CN105713579B - Compound emulsifying agent and its preparation method and application for oil base drilling fluid - Google Patents
Compound emulsifying agent and its preparation method and application for oil base drilling fluid Download PDFInfo
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Abstract
The emulsifier and its preparation method and application that the present invention relates to a kind of for oil base drilling fluid mainly solves oil-based drilling fluid emulsifying agent less varieties in the prior art, the problem of emulsifiability, heat resistance difference.The present invention is by using a kind of emulsifier for oil base drilling fluid, including following components：(1) primary emulsion, selected from least one of structure shown in formula (I)；(2) coemulsifier, selected from least one of structure shown in formula (II)；The ratio of the primary emulsion and coemulsifier meets 0 < coemulsifier:The technical solution of primary emulsion≤1, preferably resolve the above problem, it can be used as oil-based drilling fluid emulsifying agent, with good emulsifiability and heat resistance, the oil base drilling fluid stability of formation, temperature tolerance are preferable, can meet the special requirements such as strong retraction in oil field, high-temperature stratum drilling well and big displacement Special Drilling Operation, seaborne horizontal well.
Description
Technical field
The compound emulsifying agent and its preparation method and application that the present invention relates to a kind of for oil base drilling fluid.
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, also known as Water-In-Oil drilling fluid are by oil, water, emulsifier, drop
The composition such as fluid loss agents, equilibrium of activation agent, flow pattern regulator.Usually used Water-In-Oil drilling fluid water content is between 5~30%
(generally referred to as full oil base drilling fluid of the water content within 5%, not referred to as Water-In-Oil drilling fluid), but it is resistant to high temperatures up to 180 DEG C with
On Water-In-Oil drilling fluid in water content generally 5~10%, rarely exceed 15%.The content of water increases, and takes bits property, drop filter
The property lost and suspension, rheological characteristic all improve, but thermal stability and electrical stability are all deteriorated, as CN1660958 reports a kind of conjunction
At base drilling fluid, the primary emulsion used is the mixture of fatty alcohol polyoxyethylene ether ammonium sulfate and nonylphenol polyoxyethylene ether,
Although still having good rheological characteristic and emulsion-breaking voltage after aging 16 hours at 150 DEG C, water content is up to 25%.Patent CN
A kind of high-temperature water-in-oil drilling fluid of 102031095 A Shen Qing Publications, although heatproof can be to 240 DEG C, it must be by auxiliary cream
The presence of agent and calcium oxide can be only achieved application effect.Oil base drilling fluid is expensive since base fluid is based on oil, at
This height, full oil base drilling fluid is even more so, if CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsification used
Agent is one of Long carbon chain fatty acid amide, Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid ester or a variety of mixtures, is use up
Pipe have many advantages, such as low toxicity, environmental protection, it is small to reservoir damage, but its preparation cost height, limit 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 domestic oil base drilling fluid emulsifier to rely on foreign countries more
Product, and domestic 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 carrying out
Satisfaction prepares the research of stability and high efficiency oil base drilling fluid emulsifier, to solve oil-based drilling fluid emulsifying agent less varieties, emulsibility
Can be poor, not the problem of salt tolerant, non-heatproof, the ratio by improving water in oil base drilling fluid reaches the cost for reducing oil base drilling fluid
Problem provides technical support for oil base drilling fluid operation is widely applied.
In the case of exactly this high-moisture of the present invention, it is suitable for preparing answering for stability and high efficiency oil base drilling fluid
Co-emulsifier and preparation method thereof.
Summary of the invention
The first technical problem to be solved by the present invention is oil-based drilling fluid emulsifying agent less varieties in the prior art, emulsibility
The problem of energy, heat resistance difference, provides a kind of compound emulsifying agent for oil base drilling fluid.This is compound for oil base drilling fluid
Emulsifier has good emulsifiability and heat resistance, and the oil base drilling fluid containing such compound emulsifying agent can meet strong in oil field
The special requirements such as water-sensitive, high-temperature stratum and big displacement Special Drilling Operation, seaborne horizontal well drilling well.
The second technical problem to be solved by the present invention is to provide a kind of corresponding with one of solution technical problem be used for
The preparation method of the compound emulsifying agent of oil base drilling fluid.
The third technical problem to be solved by the present invention is to provide a kind of corresponding with one of solution technical problem be used for
Application of the compound emulsifying agent of oil base drilling fluid in oil base drilling fluid.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind being used for oil base drilling fluid
Compound emulsifying agent, including following components：
(1) primary emulsion, selected from least one of structure shown in formula (I)；
(2) coemulsifier, selected from least one of structure shown in formula (II)；
R4-COO(M)n, (II)
Wherein R1For containing C8~C30Aliphatic group, R2For hydrogen or R3CO, R3For C8~C30Aliphatic group, x=1~10, y
=1~40, z=0~40；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 metal, n=1, when M is alkaline-earth metal, n=0.5, when M is iron or aluminium, n=1/3；In mass, institute
The ratio for stating primary emulsion and coemulsifier meets 0 < coemulsifier:Primary emulsion≤1.
In above-mentioned technical proposal, the R1And R3It is independently selected from C11~C23Saturated or unsaturated alkyl or C11~
C23Saturated hydrocarbyl and unsaturated alkyl mixing alkyl.More preferable R1And R3Being independently selected from carbon atom number is 11,13, ten
Five, 17,19,21 saturated hydrocarbons or unsaturated alkyl or 11,13,15,17,19,21 it is full
With the mixing alkyl of hydrocarbon and unsaturated hydrocarbons.It is preferred that it be 1~20, z is 0~30 that x, which is 2~6, y,；Further preferred x is 2 or 3, y 1
~10；More preferable z is 0~20；The R4Preferably C11~C23Saturated hydrocarbyl or unsaturated alkyl；M is preferably H, zinc or alkaline earth
One of metal.
In above-mentioned technical proposal, the coemulsifier can be further most preferably from oleic acid, stearic acid, palmitinic acid, Pork and beans
One of cool acid, lauric acid, calcium oleate, calcium stearate or two kinds or more of mixture；In mass, the primary emulsion with
The ratio of coemulsifier is most preferably coemulsifier:Primary emulsion=1:(2~20).
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.
To solve above-mentioned technical problem two, the technical solution adopted in the present invention is as follows：One kind being used for oil base drilling fluid
Emulsifier preparation method, include 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 catalyst amount preferably accounts for the 0.01~10% of fatty acid methyl ester 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 reacted to obtain the fat acyl group diamines Polyoxyalkylene ethers.Catalyst amount is preferably fatty acyl hydroxyethyl
The 0.5~6.0% of 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.
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 at least one of alkali metal hydroxide, alkaline earth metal hydroxide, more preferably hydroxide
Potassium, sodium hydroxide, further preferably potassium hydroxide, dosage be preferably 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.
In above-mentioned technical proposal, b) basic catalyst in step is preferably alkaline earth oxide, alkaline-earth metal hydrogen-oxygen
At least one of at least one of compound, more preferably calcium oxide, calcium hydroxide, catalyst amount preferably account for fatty acyl
The 1~5.0% of base hydroxyethyl diamine quality.Reaction temperature is preferably 85~180 DEG C, and pressure is preferably smaller than 0.80MPa gauge pressure.
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 compound emulsifying agent for oil base drilling fluid of paste or solution state.
To solve above-mentioned technical problem three, the technical solution adopted in the present invention is as follows：A kind of oil base drilling fluid is applicable
Application of the compound emulsifying agent in oil base drilling fluid.
In above-mentioned technical proposal, the application method, those skilled in the art can be according to practical application using known normal
Knowledge is applied, such as but do not limit, with the volume matter for accounting for grease of primary emulsion contained by compound emulsifying agent and coemulsifier
Percentage meter is measured, the dosage of compound emulsifying agent is no less than 0.1%, preferably 0.1~10%；The oil base drilling fluid can be entirely
Oil base drilling fluid is also possible to Water-In-Oil drilling fluid；In the application, oil base drilling fluid can arbitrarily add those skilled in the art
Various oil base drilling fluid auxiliary agents known to member.
Fatty acyl group hydroxyethyl diamine and/or fatty acyl group diamines Polyoxyalkylene ethers prepared by the present invention are bored for oil base
The compound emulsifying agent of well liquid has good resistance to mild salt resistant character, and has good dissolubility and emulsion stability, and should
Oil-based drilling fluid emulsifying agent has the advantages that nontoxic, harmless, biological degradability is good, is suitable for as high temperature and high salt water sensitivity
The oil base drilling fluid emulsifier of layer；Furthermore of the invention preparation method is simple, and raw material is easy to get, and has preferable economy can
Row is suitable for industrial application.
Using fatty acyl hydroxyethyl diamines prepared by the present invention and/or fatty acyl group diamines Polyoxyalkylene ethers class surface-active
The compound emulsifying agent of agent and fatty acid or fatty acid salt is used for oil base drilling fluid, and mainly composition includes following component：Base oil
60~90 parts, 10~40 parts of water, 0.1~5 part of compound emulsifying agent (in terms of the quality of the primary emulsion contained by the compound emulsifying agent).The oil
Base drilling fluid heatproof is greater than 180 DEG C, API filtration can be greater than 1200V for emulsion-breaking voltage after 0ml, high temperature ageing, is a kind of heatproof
Function admirable, filter loss be small, good emulsion stability oil base drilling fluid system.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
(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 1:1) it is added 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.
【Embodiment 2】
(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 1 to calcium compound:1) it is added equipped with condensing unit, agitating device and gas distributor
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.
【Embodiment 3】
(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 1:1) it is added 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.
【Embodiment 4】
(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
Changing calcium compound, (calcium oxide and calcium hydroxide weight ratio are 1:1) N, N '-stearic bicine diester base are reacted to obtain under the action of in 150 DEG C
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.
【Embodiment 5】
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 fatty acyl 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.
【Embodiment 6】
(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
(calcium oxide and calcium hydroxide weight ratio are 1 to mixture:1) height equipped with condensing unit, agitating device and gas distributor is added
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.
【Embodiment 7】
With【Embodiment 1】Obtained compound emulsifying agent, prepare oil base drilling fluid system, the basic recipe used for
210mL5# white oil+90mL 20wt%CaCl2Aqueous solution+3wt/vol% compound emulsifying agent emulsifier+3wt/vol% organoclay
(the modified montmorillonite of hexadecyltrimethylammonium chloride)+1wt/vol% cetylamine modified+1% butadiene rubber of humic acid (number
The ten thousand)+1wt/vol%CaO powder of average molecular weight 25.
Specific experiment process is：210mL5# white oil is taken, 3wt/vol% emulsifier is then added, stirs evenly, then successively
3wt/vol% organoclay, 1wt/vol% modified humic acid, 1% butadiene rubber and 1wt/vol%CaO powder is added, continues to stir
It mixes uniformly, is eventually adding 90mL 20wt%CaCl2Aqueous solution is stirred for uniformly, obtaining stable water-in-oil type wellbore fluid
System.According to《GB/T 16782-1997 oil base drilling fluid On-Site Test Procedure》The water-in-oil type drilling fluid system is measured respectively
Rheological parameter, emulsion-breaking voltage and API filtration.Wherein rheological parameter uses the ZNN-D6 type six of the sensible special instrument factory in Qingdao sea
It is measured under 50 degrees Celsius of fast rotational viscometer, and plastic viscosity (PV), yield value is calculated according to formula (1), (2) and (3)
(YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV)；Emulsion-breaking voltage (ES) is surveyed by the DWY-2 type drilling fluid electrical stability of the sensible special instrument factory in Qingdao
Determine to measure at 50 DEG C of instrument, 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 water-in-oil type drilling fluid is put into XGRL-4 type high temp roller heating furnace, 180 DEG C of high temperature are old
Change 16h, measures rheological parameter, emulsion-breaking voltage and the API filtration of the water-in-oil type drilling fluid system, instrument and mistake respectively
Before journey is with aging, the results are shown in Table 1.
【Embodiment 8】
With【Embodiment 5】The compound emulsifying agent of synthesis, prepare oil base drilling fluid system, the basic recipe used for
270mL5# white oil+30mL 20wt%CaCl2Aqueous solution+2wt/vol% compound emulsifying agent+3wt/vol% organoclay (hexadecane
The modified organoclay of base trimethylammonium bromide)+1wt/vol% cetylamine modified humic acid+1wt/vol% EP rubbers (number
The ten thousand)+1wt/vol%CaO powder of average molecular weight 15.Together【Embodiment 7】Specific experiment process measures the water-in-oil type drilling well respectively
Rheological parameter, emulsion-breaking voltage and API filtration, test result before and after liquid system aging is as shown in table 1.
【Comparative example 1】
Together【Embodiment 7】, for difference with 3wt/vol% oleic acid substitution 3wt/vol% compound emulsifying agent, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system are determined, the results are shown in Table 2.Contrast table 1
The rheological property that data can be seen that oleic acid formation is poor, exceeds measuring range, emulsion-breaking voltage is also than emulsification dosage form of the invention
At system want low and filter loss is larger.
【Comparative example 2】
Together【Embodiment 7】, difference is with 3wt/vol%N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z
It=0) is 4 with oleic acid quality proportioning:1 substitutes compound emulsifying agent of the invention for emulsifier dosage 3wt/vol%, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system are determined, the results are shown in Table 2.Contrast table 1
Data can be seen that N, and the system that N '-bis- vegetable oil acids acyl group propane diamine is formed, emulsion-breaking voltage is also than emulsifier of the invention
The system of formation wants low and filter loss is larger.
【Comparative example 3】
Together【Embodiment 7】, difference is with 3wt/vol%N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z
It=0) is 4 with oleic acid quality proportioning:1 substitutes compound emulsifying agent of the invention for emulsifier dosage 3wt/vol%, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system are determined, the results are shown in Table 2.Contrast table 1
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】
Together【Embodiment 7】, difference is with 3wt/vol%N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z
It=0) is 4 with oleic acid quality proportioning:1 substitutes compound emulsifying agent of the invention for emulsifier dosage 3wt/vol%, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system are determined, the results are shown in Table 2.Contrast table 1
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】
Together【Embodiment 7】, difference is with 3wt/vol%N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z
It=0) is 4 with oleic acid quality proportioning:1 substitutes compound emulsifying agent of the invention for emulsifier dosage 3wt/vol%, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil type drilling fluid system are determined, the results are shown in Table 2.Contrast table 1
Data can be seen that the system of INVERMUL formation, and rheological property is poor before and after aging, exceed measuring range, emulsion-breaking voltage
Also lower than the system that emulsifier of the invention is formed.
【Comparative example 6】
Together【Embodiment 7】, difference is with N obtained in embodiment 1, N '-bis- vegetable oil acids acyl group ethoxy propane diamine
And N, N '-bis- vegetable oil acids acyl group hydroxyethyl ethylenediamine polyoxyethylene ether (y=3, z=5) quality proportioning are 4:1 is emulsifier
Dosage 3wt/vol% alternative composite emulsifier, remaining is identical, determines rheological parameter, the demulsification of water-in-oil type drilling fluid system
Voltage and API filtration, the results are shown in Table 2.
【Comparative example 7】
Together【Embodiment 7】, difference is with N obtained in 3wt/vol% embodiment 1, N '-bis- vegetable oil acids acyl group hydroxyl
Ethyl propane diamine alternative composite emulsifier, remaining is identical, determines rheological parameter, the emulsion-breaking voltage of water-in-oil type drilling fluid system
And API filtration, the results are shown in Table 2.
【Comparative example 8】
Together【Embodiment 7】, difference is with N obtained in 3wt/vol% embodiment 1, N '-bis- vegetable oil acids acyl group hydroxyl
Ethylethylenediamine polyoxyethylene ether (y=3, z=5) alternative composite emulsifier, remaining is identical, determines water-in-oil type wellbore fluid
Rheological parameter, emulsion-breaking voltage and the API filtration of system, the results are shown in Table 2.
Comparative example 7 and comparative example 1, comparative example 6~8 can be seen that the compound emulsifying agent effect in embodiment 7 most
It is good.
【Comparative example 9】
Together【Embodiment 8】, difference is with lauroyl hydroxyethyl ethylenediamine obtained in embodiment 5 and oleic acid by quality
Proportion 5:1 substitutes compound emulsifying agent of the invention for emulsifier dosage 2wt/vol%, remaining is identical, determines water-in-oil type brill
Rheological parameter, emulsion-breaking voltage and the API filtration of well liquid system, the results are shown in Table 2.
【Comparative example 10】
Together【Embodiment 8】, difference is with lauroyl hydroxyethyl ethylenediamine obtained in embodiment 5 and calcium oleate by matter
Amount proportion 5:1 substitutes compound emulsifying agent of the invention for emulsifier dosage 2wt/vol%, remaining is identical, determines water-in-oil type
Rheological parameter, emulsion-breaking voltage and the API filtration of drilling fluid system, the results are shown in Table 2.
Table 1
Table 2
Claims (9)
1. a kind of compound emulsifying agent for oil base drilling fluid, including following components：
(1) primary emulsion, selected from least one of structure shown in formula (I)；
(2) coemulsifier, selected from least one of structure shown in formula (II)；
R4-COO(M)n, (II)
Wherein, 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 when alkali metal, n=1, when M is alkaline-earth metal, n=0.5, when M is iron or aluminium, n=1/3；In mass, the main cream
Agent and the ratio of coemulsifier meet 0 < coemulsifier:Primary emulsion≤1.
2. the compound emulsifying agent according to claim 1 for oil base drilling fluid, it is characterised in that the R1And R3It is independent
Selected from C11~C23Saturated or unsaturated alkyl or C11~C23Saturated hydrocarbyl and unsaturated alkyl mixing alkyl.
3. the compound emulsifying agent according to claim 2 for oil base drilling fluid, it is characterised in that the R1And R3It is independent
The saturated hydrocarbons or unsaturated alkyl or 11, ten for being 11,13,15,17,19,21 selected from carbon atom number
Three, the mixing alkyl of 15,17,19,21 saturated hydrocarbons and unsaturated hydrocarbons.
4. the compound emulsifying agent according to claim 1 for oil base drilling fluid, it is characterised in that x be 2 or 3, y be 1~
10, z=0~20.
5. the compound emulsifying agent according to claim 1 for oil base drilling fluid, it is characterised in that the R4For C11~C23
Saturated hydrocarbyl or unsaturated alkyl.
6. a kind of preparation method of any compound emulsifying agent for oil base drilling fluid of Claims 1 to 5, including it is following
Step：
(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. hydroxyethyl diamine)
80~220 DEG C at a temperature of react 2~24 hours, preferred vacuum distillation removes unreacted raw material and generation after reaction
Methanol obtain 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)zThe preparation of H (i.e. fatty acyl group diamines Polyoxyalkylene ethers)：
In the presence of basic catalyst, fatty acyl hydroxyethyl diamines synthesized by step (a) and required ethylene oxide or ring
Ethylene Oxide is reacted to obtain the fat acyl group diamines Polyoxyalkylene ethers；
(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.
7. the preparation method of the compound emulsifying agent according to claim 6 for oil base drilling fluid, it is characterised in that step
(a) basic catalyst described in is at least one of alkali metal hydroxide, alkaline earth metal hydroxide.
8. the preparation method of the compound emulsifying agent according to claim 6 for oil base drilling fluid, it is characterised in that step
(b) basic catalyst described in is at least one of alkaline earth oxide, alkaline earth metal hydroxide.
9. any answering in oil base drilling fluid of the compound emulsifying agent for oil base drilling fluid according to claim 1~5
With.
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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 |
| CN103897671A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | High-performance composite oil-based emulsifier and its preparation method |
| CN103897172A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Phenol ether sulfonate oil-based emulsifier and preparation method thereof |
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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 |
| CN103897671A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | High-performance composite oil-based emulsifier and its preparation method |
| CN103897172A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Phenol ether sulfonate oil-based emulsifier and preparation method thereof |
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