CN105567187B - Water in oil emulsion drilling fluid and preparation method thereof - Google Patents
Water in oil emulsion drilling fluid and preparation method thereof Download PDFInfo
- Publication number
- CN105567187B CN105567187B CN201410537998.9A CN201410537998A CN105567187B CN 105567187 B CN105567187 B CN 105567187B CN 201410537998 A CN201410537998 A CN 201410537998A CN 105567187 B CN105567187 B CN 105567187B
- Authority
- CN
- China
- Prior art keywords
- drilling fluid
- water
- oil
- oil emulsion
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of water in oil emulsion drilling fluid 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 part of base oil；(2) 10~40 parts of water；(3) 2~5 parts of organoclay；(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 water in oil emulsion drilling fluids and preparation method thereof.
Background technology
Difficult with the continuous reduction and exploitation of petroleum reserves, countries in the world are increased one after another to deep formation petroleum resources
The input 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 mating 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 compositions 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 high temperature resistance 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 it is up to 25% still to have good rheological characteristic and emulsion-breaking voltage, water content after 16 hours in 150 DEG C of agings.Patent CN
A kind of high-temperature water-in-oil drilling fluid of 102031095A Shen Qing Publications, although heatproof can be to 240 DEG C, it must be by co-emulsifier
Agent and the presence of calcium oxide can be only achieved application effect.Oil base drilling fluid is expensive since base fluid is based on oil, cost
Height, full oil base drilling fluid is even more so, if CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsifier used
For one or more mixtures in Long carbon chain fatty acid amide, Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid ester, although
Has many advantages, such as low toxicity, environmental protection, small to reservoir damage, but its manufacturing cost is high, limits it and promotes the use of.
It provides currently on the market and is used as the of less types of oil-based drilling fluid emulsifying agent, and report the breast 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
Mating drilling fluid system is also less.
Oil base drilling fluid develops always relatively slowly due to being limited by cost, environmental requirement, 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, to be provided extensively using oil base drilling fluid operation
Technical guarantee.In the case of the invention exactly this high-moisture, it is suitable for fatty acyl group diamines Polyoxyalkylene ethers being emulsification
Oil base drilling fluid of agent and preparation method thereof.
Invention content
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
Heat safe problem provides a kind of new water in oil emulsion drilling fluid.This water in oil emulsion drilling fluid has heat resistance good, newborn
The good advantage of liquid stability, can be used for strong retraction, high-temperature stratum and need to bore big displacement exceptional well, seaborne horizontal well etc. it is special
In drillng operation.The second technical problem to be solved by the present invention is to provide one kind and solves the corresponding oil of one of technical problem
The preparation method of packet aqueous drilling fluid.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of Water-In-Oil Emulsified drilling
Liquid, 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；
(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 selected from logical
At least one of structure shown in formula (II)；In mass, the ratio of the primary emulsion and coemulsifier meets 0 < auxiliary
Emulsifier:Primary emulsion≤1；
In general formula, R1To contain 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, R5And R6It is independently chosen from H, C2
~C4Hydroxyalkyl in one kind.
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 the mixing alkyl of unsaturated hydrocarbons；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；R5And R6Independent is preferably in H, ethoxy, hydroxypropyl
One kind, further preferably R5And R6One kind in independent preferably H, ethoxy, more preferably R5And R6Common preferably H,
One kind in ethoxy.
In above-mentioned technical proposal, the base oil is preferably the one or more in 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 bentonite or above-mentioned quaternary ammonium salt-modified montmorillonite that the long chain quaternary that atomicity is 12,14,16,18 is modified；
Alkaline matter is preferably lime powder；Tackifier are preferably butadiene rubber, butadiene-styrene rubber, EP rubbers, polymethylacrylic acid
One or more kinds of mixtures in Arrcostab；Fluid loss additive is preferably the humic acid that long-chain organic amine is modified, and chain length is excellent
It is selected as 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.
In above-mentioned technical proposal, the coemulsifier can be further preferably from two or more in structure shown in (II)
Mixture.
In above-mentioned technical proposal, in mass, the ratio of the primary emulsion and coemulsifier is most preferably to assist breast
Agent:Primary emulsion=1:(2~10).
In above-mentioned technical proposal, the coemulsifier can be further preferably from lauric amide, myristic acid amide, palm fibre
Palmitic acid acid amide, palmitoleic acid amide, oleamide, linoleamide, leukotrienes amide, stearic amide, lauric acid monoethanol
Amide, myristic acid single ethanol amide, palmitic monoethanolamide, palmitoleic acid single ethanol amide, oleic monoethanolamide, Asia
One or two or more kinds of mixtures in oleic monoethanolamide, leukotrienes single ethanol amide, stearic acid monoethanolamide；Also
It can further preferably include the mixture of above-mentioned fatty acid amide or fatty monoethanol amide, such as but not limit by this
Vegetable fat or biodiesel known to field technology personnel are that raw material carries out amidation process with corresponding amidation reagent
Obtained from vegetable oil acid amide, vegetable oil acid single ethanol amide or vegetable oil acid diglycollic amide.
In above-mentioned technical proposal, the preparation method of the coemulsifier can be well-known to those skilled in the art
Meaning is a kind of, can be any one before this in well known preparation method disclosed in document.
The key problem in technology of the present 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.
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 Water-In-Oil Emulsified drilling
Liquid and preparation method thereof includes 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. ethoxys
Diamines) it is reacted at a temperature of 80~220 DEG C 2~24 hours, preferred vacuum distillation after reaction removes unreacted raw material
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 aliphatic 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, the fatty acyl hydroxyethyl diamines synthesized by step (a) and required ethylene oxide
Or propylene oxide is 80~180 DEG C in reaction temperature, pressure under the conditions of being less than 0.80MPa gauge pressures carries out that the fat is obtained by the reaction
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) it is suitable for the preparation of 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, are obtained described suitable for the compound of oil base drilling fluid
Emulsifier；
(d) preparation of water in oil emulsion drilling fluid
The compound emulsifying agent that step (c) is obtained and base oil, water, organoclay, the alkaline matter, tackifier, drop
Fluid loss agents mixing and emulsifying obtains the water in oil 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
To account for the 0.5~5.0% of fatty acid methyl esters monomer mass；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.
In above-mentioned technical proposal, the oil base drilling fluid compound emulsifying agent can be the primary emulsion and co-emulsifier
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 oils, is obtained
The oil base drilling fluid compound emulsifying agent of paste or solution state.
Water in oil emulsion drilling fluid prepared by the present invention, due to the use of compound emulsifying agent to make it have good heatproof resistance to
Salt performance, so that the water in oil emulsion drilling fluid has the stability of excellent high temperature.The water in oil emulsion drilling fluid is resistance to
Temperature is that a kind of heat resistance is good, filter loss up to emulsion-breaking voltage >=1200V before and after 180 DEG C, API filtration≤3ml, high temperature ageing
Small, good emulsion stability oil base drilling fluid system.
Below by embodiment, the present invention is further elaborated.
Specific implementation mode
【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 of stirrings 1 hour, slowly it is added dropwise in 35 parts, 1 hour of methyl laurate and is added dropwise.
It is reacted 6 hours at 155 DEG C, the condensed pipe of methanol generated in reaction is collected into receiving flask, 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 of oil base drilling fluid compound emulsifying agent
In terms of mass fraction, lauroyl hydroxyethyl ethylenediamine, 5 parts of vegetable oil acid list second that 50 parts of steps (a) are obtained
Alkylolamides and 5 parts of oleamides, the heating stirring at 85 DEG C are uniformly mixed, and obtain the composite emulsifying suitable for oil base drilling fluid
Agent.
(c) preparation of water in oil emulsion drilling fluid
Weigh 6 grams of the compound emulsifying agent that step (b) obtains, measurement 270mL5# white oils enter stainless steel height and stir in cup, high-speed stirring
Mix 20min, sequentially add cetyl trimethylammonium bromide modification 9 grams of organoclay, cetylamine be modified 3 grams of humic acid,
3 grams of 3 grams of EP rubbers (number-average molecular weight 150,000) and CaO powder continue high-speed stirred 20min, are eventually adding 30mL 20wt%
CaCl2Aqueous solution, then high-speed stirred 20min obtain stable water in oil emulsion drilling fluid system.According to《GB/T 16782-
1997 oil base drilling fluid On-Site Test Procedures》Rheological parameter, the emulsion-breaking voltage of the water in oil emulsion drilling fluid system are measured respectively
And API filtration.Wherein rheological parameter uses the fast rotational viscometer of ZNN-D6 types six of the sensible special instrument factory in Qingdao sea in 50
It is measured at DEG C, and plastic viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV) is calculated according to formula (1), (2) and (3)；
Emulsion-breaking voltage (ES) is measured by the DWY-2 type drilling fluid electrical stability analyzers of the sensible special instrument factory in Qingdao at 50 DEG C, API
Filter loss is measured by the multi-joint filtration device of SD types, 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 emulsion drilling fluid is put into XGRL-4 type high temp roller heating furnaces, 180 DEG C of high temperature
Aging 16 hours measures rheological parameter, emulsion-breaking voltage and the API filtration of the water in oil emulsion drilling fluid system respectively, used
Before instrument and process are 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
Pipe, receiving flask reactor in, after 150 DEG C of stirrings 1 hour, be slowly added dropwise in 70 parts, 1 hour of methyl laurate and drip
Finish.It is reacted 16 hours at 180 DEG C, the methanol generated in reaction is collected by condenser west tube in receiving flask, 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 by system temperature, opens vacuum system, and it is small to be dehydrated 2 under a high vacuum
When, then being purged 4 times with nitrogen, system reaction temperature, which is adjusted to 140 DEG C, 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 of oil base drilling fluid compound emulsifying agent
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 lauric acid amide of ethanol, are added in 150 parts of 5# white oils, the heating stirring at 90 DEG C, are uniformly mixed,
Obtain the compound emulsifying agent suitable for oil base drilling fluid.
(d) preparation of Water-In-Oil drilling fluid
Weigh 12 grams of compound emulsifying agent that step (c) obtains (with the N contained by compound emulsifying agent, N '-bis- lauroyls hydroxyl
The quality meter of ethylethylenediamine polyoxyethylene ether (y=5) and lauric acid amide of ethanol), measure 240mL5# white oils be added it is stainless
Steel height stirs in cup, high-speed stirred 20min, sequentially adds 6 grams of organoclay, the cetylamine of hexadecyltrimethylammonium chloride modification
6 grams modified of 3 grams of humic acid, 3 grams of butadiene-styrene rubber (number-average molecular weight 200,000) and CaO powder continues high-speed stirred 20min, most
60mL 25wt%NaCl aqueous solutions, then high-speed stirred 20min are added afterwards, obtains stable water in oil emulsion drilling fluid system.Together
【Embodiment 1】(b) performance before and after system aging is measured, 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
Pipe, receiving flask reactor in, after 145 DEG C of stirrings 1 hour, be slowly added dropwise in 270 parts, 1 hour of methyl stearate and drip
Finish.It is reacted 12 hours at 165 DEG C, the methanol generated in reaction is collected by condenser west tube in receiving flask.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 are with 185.4 parts of propylene oxide 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) it is suitable for the preparation of 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 '-stearic bicine diester base dihydroxy ethyl ethylenediamine polyoxy third
Alkene ether (y=1, z=10) and 10 parts of oleic monoethanolamides and 10 parts of stearic acid monoethanolamides, the heating stirring at 85 DEG C,
It is uniformly mixed, obtains the compound emulsifying agent suitable for oil base drilling fluid.
(d) preparation of Water-In-Oil drilling fluid
Weigh 6 grams of the compound emulsifying agent that step (c) obtains, measurement 210mL atoleines enter stainless steel height and stir in cup, high speed
20min is stirred, sequentially adds 10.5 grams of the organoclay of cetyl trimethylammonium bromide modification, the humic acid that lauryl amine is modified
6 grams of 6 grams, EP rubbers (number-average molecular weight 50,000) and polymethylacrylic acid cetyl ester (number-average molecular weight 500,000) mixture
And 3 grams of CaO powder, continue high-speed stirred 20min, is eventually adding 90mL 20wt%CaCl2Aqueous solution, then high-speed stirred
20min obtains stable water in oil emulsion drilling fluid system.Together【Embodiment 1】(b) performance before and after system aging, knot are measured
Fruit is 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- ethoxys propane diamine is added to cold equipped with sealing machine stirring, thermometer, straight type
Solidifying pipe, receiving flask reactor in, after 150 DEG C of stirrings 1 hour, be slowly added dropwise in 281.3 parts, 1 hour of methyl erucate and be 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, which is adjusted to 180 DEG C, 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) it is suitable for the preparation of 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 '-bis- erucic acid acyl group ethoxy propane diamine polyoxyethylene
Polyethenoxy ether (y=10, z=20) and 10 parts of oleamides, the heating stirring at 85 DEG C are uniformly mixed, and obtain being suitable for oil
The compound emulsifying agent of base drilling fluid.
(d) preparation of Water-In-Oil drilling fluid
Weigh 9 grams of the compound emulsifying agent that step (c) obtains, measurement 195mL atoleines enter stainless steel height and stir in cup, high speed
20min is stirred, sequentially adds 12 grams of the organoclay of cetyl trimethylammonium bromide modification, the humic acid 3 that cetylamine is modified
Gram, 4.5 grams of 3 grams of butadiene rubber (number-average molecular weight 180,000) and CaO powder, continue high-speed stirred 20min, be eventually adding 105mL
20wt%CaCl2Aqueous solution, then high-speed stirred 20min obtain stable water in oil emulsion drilling fluid system.Together【Embodiment 1】
(b) performance before and after system aging is measured, 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- ethoxys 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%, palmitic 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
Then water 2 hours is 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, control
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, is neutralized after cooling, dehydration, 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) it is suitable for the preparation of 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 portions of plants
Oleic monoethanolamide (it synthesizes to obtain by methyl soyate and monoethanolamine, wherein in terms of mass percentage, soybean
Soyate includes following components：Tetradecanoic acid formicester 0.557%, palmitic acid formicester 18.250%, palmitoleic acid formicester
1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, leukotrienes formicester
3.587%, surplus other.), the heating stirring at 90 DEG C is uniformly mixed, and obtains the composite emulsifying suitable for oil base drilling fluid
Agent.
(d) preparation of Water-In-Oil drilling fluid
Weigh 9 grams of the compound emulsifying agent that step (c) obtains, measurement 210mL5# white oils enter stainless steel height and stir in cup, high-speed stirring
Mix 20min, sequentially add hexadecyltrimethylammonium chloride modification 9 grams of organoclay, cetylamine be modified 3 grams of humic acid,
3 grams of 3 grams of butadiene rubber (number-average molecular weight 250,000) and CaO powder continue high-speed stirred 20min, are eventually adding 90mL 20wt%
CaCl2Aqueous solution, then high-speed stirred 20min obtain stable water in oil emulsion drilling fluid system.Together【Embodiment 1】(d) it measures
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- ethoxys 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%, palmitic 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
Then water 2 hours is 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, control
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) it is suitable for the preparation of 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 '-bis- vegetable oil acids acyl group ethoxy propane diamine polyoxy
Vinethene (y=3, z=0) and 50 parts of lauric amides, the heating stirring at 80 DEG C are uniformly mixed, and obtain being suitable for oil base brill
The compound emulsifying agent of well liquid.
(d) preparation of Water-In-Oil drilling fluid
Weigh 9 grams of the compound emulsifying agent that step (c) obtains, measurement 210mL5# white oils enter stainless steel height and stir in cup, high-speed stirring
Mix 20min, sequentially add hexadecyltrimethylammonium chloride modification 9 grams of organoclay, cetylamine be modified 3 grams of humic acid,
3 grams of 3 grams of butadiene rubber (number-average molecular weight 200,000) and CaO powder continue high-speed stirred 20min, are eventually adding 90mL 20wt%
CaCl2Aqueous solution, then high-speed stirred 20min obtain stable water in oil emulsion drilling fluid system.Together【Embodiment 1】(d) it measures
Performance before and after system aging, as a result as shown in table 1,2.
【Comparative example 1】
Together【Embodiment 5】In (d), difference is with 9g vegetable oil acid single ethanol amide alternative composite emulsifiers, remaining phase
Together, rheological parameter, emulsion-breaking voltage and the API filtration of water in oil emulsion drilling fluid system are determined, the results are shown in Table 3.
【Comparative example 2】
Together【Embodiment 5】(d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine (x=3, y=0, z=0) with
Vegetable oil acid single ethanol amide quality proportioning is 3:1 substitutes the compound emulsifying agent of the present invention for emulsifier dosage 9g, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water in oil emulsion drilling fluid system are determined, the results are shown in Table 4.Contrast table
1 data can be seen that N, and the system that N '-bis- vegetable oil acids acyl group propane diamine is formed, rheological property is poor before and after aging, super
Go out measuring range, emulsion-breaking voltage is also lower than the system that the emulsifier of the present invention is formed.
【Comparative example 3】
Together【Embodiment 5】(d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y
=0, z=3) with vegetable oil acid single ethanol amide quality proportioning be 3:1 substitutes the composite emulsifying of the present invention for emulsifier dosage 9g
Agent, remaining is identical, determines rheological parameter, emulsion-breaking voltage and the API filtration of water in oil emulsion drilling fluid system, as a result such as table
Shown in 5.1 data of contrast table can be seen that N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y=0, z=
3) system formed, system yield value, the emulsion-breaking voltage of formation are relatively low, and filter loss is larger.
【Comparative example 4】
Together【Embodiment 5】(d), difference is with N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y
=0, z=5) with vegetable oil acid single ethanol amide quality proportioning be 3:1 substitutes the composite emulsifying of the present invention for emulsifier dosage 9g
Agent, remaining is identical, determines rheological parameter, emulsion-breaking voltage and the API filtration of water in oil emulsion drilling fluid system, as a result such as table
Shown in 6.1 data of contrast table can be seen that N, N '-bis- vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y=0, z=
5) system formed, system yield value, the emulsion-breaking voltage of formation are relatively low, and filter loss is larger.
【Comparative example 5】
Together【Embodiment 5】(d), difference with INVERMUL emulsifiers (production of Halliburton Baroid companies) with
Vegetable oil acid single ethanol amide quality proportioning is 3:1 substitutes the compound emulsifying agent of the present invention for emulsifier dosage 9g, remaining is identical,
Rheological parameter, emulsion-breaking voltage and the API filtration of water in oil emulsion drilling fluid system are determined, the results are shown in Table 7.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 the emulsifier of the present invention is formed.
【Comparative example 6】
Together【Embodiment 5】(d), difference with the quality proportioning that is obtained in embodiment 5 for 3:1 N, N '-bis- vegetable oil
Sour acyl group ethoxy propane diamine and N, N '-bis- vegetable oil acids acyl group hydroxyethyl ethylenediamine polyoxyethylene ether (y=3, z=5) are breast
Agent dosage 9g substitutes the compound emulsifying agent of the present invention, remaining is identical, determines the rheology ginseng of water in oil emulsion drilling fluid system
Number, emulsion-breaking voltage and API filtration, the results are shown in Table 8.
【Comparative example 7】
Together【Embodiment 5】(d), N of the difference to be obtained in embodiment 5, N '-bis- vegetable oil acids acyl group ethoxy third
Diamines 9g substitutes the compound emulsifying agent of the present invention, remaining is identical, determines the rheological parameter of water in oil emulsion drilling fluid system, breaks
Newborn voltage and API filtration, the results are shown in Table 9.
【Comparative example 8】
Together【Embodiment 5】(d), N of the difference to be obtained in embodiment 5, N '-bis- vegetable oil acids acyl group ethoxy second
Diamines polyoxyethylene ether (y=3, z=5) 9g substitutes the compound emulsifying agent of the present invention, remaining is identical, determines Water-In-Oil emulsification and bores
Rheological parameter, emulsion-breaking voltage and the API filtration of well liquid system, 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】
Together【Embodiment 1】(d), lauroyl hydroxyethyl ethylenediamine and vegetable oil of the difference to be obtained in embodiment 1
Sour single ethanol amide presses quality proportioning 5:1 substitutes the compound emulsifying agent of the present invention for emulsifier dosage 6g, remaining is identical, determines
Rheological parameter, emulsion-breaking voltage and the API filtration of water in oil emulsion drilling fluid system, as a result as shown in table 11.
【Comparative example 10】
Together【Embodiment 1】(d), lauroyl hydroxyethyl ethylenediamine and oleic acid acyl of the difference to be obtained in embodiment 1
Amine presses quality proportioning 5:1 substitutes the compound emulsifying agent of the present invention for emulsifier dosage 6g, remaining is identical, determines Water-In-Oil emulsification
Rheological parameter, emulsion-breaking voltage and the API filtration of drilling fluid 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 2180 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 (13)
1. a kind of water in oil 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；
（4）Compound emulsifying agent including primary emulsion and coemulsifier is no less than 0.5 part, with contained primary emulsion and auxiliary breast
The quality meter of agent；
（5）0 ~ 3 part of alkaline matter；
（6）0.5 ~ 3 part of tackifier；
（7）0.5 ~ 3 part of fluid loss additive；
Wherein, the primary emulsion is selected from general formula（I）At least one of shown structure, coemulsifier are selected from general formula（Ⅱ）Institute
Show at least one of structure；In mass, the ratio of the primary emulsion and coemulsifier meets 0 < coemulsifiers:
Primary emulsion≤1；
,（I）
,（Ⅱ）
In general formula, R1To contain C8~C30Saturation or unsaturated alkyl, R2For hydrogen, x=1~10, y=1~40, z=0~40；R4For
C7~C25Aliphatic group, R5And R6It is independently chosen from H, C2~C4Hydroxyalkyl in one kind.
2. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the base oil be diesel oil, white oil,
The mixture of one or more of synthetic oil.
3. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the water is 1 ~ 30wt% electrolyte water
Solution.
4. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the organoclay is carbon chain lengths C12~
C18Long chain quaternary be modified montmorillonite.
5. water in oil emulsion drilling fluid according to claim 1, it is characterised in that R1For C11~C23Saturation or unsaturation
Alkyl or C11~C23Saturated hydrocarbyl and unsaturated alkyl.
6. water in oil emulsion drilling fluid according to claim 1, it is characterised in that x=2 ~ 6, y=1 ~ 20, z=0 ~
30。
7. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the alkaline matter is alkali metal carbon
At least one of hydrochlorate, alkali metal oxide, calcium oxide or calcium hydroxide.
8. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the tackifier are butadiene rubber, fourth
The mixture of one or more of benzene rubber, EP rubbers, polyalkyl methacrylate, bitumen or oxidized asphalt.
9. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the fluid loss additive is that long-chain is organic
The mixture of one or more of amine modified humic acid, bitumen, oxidized asphalt.
10. water in oil emulsion drilling fluid according to claim 1, it is characterised in that the water in oil emulsion drilling fluid
Preparation method includes the following steps：
(a) R1CONH(CH2)xNR2CH2CH2OH（That is fatty acyl hydroxyethyl diamines）Preparation
R in the presence of basic catalyst1COOCH3（That is fatty acid methyl ester）With NH2(CH2)xNHCH2CH2OH（That is hydroxyethyl diamine）
It is reacted 2~24 hours at a temperature of 80 ~ 220 DEG C, the methanol for removing unreacted raw material and generation after reaction obtains institute
State 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, step（a）Synthesized fatty acyl hydroxyethyl diamines and required ethylene oxide or ring
Ethylene Oxide is 85~180 DEG C in reaction temperature, and pressure under the conditions of being less than 0.80MPa gauge pressures carries out that the fat acyl group is obtained by the reaction
Diamines Polyoxyalkylene ethers；
（c）The preparation of compound emulsifying agent suitable for oil base drilling fluid
By step（a）The obtained fatty acyl hydroxyethyl diamines and/or step（b）The obtained fatty acyl group diamines
Polyoxyalkylene ethers and the coemulsifier, are uniformly mixed in the ratio, obtain the Composite Milk for being suitable for oil base drilling fluid
Agent；
（d）The preparation of water in oil emulsion drilling fluid
By step（c）Obtained compound emulsifying agent and base oil, water, organoclay, the alkaline matter, tackifier, filtrate reducing
Agent mixing and emulsifying obtains the water in oil emulsion drilling fluid.
11. water in oil emulsion drilling fluid according to claim 10, it is characterised in that in step（a）In, after reaction
Methanol by being evaporated under reduced pressure the unreacted raw material of removing and generation obtains the fatty acyl hydroxyethyl diamines.
12. water in oil emulsion drilling fluid according to claim 10, it is characterised in that in step（b）In, the alkalinity is urged
Agent is at least one of calcium hydroxide, calcium oxide.
13. water in oil emulsion drilling fluid according to claim 10, it is characterised in that in step（b）In, catalyst amount
It is the 0.5~6.0% of fatty acyl hydroxyethyl diamines quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410537998.9A CN105567187B (en) | 2014-10-13 | 2014-10-13 | Water in oil emulsion drilling fluid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410537998.9A CN105567187B (en) | 2014-10-13 | 2014-10-13 | Water in oil emulsion drilling fluid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105567187A CN105567187A (en) | 2016-05-11 |
| CN105567187B true CN105567187B (en) | 2018-10-23 |
Family
ID=55877842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410537998.9A Active CN105567187B (en) | 2014-10-13 | 2014-10-13 | Water in oil emulsion drilling fluid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105567187B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0430602A1 (en) * | 1989-11-28 | 1991-06-05 | ALBRIGHT & WILSON UK LIMITED | Functional fluids |
| CN101935521A (en) * | 2010-07-19 | 2011-01-05 | 江南大学 | Application of alcohol amide nonionic surfactant for alkali-free flooding |
| 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 |
| CN103540299A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Drilling fluid for low-pressure water-sensitive stratum |
| CN103666417A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | High-performance oil-based drilling fluid and 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 |
-
2014
- 2014-10-13 CN CN201410537998.9A patent/CN105567187B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0430602A1 (en) * | 1989-11-28 | 1991-06-05 | ALBRIGHT & WILSON UK LIMITED | Functional fluids |
| 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 |
| CN101935521A (en) * | 2010-07-19 | 2011-01-05 | 江南大学 | Application of alcohol amide nonionic surfactant for alkali-free flooding |
| 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 |
| CN103540299A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Drilling fluid for low-pressure water-sensitive stratum |
| CN103666417A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | High-performance oil-based drilling fluid and 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105567187A (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105623629B (en) | water-in-oil type drilling fluid and preparation method thereof | |
| CN104232030B (en) | Oil base drilling fluid emulsifying agent and preparation method thereof | |
| CN103146364B (en) | Strong-inhibition water-base drilling fluid | |
| CN103540298B (en) | Oil base drilling fluid and preparation method thereof | |
| CN103772698B (en) | alkyl phenol ether carboxylate and preparation method thereof | |
| CN103540297B (en) | Composite oil-based emulsifier containing fatty alcohol polyoxyethylene polypropylene oxide ether carboxylate and preparation method thereof | |
| CN103897172B (en) | 2, 2-Oxydiphenol sulfonate oil base emulsifying agent and preparation method | |
| CN103897677B (en) | The oil base drilling fluid and preparation method of oil base emulsifying agent are combined using phenolic ether sulfonate | |
| CN105713591B (en) | Invert emulsion drilling fluid and preparation method thereof | |
| CN104277801A (en) | Anti-high-temperature emulsion tackifier for water-based drilling fluid and preparation method of tackifier | |
| CN103665367B (en) | Fatty alcohol polyoxyethylene polyoxypropylene ether sulfonate and preparation method thereof | |
| CN103666417B (en) | High-performance oil-based drilling fluid and preparation method thereof | |
| CN105567184B (en) | Compound emulsifying agent and its preparation method and application suitable for oil base drilling fluid | |
| CN105567187B (en) | Water in oil emulsion drilling fluid and preparation method thereof | |
| CN105713589B (en) | inverse emulsion drilling fluid and preparation method thereof | |
| CN105623630B (en) | Oil base drilling fluid compound emulsifying agent and its preparation method and application | |
| CN105713579B (en) | Compound emulsifying agent and its preparation method and application for oil base drilling fluid | |
| CN104232036B (en) | Oil base drilling fluid and preparation method thereof | |
| CN105567186B (en) | Water-In-Oil drilling fluid and preparation method thereof | |
| CN105713585B (en) | Full oil base drilling fluid and preparation method thereof | |
| CN105713588B (en) | Non-clay full oil base drilling fluid and preparation method thereof for water-sensitive formation | |
| CN105567183B (en) | Oil base drilling fluid compound emulsifying agent and its preparation method and application | |
| CN105713590B (en) | Drilling fluid and preparation method thereof for low-pressure water-sensitive stratum | |
| CN105713587B (en) | Full oil base drilling fluid of low-density and preparation method thereof | |
| CN105713584B (en) | Compound emulsifying agent that oil base drilling fluid is applicable in and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |