CN105419751A - Highly thixotropic emulsifier for anti-high-temperature oil-in-water drilling fluid - Google Patents
Highly thixotropic emulsifier for anti-high-temperature oil-in-water drilling fluid Download PDFInfo
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- CN105419751A CN105419751A CN201510725637.1A CN201510725637A CN105419751A CN 105419751 A CN105419751 A CN 105419751A CN 201510725637 A CN201510725637 A CN 201510725637A CN 105419751 A CN105419751 A CN 105419751A
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 47
- 238000005553 drilling Methods 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 43
- 239000012530 fluid Substances 0.000 title abstract description 18
- 230000009974 thixotropic effect Effects 0.000 title abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000003921 oil Substances 0.000 claims description 37
- 239000013067 intermediate product Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 23
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229920000767 polyaniline Polymers 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 4
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- -1 Yatall MA Chemical compound 0.000 claims description 4
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical group NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 5
- 230000035484 reaction time Effects 0.000 claims 5
- 150000002632 lipids Chemical class 0.000 claims 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims 2
- 150000007524 organic acids Chemical class 0.000 claims 2
- 150000007530 organic bases Chemical class 0.000 claims 2
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 claims 2
- 229960003656 ricinoleic acid Drugs 0.000 claims 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 238000006266 etherification reaction Methods 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 239000003784 tall oil Substances 0.000 claims 1
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000518 rheometry Methods 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 16
- 238000009835 boiling Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229960000935 dehydrated alcohol Drugs 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VSKRSEHLMRRKOS-QJWNTBNXSA-N (z,12r)-12-hydroxyoctadec-9-enamide Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(N)=O VSKRSEHLMRRKOS-QJWNTBNXSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- JRRIJPJVFKVAAF-UHFFFAOYSA-N 1-chloro-3-[(3-chloro-2-hydroxypropyl)-dodecylamino]propan-2-ol Chemical compound CCCCCCCCCCCCN(CC(O)CCl)CC(O)CCl JRRIJPJVFKVAAF-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001347978 Major minor Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Colloid Chemistry (AREA)
Abstract
The present invention relates to a highly thixotropic emulsifier for an anti-high-temperature oil-in-water drilling fluid. The emulsifier mainly solves the problem that an existing anti-high temperature oil-in-water drilling fluid emulsifier has high viscosity, low shear force, and a prepared oil-in-water drilling fluid is poor in cuttings transportation. The emulsifier is prepared by a mixture of two surfactants component I and component II, wherein the component I is a Gemini quaternary ammonium salt surfactant and the component II is an amide surfactant, and the mass percentage ratio of the component I and the component II is 2:1-4:1; the molecular structure of the component I is as follows: R1-N-[(CH2CHOHCH2-N-(CH3)2(CH2)3-CONH-R2)2]2+.2Cl-; and the molecular structure of the component II is: R3-CONH-R4. The highly thixotropic emulsifier for anti-high-temperature oil-in-water drilling fluid selects a raw material containing a cyclic structure to improve the ability of high temperature resistance, so that the drilling fluid can still has highly thixotropic rheology under a high temperature condition.
Description
Technical field
The present invention relates to a kind for the treatment of agent in oil drilling technical field, especially a kind of high temperature water-in-oil drilling emulsifying agent of high thixotroping.
Background technology
When in solution containing a small amount of tensio-active agent time, greatly can reduce surface (and interface) tension force of solution, change the interfacial state of system, thus produce a series of effects such as emulsification, wetting, foaming, solubilising.In field produces, tensio-active agent can as Oilfield drilling fluid oil-water emulsifiers and water-in-oil emulsifier, wetting agent, pore forming material, defoamer, clean-out system, and oil-displacing agent etc. used for tertiary oil recovery.When tensio-active agent is used for invert oil-emulsion drilling fluid; lipophilic group stretches into oil phase; hydrophilic radical gets rid of outside oil phase due to hydrophilic oleophobic effect; therefore define at water-oil interface and align; reduce oil water interfacial tension; aqueous phase is made to be scattered in basic oil phase with stable small droplets form; a kind of wellbore stability ability is strong, protection reservoir is effective to coordinate the treatment agent such as organophilic clay and fluid loss agent to be formed; can be used for water-sensitive strata, saline bed or high-temperature stratum drilling well, there is the drilling fluid of excellent oilness and leak-off building capacity.But because the surfactivity of traditional high temperature water-in-oil drilling emulsifying agent is low, emulsion's stability is poor, insufficient to the wetting action of useful solid phase, cause viscosity high, shear force is low, the problems such as large rock-carrying ability difference, make the application of invert oil-emulsion drilling fluid be restricted.
Summary of the invention
The invention reside in and overcome that the existing high temperature water-in-oil drilling emulsifier viscosity existed in background technology is high, shear force is low, the problem of preparation invert mud large rock-carrying ability difference, and a kind of high temperature water-in-oil drilling emulsifying agent of high thixotroping is provided.The high temperature water-in-oil drilling emulsifying agent of this high thixotroping, have selected raw material containing ring texture to improve the high-temperature resistance of emulsifying agent, drilling fluid can be made still to have the rheological of high thixotroping under the high temperature conditions.
The present invention solves its problem and reaches by following technical scheme: the high temperature water-in-oil drilling emulsifying agent of this high thixotroping, mixed by component I and component I I two kinds of tensio-active agents, component I is Gemini Gemini quaternary ammonium salt style tensio-active agent, component I I is amide surfactants, and the mass percent of component I and component I I is 2:1 ~ 4:1; Described component I molecular structural formula is as follows:
R
1-N-[(CH
2cHOHCH
2-N-(CH
3)
2(CH
2)
3-CONH-R
2)
2]
2+2Cl
-component I I molecular structural formula is: R
3-CONH-R
4
R in formula
1for C
12h
25, C
14h
29, C
16h
33, C
18h
37or C
18h
29, R
2for (C
18h
28o (C
6h
9nO)
m)
nor (C
18h
28(C
6h
9nO)
m)
n, R
3for C
21h
41, C
15h
31or C
17h
33, R
4for C
6h
11or (CH
2)
3n (CH
3)
2.
Emulsifier component I of the present invention belongs to Gemini quaternary ammonium salt style tensio-active agent, containing two hydrophilic head bases in molecular structure, be connected by spacer group, such molecular structure makes Gemini surface active agent compared with conventional surfactant, effectively can stop the electrostatic repulsion between hydrophilic head base same sex electric charge, make hydrophilic radical more be closely arranged in water-oil interface, force lipophilic group to present almost vertical arrangement at water-oil interface, thus significantly reduce surface energy.Component I contains two positive charge N
+containing the amide group that adsorptive power is stronger; the electrostatic double layer zeta-potential formed is higher; emulsifying power is high, meanwhile, by introducing five-ring and benzene ring structure; provide larger steric barrier; play sterically hindered provide protection to the unstable group of high temperature, improve the thermostability of emulsifying agent, is a kind of efficient emulsifying agent of high temperature resistance.Because Gemini surface active agent has the ability of stronger reduction oil water interfacial tension, thus the cmc value of component I is much smaller compared with conventional surfactant, when the concentration of component I in oil phase is higher than cmc, its dispersion enters in oil phase and adds oil phase viscosity, can improve drilling fluid rheology performance.Containing multiple five-membered ring structure and benzene ring structure on component I molecular chain, time static between emulsifier molecules, emulsifying agent and organophilic clay, Intermolecular Forces between organophilic clay and dispersion aqueous phase, is relied on to form the space net structure of similar water base drilling fluid, reaction force attenuation or disappearance under shearing condition, make drilling fluid be provided with the rheological of high thixotroping.Component I I is the amide surfactants containing tertiary amine, composite with component I, regulates emulsifier mixture HLB value; strengthen water-oil interface film toughness, meanwhile, component I I structure contains six-ring; there is provided sterically hindered protection to the unstable group of high temperature, improve the thermostability of emulsifying agent.
The present invention can have following beneficial effect compared with above-mentioned background technology: the high temperature water-in-oil drilling emulsifying agent of this high thixotroping, have selected raw material containing ring texture to improve the high-temperature resistance of emulsifying agent, containing benzene ring structure and multiple five-membered ring structure in emulsifying agent lipophilic group, make between emulsifier molecules, Intermolecular Forces is relied on to form the space net structure of similar water base drilling fluid between emulsifying agent and organophilic clay, hot conditions lactogenesis agent ring texture plays sterically hindered provide protection, molecular structure stabilized, thus drilling fluid still has the rheological of high thixotroping under the high temperature conditions.The high temperature water-in-oil drilling emulsifying agent temperature resistance ability of this high thixotroping can reach 260 DEG C, yield value 8Pa, and ratio of dynamic shear force/yield value to plastic viscosity can reach more than 0.36Pa/mPas, has good low-shear rate viscosity, and can better suspend drilling cuttings and weighting agent.
Embodiment:
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1.
The first step is reacted, and is put on heating jacket, good and sound thermometer, agitator, water trap and condensing works by the four-hole boiling flask of 500ml.The acid of 1.0mol refined caster oil is added in four-hole boiling flask, starts stirring, and logical N
2protection, until air in flask replaced clean after, slowly add the N of 1.0mol, N-dimethyl-1,3-propylene diamine, open heating jacket switch, slowly heat up.When reactant is warming up to 120 DEG C in flask, be incubated 120 DEG C ± 2 DEG C reactions, note not making reaction mixture temperature more than 122 DEG C.Observe the water separated in water trap, when the quality separated is 17.5g, sampling detection reaction mixture acid number, and note observing water outlet situation.When acid number is less than 2mgKOH/g, if simultaneously continuously dehydration cannot be observed in 10min, terminate reaction.Generate if acid number does not reach requirement or can be observed water, continue reaction until reach requirement.Now obtain intermediate product (I) ricinoleamide propyl-dimethyl tertiary amine.
Second step reacts, and is put on iron stand, good and sound agitator, constant pressure funnel by the there-necked flask of 500ml.Pass into N
2protection, adds in flask by the intermediate product (I) of 0.5mol, opens and stirs; drip initiator A IBN; slowly add the NVP of 1mol under stirring, insulation reaction 1.5h at 70 DEG C, obtain the poly-n-vinyl ricinoleamide propyl-dimethyl tertiary amine of intermediate product (II).
Three-step reaction, is put on iron stand by the there-necked flask of 500ml, good and sound agitator, constant pressure funnel.The dehydrated alcohol of 150mL is added in flask, opens and stir, logical N
2protection, adds the 4-dodecyl polyaniline of 0.5mol, is added dropwise in flask under stirring by the epoxy chloropropane constant pressure funnel of 1.2mol, and control rate of addition, epoxy chloropropane drips off at 180-200min.Be added dropwise to complete constant temperature 40 DEG C, continue reaction 10h, reaction terminates.By underpressure distillation removing dehydrated alcohol and excessive epoxy chloropropane, obtain intermediate product (III) N, N-bis-(2-hydroxyl-3-chloropropyl) dodecyl polyaniline.
Four-step reaction, is put on heating jacket by the four-hole boiling flask of 500ml, good and sound thermometer, agitator and reflux condensate device.The dehydrated alcohol of 150mL is added in flask, starts stirring, and logical N
2protection, adds intermediate product (II) 197g and (III) 90g (ratio of the amount of substance of this two-step reaction thing is 1:1).Slowly be warming up to 80 DEG C, after back flow reaction 30h, boil off dehydrated alcohol, add the butyl of 167g, stirring is cooled to room temperature and obtains component I, is labeled as sample a1.
The four-hole boiling flask of 500ml is put on heating jacket, good and sound thermometer, agitator, water trap and condensing works.1.0mol Erucic Acid is added in four-hole boiling flask, logical N
2protection, opens heating jacket switch, slowly heats up, be warming up to 40 DEG C, insulation, after Erucic Acid melts into liquid state completely, opens and stirs, stir after 5 minutes, slowly add the hexahydroaniline of 1.0mol.Add rear be slowly warming up to 90 ~ 100 DEG C insulation 15 minutes.Be warming up to 120 DEG C, insulation reaction, observe the water separated in water trap simultaneously.When the quality separated is 17.6g, if simultaneously continuously cannot dehydration be observed, sampling detection reaction mixture acid number in 10min, and note observing water outlet situation.When acid number is less than 2mgKOH/g, reach reaction end.Generate if acid number does not reach requirement or can be observed water, continue reaction until reach requirement.After arriving reaction end, reactant is warming up to 140 DEG C of insulated and stirred 10 minutes, then removes heating jacket, stir and be cooled to room temperature.The target product now obtained is component I I Erucic Acid Cyclohexamide, is labeled as sample a2.
Component I becomes the low sticky height of the high temperature resistance of high thixotroping to cut invert mud emulsifying agent with component I I with 3:1 proportions.
Embodiment 2.
The first step is reacted, and is put on heating jacket, good and sound thermometer, agitator, water trap and condensing works by the four-hole boiling flask of 500ml.1.0mol oleic acid is added in four-hole boiling flask, starts stirring, and logical N
2protection, until air in flask replaced clean after, slowly add the N of 1.0mol, N-dimethyl-1,3-propylene diamine, open heating jacket switch, slowly heat up.When reactant is warming up to 120 DEG C in flask, be incubated 120 DEG C ± 2 DEG C reactions, note not making reaction mixture temperature more than 122 DEG C.Observe the water separated in water trap, when the quality separated is 17.5g, sampling detection reaction mixture acid number, and note observing water outlet situation.When acid number is less than 2mgKOH/g, if simultaneously continuously dehydration cannot be observed in 10min, terminate reaction.Generate if acid number does not reach requirement or can be observed water, continue reaction until reach requirement.Now obtain intermediate product (I) stearylamide propyl-dimethyl tertiary amine.
Second step reacts, and is put on iron stand, good and sound agitator, constant pressure funnel by the there-necked flask of 500ml.Pass into N
2protection, adds in flask by the intermediate product (I) of 0.5mol, opens and stirs; drip initiator A IBN; slowly add the NVP of 1mol under stirring, insulation reaction 1.5h at 70 DEG C, obtain the poly-n-vinyl stearylamide propyl-dimethyl tertiary amine of intermediate product (II).
Three-step reaction, is put on iron stand by the there-necked flask of 500ml, good and sound agitator, constant pressure funnel.The dehydrated alcohol of 150mL is added in flask, opens and stir, logical N
2protection, adds the 4-dodecyl polyaniline of 0.5mol, is added dropwise in flask under stirring by the epoxy chloropropane constant pressure funnel of 1.2mol, and control rate of addition, epoxy chloropropane drips off at 180-200min.Be added dropwise to complete constant temperature 40 DEG C, continue reaction 10h, reaction terminates.By underpressure distillation removing dehydrated alcohol and excessive epoxy chloropropane, obtain intermediate product (III) N, N-bis-(2-hydroxyl-3-chloropropyl) dodecyl polyaniline.
Four-step reaction, is put on heating jacket by the four-hole boiling flask of 500ml, good and sound thermometer, agitator and reflux condensate device.The dehydrated alcohol of 150mL is added in flask, starts stirring, and logical N
2protection, adds intermediate product (II) 190g and (III) 89g (ratio of the amount of substance of this two-step reaction thing is 1:1).Slowly be warming up to 80 DEG C, after back flow reaction 30h, boil off dehydrated alcohol, add the butyl of 167g, stirring is cooled to room temperature and obtains component I, is labeled as sample b1.
Be put on heating jacket at the four-hole boiling flask of 500ml, good and sound thermometer, agitator, water trap and condensing works.1.0mol palmitinic acid is added in four-hole boiling flask, and logical N
2protection, opens heating jacket switch, slowly heats up.When solution temperature rises to 70 DEG C, slowly start stirring, add the N of 1.0mol, N-dimethyl-1,3-propylene diamine, when in flask, reactant is warming up to 130 DEG C, insulation reaction, observes the water separated in water trap, when the quality separated is 17.6g simultaneously, sampling detection reaction mixture acid number, and note observing water outlet situation.When acid number is less than 2mgKOH/g, if simultaneously continuously dehydration cannot be observed in 10min, terminate reaction.Generate if acid number does not reach requirement or can be observed water, continue reaction until reach requirement.The i.e. palmitamide propyl-dimethyl tertiary amine now obtained, is labeled as sample b2.
Component I becomes the low sticky height of the high temperature resistance of high thixotroping to cut invert mud emulsifying agent with component I I with 3:1 proportions.
Embodiment 3.
The first step is reacted, and is put on heating jacket, good and sound thermometer, agitator, water trap and condensing works by the four-hole boiling flask of 500ml.The acid of 1.0mol refined caster oil is added in four-hole boiling flask, starts stirring, and logical N
2protection, until air in flask replaced clean after, slowly add the N of 1.0mol, N-dimethyl-1,3-propylene diamine, open heating jacket switch, slowly heat up.When reactant is warming up to 120 DEG C in flask, be incubated 120 DEG C ± 2 DEG C reactions, note not making reaction mixture temperature more than 122 DEG C.Observe the water separated in water trap, when the quality separated is 17.5g, sampling detection reaction mixture acid number, and note observing water outlet situation.When acid number is less than 2mgKOH/g, if simultaneously continuously dehydration cannot be observed in 10min, terminate reaction.Generate if acid number does not reach requirement or can be observed water, continue reaction until reach requirement.Now obtain intermediate product (I) ricinoleamide propyl-dimethyl tertiary amine.
Second step reacts, and is put on iron stand, good and sound agitator, constant pressure funnel by the there-necked flask of 500ml.Pass into N
2protection, adds in flask by the intermediate product (I) of 0.5mol, opens and stirs; drip initiator A IBN; slowly add the NVP of 1mol under stirring, insulation reaction 1.5h at 70 DEG C, obtain the poly-n-vinyl ricinoleamide propyl-dimethyl tertiary amine of intermediate product (II).
Three-step reaction, is put on iron stand by the there-necked flask of 500ml, good and sound agitator, constant pressure funnel.The dehydrated alcohol of 150mL is added in flask, opens and stir, logical N
2protection, adds the amino dodecane of 0.5mol, is added dropwise in flask under stirring by the epoxy chloropropane constant pressure funnel of 1.2mol, and control rate of addition, epoxy chloropropane drips off at 180-200min.Be added dropwise to complete constant temperature 40 DEG C, continue reaction 10h, reaction terminates.By underpressure distillation removing dehydrated alcohol and excessive epoxy chloropropane, obtain intermediate product (III) N, N-bis-(2-hydroxyl-3-chloropropyl) amino dodecane.
Four-step reaction, is put on heating jacket by the four-hole boiling flask of 500ml, good and sound thermometer, agitator and reflux condensate device.The dehydrated alcohol of 150mL is added in flask, starts stirring, and logical N
2protection, adds intermediate product (II) 197g and (III) 74g (ratio of the amount of substance of this two-step reaction thing is 1:1).Slowly be warming up to 80 DEG C, after back flow reaction 30h, boil off dehydrated alcohol, add the butyl of 167g, stirring is cooled to room temperature and obtains component I, is labeled as sample c1.
Be put on heating jacket at the four-hole boiling flask of 500ml, good and sound thermometer, agitator, water trap and condensing works.1.0mol oleic acid is added in four-hole boiling flask, and logical N
2protection, opens heating jacket switch, slowly heats up.When solution temperature rises to 70 DEG C, slowly start stirring, add the N of 1.0mol, N-dimethyl-1,3-propylene diamine, when in flask, reactant is warming up to 130 DEG C, insulation reaction, observes the water separated in water trap, when the quality separated is 17.6g simultaneously, sampling detection reaction mixture acid number, and note observing water outlet situation.When acid number is less than 2mgKOH/g, if simultaneously continuously dehydration cannot be observed in 10min, terminate reaction.Generate if acid number does not reach requirement or can be observed water, continue reaction until reach requirement.The i.e. stearylamide propyl-dimethyl tertiary amine now obtained, is labeled as sample c2.
Component I becomes the low sticky height of the high temperature resistance of high thixotroping to cut invert mud emulsifying agent with component I I with 3:1 proportions.
Institute of the present invention with medicament is commercially available.
Evaluate with reference to the emulsifying agent sample of oil and gas industry standard SY/T6615-2005 " drilling fluid emulsifying agent assessment process " to synthesis.Milk sap water oil ratio is 70:30, add 2.1% primary emulsion, 2.1% and 0.7% major-minor newborn composite emulsifier respectively, add 2% organophilic clay while stirring, 12000r/min adds calcium chloride brine after stirring 10min, water-in-oil emulsion is mixed with after continuing to stir 30min at the same rate, in high temp roller process furnace after 260 DEG C of aging 16h, electricity consumption stability meter measures the emulsion-breaking voltage ES of milk sap.Experimental result sees the following form 1.
Table 1 high temperature resistance emulsifying agent sample is evaluated
After emulsifying agent preparation milk sap 260 DEG C of aging 16h of synthesis found out by table 1, emulsion-breaking voltage is still greater than 400V, and stability is better, can temperature resistance 260 DEG C.
Be core with emulsifying agent, grind and selected the supporting treatment agent of organophilic clay, fluid loss agent and alkalinity regulator, develop a set of high thixotropic invert mud system, density 1.2 ~ 2.0g/cm
3, temperature resistance reaches 260 DEG C, and drilling fluid system over-all properties is as shown in table 2.Concrete formula is: water oil ratio 75:25 ~ 90:10+20%CaCl
2the aqueous solution+3.0 ~ 5.0% emulsifier component I+1.0 ~ 3.0% emulsifier component II+2 ~ 4% organophilic clay+1.5% calcium oxide+3 ~ 5% fluid loss agent+ground barium sulfate.
Table 2 high thixotropic invert mud comprehensive performance evaluation data sheet
(note: FL
hTHP260 DEG C, measure under 3.5MPa condition)
High thixotropic invert mud plastic viscosity is lower, and yield value is higher, can reach 8Pa, and ratio of dynamic shear force/yield value to plastic viscosity more than 0.36 has good thixotropy.By force, emulsion-breaking voltage is greater than 1000V, can temperature resistance 260 DEG C for elctrical stability and thermostability.Meanwhile, leak-off building capacity is better, and HTHP filter loss is less than 10mL, and over-all properties is good.Please describe which effect characteristic of the present invention by supplementary table 2.
Claims (7)
1. the high temperature water-in-oil drilling emulsifying agent of a high thixotroping, mixed by component I and component I I two kinds of tensio-active agents, component I is Gemini Gemini quaternary ammonium salt style tensio-active agent, and component I I is amide surfactants, and the mass percent of component I and component I I is 2:1 ~ 4:1; Described component I molecular structural formula is as follows:
R
1-N-[(CH
2cHOHCH
2-N-(CH
3)
2(CH
2)
3-CONH-R
2)
2]
2+2Cl
-component I I molecular structural formula is: R
3-CONH-R
4
R in formula
1for C
12h
25, C
14h
29, C
16h
33, C
18h
37or C
18h
29, R
2for (C
18h
28o (C
6h
9nO)
m)
nor (C
18h
28(C
6h
9nO)
m)
n, R
3for C
21h
41, C
15h
31or C
17h
33, R
4for C
6h
11or (CH
2)
3n (CH
3)
2.
2. the high temperature water-in-oil drilling emulsifying agent of a kind of high thixotroping according to claim 1, is characterized in that: described component I and the mass percent of component I I are 3:1.
3. the high temperature water-in-oil drilling emulsifying agent of high thixotroping according to claim 1, is characterized in that: the organic synthesis of described component I comprises the following steps:
(1) for the acid-base neutralisation of organic acid and organic bases reacts, both mol ratio 1:1 ~ 1.2:1, temperature of reaction 100 DEG C ~ 120 DEG C, reaction times 14h, generates intermediate product (I).
(2) for intermediate product (I) and vinyl pyrrolidone NVP react, mol ratio is 1:2 ~ 1.2:2, temperature of reaction 60 ~ 80 DEG C, reaction times 1.5h, generates intermediate product (II).
(3) be the etherification reaction of epoxy chloropropane and organic amine, mol ratio is 2:1 ~ 4:1, temperature of reaction 40 DEG C, reaction times 10h ~ 12h, generates intermediate product (III).
(4) be the quaterisation of intermediate product (II) and (III), mol ratio is 1:1 ~ 2:1, temperature of reaction 80 DEG C, reaction times 25h ~ 30h, generates the Gemini quaternary ammonium salt style tensio-active agent of phosphinylidyne-containing amine group, i.e. component I.
4. the high temperature water-in-oil drilling emulsifying agent of a kind of high thixotroping according to claim 3, is characterized in that: in described step (1), organic acid is oleic acid, Yatall MA, ricinolic acid or refining Tall oil; Organic bases is N, N-dimethyl-1,3-propylene diamine.
5. the high temperature water-in-oil drilling emulsifying agent of a kind of high thixotroping according to claim 3, is characterized in that: described step (3) organic amine is amino dodecane, tetradecy lamine, cetylamine, stearylamine or 4-dodecyl polyaniline.
6. the high temperature water-in-oil drilling emulsifying agent of high thixotroping according to claim 1, it is characterized in that: the organic synthesis of described component I I is a step organic synthesis, synthesis material is that lipid acid and organic amine react, the mol ratio of lipid acid and organic amine is 1:1 ~ 1.1:1, temperature of reaction 100 DEG C ~ 140 DEG C, reaction times 14h, generates the amide surfactants containing tertiary amine, i.e. component I I.
7. the high temperature water-in-oil drilling emulsifying agent of high thixotroping according to claim 6, it is characterized in that: described lipid acid is oleic acid, Yatall MA, plam oil, ricinolic acid or Erucic Acid, organic amine is hexahydroaniline or N, N-dimethyl-1,3-propylene diamine.
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| CN113201316A (en) * | 2021-04-25 | 2021-08-03 | 西南石油大学 | temperature/CO2pH multi-responsive emulsifier and emulsion and application thereof |
| CN114806520A (en) * | 2022-05-30 | 2022-07-29 | 长江大学 | Preparation method of shear strength improving agent for oil-based drilling fluid |
| CN116790232A (en) * | 2023-06-30 | 2023-09-22 | 中石化胜利石油工程有限公司难动用项目管理中心 | Composite brine oil-in-water invert emulsion drilling fluid system and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201316A (en) * | 2021-04-25 | 2021-08-03 | 西南石油大学 | temperature/CO2pH multi-responsive emulsifier and emulsion and application thereof |
| CN113201316B (en) * | 2021-04-25 | 2022-08-26 | 西南石油大学 | temperature/CO 2 pH multi-responsive emulsifier and emulsion and application thereof |
| CN114806520A (en) * | 2022-05-30 | 2022-07-29 | 长江大学 | Preparation method of shear strength improving agent for oil-based drilling fluid |
| CN116790232A (en) * | 2023-06-30 | 2023-09-22 | 中石化胜利石油工程有限公司难动用项目管理中心 | Composite brine oil-in-water invert emulsion drilling fluid system and preparation method thereof |
| CN116790232B (en) * | 2023-06-30 | 2024-06-07 | 中石化胜利石油工程有限公司难动用项目管理中心 | Composite brine oil-in-water invert emulsion drilling fluid system and preparation method thereof |
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