CN105713588A - Clay-free whole-oil-based drilling fluid for water-sensitive stratum and preparation method of clay-free whole-oil-based drilling fluid - Google Patents
Clay-free whole-oil-based drilling fluid for water-sensitive stratum and preparation method of clay-free whole-oil-based drilling fluid Download PDFInfo
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Abstract
The invention relates to clay-free whole-oil-based drilling fluid for a water-sensitive stratum and a preparation method of the clay-free whole-oil-based drilling fluid, and mainly solves the problems that in the prior art, by emulsion droplets and organic soil particles in oil-based drilling fluid, non-conventional low pressure and low permeability, water sensitiveness and large water-phase activity difference are caused, a solid-phase damaged stratum is easily damaged, and tolerance of the oil-based drilling fluid to water invasion is poor. The drilling fluid comprises the following components in parts by weight: 100 parts of base oil, not less than 0.5 part ofcompound emulsifier comprising a main emulsifier and an auxiliary emulsifier which are shown in a formula (I), 0.1-5 parts of tackifier, 0.5-5 parts of filtrate reducer and 0-5 parts of alkaline substances. According to the technical scheme of clay-free whole-oil-based drilling fluid for the water-sensitive stratum and the preparation method, the problems are solved well. The drilling fluid can be used for a drilling and completion production technology for an oil and gas reservoir which has non-conventional low pressure and low permeability, water sensitiveness and large water-phase activity difference and easily causes the solid-phase damaged stratum.
Description
Technical field
The present invention relates to a kind of without full oil base drilling fluid of clay and preparation method thereof, it is adaptable to unconventional low pressure and low permeability, water sensitivity and aqueous phase activity difference are big and easily cause solid phase and damage the brill well-completing process of oil-gas stratigraphic deposits.
Background technology
Along with constantly reducing and exploitation difficulty of petroleum reserves, countries in the world increase the input to bad ground 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.Current oil field both domestic and external, especially domestic elephant has subsequently entered development late stage, starts to employ the exploration and development of the oil-gas stratigraphic deposits that some low pressure and low permeability oil reservoirs, water sensitivity and aqueous phase activity difference are big and solid phase infringement is serious gradually.The exploitation difficulty of these oil-gas reservoirs is big, and drilling fluid density is required height.In order to prevent drilling fluid leakage and reservoir protec-tion, it is often necessary to the density of drilling fluid is lower than 1.0g/cm3.The system meeting these needs at present is all with gas, oil phase for density palliative.There is many deficiencies due to it in aerated mud or foam drilling fluid, and has compressibility, and pulse signal decay is serious, and horizontal well drilling, extended reach well need to use its use of MWD limit.In low-pressure low-permeability reservoir, more or less containing emulsified water in conventional oil base drilling fluid, the existence of emulsifying water droplet can cause that comparatively serious water lock occurs reservoir.
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 needs to bore that big displacement exceptional well and seaborne horizontal well etc. are special turns drilling well needs.Conventional oil base drilling fluid is generally water in oil emulsion drilling fluid, the conventional calcium chloride brine of aqueous phase therein is to balance stratum water activity, prevent water enchroachment (invasion), water in oil emulsion drilling fluid (aqueous phase content is l0%～40%) has that greasy property is excellent, strong inhibition capability, borehole wall stability and the advantage such as heat-resisting property is good, although being used widely at present, but still suffer from foot scarcely, such as drilling fluid contains a large amount of emulsifying water droplet, plastic viscosity is high, affect rate of penetration, and cause reservoir emulsion droplet to block；For keeping the stability of water-in-oil emulsion, employ a large amount of emulsifying agent, can cause that rock surface is become oleophylic from hydrophilic, cause formation damage；Drilling fluid aqueous phase activity is difficult to, by regulating to balance the activity of water in different stratum of easily collapsing at any time, therefore cannot ensure that various stratum of easily collapsing does not cause aquation to make borehole well instability etc..Therefore be not suitable for unconventional low pressure and low permeability, water sensitivity is strong and aqueous phase activity difference is big and easily causes the brill well-completing process of solid phase infringement oil-gas stratigraphic deposits.And not moisture without the full oil base drilling fluid of clay, emulsifier is few, and also without the equilibrium problem considering drilling fluid aqueous phase activity and formation water activity, thus full oil base drilling fluid is except the advantage with water in oil emulsion drilling fluid, also overcomes above-mentioned deficiency.Can be used for easily collapse stratum, saline bed, the stratum that particularly aqueous phase activity differs greatly, and the low-pressure stratum of energy decline and ocean deepwater drilling.
Research and development currently for this respect, due to the problem that can not solve to take rock, it is full oil base drilling fluid argillaceous mostly, 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 it contains organoclay, easily cause solid phase infringement, and preparation cost is high, limits it and promotes the use of.The report of the accidental full oil base drilling fluid without clay, but the water resistant of its system is invaded poor with the ability of salt contamination, also limit it and promotes the use of.Along with existing oilfield reserve declines day by day, and the exploitation in new exploratory area can run into various bad ground and environment, be badly in need of carrying out meeting low pressure and low permeability oil reservoir, water sensitivity is strong and aqueous phase activity difference is big and solid phase infringement is serious oil-gas stratigraphic deposits exploration and development without the full oil base drilling fluid system of clay, of the present invention just in this case, be suitable for this type of stratum without the full oil base drilling fluid of clay.
Summary of the invention
One of the technical problem to be solved is that in prior art, in oil base drilling fluid, emulsion droplet and organoclay granule cause unconventional low pressure and low permeability, water sensitivity strong and aqueous phase activity difference is big and easily causes the infringement problem on solid phase infringement stratum, there is provided one can solve this problem without the full oil base drilling fluid of clay, meet the special requirements such as this type of oil-gas stratigraphic deposits conventional drilling, big displacement exceptional well, seaborne horizontal well.The two of the technical problem to be solved are to provide a kind of preparation method without clay full 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 without the full oil base drilling fluid of clay, including following components:
The base oil of (1) 100 part；
(2) compound emulsifying agent of primary emulsion and coemulsifier is included no less than 0.5 part, in the quality of contained primary emulsion and coemulsifier；
The viscosifier of (3) 0.1～5 parts；
The fluid loss additive of (4) 0.5～5 parts；
The alkaline matter of (5) 0～5 parts；
Wherein, described primary emulsion at least one in structure shown in formula (I), coemulsifier at least one in the acid of structural fatty shown in formula II or carboxylate；In mass, described primary emulsion meets 0 < coemulsifier with the ratio of coemulsifier: primary emulsion≤1；
In formula, R1For containing C8～C30Saturated or unsaturated alkyl, R2For hydrogen or R3CO, R3For C8～C30Saturated or undersaturated alkyl, 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 technique scheme, the dosage of described compound emulsifying agent, in the quality of contained primary emulsion and coemulsifier, it is preferred to 0.5～5 part；R1、R3It is preferably C11～C23Saturated or unsaturated hydrocarbons, or C11～C23Saturated hydrocarbons and the mixing alkyl of unsaturated hydrocarbons, R1、R3It is more preferably 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；X is preferably 2～6, more preferably 2 or 3；Y is preferably 1～20, more preferably 1～10；Z is preferably 0～30, more preferably 0～20；Described R4It is preferably C11～C23Saturated hydrocarbyl or unsaturated alkyl；M is preferably the one in H, zinc or alkaline-earth metal；Coemulsifier can it is preferred that 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 is preferably coemulsifier with the ratio of coemulsifier: primary emulsion=1:(2～20).One or more the mixture that base oil is preferably in white oil, artificial oil, liquid paraffin；One or more the mixture that viscosifier are preferably in butadiene rubber, butadiene-styrene rubber, EP rubbers, polyalkyl methacrylate；Fluid loss additive is preferably the humic acids that long-chain organic amine is modified, and chain length is preferably C12、C16、C18；Alkaline matter is preferably lime powder.
The key problem in technology of the present invention is the selection of emulsifying agent, all polymer such as butadiene-styrene rubber, EP rubbers, polyalkyl methacrylate are all materials commonly used in the art, 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 commonly used in the art, for instance wetting agent, heavy weight additive, antibacterial etc..
In technique scheme, described more preferably do not include oil base drilling fluid usual component organoclay well-known to those skilled in the art without the full oil base drilling fluid of clay.
In technique scheme, described without the full oil base drilling fluid of clay, with contained oil phase and aqueous phase volume entire volume, more preferably include the water of 0-10%.
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:
A kind of preparation method without the full oil base drilling fluid of clay, 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.The preferred potassium hydroxide of described base catalyst, sodium hydroxide；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; fatty acyl hydroxyethyl diamidogen synthesized by step (a) is 80～180 DEG C with required oxirane or expoxy propane in reaction temperature, reacts and obtain described fatty acyl group diamidogen Polyoxyalkylene ethers when pressure is less than 0.80MPa gauge pressure.At least one in described base catalyst preferably calcium hydroxide, calcium oxide.Catalyst amount is preferably the 0.5～6.0% of fatty acyl hydroxyethyl diamidogen quality.
C described fatty acyl hydroxyethyl diamidogen that step (a) is obtained by () and/or the described fatty acyl group diamidogen Polyoxyalkylene ethers that step (b) obtains and described coemulsifier; in described ratio mix homogeneously, obtain described oil base drilling fluid compound emulsifying agent；
D () is without the preparation of the full oil base drilling fluid of clay
Compound emulsifying agent step (c) obtained is mixed homogeneously with base oil, described alkaline matter, viscosifier, fluid loss additive, obtains described without the full oil base drilling fluid of clay.
In technique scheme, a) reaction temperature in step preferably ranges from 100～200 DEG C, more preferably 120～180 DEG C；Catalyst is preferably alkali metal hydroxide or alkaline earth metal 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.B) catalyst amount is preferably catalyst amount is account for fatty acyl hydroxyethyl diamidogen quality 1～5.0%.
The present invention prepare without the full oil base drilling fluid of clay, owing to the emulsifying agent fatty acyl group diamidogen Polyoxyalkylene ethers molecular structure of use containing polyoxyethylene simultaneously, polyoxypropylene non-ionic group and amide group, make it have good heat-resistant salt-resistant performance, so that stability when this oil base drilling fluid has an excellent high temperature and high salt, there is higher water resistant and invade the ability with salt contamination, owing to system is without emulsifying water droplet, without organoclay, therefore stratum will not be caused water lock and solid phase pollute, thus solving unconventional low pressure and low permeability, water sensitivity is strong and aqueous phase activity difference big and easily causes in solid phase infringement strata drilling process the infringement problem to stratum, it is suitable for exploration and development and the popularization and application of this type of oil reservoir.
Adopt the present invention prepare be applicable to water-sensitive formation without the full oil base drilling fluid of clay, heatproof more than 150 DEG C, API filtration≤10ml, emulsion-breaking voltage >=2000V, water resistant is invaded and is reached 30%, anti-salt contamination 20%, is that a kind of heat resistance is excellent, filter loss is little, the full oil base drilling fluid system of good stability.
The present invention is further elaborated by the examples below.
Detailed description of the invention
[embodiment 1]
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%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction; the N that 60 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 oil base drilling fluid compound emulsifying agent.
D () is without the preparation of the full oil base drilling fluid of clay
Weigh oil base drilling fluid compound emulsifying agent 5 grams that step (c) obtains, measure 200mL5# white oil and add rustless steel height and stir in cup, high-speed stirred 20min, sequentially add the modified humic acids 6 grams of lauryl amine, EP rubbers (number-average molecular weight 50,000) and 6 grams of polymethylacrylic acid cetyl ester (number-average molecular weight 500,000) mixture and CaO powder 3 grams, continue high-speed stirred 20min, obtain stable without the full oil base drilling fluid system of clay.The rheological parameter of this drilling fluid system, emulsion-breaking voltage and API filtration is measured respectively according to " GB/T16782-1997 oil base drilling fluid On-Site Test Procedure ".Wherein rheological parameter adopts the ZNN-D6 type six speed rotating cylinder viscometer that Qingdao Cacumen et folium clerodendri mandarinori (Clerodendron mandarinorum Diels) reaches instrumentation factory to measure at 50 DEG C, and calculates plastic viscosity (PV), yield value (YP) and ratio of dynamic shear force/yield value to plastic viscosity (YP/PV) according to formula (1), (2) and (3)；Emulsion-breaking voltage (ES) is measured at 50 DEG C by the DWY-2 type drilling fluid electrical stability analyzer 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).Result is as shown in table 1.
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)
[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%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
In mass fraction, N, the N ＇ that 100 parts of steps (b) are obtained-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, obtain oil base drilling fluid compound emulsifying agent.
D () is without the preparation of the full oil base drilling fluid of clay
Weigh oil base drilling fluid compound emulsifying agent 8 grams that step (c) obtains, measure 200mL5# white oil and enter rustless steel height and stir in cup, high-speed stirred 20min, sequentially add the modified humic acids 3 grams of cetylamine, butadiene rubber (number-average molecular weight 180,000) 3 grams and CaO powder 4.5 grams, continue high-speed stirred 20min, obtain stable without the full oil base drilling fluid system of clay.Measuring the performance of system with [embodiment 1] (d), result is as shown in table 1.
[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 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 ethoxy propane diamine polyoxyethylene ether (y=3, z=5) 343.7 parts, molar yield 84.7%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
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 ethoxy propane diamine polyoxyethylene poly-oxygen propylene aether (y=3; z=5) and 10 parts of oleic acid; heated and stirred at 90 DEG C, mix homogeneously, obtain oil base drilling fluid compound emulsifying agent.
D () is without the preparation of the full oil base drilling fluid of clay
Weigh oil base drilling fluid compound emulsifying agent 9 grams that step (c) obtains, measure 200mL5# white oil and enter rustless steel height and stir in cup, high-speed stirred 20min, sequentially add the modified humic acids 6 grams of cetylamine, butadiene rubber (number-average molecular weight 250,000) 8 grams and CaO powder 3 grams, continue high-speed stirred 20min, obtain stable without the full oil base drilling fluid system of clay.Measuring the performance of system with [embodiment 1] (d), result is as shown in table 1.
[embodiment 4]
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%.
The preparation of (c) oil base drilling fluid compound emulsifying agent
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.
D () is without the preparation of the full oil base drilling fluid of clay
Weigh oil base drilling fluid compound emulsifying agent 6 grams that step (c) obtains, measure 200mL5# white oil and enter rustless steel height and stir in cup, high-speed stirred 20min, sequentially add the modified humic acids 3 grams of cetylamine, butadiene rubber (number-average molecular weight 200,000) 6 grams and CaO powder 3 grams, continue high-speed stirred 20min, obtain stable without the full oil base drilling fluid drilling fluid system of clay.Measuring the performance of the aging front and back of system with [embodiment 1] (d), result is as shown in table 1.
[comparative example 1]
With (d) in [embodiment 3], difference is with 9g oleic acid alternative composite emulsifying agent, and all the other are identical, determines the performance without the full oil base drilling fluid system of clay, and result is as shown in table 2.
[comparative example 2]
With (d) in [embodiment 3]; difference is with 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 9g the substitutes present invention; all the other are identical, determine the performance without the full oil base drilling fluid system of clay.Result is as shown in table 2.
[comparative example 3]
With [embodiment 3] (d); difference is with N; N ＇-bis-vegetable oil acid acyl group propane diamine polyethenoxy ether (x=3; y=0; z=3) with the compound emulsifying agent of oleic acid quality proportioning to be 4:1 be emulsifying agent 9g the substitutes present invention; all the other are identical, determine without the rheological parameter of the full oil base drilling fluid system of clay, emulsion-breaking voltage and API filtration, and result is as shown in table 2.
[comparative example 4]
With [embodiment 3] (d), being different in that the water adding different quality, all the other are identical, determine the performance without the full oil base drilling fluid system water resistant infringement of clay, and result is as shown in table 3.
[comparative example 5]
With [embodiment 3] (d), being different in that the sodium chloride brine adding 10g variable concentrations, all the other are identical, determine the performance without the anti-saline infringement of clay full oil base drilling fluid system, and result is as shown in table 4.
[comparative example 6]
With [comparative example 5], being different in that and put it into high temperature ageing 12h in roller furnace, all the other are identical, determine without clay full oil base drilling fluid system high-temperature performance after aging, and result is as shown in table 5.
Table 1 for water-sensitive formation without the full oil base drilling fluid system performance of clay
Table 2 for water-sensitive formation without the full oil base drilling fluid system performance of clay
Table 3 invades performance for water-sensitive formation without the full oil base drilling fluid system water resistant of clay
Table 4 for water-sensitive formation without the clay anti-saline performance of full oil base drilling fluid system
Table 5 for water-sensitive formation without the full oil base drilling fluid system heat-resisting property of clay
Claims (10)
1. without the full oil base drilling fluid of clay, including following components:
The base oil of (1) 100 part；
(2) compound emulsifying agent of primary emulsion and coemulsifier is included no less than 0.5 part, in the quality of contained primary emulsion and coemulsifier；
The viscosifier of (3) 0.1～5 parts；
The fluid loss additive of (4) 0.5～5 parts；
The alkaline matter of (5) 0～5 parts；
Wherein, described primary emulsion at least one in structure shown in formula (I), coemulsifier at least one in the acid of structural fatty shown in formula II or carboxylate；In mass, described primary emulsion meets 0 < coemulsifier with the ratio of coemulsifier: primary emulsion≤1；
In formula, 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.
2. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that described base oil is one or more the mixture in diesel oil, white oil, liquid paraffin, artificial oil.
3. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that described R1And R3For C11～C23Saturated or unsaturated alkyl or C11～C23Saturated hydrocarbyl and the mixing alkyl of unsaturated alkyl.
4. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that described x=2～6, y=1～20, z=0～30.
5. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that described alkaline matter is at least one in alkali carbonate, alkali metal oxide, calcium oxide or calcium hydroxide.
6. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that described viscosifier are one or more the mixture in butadiene rubber, butadiene-styrene rubber, EP rubbers, polyalkyl methacrylate, bitumen or oxidized asphalt.
7. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that described fluid loss additive is one or more the mixture in long-chain organic amine modified humic acid, bitumen, oxidized asphalt.
8. according to claim 1 without the full oil base drilling fluid of clay, it is characterised in that the preparation method of described oil base drilling fluid without clay 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; fatty acyl hydroxyethyl diamidogen synthesized by step (a) is 85～180 DEG C with required oxirane or expoxy propane in reaction temperature, reacts and obtain described fatty acyl group diamidogen Polyoxyalkylene ethers when pressure is less than 0.80MPa gauge pressure；
The preparation of (c) compound emulsifying agent:
The described fatty 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 described oil base drilling fluid compound emulsifying agent；
D () is without the preparation of the full oil base drilling fluid of clay
Compound emulsifying agent step (c) obtained is mixed homogeneously with base oil, described alkaline matter, viscosifier, fluid loss additive, obtains described without the full oil base drilling fluid of clay.
9. the preparation method without the full oil base drilling fluid of clay according to claim 8, it is characterised in that the described base catalyst in step (a) is alkali metal hydroxide.
10. the preparation method without the full oil base drilling fluid of clay according to claim 8, it is characterised in that the described base catalyst in step (b) is at least one in alkaline earth metal hydroxide, alkaline earth oxide.
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| CN110249023A (en) * | 2017-02-03 | 2019-09-17 | 沙特阿拉伯石油公司 | Enhancing filtering control packet, using its wellbore operations fluid and maintain shaft structure method |
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