CN105713591B - Invert emulsion drilling fluid and preparation method thereof - Google Patents
Invert emulsion drilling fluid and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of invert emulsion drilling fluids and preparation method thereof, mainly solve the problems, such as that Water-In-Oil Drilling fluid emulsion stability can poor, non-refractory in the prior art.The present invention by terms of mass fraction including following component: (1) 60~90 parts of base oil；(2) 10~40 parts of water；(3) 2~5 parts of organoclay；It (4) include that the compound emulsifying agent of primary emulsion (I) and coemulsifier (II) is no less than 0.5 part；(5) 0~3 parts of alkaline matter；(6) 0.5~3 parts of tackifier；The technical solution of the oil base drilling fluid of (7) 0.5~3 parts of fluid loss additive etc. and preparation method thereof, preferably resolves the problem, can be used for strong retraction, high-temperature stratum and needs to bore in the drillng operations of occasions such as big displacement exceptional well, seaborne horizontal well.
Description
Technical field
The present invention relates to a kind of invert emulsion drilling fluids and preparation method thereof.
Background technique
As the continuous reduction and exploitation of petroleum reserves are difficult, countries in the world are increased one after another to deep formation petroleum resources
The investment of exploration and development develops an urgent demand that new oil reservoir has become current each major oil companies' development.It waits verifying in China
Petroleum resources be mainly distributed on Tarim Basin, Zhunger Basin, Qaidam, spit the basins such as Kazakhstan, Sichuan, the 73% of stock number is imbedded in
Deep layer, and underground condition complex, therefore deep-well and ultradeep well oil gas drilling and matched development technique have become restriction oil
The key factor of gas development of resources.With the increase of depth of stratum, deep-well, ultradeep well formation temperature also can be higher and higher, ground
Can the hot environment of layer maintain stable performance to bring great challenge to drilling fluid.
Important component of the drilling fluid as drilling engineering, performance are directly related to the drilling well matter of deep-well, ultradeep well
Amount, drilling cost and drilling period.Relative to water-base drilling fluid, oil base drilling fluid has stronger anti-collapse inhibition, lubricity
It with good reservoir protection performance, can especially meet strong retraction and high temperature, superhigh temperature stratum, or need to bore big displacement exceptional well
And seaborne horizontal well etc. is special turns drilling well needs.Oil base drilling fluid, including full oil base drilling fluid and Water-In-Oil drilling fluid, Water-In-Oil
Drilling fluid also known as inverse emulsion drilling fluid, invert emulsion drilling fluid, are by oil, water, emulsifier, fluid loss additive, equilibrium of activation agent, stream
The composition such as type regulator.Usually used Water-In-Oil drilling fluid water content between 5~30% (water content within 5% one
As be called full oil base drilling fluid, not referred to as Water-In-Oil drilling fluid), but water in the Water-In-Oil drilling fluid resistant to high temperatures up to 180 DEG C or more
Content generally 5~10%, rarely exceed 15%.The content of water increases, and takes bits property, filtration reduction and suspension, rheological characteristic
All improve, but thermal stability and electrical stability are all deteriorated, if CN1660958 reports a kind of synthetic base drilling fluid, the master used
Emulsifier is the mixture of fatty alcohol polyoxyethylene ether ammonium sulfate and nonylphenol polyoxyethylene ether, although small in 150 DEG C of agings 16
When after still have good rheological characteristic and emulsion-breaking voltage, water content is up to 25%.102031095 A Shen Qing Publication of patent CN
A kind of high-temperature water-in-oil drilling fluid, although heatproof can to 240 DEG C, its must by coemulsifier and calcium oxide there are ability
Reach application effect.Oil base drilling fluid is expensive since base fluid is based on oil, at high cost, and full oil base drilling fluid is even more
In this way, as CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsifier used be Long carbon chain fatty acid amide,
One of Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid ester or a variety of mixtures, although there is low toxicity, environmental protection, to storage
The advantages that layer injury is small, but its preparation cost is high, limits its popularization and use.
It provides currently on the market and is used as the of less types of oil-based drilling fluid emulsifying agent, and report the cream for being used for intensified oil reduction
Agent kind is relatively more, such as US4485873, US4545912, CN100531884 report polyoxyethylated alkyl phenol second
Hydrochlorate, double tail chain polyoxyethylene sulfonic acid salt, alkyl-fragrant benzyl-polyethenoxy ether anion surfactant answering in terms of intensified oil reduction
With, but it is not directed to its purposes in terms of well-drilling liquid emulgent, it is in terms of oil base drilling fluid to rely on external product and domestic more
Matched drilling fluid system is also less.
Oil base drilling fluid due to limited by cost, environmental requirement develop always relatively slowly, the block of application also compared with
Few, as existing oilfield reserve increasingly declines, and the exploitation in new exploratory area can encounter various bad grounds and environment, be badly in need of performance
Excellent oil base drilling fluid, to solve the problems, such as that existing oil base drilling fluid emulsion-stabilizing performance is poor, not salt tolerant, non-heatproof.Pass through
The ratio for improving water in oil base drilling fluid reaches the cost for reducing oil base drilling fluid, provides for oil base drilling fluid operation is widely applied
Technical guarantee.In the case of the invention exactly this high-moisture, it is suitable for fatty acyl group diamines Polyoxyalkylene ethers as emulsification
Oil base drilling fluid of agent and preparation method thereof.
Summary of the invention
The first technical problem to be solved by the present invention is that Water-In-Oil Drilling fluid emulsion stability can be poor, no in the prior art
Problem resistant to high temperature provides a kind of new invert emulsion drilling fluid.This invert emulsion drilling fluid is good with heat resistance, lotion is steady
The advantages of determining excellent performance can be used for strong retraction, high-temperature stratum and need to bore the Special Drilling Operations such as big displacement exceptional well, seaborne horizontal well
In operation.The second technical problem to be solved by the present invention is to provide a kind of reverse phase cream corresponding with one of technical problem is solved
The preparation method of drilling fluid.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of invert emulsion drilling fluid,
Including following component in terms of mass fraction:
(1) 60~90 part of base oil；
(2) 10~40 parts of water；
(3) 2~5 parts of organoclay；
It (4) include that the compound emulsifying agent of primary emulsion and coemulsifier is no less than 0.5 part, with contained primary emulsion and auxiliary
The quality meter of assistant for emulsifying agent；
(5) 0~3 parts of alkaline matter；
(6) 0.5~3 parts of tackifier；
(7) 0.5~3 parts of fluid loss additive；
Wherein, the primary emulsion is selected from least one of structure shown in logical formula (I), and coemulsifier is selected from formula (II)
At least one of shown structural fatty alcohol polyoxyethylene poly-oxygen propylene aether carboxylic acid or carboxylate；In mass, the main emulsification
The ratio of agent and coemulsifier meets 0 < coemulsifier: primary emulsion≤1；
R4-COO(M)n, (II)
In general formula, R1For containing C8~C30Saturation or unsaturated alkyl, R2For hydrogen or R3CO, R3For C8~C30Saturation or not
The alkyl of saturation, x=1~10, y=1~40, z=0~40；R4For C7~C25Aliphatic group, M are selected from H, zinc, iron, aluminium, alkali gold
One of category, alkaline-earth metal, when M is H or alkali metal, n=1, when M is alkaline-earth metal, n=0.5, when M is iron or aluminium
When, n=1/3.
In above-mentioned technical proposal, the dosage of the compound emulsifying agent, with the quality of contained primary emulsion and coemulsifier
Meter, preferably 0.5~5 part；R1、R3Preferably C11~C23Saturation or unsaturated hydrocarbons or C11~C23Saturated hydrocarbons and unsaturation
The mixing alkyl of hydrocarbon, R1、R3More preferably carbon atom number be 11,13,15,17,19,21 saturated hydrocarbons or
Unsaturated alkyl or 11,13,15,17,19,21 saturated hydrocarbons and unsaturated hydrocarbons mixing alkyl；X is excellent
It is selected as 2~6, more preferably 2 or 3；Y is preferably 1~20, and more preferably 1~10；Z is preferably 0~30, and more preferably 0~20；
The R4Preferably C11~C23Saturated hydrocarbyl or unsaturated alkyl；M is preferably one of H, zinc or alkaline-earth metal；With quality
The ratio of meter, the primary emulsion and coemulsifier is preferably coemulsifier: primary emulsion=1:(2~20).
In above-mentioned technical proposal, the base oil is preferably one or more of white oil, synthetic oil, atoleine
Mixture；Water is preferably 15~30wt%CaCl2The aqueous solution of aqueous solution or 15~30wt%NaCl；Organoclay is preferably carbon
The modified bentonite of long chain quaternary or above-mentioned quaternary ammonium salt-modified montmorillonite that atomicity is 12,14,16,18；
Alkaline matter is preferably lime powder；Tackifier are preferably butadiene rubber, butadiene-styrene rubber, EP rubbers, polymethylacrylic acid
Mixture more than one or both of Arrcostab kind；Fluid loss additive is preferably the modified humic acid of long-chain organic amine, chain length
Preferably C12、C16、C18。
In above-mentioned technical proposal, the primary emulsion can be further preferably from two or more in structure shown in (I)
Mixture can play preferable synergistic effect.
In above-mentioned technical proposal, the coemulsifier can be further preferably from two or more in structure shown in (II)
Mixture, preferable synergistic effect can be played.
In above-mentioned technical proposal, the coemulsifier can be further most preferably from oleic acid, stearic acid, palmitinic acid, Pork and beans
The mixture of one or more of cool acid, lauric acid, calcium oleate, calcium stearate.
Key problem in technology of the invention is the selection of emulsifier, all polymer such as butadiene-styrene rubber, EP rubbers, poly- methyl
Alkyl acrylate is all substance commonly used in the art, and various polymer are preferably number-average molecular weight 1~10,000,000, more preferably
Number-average molecular weight 1~1,000,000.The preferred polymethylacrylic acid C of polyalkyl methacrylate12~C18Arrcostab.
In above-mentioned technical proposal, the oil base drilling fluid can be the primary emulsion and co-emulsifier with compound emulsifying agent
Both agent be uniformly mixed obtains, the two can also be dissolved in solvent be uniformly mixed obtain, such as the two is dissolved in 5# white oil, is obtained
The oil base drilling fluid compound emulsifying agent of paste or solution state.
The present invention can also include oil base drilling fluid auxiliary agent, such as wetting agent, heavy weight additive, fungicide commonly used in the art etc..
To solve above-mentioned technical problem two, the technical solution adopted in the present invention is as follows: a kind of invert emulsion drilling fluid
Preparation method, comprising the following steps:
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamines)
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. ethoxy
Diamines) 80~220 DEG C at a temperature of react 2~24 hours, preferred vacuum distillation removes unreacted raw material after reaction
The fatty acyl hydroxyethyl diamines is obtained with the methanol of generation；Wherein, the molar ratio of fatty acid methyl ester and hydroxyethyl diamine is
It is preferred that 1:0.1~6；The preferred potassium hydroxide of the basic catalyst, sodium hydroxide；The catalyst amount preferably accounts for fatty acid
The 0.01~10% of methyl esters quality；
(b)R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zThe system of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers)
It is standby:
In the presence of basic catalyst, fatty acyl hydroxyethyl diamines synthesized by step (a) and required ethylene oxide
Or propylene oxide is 80~180 DEG C in reaction temperature, pressure is reacted to obtain the fat under the conditions of being less than 0.80MPa gauge pressure
Acyl group diamines Polyoxyalkylene ethers；At least one of the basic catalyst preferably calcium hydroxide, calcium oxide；Catalyst amount is preferred
It is the 0.5~6.0% of fatty acyl hydroxyethyl diamines quality；
(c) preparation for the compound emulsifying agent of oil base drilling fluid
By the fatty acyl hydroxyethyl diamines that step (a) obtains and/or the fat acyl group two that step (b) obtains
Amine Polyoxyalkylene ethers and the coemulsifier are uniformly mixed in the ratio, obtain the Composite Milk for being used for oil base drilling fluid
Agent；
(d) preparation of invert emulsion drilling fluid
The compound emulsifying agent and the base oil, water, organoclay, alkaline matter, tackifier, drop that step (c) is obtained
Fluid loss agents mixing and emulsifying obtains the invert emulsion drilling fluid.
In above-mentioned technical proposal, a) the reaction temperature preferred scope in step be 100~200 DEG C, more preferably 120~
180℃；Catalyst is preferably alkali metal hydroxide or alkaline earth metal hydroxide, more preferably potassium hydroxide, and dosage is preferred
For account for fatty acid methyl esters monomer mass 0.5~5.0%；The molar ratio of fatty acid methyl ester and hydroxyethyl diamine is preferably 1~
2:1；Reaction time is preferably 6~16 hours.B) it is to account for fatty acyl hydroxyethyl two that catalyst amount, which is preferably catalyst amount,
The 1~5.0% of amine quality.
Invert emulsion drilling fluid prepared by the present invention, since the compound emulsifying agent used makes it have good heat-resistant salt-resistant
Performance, so that the invert emulsion drilling fluid has the stability of excellent high temperature.The invert emulsion drilling fluid heatproof is up to 180
DEG C, emulsion-breaking voltage is greater than 1200V before and after API filtration 0ml, high temperature ageing, be that a kind of heat resistance is good, filter loss is small, lotion
The good oil base drilling fluid system of stability, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
(a) preparation (x=2, y=1, z=0) of lauroyl hydroxyethyl ethylenediamine
By 17 parts of N-hydroxyethyl-ethylenediamine, 1.75 parts of KOH be added to equipped with sealing machine stirring, thermometer, condenser pipe,
In the reactor of receiving flask, after 120 DEG C are stirred 1 hour, slowly it is added dropwise in 35 parts of methyl laurate, 1 hour and is added dropwise.?
It is reacted 6 hours at 155 DEG C, the methanol generated in reaction is collected into receiving flask through condenser pipe, is then evaporated under reduced pressure out remaining
Low boiling point product and reaction raw materials obtain 39.7 parts of target product lauroyl hydroxyethyl ethylenediamine.
(b) preparation for the compound emulsifying agent of oil base drilling fluid
In terms of mass fraction, lauroyl hydroxyethyl ethylenediamine, 5 parts of oleic acid and 5 parts of oleic acid that 50 parts of steps (a) are obtained
Calcium, the heating stirring at 85 DEG C are uniformly mixed, obtain the compound emulsifying agent for oil base drilling fluid.
(c) preparation of invert emulsion drilling fluid
Weigh that step (b) obtains for oil base drilling fluid 6 grams of compound emulsifying agent, measure 270mL5# white oil enter it is stainless
Steel height stirs in cup, high-speed stirred 20min, sequentially adds 9 grams modified of organoclay of cetyl trimethylammonium bromide, cetylamine
Modified 3 grams of humic acid, 3 grams and 3 grams of CaO powder of EP rubbers (number-average molecular weight 150,000) continue high-speed stirred 20min, most
30mL 20wt%CaCl is added afterwards2Aqueous solution, then high-speed stirred 20min obtain stable invert emulsion drilling fluid system.It presses
Measure the rheology ginseng of the invert emulsion drilling fluid system respectively according to " GB/T 16782-1997 oil base drilling fluid On-Site Test Procedure "
Number, emulsion-breaking voltage and API filtration.Wherein rheological parameter is rotated using six speed of ZNN-D6 type of the sensible special instrument factory in Qingdao sea
Viscosimeter measures at 50 DEG C, and calculates plastic viscosity (PV), yield value (YP) and dynamic modeling according to formula (1), (2) and (3)
Than (YP/PV)；Emulsion-breaking voltage (ES) is by the DWY-2 type drilling fluid electrical stability analyzer of the sensible special instrument factory in Qingdao in 50 DEG C
Lower measurement, 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=θ600-θ300(mPa.s)
Formula (2) YP=(θ300-PV)/2(Pa)
Formula (3) ratio of dynamic shear force/yield value to plastic viscosity=YP/PV
Formula (4) FL=(FL30min﹣ FL7.5min)×2(mL)
Above-mentioned prepared invert emulsion drilling fluid is put into XGRL-4 type high temp roller heating furnace, 180 DEG C of high temperature are old
Change 16 hours, measures rheological parameter, emulsion-breaking voltage and the API filtration of the invert emulsion drilling fluid system, instrument respectively
And before process is with aging, as a result as shown in table 1,2.
[embodiment 2]
(a) preparation (x=2) of lauroyl hydroxyethyl ethylenediamine
17 parts of N-hydroxyethyl-ethylenediamine, 0.35 part of KOH are added to equipped with sealing machine stirring, thermometer, the condensation of straight type
It manages, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, is slowly added dropwise in 70 parts of methyl laurate, 1 hour and drips
Finish.It is reacted 16 hours at 180 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube, and decompression is steamed
Remaining low boiling point product and reaction raw materials are distillated, target product fatty acyl hydroxyethyl ethylenediamine is obtained.
(b) synthesis of N, N '-bis- lauroyls hydroxyethyl ethylenediamine polyoxyethylene ether (y=5, z=0)
The N that step (a) is synthesized, N ' -70 parts of bis- lauroyls hydroxyethyl ethylenediamine, 3.5 parts of calcium oxide and calcium hydroxide
(height equipped with condensing unit, agitating device and gas distributor is added for 1:1) to mixture for calcium oxide and calcium hydroxide weight ratio
It presses in reactor, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture, it is cooled to
80 DEG C, high activity, highly selective compound oxidizing calcium is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
Alkoxylating catalyst reaction solution system, is heated to 90 DEG C for system temperature, opens vacuum system, and it is small to be dehydrated 2 under a high vacuum
When, it is then purged 4 times with nitrogen, system reaction temperature is adjusted to 140 DEG C and is slowly passed through 26.4 parts of ethylene oxide, control pressure≤
0.60MPa.After reaction, system is purged with nitrogen, is neutralized after cooling, dehydration, obtains N, N '-bis- fatty acyl hydroxyethyls second
83 parts of diamines polyoxyethylene ether (y=5), molar yield 86.2%.
(c) preparation for the compound emulsifying agent of oil base drilling fluid
In terms of mass fraction, the N that 60 parts of steps (b) are obtained, N '-bis- lauroyls hydroxyethyl ethylenediamine polyoxyethylene
Ether (y=5) and 10 parts of calcium stearates, are added in 150 parts of 5# white oils, the heating stirring at 90 DEG C, are uniformly mixed, are used for
The compound emulsifying agent of oil base drilling fluid.
(d) preparation of invert emulsion drilling fluid
Weigh that step (c) obtains for oil base drilling fluid 12 grams of compound emulsifying agent [with N contained by compound emulsifying agent,
N '-bis- lauroyls hydroxyethyl ethylenediamine polyoxyethylene ether (y=5) and calcium stearate quality meter], measure 240mL5# white oil
Stainless steel height is added to stir in cup, high-speed stirred 20min, sequentially adds the modified organoclay 6 of hexadecyltrimethylammonium chloride
Gram, modified 3 grams of the humic acid of cetylamine, 3 grams and 6 grams of CaO powder of butadiene-styrene rubber (number-average molecular weight 200,000), continue high-speed stirred
20min is eventually adding 60mL 25wt%NaCl aqueous solution, then high-speed stirred 20min, obtains stable invert emulsion drilling fluid
System.With the performance before and after [embodiment 1] (b) measurement system aging, as a result as shown in table 1,2.
[embodiment 3]
(a) synthesis (x=2) of N, N '-stearic bicine diester base hydroxyethyl ethylenediamine
49 parts of N-hydroxyethyl-ethylenediamine, 2.7 parts of KOH are added to equipped with sealing machine stirring, thermometer, the condensation of straight type
It manages, in the reactor of receiving flask, after 145 DEG C are stirred 1 hour, is slowly added dropwise in 270 parts of methyl stearate, 1 hour and drips
Finish.It is reacted 12 hours at 165 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube.Decompression is steamed
Remaining low boiling point product and reaction raw materials are distillated, target product N, N '-stearic bicine diester base hydroxyethyl ethylenediamine are obtained.
(b) synthesis of N, N '-stearic bicine diester base hydroxyethyl ethylenediamine polyethenoxy ether (y=1, z=10)
203 grams of N, N '-stearic bicine diester base hydroxyethyl ethylenediamine and 185.4 parts of propylene oxide are in 7.6 parts of calcium oxide and hydrogen-oxygen
Change and reacts to obtain N, N '-stearic bicine diester base in 150 DEG C under the action of calcium compound (calcium oxide and calcium hydroxide weight ratio be 1:1)
348.5 parts of dihydroxy ethyl ethylenediamine polyethenoxy ether (y=1, z=10), molar yield 87.7%.
(c) preparation for the compound emulsifying agent of oil base drilling fluid
In terms of mass fraction, the N that 100 parts of steps (b) are obtained, N '-stearic bicine diester base dihydroxy ethyl ethylenediamine polyoxy third
Alkene ether (y=1, z=10) and 10 parts of lauric acid and 10 parts of stearic acid, the heating stirring at 85 DEG C are uniformly mixed, and are obtained for oil
The compound emulsifying agent of base drilling fluid.
(d) preparation of invert emulsion drilling fluid
6 grams of compound emulsifying agent, the measurement 210mL atoleine for oil base drilling fluid that step (c) obtains is weighed to enter not
Rust steel height stirs in cup, high-speed stirred 20min, sequentially add 10.5 grams modified of organoclay of cetyl trimethylammonium bromide,
(number is divided equally for 6 grams modified of humic acid of lauryl amine, EP rubbers (number-average molecular weight 50,000) and polymethylacrylic acid cetyl ester
Son amount 50 ten thousand) 6 grams of mixture and 3 grams of CaO powder, continue high-speed stirred 20min, are eventually adding 90mL20wt%CaCl2It is water-soluble
Liquid, then high-speed stirred 20min obtain stable invert emulsion drilling fluid system.Before [embodiment 1] (b) measurement system aging
Performance afterwards, as a result as shown in table 1,2.
[embodiment 4]
(a) preparation (x=3) of N, N '-bis- erucic acid acyl group ethoxy propane diamine
47.13 parts, KOH5.6 parts of N- ethoxy propane diamine are added to cold equipped with sealing machine stirring, thermometer, straight type
It is solidifying to manage, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, slowly it is added dropwise in 281.3 parts of methyl erucate, 1 hour and is added dropwise
It finishes.Stop after being reacted 10 hours at 170 DEG C, the methanol generated in reaction is collected into receiving flask by condenser west tube
In.Remaining low boiling point product and reaction raw materials are evaporated under reduced pressure out, target product N, N '-bis- erucic acid acyl group ethoxy are obtained
Propane diamine.
(b) synthesis of N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20)
The N that step (a) is synthesized, N ' -320 parts, 9.6 parts calcium oxide of bis- erucic acid acyl group ethoxy propane diamine and hydroxide
(calcium oxide and calcium hydroxide weight ratio are added for 1:1) equipped with condensing unit, agitating device and gas distributor calcium compound
In high-pressure reactor, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture, cooling
To 80 DEG C, high activity, highly selective compound oxidizing is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 80 DEG C, opens vacuum system, be dehydrated 2 under a high vacuum by calcium alkoxylating catalyst reaction solution system
Hour, it is then purged 3 times with nitrogen, system reaction temperature is adjusted to 180 DEG C and is slowly passed through 167.1 parts of ethylene oxide, control pressure
Power≤0.60MPa.After reacting ethylene oxide is complete, 489.4 parts of propylene oxide are added, the reaction was continued in 180 DEG C, and reaction terminates
Afterwards, system is purged with nitrogen, is neutralized after cooling, dehydration, obtain N, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene is poly-
845.7 parts of oxypropylene ether (y=10, z=20), molar yield 85.6%.
(c) preparation for the compound emulsifying agent of oil base drilling fluid
In terms of mass fraction, the N that 200 parts of steps (b) are obtained, N '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene
Polyethenoxy ether (y=10, z=20) and 10 parts of calcium oleates, the heating stirring at 85 DEG C are uniformly mixed, and obtain boring for oil base
The compound emulsifying agent of well liquid.
(d) preparation of invert emulsion drilling fluid
9 grams of compound emulsifying agent, the measurement 195mL atoleine for oil base drilling fluid that step (c) obtains is weighed to enter not
Rust steel height stirs in cup, high-speed stirred 20min, sequentially adds 12 grams modified of organoclay of cetyl trimethylammonium bromide, ten
3 grams modified of humic acid of hexamine, 3 grams and 4.5 grams of CaO powder of butadiene rubber (number-average molecular weight 180,000), continue high-speed stirred
20min is eventually adding 105mL 20wt%CaCl2Aqueous solution, then high-speed stirred 20min obtain stable rp-emulsification drilling well
Liquid system.With the performance before and after [embodiment 1] (b) measurement system aging, as a result as shown in table 1,2.
[embodiment 5]
(a) synthesis (x=3) of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine
55.3 parts of N- ethoxy propane diamine, 8.33 parts of KOH are added to cold equipped with sealing machine stirring, thermometer, straight type
It is solidifying to manage, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, methyl soyate is slowly added dropwise (with quality percentage
Content meter, methyl soyate include following components: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, palm fibre
Palmitic acid olefin(e) acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, flax
Sour formicester 3.587%, surplus other.) 277.6 parts, it is added dropwise in 1 hour.It reacts 8 hours at 165 DEG C, is generated in reaction
Methanol be collected into receiving flask by condenser west tube.Remaining low boiling point product and reaction raw materials are evaporated under reduced pressure out,
Obtain target product N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine.
(b) conjunction of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=3, z=5)
At
The N that step (a) is synthesized, N ' -256 parts, 15.4 parts calcium oxide of bis- vegetable oil acids acyl group ethoxy propane diamine and hydrogen
Aoxidizing calcium compound, (calcium oxide and calcium hydroxide weight ratio are added for 1:1) equipped with condensing unit, agitating device and gas dispersion
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture,
80 DEG C are cooled to, high activity, highly selective compound is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 90 DEG C, opens vacuum system, take off under a high vacuum by calcium oxide alkoxylating catalyst reaction solution system
It water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 34.9 parts of ethylene oxide, controlled
Pressure≤0.60MPa.After reacting ethylene oxide is complete, 114.8 parts of propylene oxide are added, the reaction was continued in 160 DEG C, reaction knot
Shu Hou purges system with nitrogen, neutralizes, dehydration after cooling, obtain N, N '-bis- vegetable oil acids acyl group hydroxyethyl ethylenediamine polyoxy
343.7 parts of vinethene (y=3, z=5), molar yield 84.7%.
(c) preparation for the compound emulsifying agent of oil base drilling fluid
In terms of mass fraction, the N that 10 parts of steps (a) are obtained, N '-bis- vegetable oil acids acyl group ethoxy propane diamine, 30 parts
The N that step (b) obtains, N '-bis- vegetable oil acids acyl group hydroxyethyl ethylenediamine polyoxyethylene ether (y=3, z=5) and 10 parts of oleic acid,
The heating stirring at 90 DEG C is uniformly mixed, obtains the compound emulsifying agent for oil base drilling fluid.
(d) preparation of invert emulsion drilling fluid
Weigh that step (c) obtains for oil base drilling fluid 9 grams of compound emulsifying agent, measure 210mL5# white oil enter it is stainless
Steel height stirs in cup, high-speed stirred 20min, sequentially adds 9 grams modified of organoclay of hexadecyltrimethylammonium chloride, cetylamine
Modified 3 grams of humic acid, 3 grams and 3 grams of CaO powder of butadiene rubber (number-average molecular weight 250,000) continue high-speed stirred 20min, most
90mL 20wt%CaCl is added afterwards2Aqueous solution, then high-speed stirred 20min obtain stable invert emulsion drilling fluid system.Together
[embodiment 1] (d) measures the performance before and after system aging, as a result as shown in table 1,2.
[embodiment 6]
(a) synthesis (x=3) of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine
55.3 parts of N- ethoxy propane diamine, 8.33 parts of KOH are added to cold equipped with sealing machine stirring, thermometer, straight type
It is solidifying to manage, in the reactor of receiving flask, after 150 DEG C are stirred 1 hour, methyl soyate is slowly added dropwise (with quality percentage
Content meter, methyl soyate include following components: tetradecanoic acid formicester 0.557%, palmitinic acid formicester 18.250%, palm fibre
Palmitic acid olefin(e) acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, flax
Sour formicester 3.587%, surplus other.) 277.6 parts, it is added dropwise in 1 hour.It reacts 8 hours at 165 DEG C, is generated in reaction
Methanol be collected into receiving flask by condenser west tube.Remaining low boiling point product and reaction raw materials are evaporated under reduced pressure out,
Obtain target product N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine.
(b) synthesis of N, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene ether (y=3, z=0)
The N that step (a) is synthesized, N ' -256 parts, 15.4 parts calcium oxide of bis- vegetable oil acids acyl group ethoxy propane diamine and hydrogen
Aoxidizing calcium compound, (calcium oxide and calcium hydroxide weight ratio are added for 1:1) equipped with condensing unit, agitating device and gas dispersion
In the high-pressure reactor of device, when being heated to 135 DEG C in logical nitrogen, 20 parts of water is added, are stirred to react 1 hour.After removing moisture,
80 DEG C are cooled to, high activity, highly selective compound is made in the sulfuric acid (20wt%) that catalyst neutralisation theoretical amount is slowly added dropwise
System temperature is heated to 90 DEG C, opens vacuum system, take off under a high vacuum by calcium oxide alkoxylating catalyst reaction solution system
It water 2 hours, is then purged 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and is slowly passed through 34.9 parts of ethylene oxide, controlled
Pressure≤0.60MPa.After reaction, system is purged with nitrogen, is neutralized after cooling, dehydration, obtains N, N '-bis- vegetable oil acids acyl
250.8 parts of base ethoxy propane diamine polyoxyethylene ether (y=3, z=0), molar yield 86.2%.
(c) preparation for the compound emulsifying agent of oil base drilling fluid
In terms of mass fraction, the N that 150 parts of steps (b) are obtained, N '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxy
Vinethene (y=3, z=0) and 50 parts of calcium stearates, the heating stirring at 80 DEG C are uniformly mixed, and are obtained for oil base drilling fluid
Compound emulsifying agent.
(d) preparation of invert emulsion drilling fluid
Weigh that step (c) obtains for oil base drilling fluid 9 grams of compound emulsifying agent, measure 210mL5# white oil enter it is stainless
Steel height stirs in cup, high-speed stirred 20min, sequentially adds 9 grams modified of organoclay of hexadecyltrimethylammonium chloride, cetylamine
Modified 3 grams of humic acid, 3 grams and 3 grams of CaO powder of butadiene rubber (number-average molecular weight 200,000) continue high-speed stirred 20min, most
90mL 20wt%CaCl is added afterwards2Aqueous solution, then high-speed stirred 20min obtain stable invert emulsion drilling fluid system.Together
[embodiment 1] (d) measures the performance before and after system aging, as a result as shown in table 1,2.
[comparative example 1]
With (d) in [embodiment 5], for difference with 9g oleic acid alternative composite emulsifier, remaining is identical, determines reverse phase cream
Rheological parameter, emulsion-breaking voltage and the API filtration of drilling fluid system, the results are shown in Table 3.Contrast table 1,2 data can be seen
Out, the rheological property that oleic acid is formed is poor, exceeds measuring range, emulsion-breaking voltage is also than the system that emulsifier of the invention is formed
Low and filter loss is larger.
[comparative example 2]
With [embodiment 5] (d), difference with N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z=0) with
Oleic acid quality proportioning is that 4:1 is that emulsifier dosage 9g substitutes compound emulsifying agent of the invention, remaining is identical, determines rp-emulsification
Rheological parameter, emulsion-breaking voltage and the API filtration of drilling fluid system, the results are shown in Table 4.Contrast table 1,2 data can be seen that
The system that N, N '-bis- vegetable oil acids acyl group propane diamine are formed, emulsion-breaking voltage are also lower than the system that emulsifier of the invention is formed
And filter loss is larger.
[comparative example 3]
With [embodiment 5] (d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y
=0, z=3) it with oleic acid quality proportioning be 4:1 is that emulsifier dosage 9g substitutes compound emulsifying agent of the invention, remaining is identical, surveys
Rheological parameter, emulsion-breaking voltage and the API filtration of invert emulsion drilling fluid system are determined, the results are shown in Table 5.Contrast table 1,2
Data can be seen that N, the system that N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y=0, z=3) is formed,
Emulsion-breaking voltage is also lower than the system that emulsifier of the invention is formed and filter loss is larger.
[comparative example 4]
With [embodiment 5] (d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y
=0, z=5) it with oleic acid quality proportioning be 4:1 is that emulsifier dosage 9g substitutes compound emulsifying agent of the invention, remaining is identical, surveys
Rheological parameter, emulsion-breaking voltage and the API filtration of invert emulsion drilling fluid system are determined, the results are shown in Table 6.Contrast table 1,2
Data can be seen that N, the system that N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y=0, z=5) is formed,
Emulsion-breaking voltage is also lower than the system that emulsifier of the invention is formed and filter loss is larger.
[comparative example 5]
With [embodiment 5] (d), difference with INVERMUL emulsifier (production of Halliburton Baroid company) and
Oleic acid quality proportioning is that 4:1 is that emulsifier dosage 9g substitutes compound emulsifying agent of the invention, remaining is identical, determines rp-emulsification
Rheological parameter, emulsion-breaking voltage and the API filtration of drilling fluid system, the results are shown in Table 7.Contrast table 1,2 data can be seen that
The system that INVERMUL is formed, rheological property is poor before and after aging, exceeds measuring range, emulsion-breaking voltage is also than cream of the invention
The system that agent is formed wants low.
[comparative example 6]
With [embodiment 5] (d), difference is the N of 4:1, N '-bis- vegetable oil with quality proportioning obtained in embodiment 5
Sour acyl group ethoxy propane diamine and N, N '-bis- vegetable oil acids acyl group hydroxyethyl ethylenediamine polyoxyethylene ether (y=3, z=5) are cream
Agent dosage 9g alternative composite emulsifier, remaining is identical, determines rheological parameter, the emulsion-breaking voltage of invert emulsion drilling fluid system
And API filtration, the results are shown in Table 8.
[comparative example 7]
With [embodiment 5] (d), difference is with N obtained in embodiment 5, N '-bis- vegetable oil acids acyl group ethoxy third
Diamines 9g alternative composite emulsifier, remaining is identical, determine the rheological parameter of invert emulsion drilling fluid system, emulsion-breaking voltage and
API filtration, the results are shown in Table 9.
[comparative example 8]
With [embodiment 5] (d), difference is with N obtained in embodiment 5, N '-bis- vegetable oil acids acyl group ethoxy second
Diamines polyoxyethylene ether (y=3, z=5) 9g alternative composite emulsifier, remaining is identical, determines invert emulsion drilling fluid system
Rheological parameter, emulsion-breaking voltage and API filtration, the results are shown in Table 10.
Comparative example 5 and comparative example 1, comparative example 6~8 can be seen that the compound emulsifying agent effect in embodiment 5 most
It is good.
[comparative example 9]
With [embodiment 1] (d), difference is pressed with lauroyl hydroxyethyl ethylenediamine obtained in embodiment 1 with oleic acid
Quality proportioning 5:1 is that emulsifier 6g substitutes compound emulsifying agent of the invention, remaining is identical, determines invert emulsion drilling fluid system
Rheological parameter, emulsion-breaking voltage and API filtration, as a result as shown in table 11.
[comparative example 10]
With [embodiment 1] (d), difference is with lauroyl hydroxyethyl ethylenediamine and calcium oleate obtained in embodiment 1
It is that emulsifier 6g substitutes compound emulsifying agent of the invention by quality proportioning 5:1, remaining is identical, determines invert emulsion drilling fluid body
Rheological parameter, emulsion-breaking voltage and the API filtration of system, as a result as shown in table 12.
Oil base drilling fluid system performance before 1 aged at room temperature of table
Oil base drilling fluid system performance after the aging 24 hours of 2 180 DEG C of table
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Table 9
Table 10
Table 11
Table 12
Claims (10)
1. a kind of invert emulsion drilling fluid, including following component in terms of mass fraction:
(1) 60 ~ 90 parts of base oil；
(2) 10 ~ 40 parts of water；
(3) 2 ~ 5 parts of organoclay；
It (4) include that the compound emulsifying agent of primary emulsion and coemulsifier is no less than 0.5 part, with contained primary emulsion and auxiliary cream
The quality meter of agent；
(5) 0 ~ 3 parts of alkaline matter；
(6) 0.5 ~ 3 parts of tackifier；
(7) 0.5 ~ 3 parts of fluid loss additive；
Wherein, the primary emulsion is selected from least one of structure shown in logical formula (I), and coemulsifier is selected from formula (II)
At least one of shown structural fatty alcohol polyoxyethylene poly-oxygen propylene aether carboxylic acid or carboxylate；In mass, the main emulsification
The ratio of agent and coemulsifier meets 0 < coemulsifier: primary emulsion≤1；
, (I)
, (II)
In general formula, R1For containing C8~C30Aliphatic group, R2For hydrogen or R3CO, R3For C8~C30Aliphatic group, x=2 ~ 6, y=1 ~ 20,
z=0~30；R4For C7~C25Aliphatic group, M are selected from one of H, zinc, iron, aluminium, alkali metal, alkaline-earth metal, when M is H or alkali
When metal, n=1, when M is alkaline-earth metal, n=0.5, when M is iron or aluminium, n=1/3.
2. invert emulsion drilling fluid according to claim 1, it is characterised in that the base oil is diesel oil, white oil, conjunction
At at least one of oil.
3. invert emulsion drilling fluid according to claim 1, it is characterised in that the water is that 1 ~ 30wt% electrolyte is water-soluble
Liquid.
4. invert emulsion drilling fluid according to claim 1, it is characterised in that the organoclay is carbon chain lengths C12~C18
The modified bentonite of long chain quaternary.
5. invert emulsion drilling fluid according to claim 1, it is characterised in that R1And R3For C11~C23Saturation or insatiable hunger
With alkyl or C11~C23Saturated hydrocarbyl and unsaturated alkyl mixing alkyl.
6. invert emulsion drilling fluid according to claim 1, it is characterised in that the alkaline matter is alkali metal carbonic acid
At least one of salt, alkali metal oxide, calcium oxide or calcium hydroxide.
7. invert emulsion drilling fluid according to claim 1, it is characterised in that the tackifier are butadiene rubber, butylbenzene
At least one of rubber, EP rubbers, polyalkyl methacrylate, bitumen or oxidized asphalt.
8. invert emulsion drilling fluid according to claim 1, it is characterised in that the fluid loss additive is long-chain organic amine
At least one of modified humic acid, bitumen, oxidized asphalt.
9. invert emulsion drilling fluid according to claim 1, it is characterised in that the preparation of the invert emulsion drilling fluid
Method the following steps are included:
(a) R1CONH(CH2)xNR2CH2CH2OH(, that is, fatty acyl hydroxyethyl diamines) preparation
R in the presence of basic catalyst1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH(, that is, hydroxyethyl diamine)
80 ~ 220 DEG C at a temperature of react 2~24 hours, vacuum distillation removes the first of unreacted raw material and generation after reaction
Alcohol obtains the fatty acyl hydroxyethyl diamines；Wherein, the molar ratio of fatty acid methyl ester and hydroxyethyl diamine is 1: 0.1 ~ 6；
(b) R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zH(, that is, fatty acyl group diamines Polyoxyalkylene ethers) preparation:
In the presence of basic catalyst, fatty acyl hydroxyethyl diamines synthesized by step (a) and required ethylene oxide or ring
Ethylene Oxide is 85~180 DEG C in reaction temperature, and pressure is reacted to obtain the fat acyl group under the conditions of being less than 0.80MPa gauge pressure
Diamines Polyoxyalkylene ethers；Catalyst amount is the 0.5~6.0% of fatty acyl hydroxyethyl diamines quality；
(c) preparation for the compound emulsifying agent of oil base drilling fluid
The fat acyl group diamines that the fatty acyl hydroxyethyl diamines and/or step (b) that step (a) obtains are obtained is poly-
Oxygen alkene ether and the coemulsifier are uniformly mixed in the ratio, obtain the compound emulsifying agent for being used for oil base drilling fluid；
(d) preparation of invert emulsion drilling fluid
The compound emulsifying agent and the base oil, water, organoclay, alkaline matter, tackifier, filtrate reducing that step (c) is obtained
Agent mixing and emulsifying obtains the invert emulsion drilling fluid.
10. invert emulsion drilling fluid according to claim 9, it is characterised in that:
The basic catalyst is selected from least one of calcium hydroxide, calcium oxide.
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| US11560508B2 (en) | 2020-07-17 | 2023-01-24 | Saudi Arabian Oil Company | Epoxidized fatty acid methyl ester as primary emulsifier for invert emulsion oil based mud |
| US11499082B2 (en) | 2020-07-17 | 2022-11-15 | Saudi Arabian Oil Company | Epoxidized fatty acid methyl ester as low-shear rheology modifier for invert emulsion oil based mud |
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| CN102027092A (en) * | 2008-05-15 | 2011-04-20 | 阿克佐诺贝尔股份有限公司 | Polyamide emulsifier based on polyamines and fatty acid/carboxylic acid for oil based drilling fluid applications |
| CN102093296A (en) * | 2010-11-30 | 2011-06-15 | 广州星业科技股份有限公司 | Synthesis method of imidazoline compound |
| CN103540298A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Oil-based drilling fluid as well as preparation method thereof |
| CN103897677A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Oil-based drilling fluid adopting phenol ether sulfonate composite oil-based emulsifier, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102027092A (en) * | 2008-05-15 | 2011-04-20 | 阿克佐诺贝尔股份有限公司 | Polyamide emulsifier based on polyamines and fatty acid/carboxylic acid for oil based drilling fluid applications |
| CN102093296A (en) * | 2010-11-30 | 2011-06-15 | 广州星业科技股份有限公司 | Synthesis method of imidazoline compound |
| CN103540298A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Oil-based drilling fluid as well as preparation method thereof |
| CN103897677A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Oil-based drilling fluid adopting phenol ether sulfonate composite oil-based emulsifier, and preparation method thereof |
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