on 25 standard rheological data as in Example Y. The results are shown in Table B below. None of the examples sedimented.

label B ".

Yoorbeeld Yloe boundary 10 sec gel 10 min gel 30 Ho. kg / cm kg / cm kg / cm Y 93.1 44.1 68.6 VI 83.3 53.8 73.5 YII 98, 63.7, 88.2 YIII 102.9 68.6 93.1

Examples IX-XI. II

Batches of 350 ml liquids, consisting of 98 L diesel oil, 3.6 kg emulsifier (Invermul, HL Industries Inc.), 3.6 kg amine lignite filtration control aid1 (Duratone, HL.

8105189 - 12 -

Industries Inc.), 2.26 lay lime, 52.7 liters of 1.5 kg / ml calcium chloride, 145 2 kg water containing barite (Baroid, HI Industries Inc.) were mixed, 15 minutes in a Hamilton Beach mixer stirred and stirred to -2.22 ° G in an ice bath. Am concentration of 5 1? » 1 kg / m2 of the clay products EM2HT / bentonite, IM2HT / bentonite and AM2HT / hectorite prepared according to examples II, III and. In addition to the two commercial clay products 2H2HT / bentonite and BM2HT / bentonite described in Examples YII and Till, were stirred in the cold liquid batches for a period of 5 minutes at low shear with a Lightnin mixer. Two cold samples in a viscometer cup were placed on a ffann 35 viscometer and at 600 rpm. stirred while the temperature rose to 21.1 ° C. The batches were then placed in a set of cup jackets preheated to 51 ° C and heated to 43 ° C. Plastic viscosity, yield strength and 10 sec. gels were measured at every 2.8 ° C increase between -1.11 ° C to 21.1 ° C and at every 5.55 ° G increase between 21.1 ° C and 43 ° 0. The results of the measurements are shown in Figure 1.

Examples ΧΙΙΙ-ΧΠΙ were stirred at 46 ° C for 15 minutes in a Hamilton Beach mixer and cooled to 26.7 ° C and tested as in Example T. The results are shown in Table G.

Table G

Tooree Glow limit 10 sec. gel 10 min. gel 2 2 2 25 Ho. _ kg / cm kg / cm_ kg / cm___ IX 205.8 73.5 93.1 X 274.4 107.8 132.3 XI 333.2 186.2 225.4 XII 245 102.9 127.4 50 XIII 245 112.7 137.2

Torques ΧΙΤ-ΧΠΙ

Liquids consisting of 65.2 l of diesel oil and 5.4 kg of gelling clay products prepared according to Examples II and III were mixed in addition to the commercial clay products 2M2HT / b onon and BM2HT / -55 bentonite and stirred in a Hamilton Beach mixer for 5 minutes at low speed. Liquids consisting of 0.14 kg of diesel oil, 8.2 kg of asphalt (Baroid asphalt, NB. Industries Inc.) and 124.7 kg of barite (Baroid, NL Industries Inc.) were prepared and mixed with the previously prepared liquids for forming lots from 550 8105189

V

-13- * ml, which were stirred in a Hamilton Beach mixer for 15 minutes.

350 ml samples of Examples XIV through XVII were tested for rheological properties as in Example I at 33 ° 9 ° C. The results are shown in Table B.

5 Table 1)

Example yield strength 10 sec gel 10 min gel * 2 2 2 Mo. kg / cm kg / cm_kg / cm_ XIV 127.4 34.3 264.6 XV 147 53.9 235.2 10 XVI 264.6 166.6 362.6 XVII 122.5 53.9 196

350 ml samples of Examples XIV through XVII were rolled at 66 ° C for 16 hours. After cooling the samples to 26.7 ° C, the sedimentation of solids was checked before measuring the rheological properties, as in Example 1 at 33.9 ° C. The results are shown in Table E.

Table E

Example yield strength 10 sec gel 10 min gel 2 2 2

Mo. kg / om kg / cm kg / cm 20 XIV 279.3 68.6 357.7 XV 392 186.2 568.4 XVI 445.9 268.5 490 XVII 181.1 191.1 539.2

Example XIV shows improved results when mixed in a non-aqueous liquid. These results show improvements in gel rapid-forming and staying low at the 10 min gel indicating maintenance of pumpability.

8105189 «- Η -

Examples XVIII-XXI

Batches of 350 ml liquids consisting of 112.8 l diesel oil, 2.72 kg emulsifier (EZ mul, HL Industries Inc.), 19.6 l water, 102 kg barite (Baroid, HL Industries Inc.), 10.5 kg Calcium chloride and 2.6 kg of gelling clay products EM2HT / bentonite and AM2HT / bentonite prepared according to example II, respectively. Ill were mixed in addition to 2M2HT / bentonite and BM2Hl / bentonite and stirred in a Hamilton Beach mixer for 20 minutes.

The 350 ml batches of Examples XVIII through XXI 10 were tested for rheological properties as in Example XI at 31 ° C. The results are shown in Table E.

label E

Example Gelling yield strength 10 sec. gel 10 min gel 2 2 2

Ho. Compound kg / cm kg / cm _ kg / cm 15 XVIII EH2HT / bentonite 44.1 19.6 24.5 XIX AM2H! U / b ent oniet 39.2 24.5 29.4 XX 2M2Hl / bentonite 44.1 24 .5 29.4 XXI BM2HT / b ent oni et 39.2 19.6 24.5

350 ml samples of Examples XVIII through XXI were hot rolled for 16 hours at 66 ° C. Ha cool the samples to 26.7 ° C

solids deposition was checked prior to measuring the rheological properties as in Example V at 28.9 ° C. The results are shown in Table G.

Table G

25 Example yield strength 10 sec. gel 10 min gel / 2 2 2 Ho.kg / cm _kg / cm kg / cm_ XVIII 53.9 24.5 39.2 XIX 53.9 24.5 24.5 XX 73.5 39.2 65.6 30 XXI 44.1 19.6 24.5

Rinse cake and filtrate were stirred back into the respective samples and the batches were aged at 177 ° C for 16 hours.

Each batch was cooled to 26.7 ° C, checked for solids sedimentation and electrical stability. The batches were stirred for 5 minutes and examined as in Example V. HT-HP filtrates were run on each batch at 177 ° C. The results are shown in Table H.

8105189 - 15 -

Table 5

Yoorbeeld Yloe border 10 sec. gel 10 min. gel 2 p 2

No. kg / er kg / cm kg / to XVIII 39.2 24.5 24.5 5 XIX 49 19.6 24.5 XX 98.8 24.5 29.4 XXI 39.2 19.6 24.5

Examples beelden-ΧΧΥΠ

Batches of 350 ml liquids consisting of 103 1 heavy oil, 3.6 kg emulsifying agent (invermul, NL Industries Inc.), 18.2 1 water, 147.4 kg barite (Baroid, NI Industries Inc.), 3, 6 kg filtration aid (Buratone, NL Industries Inc.), 10 kg calcium chloride, 1.8 kg lime and 4.1 kg gelling clays EM2HT / ben-tonite, AM2ST / bentonite and AM2HT / hectorite, prepared according to the pre-15 images II, III resp. IT, in addition to 3 hands-free products, dimethyl-di (hydrogenated tall oil) ammonium chloride, 2M2ET / bento-staple, benzyl-methyl-di (hydrogenated tall oil) ammonium chloride, BM2HT / bentonite and dimethyl-di (hydrogenated tallow oil) ammonium chloride, 2M2HT / hectorite Mix and stir for 20 minutes in a Hamilton Beaeh mixer 20.

350 ml samples of Examples XXII to XXYII were tested for rheological properties as in Example Y at 33.3 ° C. The results are shown in Table I.

Table I

25 Yoorbeeld Gelling yield strength 10 sec.gel 10 min.gel

P P P

* No. compound kg / cm kg / oin kg / to XXII EM2HT / bento staple 176.4 53.9 78.4 XXIII AM2HT / bento staple 205.8 88.2 114.7 XXIY AM2HT / hecto 209.5 112 7 132.3 reed XXY 2M2HT / bentonite 294 107.8161.7 35 XXYI BM2HT / bentonite 249.9 107.6 137.2 XXYII BM2HT / hectare 318.5 156.8 191, Ί

Rinse cake and filtrate were stirred back in each batch and the batches aged at 177 ° C for 16 hours. Each batch was cooled to 26.7 ° C and checked for solid sedimentation and electrical stability. The batches were mixed, stirred 8105189 - 16 * 10 for 10 minutes and examined as at Example Y at 32.2 ° C.

The results are shown in Table J.

label J

Yoorbeeld Yloe border 10 sec. gel 10 min. gel 2 2 2 5 No. kg / cm_kg / cm kg / cm XXII 98 78.4 107.6 XXIII 137.2 112.7 132.3 XXIT 151.9 147 161.7 XXV 166.6 88.2 127.4 10 XXVI 127.4 107 , 6 142.1 XXVII 181.3 137.2 171.5

350 ml lots of Examples XXIII, XXIY, XXY and XXVII were aged at 149 ° C, 204 ° C and 232 ° C for 16 hours. The batches were assayed at 37.2 ° C as before and the results are shown in Table E.

Table Σ

Yoorbeeld Temperatunr Yloe Limit 10 sec.gel 10 min.gel 2 2 2 No. ° C__kg / cni kg / oin kg / cm XXIII 149 102.9 102.9 112.7 20 204 220.5 68.6 147 _212_6JJ_Mil_78.4 XXIY 149 151.9 147 161.7 204 735 200.9 279.3 _212_322_107.8_171.5 25 XXY 149 186.2 137.2 181.3 204 132.3 53.9 98 _212_MJ_2 £ i2_68.6 XXVII 149 181.3 137.2 171.5 204 538 196 294 30 _212_126_§1 * 1_142_

It will be clear to the person skilled in the art that the nitvin content can be varied in many ways.

- conclusions - 8105189

Claims (18)

1. Oil-based liquid, characterized by the presence of an oil phase and about 2.85 to 142.5 kg / m 2 of an organophilic clay-gelling agent containing the reaction product of an organic cationic compound and a clay of the smectite. type with a cation exchange density of at least 75 milliequivalents per 100 g clay, which organic cation has the formula of the figure sheet, wherein B1 sekoz “is the e * 0 ** ^ a Μ-0» τ · ΓΜ41β «Βalkyl group having less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms and mixtures thereof, Rg is an alkyl group having 8 to 60 carbon atoms, and R ^ are individually selected from the group consisting of a βjJ ' -saturated alkyl group with less than 7 aliphatic carbon-15 atoms, a hydroxyalkyl group with 2 to 6 carbon atoms, an aralkyl group, an alkyl group with 1 to 22 carbon atoms and mixtures thereof, X is selected from the group consisting of phosphorus and nitrogen, and where the h the amount of the organic cationic compound is 90 to 140 milliequivalents per 100 g clay, based on 100% active clay. 2. Oil-based Yul liquid, labeled. in the presence of an oil phase and about 17.1 to 142.5 kg / m 2 of an organophilic clay gelling agent containing the reaction product comprising an organic cationic compound and a smectite type clay with a cation exchange capacity of at least 75 milliequivalents per 100 g of clay, which organic cation has the formula of the figure sheet, wherein R ^ is selected from the group consisting of a β, "-unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxyalkyl group of 2 to 6 carbon atoms and mixtures thereof, Rg is an alkyl group of 8 to 60 carbon atoms, R ^ and R ^ are individually selected from the group consisting of a β, β-unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroxyalkyl group having 2 up to 6 carbon atoms, an aralkyl group, an alkyl group having 1 to 22 carbon atoms and mixtures thereof, X is selected from the group consisting of phosphorus and nitrogen, and wherein the amount of the organ ionic cationic compound is $ 0 to 140 milliequivalents per 100 g clay, based on 100% active clay. 8105189 - 18 - 3 · Method for isolating a casing in a wellbore, in which an oil-based fill fluid is pumped into an annular space within the drill point and after which the fill fluid is gelled, characterized in that a fill fluid is used, which comprises an oil phase and approximately 17.1 to about 142.5 kg / kg of an organophilic clay gelling agent, which gelling agent contains the reaction product of an organic cationic compound and a smectite-type clay with a cation exchange capacity of at least 75 milliequivalents per 100 g clay which organic cation has the formula of the figure sheet, wherein is selected from the group consisting of a β, Y-unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroryalkyl group with 2 to 6 carbon atoms and mixtures thereof, E ^ is an alkyl group having 8 to 60 carbon atoms, E ^ and E ^ 15 are selected individually from the group consisting of a β,--unsaturated alkyl group with less than 7 aliphatic carbon atoms, a hydroryalkyl group of 2 to 6 carbon atoms, an aralkyl group, an alkyl group of 1 to 22 carbon atoms and mixtures thereof, X is selected from the group consisting of phosphorus and nitrogen, and wherein the amount of the organic cationic compound is 90 to 140 milliequivalents per 100 g clay, based on 100% active clay. Gelling agent according to claims 1-3, characterized in that the smectite-type clay is selected from the group consisting of hectorite and sodium bentonite. Gelling agent according to claims 1-3, characterized in that E 4 is a β, Y unsaturated group selected from the group consisting of cyclic groups, acyclic alkyl groups with less 7 carbon atoms, acyclic alkyl groups substituted with aromatic groups, aromatic groups substituted with aliphatic groups and mixtures thereof. Gelling agent according to claims 1-3, characterized in that E 1 / hydroxyalkyl group is selected from the group -. consisting of cyclic groups, acyclic aliphatic groups and mixtures thereof, which aliphatic groups contain hydroryl substitution at the second to sixth carbon atom. Gelling agent according to claims 1-3, characterized in that Eg contains from 12 to 22 carbon atoms. 8. Gelling agent according to claim 7, characterized in that E 4 is a long chain fatty acid group. 8105189 r - 19 - S 9. Gelation medium 1 according to claims 1 - 3, characterized in that the amount of organ cation is 100 to 130 milliequivalents per 100 g clay, based on 100% active clay. r 10. The liquid of claim 1, characterized in that the liquid additionally contains a dispersed aqueous phase containing from about 2 to about 50 percent water by volume. 11. Liquid according to claim 10, characterized in that the liquid additionally contains a water-in-oil emulsifier. 12. Liquid according to claim 11, characterized in that the emulsifying agent contains approximately 5-7 to 85.5 kg / ml liquid. 15 Yul liquid according to claim 2 or 3, characterized in that the liquid additionally contains a dispersed aqueous phase containing from about 2 to about 50 volume percent water. Yul liquid according to claim 13, characterized in that the liquid additionally contains a water-in-oil emulsifying agent. 15. Liquid according to claim 14, characterized in that the emulsifying agent contains about 5> 7 to about 85 kg / dm liquid. 25. 16. Liquid according to claim 1, characterized in that the liquid is not water-retaining. 17 Liquid according to claim 2 or 3, characterized in that the liquid is not water-retaining. 18. The liquid of claim 1, wherein the gelling agent is from about 2.85 to about. Contains 28.5 kg / m2 liquid. 8105189