CN105713579A - Compound emulsifier for oil-based drilling fluid and preparation method and application thereof - Google Patents
Compound emulsifier for oil-based drilling fluid and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an emulsifier for oil-based drilling fluid and a preparation method and application thereof, and mainly solves the problem that an emulsifier for oil-based drilling fluid in the prior art is few in varieties and poor in emulsifying property and temperature resistance. The emulsifier for the oil-based drilling fluid comprises the following components: a main emulsifier selected from at least one of structures shown in a formula (I) and an auxiliary emulsifier selected from at least one of structures shown in a formula (II). According to the technical scheme, the ratio of the main emulsifier to the auxiliary emulsifier meets the following formula: 0< the auxiliary emulsifier: the main emulsifier</= 1, the problems are solved well, the emulsifier is used for the oil-based drilling fluid, and has good emulsifying property and temperature resistance, and the formed oil-based drilling fluid is good in stability and temperature resistance, and can meet special requirements of high-water-sensitivity and high-temperature stratum drilling and large-displacement special drilling in oil fields, offshore horizontal wells and the like.
Description
Technical field
The present invention relates to a kind of compound emulsifying agent for oil base drilling fluid and its preparation method and application.
Background technology
Along with constantly reducing and exploitation difficulty of petroleum reserves, countries in the world increase the input to deep formation Oil And Gas Exploration And Development one after another, develop new oil reservoir and have become as an urgent demand of current each major oil companies development.China's petroleum resources to be verified is mainly distributed on Tarim Basin, Zhunger Basin, Qaidam, tells the basins such as Kazakhstan, Sichuan, the 73% of its stock number is imbedded in deep layer, and underground condition complex, therefore deep-well and ultradeep well oil gas drilling and supporting development technique have become the key factor of restriction petrol resources exploitation.Along with the increase of depth of stratum, deep-well, ultradeep well formation temperature also can be more and more higher, can the hot environment on stratum maintain stable performance to drilling fluid and bring great challenge.
Drilling fluid is as the important component part of drilling engineering, and its performance is directly connected to deep-well, the drilling quality of ultradeep well, drilling cost and drilling period.Relative to water-base drilling fluid; oil base drilling fluid has stronger anti-collapse inhibition, lubricity and good reservoir protection performance; especially can meet strong retraction and high temperature, superhigh temperature stratum, or need to bore that big displacement exceptional well and seaborne horizontal well etc. are special turns drilling well needs.Oil base drilling fluid, also known as Water-In-Oil drilling fluid, is made up of oil, water, emulsifying agent, fluid loss additive, equilibrium of activation agent, flow pattern regulator etc..Normally used Water-In-Oil drilling fluid water content between 5～30% (water content within 5% generally referred to as full oil base drilling fluid, it is not called Water-In-Oil drilling fluid), but high temperature resistance reaches the content of water in the Water-In-Oil drilling fluid of more than 180 DEG C is typically in 5～10%, rarely exceeds 15%.The content of water increases, take bits property, filtration reduction and suspension, rheological characteristic all to improve, but heat stability and electrical stability are all deteriorated, as CN1660958 reports a kind of synthetic base drilling fluid, the mixture that primary emulsion is AESA and NPE used, although still having good rheological characteristic and emulsion-breaking voltage at 150 DEG C after aging 16 hours, water content is up to 25%.A kind of high-temperature water-in-oil drilling fluid of patent CN102031095A Shen Qing Publication, although heatproof can to 240 DEG C, but it must can be only achieved application effect by the existence of coemulsifier and calcium oxide.Oil base drilling fluid is owing to base fluid is based on oil, therefore expensive, cost is high, full oil base drilling fluid is all the more so, as CN101215461 reports a kind of complete-oil synthetic base drilling fluid, the emulsifying agent of use is one or more the mixture in Long carbon chain fatty acid amide, Long carbon chain alkyl benzene calcium sulfonate, polyolefin carboxylic acid ester, although have low toxicity, environmental protection, to advantages such as reservoir damage are little, but its preparation cost is high, limits it and promotes the use of.
There is provided in the market and be used as the of less types of oil base drilling fluid emulsifying agent, and report that the emulsifying agent kind for intensified oil reduction is relatively many, as US4485873, US4545912, CN100531884 etc. report polyoxyethylated alkyl phenol acetate, double; two tail chain polyoxyethylene sulfonic acid salt, the application in intensified oil reduction of the alkyl-fragrant benzyl-polyethenoxy ether anion surfactant, but it is not directed to its purposes in well-drilling liquid emulgent.Domestic oil base drilling fluid emulsifying agent aspect many dependences external product, and domestic supporting drilling fluid system is also less.
Oil base drilling fluid is owing to being subject to cost, the restriction of environmental requirement develops slower always, the block of application is also less, along with existing oilfield reserve declines day by day, and the exploitation in new exploratory area can run into various bad ground and environment, it is badly in need of carrying out meeting the research preparing stability and high efficiency oil base drilling fluid emulsifying agent, few to solve oil base drilling fluid emulsifying agent kind, emulsifiability is poor, not salt tolerant, the not problem of heatproof, the Cost Problems of oil base drilling fluid is reduced by improving the ratio of water in oil base drilling fluid, technical support is provided for extensive use oil base drilling fluid operation.
In this high-moisture situation just of the present invention, it is suitable for compound emulsifying agent preparing stability and high efficiency oil base drilling fluid and preparation method thereof.
Summary of the invention
One of the technical problem to be solved is that in prior art, oil base drilling fluid emulsifying agent kind is few, the problem of emulsifiability, heat resistance difference, it is provided that a kind of compound emulsifying agent for oil base drilling fluid.This compound emulsifying agent being used for oil base drilling fluid has good emulsifiability and heat resistance, and the oil base drilling fluid containing such compound emulsifying agent can meet strong retraction in oil field, high-temperature stratum and the big special requirement such as displacement Special Drilling Operation, seaborne horizontal well drilling well.
The preparation method that the two of the technical problem to be solved are to provide a kind of compound emulsifying agent for oil base drilling fluid corresponding with solving one of technical problem.
The three of the technical problem to be solved are to provide the application in oil base drilling fluid of a kind of compound emulsifying agent for oil base drilling fluid corresponding with solving one of technical problem.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of compound emulsifying agent for oil base drilling fluid, including following components:
(1) primary emulsion, at least one in structure shown in formula (I)；
(2) coemulsifier, at least one in 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 one in H, zinc, ferrum, aluminum, 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 ferrum or aluminum, n=1/3；In mass, described primary emulsion meets 0 < coemulsifier with the ratio of coemulsifier: primary emulsion≤1.
In technique scheme, described R1And R3It is independently selected from C11～C23Saturated or undersaturated alkyl or C11～C23Saturated hydrocarbyl and the mixing alkyl of unsaturated alkyl.More preferably R1And R3It is independently selected from saturated hydrocarbons or unsaturated alkyl that carbon number is 11,13,15,17,19,21 or the mixing alkyl of the saturated hydrocarbons of 11,13,15,17,19,21 and unsaturated hydrocarbons.Preferred x is 2～6, and y is 1～20, and z is 0～30；It is preferred that x is 2 or 3, y is 1～10；More preferably z is 0～20；Described R4It is preferably C11～C23Saturated hydrocarbyl or unsaturated alkyl；M is preferably the one in H, zinc or alkaline-earth metal.
In technique scheme, described coemulsifier can further most preferably from the mixture of one or two or more kinds in oleic acid, stearic acid, Palmic acid, myristic acid, lauric acid, calcium oleate, calcium stearate；In mass, described primary emulsion most preferably is coemulsifier with the ratio of coemulsifier: primary emulsion=1:(2～20).
In technique scheme, described primary emulsion it is preferred that two or more mixture in structure shown in (I), can play good synergism.
In technique scheme, described coemulsifier it is preferred that two or more mixture in structure shown in (II), can play good synergism.
For solving the two of above-mentioned technical problem, the technical solution adopted in the present invention is as follows: the preparation method of a kind of emulsifying agent for oil base drilling fluid, comprises the following steps:
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamidogen)
R under base catalyst exists1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. hydroxyethyl diamine) reacts 2～24 hours at the temperature of 80～220 DEG C, and the reaction methanol that after terminating, preferred decompression is distilled off unreacted raw material and generation obtains described fatty acyl hydroxyethyl diamidogen.Wherein, fatty acid methyl ester is preferred 1:0.1～6 with the mol ratio of hydroxyethyl diamine.Described catalyst amount preferably accounts for the 0.01～10% of fatty acid methyl ester quality.
(b)R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zThe preparation of H (i.e. fatty acyl group diamidogen Polyoxyalkylene ethers):
Under base catalyst exists, the fatty acyl hydroxyethyl diamidogen synthesized by step (a) reacts obtain described fat acyl group diamidogen Polyoxyalkylene ethers with required oxirane or expoxy propane.Catalyst amount is preferably the 0.5～6.0% of fatty acyl hydroxyethyl diamidogen quality；
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
The described fat acyl group diamidogen Polyoxyalkylene ethers that described fatty acyl hydroxyethyl diamidogen step (a) obtained and/or step (b) obtain and described coemulsifier; in described ratio mix homogeneously, obtain the described compound emulsifying agent for oil base drilling fluid.
In technique scheme, a) reaction temperature in step preferably ranges from 100～200 DEG C, more preferably 120～180 DEG C；Catalyst is preferably at least one in alkali metal hydroxide, alkaline earth metal hydroxide, more preferably potassium hydroxide, sodium hydroxide, more preferably potassium hydroxide, and consumption is preferably and accounts for the 0.5～5.0% of fatty acid methyl esters monomer mass；The mol ratio of fatty acid methyl ester and hydroxyethyl diamine is preferably 1～2:1；Response time is preferably 6～16 hours.
In technique scheme; b) base catalyst in step is preferably at least one in alkaline earth oxide, alkaline earth metal hydroxide; being more preferably at least one in calcium oxide, calcium hydroxide, catalyst amount is preferably and accounts for the 1～5.0% of fatty acyl hydroxyethyl diamidogen quality.Reaction temperature is preferably 85～180 DEG C, and pressure is preferably smaller than 0.80MPa gauge pressure.
In technique scheme, described oil base drilling fluid compound emulsifying agent can be described primary emulsion and coemulsifier mix homogeneously obtains, both can also be dissolved in solvent mix homogeneously to obtain, as both being dissolved in 5# white oil, obtain the compound emulsifying agent for oil base drilling fluid of paste or solution state.
For solving the three of above-mentioned technical problem, the technical solution adopted in the present invention is as follows: the compound emulsifying agent that a kind of oil base drilling fluid is suitable for application in oil base drilling fluid.
In technique scheme, described application process, those skilled in the art can adopt known general knowledge to be applied according to practical application, such as but do not limit, the volume mass percent basis accounting for profit with primary emulsion contained by compound emulsifying agent and coemulsifier, the dosage of compound emulsifying agent is no less than 0.1%, it is preferable that 0.1～10%；Described oil base drilling fluid can be full oil base drilling fluid, it is also possible to be Water-In-Oil drilling fluid；In described application, oil base drilling fluid can arbitrarily add various oil base drilling fluid auxiliary agent well-known to those skilled in the art.
Fatty acyl group hydroxyethyl diamine and/or the compound emulsifying agent for oil base drilling fluid of fatty acyl group diamidogen Polyoxyalkylene ethers prepared by the present invention have good resistance to gentle salt resistant character; and there is good dissolubility and emulsion stability; and this oil base drilling fluid emulsifying agent has advantage nontoxic, harmless, that biological degradability is good, it is suitable for being used as the oil base drilling fluid emulsifying agent of high temperature and high salt water-sensitive strata；In addition the preparation method of the present invention is simple, and raw material is easy to get, and has good economic feasibility, popularization and application suitable for industrialized.
Adopting the fatty acyl hydroxyethyl diamidogen prepared of the present invention and/or the fatty acyl group diamidogen Polyoxyalkylene ethers class surfactant compound emulsifying agent with fatty acid or soap for oil base drilling fluid, it mainly comprises and includes following component: base oil 60～90 parts, 10～40 parts of water, compound emulsifying agent 0.1～5 part (quality in primary emulsion contained by compound emulsifying agent).This oil base drilling fluid heatproof more than 180 DEG C, API filtration can be that after 0ml, high temperature ageing, emulsion-breaking voltage, more than 1200V, is that a kind of heat resistance is excellent, filter loss is little, the oil base drilling fluid system of good emulsion stability.
The present invention is further elaborated by the examples below.
Detailed description of the invention
[embodiment 1]
The synthesis (x=3) of (a) N, N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine
N-ethoxy propane diamine 55.3 parts, KOH8.33 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drip methyl soyate (in weight/mass percentage composition, methyl soyate comprises following components: tetradecanoic acid formicester 0.557%, Palmic acid formicester 18.250%, palmitic olefinic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.) 277.6 parts, dropwise in 1 hour.Reacting 8 hours at 165 DEG C, the methanol generated in reaction is collected in receiving flask through condenser west tube.Decompression distills out remaining low boiling product and reaction raw materials, obtains target product N, N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine.
The synthesis of (b) N, N ＇-bis-vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=3, z=5)
The N that step (a) is synthesized; N ＇-bis-256 parts, 15.4 parts calcium oxide of vegetable oil acid acyl group ethoxy propane diamine and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing unit, agitating device and gas distributor; when limit logical nitrogen limit heating is to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After elimination moisture, it is cooled to 80 DEG C, the sulphuric acid (20wt%) slowly dripping catalyst neutralisation theoretical amount prepares high activity, high selective compound oxidizing calcium alkoxylating catalyst reactant liquor system, system temperature is heated to 90 DEG C, open vacuum system, under a high vacuum dehydration 2 hours, then purge 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and slowly passes into 34.9 parts of oxirane, control pressure≤0.60MPa.After reacting ethylene oxide is complete; add 114.8 parts of expoxy propane; reaction is continued in 160 DEG C; reaction purges system with nitrogen after terminating, neutralization, dehydration after cooling; obtain N; N ＇-bis-vegetable oil acids acyl group hydroxyethylethylene diamine polyoxyethylene ether (y=3, z=5) 343.7 parts, molar yield 84.7%.
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; the N that 10 parts of steps (a) are obtained; the N that N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine, 30 parts of steps (b) obtain; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine polyoxyethylene ether (y=3; z=5) and 10 parts of oleic acid; heated and stirred at 90 DEG C, mix homogeneously, obtain the compound emulsifying agent for oil base drilling fluid.
[embodiment 2]
The preparation (x=3) of (a) N, N ＇-bis-erucic acid acyl group ethoxy propane diamine
Joining in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask by N-ethoxy propane diamine 47.13 parts, KOH5.6 part, after stirring 1 hour in 150 DEG C, slowly dropping methyl erucate 281.3 parts, dropwised in 1 hour.Stopping after reacting 10 hours at 170 DEG C, the methanol generated in reaction is collected in receiving flask through condenser west tube.Decompression distills out remaining low boiling product and reaction raw materials, obtains target product N, N ＇-bis-erucic acid acyl group ethoxy propane diamine.
The synthesis of (b) 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 ＇-bis-320 parts, 9.6 parts calcium oxide of erucic acid acyl group ethoxy propane diamine and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing unit, agitating device and gas distributor; when limit logical nitrogen limit heating is to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After elimination moisture, it is cooled to 80 DEG C, the sulphuric acid (20wt%) slowly dripping catalyst neutralisation theoretical amount prepares high activity, high selective compound oxidizing calcium alkoxylating catalyst reactant liquor system, system temperature is heated to 80 DEG C, open vacuum system, under a high vacuum dehydration 2 hours, then purge 3 times with nitrogen, system reaction temperature is adjusted to 180 DEG C and slowly passes into 167.1 parts of oxirane, control pressure≤0.60MPa.After reacting ethylene oxide is complete; add 489.4 parts of expoxy propane; reaction is continued in 180 DEG C; reaction purges system with nitrogen after terminating, neutralization, dehydration after cooling; obtain N; N ＇-bis-erucic acid acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=10, z=20) 845.7 parts, molar yield 85.6%.
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; the N that 200 parts of steps (b) are obtained; N ＇-bis-erucic acid acyl group ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=10; z=20) and 10 parts of calcium oleates; heated and stirred at 85 DEG C; mix homogeneously, obtains the compound emulsifying agent for oil base drilling fluid.
[embodiment 3]
The synthesis (x=3) of (a) N, N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine
N-ethoxy propane diamine 55.3 parts, KOH8.33 part are joined in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask, after stirring 1 hour in 150 DEG C, slowly drip methyl soyate (in weight/mass percentage composition, methyl soyate comprises following components: tetradecanoic acid formicester 0.557%, Palmic acid formicester 18.250%, palmitic olefinic acid formicester 1.402%, stearic acid methyl ester 5.495%, oleic acid formicester 30.203%, linoleic acid formicester 36.000%, linolenic acid formicester 3.587%, surplus other.) 277.6 parts, dropwise in 1 hour.Reacting 8 hours at 165 DEG C, the methanol generated in reaction is collected in receiving flask through condenser west tube.Decompression distills out remaining low boiling product and reaction raw materials, obtains target product N, N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine.
The synthesis of (b) 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 ＇-bis-256 parts, 15.4 parts calcium oxide of vegetable oil acid acyl group ethoxy propane diamine and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing unit, agitating device and gas distributor; when limit logical nitrogen limit heating is to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After elimination moisture, it is cooled to 80 DEG C, the sulphuric acid (20wt%) slowly dripping catalyst neutralisation theoretical amount prepares high activity, high selective compound oxidizing calcium alkoxylating catalyst reactant liquor system, system temperature is heated to 90 DEG C, open vacuum system, under a high vacuum dehydration 2 hours, then purge 3 times with nitrogen, system reaction temperature is adjusted to 160 DEG C and slowly passes into 34.9 parts of oxirane, control pressure≤0.60MPa.Reaction purges system with nitrogen after terminating, and after cooling, neutralization, dehydration, obtain N, N ＇-bis-vegetable oil acids acyl group ethoxy propane diamine polyoxyethylene ether (y=3, z=0) 250.8 parts, molar yield 86.2%.
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction, N, the N ＇ that 150 parts of steps (b) are obtained-bis-vegetable oil acid acyl group ethoxy propane diamine polyoxyethylene ether (y=3; z=0) and 50 parts of calcium stearates; heated and stirred at 80 DEG C, mix homogeneously, obtain the compound emulsifying agent for oil base drilling fluid.
[embodiment 4]
The synthesis (x=2) of (a) N, N ＇-stearic bicine diester base hydroxyethylethylene diamine
Joining in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask by N-hydroxyethyl-ethylenediamine 49 parts, KOH2.7 part, after stirring 1 hour in 145 DEG C, slowly dropping methyl stearate 270 parts, dropwised in 1 hour.Reacting 12 hours at 165 DEG C, the methanol generated in reaction is collected in receiving flask through condenser west tube.Decompression distills out remaining low boiling product and reaction raw materials, obtains target product N, N ＇-stearic bicine diester base hydroxyethylethylene diamine.
The synthesis of (b) N, N ＇-stearic bicine diester base hydroxyethylethylene diamine polyethenoxy ether (y=1, z=10)
203 grams of N; N ＇-stearic bicine diester base hydroxyethylethylene diamine and 185.4 parts of expoxy propane react to obtain N in 150 DEG C under the effect of 7.6 parts of calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1); N ＇-stearic bicine diester base dihydroxy ethyl ethylenediamine polyethenoxy ether (y=1; z=10) 348.5 parts, molar yield 87.7%.
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; the N that 100 parts of steps (b) are obtained; N ＇-stearic bicine diester base dihydroxy ethyl ethylenediamine polyethenoxy ether (y=1; z=10) and 10 parts of lauric acids and 10 parts of stearic acid; heated and stirred at 85 DEG C; mix homogeneously, obtains the compound emulsifying agent for oil base drilling fluid.
[embodiment 5]
A) preparation (x=2, y=1, z=0) of lauroyl hydroxyethylethylene diamine
Joining in the reactor being furnished with sealing machine stirring, thermometer, condensing tube, receiving flask by N-hydroxyethyl-ethylenediamine 17 parts, KOH1.75 part, after stirring 1 hour in 120 DEG C, slowly dropping methyl laurate 35 parts, dropwised in 1 hour.Reacting 6 hours at 155 DEG C, the condensed pipe of methanol generated in reaction is collected in receiving flask, and then decompression distills out remaining low boiling product and reaction raw materials, obtains target product fatty acyl hydroxyethyl ethylenediamine 39.7 parts.
B () is for the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction, the lauroyl hydroxyethylethylene diamine 50 parts of steps (a) obtained, 5 parts of oleic acid and 5 parts of calcium oleates, heated and stirred at 85 DEG C, mix homogeneously, obtain the compound emulsifying agent for oil base drilling fluid.
[embodiment 6]
The preparation (x=2) of (a) lauroyl hydroxyethylethylene diamine
Joining in the reactor being furnished with sealing machine stirring, thermometer, condenser west tube, receiving flask by N-hydroxyethyl-ethylenediamine 17 parts, KOH0.35 part, after stirring 1 hour in 150 DEG C, slowly dropping methyl laurate 70 parts, dropwised in 1 hour.Reacting 16 hours at 180 DEG C, the methanol generated in reaction is collected in receiving flask through condenser west tube, and decompression distills out remaining low boiling product and reaction raw materials, obtains target product fatty acyl hydroxyethyl ethylenediamine.
The synthesis of (b) N, N ＇-bis-lauroyls hydroxyethylethylene diamine polyoxyethylene ether (y=5, z=0)
The N that step (a) is synthesized; N ＇-bis-lauroyl hydroxyethylethylene diamine 70 parts, 3.5 parts calcium oxide and calcium hydroxide mixture (calcium oxide and calcium hydroxide weight ratio are 1:1) add in the high-pressure reactor being furnished with condensing unit, agitating device and gas distributor; when limit logical nitrogen limit heating is to 135 DEG C; add 20 parts of water, stirring reaction 1 hour.After elimination moisture, it is cooled to 80 DEG C, the sulphuric acid (20wt%) slowly dripping catalyst neutralisation theoretical amount prepares high activity, high selective compound oxidizing calcium alkoxylating catalyst reactant liquor system, system temperature is heated to 90 DEG C, open vacuum system, under a high vacuum dehydration 2 hours, then purge 4 times with nitrogen, system reaction temperature is adjusted to 140 DEG C and slowly passes into 26.4 parts of oxirane, control pressure≤0.60MPa.Reaction purges system with nitrogen after terminating, and after cooling, neutralization, dehydration, obtain N, N ＇-bis-fatty acyl hydroxyethyl ethylenediamine polyoxyethylene ether (y=5) 83 parts, molar yield 86.2%.
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
In mass fraction; the N that 60 parts of steps (b) are obtained; N ＇-bis-lauroyls hydroxyethylethylene diamine polyoxyethylene ether (y=5) and 10 parts of calcium stearates; join in 150 parts of 5# white oils; heated and stirred at 90 DEG C; mix homogeneously, obtains the compound emulsifying agent for oil base drilling fluid.
[embodiment 7]
With the compound emulsifying agent that [embodiment 1] obtains, preparing oil base drilling fluid system, the basic recipe of employing is 210mL5# white oil+90mL20wt%CaCl2Humic acids+1% butadiene rubber (the number-average molecular weight 250,000)+1wt/vol%CaO powder that aqueous solution+3wt/vol% compound emulsifying agent emulsifying agent+3wt/vol% organoclay (montmorillonite that hexadecyltrimethylammonium chloride is modified)+1wt/vol% cetylamine is modified.
Specific experiment process is: take 210mL5# white oil, it is subsequently adding 3wt/vol% emulsifying agent, stirs, sequentially add 3wt/vol% organoclay, 1wt/vol% modified humic acid, 1% butadiene rubber and 1wt/vol%CaO powder, continue to stir, be eventually adding 90mL20wt%CaCl2Aqueous solution, is stirred for uniformly, obtaining stable water-in-oil type drilling fluid system.The rheological parameter of this water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration is measured respectively according to " GB/T16782-1997 oil base drilling fluid On-Site Test Procedure ".Wherein rheological parameter adopts Qingdao Cacumen et folium clerodendri mandarinori (Clerodendron mandarinorum Diels) to reach mensuration under the ZNN-D6 type six speed rotating cylinder viscometer 50 degrees Celsius of instrumentation factory, and calculates plastic viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV) according to formula (1), (2) and (3)；Emulsion-breaking voltage (ES) is measured by the DWY-2 type drilling fluid electrical stability analyzer 50 DEG C of the sensible instrumentation factory in Qingdao, and 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=(FL30minFL7.5min)×2(mL)
The above-mentioned water-in-oil type drilling fluid prepared is put in XGRL-4 type high temp roller heating furnace, 180 DEG C of high temperature ageing 16h, measuring the rheological parameter of this water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, instrument and process respectively with before aging, result is as shown in table 1.
[embodiment 8]
With the compound emulsifying agent that [embodiment 5] synthesizes, preparing oil base drilling fluid system, the basic recipe of employing is 270mL5# white oil+30mL20wt%CaCl2Humic acids+1wt/vol% EP rubbers (the number-average molecular weight 150,000)+1wt/vol%CaO powder that aqueous solution+2wt/vol% compound emulsifying agent+3wt/vol% organoclay (organoclay that cetyl trimethylammonium bromide is modified)+1wt/vol% cetylamine is modified.With [embodiment 7] specific experiment process, measuring the rheological parameter of these aging front and back of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration respectively, test result is as shown in table 1.
[comparative example 1]
With [embodiment 7], difference substitutes 3wt/vol% compound emulsifying agent with 3wt/vol% oleic acid, and all the other are identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, and result is as shown in table 2.Contrast table 1 data are it can be seen that the rheological property of oleic acid formation is poor, and all beyond measuring range, emulsion-breaking voltage is also low than the system that the emulsifying agent of the present invention is formed and filter loss is bigger.
[comparative example 2]
With [embodiment 7]; difference is with 3wt/vol%N; N ＇-bis-vegetable oil acid acyl group propane diamine (x=3; y=0; z=0) with the compound emulsifying agent of oleic acid quality proportioning to be 4:1 be emulsifying agent dosage 3wt/vol% the substitutes present invention; all the other are identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, and result is as shown in table 2.Contrast table 1 data are it can be seen that the system of N, N ＇-bis-vegetable oil acid acyl group propane diamine formation, and emulsion-breaking voltage is also low than the system that the emulsifying agent of the present invention is formed and filter loss is bigger.
[comparative example 3]
With [embodiment 7]; difference is with 3wt/vol%N; N ＇-bis-vegetable oil acid acyl group propane diamine (x=3; y=0; z=0) with the compound emulsifying agent of oleic acid quality proportioning to be 4:1 be emulsifying agent dosage 3wt/vol% the substitutes present invention; all the other are identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, and result is as shown in table 2.Contrast table 1 data are it can be seen that the system that formed of N, N ＇-bis-vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y=0, z=3), and emulsion-breaking voltage is also low than the system that the emulsifying agent of the present invention is formed and filter loss is bigger.
[comparative example 4]
With [embodiment 7]; difference is with 3wt/vol%N; N ＇-bis-vegetable oil acid acyl group propane diamine (x=3; y=0; z=0) with the compound emulsifying agent of oleic acid quality proportioning to be 4:1 be emulsifying agent dosage 3wt/vol% the substitutes present invention; all the other are identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, and result is as shown in table 2.Contrast table 1 data are it can be seen that the system that formed of N, N ＇-bis-vegetable oil acids acyl group propane diamine polyethenoxy ether (x=3, y=0, z=5), and emulsion-breaking voltage is also low than the system that the emulsifying agent of the present invention is formed and filter loss is bigger.
[comparative example 5]
With [embodiment 7]; difference is with 3wt/vol%N; N ＇-bis-vegetable oil acid acyl group propane diamine (x=3; y=0; z=0) with the compound emulsifying agent of oleic acid quality proportioning to be 4:1 be emulsifying agent dosage 3wt/vol% the substitutes present invention; all the other are identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, and result is as shown in table 2.Contrast table 1 data are it can be seen that the system of INVERMUL formation, and aging front and back rheological property is poor, and all beyond measuring range, emulsion-breaking voltage is also low than the system that the emulsifying agent of the present invention is formed.
[comparative example 6]
With [embodiment 7]; the difference N to obtain in embodiment 1; N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine and N; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine polyoxyethylene ether (y=3; z=5) quality proportioning is 4:1 is emulsifying agent dosage 3wt/vol% alternative composite emulsifying agent; all the other are identical, determine the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, and result is as shown in table 2.
[comparative example 7]
With [embodiment 7]; difference N, N ＇-bis-vegetable oil acid acyl group ethoxy propane diamine alternative composite emulsifying agents to obtain in 3wt/vol% embodiment 1, all the other are identical; determining the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
[comparative example 8]
With [embodiment 7]; the difference N to obtain in 3wt/vol% embodiment 1; N ＇-bis-vegetable oil acid acyl group hydroxyethylethylene diamine polyoxyethylene ether (y=3; z=5) alternative composite emulsifying agent; all the other are identical; determining the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
Comparative example 7 and comparative example 1, comparative example 6～8 are it can be seen that the compound emulsifying agent effect in embodiment 7 is best.
[comparative example 9]
With [embodiment 8]; the lauroyl hydroxyethylethylene diamine that difference obtains in embodiment 5 and oleic acid substitute the compound emulsifying agent of the present invention by quality proportioning 5:1 for emulsifying agent dosage 2wt/vol%; all the other are identical; determining the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
[comparative example 10]
With [embodiment 8]; the lauroyl hydroxyethylethylene diamine that difference obtains in embodiment 5 and calcium oleate substitute the compound emulsifying agent of the present invention by quality proportioning 5:1 for emulsifying agent dosage 2wt/vol%; all the other are identical; determining the rheological parameter of water-in-oil type drilling fluid system, emulsion-breaking voltage and API filtration, result is as shown in table 2.
Table 1
Table 2
Claims (10)
1. for a compound emulsifying agent for oil base drilling fluid, including following components:
(1) primary emulsion, at least one in structure shown in formula (I)；
(2) coemulsifier, at least one in 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 one in H, zinc, ferrum, aluminum, 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 ferrum or aluminum, n=1/3；In mass, described primary emulsion meets 0 < coemulsifier with the ratio of coemulsifier: primary emulsion≤1.
2. the compound emulsifying agent for oil base drilling fluid according to claim 1, it is characterised in that described R1And R3It is independently selected from C11～C23Saturated or undersaturated alkyl, or C11～C23Saturated hydrocarbyl and the mixing alkyl of unsaturated alkyl.
3. the compound emulsifying agent for oil base drilling fluid according to claim 2, it is characterised in that described R1And R3It is independently selected from saturated hydrocarbons or unsaturated alkyl that carbon number is 11,13,15,17,19,21 or the mixing alkyl of the saturated hydrocarbons of 11,13,15,17,19,21 and unsaturated hydrocarbons.
4. the compound emulsifying agent for oil base drilling fluid according to claim 1, it is characterised in that x=2～6, y=1～20, z=0～30.
5. the compound emulsifying agent for oil base drilling fluid according to claim 4, it is characterised in that x is 2 or 3, y is 1～10, z=0～20.
6. the compound emulsifying agent for oil base drilling fluid according to claim 1, it is characterised in that described R4For C11～C23Saturated hydrocarbyl or unsaturated alkyl.
7. a preparation method for the arbitrary described compound emulsifying agent for oil base drilling fluid of claim 1～6, comprises the following steps:
(a)R1CONH(CH2)xNR2CH2CH2The preparation of OH (i.e. fatty acyl hydroxyethyl diamidogen)
R under base catalyst exists1COOCH3(i.e. fatty acid methyl ester) and NH2(CH2)xNHCH2CH2OH (i.e. hydroxyethyl diamine) reacts 2～24 hours at the temperature of 80～220 DEG C, and the reaction methanol that after terminating, preferred decompression is distilled off unreacted raw material and generation obtains described fatty acyl hydroxyethyl diamidogen；Wherein, fatty acid methyl ester is 1:0.1～6 with the mol ratio of hydroxyethyl diamine；
(b)R1CONH(CH2)xNR2(CH2CH2O)y-(CH2CHCH3O)zThe preparation of H (i.e. fatty acyl group diamidogen Polyoxyalkylene ethers):
Under base catalyst exists, the fatty acyl hydroxyethyl diamidogen synthesized by step (a) reacts obtain described fat acyl group diamidogen Polyoxyalkylene ethers with required oxirane or expoxy propane；
C () is for the preparation of the compound emulsifying agent of oil base drilling fluid
The described fat acyl group diamidogen Polyoxyalkylene ethers that described fatty acyl hydroxyethyl diamidogen step (a) obtained and/or step (b) obtain and described coemulsifier; in described ratio mix homogeneously, obtain the described compound emulsifying agent for oil base drilling fluid.
8. the preparation method of the compound emulsifying agent for oil base drilling fluid according to claim 7, it is characterised in that the base catalyst described in step (a) is at least one in alkali metal hydroxide, alkaline earth metal hydroxide.
9. the preparation method of the compound emulsifying agent for oil base drilling fluid according to claim 7, it is characterised in that the base catalyst described in step (b) is at least one in alkaline earth oxide, alkaline earth metal hydroxide.
10. according to the application in oil base drilling fluid of the claim 1～6 arbitrary described compound emulsifying agent for oil base drilling fluid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 李健鹰: "《泥浆胶体化学》", 31 December 1988, 石油大学出版社 * |
Cited By (2)
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|---|---|---|---|---|
| CN112724036A (en) * | 2021-04-02 | 2021-04-30 | 苏州丰倍生物科技有限公司 | Fatty acid derivative, preparation method and application thereof |
| CN112724036B (en) * | 2021-04-02 | 2021-07-16 | 苏州丰倍生物科技有限公司 | Fatty acid derivative, preparation method and application thereof |
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