CN101421371A - Methods of preparing hydrocarbon, water and organophilic clay emulsions and compositions thereof - Google Patents
Methods of preparing hydrocarbon, water and organophilic clay emulsions and compositions thereof Download PDFInfo
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- CN101421371A CN101421371A CNA2007800137731A CN200780013773A CN101421371A CN 101421371 A CN101421371 A CN 101421371A CN A2007800137731 A CNA2007800137731 A CN A2007800137731A CN 200780013773 A CN200780013773 A CN 200780013773A CN 101421371 A CN101421371 A CN 101421371A
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Abstract
This invention relates to compositions and methods for improving the performance of organophilic organic-clay complexes, which are dispersible in organic liquids to form a gel therein. Depending on the composition of the gel, such gels may be useful as lubricating greases, oil-based muds, oil base packer fluids, paint-varnish-lacquer removers, paints, foundry molding sand binders, adhesives and sealants, inks, polyester laminating resins, polyester gel coats, cosmetics, detergents, and the like.
Description
Technical field
The present invention relates to improve the composition and the method for the performance of the close organism clay complex that in organic liquid, is used to form gel and other composition.The visual composition of described composition and as lubricating grease, oil-base mud, oil base placement fluid, paint-varnish-lacquer paint remover, paint, foundry sand binding agent, tackiness agent and sealing agent, printing ink, polyester layer pressurizing resin, polyester gel coating, makeup, sanitising agent and its analogue.
Background technology
Organic clay
As everyone knows, contain cationic organic compound and can under favourable condition, form close organism organic clay product (being referred to herein as " organic clay " and " close organism clay " (OC)) by ion-exchange and the clay reaction that contains minus layer lattice and exchangeable cation.If organic cation contains at least one alkyl that contains at least 10 carbon atoms, so described organic clay will have expansible characteristic in some organic liquid usually.For example referring to United States Patent (USP) the 2nd, 531, No. the 2nd, 966,506, No. 427 and United States Patent (USP), two patents all are incorporated herein by reference; With the works " Clay Mineralogy " of Ralph E.Grim, nineteen sixty-eight second edition (McGraw-Hill Book Company, Inc.), the 10th chapter especially, Clay-Mineral-OrganicReactions; 356-368 page or leaf-Ionic Reactions, Smectite; With 392-401 page or leaf-Organophilic Clay-Mineral Complexes (also being incorporated herein by reference).
From the commercial organic clay of introducing of earlier 1850s, increasing people has known maximum gelling (thickening) efficient that can realize described composition in the organic clay by the low molecular weight polar organic materials is added to.Described polarity organic materials has multiple title: dispersion agent (dispersant), dispersing auxiliary, solvating agent, dispersion agent (dispersion agent) and its similar title.For example referring to No. the 2nd, 677,661, the United States Patent (USP) of following United States Patent (USP): O ' Halloran; No. the 2nd, 704,276, people's such as McCarthy United States Patent (USP); No. the 2nd, 833,720, the United States Patent (USP) of Stratton; No. the 2nd, 879,229, the United States Patent (USP) of Stratton; No. the 3rd, 294,683, people's such as Stansfield United States Patent (USP).Find, when using, needn't use described dispersing auxiliary by the specially designed close organism clay that is substituted that quaternary ammonium compound obtains.Referring to United States Patent (USP): No. the 4th, 208,218, the United States Patent (USP) of No. the 4th, 105,578, people's such as Finlayson United States Patent (USP) and Finlayson.Other patent is mentioned and is used specific organic compound to strengthen close organism Dispersion of Clay; United States Patent (USP) the 4th, 434, No. 075.
In this described, known as the those skilled in the art, term parent's organism clay (OC) typically referred to the clay of a class through chemical modification, and known as the those skilled in the art, it has hydrophobicity in various degree.Described clay can derive from wilkinite, hectorite, attapulgite and sepiolite and can prepare by currently known methods.More particularly, OC typically refers to and is processed into the clay that can be scattered in the various liquid hydrocarbons and produce viscosity, and described liquid hydrocarbon includes, but is not limited to ester and the ether and the silicone oil of synthetic oil, alkene, distilled oil, vegetables oil and animal oil, vegetables oil and animal oil.
In specific forms more, preferred OC be lipid acid quaternary amine and wilkinite (a kind of mainly by montmorillonite (Na, Ca)
0.33(Al, Mg)
2Si
4O
10(OH)
2(H
2O)
nThe absorption agent stratiform pure aluminium silicate volcanic ash of forming) structure of bond.In native state, wilkinite is for absorbing the nearly hydrophilic molecule of 7 times water of its weight.
In the process that forms OC, the chemical modification of the clay that the compound of utilization such as quaternary amine carries out can be undertaken by dry method or wet method.Dry method is usually directed in process of lapping quaternary amine is sprayed onto on the dry clay.In wet method, will be scattered in the aqueous solution that contains quaternary amine through pretreated clay or natural clay powder.In general, owing to need comprise the additional processing step of filtration, drying and other procedure of processing, the wet method clay is comparatively expensive.For instance, in wet method, will guarantee higher ion-exchange degree in step after a while with the sodium hydroxide solution pretreated clays.Because the quaternary amine saturation ratio on the clay particle is higher, produces OC preferably so it has been generally acknowledged that wet method.
In the OC building-up process, the nitrogen end of quaternary amine (being water-wet side) positively charged and on the clay plate with sodium or calcium generation ion-exchange.Employed amine is generally the long chain type with 10-18 carbon atom.After about 30% of surface of clay was applied by these amine, it became hydrophobic, and the close organism that becomes after with some amine coating.
After the processing, close organism clay will only absorb and reach about 5 to 10% the water of its weight, but can absorb various oil and the grease that reaches the about 40-70% of its weight.
Quaternary amine can will be decided OC as the validity of tensio-active agent on the R group of quaternary amine.Hydrophobicity R group with 10-18 carbon atom can produce the hydrophobicity tail that makes OC can effectively be used as tensio-active agent.
As be appreciated by one of skill in the art that, also can with other hydrophilic molecule bond to clay particle to produce OC.
When introducing organic clay in the water,, produce the sodium salt of being washed off through the sodium ion of quaternary amine nitrogen metathetical positively charged and dissolved chlorion bond.The result produces the neutral organic clay tensio-active agent with solid substrate.
In oil/water system, the hydrophobic side of amine is dissolved in the organic phase (that is, oil droplet), and OC is contacted with described oil droplet.Because betide " outside " (absorbing oil with respect to the carbon that takes place in the internal clay aperture of undressed clay) of clay particle with the interaction of oil droplet, organic clay can very fast contamination.The hydrophilic edge of clay contacts with water, and generation makes OC serve as the effect of jelling agent.
In addition, close organism clay can serve as the rumbling compound in advance (prepolisher) of activated carbon, ion exchange resin and film (staiing preventing) and serve as the rumbling compound afterwards (post polisher) of oil/water separator, air-dissolving air-float (DAF) unit, vaporizer, film and scum dredger.Parent's organism clay powders can be the component or the major ingredient of cotton-shaped clay powders.OC is for removing the good absorption agent of oil, tensio-active agent and solvent (comprising methyl ethyl ketone, the trimethyl carbinol (TBA) and other chemical).
Oil-base mud
At oil-base mud or oil base drilling fluid in particular cases, in past 50 years with close organism clay as the component of drilling fluid to help to produce drilling fluid with the characteristic of promoting drilling technology.Specifically, use oil base drilling fluid to cool off and lubricate, remove and cut and keep mine entering with controlled liq and gas under pressure.Typical oil-based drilling mud comprises oil ingredient (external phase), water component (disperse phase) and close organism clay, and it mixes and forms gel (being also referred to as drilling mud or oil-base mud).Can contain or be dispersed with emulsifying agent, weighting agent (weightagent), fluid loss agent (fluid loss additive), salt and multiple other additive in the described mud.Drilling mud keeps the ability of viscosity and stability of emulsion to determine the quality of drilling mud usually.
And have the problem of the conventional oil-base mud of OC to be, and along with the progress of drilling well, viscosity and stability of emulsion forfeiture.In general, when utilizing drilling mud to creep into downwards, stability of emulsion will descend, thus need the driller will be in the extra emulsifying agent drawing-in system with the maintenance stability of emulsion.In work, emulsifying agent added to the cost that can increase drilling fluid during the drilling program in the oil-base mud.Making up this problem is, extra emulsifying agent is added to the effect that has the ability of viscosity in the weakening OC maintenance drilling fluid in the oil-base mud, and this ability weakens and needs to add OC again, and this will a) further increase not only the cost and the b of drilling fluid) but also need to add again emulsifying agent.
Therefore, need to have the oil base drilling well solution of good viscosity and stability of emulsion characteristic all the time, thereby make the viscosity of drilling well solution and stability of emulsion high all the time and stable in whole drilling program.
Well-drilling liquid emulgent
The state of the art of well-drilling liquid emulgent be crude tall oil lipid acid (crude tall oil fattyacids, CTOFAs).Crude tall oil is the product of papermaking and pulp industry and is the main by product of the kraft paper of pine or vitriol processing.Crude tall oil begins the form for tall oil soap, and described tall oil soap is that the black liquid separation that reclaims from the kraft paper pulping process obtains.The tall oil soap acidifying is obtained crude tall oil.Subsequently the fractionation of gained Tall oil is produced lipid acid, rosin and pitch.The typical chemical constitution of CTO is showed in the table 1.
Table 1-forms as the typical case of the Tall oil of primary emulsion
| Resinous acid | ||
| Sylvic acid | (CH
3)
4C
15H
17 |
11％ |
| Dehydroabietic acid | (CH
3)
4C
15H
17 |
6％ |
| Isopimaric acid | (CH
3)
3(CH
2)C
15H
23 |
4％ |
| Levopimaric acid | (CH 3) 3(CH 2)C 15H 23COOH | About 2% |
| Neoabietic acid | (CH 3) 4C 15H 17COOH | About 2% |
| Palustric acid | (CH 3) 4C 15H 17COOH | About 2% |
| Pimaric acid | (CH 3) 3(CH 2)C 15H 23COOH | About 2% |
| Total resinous acid | 29％ |
| Saponifiable matter matter not | ||
| Oat steroid enol | 0.0％ | |
| Brassicasterol | C 28H 46O | 0.0％ |
| Campestanol | 0.2％ | |
| Campesterol | C 28H 48O | 1.72％ |
| Cholesterol | C 27H 46O | 0.0％ |
| Desmosterol | C 27H 44O | 0.0％ |
| Ergosterol | C 28H 44O | Trace |
| Fucosterol | C 29H 48O | 0.0％ |
| Lanosterol | C 30H 50O | 0.0％ |
| β-sitostanol | C 29H 50O | 3.3％ |
| β-Gu Zaichun | C 29H 50O | 25.3％ |
| Stigmasterol | C 29H 52O | 0.3％ |
| Total saponifiable matter matter not | 31％ |
The main advantage of CTOFA is that it is relatively inexpensive as emulsifying agent.Yet, in oil-base mud, use CTOFA can not produce high and stable viscosity and stability of emulsion, and in the performance of optimizing close organism clay, do not allow maybe can not control viscosity as emulsifying agent.
Therefore, thus need a class effectively to increase all the time or reduce the viscosity of organic clay/water/fat liquor and stability provides higher degree control to the fluid characteristics of described emulsion emulsifying agent.More particularly, provide method and composition existence needs simultaneously to reducing the cost relevant to the control of the characteristic of described composition with the traditional oils base drilling fluid.
Summary of the invention
According to the present invention, the emulsion of describing preparation hydrocarbon, water and close organism clay with and method for compositions.
In first embodiment, the invention provides a kind of method of controlling oil and the viscosity of the emulsion of water, it comprises following steps: with the emulsifying agent of significant quantity introduce contain close organism clay (organophilic clay, in oil OC) and the emulsion of water with the required viscosity of generation in described emulsion.The emulsifying agent that is selected from hereinafter listed emulsifying agent of significant quantity is for can be used for increasing the emulsifying agent of emulsion viscosity usually.
In described first embodiment, emulsifying agent can be selected from any in the following emulsifying agent:
A.C8-C18 saturated fatty acid (saturated fatty acid, SFA) in any;
B. the adulterant of two or more different C8-C18 SFA;
C. a C8-C18 SFA and at least a 2-5n (n is the double key number order) unsaturated fatty acids (unsaturated fatty acid, adulterant UFA);
D. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil and the mustard caul-fat any vegetables oil; With
E. fatty oil.
Preferred pin is selected the amount of emulsifying agent and close organism clay to required viscosity, so that the performance maximum of close organism clay.
In one embodiment, go back preferred pin to the amount of required viscosity balance parent's organism clay and emulsifying agent so that the amount minimum of close organism clay, and the amount that increases emulsifying agent in proper order is to produce required viscosity.
In addition, can add various emulsifying agents to reduce emulsion viscosity.With described viscosity reduction emulsifying agent and emulsion fusion, and described viscosity reduction emulsifying agent can be selected from unsaturated fatty acids, resinous acid, lanolin, tocopherol, beeswax, oleum lini or the fish oil any or its combination in any one.Efficient viscosity reduction emulsifying agent is a sylvic acid.
In another embodiment, the invention provides a kind of method that is used to control oil and the viscosity of the emulsion of water, it comprises following steps: the emulsifying agent of significant quantity is introduced in the emulsion of the oil that contains close organism clay (OC) and water with the required viscosity of generation in described emulsion, wherein said emulsifying agent is the adulterant of a kind of C8-C18 saturated fatty acid (SFA) and at least a unsaturated fatty acids (UFA), and the ratio of SFA and UFA is through regulating to produce required viscosity.
In another embodiment, the invention provides a kind of method that is used to produce the hydrocarbon/water/close organism clay emulsions with required viscosity, it comprises following steps: a) with hydrocarbon external phase and water-dispersion mutually and the fusion of close organism clay; And b) emulsifying agent of introducing significant quantity.Selected emulsifying agent can and can comprise the tackify emulsifying agent and the viscosity reduction emulsifying agent from any emulsifying agent as indicated above.The amount of can be minimum by the amount that makes close organism clay and increasing emulsifying agent makes the performance maximum of close organism clay thus to produce required viscosity, obtains required viscosity.
In another embodiment, the invention provides a kind of method of controlling oil and the stability of emulsion of the emulsion of water, it comprises following steps: the emulsifying agent of significant quantity is introduced in the emulsion of the oil that contains close organism clay (OC) and water with the required stability of emulsion of generation in described emulsion, wherein said emulsifying agent is a kind of C8-C18 saturated fatty acid (SFA) and at least a unsaturated fatty acids (UFA), and the ratio of SFA and UFA is through regulating to produce required stability of emulsion.
In another embodiment, the invention provides a kind of method that increases oil and the stability of emulsion of the emulsion of water, it comprises following steps: a kind of C8-C18 saturated fatty acid (SFA) emulsifying agent of significant quantity is introduced in the emulsion of the oil that contains close organism clay (OC) and water.
In another embodiment, the invention provides a kind of glossy moist method that increases oil and the emulsion of water, it comprises following steps: at least a unsaturated fatty acids (UFA) emulsifying agent of significant quantity is introduced in the emulsion of the oil that contains close organism clay (OC) and water.
In the present invention on the other hand, the various hydrocarbon/water/close organism clay composition with required viscosity is described.Emulsion comprises hydrocarbon external phase, water-dispersion phase, close organism clay and emulsifying agent.Described emulsifying agent can be selected from:
In the i.C8-C18 saturated fatty acid (SFA) any;
Ii. the adulterant of two or more different C8-C18 SFA;
Iii. the adulterant of C8-C18 SFA and at least a 2-5n unsaturated fatty acids (UFA);
Iv. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil and the mustard caul-fat any vegetables oil; With
V. fatty oil.
In a preferred embodiment, select the amount of close organism clay and emulsifying agent at the required viscosity of described composition, so that the performance maximum of close organism clay.
In various embodiments, close organism clay can be selected from any or its combination in wet method clay or the dry method clay.
Described composition preferably has the stability of emulsion that is higher than 500 volts (volt).
In the present invention on the other hand, a kind of drilling fluid composition is described, it comprises: hydrocarbon external phase, water-dispersion phase, close organism clay and emulsifying agent, described emulsifying agent is selected from mentioned emulsifier.
In various compositions, hydrocarbon: the water ratio is that 1:1 is to 99:1 (volume/volume).
Thereby the emulsifying agent that is preferred for drilling fluid composition produces required viscosity through selecting so that the performance of close organism clay is maximum.
In another embodiment, the present invention describes a kind of method of drilling pit shaft, and it comprises following steps: a) running well series component is with the probing pit shaft; And b) oil base drilling fluid is circulated in pit shaft, described oil base drilling fluid comprises: i) hydrocarbon external phase; Ii) water-dispersion phase; Iii) close organism clay; Iv) emulsifying agent.In other embodiments, can be by adding other emulsifying agents to increase the viscosity of drilling fluid, or add any or its combination in unsaturated fatty acids, resinous acid, lanolin, tocopherol, beeswax, oleum lini or the fish oil of significant quantity to reduce the viscosity of described emulsion, regulate the viscosity of drilling fluid.
Description of drawings
The present invention will be described with reference to graphic, wherein:
Fig. 1 is the figure that illustrates the viscous effect of CTOFA under different concns and shearing rate;
Fig. 2 is the figure that illustrates the viscous effect of C18:1n-9cis under different concns and shearing rate;
Fig. 3 is the figure that illustrates the viscous effect of C18:2n-6cis under different concns and shearing rate;
Fig. 4 is the figure that illustrates the viscous effect of sylvic acid under different concns and shearing rate;
Fig. 5 is the figure that illustrates the viscous effect of C18:3n-3cis under different concns and shearing rate;
Fig. 6 is the figure that illustrates the viscous effect of C22:1n-9cis under different concns and shearing rate;
Fig. 7 is the figure that illustrates the viscous effect of C4-C22 saturated fatty acid under different shearings rate;
Fig. 8 is the figure that illustrates the viscous effect of the C10-C18 saturated fatty acid in the higher density external phase under different shearings rate;
Fig. 9 is the figure that illustrates under different shearings rate than the viscous effect of the C10-C18 saturated fatty acid in the low density external phase;
Figure 10 is the figure that illustrates the viscous effect of C4-C22 saturated fatty acid and higher quality parent organism clay under different shearings rate;
Figure 11 is the figure that illustrates the viscous effect of C4-C22 saturated fatty acid and more low-quality close organism clay under different shearings rate;
Figure 12 is the figure that illustrates the viscous effect of C8-C22 saturated fatty acid and more low-quality close organism clay under different shearings rate;
Figure 13 is the figure that illustrates the viscous effect of C8-C22 saturated fatty acid and higher quality parent organism clay under different shearings rate;
Figure 14 is the figure that illustrates the viscous effect of C8 saturated fatty acid under different concns and shearing rate;
Figure 15 is the figure that illustrates the viscous effect of C12 saturated fatty acid under different concns and shearing rate;
Figure 16 is the figure that illustrates the viscous effect of C16 saturated fatty acid under different concns and shearing rate;
Figure 17 is the figure that illustrates the viscous effect of C18 saturated fatty acid under different concns and shearing rate;
Figure 18 is the figure that illustrates the viscous effect of C22 saturated fatty acid under different concns and shearing rate;
Figure 19 is the figure that illustrates the viscous effect of C12 saturated fatty acid in the presence of the close organism clay at different concns under the different shearings rate;
Figure 20 is the figure that illustrates the viscous effect of the adulterant of C10 and C12 saturated fatty acid under different concns and shearing rate;
Figure 21 is the figure that illustrates the viscous effect of the adulterant of C8 and C12 saturated fatty acid under different concns and shearing rate;
Figure 22 is the figure that illustrates the viscous effect of the adulterant of C12 and C22 saturated fatty acid under different concns and shearing rate;
Figure 23 be illustrate under the different shearings rate and different concns as the water of disperse phase in the presence of the figure of viscous effect of C12 saturated fatty acid;
Figure 24 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and sylvic acid under different concns and shearing rate;
Figure 25 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and α-Pai Xi under different concns and shearing rate;
Figure 26 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and β-Gu Zaichun under different concns and shearing rate;
Figure 27 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and alpha-tocopherol under different concns and shearing rate;
Figure 28 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and α, β, σ and Delta-Tocopherol under different concns and shearing rate;
Figure 29 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and C18:3n-3cis under different concns and shearing rate;
Figure 30 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and C20:5n-3cis under different concns and shearing rate;
Figure 31 is the figure that illustrates the viscous effect of the adulterant of C12 saturated fatty acid and lanolin under different concns and shearing rate;
Figure 32 is the figure that illustrates the viscous effect of C12 saturated fatty acid and mellisic adulterant under different concns and shearing rate;
Figure 33 is the figure that illustrates the viscous effect of commercially available Oleum Cocois adulterant under different shearings rate;
Figure 34 is the figure that illustrates the viscous effect of lanolin under different concns and shearing rate;
Figure 35 is the figure that illustrates the viscous effect of linseed oil under different concns and shearing rate;
Figure 36 is the figure that illustrates the viscous effect of Canola oil under different concns and shearing rate;
Figure 37 is the figure that illustrates the viscous effect of safflower oil under different concns and shearing rate;
Figure 38 is for illustrating in the presence of more low-quality close organism clay and under different shearings rate the figure of the viscous effect of the Canola oil of different concns;
Figure 39 is for illustrating in the presence of more low-quality close organism clay and under different shearings rate the figure of the viscous effect of different concns safflower oil;
Figure 40 is for illustrating in the presence of more low-quality close organism clay and under different shearings rate the figure of the viscous effect of different concns Canola oil;
Figure 41 is the figure that illustrates the viscous effect of commercially available Oleum Cocois under different concns and shearing rate;
Figure 42 is the figure that illustrates the viscous effect of sweet oil under different concns and shearing rate;
Figure 43 is the figure that illustrates the viscous effect of tetradecanoic acid under different concns and shearing rate;
Figure 44 is the figure that illustrates the viscous effect of peanut oil under different concns and shearing rate;
Figure 45 is the figure that illustrates the viscous effect of Oleum Gossypii semen under different concns and shearing rate;
Figure 46 is the figure that illustrates the viscous effect of commercially available Oleum Cocois adulterant under different concns and shearing rate;
Figure 47 is the figure that illustrates red palmitic viscous effect under different concns and shearing rate;
Figure 48 is the figure that illustrates the viscous effect of palm-kernel oil under different concns and shearing rate;
Figure 49 is the figure that illustrates the viscous effect of distillation fatty oil under different concns and shearing rate;
Figure 50 is the figure that illustrates the stability of emulsion of C4-C22 emulsion;
Figure 51 is the synoptic diagram of the molecular structure of OC and monounsaturated fatty acids;
Figure 52 is the synoptic diagram of the molecular structure of OC and two-unsaturated fatty acids;
Figure 53 is the synoptic diagram of the molecular structure of OC and three-unsaturated fatty acids;
Figure 54 is the synoptic diagram of the molecular structure of three-unsaturated fatty acids and water droplet;
Figure 55 is the synoptic diagram of the molecular structure of two-unsaturated fatty acids and water droplet;
Figure 56 is the synoptic diagram of the molecular structure of monounsaturated fatty acids and water droplet;
Figure 57 is the synoptic diagram of the molecular structure of saturated fatty acid and water droplet;
Figure 58 is the figure that is described in first testing well that uses drilling well solution prepared in accordance with the present invention with respect to the average cost of every day of well depth;
Figure 59 be described in use according in second testing well of the drilling well solution of wood invention preparation with respect to the figure of the average cost of every day of well depth.
Embodiment
According to the present invention, description is through improved hydrocarbon, water and close organism clay composition and prepare described method for compositions.Composition according to the present invention has improved viscosity, and this makes it can be used for multiple application.
More particularly, the invention provides a kind of feasible effective means that can produce hydrocarbon, water and close organism clay composition, " performance " of wherein said composition in-laws organism clay can be through improving in fact, have the composition of specifying viscosity so that can be in making described composition prepare in the amount minimum of close organism clay, also be provided for producing the effective means of composition simultaneously with required adhesive characteristics.Other fluid characteristics also can be improved in described composition.
Because close organism clay can be one of component the most expensive in particular hydrocarbon/water/close organism clay composition (especially with regard to oil base drilling fluid), described method and composition can provide the remarkable cost advantage that is better than previous method and composition, and feasible generation with hydrocarbon/water/close organism clay composition of desired characteristic has higher flexibility.
More particularly, inventor of the present invention has recognized that, uses adulterant, certain plants oil and the fatty oil of adulterant, saturated fatty acid and the unsaturated fatty acids of saturated fatty acid, saturated fatty acid will effectively make hydrocarbon/water/close organism clay composition as the emulsifying agent in hydrocarbon/water/close organism clay composition viscosity than the similar hydrocarbon/water/close organism clay composition of use different emulsifiers " improvement " to some extent.In addition, inventor of the present invention has recognized that, can utilize other emulsifying agent to reduce the viscosity of described emulsion and can control various characteristics by the ratio of regulating between the various emulsifying agents in described emulsion.
In the context of specification sheets of the present invention, described composition and method all relate to oil base drilling well solution, and be as mentioned below, and described drilling well solution comprises hydrocarbon external phase, water-dispersion phase, close organism clay and emulsifying agent.The amount of hydrocarbon phase and water can be from being low to moderate 50:50 (hydrocarbon: water (volume/volume)) to not waiting up to 99:1 in the designated emulsion.At the lower limit of this scope, the lower in fact and ability that change viscosity of stability of emulsion need be added a large amount of close organism clays in the mixture to.Similarly, in the upper limit, the ability of viscosity is more difficult in the control emulsion.Therefore, 80:20 is to the roughly hydrocarbon of 90:10 (volume/volume): the water ratio is the practical ratio that is generally used for drilling well solution.
In specification sheets of the present invention, will have the hydrocarbon of 90:10 (volume/volume): the representative drilling well solution of water ratio illustrates the effect of emulsifying agent to close organism clay performance, viscosity and stability of emulsion as standard.In addition, utilize the scope of the close organism clay of relative narrower with respect to the ratio of total solution quality.In this tittle each all is elected to be practical amount to be illustrated and changes the effect with respect to the amount of other component of close organism clay and/or emulsifying agent.Although in the entire area of the ratio that described composition can prepare, do not experimentize, it will be understood by one of ordinary skill in the art that if change a parameter, will be regulated to compensate the change of other parameter another parameter so.
Therefore, in the context of specification sheets of the present invention, should be appreciated that the change of a parameter may need to change at least one other parameter to optimize the performance of described composition.For instance, if hydrocarbon is specified in described generation: the target of the composition of water ratio is to make the consumption minimum of close organism clay in the described composition, it will be understood by one of ordinary skill in the art that so, the amount that may need to regulate close organism clay and emulsifying agent in the described composition is to obtain to realize the composition of described target, although and described optimization method is not easy to conclude, should be and be appreciated by one of skill in the art that.
Experiment
With the close organism clay of difference (OC) and various hydrocarbon and emulsifier mix to measure the effect of OC, hydrocarbon and emulsifying agent to viscosity and stability of emulsion.Described experiment detects the effect of close organism clay composition (quality) and emulsifying agent structure, comprises chain length, saturation ratio, position of double bond and effect with respect to the weight percent of different external phase in-laws' organism clays.
As shown in table 2, following close organism clay is studied.
Table 2-parent organism clay
| Clay | Manufacture method | Quality/relative cost |
| IMG-400 TM | Wet method | In |
| |
Wet | High |
| Bentone | ||
| 920 TM | Dry | Low |
| Claytone | ||
| 3 TM | Wet method | In |
| Claytone EM TM | Wet method | High |
In the context of specification sheets of the present invention, term is low, neutralization is high is meant the general classification of OC being carried out about relative cost and processing stage.
Hydrocarbon
The representative hydrocarbon of being tested as external phase is showed in the table 3.
Table 3-is as the hydrocarbon of external phase
| Hydrocarbon | Relative density |
| HT 40N TM | The intermediate |
| Distillate | |
| 822 TM | Than heavy gas oil cut, acidity |
| Amodril 775 TM | Light ends |
Also can be with other hydrocarbon (ester and the ether that comprise synthetic oil, vegetables oil and vegetables oil) as external phase.
Base fluid
Produce the drilling fluid base fluid for test, indivedual compositions that wherein can change described composite are to detect the effect to drilling fluid properties.The drilling fluid base fluid be hydrocarbon, water, close organism clay and emulsifying agent can miscible mixture.The general composite of drilling fluid base fluid is showed in the table 4.
Table 4-drilling fluid base fluid
| Component | Volume % | |
| Oil | ||
| 90 | ||
| |
10 | |
| Calcium chloride (CaCl 2) | 25 weight % of water | |
| Parent's organism clay | 5.7 weight % of water * | |
| Unslaked lime (CaO) | 28.5 weight % of water * | |
| Emulsifying agent | 0.95 weight % of water * |
*Unless otherwise mentioned
Preparation
With oil, water, calcium chloride and close organism clay high-speed mixing slurries with the generation high dispersing.Continue to mix and reach 70 ℃ up to slurry temperature.Emulsifying agent is added in the individual samples of each solution and again with high-speed mixing 3 minutes.Add CaO subsequently and with high speed fusion 2 minutes.Known as the those skilled in the art, according to standard drilling fluid preparation procedure add calcium chloride as additive so that the secondary fluid stabilization to be provided.
Subsequently before test, in the container that rolls of heat, make sample thermal ageing 18-24 hour to simulate downward drilling condition.
Fluid property measurement
Using Fan Shi speed change concentric cylinder viscometer (Fann Variable Speed concentriccylinder viscometer) to carry out viscosity measures.(Round per minute, RPM) data point is collected at the some place at 600,300,200,100,6,3 rev/mins.
In specification sheets of the present invention, the viscosity that viscous effect is defined as a kind of solution that utilizes variable emulsifying agent is compared the quantity increase (Fig. 1) of use CTOFA as the viscosity of the similar solution of emulsifying agent.Relative shear stress (viscosity) is for being used at the dial reading of specifying on Fann 35 variable speed caplastometers of measuring fluid viscosity under the rpm.Think and do not represent viscous effect at the viscosity reading in the 0-20 scope under the shearing rate of 300-600rpm; Think that the viscosity reading in the 20-40 scope shows less viscous effect; Think that the viscosity reading in the 40-100 scope shows significant viscous effect, and think that being higher than 100 viscosity reading shows very significant viscous effect.
Use OFI stability of emulsion survey meter to measure stability of emulsion.Measure by carrying out each in the solution that the ES probe is inserted 120 ℉ [48.9 ℃].The ES survey meter applies increasing voltage (0 to 1999 volt (volt)) automatically between the electrode gap of described probe.The peak voltage that solution before the conduction is kept between the gap is shown as ES voltage.It should be noted that so in fact, 2000 volts stability of emulsion is not actual ES because survey meter has reached maximum capacity and in fact some measured ES values surpass 2000 volts.
Emulsifying agent research
Carry out the experiment summarized among Fig. 1-6 with the degree of unsaturation of research emulsifying agent for the effect that increases through the viscosity of modification base fluid.Under each situation, use IMG 400 to prepare base fluid as OC.As shown in Figure 1, block crude tall oil lipid acid (CTOFA) is used as emulsifying agent so that the baseline of viscosity research to be provided.CTOFA represents " state of the art " of emulsifying agent in the drilling fluid composition.
Result shown in Fig. 1-6 and the table 5 shows that block CTOFA is as the effect (Fig. 1) of the emulsifying agent of the dispersion polar phase of emulsion and the effect (Fig. 2-6) that constitutes the main lipid acid of CTOFA.
Sponifiable component (table 1) to crude tall oil is carried out initial testing.As shown in table 1, crude tall oil contains the 35-40% unsaturated fatty acids usually, and wherein most of acid is: oleic acid C18:1n-9cis, linolic acid C18:2n-6cis; 20-30% resinous acid is generally sylvic acid (diterpene) C
20H
30O
2With the 30-40% plant sterol, be generally β-Gu Zaichun.
In addition, also carry out increasing the effect of degree of unsaturation to measure to close organism clay performance about the test of the effect of α-linolic acid C18:3n-3cis and C22:1n-9cis.
The research of table 5-emulsifying agent
Fig. 1 illustrates under different CTOFA content, and block CTOFA convection cell viscosity does not have effect.In addition, under different CTOFA content, the stability of emulsion of CTOFA emulsion is less than 500 volts (table 12).
Fig. 2 illustrates under higher concentration and shearing rate, and oleic acid (C18:1n-9cis) has minimum effect as primary emulsion to the viscosity that strengthens base composition.
Fig. 3 illustrates linolic acid (C18:2n-6cis) does not have effect as primary emulsion for the viscosity that strengthens base composition.
Fig. 4 illustrates sylvic acid as the inviscid effect of primary emulsion, and shows that in fact it has the viscosity reduction effect under the dosage that increases.
Fig. 5 illustrates α-linolic acid (C18:3n-3-cis) and does not produce viscous effect as primary emulsion.
Fig. 6 illustrates mustard seed (C22:1n:9-cis) lipid acid and does not produce viscous effect as primary emulsion.
Generally speaking, the result of Fig. 1-6 shows that the main fatty acid component of block crude tall oil and crude tall oil does not produce any viscous effect.
Importantly, the main lipid acid of crude tall oil all has at least one two key in the hydrocarbon chain separately at it.
Chain length research
Referring to Fig. 7-13 and table 6, research is as the effect of the chain length of the saturated fatty acid of primary emulsion.Also study the variation of the effect of OC, oil phase composition and some additive.
The research of table 6-chain length
Fig. 7 summarizes the viscous effect of C4-C22 saturated fatty acid in the composition that comprises middle distillate oil phase and ordinary quality wet method OC (IMG 400).The result shows at C12-C18 lipid acid under the higher shear rate to have remarkable viscous effect and have less viscous effect than C12-C13 lipid acid under the low shearing rate.
Fig. 8 summarizes the viscous effect of C12-C18 saturated fatty acid in the composition that comprises heavier fraction oil phase (Distillate 822).The result shows that C11-C13 lipid acid has less viscous effect under the higher shear rate.
Fig. 9 general introduction comprise than in the composition of light fraction oil phase (Amodril) as the viscous effect of the C10-C18 saturated fatty acid of primary emulsion.The result show C11-C16 lipid acid under the higher shear rate have remarkable viscous effect and under the intermediate range shearing rate C11-C16 lipid acid have less viscous effect.Observe the peak value viscous effect about C11 lipid acid.
Figure 10 general introduction comprises in the composition of higher quality wet method adulterant OC (Bentone 150) and intermediate density oil phase HT 40N the viscous effect as the C4-C22 saturated fatty acid of primary emulsion.The result show C12-C16 lipid acid under the higher shear rate have remarkable viscous effect and under the intermediate range shearing rate C12-C16 lipid acid have less viscous effect.The peak value viscosity that it should be noted that described OC is less than utilizing the viewed viscosity of more low-quality OC among Fig. 7.Observe the peak value viscous effect about C12 lipid acid.
Figure 11 general introduction comprises in the composition of more cheap dry method adulterant OC (Bentone 920) viscous effect as the C4-C22 saturated fatty acid of primary emulsion.The result show C12 lipid acid under the higher shear rate have extremely significantly viscous effect and under the higher shear rate C12-C18 have remarkable viscous effect.Observe the peak value viscous effect about C12 lipid acid.
Figure 12 general introduction comprises in the composition of more cheap wet method adulterant OC (Claytone 3) viscous effect as the C8-C22 saturated fatty acid of primary emulsion.The result show C12-C18 lipid acid under the higher shear rate have remarkable viscous effect and under the intermediate range shearing rate C12-C18 lipid acid have less viscous effect.Observe the peak value viscous effect about C12 lipid acid.
Figure 13 general introduction comprises in the composition of expensive wet method adulterant OC (Claytone EM) viscous effect as the C8-C22 saturated fatty acid of primary emulsion.The result show C12 lipid acid under the higher shear rate have extremely significantly viscous effect and under the higher shear rate C12-C18 lipid acid have remarkable viscous effect.Observe the peak value viscous effect about C12 lipid acid.
Generally speaking, Fig. 7-13 shows that the OC quality has minimum effect for viscosity, and this explanation viscous effect need not to use the OC of higher quality.In addition, the C11-C18 saturated acid produces significantly or very significant viscous effect.
The concentration repercussion study
Referring to Figure 14-19 and table 7, study the effect of the concentration of primary emulsion at saturated fatty acid with different chain length.
The research of table 7-dose response
Figure 14 is illustrated under the higher shear rate, saturated C8 lipid acid as primary emulsion at 2.0 lipid acid: represent less viscous effect under the close organism clay ratio (w/w).
Figure 15 is illustrated under the higher shear rate, saturated C12 lipid acid as primary emulsion greater than 2 lipid acid: represent very significant viscous effect under the close organism clay ratio (w/w).When lipid acid: observe peak value viscosity when close organism clay ratio is 6.Under all shearings rate, about greater than 3 lipid acid: observe remarkable viscous effect under the close organism clay ratio.
Figure 16 is illustrated under the higher shear rate, saturated C16 lipid acid as primary emulsion greater than 3 lipid acid: represent very significant viscous effect under the close organism clay ratio (w/w).In the scope of being tested, do not observe peak value viscosity.Under the intermediate range shearing rate, about greater than 1.0 lipid acid: close organism clay ratio is observed remarkable viscous effect.
Figure 17 is illustrated under the higher shear rate, saturated C18 lipid acid as primary emulsion at 3.5 lipid acid: represent very significant viscous effect under the close organism clay ratio (w/w).When lipid acid: when close organism clay ratio is 3.5, observe peak value viscosity.Under the intermediate range shearing rate, about greater than 1.5 lipid acid: close organism clay ratio is observed remarkable viscous effect.
Figure 18 is illustrated under the higher shear rate, saturated C22 lipid acid as primary emulsion greater than 3 lipid acid: represent less viscous effect under the close organism clay ratio (w/w).
Very significant viscous effect appears down in the dosage that Figure 19 is illustrated in 1.25 pounds every barrel (ppb) close organism clays under the higher shear rate, and is occurring remarkable viscous effect greater than 0.5ppb under the close organism clay under the intermediate range shearing rate.
Generally speaking, Figure 14-19 shows and can change lipid acid at different lipid acid: close organism clay ratio is to produce viscous effect.
Adulterant research
Referring to Figure 20-22 and table 8, the effect that research is blended together saturated fatty acid.
The research of table 8-adulterant
Referring to Figure 20, illustrating increases the effect of C12 saturated fatty acid with respect to the amount of C10 saturated fatty acid.This experiment shows that under high shear rate, the C10:C12 ratio of certain limit represents significantly or very significant viscous effect, and is being higher than under the situation of threshold value, and the interaction of C10 lipid acid and C12 lipid acid will destroy viscous effect.
Referring to Figure 21, illustrating increases the effect of C12 saturated fatty acid with respect to the amount of C8 saturated fatty acid.This experiment shows that under high shear rate, the C8:C12 ratio of certain limit represents significantly or very significant viscous effect, and is being higher than under the situation of threshold value, and the interaction of C8 lipid acid and C12 lipid acid will destroy viscous effect.This experiment is further illustrated under some adulterant ratio, the enhancing of viscous effect may occur.
Referring to Figure 22, illustrating increases the effect of C22 saturated fatty acid with respect to the amount of C12 saturated fatty acid.This experiment shows that under relatively low C22 concentration, increasing the C22:C12 ratio can the negative impact viscous effect.
Generally speaking, Figure 20-22 displaying synergistic effect occurs as between the lipid acid adulterant of primary emulsion.According to relative concentration, some interactions can be positive interaction and some can be negative interaction.
Water effect research
Referring to Figure 23 and table 9, research increases the effect of water for the amount of oil phase (external phase).
Table 9-water effect research
Referring to Figure 23, illustrate and use IMG 400 OC, for C12 lipid acid, increase the effect of the volume % of water with respect to hydrocarbon phase.The result show the relative ratios that can increase water with produce significantly or very significant viscous effect up to observing steady section.
The adulterant of C12 and other lipid acid
Figure 24-32 and table 10 are showed the result with saturated C12 lipid acid and multiple other fatty acid molecule fusion.
Other lipid acid adulterant research of table 10-C12/
Referring to Figure 24, illustrating increases the effect of sylvic acid with respect to the amount of C12 saturated fatty acid.This experiment shows that the sylvic acid of relatively small amount can destroy viscous effect.
Referring to Figure 25, illustrating increases the effect of α-Pai Xi with respect to the amount of C12 saturated fatty acid.This experiment shows that α-Pai Xi can not influence viscous effect.
Referring to Figure 26, illustrating increases the effect of β-Gu Zaichun with respect to the amount of C12 saturated fatty acid.This experiment shows that when the amount of β-Gu Zaichun increased, the β-Gu Zaichun appropriateness reduced viscous effect.
Referring to Figure 27, illustrating increases the effect of alpha-tocopherol with respect to the amount of C12 saturated fatty acid.This experiment shows that alpha-tocopherol significantly reduces viscous effect when the amount of alpha-tocopherol increases.
Referring to Figure 28, illustrating increases the effect of alpha-tocopherol with respect to the amount of C12 saturated fatty acid.This experiment shows that alpha-tocopherol significantly reduces viscous effect when the amount of alpha-tocopherol increases.
Referring to Figure 29, illustrating increases the effect of highly unsaturated fatty acids (C18:3n:3cis) with respect to the amount of C12 saturated fatty acid.This experiment shows that described unsaturated fatty acids significantly reduces viscous effect when the amount of unsaturated fatty acids increases.
Referring to Figure 30, illustrating increases the effect of highly unsaturated fatty acids (C20:5n) with respect to the amount of C12 saturated fatty acid.This experiment shows that described unsaturated fatty acids significantly reduces viscous effect when the amount of unsaturated fatty acids increases.
Referring to Figure 31, illustrating increases the effect of lanolin fatty acid with respect to the amount of C12 saturated fatty acid.This experiment shows that lanolin significantly reduces viscous effect when the amount of lanolin increases.
Referring to Figure 32, illustrating increases the effect of beeswax with respect to the amount of C12 saturated fatty acid.This experiment shows that beeswax significantly reduces viscous effect when the mellisic amount increases.
Seed, plant and other oil research
Referring to Figure 33-49 and table 8, research is with the effect as primary emulsion of various seeds, plant and other oil.
Table 11-seed, plant and other oil research
The viscous effect of individual fatty acids
| Emulsifying agent | Form explanation | Two keys | Greatest viscosity (nominal) | Explanation | Graphic |
| Prifrac 5926 Prifrac 7902 Prifrac 7902 Dial Oleum Cocois Prifrac 9642 | About 94% saturated fatty acid in the commercially available prod of Oleum Cocois | 60 | Most of coconut oil product is showed remarkable v effect under the higher shear rate | 33 | |
| Lanolin | Be mainly the mixture and the IMG400 fusion of cholesterol and fatty acid ester | 10 | No v effect | 34 | |
| Linseed oil | Comprise linolenic acid (omega-fatty acid) and IMG400 fusion | A plurality of | 15 | No v effect | 35 |
| The mustard caul-fat | Comprise linolenic acid (omega-fatty acid) and IMG400 fusion | A plurality of | 35 | Less v effect | 36 |
| Thistle oil | Comprise linolenic acid and IMG400 fusion | A plurality of | 20 | No v effect | 37 |
| The mustard caul-fat | With Bentone 920 fusion | A plurality of | 80 | Low-quality OC produces remarkable v effect | 38 |
| Thistle oil | With Bentone 920 fusion | A plurality of | 15 | No v effect | 39 |
| The mustard caul-fat | With Claytone II fusion | A plurality of | 42 | Low-quality OC produces less v effect | 40 |
| The distillation Oleum Cocois | With IMG 400 fusion | Less | 250 | Very significant v effect | 41 |
| Sweet oil | Be mainly single unsaturated and how unsaturated and IMG 400 fusion | A plurality of | 60 | Remarkable v effect appears | 42 |
| Tetradecanoic acid (obtaining) by plam oil | C14 and IMG 400 fusion | Do not have | 140 | Very significant v effect | 43 |
| Peanut oil | (wherein containing palmitinic acid (C16:0) and oleic acid (C18:1)) and IMG 400 fusion | In the oleic acid 1 | 30 | Less v effect | 44 |
| Oleum Gossypii semen | Linolenic acid (C18:2n) | 2 | 28 | Less v effect | 45 |
| (containing palmitinic acid, oleic acid and linolenic acid) | With IMG 400 fusion | (linolenic acid) | |||
| Uniqema Prifrac 5926 coco-nut oil fatty acids | With IMG 400 fusion | Less | 260 | Very significant v effect | 46 |
| Red plam oil | 50:50 is saturated: unsaturated and IMG 400 fusion | Have | 68 | Remarkable v effect | 47 |
| Palm-kernel oil | 50:50 is saturated: unsaturated and Bentone 920 fusion | Have | 80 | Remarkable v effect | 48 |
| The distillation fatty oil | 40:60 is saturated: unsaturated and |
Have | 130 | Very significant v effect | 49 |
Referring to Figure 33, the viscous effect of more different commercially available Oleum Cocois.Described figure illustrates that each Oleum Cocois has remarkable viscous effect under high shear rate.
Referring to Figure 34, illustrate the effect of lanolin as primary emulsion.Utilize this lipid acid not observe viscous effect.
Referring to Figure 35, illustrate the effect of linseed oil as primary emulsion.Utilize this oil not observe viscous effect.
Referring to Figure 36, illustrate of the effect of mustard caul-fat as primary emulsion.Under the higher shear rate, utilize concentration to be higher than 3.5 described oil and observe less viscous effect.
Referring to Figure 37, illustrate the effect of Thistle oil as primary emulsion.Utilize this oil not observe viscous effect.
Referring to Figure 38, illustrate in the presence of more low-quality OC, the mustard caul-fat is as the effect of primary emulsion.Under the higher shear rate, utilize concentration to be higher than 3.0 described oil and observe remarkable viscous effect.
Referring to Figure 39, illustrate in the presence of more low-quality OC, Thistle oil is as the effect of primary emulsion.Utilize this oil not observe viscous effect.
Referring to Figure 40, illustrate in the presence of more low-quality OC, the mustard caul-fat is as the effect of primary emulsion.Under the higher shear rate, utilize concentration to be higher than 4.0 described oil and observe less viscous effect.
Referring to Figure 41, illustrate of the effect of commercially available Oleum Cocois as primary emulsion.Under intermediate range and higher shear rate, utilize concentration to be higher than 2.0 described oil and observe very significant viscous effect.In concentration is 4.0 o'clock, and peak value viscosity is 250.
Referring to Figure 42, illustrate the effect of sweet oil as primary emulsion.Under the higher shear rate, utilize concentration to be higher than 4.0 described oil and observe remarkable viscous effect.
Referring to Figure 43, illustrate the effect of tetradecanoic acid as primary emulsion.Under the higher shear rate, utilize concentration to be higher than 6 described lipid acid and observe very significant viscous effect, and under intermediate range and higher shear rate, utilize concentration to be higher than 4 described lipid acid and observe remarkable viscous effect.
Referring to Figure 44, illustrate the effect of peanut oil as primary emulsion.Under the higher shear rate, utilize concentration to be higher than 4.0 described oil and observe less viscous effect.
Referring to Figure 45, illustrate the effect of Oleum Gossypii semen as primary emulsion.Under the higher shear rate, utilize concentration to be higher than 4.0 described oil and observe less viscous effect.
Referring to Figure 46, illustrate of the effect of commercially available Oleum Cocois as primary emulsion.Under intermediate range and higher shear rate, be higher than 2.0 described oil and observe very significant viscous effect about concentration.Under intermediate range and higher shear rate, be higher than 1.0 described oil and observe remarkable viscous effect about concentration.The peak value viscosity of observing described oil is about 260.
Referring to Figure 47, illustrate of the effect of red plam oil as primary emulsion.Observe remarkable viscous effect at the described oil that utilizes concentration under the higher shear rate in the 3-4.5 scope and under for the concentration of intermediate range shearing rate at 3-4.
Referring to Figure 48, illustrate in the presence of more low-quality OC, palm-kernel oil is as the effect of primary emulsion.Under intermediate range and higher shear rate, utilize concentration to be higher than 3.0 described oil and observe remarkable viscous effect.
Referring to Figure 49, illustrate in the presence of more low-quality OC, the distillation fatty oil is as the effect of primary emulsion.Under the higher shear rate, utilize concentration to be higher than 4.0 described oil and observe very significant viscous effect.For the intermediate range shearing rate, utilize concentration to be higher than 2.0 described oil and observe remarkable viscous effect.
Generally speaking, each vegetable oil and especially various Oleum Cocois all produce very significant viscous effect.Do not observe the existence of unsaturated chain and the dependency between the viscous effect.Use more inferior OC as if to produce good viscous effect.
The emulsion-stabilizing Journal of Sex Research
Referring to Figure 50, relatively utilize the stability of emulsion of C4-C22 saturated fatty acid as the various emulsions of emulsifying agent preparation.
As comparing as the stability of emulsion of the similar emulsion of emulsifying agent preparation, can find out that stability of emulsion is higher when SFA is used as emulsifying agent with using baseline CTOFA (table 12).
Table 12-stability of emulsion CTOFA
CTOFA
(weight/0.5 1 1.5 2 2.5 3 3.5 4
Weight)
Volt 428 384 487 440 469 465 378 373
The discussion of molecular structure
Referring to Figure 51-58, schematically illustrate the molecular structure of compound in oil/water/close organism clay emulsions.Molecular structure shows that the operability in the free hydrogen bond site on the close organism clay is important for the ability that emulsion produces viscosity.It is believed that and prevent H
2O is at the OH at close organism clay edge
-Site provides edge-edge bond or makes the I of possibility of described bond influence the viscosity of oil/water miscible liquid.Parent's organism clay is depicted in the platy structure that association quaternary amine on the outside surface of clay particle reaches typical saturation ratio.A plurality of outside OH-group on parent's organism clay panel edges can form hydrogen bond with the adjacent OH-on the adjacent close organism clay plate.
Figure 51-53 more specifically illustrates increases the interactional effect of degree of unsaturation for unsaturated fatty acids and clay plate.Figure 54-56 illustrates the interaction of unsaturated fatty acids and water droplet.Should be appreciated that two keys of unsaturated fatty acids produce partial charge, it can form hydrogen bond with clay plate OH-group, and this can further influence the ability that clay particle forms hydrogen bond each other together with any stearic acid effect.It is believed that unsaturated fatty acids disturbs to disturbing emulsion to produce the mechanism of the ability of viscosity the part of clay panel edges-edge bond.Similarly, the stearic acid effect can influence the ability that unsaturated fatty acids contacts with water droplet.
Figure 57 be SFA with and with the interactional synoptic diagram of water droplet.Since saturated fatty acid only effectively with the quaternary amine and the water droplet interaction of clay plate so that the hydrophobicity tail of quaternary amine and saturated fatty acid will tangle under the situation of no stearic acid effect, be the mechanism of improved viscosity and stability of emulsion effect so believe this.
The clay performance
Data shows, comprises that the performance than low-quality clay of IMG400, Bentone 920, Claytone 3 can both provide and the suitable tackifying ability of close organism clay that comprises the higher price of Bentone 150 and Claytone EM.This observations shows the less close organism clay of needs is prepared the product with required viscosity.In addition, the cost of the required clay of described product will tail off.
In addition, data shows, for the close organism clay of specified amount, selects emulsifying agent or emulsifying agent adulterant to can be used for effectively increasing the viscosity of emulsion, and improves " performance " of close organism clay thus.
Therefore, by understanding the validity that some emulsifying agent improves the ability of close organism clay performance, the content of adulterant that can be by regulating tackify emulsifying agent (such as the C12 saturated fatty acid) or various emulsifying agents customizes the composition with desired characteristic.In fact, can be at the amount of required viscosity balance parent's organism clay and emulsifying agent so that the amount minimum of close organism clay, and the amount that increases emulsifying agent in proper order is to produce required viscosity.
Use
Drilling fluid
Specifically, the emulsion stabilization property that is provided by saturated fatty acid can be used for strengthening the characteristic of oilwell drilling liquid.In general, the past is used for the adulterant of unsaturated fatty acids the organic solution of fuel feeding well probing usefulness.As indicated above, a problem relevant with the oil well probing is, owing to there is the problem of viscous fracture, needs to reduce the amount of the drilling fluid that is utilized.In addition, the glossy wet effect that also needs control to tie compound in the caused well by the hydrogen bond between (in-well) compound in the various wells (such as borehole cuttings (drill cutting)) and the emulsifying agent.
Using saturated fatty acid to make operator effectively to make as emulsifying agent makes close organism clay consumes least and allows the good drilling fluid composition of controlling viscosity and stability of emulsion.Therefore, the method according to this invention and composition reduction can adhere to the amount of the oil base drilling fluid on the compound in the well, thereby the loss (low operator's cost) and the minimizing that reduce oil base drilling fluid are disposed relevant environmental influence and the cost of compound (such as borehole cuttings) in the contaminated well with (in case of necessity).
Field test data
Carry out test in place and reduce the cost relevant with the oil base drilling fluid program to determine whether to utilize according to composition of the present invention.Representative test in place (Figure 58 and 59) is carried out in two stages of branch.In the 1st stage, utilize based on the initial testing well 1 of drilling fluid system and 2 that uses the CTOFA emulsifying agent.When reaching casing setting depth (casing point), this system is used and has the oil base drilling fluid replacement of Bentone 920/ squeezing Canola oil (primary emulsion)/lauric acid (secondary emulsifiers).
After introducing drilling fluid prepared in accordance with the present invention, find that the rapid reduction of cost of two wells and the routine maintenance cost of drilling fluid also reduce.The cost of two wells drops to about 1000 dollars/day (or lower) from about 4000 dollars/day, reduces about 75%.Follow-up well all request for utilization person's drilling fluid begins, and under each situation, it can both keep the low daily cost mean value that No. 1 and No. 2 testing well reached.
Other application
The close organism clayish solution that contains saturated fatty acid to need to can be used for improving in the various products of viscosity/stability of emulsion of close organism clay performance and/or control combination thing, such as industrial chemical, grease and makeup.More specifically get on very well, described application can comprise lubricating grease, oil base placement fluid, paint-varnish-lacquer paint remover, paint, foundry sand binding agent, tackiness agent and sealing agent, printing ink, polyester layer pressurizing resin, polyester gel coating, makeup, sanitising agent and its analogue.
Should be appreciated that above stated specification comprises the example that notion of the present invention is described, and, wish that described example does not limit the scope of the invention as being appreciated by one of skill in the art that.
Claims (23)
1. method of controlling oil and the viscosity of the emulsion of water, it comprises introduces in the emulsion of the oil that contains close organism clay (OC) and water the emulsifying agent of significant quantity with the step of the required viscosity of generation in described emulsion, and wherein said emulsifying agent is selected from any in following each thing:
In the a.C8-C18 saturated fatty acid (SFA) any;
B. the adulterant of two or more different C8-C18 SFA;
C. the adulterant of C8-C18 SFA and at least a 2-5n unsaturated fatty acids (UFA);
D. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil, palm-kernel oil and the mustard caul-fat any vegetables oil; With
E. fatty oil.
2. method according to claim 1 is wherein selected the amount of emulsifying agent and close organism clay, so that the performance maximum of described close organism clay at described required viscosity.
3. method according to claim 1, wherein at the amount of described close organism clay of required viscosity balance and emulsifying agent so that the amount minimum of described close organism clay, and the amount that increases described emulsifying agent in proper order is to produce described required viscosity.
4. according to the described method of arbitrary claim in the claim 1 to 3, it comprises following steps in addition: with in unsaturated fatty acids, resinous acid, lanolin, tocopherol, beeswax, oleum lini or the fish oil of significant quantity any or its combination fusion to reduce the viscosity of described emulsion.
5. method according to claim 4, wherein said resinous acid are sylvic acid.
6. method of controlling oil and the viscosity of the emulsion of water, it comprises introduces in the emulsion of the oil that contains close organism clay (OC) and water step with the required viscosity of generation in described emulsion with the emulsifying agent of significant quantity, wherein said emulsifying agent is the adulterant of a kind of C8-C18 saturated fatty acid (SFA) and at least a unsaturated fatty acids (UFA), and the ratio of SFA and UFA is through regulating to produce described required viscosity.
7. a generation has the method for the hydrocarbon/water/close organism clay emulsions of required viscosity, and it comprises following steps:
A) mutually and the fusion of close organism clay with hydrocarbon external phase and water-dispersion; With
B) emulsifying agent of introducing significant quantity, described emulsifying agent is selected from any in following each thing:
In the i.C8-C18 saturated fatty acid (SFA) any;
Ii. the adulterant of two or more different C8-C18 SFA;
Iii. the adulterant of C8-C18 SFA and at least a 2-5n unsaturated fatty acids (UFA);
Iv. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil, palm-kernel oil and the mustard caul-fat any vegetables oil; With
V. fatty oil.
8. method according to claim 7, wherein said required viscosity are that amount minimum by the amount that makes described close organism clay and that increase described emulsifying agent obtains to produce described required viscosity.
9. method of controlling oil and the stability of emulsion of the emulsion of water, it comprises introduces in the emulsion of the oil that contains close organism clay (OC) and water step with the required stability of emulsion of generation in described emulsion with the emulsifying agent of significant quantity, wherein said emulsifying agent is a kind of C8-C18 saturated fatty acid (SFA) and at least a unsaturated fatty acids (UFA), and the ratio of SFA and UFA is through regulating to produce described required stability of emulsion.
10. method that increases oil and the stability of emulsion of the emulsion of water, it comprises introduces step in the emulsion of the oil that contains close organism clay (OC) and water with a kind of C8-C18 saturated fatty acid (SFA) emulsifying agent of significant quantity.
11. a method that increases oil and the glossy moisture performance of the emulsion of water, it comprises introduces step in the emulsion of the oil that contains close organism clay (OC) and water with at least a unsaturated fatty acids (UFA) emulsifying agent of significant quantity.
12. the hydrocarbon/water/close organism clay composition with required viscosity, it comprises:
Hydrocarbon external phase;
The water-dispersion phase;
Parent's organism clay; With
Emulsifying agent, described emulsifying agent is selected from:
In the i.C8-C18 saturated fatty acid (SFA) any;
Ii. the adulterant of two or more different C8-C18 SFA;
Iii. the adulterant of C8-C18 SFA and at least a 2-5n unsaturated fatty acids (UFA);
Iv. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil, palm-kernel oil and the mustard caul-fat any vegetables oil; With
V. fatty oil,
Wherein select the amount of close organism clay and emulsifying agent, so that the performance maximum of described close organism clay at the required viscosity of described composition.
13. composition according to claim 12, wherein said emulsifying agent through selecting so that the performance of close organism clay is maximum and produce required viscosity.
14. according to claim 12 or 13 described compositions, wherein said close organism clay is selected from any or its combination in wet method clay or the dry method clay.
15. according to the described composition of arbitrary claim in the claim 12 to 14, wherein said emulsion has the stability of emulsion greater than 500 volts.
16. a drilling fluid composition, it comprises:
Hydrocarbon external phase;
The water-dispersion phase;
Parent's organism clay; With
Emulsifying agent, described emulsifying agent is selected from:
In the i.C8-C18 saturated fatty acid (SFA) any;
Ii. the adulterant of two or more different C8-C18 SFA;
Iii. the adulterant of C8-C18 SFA and at least a 2-5n unsaturated fatty acids (UFA);
Iv. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil, palm-kernel oil and the mustard caul-fat any vegetables oil; With
V. fatty oil.
17. composition according to claim 16, wherein said hydrocarbon: the water ratio is 1: 1 to 99: 1 (volume/volume).
18. according to claim 16 or 17 described compositions, wherein said emulsifying agent through selecting so that the performance maximum of close organism clay, thereby produce required viscosity.
19. according to the described composition of arbitrary claim in the claim 16 to 18, wherein said close organism clay is selected from any or its combination in wet method clay or the dry method clay.
20. according to the described composition of arbitrary claim in the claim 16 to 19, wherein said emulsion has the stability of emulsion greater than 500 volts.
21. a method of drilling pit shaft, it comprises following steps:
A. the well series that turns round component is with the probing pit shaft; With
Oil base drilling fluid is circulated in described pit shaft, and described oil base drilling fluid comprises:
I. hydrocarbon external phase;
Ii. water-dispersion phase;
Iii. close organism clay; With
Iv. emulsifying agent, described emulsifying agent is selected from:
1.C8-C18 any in the saturated fatty acid (SFA);
2. the adulterant of two or more different C8-C18 SFA;
3. the adulterant of C8-C18SFA and at least a 2-5n unsaturated fatty acids (UFA);
4. be selected from Thistle oil, sweet oil, Oleum Gossypii semen, Oleum Cocois, peanut oil, plam oil, palm-kernel oil and the mustard caul-fat any vegetables oil; With
5. fatty oil.
22. method according to claim 21, it further is included in before the step b or during step b, by adding other emulsifying agents to increase the viscosity of described drilling fluid, or add any or its combination in unsaturated fatty acids, resinous acid, lanolin, tocopherol, beeswax, oleum lini or the fish oil of significant quantity to reduce the viscosity of described emulsion, regulate the viscosity of drilling fluid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74514306P | 2006-04-19 | 2006-04-19 | |
| US60/745,143 | 2006-04-19 | ||
| US60/747,152 | 2006-05-12 |
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| CN101421371A true CN101421371A (en) | 2009-04-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710968A (en) * | 2013-12-17 | 2015-06-17 | 中国石油化工集团公司 | Plugging material and drilling fluid additive and use method thereof |
| CN110291170A (en) * | 2017-02-03 | 2019-09-27 | 沙特阿拉伯石油公司 | Reversed-phase emulsion base drilling fluid and its application method |
-
2007
- 2007-04-18 CN CNA2007800137731A patent/CN101421371A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710968A (en) * | 2013-12-17 | 2015-06-17 | 中国石油化工集团公司 | Plugging material and drilling fluid additive and use method thereof |
| CN110291170A (en) * | 2017-02-03 | 2019-09-27 | 沙特阿拉伯石油公司 | Reversed-phase emulsion base drilling fluid and its application method |
| US11078396B2 (en) | 2017-02-03 | 2021-08-03 | Saudi Arabian Oil Company | Spacer fluid compositions, methods, and systems for aqueous based drilling mud removal |
| US11078397B2 (en) | 2017-02-03 | 2021-08-03 | Saudi Arabian Oil Company | Spacer fluid compositions, methods, and systems for aqueous based drilling mud removal |
| US11098232B2 (en) | 2017-02-03 | 2021-08-24 | Saudi Arabian Oil Company | Lubricants for water-based drilling fluids |
| US11248157B2 (en) | 2017-02-03 | 2022-02-15 | Saudi Arabian Oil Company | Emulsifier compositions for invert emulsion fluids and methods of using the same |
| US11365339B2 (en) | 2017-02-03 | 2022-06-21 | Saudi Arabian Oil Company | Development of retarded acid system |
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