CN105567187A - Water-in-oil emulsion drilling fluid and preparation method thereof - Google Patents
Water-in-oil emulsion drilling fluid and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a water-in-oil emulsion drilling fluid and a preparation method thereof. The water-in-oil emulsion drilling fluid provided by the invention mainly overcomes the problems of poor stability and no high temperature resistance of the emulsion of conventional water-in-oil drilling fluids. The water-in-oil emulsion drilling fluid comprises, by mass, (1) 60 to 90 parts of base oil, (2) 10 to 40 parts of water, (3) 2 to 5 parts of organoclay, (4) no less than 0.5 part of a composite emulsifier including a main emulsifier (I) as described in the specification and a coemulsifier (II) as described in the specification, (5) 0 to 3 parts of an alkaline substance, (6) 0.5 to 3 parts of a tackifier, (7) 0.5 to 3 parts of a filtrate reducer and the like. The water-in-oil emulsion drilling fluid perfectly overcomes the above-mentioned problems and can be used for high-temperature strata with strong water-sensitivity and drilling operation for special wells, offshore horizontal wells and the like needing large-displacement drilling.
Description
Technical field
The present invention relates to a kind of invert oil-emulsion drilling fluid and preparation method thereof.
Background technology
Along with the continuous minimizing of prospective oil and exploitation difficulty, countries in the world increase the input to deep formation Oil And Gas Exploration And Development one after another, develop an urgent demand that new oil reservoir has become the development of current each major oil companies.China's hydrocarbon resources to be verified mainly is distributed in Tarim Basin, Zhunger Basin, Qaidam, tells the basins such as Kazakhstan, Sichuan, 73% of its stock number is imbedded in deep layer, and underground condition complex, therefore deep-well and ultra deep well oil gas drilling and supporting development technique have become the key factor of restriction petrol resources exploitation.Along with the increase of depth of stratum, the formation temperature of deep-well, ultra deep well also can be more and more higher, and can the hot environment on stratum maintain stable performance to drilling fluid and bring great challenge.
Drilling fluid is as the important component part of drilling engineering, and its performance is directly connected to deep-well, the drilling quality of ultra deep well, drilling cost and drilling period.Relative to water-base drilling fluid; oil base drilling fluid has stronger anti-collapse inhibition, oilness and good reservoir protection performance; especially can meet strong retraction and high temperature, ultrahigh-temperature stratum, or need to bore that Large travel range exceptional well and seaborne horizontal well etc. are special turns drilling well needs.Oil base drilling fluid, also known as invert mud, is made up of oil, water, emulsifying agent, fluid loss agent, equilibrium of activation agent, flow pattern regulator etc.Between 5 ~ 30%, (water content is generally called full oil base drilling fluid to normally used invert mud water content within 5%, be not called invert mud), but high temperature resistance reaches the content of water in the invert mud of more than 180 DEG C generally 5 ~ 10%, rarely exceeds 15%.The content of water increases, take bits property, filtration reduction and suspension, rheological all to improve, but thermostability and elctrical stability are all deteriorated, as CN1660958 reports a kind of synthetic base drilling fluid, the mixture that the primary emulsion used is AESA and polyoxyethylene nonylphenol ether, although still have good rheological and emulsion-breaking voltage at 150 DEG C after aging 16 hours, water-content is up to 25%.A kind of high-temperature water-in-oil drilling fluid of patent CN102031095A Shen Qing Publication, although heatproof can to 240 DEG C, it just must can reach effect by the existence of co-emulsifier and calcium oxide.Oil base drilling fluid is because base fluid is based on oil, therefore expensive, cost is high, full oil base drilling fluid is all the more so, as CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsifying agent of use is Long carbon chain fatty acid amide, one or more mixture in Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid's ester, although have low toxicity, environmental protection, to advantages such as reservoir damage are little, but its preparation cost is high, limits it and promote the use of.
What provide as oil base drilling fluid emulsifying agent in the market is of less types, and the emulsifying agent kind that report is used for intensified oil reduction is relatively many, as US4485873, US4545912, CN100531884 etc. report polyxyethylated alkylphenol acetate, two tail chain polyoxyethylene sulfonic acid salt, the application of alkyl-fragrant benzyl-polyethenoxy ether negatively charged ion surfactant in intensified oil reduction, but do not relate to its purposes in well-drilling liquid emulgent, oil base drilling fluid aspect many dependences external product, and domestic supporting drilling fluid system is also less.
Oil base drilling fluid owing to being subject to cost, the restriction of environmental requirement develops slower always, the block of application is also less, along with existing oilfield reserve declines day by day, and the exploitation in new exploratory area can run into various bad ground and environment, be badly in need of the oil base drilling fluid of excellent property, to solve poor, not salt tolerant, non-heatproof the problem of existing oil base drilling fluid emulsion-stabilizing performance.The cost reducing oil base drilling fluid is reached, for the operation of widespread use oil base drilling fluid provides technical guarantee by the ratio improving water in oil base drilling fluid.In this just high-moisture situation described in invention, be suitable for fatty acyl group diamines Polyoxyalkylene ethers oil base drilling fluid that is emulsifying agent and preparation method thereof.
Summary of the invention
One of technical problem to be solved by this invention is the problem of poor, the non-refractory of invert mud emulsion-stabilizing performance in prior art, provides a kind of new invert oil-emulsion drilling fluid.This invert oil-emulsion drilling fluid has the advantage that heat resistance is good, emulsion-stabilizing performance is good, can be used for strong retraction, high-temperature stratum and needs to bore in the Special Drilling Operation operations such as Large travel range exceptional well, seaborne horizontal well.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the invert mud corresponding with one of technical solution problem.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of invert oil-emulsion drilling fluid, comprises following component in mass fraction:
The base oil of (1) 60 ~ 90 part;
The water of (2) 10 ~ 40 parts;
The organophilic clay of (3) 2 ~ 5 parts;
(4) compound emulsifying agent comprising primary emulsion and co-emulsifier is no less than 0.5 part, in the quality of contained primary emulsion and co-emulsifier;
The alkaline matter of (5) 0 ~ 3 parts;
The tackifier of (6) 0.5 ~ 3 parts;
The fluid loss agent of (7) 0.5 ~ 3 parts;
Wherein, described primary emulsion is selected from least one in structure shown in general formula (I), and co-emulsifier is selected from least one in structure shown in logical formula II; In mass, the ratio of described primary emulsion and co-emulsifier meets 0 < co-emulsifier: primary emulsion≤1;
In general formula, R
1for containing C
8~ C
30saturated or unsaturated alkyl, R
2for hydrogen or R
3cO, R
3for C
8~ C
30saturated or undersaturated alkyl, x=1 ~ 10, y=1 ~ 40, z=0 ~ 40; R
4for C
7~ C
25aliphatic group, R
5and R
6all independently be selected from H, C
2~ C
4hydroxyalkyl in one.
In technique scheme, the dosage of described compound emulsifying agent, in the quality of contained primary emulsion and co-emulsifier, is preferably 0.5 ~ 5 part; R
1, R
3be preferably C
11~ C
23saturated or unsaturated hydrocarbons, or C
11~ C
23stable hydrocarbon and the mixing alkyl of unsaturated hydrocarbons, R
1, R
3be more preferably stable hydrocarbon or unsaturated alkyl that carbonatoms is 11,13,15,17,19,21, or the mixing alkyl of the stable hydrocarbon of 11,13,15,17,19,21 and unsaturated hydrocarbons; X is preferably 2 ~ 6, is more preferably 2 or 3; Y is preferably 1 ~ 20, is more preferably 1 ~ 10; Z is preferably 0 ~ 30, is more preferably 0 ~ 20; Described R
4be preferably C
11~ C
23saturated hydrocarbyl or unsaturated alkyl; R
5and R
6the all independent one be preferably in H, hydroxyethyl, hydroxypropyl, more preferably R
5and R
6the all independent one be preferably in H, hydroxyethyl, is more preferably R
5and R
6the common one be preferably in H, hydroxyethyl.
In technique scheme, described base oil is preferably one or more the mixture in white oil, synthetic oil, whiteruss; Water is preferably 15 ~ 30wt%CaCl
2the aqueous solution of the aqueous solution or 15 ~ 30wt%NaCl; Organophilic clay is preferably the wilkinite or above-mentioned quaternary ammonium salt-modified polynite that carbonatoms is the long chain quaternary modification of 12,14,16,18; Alkaline matter is preferably lime powder; Tackifier are preferably one or more the mixture in cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), polyalkyl methacrylate; Fluid loss agent is preferably the humic acids of long-chain organic amine modification, and chain length is preferably C
12, C
16, C
18.
In technique scheme, described primary emulsion can two or more mixture further preferably in structure shown in (I).
In technique scheme, described co-emulsifier can two or more mixture further preferably in structure shown in (II).
In technique scheme, in mass, the ratio of described primary emulsion and co-emulsifier most preferably is co-emulsifier: primary emulsion=1:(2 ~ 10).
In technique scheme, described co-emulsifier can the preferred mixture of one or two or more kinds in lauric amide, tetradecanoic acid acid amides, palmitic amide, physetoleic acid acid amides, amine hydroxybenzene, linoleamide, linolenamide, stearic amide, lauric monoethanolamide, tetradecanoic acid single ethanol amide, palmitic monoethanolamide, physetoleic acid single ethanol amide, oleic monoethanolamide, linoleic monoethanolamide, linolenic acid single ethanol amide, stearic acid monoethanolamide further; More preferably can also comprise the mixture of above-mentioned fatty acid amide or fatty monoethanol amide, such as but not limit by Vegetable oil lipoprotein well-known to those skilled in the art or biofuel be vegetable oil acid acid amides, vegetable oil acid single ethanol amide or the vegetable oil acid diglycollic amide that raw material and corresponding amidation reagent carry out amidate action and obtain.
In technique scheme, the preparation method of described co-emulsifier can be well-known to those skilled in the art any one, can be any one before this in known preparation method disclosed in document.
Key problem in technology of the present invention is the selection of emulsifying agent, all polymkeric substance such as styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), polyalkyl methacrylate are all the materials that this area is commonly used, various polymkeric substance is preferably number-average molecular weight 1 ~ 1,000 ten thousand, is more preferably number-average molecular weight 1 ~ 1,000,000.The preferred polymethyl acrylic acid C of polyalkyl methacrylate
12~ C
18alkyl ester.
The present invention can also comprise this area common oil base drilling fluid auxiliary agent, such as wetting agent, weighting agent, sterilant etc.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of invert oil-emulsion drilling fluid preparation method, comprises the following steps:
(a) R
1cONH (CH
2) xNR
2cH
2cH
2the preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R under basic catalyst exists
1cOOCH
3(i.e. fatty acid methyl ester) and NH
2(CH
2)
xnHCH
2cH
2oH (i.e. hydroxyethyl diamine) reacts 2 ~ 24 hours at the temperature of 80 ~ 220 DEG C, and reaction terminates the methyl alcohol that rear preferred underpressure distillation removes unreacted raw material and generation and obtains described fatty acyl hydroxyethyl diamines; Wherein, the mol ratio of fatty acid methyl ester and hydroxyethyl diamine is preferred 1:0.1 ~ 6; The preferred potassium hydroxide of described basic catalyst, sodium hydroxide; Described catalyst levels preferably accounts for 0.01 ~ 10% of fatty acid methyl ester quality;
(b) R
1cONH (CH
2) xNR
2(CH
2cH
2o)
y-(CH2CHCH
3o)
zthe preparation of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers):
Under basic catalyst exists, fatty acyl hydroxyethyl diamines synthesized by step (a) and required oxyethane or propylene oxide are 80 ~ 180 DEG C in temperature of reaction, and pressure carries out under being less than 0.80MPa gauge pressure condition being obtained by reacting described fat acyl group diamines Polyoxyalkylene ethers; At least one in described basic catalyst preferably calcium hydroxide, calcium oxide; Catalyst levels is preferably 0.5 ~ 6.0% of fatty acyl hydroxyethyl diamines quality;
C () is applicable to the preparation of the compound emulsifying agent of oil base drilling fluid
The described fat acyl group diamines Polyoxyalkylene ethers that described fatty acyl hydroxyethyl diamines step (a) obtained and/or step (b) obtain and described co-emulsifier, mix in described ratio, described in obtaining, be applicable to the compound emulsifying agent of oil base drilling fluid;
The preparation of (d) invert oil-emulsion drilling fluid
Compound emulsifying agent step (c) obtained and base oil, water, organophilic clay, described alkaline matter, tackifier, fluid loss agent mixing and emulsifying, obtain described invert oil-emulsion drilling fluid.
In technique scheme, temperature of reaction preferable range a) in step is 100 ~ 200 DEG C, is more preferably 120 ~ 180 DEG C; Catalyzer is preferably alkali metal hydroxide or alkaline earth metal hydroxides, is more preferably potassium hydroxide, and consumption preferably accounts for 0.5 ~ 5.0% of fatty acid methyl ester class monomer mass; The mol ratio of fatty acid methyl ester and hydroxyethyl diamine is preferably 1 ~ 2:1; Reaction times is preferably 6 ~ 16 hours.B) catalyst levels is preferably catalyst levels is account for fatty acyl hydroxyethyl diamines quality 1 ~ 5.0%.
In technique scheme, described oil base drilling fluid compound emulsifying agent can be that described primary emulsion and co-emulsifier mix and obtain, also both can be dissolved in solvent evenly to obtain, as both being dissolved in 5# white oil, obtain the oil base drilling fluid compound emulsifying agent of paste or solution state.
Invert oil-emulsion drilling fluid prepared by the present invention, because the compound emulsifying agent used makes it have good heat-resistant salt-resistant performance, thus makes this invert oil-emulsion drilling fluid have the stability of excellent high temperature.This invert oil-emulsion drilling fluid heatproof reaches 180 DEG C, API filtration≤3ml, emulsion-breaking voltage >=1200V before and after high temperature ageing, is that a kind of heat resistance is good, filter loss is little, the oil base drilling fluid system of good emulsion stability.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation (x=2, y=1, z=0) of (a) lauroyl hydroxyethylethylene diamine
N-hydroxyethyl-ethylenediamine 17 parts, KOH1.75 part are joined in the reactor being furnished with sealing machine stirring, thermometer, prolong, receiving flask, after stirring 1 hour in 120 DEG C, slowly drips Laurate methyl 35 parts, dropwise in 1 hour.React 6 hours at 155 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through prolong, and then underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product lauroyl hydroxyethylethylene diamine 39.7 parts.
The preparation of (b) oil base drilling fluid compound emulsifying agent
In mass fraction, the lauroyl hydroxyethylethylene diamine 50 parts of steps (a) obtained, 5 parts of vegetable oil acid single ethanol amides and 5 parts of amine hydroxybenzenes, heated and stirred at 85 DEG C, mixes, and obtains the compound emulsifying agent being applicable to oil base drilling fluid.
The preparation of (c) invert oil-emulsion drilling fluid
Take compound emulsifying agent 6 grams that step (b) obtains, measure 270mL5# white oil and enter that stainless steel is high to be stirred in cup, high-speed stirring 20min, add the organophilic clay 9 grams of cetyl trimethylammonium bromide modification, the humic acids 3 grams of cetylamine modification, 3 grams, ethylene-propylene rubber(EPR) (number-average molecular weight 150,000) and 3 grams, CaO powder more successively, continue high-speed stirring 20min, finally add 30mL20wt%CaCl
2the aqueous solution, then high-speed stirring 20min, obtain stable invert oil-emulsion drilling fluid system.The rheological parameter of this invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration is measured respectively according to " GB/T16782-1997 oil base drilling fluid On-Site Test Procedure ".Wherein rheological parameter adopts the fast rotational viscosimeter of ZNN-D6 type six of the sensible instrumentation factory in sea, Qingdao to measure at 50 DEG C, and calculates plastic viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV) according to formula (1), (2) and (3); Emulsion-breaking voltage (ES) is measured at 50 DEG C by the DWY-2 type drilling fluid elctrical stability determinator of the sensible instrumentation factory in Qingdao, API filtration is measured by the multi-joint filtration device of SD type, and calculates filter loss (FL) according to formula (4).
Formula (1) PV=θ
600-θ
300(mPa.s)
Formula (2) YP=(θ
300-PV)/2 (Pa)
Formula (3) ratio of dynamic shear force/yield value to plastic viscosity=YP/PV
Formula (4) FL=(FL
30min﹣ FL
7.5min) × 2 (mL)
The above-mentioned invert oil-emulsion drilling fluid prepared is put into XGRL-4 type high temp roller process furnace, 180 DEG C of high temperature ageings 16 hours, measure the rheological parameter of this invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration respectively, instrument and process are with before aging, and result is as shown in table 1,2.
[embodiment 2]
The preparation (x=2) of (a) lauroyl hydroxyethylethylene diamine
N-hydroxyethyl-ethylenediamine 17 parts, KOH0.35 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drips Laurate methyl 70 parts, dropwise in 1 hour.React 16 hours at 180 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube, and underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product fatty acyl hydroxyethyl quadrol.
The synthesis of (b) N, N ＇-bis-lauroyl hydroxyethylethylene diamine Soxylat A 25-7 (y=5, z=0)
The N that step (a) is synthesized; N ＇-bis-lauroyl hydroxyethylethylene diamine 70 parts, 3.5 parts of calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 90 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 4 times, system temperature of reaction is adjusted to 140 DEG C and slowly passes into 26.4 parts of oxyethane, control pressure≤0.60MPa.After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain N, N ＇-bis-fatty acyl hydroxyethyl ethylenediamine polyoxyethylene ether (y=5) 83 parts, molar yield 86.2%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction; by the N that 60 parts of steps (b) obtain; N ＇-bis-lauroyl hydroxyethylethylene diamine Soxylat A 25-7 (y=5) and 10 parts of lauric acid amide of ethanol; join in 150 parts of 5# white oils; heated and stirred at 90 DEG C; mix, obtain the compound emulsifying agent being applicable to oil base drilling fluid.
The preparation of (d) invert mud
Take compound emulsifying agent 12 grams that step (c) obtains (with the N contained by compound emulsifying agent, the quality meter of N ＇-bis-lauroyl hydroxyethylethylene diamine Soxylat A 25-7 (y=5) and lauric acid amide of ethanol), measure 240mL5# white oil and add that stainless steel is high to be stirred in cup, high-speed stirring 20min, add the organophilic clay 6 grams of palmityl trimethyl ammonium chloride modification more successively, the humic acids of cetylamine modification 3 grams, 3 grams, styrene-butadiene rubber(SBR) (number-average molecular weight 200,000) and 6 grams, CaO powder, continue high-speed stirring 20min, finally add the 60mL25wt%NaCl aqueous solution, high-speed stirring 20min again, obtain stable invert oil-emulsion drilling fluid system.Measure the performance of the aging front and back of system with [embodiment 1] (b), result is as shown in table 1,2.
[embodiment 3]
The synthesis (x=2) of (a) N, N ＇-stearic bicine diester base hydroxyethylethylene diamine
N-hydroxyethyl-ethylenediamine 49 parts, KOH2.7 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 145 DEG C, slowly drips methyl stearate 270 parts, dropwise in 1 hour.React 12 hours at 165 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-stearic bicine diester base hydroxyethylethylene diamine.
The synthesis of (b) N, N ＇-stearic bicine diester base hydroxyethylethylene diamine polyethenoxy ether (y=1, z=10)
203 grams of N; N ＇-stearic bicine diester base hydroxyethylethylene diamine and 185.4 parts of propylene oxide react to obtain N in 150 DEG C under the effect of 7.6 parts of calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1); N ＇-stearic bicine diester base dihydroxy ethyl quadrol polyethenoxy ether (y=1; z=10) 348.5 parts, molar yield 87.7%.
C () is applicable to the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; by the N that 60 parts of steps (b) obtain; N ＇-stearic bicine diester base dihydroxy ethyl quadrol polyethenoxy ether (y=1; z=10) and 10 parts of oleic monoethanolamide and 10 parts of stearic acid monoethanolamides; heated and stirred at 85 DEG C; mix, obtain the compound emulsifying agent being applicable to oil base drilling fluid.
The preparation of (d) invert mud
Take compound emulsifying agent 6 grams that step (c) obtains, measure 210mL whiteruss and enter that stainless steel is high to be stirred in cup, high-speed stirring 20min, add the organophilic clay 10.5 grams of cetyl trimethylammonium bromide modification, the humic acids 6 grams of amino dodecane modification, ethylene-propylene rubber(EPR) (number-average molecular weight 50,000) and 6 grams, polymethyl acrylic acid cetyl ester (number-average molecular weight 500,000) mixture and 3 grams, CaO powder more successively, continue high-speed stirring 20min, finally add 90mL20wt%CaCl
2the aqueous solution, then high-speed stirring 20min, obtain stable invert oil-emulsion drilling fluid system.Measure the performance of the aging front and back of system with [embodiment 1] (b), result is as shown in table 1,2.
[embodiment 4]
The preparation (x=3) of (a) N, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine
N-hydroxyethyl propylene diamine 47.13 parts, KOH5.6 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drips methyl erucate 281.3 parts, dropwise in 1 hour.React at 170 DEG C after 10 hours and stop, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine.
The synthesis of (b) N, N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20)
The N that step (a) is synthesized; N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine 320 parts, 9.6 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 80 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 3 times, system temperature of reaction is adjusted to 180 DEG C and slowly passes into 167.1 parts of oxyethane, control pressure≤0.60MPa.After reacting ethylene oxide is complete; add 489.4 parts of propylene oxide; reaction is continued in 180 DEG C; after reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration; obtain N; N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20) 845.7 parts, molar yield 85.6%.
C () is applicable to the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; by the N that 100 parts of steps (b) obtain; N ＇-bis-erucic acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=10; z=20) and 10 parts of amine hydroxybenzenes; heated and stirred at 85 DEG C; mix, obtain the compound emulsifying agent being applicable to oil base drilling fluid.
The preparation of (d) invert mud
Take compound emulsifying agent 9 grams that step (c) obtains, measure 195mL whiteruss and enter that stainless steel is high to be stirred in cup, high-speed stirring 20min, add the organophilic clay 12 grams of cetyl trimethylammonium bromide modification, the humic acids 3 grams of cetylamine modification, cis-1,4-polybutadiene rubber (number-average molecular weight 180,000) 3 grams and 4.5 grams, CaO powder more successively, continue high-speed stirring 20min, finally add 105mL20wt%CaCl
2the aqueous solution, then high-speed stirring 20min, obtain stable invert oil-emulsion drilling fluid system.Measure the performance of the aging front and back of system with [embodiment 1] (b), result is as shown in table 1,2.
[embodiment 5]
The synthesis (x=3) of (a) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine
N-hydroxyethyl propylene diamine 55.3 parts, KOH8.33 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drip methyl soyate (in mass percentage, methyl soyate comprises following component: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, physetoleic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linolic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.) 277.6 parts, dropwise in 1 hour.React 8 hours at 165 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine.
The synthesis of (b) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine polyoxyethylene poly-oxygen propylene aether (y=3, z=5)
The N that step (a) is synthesized; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine 256 parts, 15.4 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 90 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 3 times, system temperature of reaction is adjusted to 160 DEG C and slowly passes into 34.9 parts of oxyethane, control pressure≤0.60MPa.After reacting ethylene oxide is complete; add 114.8 parts of propylene oxide; reaction is continued in 160 DEG C; after reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration; obtain N; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3, z=5) 343.7 parts, molar yield 84.7%.
C () is applicable to the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction, by the N that 10 parts of steps (a) obtain, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine, the N that 30 parts of steps (b) obtain, N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3, z=5) and 10 parts of vegetable oil acid single ethanol amides (are synthesized by methyl soyate and monoethanolamine and obtain, wherein in mass percentage, methyl soyate comprises following component: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, physetoleic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linolic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.), heated and stirred at 90 DEG C, mixes, and obtains the compound emulsifying agent being applicable to oil base drilling fluid.
The preparation of (d) invert mud
Take compound emulsifying agent 9 grams that step (c) obtains, measure 210mL5# white oil and enter that stainless steel is high to be stirred in cup, high-speed stirring 20min, add the organophilic clay 9 grams of palmityl trimethyl ammonium chloride modification, the humic acids 3 grams of cetylamine modification, cis-1,4-polybutadiene rubber (number-average molecular weight 250,000) 3 grams and 3 grams, CaO powder more successively, continue high-speed stirring 20min, finally add 90mL20wt%CaCl
2the aqueous solution, then high-speed stirring 20min, obtain stable invert oil-emulsion drilling fluid system.Measure the performance of the aging front and back of system with [embodiment 1] (d), result is as shown in table 1,2.
[embodiment 6]
The synthesis (x=3) of (a) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine
N-hydroxyethyl propylene diamine 55.3 parts, KOH8.33 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drip methyl soyate (in mass percentage, methyl soyate comprises following component: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, physetoleic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linolic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.) 277.6 parts, dropwise in 1 hour.React 8 hours at 165 DEG C, the methyl alcohol generated in reaction is collected in receiving flask through condenser west tube.Underpressure distillation goes out remaining lower boiling resultant and reaction raw materials, obtains target product N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine.
The synthesis of (b) N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine Soxylat A 25-7 (y=3, z=0)
The N that step (a) is synthesized; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine 256 parts, 15.4 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing works, whipping appts and gas distributor; while lead to nitrogen limit when being heated to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After removing moisture, be cooled to 80 DEG C, slowly drip the obtained high reactivity of sulfuric acid (20wt%) of catalyst neutralisation theoretical amount, the compound oxidizing calcium alkoxylating catalyst reaction solution system of highly selective, system temperature is heated to 90 DEG C, open vacuum system, dewater 2 hours under a high vacuum, then use nitrogen purging 3 times, system temperature of reaction is adjusted to 160 DEG C and slowly passes into 34.9 parts of oxyethane, control pressure≤0.60MPa.After reaction terminates, use nitrogen purging system, neutralization after cooling, dehydration, obtain N, N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine Soxylat A 25-7 (y=3, z=0) 250.8 parts, molar yield 86.2%.
C () is applicable to the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; by the N that 100 parts of steps (b) obtain; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine Soxylat A 25-7 (y=3; z=0) and 50 parts of lauric amides; heated and stirred at 80 DEG C; mix, obtain the compound emulsifying agent being applicable to oil base drilling fluid.
The preparation of (d) invert mud
Take compound emulsifying agent 9 grams that step (c) obtains, measure 210mL5# white oil and enter that stainless steel is high to be stirred in cup, high-speed stirring 20min, add the organophilic clay 9 grams of palmityl trimethyl ammonium chloride modification, the humic acids 3 grams of cetylamine modification, cis-1,4-polybutadiene rubber (number-average molecular weight 200,000) 3 grams and 3 grams, CaO powder more successively, continue high-speed stirring 20min, finally add 90mL20wt%CaCl
2the aqueous solution, then high-speed stirring 20min, obtain stable invert oil-emulsion drilling fluid system.Measure the performance of the aging front and back of system with [embodiment 1] (d), result is as shown in table 1,2.
[comparative example 1]
With (d) in [embodiment 5], difference is with 9g vegetable oil acid single ethanol amide alternative composite emulsifying agent, and all the other are identical, and determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 3.
[comparative example 2]
With [embodiment 5] (d); difference is with N; N ＇-bis-vegetable oil acid acyl group propylene diamine (x=3; y=0; z=0) be 3:1 be that emulsifying agent dosage 9g substitutes compound emulsifying agent of the present invention with vegetable oil acid single ethanol amide quality proportioning; all the other are identical, and determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 4.Contrast table 1 data can be found out, the system that N, N ＇-bis-vegetable oil acid acyl group propylene diamine is formed, and aging front and back rheological property is poor, all exceeds measurement range, and the system that emulsion-breaking voltage is also formed than emulsifying agent of the present invention is low.
[comparative example 3]
With [embodiment 5] (d); difference is with N; N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3; y=0; z=3) be 3:1 be that emulsifying agent dosage 9g substitutes compound emulsifying agent of the present invention with vegetable oil acid single ethanol amide quality proportioning; all the other are identical, and determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 5.Contrast table 1 data can be found out, the system that N, N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3, y=0, z=3) is formed, and system yield value, the emulsion-breaking voltage of formation are all lower, and filter loss is larger.
[comparative example 4]
With [embodiment 5] (d); difference is with N; N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3; y=0; z=5) be 3:1 be that emulsifying agent dosage 9g substitutes compound emulsifying agent of the present invention with vegetable oil acid single ethanol amide quality proportioning; all the other are identical, and determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 6.Contrast table 1 data can be found out, the system that N, N ＇-bis-vegetable oil acid acyl group propylene diamine polyethenoxy ether (x=3, y=0, z=5) is formed, and system yield value, the emulsion-breaking voltage of formation are all lower, and filter loss is larger.
[comparative example 5]
With [embodiment 5] (d), difference is 3:1 with INVERMUL emulsifying agent (production of HalliburtonBaroid company) and vegetable oil acid single ethanol amide quality proportioning is that emulsifying agent dosage 9g substitutes compound emulsifying agent of the present invention, all the other are identical, determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 7.Contrast table 1 data can be found out, the system that INVERMUL is formed, and aging front and back rheological property is poor, all exceeds measurement range, and the system that emulsion-breaking voltage is also formed than emulsifying agent of the present invention is low.
[comparative example 6]
With [embodiment 5] (d); the N that difference is 3:1 with the quality proportioning obtained in embodiment 5; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine and N; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3; z=5) for emulsifying agent dosage 9g substitutes compound emulsifying agent of the present invention; all the other are identical, and determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 8.
[comparative example 7]
With [embodiment 5] (d); difference is with the N obtained in embodiment 5; N ＇-bis-vegetable oil acid acyl group hydroxyethyl propylene diamine 9g substitutes compound emulsifying agent of the present invention; all the other are identical; determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 9.
[comparative example 8]
With [embodiment 5] (d); difference is with the N obtained in embodiment 5; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine Soxylat A 25-7 (y=3; z=5) 9g substitutes compound emulsifying agent of the present invention; all the other are identical; determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 10.
Comparative example 5 and comparative example 1, comparative example 6 ~ 8 can be found out, the compound emulsifying agent effect in embodiment 5 is best.[comparative example 9]
With [embodiment 1] (d); difference with the lauroyl hydroxyethylethylene diamine obtained in embodiment 1 and vegetable oil acid single ethanol amide by quality proportioning 5:1 for emulsifying agent dosage 6g substitutes compound emulsifying agent of the present invention; all the other are identical; determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 11.
[comparative example 10]
With [embodiment 1] (d); difference with the lauroyl hydroxyethylethylene diamine obtained in embodiment 1 and amine hydroxybenzene by quality proportioning 5:1 for emulsifying agent dosage 6g substitutes compound emulsifying agent of the present invention; all the other are identical; determine the rheological parameter of invert oil-emulsion drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 12.
Oil base drilling fluid system performance before table 1 aged at room temperature
Table 2180 oil base drilling fluid system performance DEG C after aging 24 hours
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Table 10
Table 11
Table 12
Claims (10)
1. an invert oil-emulsion drilling fluid, comprises following component in mass fraction:
(1) base oil 60 ~ 90 parts;
(2) 10 ~ 40 parts, water;
(3) organophilic clay 2 ~ 5 parts;
(4) compound emulsifying agent comprising primary emulsion and co-emulsifier is no less than 0.5 part, in the quality of contained primary emulsion and co-emulsifier;
The alkaline matter of (5) 0 ~ 3 parts;
The tackifier of (6) 0.5 ~ 3 parts;
The fluid loss agent of (7) 0.5 ~ 3 parts;
Wherein, described primary emulsion is selected from least one in structure shown in general formula (I), and co-emulsifier is selected from least one in structure shown in logical formula II; In mass, the ratio of described primary emulsion and co-emulsifier meets 0 < co-emulsifier: primary emulsion≤1;
In general formula, R
1for containing C
8~ C
30saturated or unsaturated alkyl, R
2for hydrogen or R
3cO, R
3for C
8~ C
30saturated or undersaturated alkyl, x=1 ~ 10, y=1 ~ 40, z=0 ~ 40; R
4for C
7~ C
25aliphatic group, R
5and R
6all independently be selected from H, C
2~ C
4hydroxyalkyl in one.
2. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described base oil is one or more the mixture in diesel oil, white oil, whiteruss, synthetic oil.
3. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described water is 1 ~ 30wt% aqueous electrolyte liquid.
4. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described organophilic clay is for being carbon chain lengths C
12~ C
18the wilkinite of long chain quaternary modification or carbon chain lengths C
12~ C
18the polynite of long chain quaternary modification.
5. invert oil-emulsion drilling fluid according to claim 1, is characterized in that R
1and R
3for C
11~ C
23saturated or unsaturated alkyl or C
11~ C
23saturated hydrocarbyl and the mixing alkyl of unsaturated alkyl.
6. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described x=2 ~ 6, y=1 ~ 20, z=0 ~ 30.
7. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described alkaline matter is at least one in alkaline carbonate, alkalimetal oxide, calcium oxide or calcium hydroxide.
8. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described tackifier are one or more the mixture in cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethylene-propylene rubber(EPR), polyalkyl methacrylate, rock asphalt or oxidized bitumen.
9. invert oil-emulsion drilling fluid according to claim 1, is characterized in that described fluid loss agent is one or more the mixture in long-chain organic amine modified humic acid, rock asphalt, oxidized bitumen.
10. invert oil-emulsion drilling fluid according to claim 1, is characterized in that the preparation method of described invert oil-emulsion drilling fluid comprises the following steps:
(a) R
1cONH (CH
2) xNR
2cH
2cH
2the preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R under basic catalyst exists
1cOOCH
3(i.e. fatty acid methyl ester) and NH
2(CH
2)
xnHCH
2cH
2oH (i.e. hydroxyethyl diamine) reacts 2 ~ 24 hours at the temperature of 80 ~ 220 DEG C, and reaction terminates the methyl alcohol that rear preferred underpressure distillation removes unreacted raw material and generation and obtains described fatty acyl hydroxyethyl diamines; Wherein, the mol ratio of fatty acid methyl ester and hydroxyethyl diamine is 1:0.1 ~ 6;
(b) R
1cONH (CH
2) xNR
2(CH
2cH
2o)
y-(CH2CHCH
3o)
zthe preparation of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers):
Under basic catalyst exists, fatty acyl hydroxyethyl diamines synthesized by step (a) and required oxyethane or propylene oxide are 85 ~ 180 DEG C in temperature of reaction, and pressure carries out under being less than 0.80MPa gauge pressure condition being obtained by reacting described fat acyl group diamines Polyoxyalkylene ethers; At least one in described basic catalyst preferably calcium hydroxide, calcium oxide; Catalyst levels is preferably 0.5 ~ 6.0% of fatty acyl hydroxyethyl diamines quality;
C () is applicable to the preparation of the compound emulsifying agent of oil base drilling fluid
The described fat acyl group diamines Polyoxyalkylene ethers that described fatty acyl hydroxyethyl diamines step (a) obtained and/or step (b) obtain and described co-emulsifier, mix in described ratio, described in obtaining, be applicable to the compound emulsifying agent of oil base drilling fluid;
The preparation of (d) invert oil-emulsion drilling fluid
Compound emulsifying agent step (c) obtained and base oil, water, organophilic clay, described alkaline matter, tackifier, fluid loss agent mixing and emulsifying, obtain described invert oil-emulsion drilling fluid.
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