GB2123804A - Dispersible alpha-aluminate monohydrate - Google Patents
Dispersible alpha-aluminate monohydrate Download PDFInfo
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- GB2123804A GB2123804A GB08316521A GB8316521A GB2123804A GB 2123804 A GB2123804 A GB 2123804A GB 08316521 A GB08316521 A GB 08316521A GB 8316521 A GB8316521 A GB 8316521A GB 2123804 A GB2123804 A GB 2123804A
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- United Kingdom
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- process according
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- alpha alumina
- reactant
- water
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 49
- 239000012530 fluid Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000005553 drilling Methods 0.000 claims abstract description 45
- 239000000047 product Substances 0.000 claims abstract description 20
- 239000000376 reactant Substances 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000002585 base Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- -1 aluminum compound Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 8
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical group [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 16
- 239000000243 solution Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 229910017089 AlO(OH) Inorganic materials 0.000 abstract 2
- 239000000463 material Substances 0.000 description 22
- 239000002243 precursor Substances 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920005613 synthetic organic polymer Polymers 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 101150112906 fitm-2 gene Proteins 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
An alpha alumina monohydrate, AlO(OH), powder, which is capable of readily dispersing in aqueous solutions to yield a shear-rate thinning mixture useful in drilling fluids, is made by reacting an acid reactant and a base reactant, at least one of which contains aluminum, in an aqueous medium in proportions to yield a solution preferably having a pH of from about 7.5 to 10. Then the mixture is heat treated at a temperature of from about 60 to 100 DEG C for a period of from about 2 to 7 hours. The excess water is removed from the product, e.g. by filtration. The solid can be optionally washed to remove by-product salts and it is then further dried to recover a solid product with greater than 35% AlO(OH).
Description
SPECIFICATION
Dispersible alpha-alumina monohydrate
This invention relates to the production of a alpha alumina monohydrate powder useful as a shear-rate thinning material in drilling fluids.
U.S. Patent No. 4,240,915 (Block) describes water-based, clay-free drilling fluids for use in drilling bore holes into subterranean formations which contain water, a water-loss inhibitor, a weighting agent and aluminum hydroxide as a viscosifying agent. The aluminum hydroxide viscosifying agent is prepared in an aqueous medium by contacting and mixing under a high degree of agitation an acid reactant and a base reactant wherein at least one of the acid or base reactants contains aluminum. The acidic reactant can be either an inorganic acid or a salt of a strong acid and a weak base. These aqueous compositions contain a significant amount of water and are expensive to transport.
To reduce the water weight, attempts have been made to dry the aluminum hydroxide.
However, when it is dried, the aluminum hydroxide powder does not readily disperse back into water to yield the original shear-rate thinning material. Thus this dried form would not be suitable for its intended use at a well site where it should be able to disperse in water to form a shear-rate thinning drilling fluid.
U.S. Patent No. 4,244,835 (Block) described one way to solve this problem of redispersing the dried aluminum hydroxide powder in water. There it was necessary to add a base such as a water soluble alkali metal hydroxide, carbonate or oxide to the mixture and it was further necessary to employ high shear mixing. This technique, however, not only requires the presence of additional chemicals which increase the cost of the drilling fluid but it also requires high shear mixing. In addition the handling of the caustic is hazardous and it may result in the pH of the reaction mixture being too high which would then require readjusting with an acidic material.
The present invention provides a dried alpha alumina monohydrate powder containing an aluminum compound which when expressed as
AIO(OH) is at least about 35% by weight. This dried powder can be readily dispersed in water to yield a highly shear-rate thinning fluid with an n value in the power law model to be discussed below of less than 0.3 without the aid of large quantities of acids, bases or excessive high shear mixing.
The shear-rate thinning alpha alumina monohydrate of the invention is formed in an aqueous system by reacting under a high degree of agitation an acid reactant and a base reactant at least one of which contains aluminum and then thermally treating the product to produce a unique alpha alumina monohydrate form of aluminum hydroxide which can be subsequently dried to a low water content, and in particular to a greater extent than ordinarily produced alpha alumina monohydrate, and then easily redispersed in water to form a shear-rate thinning material without the need for any large quantities of auxiliary dispersing agents or any expensive high shear mixing equipment.
The present invention accordingly provides a process of producing a solid, alpha, alumina monohydrate viscosifying agent containing an aluminum compound which when expressed as
AIO(OH) is present in at least about 35 percent by weight and which is redispersible in water to produce a shear-rate thinning liquid which comprises
a) contacting and mixing in an aqueous medium under a high degree of agitation an acid reactant and a base reactant at least one of which contains aluminum;
b) heating the mixture at a temperature of from about 600C to about 1 000C for a period of from about 2 to about 7 hours.
c) recovering a moist solid product; and
d) drying the moist solid product so that it has an AIO(OH) content of more than about 35 weight percent based on the total weight of product.
Heat treatment of an AIO(OH) gel prior to filtration produces a form of alpha alumina monohydrate which can be dried and later readily redispersed to yield a shear-rate thinning material.
The form of alpha alumina monohydrate described herein is also known as boehmite.
A shear-rate thinning gel is prepared in the preferred form by mixing sodium aluminate and aluminum chloride either as solutions or as solids which are added to water and combined together with high-speed mixing. The proportions are chosen so as to yield a product having a pH between about 7.5 and about 10.0. Then according to the present invention, the reaction product is heated to a temperature of from about 600C to about 1 000C for about 2-7 hours, and then a moist solid product is recovered such as by filtering. If desired, the moist product can be washed with water to remove any by-product salts. The solid product, which can be in the form of a filter cake, is then dried to a product containing at least about 35% AIO(OH). The product is characterized as containing AIO(OH) for convenience of expression, especially since upon heating most of the material is in the boehmite form.There is essentially no trihydrate present such as gibbsite or bayerite. Since there may be some aluminum present in a compound form other than boehmite, the amount of the aluminum present is being expressed by taking the aluminum in the various compounds and expressing it as alpha alumina monohydrate having the formula AIO(OH). The dried product can be readily redispersed in water to its original shear-rate thinning gel form.
In the past alpha alumina monohydrates which is suitable for subsequent dispersion in an aqueous drilling fluid has been dried to a relatively moist powder having only about a 20% AIO(OH) concentration with the remaining 80% water and by-product salts. If the powder were dried to a
significantly higher alpha alumina monohydrate
concentration, it could not be later dispersed in
water to serve as an effective vicosifying agent.
For these relatively moist 20% alpha alumina
monohydrate powder compositions, the weight of the water and salt is four times as much as is the weight of the alpha alumina monohydrate. In other words, the weight of water and salt is 400% of the weight of the alpha alumina monohydrate
present.
This is a very appreciable amount of water. To reduce shipping costs it is desirable to be able to further decrease the water content while still yielding an alpha alumina monohydrate powder which can be readily dispersed in water. By subjecting the aluminum hydroxide to the thermal treatment according to the present invention it is possible to further dry the alpha alumina monohydrate powder so as to significantly reduce the water content while still having a powder which can be redispersed in water as an effective viscosifying agent and still maintain shear-rate thinning properties after being subjected to bottom hole temperatures of 2500F (121 OC) or greater.
Other moist alpha alumina monohydrate powders can be dried under high temperatures to reduce the water content. However, those powders will not be redispersible in water without the aid of additional dispersing agents. According to the present invention it is possible to obtain a dried alpha alumina monohydrate powder where the weight of water is reduced from 400% to 200% or less based on the weight of the alpha alumina monohydrate present.
The alpha alumina monohydrate agent found useful is substantially water-insoluble. It forms a shear-rate thinning dispersion in aqueous systems. Further, the alpha alumina monohydrate agent presently possess a definite characterizing x-ray diffraction spectrum having a major characterizing diffraction peak at 6.1 1
Angstrom units. The spectrum is determined by standard techniques using the K-alpha doublet of copper as the radiation source.
Conventional alpha alumina monohydrate powders such as Catapal made by Conoco only disperse in water with difficulty to form a viscosifying agent. These conventional powders require high shear or strong acids or bases as dispersing agents. The thermally treated alpha alumina monohydrate according to the present invention can be dispersed easily without excessive high shear or strong acids or bases. The aqueous suspensions or dispersions of the thermally treated alpha alumina monohydrate agent of the present invention having the abovedescribed x-ray characterization is capable of imparting non-Newtonian, pseudoplastic properties to the aqueous system. The alpha alumina monohydrate agent can be initially formed in known manners under substantially basic conditions. It is then given the unique thermal treatment according to the present invention.The agent has hydroxyl groups as an integral part of the agent's composition including bound water of hydration.
Various methods are well known to form the desired agent. It has been found that due to the amphoteric nature of aluminum, the alpha alumina monohydrate agent of the present invention can be formed by contacting an aqueous solution or suspension of an acidic or basic aluminum containing precursor material with a neutralizing agent or wherein both an acid precursor and a base precursor are reacted together. The order of addition is not important; the reactants can be added in any order or simultaneously.
The basic precursor material can be an alkali metal aluminate which is contacted with a sufficient amount of an acidic agent such as inorganic mineral acid, as for example sulfuric, hydrochloric, nitric and the like, and preferably hydrochloric, or a salt of a strong acid and a weak base to cause the pH of the solution to be reduced to within the ranges described further and to thereby convert the aluminate to the alpha alumina monohydrate agent used in the present invention. The acid can be used in slight excess and then back titrated with a base to the desired pH to assure conversion of the precursor to the hydroxide. The aluminate precursor can be any commercially available alkali metal aluminate or the aluminate can be obtained by conventional techniques such as by the action of a base on aluminum or aluminum oxide.The aluminate normally will have an alkali metal oxide to aluminum oxide mole ratio of from about 1:1 to 2:1.
Suitable acidic precursor materials for forming the alpha alumina monohydrate agent are watersoluble, acidic aluminum salts such as aluminum halides, preferably aluminum chloride, as well as aluminum sulfate, aluminum nitrate and the like.
Aqueous solutions of these precursor materials can be contacted with a sufficient amount of water-soluble base, such as an alkali metal hydroxide as, for example, sodium hydroxide, potassium hydroxide and the like or ammonium hydroxide to cause the resultant aqueous system to have a pH within the range described below and to thereby form the desired aluminum hydroxide agent. The base should be used in an amount such that the final pH is between about 7.5 to 10.
The desired alpha alumina monohydrate agent can also be formed from an acidic aluminum precursor material such as a water-soluble acidic aluminum salt as described above with a basic aluminate as described above by contacting the precursory materials in an aqueous system in suitable ratios to cause the resultant system to have a pH within the range described below.
The aluminum hydroxide agents should be formed in an aqueous system which has a pH above about 7.5 to about 10 and preferably a pH of from about 8 to about 9.5. The drilling fluids formed with such aqueous systems having a pH within the range of about 8 to about 10.3 and preferably between about 9 to 10 exhibit the desired properties of viscosity and non
Newtonian pseudoplasticity.
The alpha alumina monohydrate agent can be formed in an aqueous system. The acidic or basic precursor material can be present in concentrations of from about 5 to 50 percent by weight based on the water present. The concentration can vary outside of this range, but should not be such as to inhibit the thorough mixing, preferably under high speed agitation, of the reactants during the formation of alpha alumina monohydrate viscosifying agent.
After the alpha alumina monohydrate has been made it is given the unique thermal treatment which will permit it to be later dried to a higher solids content. The thermal treatment consists of heating at temperatures of about 600C to about 1 000C for from about 2 to 7 hours. If the heating is conducted for too long a period the material becomes too crystalline and it looses its desirable rheological properties, e.g. it can no longer be subjected to treatment at 2500F (121 OC) for 16 hours and still maintain desirable rheology.
The above-described thermally treated alpha alumina monohydrate is capable of yielding a clay-free, (the term "clay-free" when used herein refers to the absence of drilling fluid viscosifying clays as an essential agent of the fluid and not to other materials entrained therein) water-based drilling fluid (the term "fluid" or "system" when used herein refers to water containing the alpha alumina monohydrate agent of the subject invention in solution, suspension or dispersion) having suitable rheological properties of viscosity and non-Newtonian, pseudoplasticity, that is to say, that the viscosity of the resultant waterbased drilling fluid varies inversely with respect to the shear-rate exerted on the fluid.The relationship of the shear stress with respect to shear-rate can be defined by the rheoglogical power law model relationship of TK(p)n in which
T represents the shear stress exerted on the aqueous system of the drilling fluid in units such as pounds per 100 ft2 or dynes/cm2;y is the shear-rate in units of reciprocal times such as sec-';
K is a constant having the value of the shear stress of the particular system at a shear-rate of 1 sec-l; and n is a numerical value of from greater than zero.Water-based drilling fluids containing the presently described thermally treated alpha alumina monohydrate viscosifying agent exhibit shear stress (T) properties at varying shear-rates (put) in the range of from about 10 to 400 sex~', that is, in the range normally encountered in the annular region of the bore hole, such that n of the power law relationship has a value of less than about 0.3. Such systems, therefore exhibit non
Newtonian, pseudoplastic properties to an exceptionally high and desirable degree.
When plotting log shear stress on the ordinate versus log shear-rate on the abscissa of a graph, the slopes and intercepts provide useful information. At low shear-rates, such as from about 10 to about 400 sec-', as are encountered in the annular region of the bore hole, the shear stress should increase at a low rate with respect to the shear-rate exerted on the material which is observed as a low slope (or n value according to the power law relationship) of the curve. The lower the slope of n value within this region the more desirable the fluid. In certain instances the slope may continuously or segmentally change, but it should retain an n value of about 0.3 or less.
At high shear-rates, such as above 50,000 sec-' as are found in the region of a drill bit in a drilling operation, the fluid should have a low viscosity, that is, approach the viscosity of water since this permits high drilling rates. At such viscosities the fluid approaches a Newtonian liquid and there is an increased slope of the curve with n having a value approaching or equal to unity. The value for
K in the power law relationship is the shear stress value determined or extrapolated for a shear-rate of 1 sec-' and is equivalent to the viscosity of the aqueous system at 1 sec-'.
In addition to presently finding that the thermally treated alpha alumina monohydrate agent imparts desired viscosity and pseudoplasticity to water-based drilling fluids it has been further found that this agent has excellent stability to temperature, calcium and sodium salts and various other conditions desired of a fluid used in rotary drilling of bore holes and the like. The drilling fluids containing the subject thermally treated alpha alumina monohydrate agent have been found to have high degrees of stability with respect to their rheological properties under various adverse conditions.Such fluids have been found to be stable after subjections to elevated temperatures for sustained periods of time, to high shear-rates such as are encountered at the site at the drill bit, as well as being stable in the presence of various corrosive elements such as calcium chloride, and sodium chloride which may be entrained in such fluids.
The high degree and breadth of stability of the presently achieved drilling fluid, when combined with its ability to exhibit non-Newtonian, psuedoplastic properties under varying low shear-rates of from about 10 to 400 sec-' and greater, such as are encountered in the annular region between the drill stem and the bore hole wall, aids in increasing the drilling efficiency, that is, the rate of drilling the bore hole. Drilling fluids having concentrations of from about 0.5 to about 5 percent and preferably 2 to 3 percent, active solids (as alpha alumina monohydrate yield fluid systems which have the desired properties.
The drilling fluid composition can contain other conventional drilling fluid additives such as water loss inhibitors as, for example, polyanionic cellulose and the like or cross-linked polyvinyl alcohol as described in United States Patent
Application Serial No. 239,079 filed February 27, 1981, now Patent No. 4349443, the disclosure of which is incorporated herein by reference. The drilling fluid composition can also contain weighting agents as, for example, crushed oyster shells, barite, and the like.
The term "water-based" which is used herein in describing the present invention, generally includes drilling fluids which have a liquid base comprising substantially fresh water or salt water.
However, it is to be realized that at times certain small amounts of other liquids may be emulsified or admixed with the water-based fluid. For example, drilling fluids may at times contain small amounts of oil, emulsified or admixed with the drilling fluid, the oil coming either from an oil formation drilled into or, under certain conditions, can be purposely added.
The presently described drilling fluids have several distinct advantages over fluids using conventional viscosifying agents, such as clays,
Xanthan gums or synthetic organic polymers. The presently described drilling fluids have been found to be stable to various salts commonly found in drilling fluid compositions, while the commonly used clays, such as bentonite or attapulgite, are normally sensitive to the presence of such salts and lose their ability to impart viscosity to the fluids. Such clays should, therefore, not be used as a viscosifier component of the subject drilling fluids. Xanthan gums are also used as the viscosifying agents in drilling fluids, but have the disadvantage of being expensive and unstable at high temperature conditions.The presently described drilling fluids need not contain such heat sensitive viscosifier materials as xanthan gums and, therefore, can maintain their viscosity and pseudoplasticity after subjection to elevated temperatures as is normally encountered in bore holes. Synthetic organic polymers which are used as viscosifiers in drilling fluids are expensive and are only used under special application.
The present water-based, clay-free drilling fluids, having as their viscosifying agent the thermally treated alpha alumina monohydrate agent described above and having a pH within the range of from at least about 8 to 10.3, have been found to be stable to temperature, the presence of calcium and sodium salts and to the presence of conventional drilling fluids, are substantially noncorrosive and non-destructive to metal equipment commonly used in drilling operations.
This material can be used with conventional bore hole drilling equipment in manners known to those skilled in the art to efficiently and effectively drill bore holes into subterranean formations. The pseudoplastic properties of the present drilling fluid permits effective removal of the cuttings from the area at and around the drill bit to permit more efficient drilling of the formation.
Having described the basic aspects of our invention, the following examples are given to illustrate specific embodiments thereof. The values of K in the aforesaid power law relationship are given in lb-sec/1 00 ft2; 1 Ib-sec/100 fit2=0.48 Pa.sec.
Example 1
This example illustrates the preparation of the desired product. Sodium aluminate (124.8 g.
Nalco 680) was dissolved in 2800 g. of water.
Then 99.2 g. of AICI3 6H2O was added with high speed stirring. A gelatinous product was formed, and stirring was continued for 20 minutes.
Stirring was then stopped, and the gel was allowed to set for about 1 6 hours. After reshearing with high speed stirring, the pH was adjusted to 9.5 with Na2CO3 and the material was heated to about 80-900C, with stirring, for 6 hours. After heating, the rheology was measured with an n of 0.25 and a K of 5.2 obtained. The product was filtered and washed twice with 500 ml. of water each time. The cake was dried under vacuum at room temperature to a dry powder which had the following analysis: Al2O3,40.1%; NaCI, 3.1%; total volatiles when heated to 17000 F, (9270C), 57.0%. The material was ground and sieved through a U.S. standard 1 6 mesh (1.19 mm opening) screen.X-ray diffraction analysis showed that the product was alpha alumina monohydrate with a crystallite size of 35
Angstom units.
Example 2
This example illustrates the performance testing of the product prepared in Example 1.
A mixture of 4.2 parts of the product of
Example 1 and 95.8 parts of water was mixed for 20 minutes with a Hamilton Beach mixer. The final mix contained 2.0% AIO(OH). After low shear
mixing for 4 hours with a propeller type stirrer the material was further mixed for 5 minutes with a Hamilton Beach mixer. The rheology was
determined (Haake RV-3) with a MV-1 rotor) and then was 0.30 and the K was 1.25. These values compare well to the original more concentrated
AIO(OH) mix before filtering which had an
AIO(OH) content of 3.1% and which has an n of 0.25 and a K of 5.2.
Example 3
This example shows that a dried AIO(OH) product prepared without the heating step cannot alone be redispersed to yield a shear-rate thinning fluid.
An AIO(OH) gel was prepared as in Example 1, except that the heating step before filtration was omitted. The product was dried to only 25.5% Al203 instead of 40.1% as in Example 1. The product analysis was: Al2O3, 25.5%, NaCI, 2.5%; total volatiles when heated to 1 7000F (9270C), 71.8%.
The product was treated as in Example 2 to give 2.0% AIO(OH) in water. The material did not redisperse, and the rheology was Newtonian since the n value was 1.
Claims (12)
1. A process of producing a solid, alpha alumina monohydrate viscosifying agent
containing aluminum compound which when
expressed as AIO(OH) is present in at least about 35 percent by weight and which is redispersible in water to produce a shear-rate thinning liquid, which comprises
a) contacting and mixing in an aqueous medium under a high degree of agitation an acid reactant and a base reactant at least one of which contains aluminum;
b) heating the mixture at a temperature of from about 600C to about 100 C for a period of from about 2 to about 7 hours;
c) recovering a moist solid product; and
d) drying the moist solid product so that it has an AIO(OH) content of more than about 35 weight percent based on the total weight of product.
2. A process according to Claim 1 , further comprising washing the recovered product to remove by-product salts.
3. A process according to Claim 1 or 2, wherein the acid reactant is an aluminum halide and the base reactant is an alkali metal aluminate.
4. A process according to Claim 3, wherein the alkali metal aluminate and the aluminum halide are added in proportions to yield a solution having a pH of from about 7.5 to about 10.
5. A process according to Claim 1 or 2, wherein the acid reactant is hydrochloric acid and the base reactant is sodium aluminate.
6. A process according to Claim 5, wherein the hydrochloric acid and sodium aluminate are added in proportions to yield a solution having a pH of from about 7.5 to about 10.
7. A process according to Claim 1 or 2, wherein the acid reactant is hydrochloric acid and the base reactant is potassium aluminate.
8. A process according to Claim 7, wherein the hydrochloric acid and potassium aluminate are added in proportions to yield a solution having a pH of from about 7.5 to about 10.
9. A process according to any of Claims 1 to 8, wherein the moist solid product is recovered by filtration.
10. A process according to Claim 1 substantially as hereinbefore described.
11. A dried alpha alumina monohydrate viscosifying agent made by the process of any of claims 1 to 10.
12. A process of drilling a bore hole into a subterranean formation using conventional bore hole drilling equipment, in which a drilling fluid having as its viscosifying agent the dried alpha alumina monohydrate of Claim 11 dispersed in water is circulated in the bore hole while drilling.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39111282A | 1982-06-23 | 1982-06-23 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8316521D0 GB8316521D0 (en) | 1983-07-20 |
| GB2123804A true GB2123804A (en) | 1984-02-08 |
| GB2123804B GB2123804B (en) | 1985-08-07 |
Family
ID=23545293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08316521A Expired GB2123804B (en) | 1982-06-23 | 1983-06-17 | Dispersible alpha-aluminate monohydrate |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2123804B (en) |
| NO (1) | NO832281L (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2151606A (en) * | 1983-12-21 | 1985-07-24 | Grace W R & Co | Dispersible alpha alumina monohydrate having increased viscosifying properties |
| US4780307A (en) * | 1984-10-23 | 1988-10-25 | Rafa Laboratories Ltd. | Aluminum hydroxide |
| US4849190A (en) * | 1986-05-05 | 1989-07-18 | Petroflex, Industria E Comercio S.A. | Process for the production of hydrated alumina and process for the treatment of acid wastes |
| WO2015189203A1 (en) * | 2014-06-13 | 2015-12-17 | IFP Energies Nouvelles | Gel with high dispersibility and method for preparing same |
| WO2017129497A1 (en) * | 2016-01-29 | 2017-08-03 | IFP Energies Nouvelles | Method for producing an alumina gel having a high dispersibility and a specific crystallite size |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1304963A (en) * | 1970-05-25 | 1973-01-31 |
-
1983
- 1983-06-17 GB GB08316521A patent/GB2123804B/en not_active Expired
- 1983-06-22 NO NO832281A patent/NO832281L/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1304963A (en) * | 1970-05-25 | 1973-01-31 |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2151606A (en) * | 1983-12-21 | 1985-07-24 | Grace W R & Co | Dispersible alpha alumina monohydrate having increased viscosifying properties |
| US4584108A (en) * | 1983-12-21 | 1986-04-22 | W. R. Grace & Co. | Dispersible alpha alumina monohydrate having increased viscosifying properties |
| US4780307A (en) * | 1984-10-23 | 1988-10-25 | Rafa Laboratories Ltd. | Aluminum hydroxide |
| US4849190A (en) * | 1986-05-05 | 1989-07-18 | Petroflex, Industria E Comercio S.A. | Process for the production of hydrated alumina and process for the treatment of acid wastes |
| JP2020073429A (en) * | 2014-06-13 | 2020-05-14 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Highly dispersible gel and method for preparing the same |
| FR3022235A1 (en) * | 2014-06-13 | 2015-12-18 | IFP Energies Nouvelles | HIGH DISPERSIBILITY GEL AND PROCESS FOR PREPARING THE SAME |
| CN106687412A (en) * | 2014-06-13 | 2017-05-17 | Ifp 新能源公司 | Gel with high dispersibility and method for preparing same |
| CN106687412B (en) * | 2014-06-13 | 2018-03-13 | Ifp 新能源公司 | Gel with polymolecularity and preparation method thereof |
| RU2694751C2 (en) * | 2014-06-13 | 2019-07-16 | Ифп Энержи Нувелль | Gel with high degree of dispersibility and method of its production |
| WO2015189203A1 (en) * | 2014-06-13 | 2015-12-17 | IFP Energies Nouvelles | Gel with high dispersibility and method for preparing same |
| US10858262B2 (en) | 2014-06-13 | 2020-12-08 | IFP Energies Nouvelles | Gel with high dispersibility and method for preparing same |
| WO2017129497A1 (en) * | 2016-01-29 | 2017-08-03 | IFP Energies Nouvelles | Method for producing an alumina gel having a high dispersibility and a specific crystallite size |
| FR3047238A1 (en) * | 2016-01-29 | 2017-08-04 | Ifp Energies Now | PROCESS FOR PREPARING ALUMINA GEL HAVING HIGH DISPERSIBILITY AND SPECIFIC CRYSTALLITE SIZE |
| CN108495817A (en) * | 2016-01-29 | 2018-09-04 | Ifp 新能源公司 | The method for producing the alumina gel with high degree of dispersion and specific die size |
| RU2731569C2 (en) * | 2016-01-29 | 2020-09-04 | Ифп Энержи Нувелль | Method of producing aluminum oxide gel having high dispersibility and crystallite size |
| CN108495817B (en) * | 2016-01-29 | 2021-02-02 | Ifp 新能源公司 | Method for producing alumina gel with high degree of dispersion and specific grain size |
| US11577964B2 (en) | 2016-01-29 | 2023-02-14 | IFP Energies Nouvelles | Method for producing an alumina gel having a high dispersibility and a specific crystallite size |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8316521D0 (en) | 1983-07-20 |
| NO832281L (en) | 1983-12-27 |
| GB2123804B (en) | 1985-08-07 |
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| PCNP | Patent ceased through non-payment of renewal fee |